TW201005005A - Liquid crystal alignment agent and liquid crystal display element - Google Patents

Abstract

The present invention provides a liquid crystal alignment agent with excellent printability using ink jet printing device particularly, and a liquid crystal alignment agents is capable of forming of a liquid crystal alignment film that do not apply uneven. The said liquid crystal alignment agent comprising at least one polymer selected from the group consisting polyimidic acid obtained by reacting the tetracarboxylic dianhydride with diamine and imidized polymer, and comprising a organic solvent represented by RCOOR'. (wherein, R is a alkyl group or hydroxyalkyl group having 1 to 2 carbon atoms or a straight chain alkyl group having 4 to 6 carbon atoms, R' is a branched-chain alkyl group or alkoxyalkyl group having 5 to 12 carbon atoms or a alicyclic group having 5 to 10 carbon atoms at the time of R is a alkyl group or hydroxyalkyl group having 1 to 2 carbon atoms; R' is a straight chain or branched-chain alkyl group having 4 to 10 carbon atoms at the time of R is a straight chain alkyl group having 4 to 6 carbon atoms.)

Description

201005005 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a liquid crystal alignment agent and a liquid crystal display element. More specifically, it relates to a liquid crystal alignment agent which is excellent in printability when an ink jet type printing apparatus is used, and which can form a liquid crystal alignment film which is not coated unevenly, and a liquid crystal display element which is excellent in display quality. [Prior Art] At present, as a liquid crystal display element, a TN type liquid crystal display element having a TN type (twisted nematic) © liquid crystal cell is known, which is formed of polylysine on a surface of a substrate provided with a transparent conductive film. A liquid crystal alignment film formed of ruthenium or the like is provided as a substrate for a liquid crystal display element, and two of the substrates are opposed to each other, and a nematic liquid crystal layer having positive dielectric anisotropy is formed in the gap to form a sandwich structure. The long axis of the liquid crystal molecules is continuously twisted by 90 degrees from one substrate to the other. Further, an STN (Super Twisted Nematic) liquid crystal display element capable of achieving a higher contrast ratio than a TN type liquid crystal display element, an IPS (in-plane switching) type liquid crystal display element having a small viewing angle dependence, and viewing angle dependence are also known. An optical compensation curved (OCB) type liquid crystal display element having excellent high-speed response and a VA (vertical alignment) type liquid crystal display element having nematic liquid crystal having negative dielectric anisotropy (refer to Patent Document 1) ~6). In the liquid crystal display device, the alignment control of the liquid crystal molecules is usually carried out by a liquid crystal alignment film containing these polymers as a main component, which is formed of a liquid crystal alignment agent containing a polymer such as polyamic acid or polyimine. The liquid crystal alignment film is required to have good liquid crystal alignment performance, high -4-201005005 voltage holding ratio, and no residual image. In recent years, LCD TVs have become increasingly popular, and large-scale production lines, known as the "seventh generation," have been put into operation. Moreover, the construction of a larger “eighth generation” production line is also under planning. Advantages of using a large-sized production line to increase the size of the substrate include the following: Since a plurality of panels can be produced from one substrate, engineering time can be shortened and cost can be reduced, and the liquid crystal display element itself can be enlarged. Conversely, as a disadvantage of increasing the size of the substrate, it is difficult to ensure uniformity of printing of the liquid crystal alignment agent over a wide area. In particular, in an offset printing machine which has been widely used in the printing of a liquid crystal alignment film, since it is difficult to enlarge the printing apparatus, it is considered that the offset printing method is maintained while printing on a large substrate, and the improvement of the unevenness occurs. bottleneck. In order to solve the above problems, the introduction of the non-contact type inkjet printing method has been studied, and practical application has been realized (Non-Patent Document 1). As an advantage of the inkjet printing method, the following aspects can be cited: since only a necessary amount of liquid amount is used, efficient use of the liquid crystal alignment agent can be expected; since it is not necessary to perform replacement and washing of the printing plate, it is easy to maintain; Can handle a variety of panel sizes. On the other hand, as a disadvantage, it has been pointed out that there is uneven coating due to variations in solvent removal conditions after printing, and film thickness unevenness is likely to occur between nozzles and between nozzles, and the ink jet printing method has a problem in product yield. Therefore, there is a need for a liquid crystal alignment agent which is excellent in printability when a coating film is formed by an inkjet printing method, and which can form a liquid crystal alignment film which is not coated unevenly, without impairing the various properties required for the liquid crystal alignment film. [Patent Document 1] Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 5] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. 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 thereof is to provide a liquid crystal alignment agent capable of forming a liquid crystal alignment film having no uneven coating, and display quality, particularly when an ink jet type printing apparatus is used. Excellent LCD display. Other objects and advantages of the invention will be apparent from the description which follows. According to the present invention, the above objects and advantages of the present invention, the first 'achieved by a liquid crystal alignment agent, comprising: a polyamic acid selected from the reaction of a tetracarboxylic dianhydride with a diamine and a quinone imine thereof At least one polymer in the group consisting of polymers; and an organic solvent comprising a compound represented by the following formula (A), RCOOR' (A) 201005005 hydroxyalkyl or an alkyl or alkoxy group as a carbon atom The number of linear chains or branches is attributed to the liquid crystal film of the film when the printing device is provided, and the liquid crystal is matched with the SH (super vertical) display mode, so that the group of the device, the watch, the liquid crystal TV anhydride and the diamine are reversed. In the formula (A), R is an alkyl group having 1 to 2 carbon atoms or a linear alkyl group having 4 to 6 carbon atoms, and when R is a carbon atom group or a hydroxyalkyl group, R ' is a branched alkyl group having 5 to 12 carbon atoms or an alicyclic group having 5 to 10 carbon atoms'. When R is a linear alkyl group of 4 to 6, R' is a carbon atom. A 4 to 10 alkyl group; and a second, a liquid crystal display element comprising a liquid crystal alignment film formed of the liquid crystal alignment agent. According to the present invention, it is possible to provide a liquid crystal matching agent which is excellent in ink jet type printing property and which can be formed without uneven coating. The liquid crystal alignment agent formed by the liquid crystal alignment agent of the present invention is excellent in alignment, and can be applied to liquid crystal display elements of TN type, STN type, VA type, type, IPS type, OCB type, ferroelectricity, antiferroelectricity and the like. The liquid crystal display element of the present invention having the liquid crystal alignment agent-shaped film of the present invention can be suitably applied to various devices because of its excellent display quality, for example, it can be applied to calculation of a desk clock, a count display screen, a word processor, a personal computer, a cymbal, etc. Display device. [Embodiment] Hereinafter, the present invention will be described in detail. The liquid crystal alignment agent of the present invention contains at least one polymer selected from the group consisting of polyamic acid prepared by using a tetracarboxylic acid and a quinone imidized polymer thereof. <tetracarboxylic dianhydride> As a tetracarboxylic dianhydride for synthesizing the polyglycolic acid of the present invention, for example, butane tetracarboxylic dianhydride and 1,2,3,4-cyclobutane can be cited as 201005005 Tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane Tetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4- Cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3; 4,4 '-Dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4, 5-tetrahydrofuran tetracarboxylic dianhydride, l,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-di-oxo-3-furanyl)-naphthalene [l,2- c]-furan-1,3-dione, 1,3,3&,4,5,91?-hexahydro-5-methyl-5-(tetrahydro-2,5-di-oxo-3- Furyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-ethyl-5-(tetrahydro-2, 5-dihydro-3-furanyl)-naphthalene[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-methyl- 5-(tetrahydrogen) -2,5-di-oxo-3-furyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&,4,5,915-hexahydro-7-B 5-(4-hydro-2,5-di-oxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, l,3,3a,4,5, 9b-hexahydro-8-methyl-5-(tetrahydro-2,5-di-oxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1, 3,3&,4,5,91)-hexahydro-8-ethyl-5-(tetrahydro-2,5-di-oxo-3-furanyl)-naphthalene[l,2-c]-furan -1,3-diketone, 1,3,3a,4,5,9b-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-di-oxo-3-furanyl) -naphthalene [1,2-c]-furan-1,3-dione, 5-(2,5-di-oxo-tetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxyl Anhydride, bicyclo[2.2.2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo[3.2.1]octane-2,4-dione-6 - spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-di-oxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1 , 2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2:3,5:6-dianhydride, 4,9-di 201005005 anhydride;

Oxatricyclo[5.3.1.0''6]undecane-3,5,8,10-tetraketone, an aliphatic or alicyclic ring such as a compound represented by the following formulas (1[-1] and (T_II) Tetracarboxylic acid

(In the formulae (Τ-I) and (Τ-II), R1 and R3 each represent a divalent organic group having an aromatic ring, and R2 and R4 each represent a hydrogen atom or an alkyl group, and a plurality of R2 and R4 present may each Same or different) pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic 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, 3,3',4,4'-tetraphenylnonanetetracarboxylic dianhydride, 1,2, 3,4-furantetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxybenzene Oxy) diphenyl phthalic anhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene Diphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, bis(phthalic acid Phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, Inter-phenyl-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid) -4,4'-二201005005 Phenylmethane dianhydride, ethylene glycol-bis(hydroper trimellitate), propylene glycol-bis(hydrogen trimellitate), 1,4-butanediol-double ( Dehydrated trimellitate), 1,6-hexanediol-bis(anhydrotrimellitic acid ester), 1,8-octanediol-bis(anhydrotrimellitic acid ester), 2,2-dual ( 4-hydroxyphenyl)propane-bis(hydrogen trimellitate), an aromatic tetracarboxylic dianhydride such as a compound represented by the following formula (Τ-1) to (Τ-4). They may be used alone or in combination of two or more.

-10- 201005005

(Τ-3) 〇〒η3

/CH3, ch3 (Τ-4) The tetracarboxylic dianhydride used for synthesizing the polylysine in the present invention is preferably -11-201005005 from the viewpoint that the formed liquid crystal alignment agent can exhibit good liquid crystal alignment. Containing butane tetracarboxylic dianhydride, hydrazine, 2,3,4-cyclobutanetetracarboxylic dianhydride, hydrazine, 3-dimethyl-1,2,3,4-cyclobutane selected from the above Tetracarboxylic dianhydride, 1,2,3,4-cyclopentene tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, l,3,3a,4,5,9b- Hexahydro-5-(tetrahydro-2,5-dioxaxy-3-furylnaphthalene [1,2-.]-furan-1,3-dione '1,3,33,4,5,915-hexahydro -8-Methyl-5_(tetrahydro-2,5--oxo-oxy-3-furanyl)-naphthalene [ij-c]-furan·13-dione, l,3,3a,4,5,9b -Hexahydro-5,8-dimethyl_5_(tetrahydro-2,5-di-oxo-3-furanyl)-naphthalene [l,2-c]-furan-13-dione, bicyclo [222 Buxin-7_ene-23,56· ® tetracarboxylic dianhydride, 3-oxabicyclo[3.2.octane-2,4-dione-6-spiro-3,-(tetrahydrofuran-2',5 '-Dione, 5-(2,5-di-oxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6_ Tricarboxy-2-carboxynorbornane-2:3,5:6-dianhydride, 4 , 9. Dioxatricyclo[531〇2,6]decane-3,5,8,1〇_tetraketone, pyromellitic dianhydride, 3,3; 4,4,-benzophenone Tetracarboxylic dianhydride, 3,3; 4,4,_ diphenylphosphonium tetracarboxylic dianhydride, 2 2; 3 3,-biphenyltetracarboxylic dianhydride, i,4,5,8-naphthalene tetraquinone In the compound represented by the above formula (τ-), the compound represented by the following formula (τ-5) to (Τ-7) and the φ compound represented by the above formula (τ-π) are as follows. At least one of the groups consisting of the compounds represented by the formula (Τ-8) (hereinafter referred to as "specific tetracarboxylic dianhydride (1)") tetracarboxylic dianhydride. -12- 201005005

As the specific tetracarboxylic dianhydride (1), it is particularly preferably selected from the group consisting of 1,2,3,4-cyclobutanine tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, and 1,3 , 3a, 4, 5, 9b_hexahydro-5-(tetrahydro-2,5-di-oxo-3-furanyl)-naphthalene [1,24]-furan-1,3-dione, l, 3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-di-oxo-3-furanyl)-naphthalene [l,2-c]-furan·1 , 3-dione, 3-oxabiindole [3.2.1] octane-2,4-dione-6-spiro-3,-(tetrahydrofuran-2',5'-dione), 5-( 2,5-di-side oxytetrahydro-3·furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane - 2:3, 5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.02'6]undecane-3,5,8, 10-tetraketone' pyromellitic dianhydride and At least one of the compounds represented by the above formula (T-5). The tetracarboxylic dianhydride used for synthesizing the polyamic acid in the present invention preferably contains 20 mol% or more, more preferably 40 mol% or more, and particularly preferably 60 mol% with respect to all tetracarboxylic dianhydrides. Ears above the specific tetracarboxylic-13-, 201005005 acid dianhydride (1) as described above. <Diamine> Examples of the diamine used for the synthesis of the poly-proline in the present invention include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, and 4, 4'-Diaminodiphenylethane, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl maple, 3,3'-dimethyl-4, 4'-Diaminobiphenyl, 4,4'-diaminobenzimidamide, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2'-dimethyl Base-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminolated benzene, 3,3'-bis(trifluoromethyl) -4,4'-diaminobiphenyl, 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindan, 6-amino-1-(4 '-Aminophenyl)-1,3,3-trimethylindan, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4'- Diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-( 4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)benzene飒, 1,4-bis(4-aminophenoxy)benzene, 1 3-bis(4-aminophenoxy) φ 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 group Bis(2-chloroaniline), 2,2',5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5 , 5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-(p-phenylenediisopropylidene)diphenylamine , 4,4'-(meta-phenyl diiso-propyl)diphenylamine, 2,2'-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoro Propane, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy] -Aromatic diamine such as octafluorobiphenyl; -14- 201005005 1,1-m-xylylenediamine, 1,3-propylenediamine, butanediamine, pentamethylenediamine, hexamethylenediamine, heptanediamine, octane Diamine, decanediamine, 4,4-diaminoheptyldiamine, 14-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadiene diamine, hexahydro-4,7 -methylene dimethyl dimethylene diamine 'tricyclic ring [6.2.1.02,7] Monocarbylene dimethyl diamine, 4,4'-methylene bis(cyclohexylamine), 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl) An aliphatic or alicyclic diamine such as cyclohexane; 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2.4-diaminopyrimidine, 5,6 -diamino-2,3-dicyanopyridin, 5,6-diamino '2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3, 5-trimole, 1,4-bis(3-aminopropyl) pipe trap, 2,4-diamino-6-isopropoxy-1,3,5-tri-n, 2.4-diamine -6-methoxy-1,3,5-tri-trap, 2,4-diamino-6-phenyl'1,3,5-tri-trap, 2,4-diamino-6-methyl -8-three tillage, 2,4-diamino-1,3,5-H trap, 4,6-diamino-2-vinyl-s-trisole, 2,4-diamino-5 -phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5-

Diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridine lactate, 3,8-diamino-6-phenylphenanthridine, 1,4 -diaminopiperazine, 3,6-diaminoacridine, bis(4-aminophenyl)phenylamine, 3,6-diaminocarbazole, N-methyl-3,6-di Amino carbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminoguanidine D, N,N,-bis(4-aminophenyl) Benzidine, a compound represented by the following formula (D-Ι), h2n

(DI) (In the formula (D-Ι), R5 is a monovalent organic group-15- having a cyclic structure containing a nitrogen atom selected from the group consisting of pyridine, pyrimidine, triple well, samarium, and pipe trap. 201005005 The group 'X1 is a divalent organic group), a compound represented by the following formula (D-II), and the like, and a diamine having two primary amino groups in the molecule and a nitrogen atom other than the primary amino group.

(In the formula (D-II), R6 is a divalent organic® group having a nitrogen atom-containing cyclic structure selected from the group consisting of pyridine, pyrimidine, triple trap, piperidine, and piperage' X2 each of 2 The valence organic group, the plurality of X2 present may be the same 'may be different'; a monosubstituted phenylenediamine such as a compound represented by the following formula (D-III),

(In the formula (D-III), R7 is a divalent organic group selected from the group consisting of -〇_, .coo-, -OCO-, -NHCO-, -CONH-, and -CO-, φ R8 a monovalent organic group having a skeleton or a group selected from the group consisting of a steroid skeleton, a trifluoromethylphenyl group, a trifluoromethoxyphenyl group, and a fluorophenyl group, or a carbon number of 6 a alkyl group of -3 0; a diamine organooxane such as a compound represented by the following formula (D-IV),

(In the formula (D-IV), 'R9 each represents a hydrocarbon group having a carbon number, and a plurality of R9 groups may be the same or different, and p is an integer of 1 to 3 -16 to 201005005, and q is 1 to 20 Integer); a compound represented by the following formula (D-1) to (D-5), etc.

CH,

〇>2) (D-4)

-17- 201005005 (y in the formula (D-4) is an integer of 2 to 12, and z in the formula (D-5) is an integer of 1 to 5). These diamines may be used alone or in combination of two or more. The diamine for synthesizing the poly-proline in the present invention preferably contains p-phenylenediamine, 4,4,-diaminodiphenylmethane, 4,4,-diaminodi selected from the above. Phenyl sulfide, 15-diaminonaphthalene, 2,2,-dimethyl-4,4,-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4,-di Aminobiphenyl, 2,7-diaminostilbene, 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-aminobenzene) Hexafluoropropane, 4,4,-(p-phenylenediisopropylidene)diphenylamine, 4,4'-(m-phenylenediisopropylidene)diphenylamine, 1,4-bis( 4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 1,4-cyclohexanediamine, 4,4,-methylenebis(cyclohexyl) Amine), 1,3-bis(aminomethyl)cyclohexane, a compound represented by the above formula (D-1) to (D-5), 2,6-diaminopyridine, 3,4-di Aminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazol, N- Ethyl-3,6-φ diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N,N'-bis(4-aminophenyl)benzidine, the above formula (D - a compound represented by the following formula (D-6) in the compound represented by the formula (I), a compound represented by the following formula (D-7) in the compound represented by the above formula (D-II), h2n

(D-6) -18- 201005005 Dodecyloxy-2,4-diaminobenzene, fifteen-epoxy-2,4-diaminobenzene in the compound represented by the above formula (D-III) , hexa-1,oxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, pentadecyloxy Base-2,5-diaminobenzene, cetyloxy-2,5-diaminobenzene, octadecyloxy-2,5-diaminobenzene, the following formula (〇_8)~ (〇-16) at least a compound of the group represented by the compound represented by the above formula (D-IV) and 1,3-bis(3-aminopropyl)-tetramethyldioxane in the compound represented by the above formula (D-IV) A diamine (hereinafter referred to as "specific diamine (1)").

NH2 (D-8)

H2N h2n

-19- 201005005 h2n h2n

H2n

The diamine for synthesizing the poly-proline in the present invention preferably contains 5 mol% or more, more preferably 7 mol% or more, and particularly preferably 10 mol% with respect to the total -20-201005005 diamine'. % or more of the specific diamine (1) as described above. <Synthesis of Polyproline> The polylysine in the present invention can be synthesized by reacting the above tetracarboxylic dianhydride with a diamine. The ratio of use of the tetracarboxylic dianhydride to the diamine for the synthesis reaction of the polyamic acid is preferably 0.5 to 2 equivalents based on 1 equivalent of the amine group contained in the diamine. The ratio is preferably such that it is a ratio of 〇.7~1.2 equivalent 〇^. The synthesis reaction of polylysine is preferably carried out in an organic solvent, preferably at a temperature of -2 0 to 150 ° C, more preferably at a temperature of 0 to 1 〇 0 ° C, preferably 0.5 to 24 The hour is more preferably carried out in a reaction time of 2 to 10 hours. Here, the organic solvent is not particularly limited as long as it is a solvent capable of dissolving the synthesized polyamic acid, and examples thereof include N-methyl-2-pyrrolidone and N,N-dimethylacetamide. An aprotic polar solvent such as hydrazine, dimethyl dimethyl hydrazine, dimethyl hydrazine, γ-φ butyrolactone, tetramethyl urea, hexamethylphosphonium triamine; m-methylphenol, dimethyl A phenol derivative such as phenol, phenol or halogenated phenol. The amount (a) of the organic solvent is preferably such that the total amount (b) of the tetracarboxylic dianhydride and the diamine compound is from 0.1 to 30% by weight based on the total amount (a + b) of the reaction solution. Further, when the organic solvent is used in combination with the following poor solvent, the amount (a) of the above organic solvent is understood to be the total amount of the organic solvent and the poor solvent. In the above organic solvent, a poor solvent alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, a hydrocarbon, or the like of polyglycine may be used in combination in a range in which the produced polyaminic acid is not precipitated. . As a specific example of such a poor solvent, -21 - 201005005 may, for example, be methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol or ethylene glycol. Methyl ether, ethyl lactate, butyl lactate, propyl hydrazine, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate Ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol Dibutyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diglyme, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Methyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichloro Benzene, hexane, heptane, octane, benzene, toluene, xylene, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, and the like. In the case of synthesizing polyamic acid, when the organic solvent is used together with the poor solvent as described above, the use ratio of the poor solvent is preferably 60% by weight or less based on the total amount of the organic solvent and the poor solvent, and more preferably 50 weight φ% or less, particularly preferably 40% by weight or less. As described above, a reaction solution in which polylysine was dissolved was obtained. The reaction solution may be directly supplied to the liquid crystal alignment agent to be prepared, or the polyamic acid contained in the reaction solution may be separated and supplied to the liquid crystal alignment agent for preparation, or the separated polyamic acid may be purified and then supplied. The liquid crystal alignment agent is prepared. 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 drying the precipitate under reduced pressure, or by distilling off the reaction solution by an evaporator under reduced pressure. And proceed. Further, a method in which the polylysine is redissolved in the organic solvent -22-201005005, and then precipitated with a poor solvent, or a step of steam-saturating with an evaporator once or several times, Polylactoic acid can be refined. <醯i-Iminylated Polymer> The oxime imidized polymer ' in the present invention' can be obtained by dehydrating and ring-closing the polylysine obtained as above. The tetrahydro acid dianhydride used in the synthesis of the ruthenium iodide polymer may be the same compound as the tetraruthenic dianhydride used in the synthesis of the above polyamic acid. The tetracarboxylic dianhydride used in the synthesis of the quinone imidized polymer in the present invention preferably contains at least one selected from the group consisting of alicyclic tetracarboxylic dianhydrides (hereinafter referred to as "specific tetracarboxylic acid". Tetracarboxylic dianhydride of dianhydride (2)"). Particularly preferred specific tetracarboxylic dianhydride (2) is selected from the group consisting of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydrogen) -2,5·dioxa-3-furyl)-naphthalene[12-c]-furan- l,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl -5·(tetrahydro-2,5-dioxaxy-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 3-oxabi-g ring [3.2.1 Octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2:5,-dione), 5-(2,5-di-oxotetrahydro-3-furanyl)_3_ Methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2:3,5:6-dianhydride and 4,9-dioxo At least one of the group consisting of heterotricyclo [5.3.1.02'6]undecane-3,5,8,10-tetraone. The tetracarboxylic dianhydride for synthesizing the quinone imidized polymer of the present invention preferably contains 50 mol% or more, more preferably 70 mol% or more, based on the total tetracarboxylic dianhydride, and particularly preferably contains 80 mol% or more of the specific tetracarboxylic dianhydride (2) as described above. -23-201005005 The diamine used in the synthesis of the ruthenium iodide polymer is exemplified by the same diamine as the diamine used in the synthesis of the above polyamic acid. The diamine used in the synthesis of the ruthenium iodide polymer of the present invention preferably contains at least one selected from the group consisting of the compounds represented by the above formula (D- ΠΙ) (hereinafter referred to as "specific diamine (2-1). ))) diamine. As a specific diamine (2-1), it is particularly preferably selected from the group consisting of dodecyloxy-2,4-diaminobenzene, pentadecyloxy-2,4-diaminobenzene, and hexadecyloxy group- 2,4-Diaminobenzene, octadecyloxy-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, pentadecyloxy-2,5-di Amine benzene, hexadecyloxy-2,5-diamino benzene, octadecyloxy-2,5-diamino benzene, and the above formulas (D-8) to (D-16) At least one of the group consisting of compounds. The preferred diamine used in the synthesis of the quinone imidized polymer of the present invention may be a diamine composed only of the specific diamine (2-1) as described above, or a specific diamine (2). In addition to -1), it also contains a selected one selected from the group consisting of p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 1,5-diamino φ naphthalene, 2 , 2'-Dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4,-diaminobiphenyl, 2,7-diamino fluorene , 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, 4,4'-(p-phenylene) Bis-isopropyl)diphenylamine, 4 4,-(extended phenyldiisopropyl)diphenylamine, 1,4-cyclohexanediamine, 4,4,_methylenedi(cyclohexyl) Amine), 1,4-bis(4-aminophenoxy)benzene, 4,4,-bis(4-aminophenoxy)biphenyl, the above formula (D-1)~(D-5) Compounds represented by each, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine ,3,6-diamine-24- 201005005 ΰΤη, n,n'_bis(4-aminophenyl)benzidine, n,n,-bis(4-aminophenyl)_N,N' - dimethyl-benzidine, a compound represented by the above formula (D-6) in the compound represented by the above formula (D-I), and the above formula (D-7) of the compound Ψ represented by the above formula (D-II) At least one of the group consisting of the compound represented by the above formula (III-bis(3-aminopropyl)-tetramethyldioxane in the compound represented by the above formula (D-IV) (hereinafter referred to as " The diamine of the specific diamine (2-2) ''). The diamine used in the synthesis of the quinone imidized polymer in the present invention preferably contains 0.5 mol% or more, more preferably all of the diamine. Containing 1 to 40 mol% 'further preferably contains 5 to 40 mol%, particularly preferably 5 to 30 mol% of the specific diamine (2-oxime) as described above. The ruthenium iodide polymerization in the present invention The diamine used in the synthesis of the substance preferably contains 1 to 99.5 mol%, more preferably 60 to 99 mol% of the total diamine, and particularly preferably contains 70 to 95 mol% as specified above. Diamine 2 - 2) The diamine used in the synthesis of the quinone imidized polymer in the present invention is preferably φ 2 consisting only of the above specific diamine (2-1) and a specific diamine (2- 2). The ruthenium iodide polymer in the present invention may be a fully ruthenium imidized body in which the glycine acid structure of the polyproline has a dehydration ring structure, or a guanine structure and a quinone ring structure. The ruthenium imidized polymer of the present invention has a ruthenium iodide ratio of preferably 40% or more, more preferably 80% or more. Here, the "rhodium imidization ratio" means the total amount of the structure of the proline acid in the polymer and the number of the quinone ring, and the ratio of the number of the quinone ring is expressed as a percentage. In this case, a part of the quinone ring may be an isoindole ring. -25- .201005005 The ruthenium imidization rate of ruthenium iodide can be tetramethylated by dissolving the ruthenium iodide polymer in a suitable deuterated solvent (eg deuterated dimethyl hydrazine) The decane was used as a reference material, and 1 H-NMR was measured at room temperature, and it was determined according to the following formula (1). Ruthenium amination rate (%) = (1 - AVAhcOx 100 (1) (In equation (1), A1 is the peak area originating from the NH proton near the chemical shift of 10 ppm, and A2 is the peak derived from other protons. The area, α is the mass of one sulfhydryl group in the precursor (polyglycolic acid) of the ruthenium iodide polymer, and the ratio of the number of other protons.) The dehydration ring closure reaction of poly-proline The above (i) is carried out by, for example, (i) heating the polyamic acid; (ii) dissolving the polyaminic acid in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution, and heating as needed. The reaction temperature in the method of heating the polyamic acid is preferably 50 to 200 ° C, more preferably 60 to 170 ° C. When the reaction temperature is less than 50 ° C, the φ dehydration ring closure reaction cannot be sufficiently performed. When the reaction temperature exceeds 20 (TC, the molecular weight of the obtained ruthenium iodide polymer may decrease. The reaction time is preferably from 0.5 to 7.2 hours, more preferably from 1 to 1 Torr. a method of adding a dehydrating agent and a dehydration ring-closing catalyst to a polyamic acid solution as a dehydration method An acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride may be used. The amount of the dehydrating agent is preferably OW 2 Torr 2 mol with respect to the 1 mol repeating unit of polyglycolic acid. 'A tertiary amine such as pyridine, trimethylpyridine, dimethylpyrazine or triethylamine can be used. However, it is not limited thereto. The amount of the catalyst for dehydration ring closure -26-.201005005 is preferably dehydrated relative to 1 mole. The reaction temperature of the organic solvent ring reaction exemplified as the solvent used in the synthesis of the polyamic acid is preferably 0 to 180 ° C, more preferably the reaction time. Preferably, it is 1 to 12 hours, more preferably 1 to 6 hours (the ruthenium iodide polymer obtained in the above method (i) can be supplied to a liquid crystal alignment agent for preparation, or the polymer can be purified. Further, a liquid crystal alignment agent is supplied for preparation. In another m V method (Π), a reaction solution liquid containing a ruthenium imidized polymer can be obtained, which can be directly supplied to a liquid crystal alignment agent for preparation, and the dehydrating agent and dehydration should be removed from the solution. close After the catalyst is prepared by the preparation of the catalyst, the ruthenium iodide polymer may be separated into a crystal alignment agent for preparation, or the separated ruthenium may be refined and then supplied to the liquid crystal alignment agent for preparation. From the reaction solvent solution and the dehydration ring closure For the catalyst, for example, separation and purification of the φ 醯 imidized polymer can be employed, and the same operation as described for the separation and purification of the amine acid can be employed. <End-modified polymer> Amine acid and ruthenium iodide polymer, and a terminally modified polymer which can also be adjusted in quantity. This terminal modification is to add a suitable molecular weight such as a compound, a monoisocyanate compound or the like to the reaction system when synthesizing polyglycolic acid. Here, as the monoanhydride, for example, maleic anhydride anhydride, itaconic anhydride, n-decyl succinic anhydride, and n-dodecane 3 may be exemplified as 0. 01 to 10. Dehydration is closed 1 0 ~ 1 5 0 〇C ° > to directly imidize it, in the above i. The reaction solution can also be removed from the liquid-aminated polymer solution after the reverse alignment of the liquid crystal. It is carried out as a gathering. It is synthesized by dividing the polymer into a monoanhydride and a monoamine. , phthalic acid S succinic anhydride, -27-.201005005 n-tetradecyl succinic anhydride, n-hexadecyl succinic anhydride, and the like. Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-undecylamine, and n-xylylene. Alkylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecaneamine, n-octadecylamine, n-icosylamine, and the like. The monoisocyanate compound may, for example, be phenyl isocyanate or naphthyl isocyanate. The ratio of use as a molecular weight regulator relative to 100 parts by weight

The total amount of the tetracarboxylic dianhydride and the diamine used in the formation of the polyamic acid is preferably 20 parts by weight or less, more preferably 10 parts by weight or less. <Solid Viscosity> The polylysine or ruthenium-imided polymer prepared as above has a solution viscosity of 20 to 800 mPa_s when it is formulated into a solution having a concentration of 10% by weight, more preferably 30- Solution viscosity of 500 mPa.s. The solution viscosity (mP a · 〇 of the above polymer is a concentration of 1% by weight of a polymer prepared by using a φ good solvent (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) of the polymer. Solution, ruthenium measured at 25 ° C using a 旋转-type rotary viscometer. <Organic solvent> The liquid crystal alignment agent of the present invention contains, in addition to polyilysine selected from the above, and its hydrazine imidization polymerization. An organic solvent including a compound represented by the above formula (A) is contained in addition to at least one polymer in the group of the composition. In the above formula (A), an alkyl group having 1 to 2 carbon atoms as R or a hydroxyalkyl group, preferably a methyl group or a 1-hydroxyethyl group. A straight-chain alkyl group having 4 to 6 -28-.201005005, preferably a linear alkane having 4 to 5 carbon atoms. In the above formula (A), when R is an alkyl group having 1 to 2 carbon atoms or a hydroxy group, the branched alkyl group having 5 to 12 carbon atoms as R' may, for example, be different. Amyl, 2-ethylbutyl, 4-methyl-2-pentyl, 2-ethylhexyl, 3,5,5-trimethylhexyl, etc.; as alkoxy group having 5 to 12 carbon atoms Alkyl, available For example, 3-methoxybutyl group, 4-methoxybutyl group, methoxy-3-methylbutyl group and the like; and examples of the alicyclic group having 5 to 10 carbon atoms include cyclohexyl group. , 2-methylcyclohexyl, 3,3,5·trimethylcyclohexyl, etc. ❷ In the above formula (A), when R is a linear alkyl group having 4 to 6 carbon atoms, as R' a linear or branched alkyl group having 4 to 6 carbon atoms, preferably a linear or branched alkyl group having 4 to 5 carbon atoms, and examples thereof include a butyl group, a pentyl group, an isopentyl group, and a methyl group. Examples of the compound represented by the above formula (A) include 4-methyl-2-pentyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, and acetic acid 2. _Ethylhexyl ester, cyclohexyl acetate, 2-methylcyclohexyl acetate, butyl butyrate, amyl butyrate, isoamyl butyrate, isoamyl lactate, etc. as a liquid crystal alignment agent of the present invention The organic solvent to be used may be a compound represented by the above formula (A) or a compound other than the compound represented by the above formula (A), and other organic solvents may be used. For example, N-methyl-2-pyrrolidone, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine-dimethyl dimethyl hydride Ethyl amide, butyl cellosolve, diacetone alcohol, propylene carbonate, diethylene glycol diethyl ether, ethyl 3-ethoxypropionate, γ-butyrolactam, 4-hydroxy-4-methyl- 2-pentanone, ethylene glycol monocarboxylic acid, butyl lactic acid, methyl methoxypropionate, -29- 201005005 ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol n-propyl ether, ethylene glycol Propyl ether, ethylene glycol ethyl ether acetate, diglyme, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, etc. . The solvent of the organic solvent used in the liquid crystal alignment agent of the present invention is a composition obtained by combining the compound represented by the above formula (A) with another solvent, and the components of the liquid crystal alignment agent in the liquid crystal alignment agent are not The composition is precipitated and the surface tension of the alignment agent is in the range of 20-40 mN/m. The organic solvent used in the liquid crystal alignment agent of the present invention preferably includes at least one of the compounds represented by the above formula (A), and is selected from the group consisting of N-methyl-2-pyrrolidone, γ-butyrolactone, and 1,3. - dimethyl-2-imidazolidinone, N, N-

Species (hereinafter referred to as "other specific organic solvent (1)") and a group selected from the group consisting of butyl cellosolve, diacetone alcohol, propylene carbonate, diethylene glycol diethyl ether and ethyl ethoxy propionate An organic solvent of at least one of them (hereinafter referred to as "other specific organic solvent (2)"). The organic solvent used in the liquid crystal alignment agent of the present invention preferably contains 3 to 40% by weight, more preferably 5 to 20% by weight, based on the total amount of the organic solvent, of at least one of the compounds represented by the above formula (A). The organic solvent used in the liquid crystal alignment agent of the present invention preferably contains 0.5 to 90% by weight, more preferably 35 to 85% by weight, based on the total amount of the organic solvent, of the other specific organic solvent (1) as described above. The organic solvent used in the liquid crystal alignment agent of the present invention preferably contains 0.5 to 70% by weight, more preferably 1 to 60% by weight, based on the total amount of the organic solvent, of the other specific organic solvent (2) as described above. -30-.201005005 &lt;Other components&gt; The liquid crystal alignment agent of the present invention contains at least one polymer selected from the group consisting of polyamic acid and quinone imidized polymer as described above, and contains the above formula The organic solvent of the compound represented by (A) is an essential component, but other components may be contained without impairing the effects and advantages of the present invention. Examples of such other components include a compound having at least one epoxy group in the molecule (hereinafter referred to as "epoxy group compound") and a functional decane compound. The epoxy compound may be contained in the liquid crystal alignment agent of the present invention from the viewpoint of further improving the adhesion of the formed liquid crystal alignment film to the surface of the substrate. Preferred examples of such an epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether. , neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6 -tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylamine) Methyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N-diglycidyl-benzylamine, N, N-diglycidyl-aminomethylcyclohexane or the like. The use ratio of the epoxy compound is preferably 40% by weight based on 100 parts by weight of the polymer (refer to 100 parts by weight of the total amount of the polylysine and its ruthenium iodide polymer as described above). More preferably, it is 0.1 to 30 parts by weight. The functional decane compound may, for example, be 3-aminopropyl-31-.201005005-trimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2 -Aminopropyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropyl Methyldimethoxydecane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N- Ethoxycarbonyl-3-aminopropyltriethoxydecane, N-triethoxydecylpropyltriethylenetriamine 'N-trimethoxydecylpropyltriethylenetriamine, 10-trimethyl Oxidylalkyl-1,4,7-triazadecane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6- Diazepine acetate, 9-triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl 3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxyhydrazine , N- bis (oxyethylene) -3-aminopropyl trimethoxy Silane, N- bis (oxyethylene) -3-aminopropyl triethoxy silane-like. The compounding ratio of the functional decane compound is preferably 2 parts by weight or less, more preferably 0.2 parts by weight or less based on 100 parts by weight of the polymer. &lt;Liquid crystal alignment agent&gt; The liquid crystal alignment agent of the present invention is at least one polymer selected from the group consisting of polylysine as described above and its quinone imidized polymer, and other components optionally used The solution is dissolved in an organic solvent including the compound represented by the above formula (A). The solid content concentration of the liquid crystal alignment agent of the present invention (the ratio of the total weight of the components other than the organic solvent in the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) is appropriately selected in consideration of viscosity, volatility, etc., preferably 1 to 1 Torr. % by weight -32- 201005005 range. That is, the liquid crystal alignment agent of the present invention forms a coating film as a liquid crystal alignment film by applying it to the surface of the substrate and then removing the organic solvent, and when the solid content concentration is less than 1% by weight, the coating film appears. When the thickness is too small to obtain a good liquid crystal alignment film, when the solid content concentration exceeds 10% by weight, a case where the thickness of the coating film is too thick and it is difficult to obtain a good liquid crystal alignment film is also caused, and a liquid crystal alignment agent may occur. The viscosity is increased to cause a deterioration in coating performance. A particularly preferred range of solid content concentration 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 that the solid content concentration is in the range of 3 to 9 % by weight, so that the solution viscosity can be in the range of 12 to 50 mPai. 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 in the range of 3 to 15 mPa.s. The temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably 0 ° C to 60 ° C, and more preferably 20 ° C to 40 ° C. &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. The liquid crystal display element of the present invention can be produced, for example, by the following method. (1) First, the liquid crystal alignment agent of the present invention is applied onto a pair of substrates, and a solvent is removed to form a coating film. Here, when the display mode of the liquid crystal display element to be manufactured is a vertical electric field mode such as a TN type, an STN type, or a VA type, a substrate in which a patterned transparent conductive film is provided on one surface of two-33-201005005 blocks is used as a Used on the substrate. On the other hand, when the display mode of the liquid crystal display element to be manufactured is the horizontal electric field method, the substrate provided with the transparent conductive film having the comb-tooth pattern and the substrate without the transparent conductive film are used as a pair of substrates. In either case, when a transparent conductive film is provided on the substrate, the liquid crystal alignment agent is coated on the side of the substrate having the transparent conductive film. As the substrate, for example, glass such as float glass or soda lime glass; polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, poly(alicyclic olefin) can be used. ) Plastic transparent substrates. As the transparent conductive film provided on one side of the substrate, a NESA film made of tin oxide (Sn02) (registered trademark of PPG, USA), an ITO film made of indium oxide-tin oxide (ln203-Sn02), or the like can be used. In addition, the pattern-forming transparent conductive film can be obtained by forming a pattern by a lithography lithography method after forming a pattern-free transparent conductive film; when a transparent conductive film is formed, using a mask having a desired pattern, or the like, A method of directly forming a patterned transparent conductive film or the like. The liquid crystal alignment agent is applied onto the substrate by a suitable coating method such as a roll coating method, a spin coating method, a printing method, or an inkjet method. At the time of 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 functional decane compound, a functional titanium compound or the like may be applied to the surface to be coated of the substrate. In addition, when the liquid crystal display element to which the liquid crystal alignment agent of the present invention is applied is a VA type liquid crystal display element, a projecting structure can be formed on the substrate as described in, for example, Patent Document 7 (JP-A-2002-0327058). The liquid crystal alignment agent is coated to achieve the purpose of improving the viewing angle performance. -34-.201005005 After coating, preheating (prebaking) is preferably performed for the purpose of preventing the coating agent liquid from sagging or the like. 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 0.5 to 10 minutes, more preferably from 0.5 to 5 minutes. Then, for the purpose of completely removing the solvent or the like, a baking (post-baking) step is performed. The post-baking temperature is preferably from 80 to 300 ° C, more preferably from 120 to 250 ° C. The post-baking time is preferably from 5 to 120 minutes, more preferably from 1 to 1 minute. The liquid crystal alignment agent of the present invention is coated with the organic solvent to form a coating film as a liquid crystal alignment film. In this case, when the polymer contained in the liquid crystal alignment agent of the present invention is a polyamic acid or a quinone imidized polymer having a valerine structure, it may be further heated by further heating after the coating film is formed. The dehydration ring of the proline structure is formed to form a further yttrium-immobilized coating film. The thickness of the formed coating film is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μπι φ. (2) When the display mode of the liquid crystal display element to be manufactured is VA type, the coating film formed as above can be directly used as the liquid crystal. For the use of the alignment film, the following polishing treatment may be performed as needed. On the other hand, when the display mode of the liquid crystal display element to be manufactured is a vertical electric field method or a lateral electric field method other than the VA type, a roll wound with a cloth made of a fiber such as nylon, rayon, cotton or the like is used. The coated surface is rubbed in a certain direction to be polished. Thus, the coating film is imparted with liquid crystal molecules to form a liquid crystal alignment film. In addition, the coating film after the sanding treatment is shown in, for example, Patent Document 8 (Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A process of irradiating a part of the liquid crystal alignment film with ultraviolet rays to change a pretilt angle of a partial region of the liquid crystal alignment film, or a liquid crystal alignment film as shown in Patent Document 10 (Japanese Laid-Open Patent Publication No. Hei 5-107544) After the photoresist film is formed on a part of the surface, the photoresist film is removed in a direction different from the previous sanding process, and the liquid crystal alignment film has different liquid crystal alignment energy in each region, so that the obtained liquid crystal display element can be improved. Field of view performance. (3) A pair of substrates on which the liquid crystal alignment film is formed as described above is formed. When the polishing is performed, the polishing directions of the respective liquid crystal alignment films are perpendicular or antiparallel, so that the liquid crystal alignment film faces are opposed to each other, and the two substrates are opposed to each other. In the arrangement, liquid crystal is disposed in the gap (cell gap) to constitute a liquid crystal cell. For the arrangement of the liquid crystals in a pair of substrate gaps, for example, the following two methods can be employed. The first method is a previously known method. First, the respective liquid crystal alignment films are opposed to each other, and the two substrates are disposed to face Q through a gap (cell gap), and the peripheral portions of the two substrates are bonded together with a sealant to be surrounded by the substrate surface and the sealant. After filling the liquid crystal in the interstitial space, the injection hole is closed, and the liquid crystal cell can be produced. The second method is called the DropDF (One Drop Fill) method. Applying, for example, an ultraviolet curable sealant material to a predetermined portion of one of the two substrates forming the liquid crystal alignment film, and then dropping the liquid crystal on the liquid crystal alignment film surface, and then bonding the liquid crystal alignment film to the other substrate Then, the entire surface of the substrate is irradiated with ultraviolet rays to cure the sealant, and the liquid crystal cell can be produced. -36- .201005005 In the case of any method, it is necessary to heat the liquid crystal cell to a temperature at which the liquid crystal used is in an isotropic phase, and then slowly cool to room temperature to eliminate the flow alignment during liquid crystal injection. Then, a polarizing plate is attached to the outer surface of the liquid crystal cell to obtain a liquid crystal display element of the present invention. Here, as the sealant, for example, an epoxy resin containing an alumina ball as a curing agent and a spacer can be used. Examples of the liquid crystal include a nematic liquid crystal and a disk-shaped liquid crystal. Among them, a nematic liquid crystal is preferred. For example, a Schiff's liquid crystal, an oxidized azo liquid crystal, a biphenyl liquid crystal, or a phenyl ring can be used. A hexane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, a biphenyl cyclohexane liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, or a cuba liquid crystal. Further, in these liquid crystals, cholesteric liquid crystals such as cholesteryl cholesteryl, cholesteryl phthalate, and cholesteryl carbonate may be added; and the trade names are "C-15" and "CB-15" (manufactured by Merck). A chiral agent sold; used for ferroelectric liquid crystals such as decyloxybenzylidene Q-p-amino-2-methylbutyl cinnamate. When the manufactured liquid crystal cell is a VA type liquid crystal cell, liquid crystal having negative dielectric anisotropy in the nematic liquid crystal is preferably used, and on the other hand, it is TN type, STN type, OCB type, IPS type or the like. In the case of a liquid crystal cell, a liquid crystal having positive dielectric anisotropy in a nematic liquid crystal is preferably used. The polarizer to be bonded to the outer surface of the liquid crystal may be a polarizer formed by sandwiching a polarizing film called "H film" obtained by stretching and dispersing polyvinyl alcohol and absorbing iodine, in a cellulose acetate protective film, or A polarizer made of the enamel itself. -37-201005005 [Embodiment] Hereinafter, the present invention will be more specifically described by way of examples, but the invention is not limited thereto. Synthesis Example 1 110 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetradecanoic dianhydride, 38 g (0.35 mol), 4, 4 of p-phenylenediamine as a diamine. , -diaminodiphenylmethane 20g (〇.l mole) and 3_(3,5-diaminobenzylideneoxy)cholestane 26g (0.05 mol) dissolved in 8〇〇g N- In the methyl 2-pyrrolidone (oxime), the reaction was carried out at 60 ° C for 6 hours. Take a small amount of the obtained polyaminic acid solution, add NMP' to form a solution with a polyglycine concentration of 1% by weight, and measure the solution viscosity at 25 ° C using an E-type viscometer to 60 mP a * s ° Then, 1800 g of hydrazine was added to the obtained polyamic acid solution, and then 80 g of pyridine and 1 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system is replaced with a new γ-φ butyrolactone (by the solvent replacement operation, the pyridine and acetic anhydride used in the dehydration ring closure reaction are removed to the outside of the system) to obtain about 11 〇〇g contains a solution of 15% by weight of a ruthenium iodide polymer having a ruthenium iodide ratio of about 80%. A small amount of the ruthenium iodide polymer solution was added, and γ-butyrolactone was added to prepare a solution having a ruthenium iodide polymer concentration of 10% by weight, and the solution viscosity was measured at 25 ° C using a Ε-type viscometer. It is 87 mPai. Example 1 &lt;Preparation of Liquid Crystal Aligning Agent&gt; In the solution containing the ruthenium iodide prepared above, 'addition of γ--38-201005005 butyrolactone, N-methyl-2-pyrrolidinium, Butyl cellosolve and acetic acid-methyl-2-pentyl ester (the compound represented by the above formula (A)), respectively, and the solvent composition is γ-butyrolactone: Ν-methyl-2-pyrrolidone: butyl cellosolve: acetic acid Methyl-2-pentyl ester = 30; 40; 20; 1 〇 (by weight), two solutions having a solution viscosity of 6 mPa's and 20 mPa.s. These solutions were respectively filtered through a filter having a pore size of 〇.2 μm to prepare two kinds of liquid crystal alignment agents having different concentrations. &lt;Evaluation of inkjet printability&gt; A glass substrate with a transparent electrode made of IT was washed with an ultrasonic solution in an aqueous solution and ultrapure water for 30 minutes, respectively, and then washed with ultrapure water. After 30 minutes of running water washing, ultrasonic washing was carried out for 30 minutes in isopropyl alcohol, and then dried in an oven at 100 ° C for 30 minutes. The substrate was further heated on a hot plate at 200 ° C for 1 minute to carry out dehydration. 'Using 1; ¥ ozone cleaner (3 £ &gt; 11 ^ 1 〇 111 ' (: 〇 11?. manufactured, model "?] ^ 9011 N-1") UV ozone washing to make the contact angle of water less than 1 〇 °. Using an inkjet printing device (made by Shibaura Electromechanical Co., Ltd.), at 0 200-280 mg / nozzle · 10 seconds, 2500 times / Under the conditions of nozzles and seconds, the above-prepared liquid crystal alignment agent having a solution viscosity of 6 mPa·s was subjected to two round-trip coatings on the transparent electrode surface of the glass substrate with a transparent electrode immediately after UV washing ( After four times of coating, the solvent was removed by heating at 80 ° C for 1 minute to form a coating film having an average film thickness of 100 nm. The coating film was visually inspected by a sodium lamp for interference fringe observation, and evaluation of coating unevenness was performed. There was no unevenness due to solvent removal and unevenness due to the nozzle and the head, and the ink jet printability was "good". <Evaluation of vertical alignment> -39- 201005005 Liquid crystal alignment film printer (Japanese photo E Liquid crystal with a solution viscosity of 20mPa's A transparent electric heating plate of a glass substrate made of a transparent electrode made of an ITO film was prebaked for 1 minute, and then a coating film having an average film thickness of 1 000 A was formed at 200 ° C for 10 minutes to form a pair (two pieces) on the transparent conductive film. An epoxy® liquid crystal alignment film having a liquid crystal alignment film having a diameter of 5. 5 μm added to the pair of substrates is relatively recombined and pressed to pass through the liquid crystal injection port to the pair of substrates After filling the crucible [J production, MLC-660 1 ), the liquid crystal cell was fabricated by blocking with an acrylic photo-curing inlet. The liquid crystal light was observed under the visible light, and the light leakage and vertical liquid crystal were mixed in Examples 2 to 4 In the above-mentioned Example 1, except that the g substance was used instead of the compound represented by the above formula (A), the liquid crystal alignment agent was adjusted and evaluated in the same manner as in Example 1. The results are shown in Table 1. The brush (manufactured by the brush) was coated with a coating agent on a hot plate having a pole face at 80 ° C for post-baking. Repeat the same operation to crystallize the substrate to the film. On each of the outer edges, after applying the resin adhesive, the adhesive is cured. Next, the type of liquid crystal (Merck's company adhesives in the liquid crystal injection in the Nickel bias is "good". The concentration of phthalic acid-methyl-2-pentyl vinegar listed in Table 1 is different. Two kinds - 40 - 201005005 Table 1 Kinds of the compound represented by the above formula (A) Ink jet printing vertical liquid crystal alignment Example 1 Acetic acid - methyl-2-pentyl ester Good good Example 2 Cyclohexyl acetate was good Example 3 2-Methylcyclohexyl acetate Good Practice Example 4 Isoamyl lactate was good and good [Simplified illustration] y»&gt;\ [Key symbol description] te . -41-

Claims (1)

201005005 VII. Patent application scope: 1. A liquid crystal alignment agent characterized by comprising: a group consisting of polylysine obtained by reacting tetracarboxylic dianhydride with a diamine and a ruthenium iodide polymer thereof At least one polymer in the group; and an organic solvent comprising a compound represented by the following formula (A), RCOOR, (A) wherein, in the formula (A), R is an alkyl group or a hydroxyalkyl group having 1 to 2 carbon atoms Or a linear alkyl group having 4 to 6 carbon atoms; when R is an alkyl group φ or a hydroxyalkyl group having 1 to 2 carbon atoms, R' is a branched alkyl group having 5 to 12 carbon atoms or An alkoxyalkyl group or an alicyclic group having 5 to 10 carbon atoms. When R is a linear alkyl group having 4 to 6 carbon atoms, R' is a linear chain having 4 to 10 carbon atoms. Or branched alkyl. 2. The liquid crystal alignment agent of claim 1, wherein the compound represented by the above formula (A) is a compound having a boiling point of 140 to 200 ° C and a surface tension of 18 to 30 mN/m. 3. The liquid crystal alignment agent of claim 1, wherein the compound represented by the above formula (A) # is selected from the group consisting of 4-methyl-2-pentyl acetate, 3-methoxybutyl acetate, and acetic acid. 2-ethylbutyl ester, 2-ethylhexyl acetate, cyclohexyl acetate, 2-methylcyclohexyl acetate, butyl butyrate, amyl butyrate, isoamyl butyrate and isoamyl lactate At least one of the group formed. 4. The liquid crystal alignment agent of claim 1, which is an organic solvent, further comprising N-methyl-2-pyrrolidone, γ-butyrolactone, 1,3-dimethyl-2-imidazole Linoleone, hydrazine, hydrazine-dimethylformamide, and hydrazine, hydrazine-dimethylacetamide, butyl cellosolve, diacetone alcohol, propylene carbonate, diethylene glycol diethyl ether, 3-ethoxyl Ethyl propionate, γ-butyrolactam, 4-hydroxy-4- 4-42- 201005005 methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, methyl methoxypropionate, B Diol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol ethyl ether acetate, diglyme, diethylene glycol monomethyl ether, diethylene glycol At least one of the group consisting of monoethyl ether, diethylene glycol monomethyl ether acetate, and diethylene glycol monoethyl ether acetate. 5. The liquid crystal alignment agent of claim 1, wherein the ratio of the compound represented by the above formula (A) to the total organic solvent is from 3 to 4% by weight. G 6. A liquid crystal alignment agent as claimed in claim 1 which is used for inkjet coating. A liquid crystal display element characterized by having a liquid crystal alignment film formed by the liquid crystal alignment agent according to any one of claims 1 to 6. -43- 201005005 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: ίκ 〇 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: