TW200804519A - Liquid crystal alignment agent for ink-jet coating and liquid crystal display device - Google Patents

Abstract

The present invention relates to a liquid crystal alignment agent for ink-jet coating and liquid crystal display device, and provides the liquid crystal alignment agent to form liquid crystal alignment film without poor coating and unevenness of coating due to jam of nozzle, and so can form the liquid crystal alignment film with even thickness by ink-jet coating on a substrate. The liquid crystal alignment agent for ink-jet coating is a polymer including a polyamic acid synthesized by the addition reaction of a tetracarboxylic acid dianhydride and a diamine compound and/or a imidized polymer made from imidizing the polyamic acid, and the average imidized ratio that represents the ratio of imidized bonding unit in the total amount of the aforementioned polymer is within the range of 0~55 mol%.

Description

[Technical Field] The present invention relates to a liquid crystal alignment agent for inkjet coating and a liquid crystal display element having a liquid crystal alignment film formed of the alignment agent. More specifically, when the liquid crystal alignment film is formed on the substrate by the inkjet coating method, the coating does not cause clogging of the nozzle or the like, and the coating is not uniform, and the liquid crystal alignment excellent in film thickness uniformity can be formed. A liquid crystal alignment agent for a film and a liquid crystal display element having a beautiful image. [Prior Art] Since the liquid crystal electronic calculator has been mass-produced from the viewpoints of saving space and reducing power consumption, liquid crystal display elements represented by liquid crystal displays have been applied to clocks, portable game machines, and word processors. , notebook PCs, car navigators, portable cameras, PDAs, digital cameras, mobile phones, various monitors, LCD TVs and many other fields, and continue to carry out active development. As a liquid crystal display element, a TN (Twisted Nematic) type liquid crystal display element and a TN type which are continuously twisted by 90 degrees from one substrate to another substrate using a nematic liquid crystal having positive dielectric anisotropy and a long axis of liquid crystal molecules are used. An STN (Super Twisted Nematic) type liquid crystal display element having a high contrast of a liquid crystal display element has been widely used. In recent years, in order to further improve the display quality of liquid crystal displays, VA (V ertica 1 A1 ignment) type liquid crystal display elements, IP S (I η P1 ane S witching) type liquid crystal display elements, and viewing angles have been developed with small viewing angle dependence. Optically compensated bending (OCB) type liquid crystal display elements with excellent dependence and high image response performance. In the liquid crystal display element, the member for controlling the liquid crystal alignment is a liquid crystal alignment 200804519 film. In the liquid crystal alignment film, a ruthenium-imided polymer obtained by imidating a polyamic acid and the polyphosphonium amide by a roll coating method, a spin coating method, a flexographic printing method, or the like has been studied. A method in which a liquid crystal alignment agent is applied onto a substrate and then heated to dry the coated surface. Among them, the flexographic printing method has been specifically studied for its ability to adapt to various substrate sizes and high productivity. However, the flexographic printing method has (1) a method of coating by contact with a printing plate, and a contaminant is mixed, (2) a liquid crystal alignment agent is used in a large amount (high cost), and (3) When the printing plate is changed in size of the substrate, the productivity of the plurality of types is poor, and (4) the problem of coating the substrate or the curved substrate having a large unevenness is difficult. Therefore, it is urgent to develop a substitute coating method. For this reason, a method of forming a film by a liquid crystal alignment agent by an inkjet coating method has been attracting attention as a method for solving the above problem of the flexographic printing method. The inkjet coating method has (1) can be adapted to various substrate sizes, (2) is a non-contact coating method, and thus it is possible to avoid contamination of a contaminant, and (3) use only a necessary amount of a liquid crystal alignment agent, thereby reducing cost, ( 4) Even if the size of the panel is changed, it is possible to adapt to the advantages of multiple varieties only by changing the injection mode. In the inkjet coating method, since the liquid crystal alignment agent is required to be ejected at a high speed by a very fine nozzle, the liquid crystal alignment agent used for the inkjet coating is required to have no resistance and excellent fluidity when a strong external force is applied. Further, in order to obtain a liquid crystal alignment film having uniform wettability, it is important to control the wettability of the droplets falling on the substrate. In other words, if the wettability of the liquid droplets is too large, the edge shape of the applied liquid crystal alignment film is not uniform, and if the wettability of the liquid droplets is too small, the in-plane uniformity of the liquid crystal alignment film is impaired. In order to improve the coating property of the liquid crystal alignment agent for inkjet, the liquid crystal alignment agent composition is optimized by using the surface tension of the liquid crystal alignment agent, the type of solvent used for the liquid crystal alignment agent, the solid content concentration, and the viscosity of 200804519 degrees. Investigate (refer to Patent Documents 1 to 5). However, in the actual production, when the ink jet coating is continuously performed, a problem which cannot be solved by optimizing the above parameters of the liquid crystal alignment agent such as the solvent used, the surface tension, the solid content concentration, and the viscosity is generated. For example, in general, a liquid crystal alignment agent is stored in a frozen state at a low temperature of 0 ° C or lower, and then thawed at room temperature. However, conventional liquid crystal alignment agents generate polymer agglomerates during cryopreservation, and even The condensate cannot be completely eliminated after thawing at room temperature, and it will become a cause of clogging of the ink nozzle when the ink jet apparatus is continuously operated, and as a result, poor coating and uneven coating will occur. Based on these examples, in addition to optimizing parameters such as solvent, surface tension, solid content concentration, and viscosity, the liquid crystal alignment agent for inkjet is also required to improve the amount of particles used as an agglomerate in the alignment agent. Excellent coating stability is also exhibited when the ink jet apparatus is continuously operated. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2000-240 No. The present invention has been made based on the above circumstances, and therefore, it is an object of the present invention to provide a method of applying ink by inkjet coating. When a liquid crystal alignment film is formed on a substrate, a liquid crystal alignment agent which can form a liquid crystal alignment film having excellent film thickness uniformity and which is formed by the liquid crystal alignment agent can be formed without causing poor coating and uneven coating due to clogging of the nozzle. The liquid crystal alignment film realizes the beautiful image of the liquid crystal display 200804519. According to the present invention, the above object of the present invention is first achieved by an ink jet crystal alignment agent characterized by containing a polyamic acid selected from the group consisting of an addition polymerization reaction of a tetracarboxylic acid dianhydride amine compound and a capping agent. At least one of the ruthenium iodide polymers obtained by imidization of ruthenium amide represents a ratio of oxime imidization unit of 0 to 55 mol% of the ratio of quinone imine bonding units in the total amount of the above polymer. range. Further, according to the present invention, the object of the present invention is to provide a liquid crystal display element of a liquid crystal alignment film comprising a liquid crystal alignment agent for inkjet. The liquid crystal alignment agent of the present invention is suitable for use in inkjet coating. When a liquid crystal alignment film is formed on a substrate by a coating method, coating is not caused by the nozzle, and coating is not uniform, and a film can be obtained. A liquid crystal alignment film having a uniform thickness can obtain a liquid crystal display element having a beautiful image according to the liquid crystal alignment formed by the liquid crystal alignment agent. The liquid crystal display element having the liquid crystal alignment film of the present invention can be selected from liquid crystal display elements other than φ TN type, STN type, VA type, IPS type, and OCB type, and is suitable for SH (Super Homeotropic) type, sex and anti-iron. Electrical liquid crystal display elements and the like. Moreover, the liquid crystal display element having the liquid crystal alignment film of the present invention can be used for various devices, for example, for a desktop calculator, a clock, a display board, a portable game machine, a word processor, a notebook type personal electric car navigator, Portable camera 'PD A, digital camera, action, various monitors, LCD TVs and other display devices. [Embodiment] The liquid and the second polymerization polymerization have an upper part of the inkjet nozzle plugging excellent film, which is used for digital electrophoresis through the ferroelectric effect, I, 200804519 [polyproline and hydrazine imidization polymerization The invention will be specifically described below. The liquid crystal alignment agent of the present invention contains a polyimine acid synthesized by addition polymerization of a tetracarboxylic dianhydride and a diamine compound, and a ruthenium imidized polymer obtained by imidating the above polyphosphonium hydrazide. At least one polymer. The average oxime imidization ratio indicating the ratio of the quinone imine bond unit in the total amount of the above polymer is in the range of 〇 to 55 mol%. When the average ruthenium imidization ratio is higher than 55 mol%, agglomerates of the polymer are generated during the cryopreservation of the liquid crystal alignment agent, which becomes a cause of clogging of the ink nozzle or pinhole generation. In the present invention, by setting the average ruthenium imidization ratio of the polymer to 55 mol% or less, it is possible to provide a liquid crystal alignment agent for inkjet which does not cause the above problems. [Tetracarboxylic acid dianhydride] The polyamic acid contained in the liquid crystal alignment agent of the present invention and the ruthenium iodide obtained by imidating the above polyphosphonium hydrazide are, for example, the following four-residual acid The acid anhydride is synthesized as a raw material. Examples of the tetracarboxylic acid dianhydride include butane tetracarboxylic acid dianhydride, 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, and 1,2-dimethyl-1,2,3. 4-cyclobutane tetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,3_ dichloro-1,2,3,4- Cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane IV Carboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 3,3,4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxyl ring Amyl acetal dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, l,3,3a,4,5,9b - hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&,4 ,5,91)-hexahydro-5-methyl-5-(tetrahydro 200804519

-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&,4,5,91)-hexahydro- 5-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3& 4,5,91)-hexahydro-7-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3 - Diketone, 1,3,3^,4,5,91)-hexahydro-7-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2 -c]-furan-1,3-dione, 1,3,3&,4,5,91)-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3 -furyl)-naphthalene [1,2-(:]-furan-1,3-dione, 1,3,33,4,5,91)-hexahydro-8-ethyl-5-(tetrahydrogen) -2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan·1,3-dione, 1,3,3a,4,5,9b-hexahydro-5, 8-Dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]·furan-1,3-dione, 5-(2,5 -dioxotetrahydrofuran methylene)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, 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- Base norbornane-2:3,5:6-dianhydride, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride, 4,9-dioxatricyclo[ 5.3·1·02,6]undecane-3,5,8,10-tetraketone, an aliphatic and/or alicyclic tetracarboxylic dianhydride such as a compound represented by the following formulas (1) and (2) ;

(wherein, Ri and R3 represent a divalent organic group having an aromatic ring, R2 and -10- 200804519 r4 represents a hydrogen atom or an alkyl group, and a plurality of R2 and R4 present may be the same or different); Pyromellitic dianhydride '3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,3,3,4'-benzophenonetetracarboxylic dianhydride, 2,2',3 , 3'-benzophenone tetracarboxylic acid dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2 , 3,6,7-naphthalenetetracarboxylic acid dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic acid dianhydride, 3,3',4,4'-dimethyldiphenyl Decane tetracarboxylic acid dianhydride, 3,3',4,4'-tetraphenylnonane tetracarboxylic acid dianhydride, φ 1,2,3,4-furan tetracarboxylic dianhydride, 4,4'-di ( 3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsebacic anhydride, 4,4'-di(3) , 4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene di phthalic anhydride, 3,3',4,4' - linked Pyromellitic dianhydride, Di(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, two (triphenylphthalic acid)-4,4'-diphenylether dianhydride, bis(triphenylphthalic acid)-4,4'diphenylmethane dianhydride, ethanediol-di(dehydration) Trimellitic acid ester), propylene glycol-di(hydroper trimellitate), 1,4-butanediol-di (dehydrated trimellitate), 1,6-hexanediol-di (dehydration partial) Triglyceride), 1,8-octanediol-di(hydroper trimellitate), 2,2-bis(4-hydroxyphenyl)propane-di(hydrogen trimellitate), An aromatic tetracarboxylic acid dianhydride represented by each of the formulae (3) to (5). -11- 200804519

These tetracarboxylic dianhydrides may be used alone or in combination of two or more. Among the above tetracarboxylic dianhydrides, 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,3-dimethyl-1 are preferred from the viewpoint of exhibiting good liquid crystal alignment. 2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentane tetracarboxylic acid dianhydride, 1,2,4,5-cyclohexane tetracarboxylic acid dianhydride, 2 ,3,5-tricarboxycyclopentyl acetic acid dianhydride, 5-(2,5-dioxotetrahydrofuranmethylene)-3-methyl-3-cyclohexene·1,2-dicarboxylic acid dianhydride ,l,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[l,2-c]furan-1,3- Dione, l,3,3a,4,5,9b- 12- 200804519 hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-yranyl)-naphthoquinone, 2 - c ] furan-1,3-dione, 1,3,3&,4,5,913-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3 -furyl)-naphthalene [l,2-c]furan-1,3-dione, bicyclo[2·2·2]-oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride , 3-oxabiindole [3.2'1]octane-2,4-dione-6·spiro-3,-(tetrahydrofuran-2,5,-dione), 3,5,6·tricarboxyl -2·carboxynorbornane-2:3,5·.6-dianhydride, bicyclo[3,3.0] xinyuan-2,4,6,8-tetracarboxylate Diacid anhydride, 4,9-dioxatricyclo[5.3.1.02,6]undecane-3,5,8,10-tetraketone, the following formula (6) in the compound represented by the above formula (1) And a compound represented by the following formula (9) in the compound represented by the above formula (2), pyromellitic dianhydride, and 3,3',4,4'-benzophenone IV. Carboxylic acid dianhydride, 2,3,3',4'-benzophenone tetracarboxylic acid dianhydride, 2,2 ',3,3'-benzophenone tetracarboxylic acid dianhydride, 3,3 ', 4, 4'-Diphenylstilbene tetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride. The aspect in which it is difficult to produce polymer agglomerates in cryopreservation is particularly preferable to 1,2,3,4·cyclobutanetetracarboxylic acid dianhydride, hydrazine, 3·dimethyl-1,2,3,4 - cyclobutane tetracarboxylic acid dianhydride, I, 2,4,5-cyclohexane tetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, dioxo-3-furanyl )-naphthalene H,2-c]furan-1,3-dione, 13,33,4,5,91)-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo -3-furanyl)-naphthalene H,2-c]furan-1,3-two-awake, 3-oxabiguanide[3·2·1]semi-inden-2,4 -^^-6-snail -3 - (tetramethylene furan-2,5,-dione), 3,5,6-tricarboxy-2-carboxynorbornane-2:3,5:6-dianhydride, bicyclo[3· 3.0] Octane 2,4,6,8-tetracarboxylic dianhydride, 4,9-dioxatricyclo[5·3·1·〇2,6]deca--3,5,8, A liquid crystal alignment agent composed of a polymer composed of 10-tetraketone, pyromellitic dianhydride, and 3,3,4,4'-benzophenonetetracarboxylic acid dianhydride as a raw material. -13- 200804519

When the liquid crystal alignment agent of the present invention is used for the TN type, STN type, OCB type, or VA type, it is preferred that the diamine compound used in the synthesis of the polyamic acid and the ruthenium iodide polymer has the following formula (10). Or a diamine compound each having a component exhibiting a pretilt angle represented by the following formula (11).

(wherein R5 and R6 are each independently a hydrogen atom or a methyl group, and R7 is a linear or branched alkyl group having 1 to 20 carbon atoms. Further, R8 and R9 are each independently a divalent organic group. group). -14- 200804519

(wherein a is 0 or 1, R". It is selected from the group consisting of an ether bond (), a carbonyl group (_c〇_), a mineral oxygen group (-C00-), an oxycarbonyl group (_oc〇·), a guanamine bond. (-nHC〇_, -CONH-), a thioether bond (-S-) and a divalent organic group of a methyl group, and R11 is a divalent organic group different from R!. a group of a group of a skeleton, a group having a fluorine atom or a group of a group having a linear alkyl group having 1 to 22 carbon atoms). These diamine compounds having a component exhibiting a pretilt angle are used singly or in combination of two or more kinds. Specific examples of the diamine represented by the above formula (10) include, for example, compounds represented by the following formulas (12) and (13).

-15- 200804519

Specific examples of the diamine represented by the above formula (1 1) include, for example, compounds represented by the following formulas (14) to (18).

-16- 200804519

When the liquid crystal alignment agent of the present invention is used in the TN type, the STN type, or the OCB type, it can stably exhibit 1 to 30 by using the diamine having the component exhibiting the pretilt angle represented by each of the above (12) to (18). ° LCD pretilt angle. At this time, the ratio of these diamines having a component exhibiting a pretilt angle is preferably from 0.5 to 30 mol%, more preferably from 0.7 to 20 mol%, particularly preferably from 1 to 15 mm%, based on the entire diamine. When the liquid crystal alignment agent of the present invention is used in the VA type, it is particularly preferable to use the respective formulas (14) and (15) in the diamine having the component exhibiting the pretilt angle from the viewpoint of exhibiting excellent liquid crystal vertical alignment. The compound represented. The ratio of these diamines is preferably from 8 to 60 mol%, more preferably from 9 to 50 mol%, particularly preferably from 1 to 25 mol%, based on the entire diamine. When the liquid crystal alignment agent of the present invention is used in the IPS type or the FFS type, the diamine having the component exhibiting the pretilt angle may be used. However, generally, only the diamine compound having the pretilt angle component described later may be used. Other diamine compounds are synthetic polymers. The other diamine compound which is different from the above-described diamine compound having a pretilt angle component used for the synthesis of the polymer for use in the liquid crystal alignment agent of the present invention may, for example, be the following diamine. Examples thereof include p-phenylenediamine, m-phenylenediamine, 4,4,-diaminodiphenylcarbendrie, 4,4'-diaminodiphenylethane, and 4,4,diamine. Diphenyl thioether, 4,4-tetraene-phenyl-platinum, 4,4'-diamino-2,2'-dimethylbiphenyl, 4,4'-diaminobenzimidazole Aniline, 4,4'-diaminodiphenyl ether, 1,5-diamine-17- 200804519, naphthalene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 5-amine 1-(4'-aminophenyl)-1,3,3-trimethylindan, 6-amino-1-(4'-aminophenyl)-1,3,3-tri Methyl indane '3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diamine Benzophenone, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-di [4-(4-Aminophenoxy)phenyl]anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,4-bis(4-aminobenzene) Oxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3_bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl φ group )-10-hydroquinone, 2,7-diaminopurine, 9,9-bis(4-aminobenzene)芴, 4,4' - methyl-bis(2-chloroaniline), 2,2',5,5'-tetrachloro-4,4'diaminobiphenyl, 2,2' - Dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'diaminobiphenyl, 1,4,4 '-(p-phenylene isopropylidene) diphenylamine, 4,4'-(m-phenylene isopropylidene)diphenylamine, 2,2'-bis[4-(4-amino group -2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-diamino -2,2,-dimethylbiphenyl, 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl, 1,3-φ di(4) -aminophenoxy)-2,2-dimethylpropane, 4,4'-bis(4-aminophenoxy)biphenyl, 9,9-dimethyl-2,7-diamino Anthracene diamine; 3,6-diaminosostazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-benzene 3-,6-diaminocarbazole, N,N'-bis(4-aminophenyl)-benzidine, N,N'-bis(4-aminophenyl)-N,N' - Dimethyl-benzidine, 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diamine Pyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3·dicyanopyrazine, 5,6-diamino-2,4-dihydroxypyrimidine, 2,4-di Amino-6-dimethylamino-1,3,5-triazine, 1,4-bis(3-aminopropyl)pyridazine, 2,4-diamino-6-isopropoxy- 1,3,5-triazine, -18- 200804519 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-phenyl-1 ,3,5-trisyl, 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-uj-triazine, 4,6-diamino-2-ethene Base_s_triazine, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3 ,5-Diamino-1,2,4-trimethyl, 6,9-diamino-2-ethoxyacridine lactate, 3,8-diamino-6-phenylphenanthrene , hydrazine, 4-diaminopyridazine, 3,6-diamino acridine, bis(4-aminophenyl)phenylamine, and the compounds represented by the following formulas (19) and (20) a diamine having two first-order amine groups in the molecule and a nitrogen atom other than the first-order amine group; η2ν

(wherein R13 represents a monovalent organic group having a cyclic structure containing a nitrogen atom selected from the group consisting of pyridine, pyrimidine, triazine, acridine and pyridazine, and X represents a divalent organic group).

(wherein Rm represents a divalent organic group having a ring structure containing a nitrogen atom selected from the group consisting of ruthenium ratio η, pyrimidine, triazine, osmium, and ruthenium). 1,3 · bis(aminomethyl)cyclohexane, 1,3 -propylenediamine, butanediamine 'pentanediamine, hexamethylenediamine, heptanediamine, octanediamine, decanediamine, 4,4- Diamine heptanediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadiene diamine, six-19- 200804519 hydrogen-4,7-methylene Aliphatic and alicyclic two such as methyldiamine, tricyclo[6.2.1.02'7]-undecene dimethyldiamine, 4,4'-methylbis(cyclohexylamine) An amine; a diamine organooxane represented by the following formula (21); η2ν

Ηη2 (wherein a hydrocarbon group having 1 to 12 carbon atoms is represented, and a plurality of R15 groups may be the same or different, p is an integer of 1 to 3, and q is an integer of 1 to 20). These diamine compounds which are different from the diamine compound having a component exhibiting a pretilt angle may be used singly or in combination of two or more kinds. Among them, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,7-di are preferred. Aminoguanidine, 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-di ( 4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl) linkage Benzene, 4,4'-diamino-2,2'-dimethylbiphenyl, N,N'-bis(4-aminophenyl)-benzidine, N,N'-di(4-amine Phenyl)·Ν,Ν'-dimethyl-benzidine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diamine a compound represented by the following formula (22) and a compound represented by the following formula (23) in the compound represented by the above formula (20), 1,3-di (a compound of the compound represented by the following formula (19); Amine methyl)cyclohexane, 1,4-cyclohexanediamine, 4,4'-methylbis(cyclohexylamine), the above formula (21 In the compound represented by the formula (24), 3,3'-(tetramethyldioxane-1,3-diyl)-20- 200804519 bis(propylamine) •••(2 2) Μ H2

.(twenty three)

H2n-^ch female ch3 ch3 I Si Ο 丨H ^ CH2^-NH2 . . . (24) ch3 ch3 As a particularly preferable one, p-phenylenediamine, 4,4'-diaminodiphenyl Methane, 4,4'-diamino-2,2'-dimethylbiphenyl, 4,4'-diaminodiphenyl ether, 2,7-diamino fluorene, 9,9-di ( 4-aminophenyl)anthracene, 3,3'-(tetramethyldioxane-1,3-diyl)di(propylamine), 2,2-bis[4-(4-aminophenoxyl) Phenyl]propane, 1,3-bis(aminomethyl)cyclohexane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-diamino-2, 2'-bis(trifluoromethyl)biphenyl, N,N'-bis(4-aminophenyl)-benzidine, N,N'-bis(4-aminophenyl)-N,N' - Dimethyl-benzidine. <Synthesis of Polylysine> The use ratio of the tetracarboxylic dianhydride to the diamine compound used in the polyamic acid synthesis reaction of the present invention is preferably -21 to 1 equivalent of the diamine compound. The amine group contained in 200804519 is such that the acid anhydride group of the tetracarboxylic acid dianhydride has a ratio of 0.2 to 2 equivalents, more preferably a ratio of 0.3 to 1.2 equivalents. The synthesis reaction of poly-proline is preferably carried out in an organic solvent at a temperature of from -2 to 150 Torr, more preferably at a temperature of from 〇1 to 1 Torr. 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, N,N-dimethylacetamide, and N,N. - aprotic polar solvents such as dimethylformamide, dimethylhydrazine, r-butyrolactone, tetramethylurea, hexamethylenephosphonium triamine; m-methylphenol, xylenol, phenol, halogen A phenolic solvent such as phenol may be used, and these solvents may be used alone or in combination of two or more. Further, when the total amount of the tetracarboxylic dianhydride and the diamine compound is (b), the amount (a) of the organic solvent is preferably such that the total amount of ruthenium (b) relative to the reaction solution (a + b) is An amount of 0.1 to 30% by weight. Further, in the range in which the produced polyaminic acid is not precipitated, the organic solvent may be used in combination with a poor solvent of polylactoic acid, alcohols, ketones, esters, ethers, halogenated hydrocarbons. Classes and hydrocarbons, etc. Specific examples of such a poor solvent include methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, 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 methoxypropionate Ethyl ethoxypropionate, propylene carbonate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol n-propyl ether, ethylene glycol Propyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diglyme, diethylene glycol diethyl ether, diethylene glycol monomethyl ether , diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, -22- 200804519 1,2-dichloroethane, 1,4-two Chlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, diisobutyl ketone, isoamyl propionate, isobutyric acid Esters, diisoamyl ether and the like. These poor solvents may be used singly or in combination of two or more kinds. In the preparation of the liquid crystal alignment agent, the reaction solution thus obtained can be used as it is. Further, the reaction solution is poured into a large amount of a poor solvent to obtain a precipitate, and the precipitate is dried under reduced pressure or the reaction solution is depressurized by an evaporator to obtain polylysine. Further, the polyproline is re-dissolved in an organic solvent, and then subjected to a process of precipitation by a poor solvent or a process of distilling off under reduced pressure with an evaporator, whereby the polyamine can be purified. <醯i-Iminylated Polymer> The ruthenium iodide polymer used in the liquid crystal alignment agent of the present invention can be synthesized by dehydrating and ring-closing the above polyamic acid. The so-called quinone imidized polymer here includes a partially yttrium-imided polymer partially yttrium-imidized with the above polyamic acid and a 100% quinned imidized polymer, and the following is collectively referred to as "醯亚Φ Aminated polymer". The oxime imidization ratio of the ruthenium iodide used in the liquid crystal alignment agent of the present invention is preferably 10 to 100 mol%, more preferably 20 to 95 mol%, particularly preferably 4 5 to 90 mole. %. However, when a ruthenium-imiding polymer having a ruthenium iodide ratio of more than 55 mol% is used, it cannot be used alone, and it is necessary to add an appropriate amount of polyamic acid and a sulfhydrylation ratio of 5 5 m. At least one of the quinone imidized polymers having a % or less is adjusted to have an average oxime imidization ratio of 55 mol% or less in all the polymers contained in the liquid crystal alignment agent. Here, the "rhodium imidization ratio" means the ratio of the ratio of the repeating unit of the proline in the polymer to the total number of repeating units of the phthalocyanine-23-200804519, and the ratio of the number of repeating units of the quinone imine is expressed in %. At this time, a part of the quinone imine ring is an isoindole ring and is also included in the number of repeating units of the quinone imine. As a method for synthesizing a ruthenium-imidized polymer, (1) a method of synthesizing by dehydration ring closure by heating the above polyamic acid, (π) by dissolving the above polylysine in an organic solvent A method in which a dehydrating agent and a dehydration ring-closure catalyst are added to the solution and heated to carry out dehydration ring closure as needed is carried out, and by appropriately controlling the above reaction conditions, a polymer having a desired quinone imidization ratio can be obtained. The reaction temperature in the above (I) method of heating the polyamic acid is preferably from 50 to 300 ° C, more preferably from 100 to 25 ° C. When the reaction temperature is less than 50 °C, the dehydration ring closure reaction cannot be completed. If the reaction temperature exceeds 300 °C, the molecular weight of the obtained quinone imidized polymer may be lowered. On the other hand, in the method of adding a dehydrating agent and a dehydration ring-closure catalyst to the polyamic acid solution of the above (II), an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent is preferably 0.01 to 20 moles per 1 mole of the polyamido acid repeating unit. Further, as the dehydration ring-closure catalyst, a tertiary amine such as pyridine, trimethylpyridine, dimethyl D to D-denier or triethylamine can be used. However, the dehydrating agent and the dehydration ring-closing catalyst are not limited to these examples. The amount of the dehydration ring-closing catalyst to be used is preferably 〇. 〇丨 丨〇 丨〇 相. In addition, as the organic solvent used in the dehydration ring-closure reaction, the same organic solvent as exemplified as the solvent used in the synthesis of polyamic acid can be mentioned. Further, the reaction temperature of the dehydration ring-closing reaction is preferably 〇~1 8 q, more preferably 6 0 to 1 5 01:. Further, the ruthenium iodide polymer can be purified by subjecting the reaction solution thus obtained to the same operation as the method of purifying the proline acid-free-24-200804519. <End-Modified Polymer> The poly-proline and the quinone imidized polymer constituting the liquid crystal alignment agent of the present invention may be a terminal-modified polymer having a molecular weight adjusted. By using the terminal-modified polymer, the coating characteristics and the like of the liquid crystal alignment agent can be improved without impairing the effects of the present invention. Such a terminally modified polymer can be synthesized by adding, for example, a monobasic acid anhydride, a monoamine compound, a monoisocyanate compound or the like to the reaction system in the synthesis of polyamic acid. Here, the φ is a monobasic acid anhydride, and examples thereof include a dicarboxylic acid monobasic acid anhydride, and examples thereof include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, and n-four. Alkyl succinic anhydride, n-hexadecyl succinic anhydride or the like. Further, examples of the monoamine compound include aniline, cyclohexylamine, p-ethylaniline, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, and Undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecaneamine, n-heptadecaneamine, n-octadecylamine, n. Alkylamine and the like. Further, examples of the monoisocyanurate compound include phenyl isocyanate and naphthyl isocyanate. <Molecular Weight of Polymer> Polylysine and quinone imidized polymer constituting the liquid crystal alignment agent of the present invention are passed through gel permeation chromatography (GPC, dimethylformamide solvent, converted to polyphenylene) In the molecular weight measurement carried out, the weight average molecular weight (M w) is 10,000 to 300,000, more preferably 20,000 to 250,000, particularly preferably 30,000 to 200,000, and the number average molecular weight (Μη) is 1 000~ 150,000, more preferably 2,000 to 130,000, more preferably 5,000 to 100,000. When the above-mentioned number average molecular weight (?n) is less than 100.0' or the weight average -25-200804519 molecular weight (Mw) is less than 10,000, the electric properties such as the voltage holding ratio of the formed liquid crystal alignment film may be remarkably lowered. On the other hand, when the number average molecular weight (Mn) is 150,000 or more, or the weight average molecular weight (Mw) is 300,000 or more, when the alignment agent is stored at a temperature of 0 ° C or lower, polymer agglomerates are easily generated. The clogging of the ink jet nozzle occurs, and the amount of ink ejection is unstable, resulting in poor coating. <Liquid Crystal Aligning Agent> The liquid crystal alignment agent of the present invention is obtained by subjecting a polyamic acid selected from the group consisting of a tetracarboxylic dianhydride and a diamine compound to addition polymerization, and imidating the above polyphosphonium amide. At least one polymer of the quinone imidized polymer and other additives as needed are preferably dissolved in an organic solvent. The polymer constituting the liquid crystal alignment agent indicates that the average ruthenium imidization ratio of the ruthenium bond unit ratio in the total amount of the polymer is adjusted to a range of 0 to 55 mol%. Examples of the polymer used in the present invention include (A) one or more polylysines (average oxime imidization ratio = 0%), and (B) a polyphosphonic acid and a ruthenium amide ratio. 55 mol% or less of at least one polymer of at least one ruthenium iodide polymer, (C) selected from the group consisting of polyamido acid and ruthenium iodide having a ruthenium ratio of 0 to 55 mol% a mixture of at least one polymer and a ruthenium imidized polymer having a ruthenium iodide ratio of more than 55 mol% (hereinafter referred to as "sorghum imidization polymer"), and an average yttrium imine of all polymers The rate is adjusted to less than 55 mol%. Among them, from the viewpoint of improving performance such as voltage holding ratio and image residual resistance (residual DC), it is preferred to use (B) one selected from the group consisting of polylysine and a sulfhydrylation ratio of 55 mol% or less. At least one polymer of the above ruthenium iodide polymer, (C) at least one polymer selected from the group consisting of polyamido acid and ruthenium iodide having a quinone imidization ratio of 0 to 55 mol% and sorghum A mixture of imidization rates of poly-26-200804519. Further, the average ruthenium iodide ratio in the polymer is preferably from 10 to 55 mol%, particularly preferably from 15 to 55 mol%, because high voltage retention can be obtained. Further, when (C) a mixture of at least one polymer selected from the group consisting of polyamido acid and quinone imidized polymer having a sulfonium iodization ratio of 0 to 55 mol% and a sorghum imidization polymer is used The ruthenium imidization rate of the sorghum imidization rate polymer is preferably from 60 to 100 mol%, and particularly preferably from 〜 imidization ratio of from 70 to 97 mol%. The sorghum imidized polymer is preferably used in combination with poly-proline, especially when φ is selected from 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-two Methyl•1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 4,9-dioxatricyclo[5.3.1.02,6 1 or more tetracarboxylic dianhydrides of undecane·3,5,8,10-tetraketone, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride and pyromellitic dianhydride And selected from the group consisting of p-phenylenediamine, 4,4,-diaminodiphenylmethane, 2,7-diaminostilbene, 4,4,-diaminodiphenyl ether, 9,9-di ( 4-aminophenyl)anthracene, bis(4-aminophenyl)hexafluoropropane, 4,4,-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4, -diamino 2,2,-dimethylbiphenyl φ and 3,3·(tetramethyldioxane-1,3-diyl)di(propylamine), hydrazine, hydrazine, di(4- Polyamino phthalic acid obtained by reacting one or more diamines of aminophenyl)-benzidine, hydrazine, hydrazine, -bis(4-aminophenyl)-fluorene, fluorene-dimethyl-benzidine , can obtain high voltage retention rate and resist image residue ( Left DC), the good performance of the liquid crystal alignment agent and the like is coated with consideration to this aspect of the film is preferred. At this time, the weight of the above polylysine and sorghum imidization polymer is preferably poly-proline: sorghum imidization polymer = 1 0: 9 0~9 0 : 1 0 range, more Jiawei polyproline: sorghum imidization rate polymer = 30:70~85··15 range, especially good poly-proline: sorghum imidization rate polymerization -27- 200804519 substance=50: Range of 50~80:20. The temperature at which the liquid crystal alignment agent of the present invention is formulated is preferably from 0 to 200 ° C, more preferably from 20 to 60 ° C. The organic solvent constituting the liquid crystal alignment agent of the present invention may be the same solvent as exemplified as the solvent used in the synthesis reaction of polyglycine. Among them, a solvent having a boiling point of 160 ° C or higher is preferred from the viewpoint of printability, and examples thereof include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and dimethyl fluorene. T-butyrolactone, tetramethylurea, hexamethylphosphite tridecylamine, m-methylphenol, xylene oxime, phenol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, Triethylene glycol, diacetone alcohol, butyl lactate, butyl acetate, ethyl ethoxypropionate, propylene carbonate, diethyl oxalate, diethyl malonate, ethylene glycol monobutyl ether (butyl cellosolve Agent), diglyme, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, 1, 4-dichlorobutane, o-dichlorobenzene, etc., among which N-methyl-2-pyrrolidone, r-butyrolactone, diacetone alcohol, ethylene glycol monobutyl ether (butyl cellosolve), Propylene carbonate, diethylene glycol 0 diethyl ether. A particularly preferable solvent composition is a composition obtained by combining the above solvents, and is a composition in which the polymer in the alignment agent is not precipitated and the surface tension of the alignment agent is in the range of 25 to 40 m N / m. The solid content concentration in the liquid crystal alignment agent of the present invention is selected in view of viscosity, volatility, etc., preferably in the range of 1 to 10% by weight, more preferably 1 to 5% by weight, particularly preferably 1 to 4% by weight. The liquid crystal alignment agent of the present invention is applied to the surface of a substrate to form a coating film as a liquid crystal alignment film. When the solid content concentration is less than 1% by weight, the thickness of the coating film is too small, so that a good liquid crystal alignment film cannot be obtained; when the solid content concentration exceeds 10% by weight, the viscosity of the alignment -28-200804519 occurs. It is high and cannot be stably applied, and the thickness of the coating film is too thick to obtain a liquid crystal alignment film having a uniform film thickness. The viscosity of the liquid crystal alignment agent of the present invention is a viscosity obtained by measuring a liquid crystal alignment agent at 25 ° C by a rotary viscometer, and the viscosity needs to be appropriately adjusted according to the inkjet coating device used, preferably 3 to 15 mPa «s, More preferably 4 to 10 mPa·s, and particularly preferably 5 to 9 mPai. The liquid crystal alignment agent of the present invention may further contain other additives as needed. The additive may, for example, be a functional decane-containing compound or an epoxy group-containing compound from the viewpoint of improving the adhesion to the surface of the substrate and increasing the voltage holding ratio. As such a functional decane-containing compound, for example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2- Aminopropyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyl Dimethoxyoxane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane-, N-B Oxycarbonyl-3-aminopropyltriethoxydecane, N-triethoxydecylpropyltriethylethylamine, N-trimethoxydecylpropyltriethylamine, 10- Trimethoxydecyl-1,4,7-triazadecane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6 -diazepine acetate, 9-triethoxydecyl-3,6-diazadecyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N- Benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, 3- G-propyl Oxypropyltrimethoxydecane, N-bis(oxyethyl)-3-aminopropyltrimethoxydecane, N-bis(oxyethyl)-3-aminopropyltriethoxy Decane and so on. -29 - 200804519 Further, as the epoxy group-containing compound, preferred are, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and tripropylene glycol diglycidyl ether. , polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 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-phenyleneamine, 1,3-two (N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, n, N-diglycidyl-benzylamine, N,N-diglycidyl-aminomethylcyclohexane, and the like. The mixing ratio of the functional decane-containing compound and the epoxy group-containing compound is preferably 6 parts by weight or less based on the total amount of the polyhydric acid and the ruthenium-based polymer of 1 part by weight, more preferably Preferably, it is 50 parts by weight or less. After the liquid crystal alignment agent of the present invention is sufficiently thawed to room temperature, and then measured by a particle counter, the size of the foreign matter of the particle is 1. 〇vm or more (RION (manufactured by a strand), measured by a particle sensor in a liquid値), preferably 10 pieces/ml or less, more preferably 8 pieces/ml or less, and particularly preferably 5 pieces/ml under β. When the number of foreign matter having a size of 1·〇//m or more is more than 1/ml, when the inkjet coating device is continuously used, nozzle clogging may occur, and the amount of inkjet ejection may be unstable, resulting in coating. Poorly applied. <Liquid Crystal Display Element> The liquid crystal display element of the present invention can be produced, for example, by the following method. (1) The liquid crystal alignment agent of the present invention is applied onto one surface of a substrate provided with a pattern-formed transparent conductive film by an ink-jet method, and then a liquid crystal alignment film is formed by heating the coated surface. As the substrate, for example, float glass, glass such as -30-200804519 soda lime glass; polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, alicyclic ring can be used. A plastic transparent substrate such as a hydrocarbon. As the transparent conductive film provided on one side of the substrate, an ITO film made of tin oxide (Sn〇2), NESA film (registered trademark of PPG, USA), and oxidized-tin oxide (Ιπ2〇3 - Sn〇2) can be used. Wait. The pattern of formation of these transparent conductive films is a method of lithography or a mask in advance. As the reflective electrode, a metal such as A1 or Ag, an alloy containing these metals, or the like can be used, and it is not limited to these as long as it has a sufficient reflectance. In the application of the liquid crystal alignment agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film or the reflective electrode and the liquid crystal alignment film, a functional decane-containing compound or a functional group may be previously coated on the surface of the substrate. Titanium compounds and the like. After the application of the liquid crystal alignment agent, in order to prevent the coating agent liquid from sagging, etc., it is preferred to carry out preheating (prebaking), and the prebaking temperature is preferably 30 to 300 ° C, more preferably 40 to 200 °. C, particularly preferably 50 to 150 ° C. Then, the solvent is completely removed, and a calcination (post-baking) process is carried out for the purpose of heat-imidization of the polyglycolic acid. The calcination (post-baking) temperature is preferably from 80 to 300 ° C, more preferably from 120 to 250 ° C. As described above, the liquid crystal alignment agent of the present invention containing polyglycolic acid is removed from the organic solvent to form a coating film as a liquid crystal alignment film, and further heated to cause dehydration ring closure to form a liquid crystal alignment which is further imidized. membrane. The thickness of the liquid crystal alignment film formed is preferably 0.001 to l#m, more preferably 0.005 to 0.5/zm. (2) If necessary, the surface of the formed coating film is rubbed with a roller wrapped with a cloth made of a fiber such as nylon, artificial fiber or cotton to be rubbed in a certain direction. Thus, a liquid crystal alignment film having a coating film having an alignment energy of liquid crystal molecules is formed. In addition, in addition to the method of sanding, it is also possible to apply a method of controlling the alignment energy by applying a polarized ultraviolet light to the surface of the coating film in -31-200804519. Further, in order to remove the fine powder (foreign matter) generated during the polishing treatment or the like, and to clean the surface of the coating film, it is preferred to wash the formed liquid crystal alignment film with isopropyl alcohol and/or pure water. In addition, the liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention is subjected to a process of partially irradiating ultraviolet rays to change the pretilt angle as shown in Japanese Laid-Open Patent Publication No. Hei. No. Hei. Alternatively, a resist film is partially formed on the liquid crystal alignment film subjected to the rubbing treatment as shown in Japanese Laid-Open Patent Publication No. Hei No. Hei. The treatment of the liquid crystal display element can be improved by removing the protective film and changing the alignment of the liquid crystal alignment film. (3) Two substrates on which the liquid crystal alignment film is formed are formed, and two substrates are placed oppositely through a gap (cell gap) so that the polishing directions of the respective liquid crystal alignment films are perpendicular or anti-parallel to each other, and the peripheral portions of the two substrates are The liquid crystal cell is formed by injecting a liquid crystal into a cell gap (ce 11 gap) which is separated from the surface of the substrate and the sealant by a sealant, and closes the injection hole. Then, a polarizing plate was provided on the outer surface of the liquid crystal cell, i.e., the outer surface of each of the substrates constituting the liquid crystal cell, to obtain a liquid crystal display element. Here, as the sealant, for example, an alumina ball-containing epoxy resin or the like which is a curing agent and a spacer can be used. Examples of the liquid crystal include nematic liquid crystal and dish-shaped liquid crystal. Among them, a nematic liquid crystal is preferably used, for example, a Schiff's type liquid crystal, an oxidized azo liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, or a biphenyl. A cyclohexane 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 to these liquid crystals, and the trade names "C_丨5" and "CB-15" may be added. It is used as a chiral agent sold by (Merocco). Further, a ferroelectric liquid crystal such as p-nonyloxybenzylidene-p-amino-2-methylbutylcinnamate may also be used. In addition, as a polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing plate which is obtained by stretching a polyvinyl alcohol and absorbing iodine while absorbing iodine, and which is a polarizing film called a ruthenium film, is sandwiched between a cellulose acetate protective film or A polarizing plate made of the enamel film itself. EXAMPLES Hereinafter, the present invention will be more specifically described by examples, but the present invention is not limited to the examples. In the examples and the comparative examples, the measurement of the molecular weight of the polymer, the measurement of the imidization ratio, the inkjet coating property of the liquid crystal alignment agent, the viscosity, the measurement of the number of particles, and the measurement of the voltage holding ratio of the produced cell were as follows. Method for evaluation. [Weight average molecular weight and molecular weight distribution] Manufactured by a gel permeation chromatography (GPC, manufactured by Tosoh Co., Ltd., trade name: HLC-8020/column 3: Tosoh), trade name: TSK guar dcolum α, TSK gel α — Μ, TSK gel α — 2500), polystyrene was determined by using dimethylformamide (DMF; adding 9.4 g of lithium bromide-hydrate, 1.7 g of phosphoric acid to 3 L of DMF) as a solvent. The weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) are converted. Wherein, the above Μη is a number average molecular weight. [rhodium imidization ratio] After drying the polymer under reduced pressure at room temperature, a superconducting nuclear magnetic resonance absorption apparatus (manufactured by Sakamoto Electronics Co., Ltd., trade name: ΕΧ-33-200804519 90A) was used. In the deuterated dimethyl hydrazine (DMSO-d6), 1H-NMR measurement was carried out using tetramethyl decane as a reference. In the obtained data, the ruthenium imidization ratio was calculated from the ratio of the proton peak area (near lOppm) derived from the NH group in the polymer to the peak area derived from other protons. [Inkjet Coating Property of Liquid Crystal Aligning Agent] A liquid crystal alignment agent having a solid content concentration adjusted to 3.5% by weight was stored in a freezer at -1 5 t: for 7 days, and then the alignment agent was thawed to room temperature, and JET - A CM continuous ink jet printer (manufactured by Kishu Tech Co., Ltd.) was continuously applied to the ruthenium substrate for 10 minutes to form a liquid amount of a dry film thickness of 60 nm. After continuous application for 10 minutes, further coating was carried out, and the obtained substrate coated with the alignment film was prebaked (hot plate) at 80 ° C for 1 minute, and then baked at 200 ° C (in a clean oven, After 60 minutes in a nitrogen atmosphere, the peripheral portion and the central portion of the liquid crystal alignment film were observed under a microscope at a magnification of 20, and it was judged as "good" when no unevenness was applied, and pinholes or uneven coating were observed (uneven film thickness) When it is), it is judged as "not good". The evaluation results of the inkjet coating properties of the respective alignment agents are shown in Table 2. [Viscosity] The measurement was carried out using an E-type viscosity measuring device of VISCOMETER RE1 00 (manufactured by Toki Sangyo Co., Ltd.). [Number of particles] Using a liquid particle sensor (KL-20A manufactured by RION Co., Ltd.), the number of particles having a size of 1.0 /zm or more in a 10 m 1 liquid crystal alignment agent was measured twice, with an average 値As the number of particles having a size of 1 ·〇# m or more. The measurement was carried out under the conditions of a light source wavelength of 780 nm and a sample suction rate of 10 ml/min. -34- 200804519 [Voltage Retention] In the span of 167 ms, 'apply a voltage of $ V to the liquid crystal display'. The voltage application time is microseconds. The voltage is released from the voltage in a 6 °C environment. The voltage holding ratio after 167 ms. The measuring device was made of VHR-1 manufactured by Dongyang Technology Co., Ltd. When the voltage holding ratio was 98.0% or more, it was judged to be good, and otherwise, it was judged to be bad. Synthesis Example 1 (Synthesis of Polylysine P-1) 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic acid dianhydride 38 g (0.17 mol), pyromellitic dianhydride 12 g (0.057 mol), p-phenylenediamine 19 g (0.17 mol) as a diamine compound and 30 g (0.05 8 mol) of the diamine represented by the above formula (14) are dissolved in 400 g of N-methyl-2-pyrrolidone The reaction was carried out at 60 ° C for 4 hours. In the preparation of the liquid crystal alignment agent, the polymerization solution was used as it was. Further, the molecular weight of the poly-proline in the polymerization solution (this is referred to as "polymer P - 1") was measured by gel permeation chromatography and the enthalpy was Mw 215,000,000, Mw/Mn = 6.36 ° Synthesis Example 2 (Synthesis of ruthenium iodide polymer P-2) 21 g (0.093 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic acid dianhydride as p-benzene of diamine compound 9.2 g (0.085 mol) of diamine and 4.9 g (0.0095 mol) of the diamine represented by the above formula (14) were dissolved in i4 g of N-methyl-2-pyrrolidone, and reacted at 60 ° C for 5 hours. 360 g of N-methyl-2-pyrrolidone was added to the obtained polymerization solution, and after sufficiently stirring, 7.4 g of pyridine and 9.5 g of acetic anhydride were added thereto at 110. (: dehydration ring closure for 4 hours. After the hydrazine imidization reaction, the solvent in the system is replaced with a new N-methylpyrrolidone solvent (in this operation, the ruthenium imidization reaction is removed outside the system). The pyridine and acetic anhydride used were obtained to obtain a ruthenium 200804519 polymer solution having a solid concentration of 17%. Further, the ruthenium iodide polymer in the ruthenium polymer solution (as a polymer P- The molecular weight of 2") was measured by gel permeation chromatography, and the enthalpy was Mw = 111, 〇〇〇, Mw / Μ η = 5.23, and the sulfhydrylation rate was 51%. Synthesis Example 5 (醯Synthesis of imidized polymer ρ-5) 18 g (0.080 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic acid dianhydride, p-phenylenediamine as diamine compound 2 9g (〇.〇27 Moer), 6.2g (0.012 mole) of diamine represented by the above formula (14), and 4,4,-di-aminodiphenylmethane 7·9§ (〇.〇40 0.15 g (0.0016 mol) of aniline as a monoamine for terminal modification was dissolved in I40 g of N-methyl-2-pyrrolidone, and reacted at 60 C for 4 hours. 3 6 was added to the obtained polymerization solution. 0 g N -methyl-2-pyrrolidone, after thorough stirring, add 3 g of pyridine and 16 g of acetic anhydride, and dehydrate the ring for 4 hours at 110 ° C. After the imidization reaction, the solvent in the system Solvent replacement with a new N-methyl-2-pyrrolidone (in this operation, the pyridine and acetic anhydride used in the oxime imidization reaction are removed outside the system) to obtain a quinone imine having a solid concentration of 17 wt%. The polymer solution. Further, the molecular weight of the ruthenium iodide polymer (as "Polymer #P-5") in the ruthenium iodide solution was determined by gel permeation chromatography as Mw = 91,000, Mw / Μ η = 4.19' Further, the sulfhydrylation ratio was 75%. Synthesis Examples 3, 4 and 6 to 19 and Comparative Synthesis Examples 1, 2 except for the replacement of tetracarboxylic dianhydride and diamine compound In the same manner as in Synthesis Example 1, Synthesis Example 2, and Synthesis Example 5 except for those listed in Table 1, the polylysine and the quinone imidized polymer shown in Table 1 were obtained (they were used as the polymer "ρ - 3", "Ρ-4", "Ρ-6"~"Ρ-19" and "Ρ-20", "Ρ-21").· Each polymer By appropriately adjusting the molar ratio of the tetracarboxylic dianhydride and the diamine used in the synthesis of the polyamic acid, a polymer having the viscosity shown in -36 to 200804519 in Table 1 can be obtained. Amination rate Each polymer having the ruthenium imidation rate shown in Table 1 can be obtained by appropriately adjusting the addition amount of pyridine and acetic anhydride. Further, in Table 1, acid dianhydrides A to D and diamine E to L respectively represent the following compounds: Acid dianhydride A: 2,3,5-tricarboxycyclopentyl acetic acid dianhydride dianhydride B: pyromellitic acid dianhydride dianhydride C: 1, 2, 3, 4-cyclobutane tetracarboxylic acid dianhydride dianhydride D: 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3 -furyl)-naphthalene [l,2-c]furan-1,3-dione, diamine E: diamine compound diamine represented by the above formula (14): p-phenylenediamine diamine G: 4 4,-diaminodiphenylmethanediamine oxime: diamine compound diamine I represented by the above formula (12): diamine compound diamine represented by the above formula (24): represented by the following formula (25) Diamine compound diamine oxime: 2,2'-dimethyl-4,4'-diaminobiphenyldiamine L: the above formula ( 15) indicated diamine compound

-37- 200804519 Table 1

The molar ratio of the molar ratio of the molar ratio of the molar ratio of the molar ratio of the molar ratio of the molar ratio of the molar ratio of the molar ratio of the molar ratio of the molar ratio of the molar ratio of the molar ratio of the molar ratio of the molar ratio (75)' Β(25) E(25), F(75) 153,000 (6.36) 0 Synthesis Example 2 P-2 Α(100) E(10), F(90) 111,000 (5.23) 51 Synthesis Example 3 P —3 A(100) E(20)' F(80) 105,000 (4.20) 50 Synthesis Example 4 P-4 A(iOO) E(10), F(70), G(20) 122,000 (5.44) 80 Synthesis Example 5 P-5 A(100) E(15), F(34), G(50), aniline (2) 91,000 (4.19) 75 Synthesis Example 6 P-6 B(50), C(50) G( 100) 46,000 (4,04) 0 Synthesis Example 7 P-7 A(100) G(100) 149,000 (5.71) 90 Synthesis Example 8 P-8 A(50), D(50) H(L5), 1( 10), F (87), 18-base amine (3) 32, οω (4.32) 95 Synthesis Example 9 P-9 A (50), D (50) 1 (10), F (88.5), 18 Mercaptoamine (3) 51,000 (4.32) 94 Synthesis Example 10 P-10 A(50)' D(50) J(3), 1(10), F(86.25), aniline (1.5) 40,000 (4.79) 89 Synthesis Example 11 P-11 A(50) > D(50) J(5), 1(10), F(84.25), aniline (1.5) 26,000 (3.40) 90 Synthesis Example 12 P-12 C(100) K(100 ) 48,000 (3.45) 0 Synthesis Example 13 P-13 B(50)' C(50) K(100) 57, οω (4.34) 0 Example 14 P-14 A(100) E(10), F(50) 115,000 (8.34) 0 Synthesis Example 15 P-15 A(100) L(10), F(90) 123,000 (7.64) 52 Synthesis Example 16 P— 16 A(100) L(20), F(80) 115,000 (8.34) 49 Synthesis Example 17 P-17 A(100) L(10), F(70), G(20) 146,000 (5.82) 82 Synthesis Example 18 P-18 A(100) L(15), F(34), G(50), aniline (2) 88,000 (3.99) 76 Synthesis Example 19 P-19 C(100) F(100) 110,000 (6.45) 0 Comparative Synthesis Example 1 P-20 A(100) E(20)' F(80) 98,000 (4.79) 85 Comparative Synthesis Example 2 P-21 A(100) E(20)' F(80) 350,000 (9.11) 60 -38- 200804519^ 1 To the polymer (P-1) obtained in Synthesis Example 1 to be N-methyl; a mixture ratio of a rotary ketone/ethylene glycol monobutyl ether = 30/70 N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, further relative (P-1) added 20% by weight of N,N,N',N'-tetrahydration-4,4' -Diaminodiphenylmethane, a VA type liquid crystal alignment agent having a total solid content concentration by weight %. After thoroughly stirring, the mixture was filtered through a 0.2 μm filter to obtain a liquid crystal alignment type VA of the present invention. The obtained liquid crystal alignment agent was stored in a freezer at -15 ° C for 7 days, and then thawed to room temperature. Viscosity, determination of the number of particles and inkjet experiments. The results are shown in Table 2. Further, a V A type liquid crystal device was produced as follows to measure the voltage holding ratio. The VA type liquid crystal alignment agent was applied onto a transparent conductive film provided on one surface of the glass substrate by an inkjet coating apparatus, and dried on a hot plate at 80 ° C for 1 minute, followed by a clean oven ( When baked at 200 ° C in a nitrogen atmosphere, a transparent plate having a liquid crystal alignment film having a film thickness of about 60 nm was formed. Then, on each of the outer edges of the liquid crystal alignment film of the liquid crystal coating substrate of the pair of transparent electrode/transparent electrode substrates, an epoxy resin adhesive having an alumina ball of 5.5 // m diameter is applied, and then The alignment film surface is relatively heavy and combined to cure the adhesive. Next, after the liquid crystal injection port is filled with a negative liquid crystal (Meruco MLC-203 8) between the substrates, the liquid crystal is sealed with an acrylic photocurable adhesive, and a polarizing plate is bonded to both sides of the substrate to form a polarizing plate. VA type indicator. The results of the voltage holding ratio of the obtained VA liquid crystal display device are shown in Table 2. Example 2 The polymer (P-2) obtained in Synthesis Example 2 was used in place of the polymer (P-i-2-pyryl was added to the polymerized glyceryl group as a 3.5-pore-directed agent. The pre-drying 1 small electrode base crystal of the ITO film of the invention is directly aligned with the liquid crystal, and is manufactured by the inlet sealing liquid crystal to evaluate the knot 1), and -39-200804519 does not add N, N, N', N' - 4 Glycidyl 4,4'-diaminodiphenylmethane. Further, in the same manner as in Example 1, the liquid crystal alignment agent for VA type of the present invention was obtained in the same manner as in Example 1 except that the solvent composition was a mixture weight ratio of N-methyl-2-pyrrolidone/ethylene glycol monobutyl ether: 50/50. And VA type liquid crystal display elements. The results of evaluation of viscosity, number of particles, inkjet coating properties, and voltage holding ratio are shown in Table 2. Example 3 A solvent mixture of N-methyl-2-pyrrolidone/ethylene glycol monobutyl ether was prepared except that the polymer (P-3) obtained in Synthesis Example 3 was used instead of the polymer (P-1). The VA type liquid crystal alignment agent and the VA type liquid crystal display element of the present invention were obtained in the same manner as in Example 1 except that the weight ratio was 50/50. The results of evaluation of viscosity, number of particles, inkjet coating properties, and voltage holding ratio are shown in Table 2. Example 4 The polymer obtained in Synthesis Example 4 (P-4) and the polymer obtained in Synthesis Example 6 were mixed except that (P-4):(P-6) = 50:50 (weight ratio). (P-6) In place of the polymer (P-1), the solvent composition is a mixture weight ratio of r-butyrolactone/N-methyl-2-pyrrolidone/ethylene glycol monobutyl ether = 40/3 5/ The VA type liquid crystal alignment agent and the VA type liquid crystal display element of the present invention were obtained in the same manner as in Example 1 except for the same. The evaluation results of viscosity, number of particles, inkjet coating properties, and voltage holding ratio are shown in Table 2. Example 5 The polymer obtained in Synthesis Example 5 (P-5) and the polymer obtained in Synthesis Example 6 were mixed except (?-5):(?-6)=50:50 (weight ratio). (P - 6) Substituting the polymer (P-1) and making the solvent composition a mixture weight ratio of T-butyrolactone/N-methyl-2-pyrrolidone/ethylene glycol monobutyl ether=40/35/ Other than 25, the liquid crystal alignment agent for VA type and the liquid crystal display element of VA type of the present invention were obtained in the same manner as in Example 1. The results of evaluation of viscosity, number of particles, inkjet coating properties, and voltage holding ratio are shown in Table 2. -40- 200804519 Example 6 The polymer (P-7) obtained in Synthesis Example 7 and the polymer (P-19) obtained in Synthesis Example 19 were (P-7): (P - 19) = Mixing at 20:80 (weight ratio), adding r - as r-butyrolactone / N-methyl-2-pyrrolidone / ethylene glycol monobutyl ether = 30 / 40 / 30 (weight ratio) Butyrolactone, N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, further added 10% by weight of hydrazine, hydrazine relative to the total amount of polymer (P-19) and polymer (P-7) , Ν', Ν'-tetraglycidyl-4,4'-diaminodiphenylmethane, and a liquid crystal alignment agent of IPS type having a total solid concentration of 3.5% by weight. After sufficiently stirring the mixture, the mixture was filtered through a filter having a pore diameter of 0.2 μm to prepare a liquid crystal alignment agent for IPS type of the present invention. The obtained liquid crystal alignment agent was stored in a freezer at -1 °C for 7 days, and then the alignment agent was thawed to room temperature, and the viscosity, the number of particles, and the inkjet coating property test were carried out. The results are shown in Table 2. Further, an IPS type liquid crystal display element was produced as follows, and the voltage holding ratio was measured. The IPS type liquid crystal alignment agent of the present invention prepared as described above was applied onto a transparent substrate made of a ITO film having a comb shape on one surface of a glass substrate having a thickness of 1 mm, and dried at 180 ° C. At 1 hour, a film having a dry film thickness of about 80 nm was formed. The surface of the formed coating film was subjected to a polishing treatment using a sander equipped with a roller wound with a nylon cloth to prepare a liquid crystal alignment film. Here, the grinding treatment conditions were: a roller rotation speed of 400 rpm, a table movement speed of 3 cm/sec, and a pile extrusion length of 0.4 mm. (This substrate serves as the substrate A). The IPS type liquid crystal alignment agent of the present invention prepared as described above was applied onto one surface of a glass substrate having a thickness of 1 mm by an inkjet coating apparatus, and dried at 180 ° C for 1 hour to form a coating having a dry film thickness of about 80 nm. membrane. The formed coating film surface was subjected to a rubbing treatment using a sander equipped with a roll of a nylon cloth to prepare a liquid crystal alignment film. Here, the grinding treatment conditions were: a roller rotation speed of 400 rpm, a table movement speed of 3 cm/sec, and a pile extrusion length of 0.4 mm. -41- 200804519 (This substrate serves as the substrate B). Applying an epoxy resin binder containing alumina balls having a diameter of 17 μm to the outer edge portion of the coating film surface of the substrates A and B by screen printing, the polishing directions of the respective liquid crystal alignment films are antiparallel to each other. On the other hand, the two substrates are disposed opposite each other with a gap therebetween, so that the outer edge portions are in contact with each other and pressed, and the adhesive is cured.

Then, the liquid crystal injection port is used to fill the liquid crystal between the pair of substrates (Melco Co., Ltd., MLC-20 19), and then the liquid crystal injection port is sealed with an epoxy-based adhesive, and the two sides of the substrate are attached. The polarizing plate is combined to make the polarizing direction of the polarizing plate coincide with the polishing direction of the liquid crystal alignment film of the respective substrates, thereby producing an IPS type liquid crystal display element. The results of evaluation of the voltage holding ratio of the obtained IPS type liquid crystal display element are shown in Table 2. Example 7 The polymer (p-8) obtained in Synthesis Example 8 and the polymer (P-12) obtained in Synthesis Example 12 were designated as (p-8): (P-12) = 20: 80 (by weight) dissolved in a mixed solvent of r - butyrolactone / N-methyl-2-pyrrolidone / ethylene glycol monobutyl ether (solvent weight ratio 68 / 17 / 15), and further separate Adding 2% by weight of N,N,N,,N,-tetraglycidyl-4,4 '-diaminodiphenylcarbendate relative to the total amount of the above polymer, adding 1 to the total amount of the above polymer Mw % by weight of 3-glycidoxypropyltrimethoxydecane, a liquid crystal alignment agent for TN type having a total solid concentration of 3.5% by weight. After sufficiently stirring the mixture, it was filtered through a filter having a pore size of 0·2 μm to prepare a liquid crystal alignment agent for a TN type of the present invention. After the obtained liquid crystal alignment agent was stored in a freezer at -1 °C for 7 days, the alignment agent was thawed to room temperature, and the viscosity, the number of particles, and the inkjet coating property test were carried out. The results are shown in Table 2. Further, a TN type liquid crystal display element was produced as follows, and the voltage holding ratio was measured. The TN type liquid crystal alignment agent of the present invention is applied onto a transparent conductive film made of an ITO film provided on one surface of a glass substrate by an inkjet coating device, and is heated at 8 ° C to -42 - 200804519 on the hot plate. The pre-drying was carried out for a minute, and then fired at 210 ° C for 1 minute on a hot plate to prepare a transparent electrode substrate having a liquid crystal alignment film having a film thickness of about 60 nm. The coating was subjected to a sanding treatment at a roller rotation speed of 40 rpm, a table moving speed of 30 mm/sec, and a pile length of 〇.4 mm using a roller equipped with a roller for winding a rayon cloth. The above 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. Then, on each of the outer edges of the liquid crystal alignment film of the liquid crystal alignment film coating substrate of the pair of transparent electrode/transparent electrode substrates, epoxy tree Φ grease bonding to which alumina balls having a diameter of 5.5 μm is applied is applied. Then, the liquid crystal alignment film surface is relatively recombined and pressed to cure the adhesive. Next, the liquid crystal injection port is used to charge the liquid crystal between the substrates (Melco Co., Ltd., MLC-622 1), and then the liquid crystal injection port is sealed with an acrylic photocurable adhesive, and bonded to both sides of the substrate. The polarizing plate is made into a ΤΝ-type liquid crystal display element. The results of evaluation of the voltage holding ratio of the obtained quinoid liquid crystal display element are shown in Table 2. Example 8 The polymer obtained in Synthesis Example 9 (P-9) and the polymer obtained in Synthesis Example 6 were used as (Ρ-9): (Ρ-6) = 50:50 (weight ratio) ( P-6) Substituting Polymerization® (P-8), (P-12) 〇 In addition, N,N,N',N'-tetraglycidyl_4,4,-diaminodiphenylmethane The amount added was changed to 20% by weight based on the total amount of the above polymer. The solvent composition was the same as that of Example 7 except that the mixing ratio of r-butyrolactone/N-methyl-2-pyrrolidone/ethylene glycol monobutyl ether was 71/17/12. The liquid crystal alignment agent for a TN type of the present invention and a liquid crystal display element of a TN type are obtained. The evaluation results of viscosity, number of particles, inkjet coating properties, and voltage holding ratio are shown in Table 2. Example 9 The polymer (P-10) obtained in Synthesis Example 10 was used instead of the polymer (P--43-200804519 8). The amount of N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane was changed to 1% by weight based on the total amount of the polymer, and no 3 _epoxy was added. Propoxypropyltrimethoxydecane. And make the solvent composition 7-butyrolactone / N-A

In the same manner as in Example 7, except that 72/15/13, a liquid crystal alignment agent for a tn type and a TN liquid crystal display device of the present invention were obtained. The results of evaluation of viscosity, number of particles, ink coating properties, and voltage holding ratio are shown in Table 2. Example 1

The polymer (P-11) obtained in Synthesis Example 1 1 was used in place of the polymer (1 > - 8). Further, the addition amount of >1,:^,>1',>1'-tetraglycidyl-4,4'-diaminodiphenylmethane was changed to 10 based on the total amount of the polymer. % by weight, without adding 3 _ glycidoxypropyl trimethoxy sand yard. The solvent composition was 7-butyrolactone/N-methyl-2-pyrrolidone/ethylene glycol monobutyl ether in a weight ratio of 2 to 2 2/15/13, and the same procedure as in Example 7 was carried out. The liquid crystal alignment agent for a TN type and the liquid crystal display element of the TN type of the present invention are obtained. The results of evaluation of viscosity, number of particles, ink coating properties, and voltage holding ratio are shown in Table 2. Example 1 1 In place of the polymer (P-13) obtained in Synthesis Example 13, the polymer (P-12) was replaced, and the solvent was composed of r-butyrolactone/N-methyl-2. The TN type liquid crystal alignment agent and the TN type liquid crystal display element of the present invention were obtained in the same manner as in Example 7 except that the compounding ratio of the ketone/ethylene glycol monobutyl ether was 7 2 /1 6 /1 2 . The evaluation results of the viscosity, the number of particles, the inkjet coating property, and the voltage holding ratio are shown in Table 2. Example 1 2 A liquid crystal alignment agent for VA type of the present invention and VA were obtained in the same manner as in Example 1 except that the polymer (P-14) obtained in Synthesis Example 14 was used instead of the polymer (P-1). Type liquid crystal display element. Viscosity, number of particles, inkjet coating properties, and -44-200804519 The results of evaluation of voltage holding ratio are shown in Table 2. Example 13 The polymer (P-15) obtained in Synthesis Example 15 was used instead of the polymer (p-1) without adding force □ N, N, N, N'-tetraglycidyl-4, 4, Diaminodiphenyl group. Further, in the same manner as in Example 1, the liquid crystal composition for VA type of the present invention was obtained in the same manner as in Example 1 except that the solvent composition was a mixture weight ratio of N-methyl-2-indole or ethylene glycol monobutyl ether. An alignment agent and a VA type liquid crystal display element. The results of evaluation of viscosity, number of particles, inkjet coating properties, and voltage holding ratio are shown in Table 2. Example 1 4 The polymer (P-16) obtained in Synthesis Example 16 was used instead of the polymer (P-1) without adding N, N, N', N'-tetraglycidyl-4, 4, - Aminodiphenylmethane. Further, in the same manner as in Example 1, the liquid crystal for VA type of the present invention was obtained in the same manner as in Example 1 except that the solvent composition was a mixed weight ratio of N-methyl-2-pyrrolidone/ethylene glycol monobutyl ether = 5 0 / 50. An alignment agent and a VA type liquid crystal display element. The results of evaluation of viscosity, number of particles, inkjet coating properties, and voltage holding ratio are shown in Table 2. Example 1 5 The polymer obtained in Synthesis Example 17 (P-17) and the polymerization prepared in Synthesis Example 6 were mixed except (P-17): (P-6) = 20:80 (weight ratio). Substituting (p-6) for the polymer (P-n, and making the solvent composition a mixture weight ratio of r • butyrolactone / N-methyl-2-pyrrolidone / ethylene glycol monobutyl ether = 4 In the same manner as in Example 1, except for 〇/35/25, the liquid crystal alignment agent for VA type and the liquid crystal display element of VA type of the present invention were obtained. The evaluation results of viscosity, number of particles, inkjet coating property, and voltage retention ratio are shown in the table. 2. Example 1 6 The polymer (P-18) obtained in Synthesis Example 18 and Synthesis Example 12 were used except that (P-18): (p-12) = 5 0:5 (weight ratio) was used in combination. The obtained polymer (p-12) is substituted for the polymer (P-1), and the solvent is composed of r-butyrolactone/N_methyl-45- 200804519-based 2-pyrrolidone/ethylene glycol monobutyl ether The VA type 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 mixing weight ratio was 4 〇/35/25. The viscosity 'particle number, inkjet coating property, and voltage retention ratio were obtained. The evaluation results are shown in Table 2. Comparative Examples 1 In addition to using the polymer (P-20) prepared in Comparative Synthesis Example 1 instead of the polymer (P-1), and making the solvent composition r-butyrolactone/N-methyl-2-pyrrolidone/B A liquid crystal alignment agent for VA type and a liquid crystal display element of VA type were obtained in the same manner as in Example i except that the weight ratio of the diol monobutyl ether was changed to 30 / 50 / 20,000. Viscosity, number of particles, ink jet coating The evaluation results of the suitability and the voltage holding ratio are shown in Table 2. Comparative Example 2 < In addition to using the polymer (P-21) obtained in Comparative Synthesis Example 2, instead of the polymer (P-1), the solvent composition was A liquid crystal alignment for VA type was obtained in the same manner as in Example 1 except that the weight ratio of r-butyrolactone/N.methyl-2-pyrrolidone/ethylene glycol monobutyl ether was 3 0/50/20. The evaluation results of the viscosity, the number of particles, the inkjet coating property, and the voltage holding ratio are shown in Table 2. Comparative Example 3 The same procedure as in Example 7 except that only the polymer (P-8) was used. The TN type liquid crystal alignment agent and the TN type liquid crystal display element were prepared, and the evaluation results of the viscosity, the number of particles, the inkjet coating property, and the voltage holding ratio are shown in Table 2. Comparative Example 4 The TN type liquid crystal alignment agent and the TN liquid crystal display element were produced in the same manner as in Example 8 except that the polymer (P-9) was used. The evaluation results of viscosity, number of particles, inkjet coating property, and voltage holding ratio were obtained. Listed in Table 2. -46 - 200804519

Table 2 Average of the mixing weight ratio in the polythracement _ Amination rate (%) Viscosity (mPa.s) 1.0// m Number of particles with "1" (fi/ml) Inkjet coating MB retention rate Example: P-K100) - 0 10.0 0 Good good example 2 - P-2 (100) 51 7.5 1 Good good example 3 - P-3 (100) 50 7.0 3 Good Good Example 4 P-6(50) P-4(10) 40 6.6 4 Good Good Example 5 P-6(50) P-5(20) 38 6.1 2 Good Good Example 6 P-19(80) P-7 (20) 18 9.8 1 Good good example 7 P-12(80) P-8(20) 19 5.6 3 Good good example 8 P-6(10) P-9(50) 47 6.0 4 Good good example 9 P- 12(10) P-10(20) 18 5.7 3 Good Good Practice 10 P-12(80) P-1K20) 18 5.1 2 Good Good Solid 11 P-13(80) P-8(2〇) 19 6.0 1 Good Good Example 12 P-14(100) - 0 8.0 2 Good Good Example 13 - P-15(100) 52 7.7 1 Good Good Example 14 - P-16(100) 49 7.2 1 Good Good Lung!115 P-6(80) P-17 (10) 16 6.8 1 Good good example 16 P-12 (10) P-18(50) 38 6.5 2 Good good comparison Example 1 - P-20(100) 85 6.9 15 Bad Good Comparative Example 2 - P-2K100) 60 15.0 13 Bad Good Comparative Example 3 - P-8_ 95 5.0 32 Bad Good Comparative Example 4 - P-9 ( 100) 94 5.2 27 Poor and good As can be seen from Table 2 above, the liquid crystal alignment agents obtained in Examples 1 to 16 were stored in a freezer at -15 ° C, and then thawed to room temperature, and the particles in the liquid from RION The counter observes the number of particles above 1.0 // m, resulting in fewer results of 5/ml or less. Further, when the liquid crystal alignment agent of the present invention is continuously applied by an inkjet method, it does not clog the nozzle, and exhibits excellent inkjet coating properties, and the obtained liquid crystal alignment film has no coating unevenness, pinholes, etc., and is uniform in film thickness. Excellent liquid -47- 200804519 crystal matching film. Compared to the number of particles more than 1 〇 / plug, the liquid produced is not good. The applicability of Table 2 can be achieved by the average quinone imine in the liquid crystal alignment film which is excellent in uniformity of nozzle clogging by nozzle generation. [Simple description y\\\, in the comparative example The prepared liquid crystal alignment agent has a solid/ml correspondingly, and when inkjet coating is performed, a coating unevenness, a pinhole, and the like are observed on the nozzle blocking alignment film, and it is known that the liquid crystal alignment agent of the present invention has good ink ejection. Obtained by adjusting the total amount of polyamine and ruthenium-containing polymers. As described above, according to the present invention, the ink-coating method can form a liquid crystal alignment agent which does not cause poor coating, uneven coating, and can form a film thickness alignment film when a liquid crystal alignment film is formed on a substrate, and has The liquid crystal display element of the liquid beautiful image. -48-

Claims (1)

200804519 X. Patent application scope: 1 . A liquid crystal alignment agent for inkjet, characterized in that polyphosphoric acid synthesized by addition polymerization of tetracarboxylic acid diacid field and diamine compound is selected and the above-mentioned poly The at least one polymer of the ruthenium imidized polymer obtained by imidization of guanidinium amide, and the average oxime imidization ratio of the ratio of the quinone imine bonding unit in the total amount of the above polymer is 〇~ 55% of the range of moles. 2. The liquid crystal alignment agent for inkjet according to the first aspect of the invention, wherein the weight average molecular weight of the polymer contained in the liquid crystal alignment agent is determined by gel permeation chromatography in a polystyrene-equivalent number. In the range of 10,000 to 300,000. 3. The liquid crystal alignment agent for inkjet according to the first or second aspect of the invention, wherein the number of particles having a size of 1 · 〇 μ m or more as measured by a particle counter in a liquid is 10 /ml or less. 4. The liquid crystal alignment agent for inkjet according to any one of claims 1 to 3, wherein the tetracarboxylic dianhydride which is a synthetic raw material of the above polyamic acid and ruthenium iodide is selected From 2,3,5-tricarboxycyclopentyl acetic acid succinic anhydride ' 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3·dimethyl-1,2,3,4 - Cyclobutane tetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, hydrazine, 3,3&,4,5,9!3-hexahydro-5-(tetrahydro- 2,5-dioxo-3-furanyl)-naphthalene [1,2-called furan-1,3-dione, 1,3,3&,4,5,91)-hexahydro-8-A 5-(4-hydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-indolyl]furan-1,3-dione, 3-oxa double transport [3.2.1] Xinzhi-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5,_dione), 3,5,6-tridecyl-2-residue norbornene-2: 3,5:6-dianhydride, bicyclo[3.3.]octane-2,4,6,8-tetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid Anhydride, 4,9-dioxatricyclo[5.3.1.02,6]undecane_3,5,8,1〇_-49- 200804519 At least one of a tetraketone and a pyromellitic dianhydride. 5. The liquid crystal alignment agent for inkjet according to any one of claims 1 to 4, which comprises a dianhydride selected from 1,2,3,4-cyclobutanetetracarboxylic acid, 1,3 -Dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride '2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,3',4,4'-benzophenone At least one tetracarboxylic dianhydride of tetracarboxylic dianhydride and pyromellitic dianhydride and selected from the group consisting of p-phenylenediamine, 4,4'-diaminodiphenylmethane, and 2,7-diamino fluorene , 4,4'-diaminodiphenyl ether, 9,9-bis(4-aminophenyl)anthracene, 2,2.di(4-aminophenyl) φ hexafluoropropane, 4,4 '-Diamino-2,2,-bis(trifluoromethyl)biphenyl, 4,4'-diamino-2,2'-dimethylbiphenyl and 3,3-(tetramethyl) At least one of oxane-1,3-diyl)di(propylamine) and 4,9-dioxatricyclo[5.3.1.02,6]undecane-3,5,8,10-tetraone Polylysine obtained by the diamine reaction. A liquid crystal display element comprising a liquid crystal alignment film formed of the liquid crystal alignment agent for inkjet according to any one of claims 1 to 5. -50- 200804519 VII. Designation of representative representatives: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Μ 〇 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: