TWI299057B - Agent for orienting liquid crystal - Google Patents

Description

1299057 Α7 Β7 V. INSTRUCTIONS (1) TECHNICAL FIELD (Please read the precautions on the back and fill out this page.) The present invention relates to a liquid crystal aligning agent. More specifically, it is a liquid crystal aligning agent which is particularly suitable for vertical alignment of a liquid crystal display element for a vertical alignment type, which is excellent in voltage retention characteristics, low afterimage resistance and printability. First, the Ministry of Technology and Economy, the Intellectual Property Bureau, the employee consumption cooperative, printed on the liquid crystal display device. The liquid crystal display element is known to form a liquid crystal alignment film formed on the surface of a substrate provided with a transparent conductive film, such as polylysine or polyimine. The substrate for a device has two sheets facing each other, and a nematic liquid crystal layer having positive dielectric anisotropy is formed in the gap as a unit of the sandwich structure, and the long axis of the liquid crystal molecules is continuously twisted from one substrate to the other substrate. 90 degrees Celsius, a TN type liquid crystal display element having a so-called TN (twisted nematic) type liquid crystal cell. Further, there is a development of a S T N (super twisted nematic) type liquid crystal display element having a lower cost than a T N type liquid crystal display element, and a vertical alignment type liquid crystal display element. The STN type liquid crystal display element is used for mixing a nematic liquid crystal, and the optically active substance is used as a liquid crystal. The birefringence is generated by a continuous twist state in which the long axis of the liquid crystal molecules is 180 degrees or more between the substrates. effect. On the other hand, the vertical alignment type liquid crystal display element is, for example, a liquid crystal molecule whose dielectric anisotropy is negative, and the liquid crystal is vertically oriented, and the application of a voltage causes the liquid crystal molecules to lie horizontally, having a viewing angle, contrast, and no flat grinding, and the like. Come to be active. A high pretilt angle is required for vertical orientation, and for this purpose, the orientation agent must contain a large amount of ingredients to exhibit the pretilt angle. Pre-tilt exhibiting components usually use aliphatic, alicyclic, and fluorine-based functional groups. ^Paper scale applies to Chinese national standard (€奶) 八4 specification (210/297 mm) 771 ' 1299057 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing Β7 Β7 5, invention description (2) However, there is. The inclination angle exhibits problems such as aggregation and crystallization between components, which deteriorates printability. Therefore, a vertical orientation agent which is excellent in printability, vertical orientation, low afterimage resistance, and excellent voltage retention characteristics needs to be developed. DISCLOSURE OF THE INVENTION Accordingly, an object of the present invention is to provide a liquid crystal aligning agent which is excellent in printability, defoaming property, vertical orientation, low afterimage refraction and voltage retention characteristics, and other objects and advantages of the present invention. It can be known from the following description. Means for Solving the Problems According to the present invention, the above objects and advantages are first characterized by having (A) the following formula (1)

Here, R 1 is a halogen atom, an alkyl group having 1 to 1 Å carbon atom or a fluorinated alkyl group having 1 to 10 carbon atoms, and a is an integer of 0 to 4, and the tetracarboxylic dianhydride is shown. (hereinafter also referred to as "specific tetracarboxylic dianhydride") and the non-paper scale applicable to the Chinese National Standard (CNS) A4 specification (2i〇x297 mm) (please read the notes on the back and fill out this page)

1299057 A7 B7 V. Description of invention (3) (B) (2)

(2) »· The Intellectual Property Office of the Ministry of Economic Affairs, the employee consumption cooperative, printed here, X is a divalent organic group, and R 2 is a monovalent organic group having an alicyclic backbone with 4 to 40 carbon atoms, as shown. A liquid crystal aligning agent of at least one of a polyamine acid produced by a reaction of a diamine (hereinafter also referred to as "specific diamine") and a ruthenium iodide polymer produced by dehydration ring closure of the polyglycolic acid is obtained. The liquid crystal aligning agent of the present invention is preferably a composition comprising 20 to 60% by weight of 1-methyl-2-pyrrolidone and 80 to 40% by weight of a solvent having a surface tension of 3 2 dynes/cm or less. The solvent acts as a solvent. BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. [Polyuric acid] The polylysine used in the present invention is obtained by subjecting a specific tetracarboxylic dianhydride represented by the above formula (1) to ring-opening polyaddition of a specific diamine represented by the above formula (2). . Further, the ruthenium iodide polymer used in the present invention is obtained by dehydrating and ring-closing the above polyamic acid. (Please read the note on the back and fill out this page), ιτ This paper scale applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1299057 A7 B7 V. Invention description (4) [Tetracarboxylic dianhydride The liquid crystal aligning agent of the present invention has low afterimage properties and excellent voltage holding characteristics by using the specific tetracarboxylic dianhydride represented by the above formula (1). In the above formula (1), R1 may, for example, be a halogen atom such as 'Br or the like; an alkyl group having 1 to 1 ring of a carbon atom such as a methyl group, an ethyl group or a n-propyl 'isopropyl group; or a carbon atom such as a trifluoromethyl group; 1 to 1 fluorinated alkyl group and the like. However, the 3 series 〇 to an integer of 4. Specific examples of the specific tetracarboxylic dianhydride include 1 ' 2 ' 3 ' 4 -cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3 '4-cyclobutanetetracarboxylic dianhydride 1,1,3-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-cyclobutane tetracarboxylic dianhydride, and the like. Among them, 1, 2 ′ 3 , 4 ring butyl tetracarboxylic dianhydride, and 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride are preferred. The above polylysine may also act on other tetracarboxylic dianhydrides to the extent that the effects of the present invention are not impaired. Other tetracarboxylic dianhydrides include, for example, 'butane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride' 1, 2,3,4,5-cyclohexane tetra Carboxylic dianhydride, 3,3,,4,4 / dicyclohexyltetracarboxylic dianhydride, cis- 3,7-dibutylcyclooctane-1,5-diene-1,2,5,6 —tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarbonyl-2 residue-norbornane-2:3,,5:6-dianhydride , 2, 3, 4 This paper scale applies to China National Standard (CNS) A4 specification (21〇Χ297 mm) ' (Please read the note on the back and fill out this page) 4.

Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives, Printing 1299057, Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives, Printing A7 B7 V. Inventions (5), 5 - Tetrahydrofurancarboxylic dianhydride, 1, 3, 3 a, 4, 5 9b - hexachloro-5-(tetrachloro-2,5-oxy-3-pyranyl)-naphthalene[1,2-c]-purine 1,3-dione, 1, 3, 3a, 4 , 5 , 9b - hexaamine - 5 - methyl - 5 - (tetraamyl - 2 , 5 - > oxygen - 3 - 11 - fluoranyl) - a Cai [1, 2 - c] - 13 Fuan 1 , 3-dione, 1, 3, 3 a, 4, 5, 9b - hexahydro-5-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1, 2 —c]—咲 ——1,3—dione, 1, 3, 3a, 4, 5, 9 b —hexachloro-7-methyl-5—(tetraamyl-1,5--oxygen 3-furanyl)-naphthalene [1,2-c]-furan-1,3-dione, 1 ,3 ,3a ,4 ,5 ,9b —hexahydro-7-ethyl-5 —(tetrahydro- 2,5-Dioxy-3-furyl-[1,2-c]-furan-1,3--^嗣,1,3,3a 4,5,9b—hexachloro-8-methyl-5-(tetrachloro-2,5-dioxy-3-pyranyl)=naphthalene [1,2—c]-pyranyl-1,3 — Diketone, 1, 3, 3a, 4, 5, 9b - hexahydro-8-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-c] —furan—1,3—biquinone, 1, 3, 3a, 4, 5, 9b—hexachloro-5,8-monomethyl-5—(tetrachloro-2,5—oxygen-3) π南基)-naphthalene [1,2-c]-furan-1,3-dione, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1 —Dicarboxylic dianhydride, bicyclo[2 · 2 · 2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, the following compounds of formula (3) and (4) Family and alicyclic tetracarboxylic dianhydride; This paper scale applies to Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the notes on the back and fill out this page)

1299057 A7 B7 V. INSTRUCTIONS (6) Ο Π

(3)

(4) (Please read the precautions on the back and fill out this page). (In the formula, R3 and R5 show a divalent organic group with an aromatic ring, R4 and R6 represent a hydrogen atom or an alkyl group, and most of the R4 and R6 may exist. Same or different.) Pyromellitic dianhydride, 3,4, benzophenone tetracarboxylic dianhydride, 3,3 /, 4,4 / biphenyl hydride tetracarboxylic dianhydride, 1, 3 , 4,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 /,4,4 /diphenyl ether tetracarboxylic dianhydride, 3, 3 / , 4,4 / - dimethyldiphenyl decane tetracarboxylic dianhydride, 3, 3 / , 4, 4 / - tetraphenyl decane tetracarboxylic dianhydride, 1, 2, 3, 4 - furan tetracarboxylic acid Acid dianhydride, 4,4 / bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4 >-bis(3,4-dicarboxyphenoxy)diphenyl Resin, 4,4〃-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3 /,4,4/-perfluoroisopropenyldicarbonate dianhydride, 3,4,4/-diphenyltetracarboxylic acid, 11 Ministry of Economic Affairs, Intellectual Property Office, employee consumption cooperative, printed paper scale applicable to China Household Standard (CNS) A4 Specification (210X297 mm) -9- dianhydride, p-phenylene-bis(triphenyl(triphenylphosphonate) dianhydride, bis(phenylene ether dianhydride, bis(triphenylphosphonium) Acid 1299057 A7 __^B7 V. Description of invention (7) dianhydride, bis(decanoic acid) phenylphosphineoxy phthalic acid) dianhydride, o-phenyl bis-triphenyl decanoic acid) ~4,4 / 1-2) 4,4~diphenyl ether dianhydride, bis(triphenylphosphonic acid)-4,4/diphenylmethane dianhydride, ethylene glycol-double (dehydrated triphenyl hexaformate) propylene glycol One pair (dehydrated triphenyl hexaformate), 1,4-butanediol-double (anhydrous dibenzoate), 1,6-hexanediol-double (anhydro-dihexacarboxylate)' 1 ,8 - octanediol-double (dehydrated triphenyl hexaformate), 2,2~bis(4-hydroxyphenyl)propane-double (anhydrotriphenyl hexaformate), the following formula (5) to (8) An aromatic tetracarboxylic dianhydride such as a compound. These may be used alone or in combination of two or more. (Please read the notes on the back and fill out this page)

Order 1299057 A7 B7 V. Description of invention (8)

(Please read the notes on the back and fill out this page.) The Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, printed these, butane tetracarboxylic dianhydride, 1, 2, 3, 4-cyclopentane tetracarboxylic dianhydride , 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-1,3-dicyclohexane-1,2-dicarboxylic dianhydride , cis- 3,7-dibutylcyclooctane-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 3,5,6-tricarbonyl-2-carboxynorbornane A 2:3,5:6-dianhydride, 1,3,3a,4,5,9b—six gas—5—(four gas—2,5-dioxo-3—anthranyl)—Cai [1 , 2 — c] 咲 — — 1, 3 — 2, 2, 3, 3a, 4, 5, 9b — hexahydro-8 — methyl — 5 — (tetrahydro-2,5-dioxy- 3 — D. fluorenyl)-naphthalene [1,2-c]furan-1,3-dione, 1, 3,3 a, 4, this paper scale applies to Chinese National Standard (CNS) A4 specification (210X297 mm) - 11 - 1299057 A7 ___B7_ V. Description of invention (9) 5 , 9 b - hexahydro-8 - methyl one 5 - ( Tetrahydro-2,5-dioxy-3-furanyl-naphthalene[1,2-c]furan-1,3-dione, bicyclo[2 · 2 · 2]-octyl-7-ene-2 3,5,6 —tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 / ,4,4<-benzophenone tetracarboxylic dianhydride, 3,3 /,4 / diphenyl a tetracarboxylic dianhydride, a 1,4,5,8-naphthalenetetracarboxylic dianhydride, a compound represented by the following formula (9) to (1 1 ) in the compound of the above formula (3), and the above formula (4) The compound represented by the following formula (1 2 ) in the above-mentioned compound is preferred because it exhibits good liquid crystal orientation, and particularly preferred is 1,2,3,4-cyclobutane IV. Carboxylic dianhydride, 1,3,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a ,4,5,9b—hexahydro-5-(tetrahydro-2,5-oxy-3-pyranyl)-naphthalene[1,2-c]furan-1,3-dione, double-3 ,7-dibutylcyclooctane-1,5-di-storage-1,2,5,6-tetraresidic acid dianhydride, 3,5,6-tricarbonyl-2-carboxylate Alkane-2: 3,5:6-dianhydride, 1, 3, 3a, 4' 5 , 9b - hexahydro-8-methyl-5-(tetrahydro-2,5-dioxy-3-furanyl a naphthalene [1,2 -c]furan-1,3-dione, pyromellitic dianhydride and a compound represented by the following formula (9). This paper scales the financial standard (CNS) A4 specification (210X297 mm) (please read the note on the back and fill out this page), 11 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 1299057 V. Invention description (10 ) A7 B7

1299057 A7 B7 V. INSTRUCTIONS (11) Compounds with a phenylenediamine structure. The alicyclic backbone having 4 to 40 carbon atoms may, for example, be an alicyclic backbone derived from cycloalkane such as cyclobutane, cyclopentane, cyclohexane or cyclodecane; a steroid of cholesterol, cholesteryl or the like The backbone; the norbornene backbone, the rutile backbone, etc., among which the Yi backbone is preferred. Further, the organic group having an alicyclic backbone represented by R 2 in the above formula (2) may be a hydrocarbon halogen atom-substituted one. Further, in the above formula (2), the divalent organic group represented by X may be exemplified by one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one Methyl, suspicion, phenyl and the like. Among these, the 'excellent ones' are one-on-one, one C, one, one, one, and one. Specific examples of the specific diamine include compounds represented by the formulae (13) to (18). Printed by the Consumers' Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs (please read the notes on the back and fill out this page)

Appropriate standard country i use appropriate ▲ ruler piece paper I PCT 7 9 2 1299057 A7 B7 V. Invention description (12)

zCH3, CH3 (16) (18) (Please read the notes on the back and fill out this page)

Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumers' Cooperatives. In the synthesis of the above polyamic acid, other diamine compounds may be used to the extent that the effects of the present invention are not impaired. Other diamine compounds may, for example, be p-phenylenediamine, o-phenylenediamine, 4,4/diaminodiphenylmethane, 4,4/diaminodiphenylethane, 4,4/1 Diaminodiphenyl sulfide, 4,4 / diaminobiphenyl, 3,3 '-dimethyl-4,4 This paper scale applies to China National Standard (CNS) ΜSpecifications (210X297 public ^ _ 15 A 1299057 A7 B7 V. INSTRUCTIONS (13) ——Diaminobiphenyl, 4,4/diaminophenylbenzophenidine, 4,4/diaminodiphenyl ether, 1,5-diamine Naphthyl, 3,3-dimethyl (please read the notes on the back and fill out this page) —4,4 / —diaminobiphenyl, 5-amino- 1 — ( 4 — monoaminophenyl ) 2,3,3-trimethylindan, 6-amino-1-(4-aminophenyl)-1,3,3-trimethylindan, 3,4/-diaminodi Phenyl ether, 3,3 / -diaminobenzophenone, 3,4 / -diaminobenzophenone, 4,4 / -diaminobenzophenone, 2,2-double [4 Aminophenoxy]phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2, 2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl], 1,4-bis[4-aminophenoxy Benzene, 1,3, bis(4-aminophenoxy)benzene, 1,3 -bis(3-aminophenoxy)benzene, 9, 9-bis(4-aminophenyl)-10 -hydroquinone, 2,7-diaminopurine, 9,9-bis(4-aminophenyl)anthracene, 4, 4>-methyl-bis(2-chloroaniline), 2,2/, 5,5<-tetrahydro-4,4,-diaminobiphenyl, 2,2·-dichloro-4,4-diamino- 5,5-dimethoxybiphenyl, 3,3 — — Ministry of Economic Affairs, Intellectual Property Officer, X Consumer Cooperative, Printing and Extrusion 2 Benzene Fluorylation,} Trimethylaniline {Fluorophene Benzene Oxygenate, Diphenyl II } I \)/ Base ' 2 1—One V Base A2 | οα 4 propyl m, yl { , exo 3 2 amine to 4 iso | II } , phenyl 2 yl 4 9 phenyl I amine c 1 联 { yl 2 t C yl 1 amine I diamine ' -, I under 2 4 4 4 ' , | , C , 4 benzene ; -4-4 hydrazine 4 , 4 , 4 fluorodi , amine aceane , octa 4 benzoic propyl D aryl I double I fluorinated Base} 'Six} Oxygen isotherm 2 D-based benzene-propyl, ketone} The paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) -16 - 1299057 A7 B7 V. Description of invention ( 14) CH3

CH3 CH3 (19) CH3

CH3 CH3 (20) (Please read the note on the back and fill out this page.) Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, printed 1,1 - meta-xylene diamine, 1,3-dipropylenediamine, tetramethyl Diamine, pentamethylamine, hexamethylenediamine, heptamethylamine, octamethylamine, hexamethylenediamine, 4,4 bisaminosolemethyl Amine, 1,4-diaminocyclohexyl ring, isophorone diamine, tetrahydrodicyclopentadiene diamine, hexahydro-4,7-tetra bridge indanone di-methyldiamine, tricyclic [6 · 2 · 1 · 02, 7] an extended eleven dimethyldiamine, 4 4 / a methyl (cyclohexyl) and other aliphatic and alicyclic diamines; 2,3-diaminopyridine, 3,4-diaminopyridine, 2,4 This paper scale applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -17^ 1299057 A7 B7 V. Description of invention (15) Aminopyrimidine, 5,6 — Diamino- 2,3-dicyano 6-diamino- 2,4-dihydroxypyrimidine, 2,4-ylamino- 1 '3,5-three tillage, 1,4-amino group 6-isopropoxy 6-dimethylaminopropyl ) pipetidine pyridinium, diamine bis 5 5 - morphine, 4 - diamino ethoxylated s three tillage, 2 2, 4 -1, 1, 3 - three tillage, 2,4 one, 4 - two Amino-, 5-tris- 2, 4-monoamino- 6-phenyl-1 6 methyl-s-triazine; 4,6-diamine 6-diaminopurine, 5'-6-diamine-two Amino-phenylthiazole, 2 - 2 5 -1 2 -amino 2-ethoxy acyl lactate * Aminyl fluorene phenanthrene 1 , 4 - fluorene, formula (with 2 -amino group double (4-Aminophenyl)aniline and the lower compound, the diamine of the intramolecular atom; the base 5-yl-l 4-triazole, 6,8 ~ 3-dimethyl urine (please read the back of the note first) Please fill out this page again) 3,62 2) and the diamino-amino-diamine group, (2 3 amino group with 9-dihexa-benzopyridinium,) Printed by employee consumption cooperatives

H2N (22) (wherein R 7 is a one-valent organic group containing a cyclic structure selected from the group consisting of pyridinium and nitrogen atoms, and X is a divalent organic _ This paper scale applies to Chinese national standards (CNS) A4 size (210X297 mm) 1299057 A7 B7 V. Description of invention (16) H2N—^

r* Ο- ΝΗ2 (23) (wherein R represents a divalent organic group having a cyclic structure selected from a nitrogen atom selected from the group consisting of pyridine, pyrimidine, tri-till, piperidine and piperazine, and X represents a divalent organic group, Most of the existing Xs may be the same or different.) The diamine-based organic decazins of the following formula (2 4 ); printed by the Intellectual Property Office of the Ministry of Economic Affairs

(Please read the notes on the back and fill out this page.) Clothing. Order

This paper scale applies to Chinese National Standard (CNS) Α4 specification (210X297 mm) -19 - Ϊ299057 phenylene 4 benzene 2 3 amine) 2 Description of invention (17) 7~Diamino hydrazine, 4, Aminophenoxy oxime, 2, alkane, 2, 4 4-(4-month-female-phenyl)yl]hexafluoropropanediamine-diphenyl ether, 2,2-yl)phenyl]propane, 9,9-double 2-double 4 one (4 -amine 2 -bis(4-aminophenyl)diphenylamine, 1 ~ month female, 4 '4 a stretch of ~aminophenoxy" above formula (5), (2'4-diamino B, the compound shown in the above table 8)) benzene, 1 9 ) to 6) of the pyridine, the formula (2 and the above compound. Isopropyl propylene double 4, 4 (21 combination 2,4 2 ) a compound of the formula (2 (cyclohexylamine), 1 phenylphenoxy) hexafluoro, 4 -, 4 -1 (4-aminophenoxy), the above, 2, 6 - The diaminopyridyldiamine group represents a compound of 3), and the compound of the formula is the following formula (the next bis(4-yl)propane cyclohexyl( ) complex (pyridine, 2 7 formula) ((Please read the notes on the back and fill out this page again) Order - COO —CH2CH2

The Ministry of Intellectual Property of the Ministry of Light, Ministry of Commerce, and the Consumer Cooperatives printed the ratio of the specific diamine in the total diamine component of all the polymers contained in the liquid crystal aligning agent of the present invention, at 10% by mole relative to the total amount of the diamine component. The above is better, and more than 20% by mole is more preferable. When the ratio is less than 1 莫 mole %, sufficient vertical orientation may not be obtained. This paper scale is applicable to China National Standard (CNS) A4 specification (210X297 mm) · 20-1259057 A7 B7 V. Description of invention (18) [Synthesis of polyaminic acid] Tetracarboxylic acid for the synthesis of polylysine The ratio of the dianhydride and the diamine to be used is 1 equivalent of the amine group of the diamine, and the anhydride group of the tetracarboxylic dianhydride is preferably 〇 2 to 2 equivalents, and the ratio of 0 to 3 to 1.2 equivalents. The ratio is better. The synthesis reaction of polylysine is preferably carried out in an organic solvent at a temperature of from 20 ° C to 150 ° C, preferably from 0 to 100 °. Here, the organic solvent is only required to be capable of dissolving the polyamic acid, and is not particularly limited, and examples thereof include, for example, 1-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethyl group. An aprotic polar solvent such as guanamine, dimethyl sulfoxide, butyrolactone, tetramethyl urea 'hexamethylphosphonium triamine, etc.; a phenolic solvent such as m-cresol, xylenol, phenol or halogenated phenol. Further, the amount of the organic solvent used (α) is usually such that the total amount (/3) of the tetracarboxylic dianhydride and the diamine compound is, relative to the total amount of the reaction solution (α + /3 ), at 0 · 1 It is preferably up to 30% by weight. Further, in the above organic solvent, a weak solvent alcohol of poly-proline, a ketone, an ester, an ether, a halogenated hydrocarbon, a hydrocarbon or the like may be used insofar as the produced polyamine does not precipitate. Specific examples of such weak solvents include methanol, ethanol, isopropanol, cyclohexanol, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol, propylene glycol, 1,4-butanediol, and the like. Ethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxy Propionate, ethyl ethoxy propionate, diethyl oxalate, diethyl malonate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ether (please read the back first) Note: Please fill out this page)

Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumer Cooperatives, Printed Paper Scale Applicable to China National Standard (CNS) Α4 Specification (210X297 mm) -21 - 1299057 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed A7 _ B7 V. Invention Description (19 'Ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene Alcohol monoethyl acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorinated benzene, o-dichlorobenzene, hexane, heptane, Octane, benzene, toluene, xylene, and the like. As described above, a reaction solution in which polylysine is dissolved can be obtained. Then, the reaction solution is poured into a large amount of a weak solvent to obtain a precipitate, and the precipitate is dried under reduced pressure to obtain a polyamic acid. Further, the polyamic acid is dissolved again in an organic solvent and then precipitated as a weak solvent. The polyamine acid can be purified after one or several times of these steps. [Synthesis of ruthenium iodide polymer] The ruthenium iodide polymer constituting the liquid crystal aligning agent of the present invention can be synthesized by dehydration ring closure of the above polyglycolic acid. The dehydration ring of polylysine can be used, (i) heating the poly-proline, or (ii) dissolving the poly-proline in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution, and It is carried out by heating if necessary. Further, the ruthenium iodide polymer used in the present invention may further contain a partial dehydration ring closure, and the ruthenium imidization ratio (the ratio of the repeating unit forming the quinone ring in all repeating units of the polymer expressed by %) Less than 100% of the imidized polymer. In the above method (1), the method of heating the poly-proline is carried out, and the reaction temperature is applied to the Chinese national standard (mouth ~ 5) eight 4 specifications (210 parent 297 mm) -22 - (please read the back note first) Please fill out this page again.

1299057 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A7 B7 5, invention description (20) is usually at 50 to 200 °C, preferably 60 to 170 °C. When the reaction temperature is less than 50 °C, the dehydration ring-closure reaction may not proceed sufficiently. If the reaction temperature exceeds 200 °C, the molecular weight of the obtained polyamic acid (B) may be lowered. On the other hand, in the above method (i i ) in which a dehydrating agent and a dehydration ring-closing catalyst are added to the polyaminic acid solution, an acid anhydride such as 'acetic anhydride' propionic anhydride or trifluoroacetic anhydride can be used. The amount of the dehydrating agent' depends on the desired imidization ratio, and is usually in the range of from 0.01 to 20 moles per mole of the repeating unit of the poly-proline. Further, the dehydration ring-closing catalyst can be, for example, a tertiary amine such as pyridine, collidine, lutidine or triethylamine. However, it is not limited to this. The amount of the dehydration ring-closing catalyst is preferably from 0. 01 to 10 m with respect to 1 mol of the dehydrating agent used. The rate of hydrazine imidation can be increased with the increase of dehydrating agent and dehydration ring-closing agent. From the viewpoint of printability, the ruthenium imidation ratio is preferably 70% or less. Further, the organic solvent used for the dehydration ring-closing reaction can be exemplified as an organic solvent used for the synthesis of poly-proline. The reaction temperature of the dehydration ring closure is usually from 0 to 180 ° C, preferably from 10 to 150 t. Further, for the reaction solution thus obtained, the ruthenium iodide polymer can be purified by the same method as the purification of polylysine. [End-Modified Polymer] Poly-proline and quinone-imidized polymers may also be end-modified with a molecular weight adjusted. By the use of the terminal-modified polymer, the coating properties and the like of the liquid crystal aligning agent can be improved without impairing the effects of the present invention. This type of end repair 1 paper size is applicable to China National Standard (CNS) A4 specification (210X 297 mm) -23: (Please read the note on the back and fill out this page)

1299057 Α7 Β7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (21) The formula can be synthesized in the reaction system by adding monoanhydride, monoamine compound, monoisocyanate compound, etc. in the synthesis of poly-proline. Here, the monoanhydride may, for example, be maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl succinic anhydride or the like. Further, the monoamine compound may, for example, be aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-undecylamine, and positive ten II compound amine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecane, n-heptadecaneamine, n-octadecylamine, n-icosylamine, and the like. Further, examples of the monoisocyanate compound include phenyl isocyanate, naphthyl isocyanate, and the like (logarithmic viscosity of the polymer). The polyglycolic acid and the quinone imidized polymer obtained as described above have a logarithmic viscosity (7?ln). The lanthanide is preferably 0. 05 to 10 com/g, and more preferably 0.05 to 5 com/g. The logarithmic viscosity (7? ln) in the present invention is determined by using N-methyl-2-pyrrolidone as a solvent for a solution having a concentration of 0 · 5 g / 1 〇〇 ml at 30 ° C for viscosity measurement. It is obtained according to the following formula (i). Ln_ 1 η (solution flow time / solvent flow time) "7^ compound weight concentration) ") [liquid crystal aligning agent] The liquid crystal aligning agent of the present invention is usually dissolved in an organic solvent to contain the paper scale. China National Standard (CNS) Α4 Specifications (210X297 mm) -24 - (Please read the notes on the back and fill out this page)

1299057 A7 B7 Printed by the Ministry of Economic Affairs, Intellectual Property Office, Staff and Consumer Cooperatives. V. Inventive Note (22) The above polylysine and/or ruthenium imidized polymer. The temperature at which the liquid crystal director of the present invention is prepared is usually from 0 ° C to 200 t: and preferably from 20 ° C to 60 ° C. The organic solvent constituting the liquid crystal aligning agent of the present invention can be exemplified as a solvent for a synthetic reactant of polyglycine. Further, a weak solvent which can be used for the synthesis reaction of poly-proline is also suitably selected. Among these, a solvent having a monomethyl-2-pyrrolidone and a surface tension of 3 2 dynes/cm or less is preferred. The solvent having a surface tension of 3 2 dynes/cm or less may, for example, be 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy group. Propionate, ethyl ethoxy propionate, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve), ethylene Alcohol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate Ester, diethylene glycol monoethyl ether acetate, and the like. 1 The ratio of monomethyl-2-pyrrolidone to a solvent having a surface tension of 3 2 dynes/cm or less is 20 to 60% by weight of 1-methyl-2-pyrrolidone, and the surface tension is 3 2 dyne. The solvent of /min or less is preferably 80 to 40% by weight. When the ratio is out of the range, the polymer precipitates and the leveling property is insufficient, so that the printing property is not perfect. The solid content concentration in the liquid crystal aligning agent of the present invention is selected in consideration of viscosity, volatility, etc., and is preferably in the range of 1 to 1% by weight. That is, the liquid crystal aligning agent of the present invention is applied to the surface of the substrate to form a coating film of the liquid crystal alignment film. When the solid content concentration is less than 1% by weight, the coating film is too thin (please read the back of the back sheet and fill in the page) clothes.

, 1T

This paper scale is applicable to China National Standard (CNS) A4 specification (210X297 mm) 1299057 A7 B7 V. Invention description (23) Liquid crystal orientation film is not allowed, and when the solid content concentration exceeds 10% by weight, the coating film is too thick. A good liquid crystal alignment film, and the viscosity of the liquid crystal aligning agent is increased to deteriorate the coating property. The liquid crystal aligning agent of the present invention may contain a functional decane compound or an epoxy compound in order to improve the adhesion to the surface of the substrate within a range not impairing the target physical properties. The functional decane compound may, for example, be 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropane Triethoxy decane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethyl Oxaloxane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-oxopropyltrimethoxydecane, N-ethoxylate Carbonyl-3-aminopropyltriethoxydecane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxydecylpropyltriethylenetriamine, 10-trimethoxydecane Base-1,4,7-trioxane, 10-triethoxydecyl-1,4,7-trioxane, 9-trimethoxydecyl- 3,6-didecyl Acetate, 9-triethoxydecyl- 3,6-dimercaptoacetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-amine Propyl triethoxy oxime, N-phenyl-3 Aminopropyltrimethoxydecane, N-phenyl-3-monoaminopropyltriethoxydecane, N-bis(oxyethylene)-3-aminopropyltrimethoxyphthalate, N-double ( Oxyethylene) 3-aminopropyltriethoxydecane, and the like. Examples of the epoxy group-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and propylene glycol diepoxypropyl ester (please read the back sheet and read this page).

, 1T

Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumer Cooperatives Printed on this paper scale applicable to China National Standard (CNS) A4 specification (210 X 297 mm) -26 - 1299057 A7 B7 V. Description of invention (24) Ether, tripropylene glycol diepoxypropyl Ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol epoxide (please read the back of the note before you fill out this page) Dipropyl ether, 2,2-dibromo neopentyl glycol diepoxypropyl ether ' 1 ' 3 ' 5 '

6 —tetraepoxypropyl-2,4-hexanediol, n,n,NN—tetraepoxypropylm-xylylenediamine, 1,3—bis(N,N-diethylenepropylpropylamino) Methyl)cyclohexane, N,N,tetramethyloxypropyl~4,4/-diaminodiphenylmethane, 3-(N-allyl-N-epoxypropyl)aminopropyl Trimethoxy decane, 3-(N'N-diepoxypropyl)aminopropyltrimethoxy sand or the like. [Liquid Crystal Display Element] The liquid crystal display element 'made by the liquid crystal aligning agent of the present invention can be produced, for example, by the following method. Printed by the Ministry of Economic Affairs, the Intellectual Property Officer X Consumer Cooperative, (1) on the surface of one of the substrates provided with the patterned transparent conductive film, by, for example, roll coating, spin coating, printing, etc. The coated surface is heated to form a coating film. Here, the substrate may be, for example, a glass such as float glass or soda glass; a transparent substrate such as polyethylene terephthalate, polybutylene terephthalate, polyether or polycarbonate; . The transparent conductive film provided on one side of the substrate can be made of tin oxide (S η 〇 2 ) NES Α film (registered trademark of PPG, USA) and indium tin oxide (I n2 〇 3 - Sn 〇 2). I TO film, etc., the patterning of these conductive films can be performed by photolithography or by using a pre-mask. When the liquid crystal aligning agent is applied, the adhesion between the surface of the substrate and the transparent conductive film and the coating film is better, and the surface of the substrate may be pre-coated with the functional sandpaper. The Chinese National Standard (CNS) A4 specification (210X297) is applicable. PCT - -27 - 1299057 A7 B7 V. INSTRUCTIONS (25) (Please read the notes on the back and fill out this page) Alkane compounds, functional titanium compounds, etc. After coating the liquid crystal aligning agent, the heating temperature is 80 to 300 ° C to 120 to 250. (: is preferred. However, the liquid crystal aligning agent of the present invention containing poly-proline is obtained by removing the organic solvent after coating to form a coating film as an oriented film, and then performing dehydration ring closure by heating, thereby further yttrium-imiding Coating film. The thickness of the formed coating film is usually from 0. 001 to 1 micron, preferably from 0. 005 to 〇. 5 micrometers. (2) The coated film surface will be formed to be wound with, for example, nylon, rongrong, cotton. The roller of the fiber cloth is rubbed in a certain direction for flat grinding treatment, whereby the orientation of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film. Further, the liquid crystal alignment film formed by the liquid crystal aligning agent of the present invention, For example, as disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 6-2 2 3 6 6 , which is disclosed in Japanese Laid-Open Patent Publication No. Hei. The method described in 97 P 1 7 5 〃, the method of forming an electrode in the same plane (IPS method), or the liquid crystal alignment film which is subjected to flat grinding as shown in Japanese Patent Laid-Open Publication No. Hei 5-1075 Surface, part of the formation of a resist film, in a different direction from the previous direction After removing the resist film and using the treatment of changing the liquid crystal orientation energy of the liquid crystal alignment film, the visual field characteristics of the liquid crystal display element can be improved. The Ministry of Economic Affairs, Intellectual Property Bureau, employee consumption cooperative printing (3) making two pieces of the above liquid crystal The substrate of the directing agent is such that the flattening directions of the liquid crystal alignment films are perpendicular or anti-parallel, and the two substrates are disposed opposite to each other with a gap (cell gap), and the two substrates are bonded together by a sealing agent to inject the liquid crystal alignment agent. Filling the surface of the substrate and the cell gap partitioned by the sealant, sealing the injection hole to form a liquid crystal cell. Then, the outer surface of the liquid crystal cell, that is, the other surface of each substrate constituting the liquid crystal cell, will be polarized. The paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1299057 A7 B7 5. Inventive Note (26) The board is bonded so that its polarization direction and the flat direction of the liquid crystal alignment film formed on one side of the substrate Uniform or vertical, that is, a liquid crystal display element. Here, the 'sealant can be used, for example, an epoxy resin containing a hardener and an alumina ball as a spacer. Nematic liquid crystal and smectic liquid crystal, among which nematic liquid crystal is preferable, for example, Schiff base liquid crystal, oxidized azo liquid crystal, biphenyl liquid crystal 'phenyl ring system liquid crystal, ester type Liquid crystal, triphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, Kuban liquid crystal, etc. Further, these liquid crystals may also be added, for example, 'chlorinated bile甾, cholesteryl phthalate, cholesteryl carbonate and other cholesteric liquid crystals and towels sold under the trade name "C-15" "CB-15" (made by Merck) for use in palms, etc. It is also possible to use a strong dielectric liquid crystal such as bis-dimethoxy benzene to form methyl-p-amino-2-methylbutyl cinnamate, and a polarizing plate bonded to the outer surface of the liquid crystal cell, A polarizing film of a so-called enamel film, a polarizing plate sandwiched by a cellulose acetate protective film, or a polarizing plate formed only by the ruthenium film itself, in which the vinyl alcohol is extended and oriented. Further, the liquid crystal aligning agent of the present invention is suitable for a liquid crystal display element of a ΜV Α (multi-domain direct) method. Μ The V A mode is as shown in "Liquid Crystal Vol. 3 Νο·2117 (1999)" or Special Open 1 1 - 2 5 8 6 0 5 , and the vertical orientation mode in which the projection is a directional regulation mechanism is used. The bumps may be formed on the side of the T F Τ substrate and on the side of the color filter, or may be provided on the side of the color filter, and the slits may be provided on the side of the T F Τ. This paper size is applicable to China National Standard (CNS) Α4 specification (210X297 mm) (please read the note on the back and fill out this page). Clothing and Customs Ministry of Commerce Intellectual Property Bureau Staff Consumer Cooperative Printed 1299057 Α7 Β7 V. Invention DESCRIPTION OF THE INVENTION (Examples) Hereinafter, the present invention will be more specifically described by way of examples, but the invention is not limited to the examples. [Polymerization rate of ruthenium of polymer] The polymer was dried under reduced pressure at room temperature, dissolved in dihydrogenated dimethyl sulfoxide, and tetramethyl decane was used as a standard substance. 1 Η-NMR was measured at room temperature. (ii) Find. Ruthenium amination rate (%) II (l^Ai/AS α)χ 1〇〇( ii ) A1 : Peak area of protons from NH group (1 〇p pm) A2: Peak area from other protons α : In the polymer precursor (poly-proline), the ratio of the number of other protons to the protons of one sulfhydryl group (printability) is printed by "Wentlot Code" (manufactured by Nippon Photo Printing Co., Ltd.). The substrate after post-baking was observed under a microscope. No uneven printing 〇

There is uneven printing X [How to make liquid crystal display elements] This paper size is applicable to China National Standard (CNS) Α4 specifications (210X297 mm) -30 - (Please read the notes on the back and fill out this page) Φ. Ministry of Intellectual Property Bureau employee consumption cooperative printed 1299057 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (28) Production of liquid crystal display device (1) ·· Set on the side of the substrate with a thickness of 1 mm On the transparent conductive film formed by the IT 0 film, the liquid crystal aligning agent was applied by a spin coater, and dried at 80 ° C for 1 hour at 180 ° C to form a coating film having a dry film thickness of 60 Å. Next, the flat grinding machine which rolls the roll of the cloth is used for the flat grinding process, and the orientation of the liquid crystal molecules of the film is imparted to form a liquid crystal alignment film. Here, the flat grinding conditions are as follows: the speed of the light cylinder is 4 0 0 r p m, and the speed of the platform moving is 3 0 m/s, which is enough to enter the length of 0·43⁄4 m. Two sheets of the substrate on which the liquid crystal aligning agent was formed were prepared as described above, and an epoxy resin-based adhesive containing alumina balls was applied by screen printing on the outer edge portions of the respective substrates, and then the two substrates were placed in the direction of the separator to make the flat grinding. In the opposite direction, the outer edge portions are pressed against each other to harden the adhesive. The negative-type nematic liquid crystal is injected into the cell gap which is defined by the adhesive on the surface of the substrate and the outer edge portion, and the injection hole is sealed by epoxy bonding to form a vertical alignment type liquid crystal display element. (hereinafter referred to as "liquid crystal display element 1". Production of liquid crystal display element (2): As shown in Fig. 1, a bumped glass substrate (A) with a positive resist formed by a positive resist is formed. And a glass substrate (B) having an IT 〇 pattern, each printed with a liquid crystal aligning agent, dried at 80 ° C for 1 minute and then at 180 ° C for 1 hour to form a coating film having a dry film thickness of 600 angstroms. Prepare two substrates with liquid crystal alignment agent as described above, and use the substrate (this paper size is generally Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the note on the back and fill in this page)

τ

1299057 A7 B7 V. INSTRUCTION OF THE INVENTION (29) B) The epoxy resin-based adhesive containing an alumina ball having a particle size of 3 .. 5 μm is applied by screen printing at the outer edge portion, as shown in Fig. 1 Two substrates were bonded together. The cell gap scribed by the adhesive on the surface of the substrate and the outer edge portion is filled with a negative liquid crystal ML C 6 6 8 made by Merck, and the injection hole is sealed with an epoxy adhesive. A vertical alignment type liquid crystal display element (hereinafter referred to as "liquid crystal display element 2") is produced. [Pretilt angle] The pretilt angle was calculated from the slip of the symmetrical angle of the liquid crystal at 25 °C by 〇M S — J 3 by the company. [Voltage retention ratio of liquid crystal display element] After the liquid crystal display element was applied at a voltage of 5 volts at an application time of 60 microseconds at an interval of 167 msec, the voltage holding ratio after the release of 167 msec was measured. The measuring device was made up of V H R -1 manufactured by Dongyang Technology Co., Ltd. [Residual DC voltage] The liquid crystal display element is superimposed with a DC of 1 〇 volts, and a rectangular wave of 2.0 volts is applied at an ambient temperature of 70 ° C for 1 hour, and remains after the DC voltage is cut off. The voltage in the liquid crystal cell was measured by a scintillation erasing method to determine a residual DC voltage. Synthesis Example 1, 2, 4, 5, Comparative Synthesis Examples 1 and 2 This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the notes on the back and fill out this page)

Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, Printed 1299057 A7 ^_______B7 V. Description of Invention (30) 1 to 50 gram of 1-methyl-2-pyrrolidone followed by Addition of Diamine, Tetracarboxylic Acid dianhydride, The solid content concentration of the monomer feed shown in Table 1 was changed to 20% by weight, and the mixture was reacted at room temperature for 4 hours to obtain poly-proline. Synthesis Example 3 After adding 1 -methyl-2-pyrrolidone to the polyglycine of Synthesis Example 2 to have a solid content concentration of 5% by weight, a catalyst was added according to the composition of Table 1, and a dehydration ring-closing reaction was carried out at 80 ° C. hour. Further, the reaction mixture was poured into diethyl ether, precipitated, recovered, and dried to obtain a polymer having a hydrazine imidation ratio of 20%. (Please read the notes on the back and fill out this page.) Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumer Cooperatives, Printed Paper Size Applicable to China National Standard (CNS) A4 Specification (210X297 mm) -33 - 1299057 A7 B7 V. Description of Invention (31) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Printed Table 1 Synthesis Example Feeding Monomer (Mole %) Logarithmic Viscosity (Male/G) Rhodium Amination Catalyst Amination Rate (%) Anhydride II Aminopyridine/acetic anhydride 1 CB (100) PDA (50) Diamine of formula (13) (50) 0.89 Μ J 0 2 CB (80) DMCB (20) PDA (75) Diamine of formula (13) (25 0.76 Μ ^\\\ 0 3 CB(80) DMCB(20) PDA(75) Diamine (25) of formula (13) 0.76 1.0/1.0 20 4 CB(80) DMCB(20) PDA(75) (14) Diamine (25) 0.70 Μ j \ w 0 5 CB (80) DMCB (20) Diamine of formula (13) (100) 0.65 Μ j \ \\ 0 Comparative Synthesis Example 1 DSDA (IOO) PDA (95) Diamine of formula (13) (5) 1.09 Μ j\\\ 0 2 CB(100) PDA(50) n-octadecyloxy-1,4-diaminobenzene (50) 0.71 Μ j \ \\ 0 (Please read the note on the back and fill out this page) This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) ) -34 - 1299057 A7 B7 V. INSTRUCTIONS (32) CB : 1 , 2, 3, 4 -Cyclobutane tetracarboxylic dianhydride DMCB : 1 , 3 - dimethyl - 1 , 2 , 3 ' 4 - ring Butane tetracarboxylic dianhydride PDA: p-phenylenediamine DS d A : diphenyl terephthalic acid dianhydride Examples 1 to 5 and Comparative Examples 1 and 2 The polymer obtained in the synthesis example was dissolved in Table 2. After the solvent, the liquid crystal director was filtered through a 1 micron filter. These liquid crystal alignment agents are used to produce liquid crystal display elements. The evaluation results of these liquid crystal aligning agents and liquid crystal display elements are shown in Table 2. (Please read the notes on the back and fill out this page)

Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumer Cooperatives. This paper scales the General Chinese National Standard (CNS) A4 specification (210 X 297 mm) -35 - 1299057

7 7 AB V. INSTRUCTIONS (33) Table 2 Example Polymer solvent (% by weight) Printability pretilt angle (°) Voltage retention (%) Residual DC (millivolt) 1 Synthesis Example 1 1_Methyl-2 - pyrrolidone (50) butyl cellosolve (50) 〇 89.5 98.3 20 2 Synthesis Example 2 μmethyl-2-pyrrolidone (50) butyl cellosolve (50) 〇 89.5 98.5 20 3 Synthesis Example 3 1-Methyl-2- Pyrrolidone (60) butyl cellosolve (40) 〇 89.7 98.6 10 4 Synthesis Example 4 1-Methyl-2-pyrrolidone (50) Butyl cellosolve (50) 〇 89.4 98.8 20 5 Synthesis Example 5 1-Methyl-2- Pyrrolidone (30) butyl cellosolve (70) 〇89.8 96.5 30 Comparative Example 1 Comparative Synthesis Example 1 1-Methyl-2-pyrrolidone (50) butyl cellosolve (50) 〇79.3 79.0 100 2 Comparative Synthesis Example 2 μMethyl ·2·Pyrrolidone (50) Butyl cellosolve (50) X 89.6 98.0 20 (Please read the note on the back and fill out this page) Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed Examples 6 to 10, Comparative Example 3 After the polymer of the synthesis example was dissolved in the solvent shown in Table 3, the liquid crystal aligning agent was prepared by filtration through a filter medium of 1 μm. The liquid crystal display element 2 was produced using these liquid crystal aligning agents. Evaluation results of these liquid crystal alignment agents and liquid crystal display elements This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) _ 36 _ 1299057

7 B V. INSTRUCTIONS (34) The combination is shown in Table 3. Ministry of Economic Affairs Intellectual Property Bureau Staff Consumption Cooperation Duban Table 3 Example Polymer Solvent (% by weight) Voltage Retention (%) Residual DC (millivolt) 6 Synthesis Example 1 1 -Methyl-2-pyrrolidone (50) Butyl Solution Fibrous (50) 98.1 30 7 Synthesis Example 2 methyl-2-D pyrrolidone (50) butyl cellosolve (50) 98.3 30 8 Synthesis Example 3 1 -Methyl-2-pyrrolidone (60) butyl cellosolve ( 40) 98.4 20 9 Synthesis Example 4 1-Methyl-2-D pyrrolidone (50) Butyl cellosolve (50) 98.6 40 10 Synthesis Example 5 1-Methyl-2-pyrrolidone (30) Butyl solution Fibrous (70) 96.2 60 Comparative Example 3 Synthesis Example 6 1-Methyl-2-pyrrolidone (50) Butyl cellosolve (50) 97.8 190 (Please read the notes on the back and fill out this page) This paper size applies to China. National Standard (CNS) A4 Specification (210X297 mm) _ 37 - 1299057 A7 B7 V. DESCRIPTION OF THE INVENTION (35) BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view of a VA type liquid crystal cell used in an embodiment of the present invention. DESCRIPTION OF REFERENCE NUMERALS 1 color filter side electrode (I τ〇) 2 liquid crystal alignment film 3 pixel electrode (IT〇) 4 orientation restricting mechanism (bump) 5 orientation restricting mechanism (slit) 6 liquid crystal molecule effect of the invention according to the present invention When the liquid crystal alignment film is formed, the liquid crystal alignment film is excellent in vertical alignment property, and can form a liquid crystal alignment film having high voltage holding characteristics, low afterimage resistance, and excellent printability, and is suitable for a liquid crystal alignment agent of a vertical alignment type liquid crystal display element. (Please read the notes on the back and fill out this page)

Printed by the Consumer Intellectual Property Office of the Ministry of Economic Affairs -38- This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm)

Claims (1)

12990 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A8 B8 C8 D8 Sixth, the scope of application for patents 1 · A liquid crystal aligning agent, which is characterized by: (A) Formula (1) [Chemical 1] 0 .· (1) Here, 'R1 is a halogen atom, an alkyl group having 1 to 1 carbon atom or a fluorinated alkyl group having 1 to 10 carbon atoms, and a is 〇 to an integer of 4, and the tetracarboxylic acid is shown. Acid dianhydride and (B) the following formula (2) [Chemical 2] • (2) Here, X is a divalent organic group, and R 2 is a monovalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms, and the polyamine acid formed by the reaction of the diamine shown and the poly At least one of a ruthenium imidized polymer formed by dehydration of a proline, and 2 to 60% by weight of 1-methyl-2-pyrrolidone and 80% of other solvents having a surface tension of 3 2 dynes/cm or less 40% by weight This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) (Please read the back note first and then fill out this page) 1299057 A8 B8 C8 D8 The scope of application is as follows. Fan Liyuan special instructions Please show the liquid crystal type to the straightening agent to the crystallization liquid item hanging on the system (please read the back of the precautions and then fill out this page). Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the consumer cooperatives. This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -40 -