TW200946563A - Liquid crystal aligning agent and liquid crystal display element - Google Patents

Abstract

The present invention provides a liquid crystal aligning agent which providing a liquid crystal aligning film with good voltage hold ratio and afterimage properties The above liquid cryastal aligning agent comprising at least one polymer selected from the group consist of a polyamic acid and an imide polymer thereof, wherein the polyamic acid is obtained by reacting a tetracarboxylic dianhydride with a diamine which comprising a compound represented by the formula (I) or (II) below: wherein, n1 are integers of 1 to 8 respectively.

Description

.200946563 VI. Description of the Invention: Λ Technical Field of the Invention The present invention relates to a liquid crystal alignment agent and a liquid crystal display element. [Prior Art] As a liquid crystal display element, a TN type liquid crystal display element having a so-called TN type (twisted nematic) liquid crystal cell is known, which is formed of a polyimide film or the like on the surface of a substrate on which a transparent conductive film is provided. A liquid crystal alignment film is used as a substrate for a liquid crystal display element, and a pair of (two pieces) are disposed opposite each other, and a nematic liquid crystal layer having positive dielectric anisotropy is filled in the gap therebetween 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, recently, an STN (Super Twisted Nematic) type liquid crystal display element having a higher load ratio than a TN type liquid crystal display element has been developed. Such an STN type liquid crystal display device uses a substance which is a chiral agent which is an optically active substance in a nematic liquid crystal, and is used as a liquid crystal by a continuous twist of 180 degrees or more between substrates by the long axis of the liquid crystal molecule. The birefringence effect produced by the state. The alignment of the liquid crystals in these TN type liquid crystal display elements and STN type liquid crystal display elements is usually produced by a liquid crystal alignment film which has been subjected to a rubbing treatment. Further, as a liquid crystal display element of a different type from these, a VA (Vertical Alignment) type liquid crystal display element in which liquid crystal molecules having negative dielectric anisotropy are vertically aligned on a substrate is also known. In the VA liquid crystal display device, when a voltage is applied between the substrates to tilt the liquid crystal molecules in a direction parallel to the substrate, it is necessary to tilt the liquid crystal molecules from the substrate normal direction in one direction in the substrate surface. As a means for this purpose, for example, an MVA method in which protrusions are formed on ITO 200946563 to control the alignment direction of liquid crystals (Patent Document 1 and Non-Patent Document 1), and an EVA method in which an electrode structure is designed to control an alignment direction has been proposed (Non-Patent Literature) 2) A method of modifying the alignment film by light irradiation to control the alignment direction of the alignment direction (see Non-Patent Document 3). Further, polyimine which is obtained by polycondensation of tetracarboxylic dianhydride and diamine is known to have excellent heat resistance and chemical resistance. Therefore, polyimine has been used in various applications, particularly in the fields of electricity and electronic materials, and has been widely used as a protective material and an insulating material. In particular, in the use of the alignment film 0 of a liquid crystal display element, from the viewpoint of durability of a coating film, polyimine has been mainly used so far. However, in order to improve the performance of the liquid crystal display element and to increase the density of the display, the surface properties of the polyimide have been particularly emphasized, and the prior polyimine alignment film has also been required to have excellent performance. For example, liquid crystal alignment control force, pretilt performance, afterimage performance, etc., require higher performance. A liquid crystal alignment film made of polyimine, usually, an organic solvent solution of a soluble ruthenium-imiding polymer which is a polyaminic acid as a polyimine precursor or a dehydration ring-closing thereof The liquid crystal alignment agent is applied onto a substrate and heated to imidize the oxime. According to Patent Document 2, by using the formula (III) or (IV)

200946563 (In the formulae (III) and (IV), the diamine-synthesized polyamine or the quinone imidized polymer liquid crystal alignment agent of the structure represented by 4 or 6) can form a stable Pre-tilt liquid crystal alignment film. This technique achieves stabilization of the pretilt angle by introducing a liquid crystal-like skeleton derived from the diamine represented by the above formula (III) or (IV) onto the liquid crystal alignment film. It is said that a liquid crystal alignment film for a VA liquid crystal display element (hereinafter also referred to as "vertical alignment type liquid crystal alignment film") having excellent vertical alignment property can be formed by using a polymer having such a structure. However, in Patent Document 2, 电压 does not improve voltage holding ratio and afterimage performance. Further, in Patent Document 3, it is reported that it is synthesized by using a tricarboxylic dianhydride containing 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6-dianhydride as a tetracarboxylic dianhydride. The liquid crystal alignment agent of the polymer can achieve high voltage retention in the high temperature field. However, this technique still does not improve the afterimage performance. Here, if attention is paid to liquid crystal display, the manufacturing steps of the display elements have been significantly advanced in recent years. For example, as a method of filling a liquid crystal material into a gap between a pair of substrates, a pair of substrates are previously disposed to face each other through a gap, and a method of collecting liquid crystal into the gap is employed. In recent years, as a new method for replacing bismuth, a liquid crystal dropping (〇neDropFill=ODF) method has been proposed (Patent Document 4). The ODF method is a method in which droplets of a liquid crystal material are dropped on a liquid crystal alignment film of a substrate, and the liquid crystal droplets are pressed and expanded by opposing substrates, and the substrate is bonded under vacuum. According to this method, there is an advantage that the time required for the liquid crystal charging step can be greatly shortened, but dripping marks are generated in the liquid crystal dropping portion, and when it is made into a liquid crystal display element, it can be pointed out that the drop mark can be visually observed. The problem of uneven liquid crystal alignment. This liquid crystal 200946563 alignment unevenness is considered to be a partial disturbance of the alignment of the liquid crystal alignment film due to the impact when the liquid crystal material is dropped onto the liquid crystal alignment film. In order to solve this problem, an attempt has been made to solve the problem by the liquid crystal alignment film material (Patent Document 5), but it is still not satisfactory. In particular, when the Va type liquid crystal display element is manufactured by the 〇DF method, it is required to suppress the above-described liquid crystal alignment unevenness. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei 09-278724 (Patent Document 3) Japanese Patent Laid-Open Publication No. Hei No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. JP-A-5-107544 [Patent Document 9] Japanese Laid-Open Patent Publication No. Hei-4-281427 (Non-Patent Document 1) "Liquid Crystal", Vo 1 · 3, N 〇. 2, 1 1 7 (19.9) Φ [Non-Patent Document 2] "Liquid Crystal", Vo 1.3, No. 4, 272 (1999) [Non-Patent Document 3] "Jpn J. Appl. phys." Vol 36, L428 (1999) [Invention] A first object of the invention is to provide a liquid crystal alignment agent capable of forming a liquid crystal alignment film excellent in voltage holding ratio and afterimage performance. A second object of the present invention is to provide a liquid crystal alignment agent which can form a liquid crystal 200946563 alignment film which does not cause liquid crystal alignment unevenness due to liquid crystal dropping even when the ODF method is employed in the liquid crystal charging step. Such a liquid crystal alignment agent of the present invention can be preferably used for the formation of a liquid crystal alignment film of a vertical alignment type liquid crystal display element. Another object of the present invention is to provide a liquid crystal display element which is excellent in quality. Other objects and advantages of the invention will be apparent from the description which follows. The present inventors have conducted intensive studies in view of the above circumstances, and as a result, it has been found that by using a liquid crystal alignment agent containing a specific polymer synthesized using a diamine having a specific structure, it is possible to form a G liquid crystal excellent in voltage holding ratio and afterimage performance. The alignment film is achieved, thereby achieving the present invention. That is, the above objects and advantages of the present invention, first, achieved by a liquid crystal alignment agent comprising at least one polymer selected from the group consisting of polylysine and its quinone imidized polymer, the polyfluorene The amine acid is obtained by reacting a tetracarboxylic dianhydride with a diamine containing at least one selected from the group consisting of compounds represented by the following formulas (I) and (II),

(In the above formula, nl is each independently an integer of 1 to 8). The above objects and advantages of the present invention, and secondly, achieved by a liquid crystal display element having the liquid crystal alignment film formed of the above liquid crystal alignment agent, and the above objects and advantages of the present invention, and third, by the above formula (1) or Π) The compound represented is achieved. The liquid crystal alignment agent of the present invention can form a liquid crystal alignment film excellent in voltage holding ratio and afterimages @仓巨200946563. Further, in the liquid crystal alignment agent of the present invention, even when the ODF method is employed in the liquid crystal charging step, a liquid crystal alignment film which does not cause liquid crystal alignment unevenness due to liquid crystal dropping can be formed. The liquid crystal alignment agent of the present invention can be used for a TN type and STN type liquid crystal display element, etc., and is particularly suitable for a VA type liquid crystal display element. The liquid crystal display element of the present invention can be effectively used for various devices, for example, display devices applicable to calculators, watches, desk clocks, counting display screens, word processors, personal computers, liquid crystal televisions, and the like. [Embodiment] Hereinafter, the present invention will be specifically described. The liquid crystal alignment agent of the present invention comprises at least one polymer selected from the group consisting of polyamic acid and a quinone imidized polymer thereof, the polyamic acid and the tetracarboxylic dianhydride are selected from the above formula ( The diamine reaction of at least one of the compounds represented by I) and (II) is carried out. <tetracarboxylic dianhydride> As the tetracarboxylic phthalic anhydride which can be used for the synthesis of the polyamic acid used in the present invention, for example, butane tetracarboxylic dianhydride and 1,2,3,4-ring are exemplified. Butane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-ring Butane tetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4·cyclobutane tetracarboxylic 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, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,33, 4,5,91)-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2<]-furan-1,3-dione, l,3 , 3a,4,5,9b-hexahydro-5-methyl-5-(tetrahydro-2,5-dioxo-3-furan 200946563)-naphthalene [l,2-c]·furan-1 ,3·二_,13,3&4,591)_六氡_5ethyl-5-(tetrahydro-2'5-dioxo-3-furanyl)-naphthalene [u.cpfuran-1dione , 1'3,3&,4,5,9-hexahydro-7-methyl-5_(tetrahydro-2,5-dioxo-furanyl)- [1,2-C]-furan·U·dione, hexamethylene-6-(tetrahydro-2,5-dioxo-3-furanylnaphthalene furanone, 1,3'3&,4,5,915-hexahydro-8-methyl_5_(tetrahydro-2,5-dioxo-3-'furanyl)-naphthalene n,2-C]-furan-!, 3·dione, ^, “, ^ hexahydro + ethyl-5-(tetrahydro-2,5-monooxy-3-furanyl)-naphthofuran·ι % diβ-ketone, 1,3 ,3a,4,5,9b-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan ·丨, 3_dione, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, bicyclo[2 2 2]•xin_7 Alkene 2'3,5,6-tetracarboxylic dianhydride, 3_oxabicyclo[3 21]octane-2,4·dione_6_ spiro-3'-(tetrahydrofuran-2,,5,_ Diketone), 5-(2,5-dioxotetrahydro-3-ylpyranyl)-3-methyl_3_cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxyl 2-carboxymethyl norbornane-2:3,5:6-dianhydride, 4,9-dioxatricyclo[531〇26]deca--3,5'8,10-tetraketone, lower An aliphatic or alicyclic tetracarboxylic acid such as a compound such as -^ and ^1(1)

(Τ-Ι)

(Τ-ΙΙ) (wherein R1 and R3 each represent a divalent organic group fluorene having an aromatic ring, and R2 and R4 each represent a hydrogen atom or a yard group, and a plurality of R2 and R4-10-200946563 present may be the same, Also different); pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenyltricarboxylic dianhydride 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride , 3,3',4,4'-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-dicarboxyphenoxy Diphenyl calcane, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane phthalic anhydride, 3,3',4,4'-perfluoroisopropylidene Phthalic phthalic anhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, bis(phthalic acid) Phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride , m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid) )-4,4'-diphenylmethane dianhydride, ethylene glycol-bis(hydroper trimellitate), propylene glycol-bis(hydroper trimellitate), 1,4-butanediol-double ( Dehydrated trimellitate), 1,6-hexanediol-bis(anhydrotrimellitic acid ester), 1,8-octanediol-bis(dehydrated trimellitate), 2,2-double (4-hydroxyphenyl)propane-bis(hydrogen trimellitate), an aromatic tetracarboxylic dianhydride such as a compound represented by the following formulas (T-1) to (T-4), and the like. They may be used alone or in combination of two or more. -11 - 200946563

φ The synthetic anhydride of polyglycine used in the present invention is preferably selected from the group consisting of butane tetracarboxylic dianhydride, acid dianhydride, and 1,3-dimethyl hydride. 1,2-,3,4-cyclobutanetetracyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentacarboxy-2-carboxymethylnorbornane-2:3,5 :6-di|hydrogen-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalenone, 1,3,3&,4,5,91)-hexahydro-8-A Angle of orientation of the tetracarboxylic acid di 3 liquid crystal used in the group 5-(tetrahydro)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3a,4, 2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-based acetic acid dianhydride, 3,5,6-dry, l,3,3a,4,5,9b-six [l,2-c]-furan-1,3-di-2,5-dioxo-3-furan, 5,9 b · /, chloro-5,8 - monomethyl-12- 200946563 ke - 5 -(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, bicyclo[2.2.2]-oct-7-ene- 2,3,5,6-tetracarboxylic dianhydride, 3-oxabiindole [3.2.1]octane·2,4-dione-6-spiro-3'-(tetrahydrofuran-2', 5' -dione), 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1 ,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.02' 6] undecane-3,5,8,10-tetraketone, pyromellitic dianhydride, 3,3',4,4,-benzophenonetetracarboxylic dianhydride, 3,3',4, 4'-diphenylphosphonium tetracarboxylic dianhydride, 2,2',3,3,-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid diacetic anhydride, the above formula ( The compound represented by the following formula (T-5) to (T-7) in the compound represented by T-I) and the compound represented by the above formula (T-II) are represented by the following formula (T-8); A tetracarboxylic dianhydride of at least one of the group consisting of compounds (hereinafter referred to as "specific tetracarboxylic dianhydride").

As the specific tetracarboxylic dianhydride, it is preferably selected from 1,2,3,4-cyclobutanetetracarboxylic acid-13-200946563 dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1, 3,3&,4,5,91)_hexanitro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-咲 __13_二Ketone, 1,3,3&,4,5,91>-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-indolyl)-naphthalene [l,2 -c]-furan-1,3-dione, 3-oxabicyclo[3.2·ι]辛院_2 4_dione-6-spiro-3'·(tetrahydrofuran-2',5'-dione) , 5-(2,5·dioxotetrachloro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tris-2 -carboxymethylnorbornane-2:3,5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.02,0]undecane·3,5,8,10·tetraketone, At least one of the group consisting of pyromellitic dianhydride and a compound represented by the above formula (Τ-1), particularly preferably 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5:6-dianhydride. The tetraphthalic anhydride used in the synthesis of the polyamic acid used in the present invention preferably contains 80 mol% or more of the specific tetracarboxylic dianhydride as described above, and more preferably contains all of the tetracarboxylic dianhydride. 90% or more, particularly preferably 95% or more. <Diamine> The diamine used in the synthesis of the polyamic acid used in the present invention contains at least one selected from the group consisting of the compounds represented by the above formulas (I) and (II). In the above formulae (I) and (II), nl is preferably each an integer of from 3 to 6. The two amino groups bonded to the benzene ring are preferably at the 2, 4 or 3, 5 positions with respect to the other substituents. The compound represented by the above formula (I) can be obtained by, for example, dehydrohalogenating a corresponding 4-(4-(4-n-alkylcyclohexyl)cyclohexyl)phenol with a halogenated dinitrobenzene. The dinitro compound is reduced and synthesized. The compound represented by the above formula (II) can be obtained, for example, by esterification of the corresponding 4-(4-(4-n-alkylcyclohexyl)cyclohexyl)phenol with dinitrobenzoguanidine chloride -14-200946563 The obtained dinitro compound is reduced and synthesized. The compound represented by each of the above formulas (I) and (II) may have a benzene ring optionally substituted by one or two alkyl groups (preferably methyl groups) having 1 to 4 carbon atoms. The diamine used in the synthesis of the polyamic acid used in the present invention may be at least one selected from the compounds each represented by the above formulas (I) and (II), or may be selected from the above formula ( At least one of the compounds represented by each of I) and (II) is used in combination with other diamines. 〇 As the other diamine which can be used in combination here, for example, a compound represented by the following formula (D-I) can be cited.

(In the formula (D-Ι), X1 represents a divalent organic group selected from the group consisting of -〇-, -COO-, -OCO-, -NHCO-, -CONH-, and -CO-, and R5 represents a steroid skeleton. a monovalent organic group, R6 represents an alkyl group having 1 to 4 carbon atoms, a1 represents an integer of 0 to 3, and a compound represented by the following formula (D-II),

(In the formula (D-II), X2 each represents a divalent organic group selected from the group consisting of -0, -COO-, -OCO-, -NHCO-, -CONH-, and -CO-, and R7 represents a steroid skeleton a divalent organic group, each of R* represents an alkyl group having 1 to 4 carbon atoms, and a2 each represents an integer of 〇~3), such as a diamine having a steroid skeleton; -15- 200946563 p-phenylenediamine, Phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl sulfide, 4,4'-diamino Phenyl maple, 4,4'-diaminobenzilanilide, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-di Aminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,3' -bis(trifluoromethyl)-4,4'-diaminobiphenyl, 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindan, 6-amino- 1-(4'-Aminophenyl)-1,3,3-trimethylindan, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4' -0 diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis[4-(4-amino Phenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, double [ 4-(4-Aminophenoxy)phenyl]anthracene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-double (3-Aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroquinone, 2,7-diaminopurine, 9,9-dimethyl-2,7-diamino Ruthenium, 9,9-bis(4-aminophenyl)anthracene, 4,4'-methylene-bis(2-chloroaniline), 2,2',5,5'-tetrachloro-4,4' -diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 〇3,3'-dimethoxy-4,4'- Diaminobiphenyl '4,4'-(p-phenylene diisopropylidene) bisaniline, 4,4'-(m-phenylene diisopropylidene) bisaniline, 2,2'-double [ 4-(4-Amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4 An aromatic diamine such as '-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl or 4,4'-bis(4-aminophenoxy)biphenyl; 1-m-xylylenediamine, 1,3-propanediamine, Butanediamine, pentanediamine, hexamethylenediamine, heptanediamine, octanediamine, decanediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienediamine , hexahydro-4,7-methylene quinone dimethylene-16 - 200946563 bisdiamine, tricyclo[6.2.1.02,7]undecene dimethyldiamine, 4,4,-methylene bis ( Aliphatic diamines such as cyclohexylamine, 1,3-bis(aminomethyl)cyclohexane' 1,4-bis(aminomethyl)cyclohexane and alicyclic diamines; 2,3-diamino Pyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3·difluoropyridinium, 5,6-diamino- 2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-tri-trap, 1,4-bis(3-aminopropyl)piped, 2,4-di Amino-6-isopropoxy-1,3,5-three tillage, 2,4-diamino-6-methoxy-1,3,5-three tillage, 2,4-diamino-6-benzene φ φ -1,3,5-triazine, 2,4-diamino-6-methyl-s-tripper, 2,4-diamino-1,3,5-three tillage, 4,6-di Amino-2·vinyl-s-triple, 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-ethoxy acridine lactate, 3,8-diamino-6-phenylphenanthridine, 1,4-diaminopiperidin , 3,6-diaminoacridine, bis(4-aminophenyl)phenylamine, 3,6-diaminocarbazole, oxime-methyl-3,6-diaminocarbazole, oxime-ethyl- 3,6-diaminocarbazole, fluorenyl-phenyl-3,6-diaminocarbazole, anthracene, Ν'-bis(4-aminophenyl)benzidine, anthracene, Ν'-bis(4-aminobenzene φ base)-Ν, Ν'-dimethylbenzidine, a compound represented by the following formula (D-III),

(In the formula (D-III), R9 represents a monovalent organic group having a nitrogen atom-containing cyclic structure selected from the group consisting of pyridine, pyrimidine, triple trap, piperidine, and pipe trap, and X3 represents a divalent organic group, Rle An alkyl group having 1 to 4 carbon atoms, a3 represents an integer of 〇3, and a compound represented by the following formula (D-IV) '-17-.200946563

(In the formula (D-IV), R11 represents a divalent organic group having a nitrogen atom-containing cyclic structure selected from the group consisting of pyridine, pyrimidine, triple trap, piperazine, and piperazine, and each of X4 represents a divalent organic group. Each of the plurality of X4 groups may be the same or different, each of R12 represents a group having 1 to 4 carbon atoms, and a4 each represents an integer of 0 to 3, and has two primary amino groups in the molecule and the primary amino group. a diamine of a nitrogen atom; a monosubstituted phenylenediamine such as a compound represented by the following formula (D - V),

(In the formula (D - V), X5 represents a divalent organic group selected from the group consisting of _〇_, _c〇〇-, _〇c〇_, -NHCO-, -CONH-, and -CO-, and R13 represents an optional a monovalent group having a group derived from a trifluoromethylphenyl group, a trifluoromethoxyphenyl group and a fluorophenyl group or an alkyl group having 6 to 30 carbon atoms, and R14 is a carbon atom a base of 1 to 4, a5 is not an integer of ～3; a diaminoorganooxane such as a compound represented by the following formula (d- νι),

(In the formula (D-VI), each of R15 in which R15 represents a hydrocarbon group having 12 carbon atoms may be the same or different, p is an integer of 丨~], and q is an integer of 1 to 20); The following formula (D - υ ~ (Ε) - 2) each of the compounds represented by -18-200946563, H2Nv4f = \ / = yNH2 \_^ coffee 4 - 0 (D-1)

(y in the formula (D-1) is an integer of 2 to 12, and z in the formula (d-2) is an integer of Ο 1 to 5). The aromatic diamine and the benzene ring of the compound represented by each of the above formulas (D-1) and (D-2) may be optionally one or more alkyl groups having 1 to 4 carbon atoms (preferably A). Base) replaced. These diamines may be used alone or in combination of two or more. R6, R8, R10, R12 and R14 in the above formulae (D-I), (D-II), (D-III), (D-IV) and (DV) are each preferably a methyl group, al, a2. Each of a3, a4 and a5 is preferably 0 or 1, more preferably 0. The steroid skeleton in R5 and R6 of the above formulae (D-Ι) and (D-II) is a skeleton consisting of a cyclopentane-perhydrophenanthrene nucleus or one or two of its carbon-carbon bonds. The above is changed to the skeleton of the double bond. The monovalent organic group of R5 having such a steroid skeleton and the divalent organic group of R6 each preferably have a group having from 17 to 40 carbon atoms, more preferably a group having from 17 to 30 carbon atoms. . Specific examples of R5 include, for example, cholestyl-3-yl, cholest-5-en-3-yl, cholest-24-en-3-yl, cholest-5-24-diene-3 -yl, lanostan-3-yl, lanolin-5-en-3-yl, lanolin-24-en-3-yl'lanethin-5,24-dien-3-yl, etc.; as R6 Specific examples thereof include, for example, cholestane-3,6-diyl, cholest-5-ene-3,6-diyl, cholest-24-ene-3,6--19-200946563 diyl, Cholestane-3,3-diyl, lanostane-3,6-diyl, lanostane-3,3-diyl, and the like. Specific examples of the compound represented by the above formula (D - I) include compounds represented by the following formulas (D-3) to (D-7), respectively.

Specific examples of the compound represented by the above formula (D - II) include compounds represented by the following formulas (D-9) to (D-11). -20- 200946563

In the above-mentioned other diamine, at least one selected from the group consisting of a compound represented by the above formula (D-I) and a compound represented by the above formula (D-η) (hereinafter referred to as " Other specific diamines (1)") and selected from the group consisting of p-phenylenediamine, 4,4,-diaminodiphenylmethane, 4,4,diaminodiphenylthioxanthene, 1,5-diaminonaphthalene, 2 , 2'-dimethyl-4,4,-diaminobiphenyl, 2,2,-bis(trifluoromethyl)-4,4,diaminobiphenyl, 2,7-diaminopurine, 4, 4,_Diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9-bis(4-hydroxyphenyl)anthracene, 2,2-double [4-(4-Aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(p-phenylene diisopropylidene Diphenylamine, 4,4'-(m-phenylene diisopropylidene) bisaniline, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxyl) Biphenyl, 1,4-cyclohexanediamine, 4,4'-methylenebis(cyclohexylamine), 1,3 bis(aminomethyl)cyclohexane, 2,6-diamino Pyridine, 3,4-diaminopyridine, 2,4-diamine Pyrimidine, 3,6-diamino-21- 200946563 acridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-fluorenyl-3,6-di An aminocarbazole, N-phenyl-3,6-diaminocarbazole, N,N,-bis(4-aminophenyl)benzidine, a compound of the above formula (D-III) (D-12) a compound represented by the following formula (D-13) in the compound represented by the above formula (D-IV),

Dodecyloxy-2,4-diaminobenzene, pentadecyloxy-2,4-diaminobenzene, hexadecyloxy-2,4_ in the compound represented by the above formula (D-V) Diaminobenzene, octadecyloxy-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, pentadecyloxy-2,5-diaminobenzene, hexadecane a compound represented by the formula (D-VI) and a compound represented by the above formula (D-VI), wherein the compound represented by the formula (D_M) to (D-i6) is a compound represented by the above formula (D-VI). At least one of the groups consisting of 1'3-bis(3-aminopropyltetramethyldioxane) (hereinafter referred to as "other specific diamine (2)"), -22-200946563

The diamine used in the synthesis of the poly-aracine used in the present invention preferably contains at least 5 mol% or more of at least a compound selected from the above formulas (1) and (π) with respect to all diamines. More preferably, it contains 1 ί > 〜 9 〇 mol %, further preferably contains 20 to 80 mol %, and particularly preferably contains 3 〇 5 〇 mol %.

The diamine used in the synthesis of the polylysine used in the present invention preferably contains at least one selected from the group consisting of the compounds represented by the above formulas (I) and (II), and preferably further selected from the others described above. At least one of the group consisting of the specific diamine (1) and the specific diamine (2) preferably contains 10 to 90 mol% of these diamines, more preferably 20 to 80 mol%, based on the entire diamine. Further preferably, it contains 50 to 70 mol%. The diamine used in the synthesis of the polyamic acid used in the present invention is particularly preferably any one of the following (1) or (2). (1) at least one selected from the group consisting of the compounds represented by the above formulas (I) and (Π) in the above ratio, and preferably contains 10 to 90 mol% of other specific diamines relative to all diamines (2) More preferably contains 20~80 mol%, and the step of -23-200946563 preferably contains 50~70 mo. /. . (2) at least one selected from the group consisting of the compounds represented by the above formulas (I) and (II) in the above ratio, and preferably contains 1 to 20 mol% of other specific diamines relative to all diamines (1) ), more preferably contains 5 to 10 mol%. In the case of the above formula (2), it is preferred to contain at least one selected from the group consisting of the compounds represented by the above formulas (I) and (II), and other specific diamines (1) and other specific diamines (2). amine. As a content ratio thereof, at least one selected from the group consisting of the compounds represented by the above formulas (I) and (II) and the other specific diamine (1) thereof are each in the above ratio, for a specific diamine (2) It is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, based on the entire diamine. <Synthesis of Polylysine> The polylysine used in the present invention can be synthesized by reacting the above-described tetracarboxylic dianhydride with a diamine. The use ratio of the tetracarboxylic dianhydride to the diamine supplied to the polyaminic acid synthesis reaction is preferably 0.5 to 2 equivalents based on 1 equivalent of the amino group contained in the diamine. The ratio is more preferably such that it is a ratio of 0.7 to 1.2 equivalents. The synthesis reaction of polylysine is preferably carried out in an organic solvent, preferably at a temperature of from -2 to 150 ° C, more preferably from 0 to 100 ° C, preferably from 0.5 to 1 20 hours, more preferably It is carried out with 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. Non-quality-24- 200946563 sub-polar solvent such as N,N-dimethylformamide, dimethyl sulfoxide, 7-butyrolactone, tetramethylurea, hexamethylphosphonium triamine; A phenolic solvent such as phenol, xylenol, 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 〜 to 30% by weight based on the total amount (a + b) of the reaction solution. Further, when an organic solvent is used in combination with the following poor solvent, the amount of the organic solvent is understood to mean the total amount of the organic solvent and the poor solvent. In the organic solvent, a solvent alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, or a hydrocarbon may be used in combination with a polyglycine in a range in which the produced polyamine is not precipitated. Wait. Specific examples of such a poor solvent include methanol, ethanol, isopropanol 'cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, and lactic acid. Ethyl ester, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethoxy propyl Ethyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene Alcohol dimethyl ether, ethylene glycol acetate acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate , diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, Heptane, octane, benzene, toluene, xylene, isoamyl propionate, isoamyl isobutyrate, isoamyl ether, and the like. In the synthesis of poly-proline, when the organic solvent is used in combination with a poor solvent, the use ratio of the poor solvent is preferably 20% by weight or less based on the total amount of the organic solvent and the poor solvent, and more preferably 1%. Below weight%. As described above, a reaction solution in which polylysine was dissolved was obtained. The reaction -25-.200946563 solution can be directly supplied to the preparation of the liquid crystal alignment agent, or the poly-proline acid contained in the solution can be separated and supplied to the liquid crystal alignment agent, and the separated polyamic acid can be refined. Supply liquid crystal preparation. The separation of the polyamic acid can be carried out by dissolving a large amount of the poor solvent in the above reaction to obtain a precipitate, and drying the method under reduced pressure or by subjecting the reaction solution to distillation under reduced pressure in an evaporator. The polyaminic acid can be purified by re-solving the poly-proline in a solvent and then precipitating it with a poor solvent or by subjecting to a vacuum distillation. <醯i-Iminylated Polymer> The ruthenium-imidized polymer used in the present invention may be deuterated by the guanidine structure of the poly-proline acid, and may be a polyamine. The acid has a complete ruthenium imide structure of a proline structure, and may also be a ruthenium-based polymer of a guanidine structure. The ruthenium imidization ratio used in the present invention is preferably 50% or more, more preferably 55 to 95%, particularly 90%. Here, the "yttrium imidization ratio" means the ratio of the ratio of the number of the proline structure in the polymer to the number of the ruthenium ring of the number of the quinone ring, expressed as a percentage. At this time, a part of it may also be an isoindole ring. The dehydration ring closure of the polyamic acid can be carried out by (i) heating the polyfluorene method, or (ii) by dissolving the polyphthalic acid in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst, and heating as needed. The reaction temperature in the method for heating poly-proline in (i) above is carried out, or the liquid of the alignment agent is introduced into the precipitate. Dissolved in a useful evaporator and prepared as above. The dehydrated ring-locked amine ring and the enthalpy of the compound are 60~ 醯 imidization count, and the method of the solution is preferably -26-200946563 50~200 °C, more preferably 60 to 170 °C «When the reaction temperature is less than 50 °C, the dehydration ring-closure reaction cannot be sufficiently carried out. If the reaction temperature exceeds 200 t, the molecular weight of the resulting marinated imidized polymer may decrease. The reaction time is preferably from 1 to 120 hours, more preferably from 2 to 3 hours. In the method of adding a dehydrating agent and a dehydration ring-closure catalyst to the polyaminic acid solution of the above (ii), as the dehydrating agent, for example, an amount of an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used. Preferably, the 1 molar repeating unit relative to the polyamic acid is 0.01 to 20 moles. Further, as the φ dehydration ring-closing catalyst, a tertiary amine such as pyridine, trimethylpyridine, dimethylpyridine or triethylamine can be used. However, it is not limited to these. The amount of the dehydration ring-closing catalyst is preferably 0.01 to 10 moles per 1 mol of the dehydrating agent. In addition, as the organic solvent used in the dehydration ring-closure reaction, an organic solvent exemplified as a solvent used in the synthesis of polyglycolic acid can be mentioned. The reaction temperature of the dehydration ring closure reaction is preferably from 0 to 180 ° C, more preferably from 10 to 150 ° C, and the reaction time is preferably from 0.5 to 30 hours, more preferably from 2 to 10 hours. 〇 Prepared in the above method (1) The quinone imidized polymer may be directly supplied to the liquid crystal alignment agent, or the obtained quinone imidized polymer may be purified and then supplied to the liquid crystal alignment agent. Further, in the above method (ii), a reaction solution containing a ruthenium iodide polymer is obtained. The reaction solution may be directly supplied to the liquid crystal alignment agent, or may be supplied from the reaction solution to remove the dehydrating agent and the dehydration ring-closing catalyst, and then supplied to the liquid crystal alignment agent. The ruthenium iodide polymer may be separated and supplied to the liquid crystal. The formulation of the alignment agent or the separation of the separated ruthenium-imiding polymer may be supplied to the liquid crystal alignment agent. The dehydrating agent and the dehydrated -27-200946563 ring catalyst are removed from the reaction solution, and a method such as solvent replacement can be employed. The separation and purification of the ruthenium iodide polymer can be carried out in the same manner as described above for the separation and purification method of polyglycine. <Terminal-modified polymer> Each of the above-mentioned poly-proline and ruthenium-based polymers may be a terminal-modified polymer having a molecular weight adjusted. In the synthesis of an amine acid, a suitable molecular weight adjusting Φ agent such as a monoanhydride, a monoamine compound or a monoisophthalate compound is added to the reaction system to synthesize it. Here, examples of the monoanhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl group. Succinic anhydride and the like. The monoamine compound may, for example, be aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-indolamine, ortho- 12 Amine, Zhengtiya, amine, tetradecylamine, n-pentadecylamine, n-hexadecaneamine, n-heptadecaneamine, n-octadecylamine, n-icosylamine, and the like. The monoisocyanate compound may, for example, be phenyl isocyanate or naphthyl isocyanate. The use ratio of the molecular weight modifier is preferably 20 parts by weight or less, more preferably 10 parts by weight or less based on the total amount of the tetracarboxylic dianhydride and the diamine used in the synthesis of the polyglycolic acid. <Solid viscosity of polymer> Polylysine or quinone imidized polymer prepared as above, when formulated into a solution having a concentration of 10% by weight, preferably has a solution viscosity of 20 to 800 mPa·s. More preferably, it has a solution viscosity of 30 to 500 mPa.s. The solution viscosity (mP a. s) of the above polymer is formulated into a good solvent of -28-200946563 (for example, N-methyl-2-U bis, • vinegar, etc.) using the polymer. The concentration of 10% by weight of the polymer solution was measured by an E-type rotary viscometer at 25 °C. <Other components> The liquid crystal alignment agent of the present invention contains at least one polymer selected from the group consisting of polylysine as described above and its quinone imidized polymer as an essential component. Further components may be further contained without prejudice to the effects and advantages of the present invention. As such other components, for example, other polymers, compounds having at least one epoxy group in the molecule (hereinafter referred to as "epoxy compounds"), and functional decane compounds can be listed. The other polymer may, for example, be a polyorganooxime, a tetracarboxylic dianhydride, and a polyamine obtained by reacting a diamine of any of the compounds represented by the above formulas (I) and (II). Proline (hereinafter referred to as "other poly-proline") and its quinone imidized polymer (hereinafter referred to as "other quinone imidized polymer"), polyglycolate, polyester, polyamine , weaving vitamin derivatives, polycondensation, polystyrene derivatives, poly(phenylethylidene-phenylmaleimide) derivatives, poly(meth)acrylates, and the like. Among them, other polyaminic acid or other acid imidized polymers are preferred from the viewpoint of excellent varnish properties and electrical properties. The tetracarboxylic dianhydride used in the synthesis of other polyaminic acid and other quinone imidized polymers is the same as exemplified as the tetracarboxylic dianhydride used in the synthesis of the above polyamic acid. The diamine used in the synthesis of other polyaminic acid and other quinone imidized polymers is the same as exemplified as the other diamine which can be used in the synthesis of the above polyamic acid. In this case, it is preferred to contain 70 mol% or more of at least one of -29 to 200946563 selected from other specific diamines (1) and (2) with respect to all diamines, and particularly preferably contain 90 mol%. The above diamine. Other polylysines and other quinone-imidized polymers 'as a diamine, except for using a diamine which does not contain any of the compounds represented by the above formulas (I) and (II), may be used as a poly The method described for the synthesis of proline and ruthenium iodide polymers is synthesized in the same manner. Among other polyaminic acids and other quinone aminated polymers, other polylysines are preferred. The use ratio of the other polymer in the liquid crystal alignment agent of the present invention is a total amount of the polymer (refers to a polymerization of a tetracarboxylic dianhydride and a diamine containing the compound represented by the above formula (1) or (11) ❹. The total amount of the proline acid and its quinone imidized polymer and optionally other polymers is the same, preferably 80% by weight or less, more preferably 60% by weight or less, still more preferably 40% by weight. the following. The epoxy group compound may be used from the viewpoint of further improving the adhesion of the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention to the surface of the substrate, and examples thereof include ethylene glycol diglycidyl ether and polyethylene glycol. Alcohol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trihydroxyl Methylpropane triglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, N,N,N',N'-tetraglycidyl-m-xylylenediamine , 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, hydrazine, hydrazine, hydrazine, Ν'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N-diglycidyl-benzylamine, N,N-diglycidyl-aminomethylcyclohexane, and the like. The mixing ratio of these epoxy compounds is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight, based on 100 parts by total of the total amount of the polymer. -30-200946563 The functional decane compound may, for example, be 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane or 2-aminopropyl. Triethoxy decane, ν·(2-aminoethyl)-3-aminopropyltrimethoxydecane, Ν-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3 -ureidopropyltrimethoxydecane,3·ureidopropyldiethoxylate, Ν-ethoxylated 3-(aminopropyldimethoxy), Ν-ethoxycarbonyl-3- Aminopropyltriethoxydecane, Ν-triethoxydecylpropyltriethylenetriamine, Ν-trimethoxydecylpropyltriethylenetriamine, 10-trimethoxydecane-1, 4,7-triazadecane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6-diazepineacetic acid Ester, 9-triethoxydecyl-3,6-diazadecyl acetate, 9-trimethoxydecylmethyl 3,6-diazepine, 9-triethoxy Methyl decyl-3,6-diazepine, Ν-benzyl-3-aminopropyltrimethoxydecane, Ν-benzyl-3-amino Triethoxy decane, fluorenyl-phenyl-3-aminopropyltrimethoxy decane, fluorenyl-phenyl-3-aminopropyltriethoxy decane, glycidoxymethyltrimethoxy decane, Glycidoxymethyltriethoxydecane, 2-cyclopropoxypropoxyethyltrimethoxydecane, 2-glycidoxyethyltriethoxydecane, 3-epoxypropoxy Propyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, and the like. The mixing ratio of these functional decane compounds is preferably 2 parts by weight or less, more preferably 0.2 parts by weight or less based on 100 parts by total of the total amount of the polymer. <Liquid crystal alignment agent> 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 ruthenium iodide polymer, and root-31-200946563 Other ingredients which are optionally added are preferably formed by dissolving the content. As the above polymer, it is possible to use only the ruthenium iodide polymer or the polyglycolic acid. The liquid crystal alignment agent of the present invention preferably contains a ruthenium iodide polymer or a polyamic acid and a ruthenium imine. Here, the amount of the ruthenium iodide ring of the ruthenium imine ring is compared with the number of the polyphthalic acid structures contained in the liquid crystal alignment agent and the total amount of the ruthenium iodide polymer and the number of the quinone ring. The ratio (hereinafter referred to as "average 醯s when the liquid crystal alignment agent of the present invention contains other polyamic acid and other substances, the average oxime imidization rate should be understood to include the number thereof" is preferably 40% or more, more preferably 45 to 90%, the specific name of the liquid crystal alignment agent of the present invention may be used as a solvent used in the synthesis reaction of polylysine as described above, and may be appropriately selected and used in combination as a polyQ reaction. A solvent which is exemplified as a poor solvent. Examples of the agent which may be contained in the liquid crystal alignment agent of the present invention include N-methyl-2-pyrrolidone, r _ decylamine, N,N-dimethylformamide, and N. , N-dimethylethyl-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, methyl oxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, Ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol fiber), ethylene glycol dimethyl ether Ethylene glycol ethyl ether acetic acid _ ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol in an organic solvent, can also be only ruthenium iodide polymerized polymer, compared to polymer histidine The proline acid structural polymer has a amide amination rate. When the yttrium imidization polymerization is calculated, it is 50 to 80%. Machine solvent, which can be exemplified by the synthesis of lysine which is exemplified by solvent, especially organic butyrolactone, r-butyl, decylamine, butyl 4-hydroxyacetate, methyl ether, ethylene glycol n-butyl ether (butyl hydride i, Diethylene glycol monoethyl ether, digan-32- 200946563 alcohol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, isoamyl propionate isoamyl butyrate, diisobutyl ketone, isoprene Ether, ethylene carbonate, carbon diester, etc. These may be used singly or in combination of two or more. Particularly preferred solvent composition is such that the constituent polymer obtained by combining the above solvents does not precipitate from the alignment agent, and The composition of the surface tension of the alignment agent is in the range of 25 to 40 mN/m. The solid content concentration of the liquid crystal alignment agent of the present invention (the total weight of the liquid crystal alignment agent other than the solvent is tl φ of the total weight of the liquid crystal alignment agent, considering viscosity, The liquid crystal alignment agent of the present invention is formed by removing the solvent from the substrate to form a coating film as a liquid crystal alignment film when the solid content is less than 1% by weight. When the film will appear In the case where the liquid crystal alignment film is too small to be good, when the solid content concentration exceeds 10, the thickness of the coating film is too thick, and it is also difficult to obtain a good liquid film, and the viscosity of the liquid crystal alignment agent increases. The solid content concentration range which causes the coating performance to be excellent is different depending on the method used when the liquid crystal alignment agent is applied to the substrate. For example, when the spin coating method is used, the range of 1.5 to 4.5% by weight is preferably used. When the content concentration is in the range of 3 to 9 wt%, the solution can be adhered to the range of 12 to 50 mPa > s. When the ink jet method is used, the solid concentration is preferably 1 to 5 wt%. The range can be such that the viscosity of the solution is in the range of 3 to 15 mPa*s. The temperature at which the liquid crystal alignment agent of the present invention is formulated is preferably 〇°c-°C, more preferably 20 °C to 6 (TC. <Liquid crystal display element>, isocyanate, is in the middle: rate) %. The surface concentration is obtained. The amount % crystal matching. Apply to, the solidity falls in the -33- -200 200946563 The liquid crystal display element of the present invention has the above The liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention. The liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention can exhibit a high voltage holding ratio and a good performance when used as a vertical alignment type liquid crystal alignment film. Residual image performance The liquid crystal display element of the present invention can be produced, for example, by the following method: (1) The liquid crystal alignment of the present invention is applied by an appropriate coating method such as a roll coating method, a spin coating method, a printing method, or an inkjet method. The agent is applied to one surface of the substrate on which the transparent conductive film forming the pattern is provided, and then the coating film is formed by heating the coated surface. Here, as the substrate, for example, glass such as float glass or soda lime glass; polyparaphenylene can be used; A transparent substrate made of plastic such as ethylene glycol dicarboxylate, polybutylene terephthalate, polyether mill, polycarbonate, or alicyclic polyolefin. As the transparent conductive film provided on one surface of the substrate, for example, a NESA film made of tin oxide (Sn02) (registered trademark of PPG, USA), an ITO film made of indium tin oxide (Mn 203-Sn02), or the like can be used. These transparent conductive film patterns can be formed by photolithography or a method of using a photomask in advance when forming a transparent conductive film. In the application of the liquid crystal alignment agent, in order to further improve the adhesion between the surface of the substrate and the transparent conductive film and the coating film, a functional decane compound, a functional titanium compound or the like may be applied to the surface of the substrate in advance. After the application of the liquid crystal alignment agent, it is preferred to perform preheating (prebaking) for the purpose of preventing the liquid of the applied alignment agent from sagging. The prebaking temperature is preferably from 30 to 200 ° C, more preferably from 40 to 150 ° C, and particularly preferably from 40 to 100 ° C. The prebaking time is preferably from 0.25 to 10 minutes, more preferably from 0.5 to 5 minutes. After the solvent is completely removed, it is preferred to further carry out the heating (post-baking) step. The post-baking temperature is preferably from 80 to 300 ° C, more preferably from 120 to 250 ° C. After -34-.200946563, the baking time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. The liquid crystal alignment agent of the present invention forms a coating film as an alignment film by coating after removing the organic solvent as described above, and when the polymer contained in the liquid crystal alignment agent of the present invention is a polyamic acid or a quinone imine In the case of a quinone imidized polymer having a ring structure and a proline structure, it is also possible to carry out a dehydration ring-closure reaction by further heating after forming a coating film to form a further yttrium-imided coating film. The thickness of the coating film formed here is preferably 0.001 to Ιμηη, more preferably 0.005 to 0.5 μm 〇Ο (2) The coating film formed as described above may be used as a vertical alignment type liquid crystal alignment film as it is, or may be optionally used. The coating film surface is rubbed in a certain direction by a roll wrapped with a cloth made of a suitable fiber such as nylon, rayon, cotton or the like, and then used as a liquid crystal alignment film. In addition, the liquid crystal shown in the patent document 6 (Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A process in which a part of the alignment film is irradiated with ultraviolet rays to change a pretilt angle of a portion of the liquid crystal alignment film, or a part of the surface of the liquid crystal alignment film is shown in Patent Document No. 8 (Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei. After the protective film is formed, the treatment for removing the protective film after the rubbing treatment is performed in a direction different from the previous rubbing treatment, so that each liquid crystal alignment film has a different liquid crystal alignment energy can improve the field of view performance of the obtained liquid crystal display element. When the surface of the coating film is polished, it can be cleaned as needed. (3) Two substrates on which the liquid crystal alignment film was formed as described above were prefabricated, and liquid crystal cells were fabricated by arranging liquid crystals between the two substrates. For the production of the liquid crystal cell, for example, the following two methods can be cited. -35- 200946563 The first method is a previously known method. First, the two substrates are opposed to each other through a gap (cell gap), and the respective liquid crystal alignment films are opposed to each other, and the peripheral portions of the two substrates are bonded together with a sealant to the interstitial space surrounded by the substrate surface and the sealant. After filling the liquid crystal, the liquid crystal cell can be obtained by closing the injection hole. The second method is called the 〇DF (〇ne 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 onto the film surface after the liquid crystal alignment film is bonded to the film surface, and bonding the other substrate to match the liquid crystal The film is oriented oppositely, and then the entire surface of the substrate is irradiated with ultraviolet rays to cure the sealant, thereby obtaining a liquid crystal cell. The liquid crystal alignment agent of the present invention has an advantage that a liquid crystal display element which does not cause liquid crystal alignment unevenness due to liquid crystal droplets can be obtained even when a VA liquid crystal display element is produced by an ODF method. This advantage is particularly remarkable when the liquid crystal alignment agent of the present invention comprises a diamine-synthesized polymer containing a specific diamine (1) in addition to at least one of the compounds represented by the above formulas (I) and (II). . In the case of using any of the above first and second methods, it is necessary to subsequently 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 remove the liquid crystal charge. Flow alignment. Then, the liquid crystal display element of the present invention can be obtained by laminating a polarizing plate on the outer surface of the liquid crystal cell. 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 nematic liquid crystal and dish-shaped liquid crystal. Among them, a nematic liquid crystal is preferable, and for example, a Schiff base liquid crystal, an azo-based liquid crystal, a biphenyl liquid crystal, or a benzene-36-200946563 can be used. A cyclohexane 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, a cuba liquid crystal or the like. Further, in the liquid crystal, cholesteric liquid crystal such as cholesteryl cholesteryl, cholesteryl phthalate or cholesteryl carbonate may be further added; and the trade names "C-15" and "CB-15" (manufactured by MERCK Co., Ltd.) may be further added. Used as a chiral agent for sale. The polarizing plate to be bonded to the outer surface of the liquid crystal may be a polarizing plate made by sandwiching a polyvinyl alcohol and absorbing iodine, and a polarizing film, which is called a "ruthenium film", is sandwiched between the 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. The solution viscosity of the polymer and the ruthenium iodide ratio of the ruthenium iodide polymer in the following synthesis examples were evaluated by the following methods. [Solid viscosity of the polymer] 溶液 The solution viscosity of the polymer is determined by measuring the polymer solution indicated in each synthesis example using a Ε-type viscometer at 25 °C. [The ruthenium imine ratio of the ruthenium iodide polymer] The ruthenium iodide polymer is dried under reduced pressure at room temperature, and then dissolved in a deuterated dimethyl sulphate, using tetramethyl decane as a reference. The iH-NMR was measured at room temperature and determined by the formula shown by the following formula (i). Ruthenium amination rate (%) = (1 - Al/A2x a )xl 〇〇(i) A1 : peak area A2 originating from the NH matrix near 10 ppm: peak area from other protons -37- 200946563 α : ratio of the number of other protons relative to one NH proton in the polymer precursor (polyglycolic acid). <Synthesis of diamine represented by the above formula (I) or (II)> The following synthesis examples are repeated as necessary to ensure the necessary amount of the product in the subsequent synthesis example. Synthesis Example 1 (Synthesis of 1-(2,4-diaminophenoxy)-4-(4-(4-n-pentylcyclohexyl)cyclohexyl)benzene) 1-(2) was synthesized according to the following Scheme 1 4-Diaminophenoxypurinyl-4-(4-(4-n-pentylcyclohexyl)cyclohexyl)benzene (hereinafter also referred to as "diamine oxime").

NOs

Synthetic Route 1 20.3 g (0.1 mol) of 1-chloro-2,4-dinitrobenzene and 32.9 g of 4-(4-(4-n-pentylcyclohexyl)cyclohexyl)phenol (under nitrogen) 0.1 mol (mole) and potassium carbonate 41.4 g (0.3 mol) were dissolved in 500 m of dimethylformamide and allowed to react at room temperature for 6 hours. 500 ml of distilled water was added to the reaction solution and stirred well, and then extracted with 500 ml of chloroform, and the obtained organic layer was extracted and washed with distilled water. The organic layer after washing was dehydrated with magnesium sulfate, and the solvent was removed by a rotary evaporator to obtain 47.0. g 1-(2,4-Dinitrophenoxy-38- 200946563 yl)-4-(4-(4-n-pentylcyclohexyl)cyclohexyl)benzene. Then, under a nitrogen atmosphere, to the above 1-(2,4-dinitrophenoxy)·4-(4-(4-n-pentylcyclohexyl)cyclohexyl)benzene 24.8 g (0.05 mol) Palladium/carbon (Pd/C) 18.2 g and 300 ml of tetrahydrofuran were added, and the mixture was stirred at 70 ° C for 1 hour. To the mixture was added 30 ml of hydrazine monohydrate, and the mixture was stirred at 80 ° C for 3 hours under nitrogen to carry out a reaction. After completion of the reaction, the catalyst was filtered off, the filtrate was concentrated, and then further dissolved in 300 ml of chloroform, and the organic solvent layer was extracted and washed with distilled water. The organic solvent layer was dried over magnesium sulfate and concentrated on a rotary evaporator to give a crude product of diamine A. The crude product was purified by column chromatography, and then solvent was evaporated to yield 18. Synthesis Example 2 (Synthesis of 4-(4-(4-n-pentylcyclohexyl)cyclohexyl)phenyl ester of 3,5-diaminobenzoic acid) Synthesis of 3,5-diaminobenzoic acid according to the following Scheme 2 4-(4-(4-n-pentylcyclohexyl)cyclohexyl)phenyl ester (hereinafter also referred to as "diamine B").

Synthetic Route 2 4-(4-(4-n-pentylcyclohexyl)cyclohexyl)phenol 32'9g (0.1 旲), triethylamine 〇.6g (0105 mol) and tetrahydrofuran under nitrogen atmosphere 3 〇〇 ml was mixed and dissolved under stirring. To the solution, a mixture of 21.8 g (0.105 mol) of 3,5-dinitrobenzimid chloride and 100 ml of tetrahydrofuran was added dropwise to the solution for 3 minutes, and the mixture was stirred at room temperature for 3 hours. . After the precipitated salt was filtered off, the filtrate was concentrated, and then dissolved in 300 ml of chloroform, and extracted with distilled water. The organic layer was dried over magnesium sulfate and concentrated using a rotary evaporator. The crude product thus obtained was purified by column chromatography, and then solvent was removed to give 51.2 g of 4-(4-(4-n-pentylcyclohexyl)cyclohexyl)phenyl 3,5-dinitrobenzoate. Then, chlorination was carried out to the above-mentioned 3,5-dinitrobenzoic acid-4- 4-(4-(4-n-pentylcyclohexyl)cyclohexyl)phenyl ester 26.1 g (0.05 mol) under a nitrogen atmosphere. Tin dihydrate 112_8 g (0.5 mol) and ethyl acetate 400 nU were heated under reflux for 3 hours to carry out a reaction. After completion of the reaction, the reaction solution was mixed with 400 ml of a saturated potassium fluoride aqueous solution. After thorough stirring, the mixture was separated, and the obtained organic layer was extracted and washed with distilled water. Then, the organic layer was dehydrated with magnesium sulfate, concentrated by a rotary evaporator, and then purified by column chromatography, and then solvent was removed to obtain 1 7.4 g of diamine B. Synthesis Example 3 ® The diamine C represented by the following formula was synthesized by the method described in Patent Document 2 (JP-A No. 9-278724). (CH2)4-CH3 nh2 diamine c Synthesis Example 4 The compound represented by the above formula (D-5) is synthesized by the method described in Patent Document 9 (JP-A No. 4-281427) (hereinafter referred to as "compound" (D — 5 ) ”) -40- 200946563 <Synthesis of a brewed imidized polymer> Synthesis Example 5 3,5,6-tricarboxy-2-carboxymethylnorbornane as tetracarboxylic dianhydride 12.5 g (0.05 mol) of alkane-2:3,5·6-dianhydride, and 3-2 g (0.03 mol) of p-phenylenediamine as a diamine and 8.7 g (0.02 g of a diamine synthesized in the above Synthesis Example 1) Mohr) was dissolved in 98 g of N-methyl-2-pyrrolidone (NMP) and reacted at 60 ° C for 6 hours. A small amount of the obtained polyaminic acid solution was taken, and NMP was added to prepare a solution having a polyaminic acid concentration of 10% by weight, and the viscosity of the solution was determined to be 51 mPa·s. Then, 120 g of NMP was added to the obtained polyamic acid solution, and 20 g of pyridine and 20 g of acetic anhydride were further added, and a dehydration ring-closing reaction was carried out for 4 hours under litre. After the dehydration ring closure reaction, the solvent in the system is replaced with a new γ-butyrolactone solvent (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. The same applies hereinafter). About 170 g of a solution containing a ruthenium iodide polymer (A-1) having a ruthenium iodide ratio of about 90%. This solution was prepared into a γ-butyrolactone solution having a polymer concentration of 10% by weight, and the measured solution viscosity was 62 mP a·s. © Synthesis Example 6 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6-dianhydride as tetracarboxylic dianhydride 12.5 g (0.05 mol) and as two The amine p-phenylenediamine 3.2g (0.03 mole) and the diamine B9.2g (0.02 mole) are dissolved in 98g NMP, and reacted at 6 (TC for 6 hours). A small amount of the obtained polyaminic acid solution is added to the NMP. A solution having a polyglycolic acid concentration of 10% by weight was measured, and the measured solution viscosity was 6 1 mPa·s. Then, 120 g of NMP was added to the obtained polyamic acid solution, and then 2 μg of pyridine and 20 g of acetic anhydride were added. 4 hours of dehydration ring closure at U 〇 ° C. Anti-41 - 200946563. After the dehydration ring closure reaction, the solvent in the system was replaced with a new γ-butyrolactone solvent to obtain about 160 g of yttrium imidization rate. 90% solution of ruthenium iodide polymer (A-2). The solution was formulated into a γ-butyrolactone solution having a polymer concentration of 10% by weight, and the measured solution viscosity was 71 mpa.s. 7 llg (0.05 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 3.2 g (0.03 mol) and diamine A8 of p-phenylenediamine as diamine. 7g (0.02 The ear is dissolved in 93g of NMP at 60% (6: hour). A small amount of the obtained polyaminic acid solution is added, and NMP is added to form a solution having a concentration of polyglycine of 10% by weight, and the viscosity of the solution is determined to be 48 mPa. Then, 120 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 20 g of pyridine and 20 g of acetic anhydride were further added, and a dehydration ring-closure reaction was carried out for 4 hours at ll ° C. After the ring closure reaction, a solvent of the system was replaced with a new γ-butyrolactone to obtain about 160 g of a solution containing a ruthenium iodide polymer (A-3) having a ruthenium iodide ratio of about 90%. The solution was formulated into a γ-butyrolactone solution having a polymer concentration of 10% by weight, and the measured solution viscosity was 58 mPa-s. Synthesis Example 8 3,5,6-three as tetracarboxylic dianhydride Carboxy-2-carboxymethylnorbornane-2:3,5:6-dianhydride 12.5 g (0.05 mol), and p-phenylenediamine as diamine 3.2 g (0.03 mol), diamine A 6.5 g (0.015 mol) and compound (D-5) 2.6 g (0_005 mol) were dissolved in l〇〇g NMP and reacted at 60 ° C for 6 hours. A small amount of the obtained polyaminic acid solution was added and NMP was added. to make A solution having a lysine concentration of 10% by weight, the measured solution viscosity is 47 mP a. s" Then, 124 g of NMP is added to the polylysine solution, and then -42-200946563 2〇g pyridine and 20 g of acetic acid are added. The anhydride was subjected to a dehydration ring-closure reaction at 110 ° C for 4 hours. After the dehydration ring closure reaction, a solvent of the system was replaced with a new butyrolactone to obtain a solution of about 180 g of a ruthenium iodide polymer (A-4) having a ruthenium iodide ratio of about 90%. This solution was formulated into a γ-butyrolactone solution having a polymer concentration of 10% by weight, and the measured solution viscosity was 57 mPa·s. » Synthesis Example 9 3,5,6-tricarboxyl group as tetracarboxylic dianhydride 2-carboxymethyl norbornane-2··3,5:6-dianhydride 12.5 g (0.05 mol), p-phenylenediamine oxime 3.2 g (0.03 mol) as diamine, diamine B 6.9 g (0.015 mol) and compound (D-5) 2.6 g (0.005 mol) were dissolved in 101 g of NMP and reacted at 60 ° C for 6 hours. A small amount of the obtained polyaminic acid solution was taken, and NMP was added to prepare a solution having a polyglycine concentration of 10% by weight, and the solution viscosity was determined to be 46 mPa·s. Then, 126 g of NMP was added to the obtained polyaminic acid solution, and 20 g of pyridine and 20 g of acetic anhydride were further added, and a dehydration ring-closing reaction was carried out for 4 hours at ll °C. After the dehydration ring closure reaction, the solvent in the system was replaced with a new γ-butyrolactone to obtain about 185 g of a ruthenium iodide polymer (A-5) having a ruthenium iodide ratio of about 90%. Solution. To the solution, a γ-butyrolactone solution having a polymer concentration of 10% by weight was prepared, and the measured solution viscosity was 56 mPa·s. Synthesis Example 1 As a tetracarboxylic dianhydride, 11.2 g (0.05 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3.2 g (0.03 mol) of p-phenylenediamine as a diamine, Diamine A 6.5 g (0.015 mol) and compound (d-5) 2.6 g (0.005 mol) dissolved in 94 g of NMP 'reacted at 60 ° C for 6 hours. A small amount of the obtained polyamic acid solution was added to NMP to prepare a solution having a polyglycine concentration of 1% by weight, and the solution viscosity was determined to be 45 mPa·s. -43- 200946563 Then, l18 g of NMP was added to the obtained polyamic acid solution, and 2 g of pyridine and 20 g of acetic anhydride were further added, and a dehydration ring-closing reaction was carried out for 4 hours at n °C. After the dehydration ring closure reaction, a solvent of the system was replaced with a new γ-butyrolactone to obtain about 180 g of a solution containing a ruthenium iodide polymer (A-6) having a ruthenium iodide ratio of about 90%. The solution was formulated into a butyrolactone solution having a polymer concentration of 10% by weight, and the measured solution viscosity was 58 mPa. S 0 Synthesis Example 11 © 3,5,6-tricarboxyl group as tetracarboxylic dianhydride 2-carboxymethylnorbornane-2:3,5:6-dianhydride 12.5 § (0_05 mol), and as a diamine, p-phenylenediamine 3.2 g (0.03 mol), diamine A 6.5 g ( 0.015 moles and compound (D-5) 2.6 g (0.005 mol) were dissolved in 100 g of NMP and reacted at 60 ° C for 6 hours. A small amount of the obtained polyaminic acid solution was taken, and NMP was added to prepare a solution having a polyglycine concentration of 10% by weight, and the viscosity of the solution was determined to be 47 mP a·s. Then, 1 243 g of NMP was added to the obtained polyaminic acid solution, and 4 g of pyridine and 5 · 1 g of acetic anhydride were further added thereto, and dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new γ-butyrolactone to obtain about 17 〇g of a ruthenium iodide polymer having a ruthenium iodide ratio of about 45% (A-7). The solution. This solution was formulated into a γ-butyrolactone solution having a polymer concentration of 10% by weight, and the measured solution viscosity was 63 m P a·s 〇 合成; Synthesis of other polymers > (Other yttrium-imidized polymers) Synthesis of Synthesis Example 1 2 3,5,6-Tricarboxy-2-carboxymethylnorbornane-44-200946563-2:3,5:6-dianhydride as a tetracarboxylic dianhydride 125 g (0.5 Mohr), 32 g (0.3 mol) of p-phenylenediamine as diamine and C70 g (0.2 mol) of diamine were dissolved in 9 μg of NMP and reacted at 60 ° C for 6 hours. Take a small amount of the obtained polyaminic acid solution, add NMP to form a solution having a concentration of polyglycine of 10% by weight, and determine the viscosity of the solution to be 55 mPa. S °, then add ll〇〇g to the obtained poly-proline solution. NMP was further added with 200 g of pyridine and 200 g of acetic anhydride, and a dehydration ring-closure reaction was carried out for 4 hours at 〇 ° °c. After the dehydration ring closure reaction, the solvent in the system was replaced with a new solvent of γ-butyrolactone to obtain about 1600 g of a ruthenium iodide polymer having a ruthenium iodide ratio of about 90% (A-8). The solution. To the solution, a γ-butyrolactone solution having a polymer concentration of 10% by weight was prepared, and the measured solution viscosity was 6 5 mP a·s. Synthesis Example 1 3 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6-dianhydride as tetracarboxylic dianhydride 12.5 g (0.05 mol), and as Diamine p-phenylenediamine 4.3 g (0.04 mol) and compound (D-5) 5.2 g (0.01 mol) were dissolved in 88 g of NMP and reacted at 60 ° C for 6 hours. A small amount of the obtained polyaminic acid solution was taken, and NMP was added to prepare a solution having a polyglycine concentration of 10% by weight, and the solution viscosity was determined to be 45 mPa-s. Then, U〇g NMP was added to the obtained polyamic acid solution, and 20 g of pyridine and 20 g of acetic anhydride were further added, and a dehydration ring-closing reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, a solvent of the system is replaced with a new γ-butyrolactone to obtain about 170 g of a solution containing a ruthenium iodide polymer (A-9) having a ruthenium iodide ratio of about 90%. . The solution was formulated into a γ-butyrolactone solution having a polymer concentration of 10% by weight, and the measured solution viscosity was 55 mP a· -45- 200946563 (synthesis of other polylysine) Synthesis Example 1 4 Pyromellitic dianhydride 55 g (0.25 mol) of carboxylic acid dianhydride and 49 g (0.25 mol) of 1,2,3,4-cyclobutane tetracarboxylic dianhydride, p-phenylenediamine 54 g as diamine (0.5 mol) was dissolved in 630 g of NMP and reacted at 60 ° C for 6 hours. About 1200 g of a solution containing 20% by weight of polyamic acid (B-1) was obtained. A small amount of the polyaminic acid solution was taken, and NMP was added to prepare a solution having a polyglycine concentration of 10% by weight, and the measured solution viscosity was 70 mPa's. Example 1 <Preparation of Liquid Crystal Aligning Agent> The solution containing the quinone imidized polymer (A-1) prepared in the above Synthesis Example 5 and the polyglycine containing product obtained in the above Example 14 ( The solution of B-1) is mixed with (A-1):(B-1)=80:20 by weight ratio of the polymer contained in each solution, and r-butyrolactone, NMP and butyl are added thereto. The fiber preparation is formulated into a solution of r-butyrolactone: NMP: butyl cellosolve = 71: 17 : Ο 12 (by weight), and a solid content concentration of 2.5% by weight. This solution was filtered through a filter having a pore size of Ιμηη to prepare a liquid crystal alignment agent (S-1). The average oxime imidization ratio of the polymer contained in the liquid crystal alignment agent is shown in Table 1. <Production of Vertical Alignment Type Liquid Crystal Cell> The liquid crystal alignment agent (s-ι) was applied onto a transparent electrode surface of a glass substrate having a transparent electrode made of a ruthenium film by spin coating, and heated at 80 ° C. After prebaking for 1 minute on the plate, it was post-baked on a hot plate at 200 ° C for 10 minutes to form a coating film (liquid crystal alignment film) having an average thickness of 60 ηηη. This operation was repeated to fabricate a pair of (two) base-46 - .200946563 plates having a liquid crystal alignment film on the transparent electrode surface. On each of the outer edges of the pair of liquid crystal alignment films having the liquid crystal alignment film, an epoxy resin adhesive having a diameter of 5.5 μm is applied, and the liquid crystal alignment film faces are relatively overlapped. And press, and then the adhesive is cured. Then, a negative liquid crystal (MLC-6608, manufactured by MERCK Co., Ltd.) was deposited between the pair of substrates through the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photocurable adhesive to produce a vertical alignment type liquid crystal cell. For the liquid crystal cell, evaluation of voltage holding ratio and afterimage performance was performed as follows. Evaluation 〇 The results are shown in Table 1. <Evaluation of voltage holding ratio> A voltage of 1 V was applied to the above-mentioned vertical alignment type liquid crystal cell at 65 ° C for a time span of 167 msec, and the application time was 60 μsec, and then the voltage was released to 167. The voltage holding ratio after milliseconds. The measuring device was a VHR-1 manufactured by TOYO Corporation. <Evaluation of afterimage performance> A vertical alignment was produced in the same manner as in the above-mentioned <Production of Vertically Oriented Liquid Crystal Cell, except that a glass substrate having two ITO transparent electrodes having the pattern shown in Fig. 1 was used as the substrate. Liquid crystal cell. In the environment of 40 to 50 ° C, while the backlight was irradiated to the liquid crystal cell, 6.0 V was applied to the electrode A, and a DC voltage of 0.5 V for 168 hours was applied to the electrode B. After the stress was released, a DC voltage of 0.1 to 5.0 V was applied to the electrodes A and B at a gradient of 0. IV, and the afterimage performance was judged based on the difference in luminance between the electrodes A and B at each voltage. When the luminance difference was not identified, the afterimage performance was judged as "excellent", and when the luminance difference was small, the afterimage performance was judged as "good", and when the luminance difference was large, the afterimage performance was judged as "poor". -47-.200946563 Examples 2 to 1 2 and Comparative Examples 1 to 3 Liquid crystal alignment agents (S-2) to (S - were prepared in the same manner as in Example 1 except that the polymer compositions listed in Table 1 were used. 12) and (R-1)~(R-3), liquid crystal cells were produced and evaluated. The evaluation results are shown in Table 1. Further, the number in the parentheses after the name of the polymer species in Table 1 is the amount (parts by weight) of the polymer contained in the polymer solution used, and the polyamines were not used in Examples 9 to 11 and Comparative Example 3. Solution. Table 1 Liquid crystal alignment agent Liquid crystal cell name Polymer Average 醯 imidization rate Gu retention rate afterimage performance 醯 imidized polymer turning (parts by weight) Polyzinc acid surface (parts by weight) Example 1 S-1 Al (80 Bl(20) 66% 99% Excellent Example 2 S-2 A-2(80) Bl(20) 66% 99% Good Example 3 S-3 A-1(60) Bl(40) 46% 98 % Excellent Example 4 S-4 A-2(60) Bl(40) 45% 97% Good Example 5 S-5 A-3(80) Bl(20) 67% 99% Excellent Example ό S-6 A-4(80) B-1 (20) 66% 99% Excellent Example 7 S-7 A-5(80) B-1 (20) 66% 99% Good Example 8 S-8 A-6 ( 80) Bl(20) 67% 99% Excellent Example 9 S-9 A-4(100) jfrrf. J\\\ 90% 99% Excellent Example 1〇S-10 A-5(100) AttC. IWIT 90% 99% Good example π S-11 A-6(100) te j\y\ 90% 99% Excellent Example 12 S-12 A-7(80) B-1 (20) 36% 98% Excellent Comparative Example 1 R-1 A-8(80) B-1(20) 68% 96% Bad Comparative Example 2 R-2 A-9(80) Bl(20) 68% 98% Good Comparative Example 3 R- 3 A—9 (100) 4 nC m 90% 99% Excellent-48-200946563 Example 1 3 <Evaluation of liquid crystal alignment unevenness performance> The liquid crystal alignment agent prepared in the above Example 6 was spin-coated. -6) After being pre-baked on a transparent electrode surface of a glass substrate having a transparent electrode made of an ITO film, it was prebaked on a hot plate at 80 ° C for 1 minute, and then baked on a hot plate at 200 ° C for 10 minutes to form an average. A coating film (liquid crystal alignment film) having a thickness of 6 〇 nm. This operation was repeated to fabricate a pair of (two) substrates having a liquid crystal alignment film on the surface of the transparent electrode. 〇 On the liquid crystal alignment film surface of one of the substrates having the liquid crystal alignment film produced above, water droplets of 5 μl of ultrapure water were dropped from a position of 5 mm high by a micropipette, and naturally dried at room temperature. A vertical alignment type liquid crystal cell was produced in the same manner as in the above-described Example 1, except that a pair of substrates including a substrate having an impact on the liquid crystal alignment film surface by droplet dropping as described above was used. A rectangular wave of 6.0 V (peak-to-peak) and 30 Hz was applied to the liquid crystal cell at room temperature, and when observed under a crossed Nicol prism, ultrapure as a liquid crystal misalignment was observed without observation. When the water droplets were traced, the liquid crystal alignment unevenness performance was evaluated as "excellent". When fine droplet marks were observed, the liquid crystal alignment unevenness performance was evaluated as "good", and when the droplet marks were clearly observed, the liquid crystal alignment unevenness performance evaluation was performed. It is "bad". The results are shown in Table 2. Among them, the dropping of the above-mentioned ultrapure water droplets is an alternative evaluation for investigating the impact of the impact of liquid crystal dropping in the ODF step. Example 1 4 to 19 and Comparative Examples 4 and 5 In the same manner as in the above-described Example 13, except that the liquid crystal alignment agent was used as listed in Table 2, respectively, the liquid crystal alignment film was deposited by ultrapure water drop-49-.200946563 A pair of substrates having a surface on which the impact occurred were used to fabricate a vertical alignment type liquid crystal cell, and evaluation of the liquid crystal alignment unevenness performance was performed. The results are shown in Table 2. Table 2 Liquid crystal alignment agent name Liquid crystal alignment unevenness performance Example 13 S-6 Preferred embodiment 14 S-7 Excellent embodiment 15 S-8 Excellent embodiment 16 S-9 Excellent embodiment 17 S-10 Excellent example 18 S - 11 Preferred Embodiment 19 S- 12 Good Comparative Example 4 R-2 Poor Comparative Example 5 R-3 Poor [Simplified description of the drawings] Fig. 1 is a schematic view showing the structure of a transparent electrode for evaluation of afterimage performance. [Main component symbol description] 4K 〇

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Claims (1)

200946563 VII. Patent application scope: 1. A liquid crystal alignment agent characterized by comprising at least one polymer selected from the group consisting of polylysine and its quinone imidized polymer. A tetracarboxylic dianhydride is obtained by reacting a diamine containing a compound represented by the following formula (I) or (Π), In the above formula, nl is each independently an integer of 1 to 8. 2. The liquid crystal alignment agent of claim 1, wherein the diamine further contains at least one compound selected from the group consisting of the following formula (D-Ι) and the following formula (D-II), In the formula (D - Ο, χ1 represents a divalent organic group selected from the group consisting of 〇-, -COO-, -OCO-, -NHCO-, CONH·, and -CO-, and R5 represents a monovalent organic group having a steroid skeleton The group 'R6 represents an alkyl group having a carbon number of i to 4, and a1 represents an integer of 0 to 3. In the formula (D~Π), X2 each represents a group selected from -〇-, -COO-, -OCO-, - a divalent organic group of NHCO-, -CONH-, and -CO-, R7-51-200946563. Representing a divalent organic group having a steroid skeleton, each of R8 represents an alkyl group having 1 to 4 carbon atoms, a2 Each of which represents an integer of 0 to 3. 3. The liquid crystal alignment agent of claim 1 or 2, wherein the tetracarboxylic dianhydride contains 3,5,6-tricarboxy-2-carboxymethylnorbornane-2 A liquid crystal alignment agent according to claim 1 or 2, which further comprises at least one selected from the group consisting of polylysine and its quinone imidized polymer. A polymer obtained by reacting a tetracarboxylic dianhydride with a diamine which does not contain any of the compounds represented by the above formulas (I) and (II). Liquid crystal alignment agent of the first or second range, The amount of the proline structure of the polyamido acid contained in the liquid crystal alignment agent and the total number of the proline structure and the number of the quinone ring of the ruthenium iodide polymer, The aminated polymer has an amount ratio of the quinone ring of 40% or more. 6. The liquid crystal alignment agent according to claim 1 or 2, wherein the ruthenium is used for forming a vertical alignment type liquid crystal alignment film. A liquid crystal display element comprising a liquid crystal alignment film formed by the liquid crystal alignment agent according to any one of claims 1 to 6. 8. A compound represented by the above formula (I) 9. A compound represented by the above formula (II). -52-