TW556030B - Vertical alignment type liquid crystal aligning agent - Google Patents

Abstract

The object of the present invention is to provide a vertical alignment type liquid crystal aligning agent which contains a polymer component with two kinds of amic acid recurring units and imide recurring units. The vertical alignment type liquid crystal aligning agent has excellent vertical alignability, so that it is short in the afterimage erasing time of a liquid crystal display element and suitably used for an MVA system liquid crystal display element.

Description

556030 A7 B7 V. Description of the Invention (ii) Technical Field The present invention relates to a liquid crystal vertical alignment liquid crystal aligning agent. In more detail, it is related to the vertical alignment, printability of liquid crystal, and the afterimage removal time of liquid crystal display elements. It is particularly suitable for liquid crystal vertical alignment liquid crystal aligning agents for MV A (multi-domain vertical alignment) type liquid crystal display elements. Prior art At present, it is known that liquid crystal display elements are formed on the surface of a substrate provided with a transparent conductive film, and a liquid crystal alignment film such as polyamic acid or polyimide is used as a substrate for a liquid crystal display element. In the gap, a positive dielectric anisotropic nematic liquid crystal layer is formed into a sandwich structure. The long axis of the liquid crystal molecules is continuously twisted 90 degrees from one substrate to the other. TN type liquid crystal display element. In addition, S T N (Super Twisted Nematic) type liquid crystal display elements with higher contrast and less viewing angle dependence than T N type liquid crystal display elements, and vertical alignment type liquid crystal display elements are also under development. This STN type liquid crystal display element uses a nematic liquid crystal doped with an optically active substance, and the major axis of the liquid crystal molecules is continuously twisted above 180 degrees between the substrates. Refraction effect. In response to this, v liquid crystal " Vol. 3 No. 2 1 1 7 (1 999) and Japanese Patent Laid-Open No. 1 1-2 5 86 0 5 proposed to form protrusions on the I TO to control the orientation of the liquid crystal, said It is a vertically-aligned liquid crystal display device of the M VA method. The VA VA-type liquid crystal display element has excellent viewing angle and contrast, and is formed with a liquid crystal alignment film, which can be applied without flat grinding. The process has excellent paper dimensions and applies Chinese National Standard (CNS) A4 specifications (210X297 mm) I --- -· ---- ^ 费 一 I (Please read the notes on the back before filling this page)

, 1T Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -4-55603ο A7 V. Description of invention (2). The liquid crystal alignment film used in the MV A method has performance requirements such as excellent vertical alignment of the liquid crystal, and short removal time of the afterimage of the liquid crystal display element. DISCLOSURE OF THE INVENTION The object of the present invention is to provide liquid crystal display elements with excellent vertical orientation, so that the afterimage removal time of liquid crystal display elements is short, which is suitable for MV A-mode liquid crystal display. Other objects and advantages of the present invention will be apparent from the following description. According to the present invention, the above-mentioned object and advantages of the present invention are characterized by including: (A) a repeating unit having the following formula (I-1), and (b) a repeating unit having the following formula (I-2) The polymer's liquid crystal vertical alignment liquid crystal alignment agent is achieved. (Please read the notes on the back before filling this page)

HNOC CONH—Q1-HOOC ΠΟΟΗΗ 1-1) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the basic machine has a price of 2 series, the IX Q basic machine has a price of 4 series, P Chinese style

ΟΜΠ yo

I.NC Q2- / This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) -5- 556030 A7 B7 V. Description of the invention (3) In the formula, P2 is a 4-valent organic group, and Q2 is under The formula (Q-i) below (Q-2) is the divalent base. Description

X1-R1 (Q-1) where X1 is a single bond, 101, ~ c0-, -c00--0c0, a nhc01, a cnh-, a s group, R1 It is an alkyl group having 10 to 20 carbon atoms, a monovalent organic group having an alicyclic skeleton having 4 to 4 carbon atoms or a monovalent organic group having 6 to 20 carbon atoms having a fluorine atom. Or Nobuyoshi (Please read the notes on the back before filling in this page)

X2—R2—χ3

(Q — 2) X2 and X3 are the same or different in the printed format of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, which are single bonds, 100-C0-NHCO-^-CONH 1, -S-or aryl, R2 is a divalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms. C〇〇〇C〇—,-Brief description of the drawing The first figure is a VA-type liquid crystal element used in the embodiment of the present invention. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm)- 6 556030 A7 B7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Embodiments of the Invention The present invention will be described in detail below. The liquid crystal vertical alignment liquid crystal aligning agent of the present invention is preferably constituted by dissolving the polymer component in an organic solvent. The polymer component in the present invention is ① a polyamic acid (hereinafter also referred to as "(A) component") containing (A) a repeating unit having the above formula (I-1) and (B) having the above formula (I -2) fluorinated polymers of repeating units (hereinafter also referred to as "(B) component"), or fluorinated acid prepolymers containing (A) repeating units of the above formula (I-1) and (B) A block copolymer of a fluorene imine prepolymer having a repeating unit of the above formula (I-2) is preferable, and the above ① is more preferable. In the above ①, the component (A) is a polyamidic acid system. It is obtained by the reaction of tetracarboxylic dianhydride and diamine. (B) component 醯 imine compound is tetracarboxylic dianhydride and H2N- Q2-NH2 (where Q2 is the same as the definition of formula (I-2)). Polyamines obtained by the reaction of amines (hereinafter also referred to as "specific diamines") are obtained by dehydration and ring opening. (A) Polyfluorinated acid < tetracarboxylic dianhydride > Specific examples of the tetracarboxylic dianhydride used in the synthesis of the polyamine acid of the component (A) are 1,2,3,4 monocyclobutanetetracarboxylic acid Acid dianhydride, 1, 2-dimethyl-1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride, 1, 3-dimethyl (Please read the notes on the back before filling this page) This paper Standards are applicable to Chinese National Standard (CNS) A4 specifications (210X297 mm) 556030 A7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs B7 V. Invention Description (5) 1,2,3,4 Monocyclobutanetetracarboxylic acid Dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4 tetramethyl-1,2,3,4-cyclobutane Tetracarboxylic dianhydride, 1,2,3,4 monocyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,, 4,4-dicyclohexyl Tetracarboxylic dianhydride, cis-3,7-dibutylcyclooctane-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentane Acetic dianhydride, 3,5,6, -tricarbonyl-2-carboxy-ortho- spinane-2: 3, 5: 6 —Dianhydride, 2,3,4,5 -tetrahydrofurantetracarboxylic dianhydride, 1,3,3 a, 4,5,9b —hexagas-5 — (tetragas-2, 5 —dione group-3 —Furanyl) —naphtho [1,2, c] furan-1,3-dione, 1,3,3a, 4,5,9b —hexahydro-5 monofluorenyl-5 — (tetrahydro-2 , 5 -diketo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9 b-hexahydro-5-ethyl 5 — (tetrahydro-2,5 —diketo-3-1: 1 furanyl) —naphtho [1,2, c] pyran-1,3,2,1,3,3a ， 4,5'9b —hexazine-7 —methyl-5 — (tetrahydro-2,5-diketo-3—furanyl) —naphtho [1,2, c] furan-1,3 — Dione, 1, 3, 3a, 4, 5, 9b —hexahydro-8-methyl-5 — (tetrahydro-2,5 —diketyl-3 -furanyl) —naphtho [1, 2 — C] furan-1, 3-dione, 1,3,3a, 4,5,9b—hexahydro-8-ethyl-5— (tetrahydro-2,5-dione-3-furan ) —Naphtho [1,2, c] -1, 3_ dione, 1, 3, 3a, 4 (please read the precautions on the back before filling this page) > equipment ·, \-口 -ΙΦ This paper size applies to China National Standard (CNS) A4 specifications (210X 297 mm) -8- 556030 A7 B7 V. Description of the invention (6) '5' 9b —Hexamin 5 '8 — — ^ Amino-5 — (Tetrachloro-2' 5 —Diketo — 3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 5- (2,5-diketyltetrahydrofurfuryl) -1,3-methyl-1,3-cyclohexene -1,2-dicarboxylic dianhydride, bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxybicyclo [3,2,1 ] Octane-2,4-dione-6-spiro-3 /-(tetrahydrofuran-dione), alicyclic tetracarboxylic dianhydride of the following formulae (Π) and (III); (Please read the back first (Notes for filling in this page)

C

(Π) Printed by the Consumer Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs

(III) wherein R3 and R6 represent a divalent organic group having an aromatic ring, R4 and R5 represent a hydrogen atom or an alkyl group, and most of R4 and R5 may be the same or different. This paper size applies Chinese National Standard (CNS) A4 specification (210 × 297 mm) -9-556030 Α7 Β7 V. Description of the invention (7) (Please read the notes on the back before filling this page) Butanetetracarboxylic dianhydride Aliphatic tetracarboxylic dianhydride; pyromellitic dianhydride, 3, 3, 4, 4, 4-diphenyl ketone tetracarboxylic dianhydride, 3, 4, 4, 4 > Acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 /, 4, 4, diphenyl ether tetracarboxylic acid Dianhydride, 3, 3 ^, 4, 4 'Monomethyl Silanetetracarboxylic Dicarboxylic Anhydride printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, 3,3 >, 4,4 " Monotetraphenyl Sarane tetracarboxylic dianhydride, 1,2,3,4 monofurantetracarboxylic dianhydride, 4, 4 / -bis (3,4-dicarboxyphenoxy) dibenzoarsuccinic anhydride, 4, 4 > One bis (3,4 dicarboxyphenoxy) diphenylsulfonic anhydride, 4, 4 / one bis (3,4 dicarboxyphenoxy) diphenylpropane dianhydride, 3, 3, , 4,4, _Perfluoroisopropylidene phthalic dianhydride, 3,3,, 4,4 / Biphenyltetracarboxylic acid di Bis (phthalic acid) phenylphosphine oxide dianhydride, terephthalic bis (triphenylphthalic acid) dianhydride, m-phenylene bis (triphthalic acid) dianhydride, bis (triphenylphthalic acid) -1,4 / Diphenyl ether dianhydride, bis (triphenylphthalic acid) -1,4 < -diphenylmethane dianhydride, ethylene glycol bis (trimellitic anhydride ester), propylene glycol bis (trimellitic anhydride ester), 1,4 monobutadiene Alcohol bis (trimellitic anhydride ester), 1,6-hexanediol bis (trimellitic anhydride ester), 1,8-octanediol bis (trimellitic anhydride ester), 2,2-bis (4-hydroxyphenyl) propane bis (trimellitic anhydride ester) ), Aromatic tetracarboxylic dianhydrides such as aromatic tetracarboxylic dianhydrides having a steroid skeleton in the following formulae (1) to (4). These can be used alone or in combination of two or more. This paper size applies to the China National Standard (CNS) A4 specification (210X297 mm) -10- 556030 A7 B7 V. Description of the invention (8) CH3 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

(Please read the precautions on the back before filling this page) This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -11 556030 A7 B7 V. Description of the invention (9), 3-dimethyl-1 , 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl_1,2,3,4-cyclobutanetetracarboxylic acid (Please read the notes on the back first Fill in this page again) dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5 ~ tricarboxycyclopentylacetic dianhydride, 5- (2,5-dione group) Tetrahydrofurfuryl) —3-Methyl-3, cyclohexene-1,2-dicarboxylic dianhydride, cis-3,7-dibutylcyclooctane-1, 5-diene-1, 2 , 5,6-tetracarboxylic dianhydride, 3,5,6-tricarbonyl- 2-carboxyorthospinane ~ 2: 3,5: 6-dianhydride, 1,3,33,4,5,9 乜~ Hexahydro-5— (tetrahydro-2,5-diketo-3—furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a ′ 4, 5, 9b —hexachloro-8 —methyl-5 — (tetraaza-2 ′ 5 to diketo-3 —furanyl) —naphtho [1,2-c] furan Mono 1,3-diketone, 1,3,3a, 4,5,9b —hexakis — 5 '8-dimethyl_5 — (tetrahydro-2, 5-diketo-3-furanyl) Mononaphtho [1,2-c] furan-1,3-dione, bicyclic [2 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, 2,2] Octano-7-ene-2,3,5, 6-tetracarboxylic dianhydride, 3-oxybicyclo [3,2,1] octane-2,4-dione-6-spiro-3 >-(tetrahydrofuran-1,5 > -dione), the following formula ( Π) Compounds of the following formulae (5) to (7), compounds of the formula (111) of the following formula (8), butane tetracarboxylic dianhydride, pyromellitic dianhydride, 3 , 3 > 4,4 —diphenyl ketone tetracarboxylic dianhydride, 3,3,, 4,4 ^ —biphenylsulfotetracarboxylic dianhydride, 1,4,5, 8 -naphthalenetetracarboxylic acid The dianhydride and the like are preferred from the appearance of good liquid crystal orientation and electrical characteristics. These tetracarboxylic dianhydrides can be used alone or in combination of two or more. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -12- 556030 A7 B7 V. Description of the invention (10) Use.

This paper size applies to Chinese National Standard (CNS) A4 specification (210'〆297 mm) -13 · 556030 Α7 Β7 V. Description of the invention (diamine, • m-phenylene · diamine, 4, 4'-diaminodiamine : Phenylmethane 4 '4 >--Diaminobenzene 1 Saiyanyuan, 4, 4 /-Diaminodiphenylimine Λ 4, 4-Diaminodiphenylbenzene, 2, 2 > -Dimethy — 4 5 4 > > — diamine 3 S biphenyl, 3,3 dimethyl-4,4 > — diamine biphenyl, 4,4 diaminophenylanilide, 4, 4 / — diamino diphenyl ether, 1, 5 — diamine 3 S naphthalene, 3 3 〆-dimethyl-1 4 5 4 — bis (Please read the precautions on the back before filling out this page) Amine Biphenyl, 5-amino-1, 1- (4-aminoaminophenyl) -1, 3, 3-trimethylindane, 6-amino-1, 1- (4-aminoaminophenyl) -1 , 3,3-Tris-fluorenylindan, 3,4 / -diaminodiphenyl ether, printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs, 3,3-diaminodiphenyl ketone, 3,4 / —Diaminodiphenyl ketone, 4,4 diamine Diphenyl ketone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4-mono (4-monoaminophenoxy) phenyl] hexafluoropropane , 2,2-bis (4-aminoaminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4-mono (4-aminoaminophenoxy) hexafluoropropane, 2,2-bis [ 4- (4-aminoaminophenoxy) 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-hydroanthracene, 2,7-diaminofluorene, 9,9-bis (4- Aminophenyl) fluorene, 4,4-methylenebis (2-chloroaniline), 2,5,5-tetrachloro-4,4 > -diaminobiphenyl, 2,2 ^ -dichloro- 4,4 > -diamino-5,5 / -dimethoxybiphenyl, 3,3 / -dimethoxy-4, -diaminobiphenyl, 1,4,4 > Phenylisopropylidene) bisaniline, 4,4 >—( m-phenyleneisopropylidene) bisaniline, 2,2 This paper size applies to China National Standard (CNS) A4 specification (210 × 297 mm) -14-556030 A7 B7 V. Description of the invention (12) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs — Double C 4 — (4 — Amine — _L ^ Fluoropropane 4 4 — Diamine) Biphenyl 4 5 4 — Double (( Oxy]-octafluorobiphenyl and other aromatic di 1 3-propylene diamine Λ tetramethylene diamine > heptamethylene diamine > octa 4, 4-diamino heptamethylene diiso Fluorone diamine tetrahydrodicyclopentaneindane dimethylene diamine dicyclo one carbene dimethyl diamine 4 4 etc. aliphatic and alicyclic diamine; r 2 3 — monoamine Pyridine 2 Pyridine 2, 4-diamino 3-dicyanopyrazine 5 y 6-2, 4-diamino-6-di 1, 4-bis (3-aminopropyl 6 — Isopropoxy — 1, 3 5 5 — Methoxy — 1 3 5 — Triyl — 1, 3 3 5 — Diazine 2 — Triazine Λ 2 4 — Diamino — Diamino — 2 — Ethylene —S —phenylthiazole 2 6 —diamino 3 —dimethyl Pyrimidine 3 5 5 6 > 9 — Diamino — 2 — B The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 2-trifluoromethylphenoxy) phenyl] 2, 2 /-bis (trifluoromethyl 4 monoamino-2-difluoromethyl) aniline; 1, 1-m-xylylene diamine, diamine, pentamethylene diamine, hexamethylene methylene Diamine, unamethylenediamine, amine, 1,4-diaminocyclohexane, monosuccinic amine, hexahydro-4,7-m [6.2.1.02 · 1 2] -ten / a Methylbis [Cyclohexylamino] (Please read the precautions on the back before filling out this page) -15-1 1-Diaminopyridine, 3,4-Dipyrimidine, 5,6-Diamino-2, 2 Amino-2,4-dihydroxypyrimidinylmethylamino-1,3,5-triazinyl) piperidine, 2,4-diamino-triazine, 2,4-diamino-6-oxazine , 2,4-diamino-6-benzene, 4-diamino-6-methyl-s 1, 3,5-triazine, 4,6-triamidine, 2,4-diamino-5 — Purine, 5,6-diamino-1, —diamino-1, 2, 4-triazole 2 oxyacridine Acid esters, 3, 8-di 556030 A7 B7 V. Description of the invention (13) (Please read the precautions on the back before filling out this page} Amino-6-phenylphenanthridine, 1 '4 --- ^ amino Shouting, 3 '6-a * aminoacridine, bis (4-aminophenyl) phenylamine, etc., there are two primary amine groups in the molecule and diamines with nitrogen atoms other than the primary amine group; Diamine organosiloxanes of formula (IV) and the like. These diamines can be used alone or in combination of two or more. R7 R7 one CH seven negative 0-1) XNH2 0V) where R7 represents a hydrocarbon group having 1 to 12 carbon atoms, most of R7 may be the same or different, P is an integer of 1 to 3, and Q is 1 to 2 An integer of 0. The Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs printed these to p-phenylenediamine, 4,4 " -diaminodiphenylmethane, 4,4 /-diaminodiphenyl aso, 2, 2 / —Dimethyl-4,4 / monodiaminobiphenyl, 1,5-diaminonaphthalene, 2,7-diaminofluorene, 4,4 > —diaminodiphenyl ether, 2,2 —Bis [4- — (4-aminophenoxy) phenyl] propane, 9,9—bis (4-aminoaminophenyl) hydrazone, 2 ′ 2—bis [4-mono (4-aminoaminophenoxy) ) Phenyl] hexahydropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 >-( p-phenylenediisopropylidene) bisaniline, 4,4 > one ( M-phenylenediisopropylidene) diphenylamine, 1,4-cyclohexanediamine, 4,4 / methylenebis (cyclohexylamine), 1,4-bis (4-aminoaminophenoxy) benzene, 4,4 " * — bis (4-monoaminophenoxy) biphenyl, 2,6-diaminopyridine, 3, 4-diaminopyridine, 2,4-diaminopyrimidine, 3, 6-diaminoacridine and the like are preferred. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 1 '-16-556030 A7 B7 V. Description of the invention (14) (Please read the notes on the back before filling this page) 1B) Imine Polymers < tetracarboxylic dianhydride > Tetracarboxylic dicarboxylic acid diimidated polymers used to synthesize (B) component are the same as those described above for synthesizing poly (amino acid) component (A) Carboxylic dianhydride. Among these, alicyclic tetracarboxylic dianhydride is preferred, and specific examples include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1, 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3, 4 Monocyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5- (2,5-diketyltetrafurfurylidene) -3-methyl-cyclohexane Mono-1,2-dicarboxylic dianhydride, cis-3,7-dibutylcyclooctane-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 3,5, 6 -Tricarbonyl-2-carboxy-ortho- spinane-2: 3,5: 6-dianhydride, 1,3,3a, 4,5,9b-hexahydro —5 — (tetrahydro-2 ′ 5—diketo-3—furanyl) -naphthalene hydrazine [1, 2 — c] Furan—Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 8 1 a | 咲 | 1 I } 3 hydrogen sulfonation, hydrogen radical, tetra-C 12 hexaran 3 c | 7, I furan, 12 13 b I 1 5, oct t 9 3, I 1 I ring, I fluorenyl ^ fluorene bis 5-methyl dimethyl 2 oxygen, keto-mononaphthalene, 4 4 3-12 3, |, 8 λ-y,, a 10IX, radical cxi liver 3, | 5 ran C bis, 2 ran | furanic acid 3 | fluorene I double residue, gas ^ ~~ ^ six 3, four 1 four C one I ketone I, (-b-based di 6 ketone | 2 9 ketone I, two 5, 'two 3 5 | | 1—I LO I, ,, 3 S [, 5 13, Pyrene 4, I, 1 I Naphthalene, 2 Glue 2 This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) -17- 556030 A7 B7 V. Description of the invention (15) ] Octa-2,4-dione-6-spiro-3 (tetrahydro1: 1 furan-2 (please read the notes on the back before filling this page) '5 / -dione), the above formula (II ) Among the compounds of the following formulae (5) to (7) and the compounds of the above formula (in) The compound of the formula (8) is preferred from the viewpoint of exhibiting good liquid crystal orientation and electrical characteristics, and particularly preferred are 1, 2, 3, 4 monocyclobutanetetracarboxylic dianhydride, 1, 3-dimethyl-1,2,3,4, monocyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,3,3 a, 4, 5, 9b —Hexahydro-5— (tetrahydro-2,5-dione—3—1: 1furanyl) —Cai Bing [1,2-c] Huangan-1,3—One wake, 1,3 , 3a, 4,5,9b —Hexahydro-8—methyl-5— (tetrahydro-2,5-diketo-3—furanyl) —naphtho [1,2, c] furan-1 , 3-dione, cis-3,7-dibutylcyclooctane-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 3,5,6-tricarbonyl_2 —Carboxy-ortho- spinane-2: 3,5: 6-dianhydride, 3-oxybicyclo [3,2,1] octane-2,4-dione—6-spiro—tetrahydrofuran—-dione) and the above formula (1) The compound. These tetracarboxylic dianhydrides can be printed singly or in combination of two or more types using the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. These tetracarboxylic dianhydrides can be obtained from the viewpoint of the electrical characteristics of the resulting liquid crystal alignment film. As the acid dianhydride, an alicyclic tetracarboxylic dianhydride is preferably used in an amount of 50 mol% or more. That is, in the above formula (I-12), the tetravalent organic group represented by P 2 is a repeating unit having a base of an alicyclic structure, accounting for 50 mol% or more of all repeating units in the component (B). good. Other than alicyclic tetracarboxylic dianhydride (preferably the same as the alicyclic tetracarboxylic dianhydride. The size of the paper is applicable to the Chinese National Standard (CNS) A4 specification (21〇297297 mm) ′ -18-556030 Ministry of Economic Affairs wisdom Printed by A7 B7, Consumer Cooperatives of the Property Bureau. V. Description of the invention (16) For dianhydride) Preferred tetracarboxylic dianhydride. It has aromatic tetracarboxylic acids with steroid skeletons of the above formulas (1) to (4). Dianhydride, etc. < Diamine > A specific diamine 'for synthesizing the (i) imine polymer of the component (B) is a diamine having the above formula (Q-1) and the above formula (Q-2). These are used alone or in combination of two or more. In the above (Q-1), the alkyl group having 10 to 20 carbon atoms represented by R1 includes, for example, n-decyl, n-dodecyl, n-pentadecyl, n-heptadecyl, and n-octadecyl , Zhengjiyuanji and so on. Further, the organic group having an alicyclic skeleton having 4 to 40 carbon atoms represented by R1 in the above formula (Q-1) and R2 in the above formula (Q-2) includes, for example, cyclobutane, cyclopentane, Cyclohexane, cyclodecane and other cycloalkane-derived bases with alicyclic skeletons; Cholesterol and cholostanols with steroidal skeletons; Original spinane, adamantane and other bridged alicyclic skeletons Zhiji and so on. Among these, a base having a steroid skeleton is particularly preferable. The above-mentioned organic group having an alicyclic skeleton may also be a group substituted with a halogen atom, preferably a fluorine atom, a fluorine-containing alkyl group, and more preferably a trifluoromethyl group. In the above formula (Q-1), the fluorine-containing group having 6 to 20 carbon atoms represented by R1 includes straight-chain alkyl groups having 6 or more carbon atoms such as n-hexyl, n-octyl, and n-decyl; Cyclohexyl, cyclooctyl and other alicyclic hydrocarbon groups having 6 or more carbon atoms; hydrogen atoms in organic groups such as phenyl and biphenyls having 6 or more carbon atoms such as aromatic hydrocarbon groups are partially or entirely fluorine atoms Or trifluoromethyl and other groups containing Daiyuan. (Please read the precautions on the back before filling out this page) The paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -19-556030 A 7 B7 V. Description of the invention (17) In addition, the above formula (Q -1) X1 and X2 and X3 in (Q-2) above are independent of each other. They are single bond, —〇—, one C ◦ one, (Please read the notes on the back before filling this page) —C 001, 100C01, -NHC01, -CONH-, -S- or arylene. Examples of the arylene group include phenylene, tolyl, biphenylene, and naphthyl. Among these, particularly good ones are-◦-, -c01, -10c01, the basis of the table. Specific examples of the diamine having the group represented by the above formula (Q-1) include dodecyloxy-2,4-diaminobenzene, pentadecyloxy 2 '4diaminoamine, ten The hexaalkoxy-2,4-diaminobenzene and octadecyloxy-2,4-diaminobenzene are preferably compounds represented by the following formulae (9) to (1 4). CHa

/ CH3 \ 〇13 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs CH3 / CH3

20- 556030 A7 B7 V. Description of the invention (18) CH3 HaC CH (CH2) 3CH = C / CH3 CH3

This paper size applies to China National Standard (CNS) A4 (210X297 mm)

-21-556030 A7 B7 V. Description of the invention (19) CH3 Η2νΌ-

/ CH3 \ (： Η3 (16) (Please read the notes on the back before filling in this page) Among the printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, the best ones are the above formulas (9), (10), (13), (14), (15) The compounds shown in (15). (B) In the synthesis of the component, the ratio of the specific diamine used is 5 mol% or more of all the diamines used in the synthesis of the (B) component. It is more preferable that it is 10 mol% or more. When the use ratio of a specific diamine is less than 5 mol%, sometimes vertical alignment may not be sufficient. That is, in all repeating units having an imine ring, the above is described. The ratio of the repeating unit represented by the formula (I-2) is preferably 5 mol% or more, and more preferably 10 mol% or more. Other diamines that can be used with specific diamines are used in the synthesis as described above ( A) The diamine of the polyamidoamine. Among these are p-phenylenediamine, 4,4 / monodiaminodiphenylmethane, 4,4 > -diaminodiphenylaso, 2, 2 > —Dimethyl — 4 This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 public envy) -22- 556030 A7 B7 V. Description of the invention (20) , 4 〃 diamino biphenyl, 1, 5- diamino naphthalene, 2, 7-diamine (Please read the precautions on the back before filling this page) 本页, 4, 4 diamino diphenyl ether '2,2-bis [4-mono (4-aminoaminophenoxy) phenyl] acetone, 9' 9-bis (4-aminoaminophenyl) fluorene, 2,2-bis [4 — (4- Aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-monoaminophenoxy) hexafluoropropane, 4,4-mono (p-phenylene diisopropylidene) bisaniline, 4,4 / Mono (m-phenylenediisopropylidene) bisaniline, 1, 4 monocyclohexanediamine, 4, 4 / monomethylene bis (cyclohexylamine), 1, 4-bis (4-aminophenoxy) ) Benzene, 4, 4-bis (4-aminophenyldioxy) biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3 , 6-diaminoacridine, diaminoorganosiloxane shown in the above formula (IV), etc. are preferred. These are used alone or in combination of two or more. Intellectual Property Bureau, Synthetic Economy of Polyamic Acid Printed by Employee Consumer Cooperatives for use in polyamide ((A) and (B) precursors) The ratio of the tetracarboxylic dianhydride and diamine used in the synthesis reaction is 1 equivalent of the amine group of the diamine, and the anhydride group of the tetracarboxylic dianhydride is preferably 0.2 to 2 equivalents, preferably 0. 3 to 1.2 equivalents are more preferred. The synthesis reaction of polyamic acid is in an organic solvent, preferably at 20 ° C to 150 ° C, and more preferably at 0 to 10 It is carried out at a temperature of 0 ° C. Here, if the organic solvent can dissolve the synthesized polyamic acid, there are no special restrictions, such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N — Dimethylformamide, Dimethoate, r_ Butyrolactone, This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) -23- 556030 Α7 Β7 V. Description of the invention (21 ) Aprotic polar solvents such as tetramethyl urea, hexamethylphosphortriamide, etc .; phenol solvents such as m-cresol, xylenol, phenol, and halogenated phenol. In addition, the amount (α) of the organic solvent is based on the total amount (cold) of the tetracarboxylic dianhydride and the diamine compound to the total amount of the reaction solution (α-/ 3). The amount may be from 0.1 to 30% by weight. Is better. As the organic solvent, as long as the produced polyamic acid does not precipitate, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, etc., which are weak solvents of polyamic acid, can be used. Specific examples of these weak solvents include methanol, ethanol, isopropanol, cyclohexanol, 4-methyl-4-methyl-2-pentanone (diacetone alcohol), ethylene glycol, propylene glycol, and 1,4-butane Alcohol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, ethyl acetate, butyl acetate, Methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, Ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monofluorenyl ether, Diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, Trichloroethane, chlorinated benzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, etc. As described above, a reaction solution obtained by dissolving polyamic acid is 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 polyamic acid. In addition, the process of re-dissolving the polyamic acid in an organic solvent and then precipitating it as a weak solvent, after one or more times, this paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) (Please read first Note on the back, please fill out this page again} ▼ Installation · Printed by 1T Intellectual Property Bureau of the Ministry of Economic Affairs Employee Cooperatives -24- 556030 A7 B7 V. Description of the invention (22) Polyamic acid can be purified. (Please read the back first (Notes on this page, please fill out this page) 1) Synthesis of imidized polymer ((B) component) The (B) component can be synthesized by dehydration and ring closure of part or all of the above polyamic acid. B) component, the ratio of repeating units having a fluorene imine ring in all repeating units (hereinafter also referred to as "fluorine imidization ratio") is preferably 40 mol% or more, and more preferably 70 mol% or more The use of polymers with an imidization rate of 40 mol% or more is beneficial to the preparation of a liquid crystal aligning agent that can form a liquid crystal aligning film with a short afterimage removal time. The dehydration ring closure of polyamic acid can be borrowed (i ) A method of heating polyfluorinated acid, or (ii) The acid is dissolved in an organic solvent, and a dehydrating agent and a dehydration ring-closing catalyst are added to the solvent, and the method is performed by heating if necessary. The reaction temperature of the method (i) for heating the polyamic acid is preferably 50 to 200 ° C. 60 to 170 ° C is more preferable. The dehydration ring-closure reaction is difficult to fully proceed at a reaction temperature of less than 50 ° C, and the molecular weight of the amidine polymer obtained when the reaction temperature exceeds 200 ° C is low. Employees of the Bureau of Intellectual Property, Ministry of Economic Affairs Printed by a consumer cooperative. On the other hand, in the method of (ii) above, adding a dehydrating agent and a dehydrating closed-loop catalyst to a polyamic acid solution, the dehydrating agent may be an acid anhydride such as acetic anhydride, propionic anhydride, trifluoroacetic anhydride. The amount varies depending on the desired rate of imidization, but it is preferably 1 mol to 0.1 to 20 mol per repeating unit of polyamic acid. In addition, dehydration ring-closing catalysts such as pyridine, The tertiary amines such as Liding, Lutidine, triethylamine, etc., but are not limited to these. The amount of dehydration ring-closing catalyst is preferably 1 mol to 0.01 mol of the dehydrating agent used.率 The imidization rate can vary with the amount of the above-mentioned dehydrating agent and dehydrating ring-closing agent. This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) -25- 556030 A7 ____B7 V. Description of the invention (23) (Please read the precautions on the back before filling this page) Add more and increase. The organic solvents used in the dehydration ring-closing reaction include, for example, the organic solvents used in the synthesis of polyamic acid. The temperature of the dehydration ring-closing reaction is preferably 0 to 180 ° C, and 10 to 150 ° C. It is even better. The reaction solution thus obtained can be purified by the same operation as that of purifying polyamic acid. The terminally modified polymer is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The (A) component and (B) component in the present invention may also be terminal-modified types having a molecular weight adjusted. The use of the terminal-modified polymer can not impair the effect of the present invention, improve the coating characteristics of the liquid crystal aligning agent, and the like. Such a terminally modified polymer can be synthesized by adding an acid monoanhydride, a monoamine compound, a monoisocyanate compound, etc. to the reaction system when synthesizing polyamino acid. Here, the acid monoanhydride includes, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsalicylic anhydride, n-dodecylsalicylic anhydride, n-tetradecylsalicylic anhydride, and n-hexadecylwater Salicylic anhydride, etc. Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, and n-dodecylamine. Alkylamine, n-tridecylamine, n-tetradecanylamine, n-pentadecanylamine, n-hexadecylamine, n-heptadecanylamine, n-octadecylamine, n-eicosylamine, etc. Examples of the monocyanate compound include phenyl isocyanate, naphthyl isocyanate, and the like. The logarithmic viscosity of the polymer is used in the polymer of the present invention. The logarithmic viscosity (々 ^ η) of the polymer is preferably 0.05 to 10 g / g, and 0.05 to 5 g / g. Applicable to China National Standard (CNS) A4 specification (210 × 297 mm) 26- 556030 A7 B7 5. The invention description (24) is good. (Please read the precautions on the back before filling this page) The logarithmic viscosity (^ ln) in the present invention is N-methyl-2 2-pyrrolidone as the solvent, with a concentration of 0.5 g / 100 ml The viscosity of the solution was measured at 30 ° C, and it was calculated by the following formula (i). (X = ln (solution run-down time / solvent run-down time) Γ (weight concentration of polymer) 1 When the block copolymer is used in the polymer of the present invention as the block copolymer shown in 0 above, an amine at the end can be synthesized individually Amidine prepolymers based on amino or anhydride groups, and amidine prepolymers with acid anhydride or amine groups at the ends, the amine groups at the ends of each prepolymer are combined with the anhydride groups to produce block copolymers. The method for synthesizing acid prepolymer is the same as the method for synthesizing the polyfluorinated acid; the method for synthesizing the prepolymer is the same as the method for synthesizing the fluorinated polymer described above. In addition, the selection of the terminal functional group, It can be adjusted by the adjustment of the amount of tetracarboxylic dianhydride and diamine during the synthesis of polyamic acid. The liquid crystal alignment printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs [[The liquid crystal alignment agent of the present invention is composed of the above polymer components The (A) component and the (B) component are preferred, and are usually composed of a solution dissolved in an organic solvent. The mixing ratio of the (A) component polyfluoric acid and the (B) component fluorinated polymer, 9 9. 9 9 / 0. 0 1 to 10/90 is preferred, 99. 99 / 0. 1 to 4 0/60 is particularly good. This paper size applies the Chinese National Standard (CNS) A4 (210X297 mm) -27- 556030 A7 B7 V. Description of the invention (25) When the liquid crystal aligning agent of the present invention is prepared The temperature is preferably 0 ° C to 200 t. 20 ° C to 60 ° C is more preferred. (Please read the precautions on the back before filling this page) The organic component of the liquid crystal alignment agent of the present invention Solvents include, for example, N-methyl-2-pyrrolidone, r-butyrolactone, r-butyrolactam, N, N-methylformamide, N, N-dimethylacetamide, 4-one Guinea- 4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl Ether, ethylene glycol ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ether acetate, diethylene glycol diethylene glycol Methyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, etc. Ministry of Economic Affairs The solid content concentration of the liquid crystal aligning agent printed by the employee's cooperative of the property bureau is selected in consideration of viscosity and volatility, and is preferably 1 to 10% by weight. The liquid crystal aligning agent of the present invention is coated on the surface of the substrate to form The coating film is a liquid crystal alignment film. When the solid content concentration is less than 1% by weight, the thickness of the coating film is too low, which makes it difficult to obtain a good liquid crystal alignment film. When the solid content concentration exceeds 10% by weight, the coating film thickness is too large and it is also difficult to obtain. A good liquid crystal aligning film, and the viscosity of the liquid crystal aligning agent is increased, and the coating characteristics are deteriorated. The liquid crystal aligning agent of the present invention can also include a component from the viewpoint of improving the adhesion to the substrate surface within a range that does not damage the target physical properties. Functional sand compound, epoxy compound. Examples of the functional silane compound include 3-aminopropyltrimethoxy sand courtyard, 3-aminopropyltriethoxy stone courtyard, 2-aminopropyldimethoxy sand courtyard, 2- Aminopropyltriethoxy This paper is sized for the Chinese National Standard (CNS) A4 (210X297mm) -28- 556030 A7 B7 V. Description of the invention (26) (Please read the notes on the back before filling this page) Silane, N- (2-aminoethyl) -3-aminopropyltrimethoxysarane, N- (2-aminoethyl) -3-aminoaminomethyldimethoxysilane, 3 -ureidopropyltrimethoxysilane, 3 -ureidopropyltriethoxysilane, N -ethoxycarbonyl-3 -aminopropyltrimethoxysilane, N -ethoxycarbonyl-3 — Aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenediamine, N-trimethoxysilylpropyltriethylenediamine, 1 0-dimethoxylithium— 1, 4,7-2 0 yacrylate, 9 -trimethoxysilyl 3, 6-diazinyl acetate, 9-triethoxy silyl 3, 6-diazinyl acetate , N-benzyl-3-amine Propyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-amino Propyltriethoxysilane, N-bis (ethylene oxide) -3-aminopropyltrimethoxysilane, N-bis (ethylene oxide) -3-aminopropyltriethoxysilane, etc. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The epoxy compounds are, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and tripropylene glycol diepoxy. Propyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6 monohexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol Diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N ,, N --- tetraglycidyl-xylylenediamine, 1, 3 —Bis (N, N -diglycidylaminomethyl) cyclohexane, N, N, N ,, tetraglycid-4,4 / monodiaminodiphenylmethane, 3-( N-allyl-N-glycidylaminopropyltrimethoxysilane, 3- (N, N-glycidyl) aminopropyl This paper is sized for China National Standard (CNS) A4 (210X 297mm) -29- 556030 A7 —B7 V. Description of the invention (27) Trimethoxytriol. (Please read the precautions on the back before filling this page) The mixing ratio of these functional silane compounds and epoxy compounds is preferably 100 parts by weight or less to 40 parts by weight of the polymer. 30 parts by weight is more preferred. In particular, the addition of an epoxy compound can improve the scratch resistance of the obtained liquid crystal aligning agent film. Particularly preferred epoxy compounds are, N, N ,, N--tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N -glycidylaminomethyl) cyclohexane, N, N, N ', N, -tetraepoxypropyl-4,4, -diaminodiphenylmethane, 3- (N-allyl-N-epoxypropyl) aminopropyltrimethyl Nitrogen-containing epoxy compounds such as oxysilane, 3- (N, N-diepoxypropyl) aminopropyltrimethoxysilane, and the like. The liquid crystal aligning agent of the present invention is suitable for a vertical alignment type liquid crystal display element in which at least one of the substrates forming the liquid crystal element has a protruding shape. The liquid crystal display element includes a liquid crystal display element of the MV A method. Μ VA mode is as shown in `` LCD Vol. 3 No. 2 1 17 (1999) " or JP 1 1 — printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 2 5 8 6 0 5 The vertical orientation mode used as the orientation specification means. The protrusions may be formed on the T F T substrate side and the color filter side, respectively, or the protrusions may be formed on the color filter side, and the slits may be formed on the T F T side. Examples The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples.量 Imidization rate measurement method This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -30- 556030 A7 B7 V. Description of invention (28) (Please read the precautions on the back before filling this page ) The polymer was dried under reduced pressure at room temperature, and then dissolved in deuterated dimethylarsone. Using tetramethylsilane as a standard material, measured by 1 1-NMR at room temperature, and determined by the following formula (ii). .醯 Imidization rate (^ XI-AVa ^ oOxIOO (ii) A1: Peak area of protons from NH group (l0 pm) A2: Peak area of other protons ^: Polymer precursor (Polyamine In the acid), there are 1 proton for NH group and the ratio of the number of other protons. The manufacturing method of the liquid crystal display element is as shown in FIG. 1. There is a glass substrate (A) with IT0 with a protrusion formed by a positive resist, and IT 0 pattern glass substrates (B), each printed with a liquid crystal aligning agent, were dried at 80 t for 1 minute, and then dried at 180 t for 1 hour, forming a coating film with a dry film thickness of 600 angstroms. As described above, the property bureau employee consumer cooperative printed two substrates with a liquid crystal alignment film formed, and the outer edge of the substrate (B) was coated with epoxy resin containing alumina balls with a particle size of 3.5 microns by screen printing. After the resin-based adhesive, two substrates were bonded together in the positional relationship shown in Figure 1. The surface of the substrate and the outer edge of the substrate were divided into the cavity of the device divided by the adhesive, and injected with a liquid crystal ML C 6 6 0 8 manufactured by Merck. Then, the injection hole is blocked with an epoxy-based adhesive to produce a vertical alignment type liquid crystal display element. In Figure 1, '1 series color filter side electrode (IT〇), 2 series liquid crystal alignment film' 3 series pixel electrode (I τ〇), 4 series orientation specification means (this paper standard applies Chinese National Standard (CNS) a4 specification (210X297 mm) -31-556030 A7 _____ B7___ 5. Description of the invention (29) (Please read the precautions on the back before filling this page) (protrusion), 5 series orientation specification means (gap), and 6 series liquid crystal The numerator. The liquid crystal display element at a vertical voltage of 0FF and an alternating current of 12 volts (peak-to-peak) is observed under crossed Nicols. The voltage retention rate of the liquid crystal display element is 5 volts and 60 microseconds. The application time is 167 milliseconds after the span is applied, and the voltage retention rate is measured after 167 milliseconds after the application is released. The measuring device is used to remove the afterimage of the VHR-1 liquid crystal display element made by Toyo Technica Co., Ltd. Time at the liquid crystal display element, 30 Hz, 3.0 V rectangular wave with DC 3.0 V, AC 6.0 V (peak-to-peak) overlapping, applied for 20 hours at 70 ° C ambient temperature , Make the voltage be 0 f F, and measure the removal time of afterimage by visual inspection Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs < Synthesis of Polymers > Synthesis Examples 1 to 10 N-methyl-2-pyrrolidone 'was added according to the composition of Table 1 in order, and diamine and tetracarboxylic acid were added sequentially. The dianhydride was 30% by weight of solid content concentration in Synthesis Examples 3, 4, 6, 8 and 9 and was reacted at 60 ° C for 6 hours. The concentration of solid content in Synthesis Example 1, 2, 5, 7, and 10 series was 2%. % By weight, applicable to Chinese papers (CNS) A4 specifications (210X297 mm) -32- 556030 A7 B7 at room temperature. The description of the invention (30) should take 6 hours to obtain the polyamidine of logarithmic viscosity in Table 1. Acids I to X. Table 1 Synthesis Example Polymer Anhydride Logarithmic Viscosity of Diamine (Common / g) 1 I TCAAH (50) PDA (45) / Diamine ② (5) 1.18 2 II PMDA (25) / CB (25) DDM (50) 1.33 3 III TCAAH (50) PDA (40) / Diamine® (10) 1.34 4 IV TCAAH (50) PDA (37.5) / Diamine② (12.5) 1.02 5 V PMDA (25) / CB (25) DDE ( 50) 1.33 6 VI TCAAH (50) PDA (35) / diamine② (12.5) / diamine④ (2.5) 1.04 7 VII TCAAH (50) PDA (45) / diamine① (5) 1.22 8 VIII TCAAH ( 50) PDA (3 7 · 5) / diamine① / (12.5) 1.09 9 IX TCAAH (50) PDA (20) / diamine③ (30) 1.18 10 X CB (50) MTB (50) 1.02 () Molar% TCAAH: 2 '3,5-tricarboxycyclopentylacetic acid CB: 1' 2,3,4-cyclobutane tetracarboxylic dianhydride PMD A: pyromellitic dianhydride Financial Information Standard (CNS) Α4 Specification (21GX297 Public Director) I -----.---- # 批 衣 I- ^ (Please read the precautions on the back before filling this page)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, 1T-33- 556030 A7 B7 4 Diamine Biphenyl V. Description of the Invention (31) PDA: p-phenylenediamine CDE: 4, 4 — monoamine monophenyl ether DDM : 4,4,1-diaminodiphenylmethane MTB: 2, 2 /-dimethyldiamine ①: diamine diamine of formula (9) ②: diamine diamine of formula (10) ③: Diamine diamine of formula (1 3) ④: Synthesis Examples of Diaminopropyl Tetramethyldisilazane 11 to 18 Each polyamic acid in Table 2 is diluted with N-methyl-2-pyrrolidone to a solid content The concentration was 5 wt%, and pyridine and acetic anhydride were added to each polyamine for synthesis of diamine. (: Stir for 4 hours to synthesize fluorene imidized polymers ① to ⑧. This polymer solution is reprecipitated with diethyl ether to obtain a white powder of fluoridized imidate polymers. The polyimide ratios of the obtained polymers are listed in the table. 2. (Please read the notes on the back before filling this page) The paper size printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs applies to the Chinese National Standard (CNS) a4 size (210 X 297 mm) -34- 556030 A7 B7 5 Description of the invention (32) Table 2 Synthesis Example Polyammonium sulfonium imidized polymer nth steep / fluorinated anhydride (Mole, fluorinated imidization rate (%) 11 I ① 5.0 / 3.0 V / u / > Q 〇12 III ② 5.0 / 3.0 〆y > 90 13 IV ③ 5.0 / 3.0 > 90 14 VI ④ 5.0 / 3.0 ^ y \ j > 90 15 VI ⑤ 1.5 / 1.5 60 16 VII ⑥ 5.0 / 3.0 > 90 17 VIII ⑦ 5.0 / 3.0 > 90 18 IX ⑧ 5.0 / 3.0 > 90 (Please read the notes on the back before filling out this page) Employees ’Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed Examples 1 to 14, Comparative Examples 1 to 3 polyamidic acid (component (a)), fluorinated polymer (B) component obtained in Synthesis Examples 1 to 18, and If necessary, the additive n, N, N /-tetraglycidyl-4,4 diaminodiphenylmethane (epoxy compound) is mixed according to the composition of Table 3 to prepare a solid content concentration of 6.0% by weight The vertical alignment type liquid crystal aligning agent of the present invention was obtained. The liquid crystal aligning agent was used to make liquid crystal display elements for various evaluations. The results are shown in Table 4. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm)- 35- 556030 A7 B7 V. Description of the invention (33) Table 3 (A) Poly (B) polyimide solvent additive Aminated polymer 11 (80) ③ (20) BL (4 0) / NMP (50) / BC (1 0) 20 2 11 (80) ① (20) BL (6 0) / NMP (2 0) / BC (2 0) 20 3_ 11 (80) ② (20) BL (40) / NMP ( 50) / BC (10) 20 4 V (80) ④ (30) BL (40) / NMP (50) / BC (10) 20 5 V (80) ⑤ (20) NMP (60) / DAA (40) 20 Real 6_ V (80) ⑥ (20) BL (40) / NMP (50) / BC (10) 20 7_ V (80) ⑦ (20) BL (40) / NMP (5 0) / BC (1 0 ) 20 Apply 8 V (80) ⑧ (20) BL (4 0) / NMP (5 0) / BC (1 0) 20 9 X (80) ④ (20) BL (40) / NMP (5 0) / BC (1 0) 20 cases 10 X (80) ⑤ (20) NMP (60) / DAA (40) 20 11 11 (90) ③ (10) BL (40) / NMP (50) / BC (10) 20 12 11 (50) ③ (50) BL (4 0) / NMP (5 0) / BC (1 0) 20 13 11 (80) ③ (20 ) BL (40) / NMP (50) / BC (10) 14 X (80) ④ (20) BL (40) / NMP (50) / BC (10) than 1 1 (100)-one BL (30) / NMP (70) 20 than 2 IV (100) — BL (30) / NMP (70) 20 Example 3 VI (100) ~ BL (30) / NMP (70) 20 (Please read the precautions on the back before filling (This page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs * The numbers in () are as follows. (A) component, (B) component:% by weight of the entire polymer Solvent: Various solvents by weight of the entire solvent * The additive amount is 100 parts by weight of the polymer and parts by weight of the additive. * The codes of each solvent are as follows. BL: r-butyrolactone NM: N-methyl-2-pyrrolidone BC ·. Butyl cellosolve_ DAA ·· 4 —hydroxy-4 —methyl-2 —pentanone (diacetone alcohol This paper is applicable to Chinese countries Standard (CNS) A4 specifications (210X297 mm) -36- 556030 A7 B7 Table 4 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (34) Vertical orientation voltage retention (%) Afterimage removal time ( Second) Example 1 Good 98.8 40 Example 2 Good 98.6 50 Example 3 Good 98, 6 45 Example 4 Good 98.7 20 Example 5 Good 98.4 45 Example 6 Good 98.6 80 Example 7 Good 98.7 50 Example 8 Good 85.2 90 Example 9 Good 98.6 20 Example 10 Good 98.7 35 Example 11 Good 98.8 30 Example 12 Good 98.8 50 Example 1 3 Good 98.2 30 Example 14 Good 98.2 30 Comparative Example 1 Good 99.0 250 Comparative Example 2 Good 99.2 200 Comparative Example 3 Good 98.4 150 Comparative Example 4 Defective use of the liquid crystal aligning agent of the present invention can obtain good vertical alignment of the liquid crystal, short afterimage removal time, and is suitable for the liquid crystal of the VA method Liquid crystal alignment film for display elements. Appropriate size for domestic use (Medium size 210X297 mm) (Please read the precautions on the back before filling this page) -37-

Claims (1)

556030 Thai A8 B8 C8 D8 VI. Patent application scope 1 1. A liquid crystal vertical alignment liquid crystal aligning agent, characterized in that it contains (A) a repeating unit with the following formula (I-1), and (B) with the following formula (I-12) Polymers of repeating units, HOOC, .COOHψHNOC〆, CONH —Qx where P1 is a tetravalent organic group and Q1 is a divalent organic group; (Please read the notes on the back before filling this page) Ο 0 〇 0 wherein p 2 is a tetravalent organic group, and Q 2 is a divalent group of the following formula (Q — 1) or the following formula (Q — 2), X1—R1 (Q-1) In the printed format of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, the X1 system is Zhuo Jian, 101, 1 c01, 1 c001, —0C〇, 1 NHC 〇 —, One C Ο Ν Η —, one S — or a square group, R1 is an alkyl group having 10 to 20 carbon atoms, and a monovalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms or 6 to 6 carbon atoms Valent organic group containing fluorine atom of 20; Chinese paper standard (CNS) A4 specification (210X297 mm) is adopted for this paper size -38- 556030 Α8 Β8 C8 D8 Patent application scope 2 -X2—R2—χ3_ (Q — 2) In the formula, X2 and X3 are the same or different, and are single bonds,-, -CO1, -10c01, -n: HC0-C0-C0N Η1, -S-or extension An aryl group, R2 is a divalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms. 2. The liquid crystal aligning agent according to item 1 of the scope of patent application, wherein the polymer has repeating units of the above formula (〗 _ 2) in the repeating unit of all fluorene imine rings of 5 mole% or more. 3 · If the liquid crystal aligning agent in item 1 of the patent application scope, use its vertical alignment type liquid crystal display element to form at least one substrate of the liquid crystal element · Has a protruding shape. (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper size applies to China National Standard (CNS) Α4 specification (210 × 297 mm) -39-