TW201022330A - Liquid crystal aligning agent, liquid crystal display element and compound - Google Patents

Abstract

The purpose of the present invention is to provide a liquid crystal aligning agent which has high voltage conservation rate and also has both excellent properties of vertical alignment and printing; and liquid crystal display element showing great vertical alignment property and high voltage conservation rate is also provided. The solution mean of the present invention is the said liquid crystal aligning agent which comprises (A) at least one polymer selected from the group consisting of polyamic acid and polyimide; and (B) a specific compound which is representative by a compound represented the formula (B-3-2-2-l). The said liquid crystal display element comprises a liquid crystal alignment film formed of the mentioned above liquid crystal aligning agent.

Description

201022330 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to liquid crystal alignment agents, liquid crystal display elements, and compounds. [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 polylysine, polyphthalamide on the surface of a substrate provided with a transparent conductive film. A liquid crystal alignment film formed of an amine or the like, as a substrate for a liquid crystal display element, two substrates are opposed to each other, and a nematic liquid crystal layer having positive dielectric anisotropy is formed in a gap therebetween to form a unit cell of 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) type liquid crystal display element having a higher contrast ratio and a smaller viewing angle dependency than a TN type liquid crystal display element has been developed. Such an STN type liquid crystal display device uses a liquid crystal in which a chiral agent as an optically active substance is blended in a nematic liquid crystal as a liquid crystal by using a long axis of liquid crystal molecules to continuously twist more than 180 degrees between substrates. The birefringence effect produced by the state of the amplitude. G In recent years, development of a novel liquid crystal display element has been active, and as one of them, as described in Patent Document 1, it is proposed that two electrodes for driving a liquid crystal are arranged in a comb shape on one side of a substrate, so that A transverse electric field type liquid crystal display element that controls an electric field parallel to the substrate surface to control liquid crystal molecules. This component is often referred to as an in-plane switching type (IPS type), and its viewing angle performance is known to be excellent. Further, as a liquid crystal display element having a function different from the above, it is proposed that a liquid crystal molecule having negative dielectric anisotropy is vertically aligned on a substrate, which is referred to as MVA (Multi domain Vertical Alignment) type and 201022330 PVA (Patterned Vertical Alignment). A type of vertical alignment type liquid crystal display element. These MVA-type and PVA-type vertical alignment type liquid crystal display elements are excellent not only in the viewing angle and contrast but also in the formation of the liquid crystal alignment film without performing the polishing treatment or the like, and are therefore excellent in the production steps. The ability to vertically align liquid crystal molecules on a substrate (vertical alignment) is known to be exhibited by using a polymer having a bulky substituent on a side chain as a material of a liquid crystal alignment film. Thus, a method of using a monomer having a bulky substituent (pretilt-expressing monomer) in the synthesis of a polymer has been proposed. For example, in Patent Document 2, a method of using a polymer obtained by using 1-octadecyloxy-2,4-diaminobenzene as a pretilt-expressing monomer is proposed. Also, in Patent Documents 3 and 4, cholesteryl-3,5-diaminobenzoic acid ester, stearyl stearate (3,5-diaminobenzoic acid ester), cholesteric is disclosed. As the pretilt angle-expressing monomer, an alkyl-3,5-diamino benzoate or the like is disclosed, and in Patent Document 5, cholesteryl-2,4-diaminobenzene or the like is disclosed. As the liquid crystal alignment film, a liquid crystal alignment agent which exhibits stable vertical alignment can be obtained by using a polymer which is synthesized in a large amount using these pretilt-expressing monomers. However, from the viewpoint of increasing the size of the panel in recent years and increasing the product yield, it is required to have high voltage holding ratio and printability. However, it is known that when a polymer which is synthesized using a large amount of pretilt-expressing monomer as described above is used as a liquid crystal alignment agent, printability is particularly remarkably deteriorated, and good vertical alignment property and good printability are considered. In a relationship that requires trade-offs. Therefore, a liquid crystal alignment agent having a high voltage holding ratio, a good vertical alignment property, and a good printability is expected. CITATION LIST Patent Literature 201022330 Patent Document Patent Document 1 Patent Document 2 Patent Document 3 Patent Document No. 2004-33 1 937 Publication No. 2004 - 262921 [Abstract] e

A first object of the present invention is to provide a liquid crystal alignment agent having a high voltage holding ratio and good vertical alignment property and good printability. It is also an object of the present invention to provide a liquid crystal display element which exhibits good vertical alignment and high voltage retention. 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, first, are achieved by a liquid crystal alignment agent comprising (A) at least one polymer selected from the group consisting of polylysine and polyamidiamine, and (B) a compound having an epoxy group and a group of the following formula (2%, R^-irR11)n1)n2 (zn-f〇Η2ή^-〇ΟΟΗ (20) (in the formula (2e) R1 is an alkyl group having 4 to 40 carbon atoms or a fluoroalkyl group having 4 to 40 carbon atoms or a hydrocarbon group having a steroid skeleton having 17 to 5 1 carbon atoms; Z1 is a single bond, * -0-, *-C00 - or *-〇CO- (wherein the bond of the tape is located on the R1 side), R11 is a cyclohexylene group or a phenyl group, and nl is 1 or 2, 201022330 wherein when nl is 2, The two Rn may be the same or different from each other, n2 is 0 or 1; Z11 is *-0-, *-C00- or *-OCO- (where the bond of the band is on the R1 side), and n3 is 0~2 The integer of the above, N4 is 0 or 1). The above object and advantages of the present invention are achieved by a liquid crystal display element having a liquid crystal alignment film formed of the above liquid crystal alignment agent. φ The vertical alignment type liquid crystal alignment agent of the present invention, In printing The printing unevenness is substantially not generated on the substrate, and a liquid crystal alignment film which is uniform and has good vertical alignment property can be formed. The liquid crystal display element of the present invention exhibits good vertical alignment and good voltage retention rate' The display performance is excellent. The liquid crystal display element of the present invention can be effectively used for various devices, for example, a display device which can be used for a calculator, a watch, a desk clock, a counter display screen, a word processor, a personal computer, a liquid crystal television, etc. Optimum form of the present invention The liquid crystal alignment agent of the present invention contains (A) at least one polymer selected from the group consisting of polyproline and polyimine, and (B) having an epoxy group and the above formula (2β) a compound of the group shown (hereinafter also referred to as ''(B) compound)). <(A) Polyglycine, Polyimine> Polylysine can be obtained by using tetradecanoic dianhydride The diamine reaction is obtained, and the polyimine can be obtained by dehydration and ring closure of the polyamic acid. [Tetracarboxylic dianhydride] 201022330 As a tetracarboxylic dianhydride used in the synthesis of polylysine, Can be cited, for example, Tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4·cyclobutane tetracarboxylic dianhydride, 1, 3-Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2 , 3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5 - cyclohexane tetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 2,3,4, 5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3&,4,5,91)-hexahydro-5-(tetrahydro-2,5-dioxoindole-3-furanyl)-naphthalene [l ,2-c]-furan-1,3-dione, 1,3,3&,4,5,91>-hexahydro-5-methyl-5-(tetrahydro-2,5-dioxo -3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,38,4,5,91)-hexahydro-5-ethyl-5-(four Hydrogen-2,5-dioxo-3·furanyl)-naphthalene [i,2-c]-furan-1,3-dione, 1,3,3&,4,5,913-hexahydro•7- Methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-<;]-furan-1,3-dioxene, i,3,3a,4 ,5,9b-hexa-7-ethyl-5-(tetraammine-2,5-?-oxo-3-furanyl _Naphthalene [i,2-c]-furan-1,3-dione, 1,3,3&,4,5,91)-hexahydro-8-methyl_5-(tetrahydro-2,5 -dioxo-3-furanyl)-naphthalene [1,2-(;]-furan-1,3-1,3-one, 1,3,3&,4,5,91)-hexahydro-8- Ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-(;]-furan-1,3-dione, 1,3,3&,4 ,5,91)-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-(indole-furan·1, 3-diketone, bicyclo[2.2.2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo[3·2·1]octane-2,4 Diketo-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 .〇2,6]"!--Alkane-3,5,8,10-tetraketone, compounds represented by the following formulas (T-I) and (T-II), etc. Carboxylic acid 201022330 dianhydride or alicyclic tetracarboxylic dianhydride; V _ ]VR1~7 (I/0 (Τ-Ι) y 0 "Η 1 叫. (Τ-ΙΙ) ϊ (wherein R1 and R3 are each 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 be the same or different ); pyrethic acid dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl maple tetracarboxylic 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-furan Tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) oxime Phenyl phthalic anhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene di-orthobenzene Dicarboxylic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, di(phthalic acid) phenylphosphine Oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, inter-phenylene- Bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4' -diphenylmethane dianhydride, ethylene glycol-di(hydrogen trimellitate), propylene glycol-di(hydroper trimellitate), 1,4-butanediol-di(hydrogen trimellitate) ), 1,6-hexanediol-di(hydrogen trimellitate), 1,8-octanediol-di (dehydrated trimellitic acid 201022330 ester), 2,2-bis(4-hydroxyphenyl) An aromatic tetracarboxylic dianhydride such as a compound represented by a propane-di(hydrogen trimellitate) or a compound represented by the following formulas (T-1) to (T-4). They may be used alone or in combination of two or more.

❹ -10- 201022330

ο. The compound represented by the above formula (τ - I), for example, a compound represented by the following formulas (T-5) to (T-7), and the like, are represented by the above formula (T-II)-11 - 201022330. The compound may, for example, be a compound represented by the following formula (τ - 8).

Among them, from the viewpoint of making it possible to exhibit good liquid crystal alignment, it is preferred to use a butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3. -Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl Acetic acid dianhydride, ® l,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-(;]- Furan-1,3-dione, 1,3,3,4,5,91)-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl) -naphthalene [1,2-(:]-furan-1,3-dione, l,3,3a,4,5,9b-hexahydro-5,8-dimethyl-5-(tetrahydro-2) ,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, bicyclo[2.2.2]-oct-7-ene-2,3,5, 6-tetracarboxylic dianhydride, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione) , 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2- Carboxymethylnorbornane-12· 201022330 -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'-diphenyltricarboxylic dianhydride, 2,2',3,3'- a biphenyltetracarboxylic dianhydride, a 1,4,5,8-naphthalenetetracarboxylic dianhydride, a compound represented by the above formula (T-5) to (T-7), and a compound represented by the above formula (T-8) At least one of the group consisting of compounds (hereinafter referred to as "specific tetracarboxylic dianhydride"). As a specific tetracarboxylic dianhydride, it is particularly preferably selected from 1,2,3,4-cyclobutanetetracarboxylic acid. Dihydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3&,4,5,91>-hexahydroφ-5-(tetrahydro-2,5-dioxo- 3-furyl)-naphthalene [1,2-(:]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydrogen) -2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 3-oxabicyclo[3.2.1]octane-2,4- Diketo-6-spiro-3'-(tetrahydrofuran.2,5,-dione), 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3. Hexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6-dianhydride, 4,9-dioxatricyclo[ 5.3_1_〇2'6]undecane_3,5,8,10·tetraketone, coke honey Composed of at least one compound of the group represented by - dianhydride and the above-described formula (5 Τ). The ratio of use of G as the specific tetracarboxylic dianhydride is preferably 10 mol% or more, more preferably 20 mol% or more, and still more preferably 40 mol% or more based on the total tetracarboxylic dianhydride. As the tetracarboxylic dianhydride used in the synthesis of the polylysine of the present invention, it is preferred to use only the specific tetracarboxylic dianhydride as described above. [Diamine] Examples of the diamine used in the synthesis of polylysine include, for example, a p-aminoamine phenyldiyl group 4, an amine, a second compound, a 45-fluorene, a 5^4 group, and a diphenyl ether disulfide group. Aminobenzenediphenyl 45-yl 4,amine,--amine 4»-di 4, benzene, m-al'ethylaminodiphenylbenzene-II-201022330 Maple, 3,3'-dimethyl-4, 4'-Diaminobiphenyl, 4,4'-diaminobenzimidamide, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2'-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-trimethylindoline, 6-amino-1-(4) '-Aminophenyl)-1,3,3-trimethylindoline, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4' -diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-di[4- (4-Aminophenoxy)phenyl]hexa-oxypropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy) Phenyl] milled, 1,4-two ( 4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 1,3-bis(4-aminophenoxy)benzene, 1,3-di 3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroquinone, 2,7-diaminoguanidine, 9,9-dimethyl-2,7- Diamino hydrazine, 9,9-bis(4-aminophenyl) fluorene, 4,4'-methylene-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'-(inter-p-phenylenediphenylene)diphenylamine, 2,2'-bis[4-(4-Amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-diamino-2,2'-di(trifluoro Methyl)biphenyl, 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl, 3,5-diaminobenzoic acid, 1,4- An aromatic diamine such as a compound represented by the following formula (D-1) to (D-5), bis(4-aminophenyl) hydrazine, -14- 201022330

, CH3

COO <j:H3

(D-1

(D-4)

(D-5) (wherein y in the formula (D-4) is an integer of 2 to 12, an integer of the formula (D-1 to 5); 1,1-m-xylylenediamine, 1,3-propanediamine , butane diamine, C amine, heptane diamine, octane diamine, decane diamine, 1,4-diaminocyclo ketone diamine, tetrahydrodicyclopentadiene diamine, hexahydro-4,7- 3 methyl diamine, tricyclo [6.2.1.02'7] eleven alkyl dimethyl methylene di(cyclohexylamine), 1,3-bis(aminomethyl)cyclohexane, 5) The z in the group is an aliphatic diamine such as a diamine, hexane dihexane, isophoramethyl quinone diimylene diamine or 4,4'-1,4-di(amino-15-201022330 methyl)cyclohexane. Or an alicyclic diamine: 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4·diaminopyridine, 2.4-diaminopyrimidine, 5,6-diamino-2 , 3-dicyanopyridine, 5,6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-trisole, 1 , 4-bis(3-aminopropyl) hydrazine, 2,4-diamino-6-isopropoxy-1,3,5-tri-trap, 2.4-diamino-6-methoxy -1,3,5-three tillage, 2,4-diamino-6-phenyl-1,3,5-three tillage, 2,4-diamino-6-methyl-3-three tillage, 2,4-diamino-1,3,5-tri-trap, 4,6-di 2-vinyl-s-tripper, 2,4-diamino-5-phenylthiazolidine, 2,6-diaminostilbene, 5,6-diamino-1,3-di Methyl uracil, 3,5-diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridinyl lactate, 3,8-diamino-6 -phenylphenanthridine, 1,4-diamine hydrazine, 3,6-diaminoacridine, bis(4-aminophenyl)phenylamine, 3,6-diaminocarbazole, N -Methyl-3,6-diaminocarbazole, oxime ethyl 3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N,N,-di (4-Aminophenyl)benzidine, :N,N'-bis(4-aminophenyl)-N,N,-dimethyl-benzidine, a compound represented by the following formula (D-Ι) ,

(In the formula (D-I), R5 is a monovalent organic group having a nitrogen atom-containing ring structure selected from the group consisting of pyridine, pyrimidine, tri-till, acridine, and argon, X1 is a divalent organic group, and R6 is An alkyl group having 1 to 4 carbon atoms, and an al is an integer of 0 to 3), and a compound represented by the following formula (D-II) has two primary amino groups in the molecule and a nitrogen atom other than the primary amine group. Diamine, -16- 201022330

(In the formula (D-II), r7 is a divalent organic group having a nitrogen atom-containing ring structure selected from the group consisting of pyridine, pyrimidine, triplet, yttrium, and yttrium, and each of X2 is a divalent organic group. Each of the plurality of X2's may be the same or different, and each of R8 is an alkyl group having a carbon number of i to 4, and each a2 is an integer of 0 to 4), and a compound represented by the following formula (D-III) Monosubstituted phenylenediamine, hydrazine

(In the formula (D - ΠΙ), R9 is - 0_, -COO-*, -OCO-*, -NHCO-*, -CONH-* (where 'the above-mentioned bond and rig bond) or CO - ' Rle is 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~ An alkyl group of 30, R11 is an alkyl group having a carbon number of 丨4, and φa3 is an integer of 0 to 3); a diaminoorganosiloxane such as a compound represented by the following formula (D-IV);

(In the formula (D-IV), each of Ri2 is a hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R12 groups may be the same or different, each p is an integer of ～3, and 9 is i~20. Integer). These diamines may be used singly or in combination of two or more. • 17-201022330 The benzene ring of the above aromatic diamine may optionally be one or two or more alkyl groups having 1 to 4 carbon atoms (preferably a Base) replaced. R6, R8 and R11 in the above formulae (D-I), (D-II) and (D-III) are each preferably a methyl group.

Each of al, a2 and a3 is preferably 0 or 1, more preferably I

The monovalent organic group having a steroid skeleton of R1Q in the above formula (D - III) is preferably a group having 17 to 51 carbon atoms, more preferably a group having 17 to 30 carbon atoms. Specific examples of such RU having a steroid skeleton include, for example, cholestyl-3-yl, cholest-5-ene-3yl, cholest-24-en-3-yl, cholest-5 , 24-dien-3-yl, lanostane-3, and the like. Specific examples of the compound represented by the above formula (D - I) include, for example, a compound represented by the following formula (D-6);

Specific examples of the compound represented by the above formula (D - II) include, for example, a compound represented by the following formula (D-7); ^—〇^-〇~叫-〇-〇-叫(D-7) Specific examples of the compound represented by the above formula (D - III) include, for example, dodecyloxy-2,4-diaminobenzene, pentadecyloxy-2,4-diaminobenzene, and sixteen Alkoxy-2,4-diaminobenzene, octadecyloxy-2,5-diaminobenzene, dodecyloxy-2,5·diaminobenzene, heptadecyloxy-2 , 5-diaminobenzene, hexadecyloxy-2,5-diaminobenzene, and a compound represented by the following formula (D-8) to (D-16). -18- 201022330

(D-8) h2n

❿ h2n h2n h2n h2n h2n h2n h2n h2n -19- 201022330

Oco—<〉—cf3 (D-14)

(D-15)

The diamine used in the synthesis of the poly-proline in the liquid crystal alignment agent of the present invention preferably contains p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'- selected from the above. Diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 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-di (4-aminophenyl)hexafluoropropane, 4,4'-(p-phenylenediisopropylidene)diphenylamine, 4,4'-(m-phenylenediphenylene)diphenylamine, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 1,4-diaminocyclohexane, 4,4'- Methylene bis(cyclohexylamine), 1,3-bis(aminomethyl)cyclohexane, 3,5-diaminobenzoic acid, 1,4-bis(4-aminophenyl)-fluorene The compound represented by the above formula (D-1) to (D-5), 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diamine Pyridine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminopurine-20-201022330 azole, N-ethyl-3,6- Diaminocarbazole, N-phenyl-3,6-diaminocarbazole, anthracene, Ν'-bis(4-aminophenyl)benzidine, anthracene, Ν'-bis(4-aminobenzene) ), Ν'-dimethylbenzidine, a compound represented by the above formula (D-6), a compound represented by the above formula (D-7), and 1,3-bis(3-aminopropyl)- a diamine of at least one selected from the group consisting of tetramethyldioxane (hereinafter referred to as "specific diamine (1)") and a group selected from the group consisting of compounds represented by the above formula (D-III) At least one (hereinafter referred to as "specific diamine (2)") diamine. More preferably, it is selected from p-phenylenediamine, 4,4'-diamino Φ diphenylmethane, 2,2'-dimethyl-4,4, diaminobiphenyl, as a specific diamine (1). 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,7-diaminostilbene, 4,4'-diaminodiphenyl ether, 2,2- Bis[4-(4-aminophenoxy)phenyl]propane, 2,2·bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenoxy)benzene 4,4'-bis(4-aminophenoxy)biphenyl, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), 1,3-two (Aminomethyl)cyclohexane, a compound represented by the above formula (D-1) to (D-3), 2,6-diaminopyridine, 3,6-diaminocarbazole, N-A -3,6-diaminoazolazole, N,N'-bis(4-aminophenyl)benzidine, anthracene, Ν'-bis(4-aminoindenylphenyl)-oxime, Ν'- Dimethylbenzidine, 3,5-diaminobenzoic acid, 1,4-bis(4-aminophenyl)-indole, and 1,3-bis(3-aminopropyl)-tetramethyl At least one of the group consisting of dioxane. The specific diamine (2), more preferably the compound represented by the above formula (D-III), is selected from the above formula (D-8), the above formula (D-1), the above formula (D-11), and the above. At least one of the group consisting of the compounds represented by the formula (D-14) and the above formula (D-15). The diamine used in the synthesis of the poly-proline in the liquid crystal alignment agent of the present invention preferably contains 10 mol% or more of the specific 21-201022330 diamine (1) as described above with respect to all the diamines. The best system contains 20 mol% or more, and the special system contains 4 mol% or more. Further, the diamine used in synthesizing the polyamic acid in the liquid crystal alignment agent of the present invention preferably contains: 60 mol% of the specific diamine (2) as described above, more preferably all of the diamine. Containing 5~5〇mol%, especially good containing 8~40 mol%» [Synthesis of poly-proline] The poly-proline in the liquid crystal alignment agent of the present invention can be obtained by making tetracarboxylic acid as described above The acid dianhydride is reacted with a diamine to obtain. φ The ratio of use of the tetracarboxylic dianhydride to the diamine supplied to the polyaminic acid synthesis reaction is preferably 0.5 to 2 based on 1 equivalent of the amine group contained in the diamine. The ratio of the equivalents is more preferably such that it is a ratio of 〇.7 to K2 equivalent. The synthesis reaction of polylysine is preferably carried out in an organic solvent, preferably at a temperature of from -20 to 150 ° C, more preferably from 0 to 100 ° C. The reaction time is preferably from 0.2 to 120 hours, more preferably from 0.5 to 72 hours. The organic solvent which can be used herein is not particularly limited as long as it is a solvent capable of dissolving the synthesized polyamidodecanoic acid, and examples thereof include N-methyl-2·pyrrolidone and N,N-dimethyl B. Aprotic polar solvents such as guanamine, N,N-dimethylformamide, dimethyl hydrazine, r-butyrolactone, tetramethylurea, hexamethylphosphonium triamine; m-methylphenol, A phenolic phenol solvent such as xylenol, phenol or halogenated phenol. Further, the amount of the organic solvent (a: when the organic solvent is used together with the poor solvent described below means the total amount thereof), preferably the total amount of the tetracarboxylic dianhydride and the diamine (b) is relatively The total amount (a + b) of the reaction solution is an amount of 0.1 to 30% by weight. In the above organic solvent, alcohols, ketones, esters, and ethers which are generally considered to be poor solvents of polyproline are used in the range of -22-201022330 which does not precipitate the produced polyaminic acid. Classes, halogenated hydrocarbons, hydrocarbons, and the like. 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, A

Ethyl ester, diethyl ether, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl 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 monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloro Methane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane 'benzene, toluene, xylene, two Isobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, and the like. In the case of synthesizing polyamic acid, when the organic solvent is used in combination with the above-mentioned poor solvent, the use ratio of the poor solvent is preferably 25% by weight or less based on the total amount of the organic solvent and the poor solvent. Preferably it is 10% 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, or may be prepared by separating the polyamic acid contained in the reaction solution and then supplying the liquid crystal alignment agent, or may be obtained by refining the separated polyamic acid. Modulation of liquid crystal alignment agent. When polypyridic acid is dehydrated and closed to form polyimine, the above-mentioned -23-201022330 reaction solution can be directly supplied to the dehydration ring-closure reaction, or the polytyramine acid contained in the reaction solution can be separated and supplied to the dehydration ring closure. The reaction may be carried out or the separated polylysine may be purified and then supplied to a dehydration ring closure reaction. The separation of the poly-proline can be carried out by introducing the above reaction solution into a large amount of poor solvent to obtain a precipitate, and then drying the precipitate under reduced pressure or decompressing the organic solvent in the reaction solution with an evaporator. The distillation method is carried out. Further, the polyamine can be purified by dissolving the polylysine in an organic solvent, then precipitating it with a poor solvent, or performing a step of distilling off a few times or by vacuum using an evaporator. acid. [Synthesis of Polyimine] The polyimine which may be contained in the liquid crystal alignment agent of the present invention can be subjected to dehydration ring-closure imidization by reacting a polyamic acid obtained by reacting a tetracarboxylic dianhydride with a diamine. be made of. The tetraruthenic dianhydride used in the synthesis of the polyimine in the liquid crystal alignment agent of the present invention may be the same as the above compound of the tetracarboxylic acid ruthenium anhydride used in the synthesis of polyamic acid. The diamine used in the synthesis of the polyimine in the liquid crystal alignment agent of the present invention may be the same as the above compound as the diamine used in the synthesis of polyamic acid. The diamine is preferably a diamine containing the above specific diamine (1). The diamine used in the synthesis of the polyimine in the liquid crystal alignment agent of the present invention preferably contains a selected from the group consisting of p-phenylenediamine, 4,4,-diaminodiphenylmethane, and 3,5-diaminobenzene. Formic acid, iota, bis(4-aminophenyl)-fluorene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 1,3-di(aminomethyl) At least one of a group consisting of cyclohexane and ^-bis(mono)-aminopropyl)-tetramethyldioxane (hereinafter referred to as "-24-201022330" as "specific diamine (1')")) A diamine of a compound represented by the formula (D-III) (hereinafter referred to as "specific diamine (2')"). The diamine used in the synthesis of the polyimine in the liquid crystal alignment agent of the present invention preferably contains 1 〇 mol% or more of the specific diamine (1 ') as described above, and more preferably contains all of the diamines. 20 mol% or more, and particularly preferably 40 mol% or more. Further, the diamine used in the synthesis of the polyimine in the liquid crystal alignment agent of the present invention preferably contains 1 to 60 mol% of the specific diamine (2,) as described above with respect to all the diamines. It contains 5 to 50 mol%, and the special φ system contains 8 to 40 mol%. The polyimine may be a complete hydrazine imide of a lysine structure in which the starting lysine has a dehydration ring structure, or may be a part of a valeric acid structure, a dehydration ring closure, a guanine structure and a hydrazine structure. Part of the quinone imine compound coexisting with the imine ring structure. The polyimine in the liquid crystal alignment agent of the invention preferably has a ruthenium iodide ratio of 20% or more, more preferably 3 5 to 9 9 %, particularly preferably 45 to 95%. The above ruthenium amination ratio is a total of the number of guanamine structures and the number of quinone ring structures in the polyimine, and the ratio of the G number of the quinone ring structure is expressed as a percentage. At this time, a part of the quinone ring may also be an isoindole ring. The ruthenium iodization rate can be known from the W-NMR of polyimine. The dehydration ring closure of the polyamido acid of the synthetic polyimine, preferably (i) by heating the poly-proline, or (ii) The polyhydrazine acid is dissolved in an organic solvent, and a dehydrating agent and a dehydration ring-closure catalyst are added to the solution and heated as needed. The reaction temperature in the method of heating poly-proline in the above (i) is preferably 50 to 200 ° C, more preferably 60 to 170 ° C. When the reaction temperature is less than 50 °C, -25-201022330, the dehydration ring-closure reaction cannot be sufficient. If the reaction temperature exceeds 20 (rc, the molecular weight of the obtained polyimine will decrease. The reaction time is preferably 0.5~) 168 hours, more preferably 0.5 to 72 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 a dehydrating agent, for example, acetic anhydride, propionic anhydride, trifluorocarbon can be used. An acid anhydride such as acetic anhydride, and the amount of the dehydrating agent is preferably 1 to 20 moles per 1 mole of the repeating unit of polyglycolic acid. Further, as the dehydration ring-closing catalyst, for example, pyridine or trimethylpyridine may be used. A tertiary amine such as dimethyl pyridine or triethylamine. However, it is not limited thereto. The amount of the dehydration ring-closing catalyst is preferably 0.01 to 10 moles relative to the dehydrating agent used for 1 mole. The organic solvent used for the reaction is exemplified as the organic solvent used for the synthesis of the polyamic acid. The reaction temperature of the dehydration ring-closure reaction is preferably from 0 to 180. °C, more preferably 10 to 150 ° C. The reaction time is preferably 0.5 to 168 hours, more preferably 0.5 to 72 hours. The polyimine obtained in the above method (i) can be directly supplied to the solution. The preparation of the twinning agent may be carried out, or the obtained polyimine may be purified and then supplied to the liquid crystal alignment agent. Further, in the above method (ii), a reaction solution containing a polyimide may be obtained. The solution may be directly supplied to the preparation of the liquid crystal alignment agent, or may be prepared by removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, and then preparing the liquid crystal alignment agent, and also preparing the liquid crystal alignment agent after separating the polyimine. Alternatively, the separated polyimine may be purified and then supplied to a liquid crystal alignment agent, and the dehydrating agent and the dehydration ring-closure catalyst may be removed from the reaction solution, for example, by solvent replacement or the like. Separation and purification of the polyimine. It can be carried out in the same manner as described above as the separation and purification method of poly-26-201022330 proline. [End-modified polymer] Liquid crystal alignment of the present invention The poly-proline or polyimine which may be contained may also be a terminal-modified polymer having a molecular weight adjusted. By using a terminal-modified polymer, the liquid crystal can be further improved without impairing the effects of the present invention. The coating property of the alignment agent, etc. The terminal-modified polymer can be carried out by adding a molecular weight modifier to the polymerization reaction system during the synthesis of the poly-proline, and as the molecular weight modifier, for example, monoanhydride, single An amine compound, a monoisocyanate compound, etc. Examples of the monoanhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl amber. An acid anhydride, n-hexadecyl succinic anhydride, etc. Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, and Indoleamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecaneamine, n-octadecane Amine, n-eicosylamine oxime, etc. The monoisocyanate compound may, for example, be phenyl isocyanate or naphthyl isocyanate. The use ratio of the molecular weight modifier is preferably 10 parts by weight or less, more preferably 6 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] Polylysine and polyimine prepared as described above preferably have a solution viscosity of 20 to 800 mPa·s when formulated into a solution having a concentration of 10% by weight, more preferably 30 ~500 mP as solution viscosity. -27- 201022330 The solution viscosity (mPa's) of the above polymer is a concentration of 10% of a good solvent (r-butyrolactone, N-methyl-2-pyrrolidone, etc.) for detecting the polymer. % of the polymer solution, measured by an E-type rotary viscometer at 25 ° C. &lt;(B) Compound&gt; The compound (B) in the liquid crystal alignment agent of the present invention is a compound having an epoxy group and a group represented by the above formula (2%). This compound (B) is preferably made (b1) a compound having 2 to 8 epoxy groups (hereinafter referred to as "compound φ (bl)") 1 molar and (b2) a compound represented by the following formula (2) (hereinafter referred to as "compound (b2) )))) 1~(η-1) a molar component (wherein n is the number of epoxy groups of the above compound (bl)), ri^ziH-rii4^)^ziHch2-) ^cooh (2) (In the formula (2), R1, R11, Z1', Z11, nl, n2, n3 and n4 are respectively the same as defined in the above formula (2%) [compound (bl)] as the present invention The compound (b1) is preferably a compound having a structure represented by the following formula (bi-1) or (bl-2). /0 -Ο-CH2-(b1-1)

N \ CH2

(b1-2) The compound (b1) having a structure represented by the above formula (bl-1) is preferably a compound having two structures represented by the above formula (bl-1), and a specific example thereof is -28-201022330 Examples thereof include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexanediol diglycidyl ether. Glycerol diglycidyl ether 'benzene-1,4-diol diglycidyl ether, 2-methylbenzene-1,4-diol diglycidyl ether, 2-ethylbenzene-1,4-diol Diglycidyl ether, 2-n-hexylbenzene-1,4-diol diglycidyl ether, 2-n-dodecylbenzene-1,4·diol diglycidyl ether, 2-trifluoromethyl Alkylbenzene-1,4-diglycidyl ether, 2,5-diethylbenzene-1,4-diol diglycidyl ether, and the like.化合物 The compound (b1) having the structure represented by the above formula (bl-2) is preferably a compound having one or two structures represented by the above formula (bl_2), and specific examples thereof include n, n. ,n',n'-tetraglycidyl-5-amino-1-(4'-aminophenyl)-1,3,3-trimethyldihydrogen, n,N,N,,N ,-tetraglycidyl-6-amino-1(4'-aminophenyl)-l,3,3-trimethylindoline, N,N,N',N'-tetraglycidyl Base-2,7-diaminopurine, N,N,N,,N,-tetraglycidyl-4,4'-(p-phenylisopropylene)diphenylamine, ^:^',: ^'-Tetraglycidylbutanediamine, :^,:^,:^',&gt;|'-tetraglycidylhexamethylenediamine, N,N,N',N'-tetraglycidyl- 3,6-diaminocarbazol, a compound of the following formula (bl-2 to 1)~(bl-2 to 4), etc., -29- 201022330 (R&gt;d (R)c (b1 -2-1)

-(CH2)a-~ G

(b1-2&gt;4) (In the above formula, B is a single bond, a methylene group, a stretching group having 2 to 12 carbon atoms, -〇-, -coo_, _〇C〇_, -NHCO·, -CONH-, -C0-, -〇-(CH2)g-〇- ' _S-, -S〇2-, -C(CH3)2_, _C(C2H5)2- or

-C(CF3)2·, wherein the above g is an integer of 1 to 丨2, and when a plurality of B are present, each of the plurality of B may be the same 'may be different, and each of R is independently a hydrogen atom and has 1 carbon atom. The alkyl group having ～6 and the fluoroalkyl group 'a having a carbon number of 丨~# are each independently 〇 or l, and each b is independently an integer of 〇3, and c is each independently an integer of 〇4. d is an integer of 〇~5, e is each independently an integer of 0 to 10, f is an integer of 0 to 11, and G is each a glycidyl group). In the above formula (bl - 2-1) to (bl - 2 - 4), two B or B and -(CH2)a-NG2 attached to a benzene ring or a cyclohexane ring are preferably respectively located 1,4-position of the benzene ring or ring of the ring. Specific examples of the compound represented by the above formula (bl-2 - 1) include, for example, N,N-diglycidylaminobenzene, N,N-diglycidyl-2-n-hexylaminobenzene, n , N-diglycidyl-2,2'.dimethyl-4-amino-30-201022330 biphenyl, n,n-diglycidylaminomethylbenzene, etc.; as the above formula (bl-2) Specific examples of the compound represented by 2) include, for example, N,N-diglycidylaminocyclohexane, hydrazine, hydrazine-diglycidylaminomethylcyclohexane, and the like; Specific examples of the compound represented by 2 to 3) can be exemplified by, for example, N,N,N',N'-tetraglycidyl-p-phenylenediamine, 1^,^[,1^', :^,-four shrinkage Glyceryl-m-phenylenediamine, 1^,:^^', :^-tetraglycidyl-2-methyl-1,4-phenylenediamine, &gt;[,1^,]^,,1^ '-tetraglycidyl-2-n-propanyl-1,4-phenylenediamine, N,N,N,,N,-tetraglycidyl-2-n-hexyl-1,4-phenylenediamine, 1^,:^,:^',:1^,-tetraglycidyl-2-trifluoromethyl-1,4-phenylenediamine, N,N,N,,N,- Tetraglycidyl-2,5-dimethyl-1,4-phenylenediamine, N,N,N,,N,-tetraglycidyl-2,2,-dimethyl-4,4'- Diaminobiphenyl, &gt;^&gt;^,::^,-tetraglycidyl-2,2,-diethyl-4,4'-diaminobiphenyl, 1&gt;1, &gt; ,,1^'-tetraglycidyl-2,2,-ditrifluoromethyl-4,4'-diaminobiphenyl, N,N,N,,N,-tetraglycidyl-3, 3'-Dimethyl-4,4'-diaminobiphenyl, N,N,N,,N'-tetraglycidyl-3,3,-diethyl-4,4'-diamino Bismuthene, 2,2-bis[4-(N,N-diglycidyl-4-aminophenoxy)phenyl]propane, N,N,N',N,-tetraglycidyl- 4,4,-Diaminodiphenylmethane, ]^,:^,1^,,:^,-tetraglycidyl-4,4,-diaminodiphenylethane, N,N, N,,N,-tetraglycidyl_4,4'-diaminodiphenyl ether, N,N,N,,N,-tetraglycidyl-4,4'-diaminodiphenyl Thioether, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenyl milling, N,N,N,,N,-tetraglycidyl-4,4, -diaminodiphenylbenzamide , N,N,N',N,-tetraglycidyl-4,4,-diaminodiphenyl ketone, 2,2·bis[4-(N,N-diglycidyl-4-amine Phenoxy group) phenyl] hexafluoropropane, -31- 201022330 2,2-bis(N,N-diglycidyl-4-aminophenyl)hexafluoropropane, 2,2-di[4- (N,N-diglycidyl-4-aminophenoxy)phenyl]anthracene, 1,4-bis(anthracene, fluorene glyceryl-4-aminophenoxy)benzene, 4, 4'-bis(N,N-diglycidyl-4-aminophenyl)biphenyl, 1,3-bis(N,N-diglycidyl-4-aminophenoxy)benzene, 1 , 3·2 (Ν,Ν-diglycidyl-3-aminophenoxy) benzene, hydrazine, hydrazine, hydrazine, Ν'-tetraglycidyl-m-xylylenediamine, etc.; Specific examples of the compound represented by bl-2 - 4) include, for example, N,N,N',N'-tetraglycidyl-1,4-diaminocyclohexane, Φ N, N, N', N'-tetraglycidyl-1,3-bis(aminomethyl)cyclohexane, ^:^',:^'-tetraglycidyl-1,4-bis(aminomethyl)cyclohexane Alkane, &gt;1,^[,:^',:^'-tetraglycidyl-4,4'- Methyl bis (cyclohexylamine) and the like. Among them, the compound (b1) preferably has one or two of the above formulas (bl - 2) from the viewpoint of the reactivity of the epoxy group and the perpendicular alignment of the formed liquid crystal alignment film. As a particularly preferable compound, N,N-diglycidylaminobenzene, N,N-diglycidylaminomethylcyclohexane, anthracene, fluorene-diglycidyl hydrazine Aminomethylbenzene, hydrazine, hydrazine, hydrazine, Ν'-tetraglycidyl-p-phenylenediamine, hydrazine, hydrazine, hydrazine, Ν'-tetraglycidyl-2,2'-dimethyl -4,4'-diaminobiphenyl, &gt;1,&gt;1,&gt;1',:^'-tetraglycidyl-2,2'-ditrifluoromethyl-4,4'- Diaminobiphenyl, 2,2-bis[4·(Ν,Ν-diglycidyl-4-aminophenoxy)phenyl]propane, hydrazine, hydrazine, Ν', Ν'-tetraglycidyl Base-4,4,diaminodiphenylmethane, anthracene, oxime, Ν', Ν'-tetraglycidyl-4,4'-diaminodiphenyl ether, &gt;1, 虬:^' ,:^'-tetraglycidyl-4,4'-diaminodiphenyl ketone, 2,2-bis[4-(indole, Ν-diglycidyl-4-aminophenoxy Phenyl]hexafluoropropane, hydrazine, hydrazine, hydrazine, Ν'-tetraglycidylhexamethylenediamine, hydrazine, hydrazine, hydrazine, Ν'-tetraglycidyl-32- 201022330 -1,3-two ( Aminomethyl)benzene, N,N,N',N'-tetraglycidyl-m-xylylenediamine and N,N,N',N,-tetraglycidyl-1,3-di (amine Methyl)cyclohexane. [Compound (b2)] The compound (b2), as the alkyl group having 4 to 40 carbon atoms of R1 in the above formula (2), is preferably an alkyl group having 6 to 40 carbon atoms, specifically ' For example, a hexyl group, an octyl group, a decyl group, a dodecyl group, a hexadecyl group, an octadecyl group or the like; ❹ is a fluoroalkyl group having 4 to 40 carbon atoms, preferably 4 carbon atoms. The fluoroalkyl group of -20 is specifically, for example, a trifluoromethylpropyl group, a trifluoromethylbutyl group, a trifluoromethylhexyl group, a trifluoromethylsulfonyl group, a pentafluoroethylpropyl group, or a fifth group. The fluoroethyl butyl group, the pentafluoroethyl octyl group, etc., and the hydrocarbon group having a carbon atom number of 17 to 51 having a steroid skeleton, for example, each represented by the following formulas (R1 - 1) to (R1 - 3) Group, etc.

(In the formula (R1 - 1) to (1^-3), it is represented by a linking bond). In the above formula (2), the cyclohexylene group and the phenyl group of R11 are preferably n-cyclohexylene and 1,4-, respectively. Stretch phenyl. As a divalent group represented by -(Rn)nl- in the above formula (2), as η 1 is 1, preferably, for example, 丨, 4 _ -33- 201022330 phenyl, 1,2- Examples of the case where n1 is 2, and examples thereof include a group represented by 4, 4'-biphenyl, 4,4'-dicyclohexyl, and the following formula, and the like.

Fortunately

(In the above formula, the link with " " is located on the R1 side.

N3 in the above formula (2) is preferably 2. Preferred examples of the compound (b2) in the invention include stearic acid, hexyloxybenzoic acid, octyloxybenzoic acid, decyloxybenzoic acid, dodecyloxybenzoic acid, and octadecyloxy group. Benzoic acid, trifluoromethylbenzoic acid, trifluoromethoxybenzoic acid, trifluoromethylpropoxybenzoic acid, trifluoromethylbutoxybenzoic acid, hexafluoropropoxybenzoic acid, the following formula ( B2 — 1) and (b2 – 2) each represented by a compound or the like.

COOH (b2-1)

(b2-2) The preferred compound (B) in the liquid crystal alignment agent of the present invention is a compound (b1) molar and a compound (b2) 1 to (η-1) molar (as described above) η is a compound obtained by reacting an appropriate solvent in the solvent of -34 to 201022330, which is a compound of the compound (b). The compound (b2) is more preferably used in a ratio of 1 to (η/2) moles when n is an even number, and {(11) when η is an odd number with respect to 1 mole of the compound (b1). +1)/2} Moer. For example, when the compound (b1) is a compound having two structures represented by the above formula (bl-2) (where the number of epoxy groups is 4), relative to 1 mole of the compound (bl), the compound ( B2) 1 to 3 moles can be used, preferably 1 to 2 moles are used. The organic solvent which can be used for the above-mentioned reaction is exemplified as the organic solvent which can be used as the φ synthesis of the above polyamic acid. Preferably, it is an aprotic organic solvent, and specifically, N-methyl-2-pyrrolidone, acetonitrile, dimethyl hydrazine, N,N-dimethylacetamide, N,N-dimethyl Mercaptoamine, N,N-dimethylimidazolidinone, dimethyl submilling, 7-butyrolactone, tetramethylurea, hexamethylphosphonium triamine, and the like. The ratio of the total weight ratio of the compound (b1) to the compound (b2) in the reaction solution is preferably 1% by weight or more, and more preferably 5 to 50% by weight.温度 The temperature at the time of the above reaction is preferably from 20 to 250. (:, more preferably 50 to 180 ° C. The reaction time is preferably from 0.1 to 72 hours, more preferably from 5 to 48 hours. Thus, a solution containing the preferred compound (B) can be obtained. The preparation of the liquid crystal alignment agent of the present invention may be directly supplied, or the preparation of the liquid crystal alignment agent of the present invention may be carried out after separating the 'refined (B) compound from the reaction solution. The compound (B) is separated and purified from the reaction solution, for example, A liquid-liquid extraction method, a column chromatography method, a distillation method, etc. The preferred compound (B) in the present invention is a reaction of a part of the epoxy group of -35-201022330 which the compound (b1) has with the compound (b2). Therefore, it has both an epoxy group derived from the compound (b1) and an RI group derived from the compound (b2). Therefore, by allowing the liquid crystal alignment agent of the present invention to contain the compound (B), the liquid crystal alignment can be prevented from being impaired. A liquid crystal alignment film having a good vertical alignment property is formed under the premise of the printing property of the agent. The more preferable examples of the compound (B), for example, each of the following formulas (B to 1) to (B-4) Compounds, etc., (R)c,

(In the above formula, B is a single bond, a methylene group, an alkylene group having 2 to 12 carbon atoms, ·0-, _c〇〇-, -〇co·, -NHC〇-, -CONH-, - CO-, •〇'(CH2)g-0-, -S〇2-, -C(CH3)2-, -C(C2H5)2- or 'C(CF3)2-, wherein the above g is 1 An integer "~12" When there are a plurality of B's, the multiple entropy B may be different from each other, or may be different. R is independently a hydrogen atom, an alkyl group having a carbon number, or a fluorine having a carbon number of 1 to 4. Alkane, a each independently 〇 or 11 b is independently an integer of 〇 〜 3, -36 - 201022330 C are each independently an integer of 〇 〜 4, and d is an integer 〇 5 5 'e each independently An integer of 0 to 10, where f is an integer of 〇~; X1 is a glycidyl group, and X11 is a group represented by the following formula (3-1) or (3-2),

Rl+Zl^RlI-^^zMCH2t^CO〇-CH2-CH-〇H2-

0H 丨(3-1 ) ri^zi4-rii^^ziHch2^^coo-ch-ch2—CH2〇H ( 3-2 ) Ο (in equations (3–1) and (3-2), R1 and R11 , Z1, Z&quot;, n1, n2 and n4 are the same as defined in the above formula (2), respectively, and χΐ11 and XlV are each independently a glycidyl group or a group represented by the above formula (3 - ^ or (a) - 2) Among them, Tejia is a compound represented by the following formulas (Β-1_υ~(B_l-3), (B-21:1), and (Β-3_1)~(Β-3-4),

(Β-2-1) -37- 201022330

(B-3-1)

~ (B-4) has the same meaning). Here, a group represented by the above formula (3-1) and a group represented by the above formula (3-2) may be present in one molecule (B), and may also have a formula represented by the above formula (3-1). The compound of the group (B) is used in combination with the compound (B) having a group represented by the above formula (3-2). The use ratio of the compound (B) in the liquid crystal alignment agent of the present invention is at least one polymer selected from the group consisting of polyglycolic acid and polyamidimide (hereinafter referred to as "1" by weight based on 1 part by weight of (A). (A) Polymer"), preferably from 1 to 40 parts by weight, more preferably from 0.1 to 30 parts by weight, still more preferably from 2 to 25 parts by weight. &lt;Other Additives&gt; The liquid crystal alignment film of the present invention contains the (A) polymer and the (B) compound as described above as essential components, and may further contain other components as needed. As such other components, for example, (C) a compound having at least one epoxy group in the molecule (excluding the compound of the above (B), and -38-201022330 is simply referred to as "epoxy compound". ), (D) a functional decane compound or the like. [(C) Epoxy compound] The (C) epoxy compound can be used from the viewpoint of further improving the adhesion of the formed liquid crystal alignment film to the surface of the substrate. As the (C) epoxy group which can be used herein, the same compound as the above compound (b1) can be mentioned. Among them, preferred are ethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexane. Alcohol, 1^ small, :^', 1^'-tetraglycidyl-m-phenylenedi-yl-methylamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, 1 ^,1^,:^,:^'-tetraglycidyl-4,4'-diaminodiphenylmethane, ratio: ^-diglycidyl-benzylamine, N,N-diglycidyl - Amine methylcyclohexane or the like. The compounding ratio of the (C) epoxy compound is preferably 30 parts by weight or less, more preferably 0.1 to 25 parts by weight, per 100 parts by weight of the (A) polymer. Further, the total ratio of the use ratio of the (C) epoxy compound to the use ratio of the (B) compound is preferably not more than 40 parts by weight based on 100 parts by weight of the (A) polymer. φ [(D) Functional decane compound] The above (D) functional decane compound can be used from the viewpoint of further improving the printability of the liquid crystal alignment agent of the present invention. As such a (D) functional decane compound, for example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2- Aminopropyltriethoxydecane, Ν(2-aminoethyl)-3-aminopropyltrimethoxydecane, Ν-(2-aminoethyl)-3-aminopropyl Dimethoxyoxane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane 'N-B Oxycarbonyl-3-amino-39-201022330 propyltriethoxydecane, N-triethoxydecylpropyltriethylenetriamine, N-trimethoxydecylpropyltriethylenetriamine, 10-trimethoxydecyl-1,4,7-triazadecane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3 , 6-diazaindolyl acetate, 9-triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxy Silane, N- bis (oxyethylene) -3-aminopropyl trimethoxy Silane, N- bis (oxyethylene φ enyl) -3-aminopropyl triethoxy silane-like. The use ratio of these (D) functional decane compounds is preferably 2 parts by weight or less, more preferably 1 part by weight or less based on 100 parts by weight of the (A) polymer. &lt;Liquid Crystal Aligning Agent&gt; The liquid crystal aligning agent of the present invention is obtained by dissolving the (A) polymer and the (B) compound as described above and optionally adding other additives as needed, preferably in an organic solvent. of. Q The organic solvent which can be used in the liquid crystal alignment agent of the present invention is exemplified as a solvent which can be used as a synthesis reaction of polyglycine. Further, it is also possible to appropriately select a poor solvent which can be used in combination as a synthetic reaction of polylysine. Preferable examples of such an organic solvent include, for example, N-methyl-2-pyrrolidone, r-butyrolactone, 7-butylide, N,N-dimethylformamide, N,N- Dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethoxypropyl propionate Ester, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl-40-201022330 cellosolve), ethylene glycol dimethyl ether , ethylene glycol ethyl ether acetate, diglyme, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether Acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, and the like. They may be used singly or in combination of two or more. A particularly preferable solvent composition is a composition obtained by combining the above solvents, so that the (A) polymer and the (B) compound and other additives optionally blended in the liquid crystal alignment agent are not precipitated, and the surface of the liquid crystal alignment agent is made. The tension falls in the range of 25~40 mN/m ❿ composition. The solid content concentration of the liquid crystal alignment agent of the present invention (the ratio of the total weight of the liquid crystal alignment agent other than the organic solvent to the total weight of the liquid crystal alignment agent) is selected in consideration of viscosity, volatility, etc., preferably 1 to 10 parts by weight. The range of %. That is, the liquid crystal alignment agent of the present invention forms a coating film as a liquid crystal alignment film by applying it to the surface of the substrate and removing the organic solvent, and when the solid content concentration is less than 1% by weight, the thickness of the coating film will occur. When it is too small to obtain a good liquid crystal alignment film, the other side, when the solid content concentration exceeds ίο重量%, the thickness of the coating film is too thick and it is difficult to obtain a good liquid crystal alignment film, and There is a case where the viscosity of the liquid crystal alignment agent is increased to deteriorate the coating performance. A particularly preferable range of solid content concentration differs depending on the method used to coat the liquid crystal alignment agent on the substrate. For example, when the spin coating method is employed, it is particularly preferably 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 mPa·s. When the ink jet method is employed, it is particularly preferable that the solid content concentration is in the range of 1 to 5% by weight, so that the viscosity of the solution -41 to 201022330 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 〜100 ° C, more preferably 20 ° C to 60 ° C. The liquid crystal alignment agent of the present invention is particularly suitable for forming a vertical alignment type liquid crystal display element. The liquid crystal alignment film used. &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, and is a more preferable operation mode of the liquid crystal display element of the present invention, and a vertical alignment type can be cited. Hereinafter, a method of producing a vertical alignment type liquid crystal display element using the liquid crystal alignment agent of the present invention will be described. The liquid crystal display element of the present invention can be produced, for example, by the following steps (1) to (3). (1) First, a coating film is formed on a substrate by applying the liquid crystal alignment agent of the present invention onto a substrate and then heating the coated surface. The two substrates provided with the patterned transparent conductive film are used as a pair, and the liquid crystal alignment agent of the present invention is preferably coated on each of the transparent substrates by a roll coating method, a spin coating method, a printing method, or an inkjet method. A coating film is formed on the surface on which the conductive film is formed, and then each coated surface is heated. Since the liquid crystal alignment agent of the present invention is excellent in printability, it is preferable to use a printing method as a coating method. Here, as the substrate, for example, glass such as float glass or soda lime glass, polyethylene terephthalate, polybutylene terephthalate, polyether selenide, polycarbonate, and alicyclic polyolefin can be used. Such as plastic transparent substrate. As the transparent conductive film provided on one surface of the substrate, a NESA film (registered trademark of PPG, USA) made of tin oxide (Sn02), an ITO film made of indium oxide-42-201022330-tin oxide (In203-Sn02), or the like can be used. The pattern-forming transparent conductive film can be obtained by, for example, a method of forming a pattern by photolithography after forming a transparent conductive film without a pattern, a method of using a mask having a desired pattern when forming a transparent conductive film, or the like. 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 or a functional titanium may be preliminarily coated on the surface of the substrate on which the coating film is to be formed. Pretreatment of compounds and the like. After the liquid crystal alignment agent is applied, preheating (prebaking) is preferably performed for the purpose of preventing the liquid crystal alignment agent liquid φ from dripping. The prebaking temperature is preferably from 30 to 200 ° C, more preferably from 40 to 150 ° C, particularly preferably from 40 to 1 ° C. The prebaking time is preferably from 0.1 to 10 minutes, more preferably from 0.5 to 5. minute. Then, in order to completely remove the solvent and 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 1 to 300 minutes, more preferably from 2 to 120 minutes. The liquid crystal alignment agent of the present invention forms a coating film as an alignment film by removing an organic solvent after coating, and the polymer contained in the liquid crystal alignment agent of the present invention is a poly-proline or a quinone ring structure and a guanamine In the case of an acid-structured polyimine, it is also possible to carry out a dehydration ring-closure reaction by further heating after forming a coating film to form a coating film which is further imidized. The thickness of the coating film formed herein is preferably 0.001 to Ιμχη, more preferably 0.005 to 0.5/zm. (2) The coating film formed as described above may be used as a liquid crystal alignment film for a vertical alignment type liquid crystal display element as it is, or the coating film surface may be optionally subjected to a rubbing treatment. The sanding treatment can be carried out by rubbing the coating film surface in a certain direction by a roll wrapped with a cloth such as nylon, rayon, or cotton-43-201022330. (3) Two substrates on which the liquid crystal alignment film was formed as described above were prepared, and liquid crystal cells were produced by arranging liquid crystal between the two substrates. For the production of the liquid crystal cell, for example, the following two methods can be cited. The first method is a previously known method. First, the two substrates are opposed to each other through a gap (cell gap) so that the respective liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded together by a sealant to the crystals surrounded by the substrate surface φ and the sealant. After filling the liquid crystal in the interstitial space, the injection hole is closed, and the liquid crystal cell can be obtained. 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 on which the liquid crystal alignment film is formed, and then dropping the liquid crystal on the liquid crystal alignment film surface, bonding the other substrate, and causing the liquid crystal alignment film to face each other The liquid crystal cell can be obtained by irradiating the entire surface of the substrate with ultraviolet rays to harden the sealant.采用When using any of the above 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 alignment when the liquid crystal is charged. Then, pass through the liquid crystal cell. The liquid crystal display element of the present invention can be obtained by laminating a polarizer on the outer side surface. Here, as the sealant, for example, an epoxy resin containing an alumina ball as a curing agent and a separator, or the like can be used. Examples of the liquid crystal include nematic liquid crystal and dish-shaped liquid crystal. Among them, a preferred nematic liquid crystal can be, for example, a Schiff's-type liquid crystal, an oxidized -44-201022330 azo-based liquid crystal, or a biphenyl-based liquid crystal. Phenylcyclohexane liquid crystal, ester liquid crystal, diphenyl liquid crystal, biphenyl ring liquid crystal, mute liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, cubic liquid crystal, etc. . Further, in these liquid crystals, cholesteric liquid crystals such as cholesteryl cholesteryl, cholesteryl phthalate, and cholesteryl carbonate may be further added; under the trade names "C-15" and "CB-15" (manufactured by Merck & Co., Inc.) A chiral agent sold; used for ferroelectric liquid crystals such as decyloxybenzylidene-amino-methyl-2-cinnamate. Q, as a polarizer to be bonded to the outer surface of the liquid crystal cell, a polarizer which is obtained by sandwiching a polarizing film called "H film" which is a "H film" in which polyvinyl alcohol is extended and absorbing iodine, is placed on a cellulose acetate protective film, or Η A polarizer made of the film itself. (Embodiment) Hereinafter, the present invention will be more specifically described by way of Examples, but the present invention is not limited to these Examples. The solution viscosity of the following polymer solution and the oxime imidization ratio of the polyimine were evaluated by the following methods, respectively. [Solid viscosity] The solution viscosity (mPa.s) of the polymer was measured at 25 °C using an E-type rotary viscometer with a solution having a polymer concentration of 10% by weight prepared using the solvent specified in each of the Synthesis Examples. [醯imination rate] The polyimine was dried under reduced pressure at room temperature, dissolved in deuterated dimethyl sub-mill, and tetramethyl decane was used as a reference material. 1H-NMR was measured at room temperature. It is obtained by the following formula (1). -45- .201022330 醯 imidization rate (%) = (1 - Α" Α 2 χ α ) χ 100 (1) (In equation (1), A1 is the peak area originating from the NH matrix near the chemical shift of 10 ppm. , A2 is the peak area derived from other protons, and α is the proton of one sulfhydryl group in the precursor of the polyimine (poly-proline), the ratio of the number of other protons.) &lt;(Β) Synthesis of Compounds &gt; Synthesis Example Β1 (Ν-(2-hydroxy-3-n-octyloxybenzylideneoxy)propyl-indole, Ν', Ν'-triglycidyl-m-xylylenediamine and Synthesis of a mixture of Ν-(3-hydroxy-2-n-octyl oxybenzoyloxy) propyl-hydrazine, Ν', Ν'-triglycidyl-m-xylylenediamine) under nitrogen atmosphere In a 200 ml three-necked flask, 18.0 g (0.05 mol) of ν, Ν, Ν', Ν,-tetraglycidyl-m-xylylenediamine and 12.5 g of 4-n-octyloxybenzoic acid (0.05) The mixture was mixed, and 12.2 g of N-methyl-2-diazolone was added and stirred. The reaction was carried out by mixing it under nitrogen for 4 hours to obtain about 150 g of 20% by weight of &gt; (2-carbyl_3_n-octyloxybenzylideneoxy)propyl-N,N' , N'-triglycidyl-m-xylylenediamine and hydrazine N-(3-hydroxy-2-n-octyloxybenzylideneoxy)propyl-N,N,,N,triglycidyl- A solution of a mixture of m-xylylenediamine. Synthesis Example B2 (N-(2-hydroxy-3-n-dodecyloxybenzylideneoxy)propyl 4,:^',1^'-triglycidyl Benzyl-m-xylylenediamine and 11^(3_----------------------------------------------------- Synthesis of the mixture) In a three-necked flask of 20〇1111 under nitrogen atmosphere, ^:^,,;·· tetraglycidyl-m-xylylenediamine 18.0 g (0.05 m) and 4 positive eleven 15.3 g of oxybenzoic acid was mixed, and 133 &amp; N-methyl-46-201022330-based 2-pyrrolidone was added and stirred. It was stirred by stirring at 100 ° C for 4 hours under nitrogen. The reaction was carried out to obtain about 165 g of 20% by weight of N-(2-hydroxy-3-n-dodecyloxybenzylideneoxy)propyl-indole, Ν', Ν'-triglycidyl-m-phenylene Methylamine and Ν·(3·hydroxy-2-n-dodecyloxybenzylideneoxy)propyl-indole, Ν', Ν'-triglycidyl- A solution of a mixture of m-xylylenediamine. Synthesis Example Β3 (Ν·(2-hydroxy-3-n-dodecyloxybenzylideneoxy)propyl-:^,^[',1^'-three Glycidyl-4,4'-diaminodiphenylmethane and]^-(3-hydroxy-2·n-dodecyloxybenzylideneoxy)propyl-indole, Ν', Ν'- Synthesis of a mixture of trisqualane φ oil-based 4,4'-diaminodiphenylmethane) In a 200 ml three-necked flask under nitrogen atmosphere, Ν, Ν, Ν', Ν'-four shrinkage Glyceryl-4,4'-diaminodiphenylmethane 21. lg (0.05 mol) and 4-n-dodecyloxybenzoic acid 15.3 g (0.05 mol) were mixed, and 145.6 g of N-A was added. Base-2-pyrrolidone and stirred. The reaction was carried out by stirring it under nitrogen at 6 ° C for 6 hours to obtain about 180 g of 20% by weight of N-(2-hydroxy-3-n-dodecyloxybenzylideneoxy)propyl-N. , N', N'-triglycidyl-4,4'-diaminodiphenylmethane and N-(3-hydroxy-2-n-decadecyloxyalkoxy)propyl- A solution of a mixture of N,N',N'-triglycidyl-4,4'-diaminodiphenylmethane. Synthesis Example 4 (Ν·(2-hydroxy-3-trifluoromethylpropoxybenzylideneoxy)propyl-indole, Ν', Ν'-triglycidyl-m-xylylenediamine and ν· Synthesis of (3-hydroxy-2-trifluoromethylpropoxybenzylideneoxy)propyl-anthracene, Ν', Ν'-triglycidyl-m-xylylenediamine mixture) under nitrogen atmosphere 'In a 200 ml three-necked flask, Ν, Ν, Ν', Ν, -tetraglycidyl-m-xylylenediamine 18.0 g (0.05 mol) and 4-trifluoromethylpropoxybenzoic acid 9.5 G (0.05 mol) was mixed, and lio.igN-methyl-47-201022330-based 2-pyrrolidone was added and stirred. The reaction was carried out by stirring at 100 ° C for 4 to 5 hours under nitrogen to obtain about 136 g of 20% by weight of N-(2-hydroxy-3-trifluoromethylpropoxybenzylideneoxy)propyl group. Ν,Ν',N '-triglycidyl-m-xylylenediamine and N-(3-hydroxy-2-trifluoromethylpropoxybenzylideneoxy)propyl-N,N',N A solution of a mixture of '-triglycidyl-m-xylylenediamine. Synthesis Example B5 (Synthesis of a mixture of a compound (B-3-2-1-1) and a compound (b-3-2~1~2)) The compound 丨_丨&gt; was synthesized according to the following Synthesis Scheme 1. A mixture of compounds (B-3 - 1 - 2).

-48- 201022330

Synthetic Route 1 N, n, N, N,-tetraglycidyl-m-xylylenediamine 18.0 g (005 mol) and compound in a 2 〇〇 ml three-necked flask under nitrogen atmosphere (152_l) 24.4 g (〇.〇5 mol) was mixed, and n〇lg N-methyl-2-pyrrolidone was added and stirred. The reaction was carried out by stirring it under nitrogen for 4.5 hours under nitrogen to obtain about 192 g of a mixture containing 20% by weight of a compound (B-3-2-1-1) and a compound (B-3-2 - 1 - 2). The solution. -49- 201022330 Synthesis Example B6 (Synthesis of a mixture of compound (B-3 2 - 2 - 1) and compound (b - 3 - 2 - 2 - 2)) Compound (B-3) was synthesized according to the following Scheme 2 — 2— 2 — A mixture of compounds (B — 3 — 2 — 2 — 2).

G will be route 2 in a 200 ml three-necked flask under nitrogen, n, N, N, N'-tetraglycidyl-m-xylylenediamine 18. 〇g (〇·05 Moel) The compound (b2-2) was mixed with 17.6 g (0.05 mol) to add H〇.lg N-methyl-2-pyrrolidone and stirred. The reaction was carried out by stirring it under nitrogen at 1 ° C for 4.5 hours to obtain about 187 g of a compound containing 20% by weight of a compound (B 3 - 2 - 2 - 1 ) and a compound (B - 3 - 2 - 2 - 2). a solution of the mixture. &lt;(A) Synthesis of Polymer&gt; -50-.201022330 [Synthesis of Polyimine] Synthesis Example PI 01 to PI 13 To N-methyl-2·pyrrolidone, sequentially added to Table 1 The amounts of the diamine and the tetracarboxylic dianhydride were adjusted to a solution having a monomer concentration of 20% by weight, and the reaction was carried out at 60 ° C for 4 hours to obtain a polyglycine-containing solution. A small amount of each solution was taken, and N-methyl-2-pyrrolidone was added to prepare a solution having a polyglycine concentration of 10% by weight. The measured solution viscosity is shown in Table 1. Then, to each of the above polylysine solutions, pyridine and acetic anhydride shown in Table 1 were added to the 1 molar protonic acid unit of the polyamine Q acid, respectively, at 110°. The mixture was heated under c for 4 hours to carry out a dehydration ring closure reaction. After the dehydration ring closure reaction, the solvent in the system is replaced with a new N-methyl'yl-2-pyrrolidone (in this operation, the pyridine and acetic anhydride used in the dehydration ring-closure reaction are removed to the outside of the system), respectively. A solution containing 16% by weight of polyimine (PI-1)~(PI-13). The ruthenium imidization ratio of each polyimine contained in these polyimine solutions, and the N-methyl-2-pyrrolidone solution having a polyamidene concentration of 10% by weight. The solution viscosity is shown in Table 1, respectively. [Synthesis of Polyamine] Synthesis Examples PA01 to PA03 Reactions were carried out in the same manner as in the above Synthesis Examples PI 01 to PI 13 except that the diamine and the tetracarboxylic dianhydride were each shown in Table 1. A solution containing polylysine (PA-1)~(PA-3). A small amount of each solution was taken, and N·methyl-2-pyrrolidone was added to prepare a solution having a polyglycine concentration of 10% by weight. The measured solution viscosity is shown in Table 1. -51- 201022330

Polymer name PI-1 PI-2 PI-3 PI-4 PI-5 PI-6 PI-7 PI-8 PI-9 〇1 E 1 s &lt;N 1 E m 1 S TH 1 &lt;N i PA -3 ||? Fine 1 bran 冏鸪Sil _ 麴 in iT) In 00 m Ό VO m Os (N 寻 m 1 1 1 鹛醯 imidization rate (%) 沄yr) yn 〇§ § jn In oo 00 1 1 1 μ m ΠΓΓ*&gt; 5S acetic anhydride (mole multiple) ο op 〇〇〇(N 〇(N 〇&lt;N o (N &lt;N &lt;N 〇1 1 1 mine ο Ppoo in 〇&lt;N 〇ri 〇(N 〇&lt;N in &lt;N o 1 1 1 Ilf sil ill | age key οο 〇\ &lt;N Os 〇\ &lt;s (N 〇\ 00 o 〇\ m &lt;N in 00 o 00 m yn 11 quantity (mmol) ο FH 〇o T&quot;H ooo O ϊ-Η o Ψ &lt; o 〇TH o rH O oo O »·Μ o 辙a 1 •4-» r —^ 1 — 1 H-* 1 1 «Μ 1 T—H 1 — 1 1 1 +-» 1 4-» tH 1 T&quot;H 1 — CN 1 s-» (N 1 know rH 1 铿II (mmol) 80/20 90/10 80/20 90/10 70/10/20 80/10/10 70/20/10 40/50/10 70/20/10 70/20/10 70/20/10 70/20/10 60/40 oo 〇1·^ Μ Γ\ tlmll Ρ d_l/d—6 d 1/d-6 ! .............. .id~\/ d~7 d—1/d—7 dl/d-6/d-7 d- l/d-6/d-7 1 (N 1 Π3 d — 1/d—2/d_6 dl/d-3/d-6 d—1/d—3/d—7 dl/d-4/d -6 d— l/d_5/d_6 V〇1 T3 d-2 d-3 rH 1 T3 Synthesis example PI 01 PI 02 PI 03 PI 04 PI 05 PI 06 PI 07 PI 08 PI 09 PI 10 PI 11 PI 12 PI 13 PA 01 PA 02 PA 03 -^- 201022330 The abbreviation of 'diamine and tetracarboxylic dianhydride in Table 1 respectively has the following meanings. &lt;Diamine&gt; d - 1 : p-phenylenediamine d-2: 4,4'-diaminodiphenylmethane d-3: 2,2'-dimethyl-4,4'-diamine Base benzene d-4: 1,3-bis(aminomethyl)cyclohexane oxime d-5: 1,3-bis(3-aminopropyl)tetramethyldioxane d-6: Diamine d-7 represented by the above formula (D-1): diamine represented by the above formula (D-8) &lt;tetracarboxylic dianhydride&gt; t-1 : 2,3,5-tricarboxycyclopentane Acetic acid dianhydride t-2: 1,2,3,4-cyclobutane tetracarboxylic dianhydride Example 1 &lt;Preparation of liquid crystal alignment agent&gt; e Only converted to polyimine (PI-1) A polyiminamide (PI-1)-containing solution prepared in the above-mentioned Synthesis Example PI 01 is equivalent to 100 parts by weight as (A) polymer to which r-butyrolactone and N-methyl- are added. 2-pyrrolidone and butyl cellosolve, and N-(2-hydroxy-3-n-octyloxy group) obtained in the above Synthesis Example B1 in an amount equivalent to 5 parts by weight of the compound (B) contained therein Benzyl oxime)propyl-N,N',N'-triglycidyl-m-xylylenediamine and N-(3-hydroxy-2.n-octyloxybenzene-53- 201022330 formamidine )propyl-]^ a solution of a mixture of 1^,,1^,-triglycidyl-m-xylylenediamine as the compound (B), and 10 parts by weight of N,N,N',N'-tetraglycidyl-4, 4'-Diaminodiphenylmethane as (C) epoxy compound, the solvent composition is r - butyrolactone · N - methyl-2-pyrrolidone: butyl cellosolve = 40 : 30 : 3 0 (weight ratio), a solution having a solid content concentration of 6.5% by weight. The solution was visually observed as a clear liquid without turbidity. This solution was filtered through a filter φ having a pore size to prepare a liquid crystal alignment agent, and the following printability evaluation was performed. Further, in the same manner as above, the solvent composition was adjusted to be r-butyrolactone: methyl-2-pyrrolidone: butyl cellosolve = 40:30:30 (weight ratio), and the solid content concentration was 4.0% by weight. /. The solution was filtered through a filter having a pore size of 〇.2#m to prepare a liquid crystal alignment agent, which was supplied to the following evaluation of vertical alignment and voltage retention. &lt;Printability evaluation&gt; The liquid crystal compounding agent having a solid content concentration of 6.5% by weight prepared as described above was coated with a liquid crystal alignment film printer (manufactured by Photographic Printing Co., Ltd., trade name "Angstroma"). The transparent electrode surface of the glass substrate made of the ITO film transparent electrode was heated on a hot plate at 80 ° C for 1 minute (prebaking) to remove the solvent, and then heated on a hot plate at 200 ° C for 10 minutes (post-baking) ), a coating film having an average film thickness of 750 angstroms was formed. The coating film was visually observed to investigate the degree of uneven printing. Here, when there is no visible unevenness or surface unevenness on the surface of the coating film, the printability -54 - 201022330 is evaluated as "very good", and when the surface of the coating film is extremely finely uneven or uneven, printing is performed. The evaluation was "good", and it was observed that the streaky unevenness or the surface unevenness or the evaluation of the two tests was unacceptable. At this time, the above liquid crystal alignment agent was "very good". &lt;Evaluation of Vertical Orientation&gt; [Production of Liquid Crystal Display Element for Vertical Alignment Evaluation] φ A liquid crystal alignment agent having a solid content concentration of % prepared above was applied to a glass surface having a thickness of 1 mm by a spin coater. The ITO film was placed on a transparent conductive film, and then heated on a hot plate for 1 minute (prebaking) to remove the solvent, and then heated in a clean oven for 60 minutes (post-baking) to form a coating film having a film thickness. The coating film was smashed with a grinding speed of 400 rpm, a table moving speed of 3 cm/sec, and a length of 0.4 mm using a roller equipped with a rayon fabric. The substrate was heated in a clean oven at 100 ° C for 1 minute in pure water, and dried to obtain a substrate having a polished coating film. Repeat the operation to make a pair (two pieces) of polished plates. On each outer edge of the coating film forming surface of the pair of substrates, an epoxy resin having a diameter of 3.5/zm is bonded to the stripe film as a coating film, and the printing printability is 4.0 substrate. A 80 ° C plus 200 ° C 0,0 8 from the m machine, in the roll and fluff squeezing treatment. After the F wave was washed for 1.0 minute, the base of the series of coatings was coated with the additive, and then the -55-201022330 dicrystalline liquid solution was leveled and turned against the joint. The hardening agent film is coated and adhered to each other, and the negative phase liquid crystal is injected between the substrates to the surface of the liquid crystal substrate (MLC, MLC) After -6 6 0 8), the liquid crystal injection port was sealed with an acrylic photocurable adhesive, and a polarizing plate was bonded to both surfaces of the substrate to produce a liquid crystal display element for evaluation of the vertical alignment. [Evaluation of Vertical Orientation] φ The pretilt angle of the liquid crystal display element was measured by a crystal rotation angle method to be 89.5°. In addition, it is known that the sanding process can reduce the pretilt performance. Therefore, although the liquid crystal alignment film having a pretilt angle of 89.0° or more is obtained by the rubbing treatment, it can be said that the vertical alignment property is extremely excellent. &lt;Evaluation of Voltage Retention Rate&gt; [Production of Liquid Crystal Display Element for Voltage Retention Rate Evaluation] In the above, in addition to the polishing treatment and the subsequent ultrapure water washing and drying operation, the above &lt;vertical In the same manner as in the production of the liquid crystal display element for the evaluation of the vertical alignment, the liquid crystal display element for voltage holding rate evaluation was produced in the same manner. [Evaluation of Voltage Retention Rate] A voltage of 5 V was applied to the liquid crystal display element manufactured above at 60 ° C for a time span of 167 μsec, the voltage application time was 60 μsec, and then the voltage was released from the voltage to 167 msec. After the voltage holding ratio, the voltage holding ratio of the liquid crystal display element was 99.3%. -56- 201022330

实施 Examples 2 to 4 5 and Comparative Examples 1 to 1 1 Except that the types and amounts of the (A) polymer, the (B) compound, and the (C) epoxy compound are respectively shown in Table 2, the above examples In the same manner, liquid crystal alignment agents of two concentrations of solid content concentrations of 6.5% by weight and 4.0% by weight were prepared and evaluated. The evaluation results are shown in Table 2. -57- 201022330

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Ρ! oo 201022330 is Voltage 1 retention rate (%) 1 99.6 99.6 99.3 99.3 99.5 99.5 ___99,5__ 99.7 99.3 99.4 99.4 __99,5__ __99Λ__ __99,5__ 99.2 99.1 99.5 99.5 99.7 99.3 Vertical alignment m 89.8 89.8 89.7 89.9 89.9 88.9 89.0 89.8 89.6 89.6 89.7 89.7 89.2 89.7 89.1 89.6 89.5 89.5 89.0 89.0 Printability I Good 1 Very good Very good Very good 1 Very good 1 1 Good I 丨 Good 1 1 Good 1 1 Very good 1 丨 Very good 1 i Very good 1 1 Very good 1 Good 1 Good 1 Very good § Very good Very good 6.5 % by weight The appearance of the solution is free of turbidity, transparent, no turbidity, transparent, no turbidity, transparent, no turbidity, transparent, no turbidity, transparent, no turbidity, transparent, no turbidity. Transparent, no turbidity, transparent, no turbidity, transparent, no turbidity, transparent, no turbidity, transparent, no turbidity, transparent, no turbidity, transparent, no turbidity, transparent, no turbidity, transparent, no turbidity, No turbidity, no turbidity, no turbidity, no turbidity, no turbidity, no transparency; π m 秘 mg 份ο ο wi Ο Ο Ο Ο 〇 1 1 U 1 U 1 c-1 1 CN| 1 〇(N 1 〇1 U 1 c-1 I CN 1 υ 1 c-1 1 ra 1 u (N 1 U &lt;Ν 1 υ cs 1 υ 1 υ 1 U 1 c-1 1 CN 1 υ &lt;Ν 1 υ cs 1 Ο (Ν 1 U &lt;Π rV) Parts by weight 〇〇〇〇〇 ο X s Type 1 B-3 1 B-3 1 B-1 1 B-2 1 B-2 1 B-4 1 B-4 1 B-3 丨b-1 1 B-2 Ib-2 Β-2 丨B-4 丨B-2 1 B-4 1 ffl 1 P3 Β-3 B-3 B- 4 1 (A) Polymer € 11⁄2] S 〇 00 1 〇: 1 1 g· 〇1 s Ο 1 E 〇, 丨 brick CS 1 5: /-S ο 1 /-·Ν 沄1 g* 1 〇in fH 1 1 1 s cs 1 委 S' T s jo 1 g TK 00 1 5: O cs 1 S' cn I α: ο 1 § 1 s § 1 s 1 S' 1 1 T 沄&amp;S 1 T s 1 ίη 1 s Τ ί〇1 κ, s 1 1 r? 1 沄 VO 1 P: 1 embodiment 21 I embodiment 22 1 embodiment 23 1 丨 embodiment 24 1 embodiment 25 embodiment 26 embodiment 27 Example 28 Example 29 Example 30 Example 31 Example 32 Example 33 Example 34 Example 35 Example 36 Example 37 Example 38 Example 39 Example 40 - 6ς_ 201022330 ο Voltage iF m 99.6 98.9 99.1 99.3 99.5 97.8 96.9 95.7 98.1 98.4 97.1 965 98.1 98.3 98.2 98.1 Vertical alignment fi 89.0 89.3 89.5 89.7 89.8 85.3 86.6 83.4 85.5 87.8 87.5 86.4 85.7 87.2 88.6 On 印刷 Printability I Good _1 Good good Good I Good very good Very good Unqualified I Good very good Very good Unqualified Very good 11⁄2 ρπ The appearance of the solution is no turbid, transparent, no turbid, transparent No turbid, transparent, no turbidity, transparent, no turbidity, transparent, no turbidity, transparent, no turbidity, transparent, no turbidity, transparent, no turbidity, transparent, no turbidity, transparent, no turbidity, transparent, no turbidity, transparent, no turbidity, transparent, no turbidity, transparent, i_ Γ No turbidity, transparent, no turbidity, transparent &lt;π m 嫲mu parts by weight Ο in 〇〇〇〇&lt;Ti 〇〇〇骚«Imil P (Ν 1 υ (Ν 1 ο cs 1 υ CN 1 U CN 1 〇 1 u &lt;N 1 u (N 1 〇1 U 1 U CN 1 1 α CN 1 〇1 U 1 U 1 U Pine 4π Λ3 parts by weight &lt;Ν (N wo 〇ο ο 〇 〇〇ο 〇ο ο 〇&gt;- m &lt;&lt;mi1 P Β-2 Β-5 Β-5 B-5 B-5 II 1 1 1 1 I 1 1 I 1 (Α) polymer € iW dmij Ψπη^ PI - 9(50)/ΡΑ-2(50) ΡΑ-3 m 1 PA-3 PA-3 PI-1(100) PI-1(100) PI-4(100) PI-5(100) PI-13(100) PI-1(50)/PA-1(50) PI-1(50)/PA-2(50) PI-1(50)/PI-4(50) PI-1(50 /PI-4(50) PI-13(20)/PA-1(80) PA-3 Example 41 Example 42 Example 43 Example 44 Example 45 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 -09- 201022330 In addition, the abbreviations of the compound (B) and the epoxy group (C) in Table 2 are as follows. meaning. &lt;(B) Compound&gt; B-1: N-(2-hydroxy-3-n-octyloxybenzylideneoxy)propyl-oxime synthesized in the above Synthesis Example B1, Ν', Ν'-three Glycidyl-m-xylylenediamine and N-(3-hydroxy-2-n-octyloxybenzylideneoxy)propyl-N,N',N'-triglycidyl-m-xylylenediamine Mixture B-2: N-(2-hydroxy-3-n-dodecane Φ oxybenzylideneoxy)propyl-n,n',n'-triglycidyl synthesized in the above Synthesis Example B2 - m-xylylenediamine and N-(3-hydroxy-2-n-dodecyloxybenzylideneoxy)propyl-N,N,,N,-triglycidyl-m-xylylenediamine Mixture B-3: N-(2-hydroxy-3-n-dodecyloxybenzhydryloxy)propyl group synthesized in the above Synthesis Example B3 as a guana, &gt;^'-triglycidyl-4 , 4'-Diaminodiphenylmethane and N-(3-hydroxy-2-n-dodecyloxybenzylideneoxy)propyl-:^,1^',;^'-triglycidyl Mixture of benzyl-4,4'-diaminodiphenylmethane B-4: N-(2-hydroxy-3-trifluoromethylhydrapropoxybenzyl methoxycarbonyl) synthesized in the above Synthesis Example B4 propyl-N,N',N'-triglycidyl- a mixture of xylylenediamine and N-(3-hydroxy-2-trifluoromethylpropoxybenzylideneoxy)propyl-N,N',N'-triglycidyl-m-xylylenediamine B-5: a mixture of the compound (B-3-2-1-1) synthesized in the above Synthesis Example B5 and the compound (B-3-2-1-2) B-6: a compound synthesized in the above Synthesis Example B6 ( B—3—2— 2— 1) Mixture with Compound (B - 3 - 2 - 2-2) &lt;(C) Epoxy Compound&gt;〇-1:&gt;1,1^,1^,&gt;1'-tetraglycidyl-4,4,diaminodiphenylmethyl-61- 201022330 Institute C-2: Ν,Ν,Ν',Ν'-tetraglycidyl-m-xylylenediamine The above (A) polymer is supplied to the liquid crystal alignment agent in the form of a polymer solution prepared in the above Synthesis Example, and the amounts (parts by weight) in Table 2 are converted into the polymer contained in the used solution. value. In Examples 26 to 41 and Comparative Examples 6 to 10, two polymers were used as the (A) polymer, respectively. The above (A) polymer and (B) compound are respectively supplied to a liquid crystal alignment agent in the form of a solution synthesized in the above synthesis example, and the amounts (% by weight) in Table 2 are all converted into the solution used. The amount of (A) polymer or (B) compound is 値. [Simple description of the map]

Arrt. No 0 [Description of main component symbols] None.

-62-

Claims (1)

201022330 VII. Patent application scope: 液晶. A liquid crystal alignment agent characterized by containing (A) at least one polymer selected from the group consisting of polyamic acid and polyimine, and (B) having an epoxy a compound of the group represented by the formula (2°): Rx-f Z^R11 )n1 ^H-^HCHz^^COOH (2°) (In the formula (2°), R1 is a carbon atom Is an alkyl group of 4 to 40 or a fluoroalkyl group having 4 to 40 carbon atoms, or a hydrocarbon group having a carbon atom number of 17 to 51 having a steroid skeleton; Z1 is a single bond, *-0·, * -C00- or *-〇CO· (wherein the bond with "is located on the R1 side", R11 is a cyclohexyl group or a phenyl group, and nl is 1 or 2, wherein when nl is 2, two R11 can be mutually The same or different, n2 is 0 or 1; ❹ Z11 is *-0-, *-C00- or *-0 (:0- (where the connection key is on the V side), n3 is 0~2 2. The liquid crystal alignment agent of claim 1, wherein the compound (b) is a compound 1 molar having (b) having 2 to 8 epoxy groups. B2) The compound 1~(n-1) represented by the following formula (2) Compound prepared 'above wherein compound η (BL) of the number of epoxy groups possessed, Section -63- .201022330 ⑽11⑽ gestures (2) The compound (In the formula (2), R1, Rli, z1, ζπ, nl, n2, n3 and n4 are respectively the same as defined in the above formula (2°)) 3. The liquid crystal alignment agent of the second aspect of the patent application 'where ( B) the compound is at least one selected from the group consisting of compounds represented by the following formulas (B-1) to (B-4) yN—(CHz), (Β-3) X\ ΧΠΙ (CH2)a (Β-4) (In the above formula, hydrazine is a single bond, a methylene group, an alkylene group having 2 to 12 carbon atoms, -0-, -COO--0-(CH2)g-0-'-S--oco- 'S 0 2 - •NHC〇-, -CONH-, -CO- ' -C(CH small-, -C(C2H〇2- or -C(CF3)2_' where the above integers of S舄1~12, When a plurality of B are present, each of the plurality of B may be phased or different; and r is each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a fluorine-based group having 1 to 4 carbon atoms; a are each independently 〇 or 1; b are each independently an integer of 〇~3; c are each independently an integer of 〇~4; (1 is an integer of 〇~5; and e are each independently an integer of 〇10 ; [An integer of 0 to 11; X1 is a condensed -64-.201022330 hydroglyceryl group; X11 is a group represented by the following formula (3-1) or (3-2) '-〒 H-CH2-OH ( 3-1) 咐7 11 (4) Ratio (10) Yiguang Buyi CH20H (3-2) (in equations (3-1) and (3-2), R1, Rn, Z1, Z11, nl, n2, n3 and N4 is the same as defined in the above formula (2), respectively; and ΧΙΠ and XIV are each independently a glycidyl group or a group represented by the above formula (3 - 1) or (3 - a 2). The liquid crystal alignment agent according to any one of claims 1 to 3, which further contains an epoxy compound other than the compound (B). 5. The liquid crystal alignment agent of claim 1, wherein (B) The use ratio of the compound is 0.01 to 40 parts by weight with respect to 100 parts by weight of the (A) polymer. 6. A liquid crystal display element characterized by having any one of items 1 to 5 of the patent application scope. a liquid crystal alignment film formed of a liquid crystal alignment agent. The compound [b] is characterized in that (bl) a compound 1 molar having 2 to 8 epoxy groups and (b2) represented by the above formula (2) a compound obtained by a molar reaction of a compound 1 to (n-1), wherein η is the number of epoxy groups of the above compound (bl). -65- 201022330 IV. Designated representative figure: (1) Designation of the case The representative picture is: None. (2) The symbol of the symbol of this representative figure is simple: Μ. 5. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: (B-3-2-2-1)