TW583426B - Vertically aligning-type liquid crystal aligner and liquid crystal display element using the same - Google Patents

Abstract

To provide a vertically aligning-type liquid crystal aligner having excellent vertical alignability, giving short erasing time of an afterimage of a liquid crystal display element, and preferably used for a liquid crystal display element of EVA system or of photo-aligning system photo-aligning by polarized UV-ray irradiation, and a liquid crystal display element using the aligner. This vertically aligning-type liquid crystal aligner comprises a polyamic acid and/or imidized polymer thereof containing a specific structure diamine.

Description

583426 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (1) [Technical Field of the Invention] The present invention relates to a vertical alignment type liquid crystal alignment agent and a liquid crystal display element using the same. More specifically, the present invention provides an EVA (Electrically Vertical Alignment) liquid crystal display element that is extremely suitable for use in liquid crystal display elements that have vertical alignment, printability, and extremely short afterimage erasing time in liquid crystal display elements. The vertical liquid crystal alignment agent of the vertical alignment type liquid crystal display element of the light alignment method of alignment by polarized ultraviolet light irradiation. [Prior art] At present, it is known that a liquid crystal display element is formed on the surface of a substrate provided with a transparent conductive film. A liquid crystal alignment film made of polyamic acid, polyimide, or the like is formed as a substrate for a liquid crystal display element. The substrate is arranged in two opposite directions, and a nematic liquid crystal layer with positive dielectric anisotropy is formed in the gap as a unit cell of a sandwich structure, so that the major axis of the liquid crystal molecules is from one side to the other. The substrate is continuously rotated 90 degrees toward the other substrate, that is, a TN type liquid crystal display element having a TN type (Twisted Nematic) liquid crystal cell. For example, STN (Super Twisted Nematic) type liquid crystal display elements which have higher contrast than TN type liquid crystal display elements and have lower dependence on viewing angle have been developed. The aforementioned STN type liquid crystal display device is doped with a mirroring agent as an optically active substance in a nematic liquid crystal for use as a liquid crystal, and uses a long axis of liquid crystal molecules to continuously twist 180 degrees between substrates. Multi-refraction effect produced by the above state. In contrast, "Liquid Crystal" νο1 · 3 Νο · 4 272 (1999) revealed that (please read the precautions on the back before filling out this page)-The size of the paper used for binding and binding is applicable to the Chinese National Standard (CNS) Α4 Specifications (210X297 mm) -4- 583426 A7 B7 V. Description of the invention (2) EVA method of re-processing the electrode structure to accurately control the orientation direction, "Jpn Appl · Phys." Vol 36 428 (1997) It discloses a proposal of a vertical alignment type liquid crystal display element such as a light alignment method that modifies the alignment film to control the alignment direction due to light irradiation. The aforementioned vertical alignment type liquid crystal display element has excellent viewing angle, contrast, etc., and also forms a liquid crystal alignment film. It is not necessary to use the excellent surface of the manufacturing process such as rubbing treatment. However, as described above, when compared with TN and STN types, the performance is still insufficient, especially the vertical alignment and liquid crystal display elements need to be improved. Performance such as afterimage erasing time. [Objective of the Invention] The present invention provides an E which is extremely suitable for use in liquid crystal display elements with excellent vertical alignment and extremely short afterimage erasing time. A liquid crystal display element of the VA type or a vertical liquid crystal alignment agent of a liquid alignment type liquid crystal display element that can perform light alignment by a polarized ultraviolet irradiation method and a liquid crystal display element using the same. Other objects and advantages of the present invention will be described through the following. It is understood that [contents of the invention] According to the contents of the present invention, the purpose and advantages of the present invention are to provide a vertical alignment type liquid crystal alignment agent, which contains a repeating unit selected from the following formula (I-1) Polymers with at least one repeating unit among the repeating units shown in the following formula (I-2) (hereinafter, referred to as "the specific paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm)) (Please read first Note on the back, please fill in this page again) Binding and printing printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -5- 583426 A7 B7 V. Description of Invention (3) Polymers ").

HOOC .COOH / HNOC CONH—Q1

1 — 1 (where P1 is a tetravalent organic group, and Q1 is a group represented by the following formula (Q-1) or (Q-2)).

(Please read the notes on the back before filling in this page.) Binding and binding (where P2 is a 4-valent organic group, Q2 is a base other than the following formula (Q-1) or (Q-2)). R1 (Q-1) (where X is 101, -c01, -c001, -10C01, -NHC ◦--CON-, -s-, Base, bivalent base selected from alkane and phenyl with 2 to 6 carbons. This paper size applies to China National Standard (CNS) A4 (210X297 mm). Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs.

-6- 583426 A7 B7 V. Description of the invention (4) R1 is an alkyl group having 10 to 20 carbon atoms, a monovalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms or a fluorine atom having 6 or more carbon atoms (1-valent organic group).

X ~ R

(Q-2)

(In the formula, X is 010 OCO-'-NHCO C〇C〇〇-C 〇 N Η I. 嶒 (Please read the precautions on the back before filling this page) • Packing, methyl, carbon number A divalent group selected from an alkylene group of 2 to 6 and a phenylene group, and R2 is a divalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms or a monovalent organic group having a fluorine atom having 6 or more carbon atoms. base). [Embodiments of the invention] The present invention will be further described below. The vertical alignment type liquid crystal alignment agent (hereinafter referred to as "liquid crystal alignment agent") of the present invention is made up of a specific polymer dissolved in an organic solvent. The specific polymer described above is a fluorinated polymer having a structure obtained from polyfluorinated acid or polyfluorinated acid through dehydration ring closure (fluorinated). The fluorene imidization polymer is a polyfluorene imide containing 100% dehydration ring closure (fluorene imidization), or a polymer obtained by partial dehydration ring closure (fluorene imidization). In addition, the liquid crystal alignment agent of the present invention may include both polyamidic acid and amidine polymer. The polymer composition of the liquid crystal alignment agent of the present invention, the above paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) Printed by the Consumer Cooperative 583426 A7 _________ B7_ 5. Description of the invention (5) The repeating unit shown in formula (Q-1) accounts for more than 5 mol% of all repeating units. [Polyamidate] < Tetracarboxylic dianhydride > The tetracarboxylic dianhydride used in the synthesis of the polyamic acid is preferably an alicyclic tetracarboxylic dianhydride. Specific examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4,4-cyclobutanetetracarboxylic dianhydride Anhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,1,2,3,4-cyclobutanetetracarboxylic dicarboxylic acid Anhydride, 1,2,3,4-tetrafluorenyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4 monocyclopentanetetracarboxylic dianhydride, 1,2 , 4,5-cyclohexanetetracarboxylic dianhydride, 3,3,, 4,4, -dicyclohexyltetracarboxylic dianhydride, cis-3,7-dibutylcyclooctyl-1,5- Diene-1,2,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,5 '6-tricarbonyl- 2-carboxyorthospin-2: 3,5: 6-dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3 a '4' 5 '9b —hexamine-5 (tetrachloro-2' 5 — — * Oxo-3furyl) -naphthalene [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5methyl-5- ( Tetrahydro_2,5 -dioxo one 3 —pyranyl) —naphthalene [1 ′ 2 — c] —furan-1, 3-dione, 1, 3, 3 a, 4, 5, 9 b -hexahydro-5 -ethyl-5 (tetra Hydrogen—2,5—dioxo-3—furan The basic paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) 4-. ------ (Please read the notes on the back before filling this page) -8- 583426 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (6)) —Naphthalene [1, 2 — c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-methyl-5 (tetrahydro-2, 5-dioxo-3-furanyl ) —Naphthalene [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexakis-methyl-5 (tetrahydro-2,5-dioxo -3-furanyl) -naphthalene [1,2-c] -pyran-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-ethyl-5 (tetrahydro Mono-2,5-dioxo-3-furanyl) naphthalene [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b Hexahydro-8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphthalene [1,2, c] -pyran-1,3-dione, 1,3, 3a, 4,5,9 b-hexahydro-8-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphthalene [1,2-c] -furan-1,3 —Dione, 1, 3, 3a, 4, 5, 9b —hexahydro-5,8 —dimethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) —naphthalene [1, 2 -c] -pyran-1,2-dione, 5- (2,5-dioxotetrafuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid di Anhydride, bicyclo [2,2,2] -octyl-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo [3,2,1] octane-2, 4-one ketone-6-spiro-3- (tetrahydrofuran-2 ', 5'-one ketone), compounds represented by the following formulae (I) and (II), etc .; (Please read the precautions on the back before reading (Fill in this page)

、 1T This paper size is applicable to China National Standard (CNS) A4 (210X297mm) -9-583426 A7 B7

C

0 ⑴ 0 R5 R5 0 R- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (II) (where R3 and R5 are divalent organic groups with aromatic rings, R4 and R6 are hydrogen atoms or alkyl groups, and they exist in plural (R4 and R6 may each be the same or different). Other tetracarboxylic dianhydrides are, for example, aliphatic tetracarboxylic dianhydrides such as butane tetracarboxylic dianhydride; pyromellitic dianhydride, such as 3,3, '4,4'-benzophenone tetracarboxylic acid Acid dianhydride, 3,3,4,4'-biphenylsulfotetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid Dianhydride, 3,3 ', 4,4'diphenyl ether tetracarboxylic dianhydride, 3,3,, 4,4' monodimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ,, 4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4,1-bis (3,4-dicarboxyphenoxy) diphenyl Sulfide dianhydride, 4,4 'one bis (3,4 one dianxiangylphenoxy) diphenylsulfonic dianhydride, 4,4' one bis (3 '4 one dicarboxylic acid 0 0 National Standard (CNS) A4 Specification (210X297 mm) (Please read the precautions on the back before filling out this page) -Packing ·, 11 -10- 583426 A7 B7 V. Description of the Invention (8) Phenyloxy) Diphenyl Propane dianhydride, 3,3 ', 4,4' monoperfluoroisopropylenediphthalic dianhydride, 3,3 ' 4,4'-diphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine dianhydride, P-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene Bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl_dianhydride, bis (triphenylphthalic acid) -4,4 ' Diphenylmethane dianhydride, ethylene glycol bis (anhydrotrimellitic acid ester), propylene glycol-bis (anhydrotrimellitic acid ester), 1,4 monobutylene glycol bis (anhydromelic acid trimellitate) ), 1,6-hexanediol mono-bis (anhydrotrimellitate), 1,8-octanediol mono-bis (anhydrotrimellitate), 2,2-bis (4-monohydroxyphenyl) Aromatic tetracarboxylic dianhydride and the like such as propane-bis (anhydrotrimellitic acid ester) and compounds represented by the following formulae (1) to (4). These can be used individually by 1 type or in combination of 2 or more types. (Please read the precautions on the back before filling out this page) The paper size printed by the S Industrial Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -11-583426 A7 B7 V. Invention Note (9) H3 C. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

H3H3 (Please read the notes on the back before filling this page) This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) -12- 583426 A7 B7 V. Description of the invention (10 Fatty acid tetracarboxylic acid described above Among the dianhydrides, 1 1 2 3 4 —cyclobutanetetracarboxylic dianhydride Λ 1 3 —dimethyl — 1 9 2 3, 4 —cyclobutanetetracarboxylic dianhydride Λ 1 2 3 4 — tetramethyl — 1 5 2 > 3 4 — bad butyl tetracarboxylic dianhydride Λ 1 2, 3 9 4 — TM. Bad pentane tetracarboxylic dianhydride 2 3 5 5 — tricarboxyl • rm m pentylacetic dianhydride, 5 — (2, 5 —dioxotetrahydrofuryl) — 3 —methyl — 3 —cyclohexene — 1 2 —dicarboxylic dianhydride, cis — 3, 7 —monobutyl IS m octyl — 1 5 —Diene— 1 2 5 5 6 —tetracarboxylic dianhydride 3 5 5 6 —dim group — 2 —carboxyl orthocyanine — 2: 3? 5: 6 — monoanhydride, 1 9 3 > 3 a, 4, 5 9 b — -Γ. / \ Hydrogen — 5 — (tetrahydro — 2, 5 — — ^ oxo — 3 Furanyl) — naphthalene C 1 2 — C) furan — 1 5 3 — —. Ketones 1 3, 3 a 4 5 5 9 b —, r, · hydrogen — 8 — methyl — 5 — (tetrahydro-2, 5 — dioxo — 3 — furanyl)-naphthalene [1 (Please read the notes on the back before filling out this page) Pack. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 2 — c] Furan -1, 3 — Dione, 1, 3, 3a, 4, 5, 9b —hexahydro-5,8 —dimethyl-5 — (tetrahydro-2,5-dioxo-3 -furanyl) —naphthalene [1, 2-c] furan-1,3-dione, bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo [ 3,2,1] octane-2'4-one-one-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), the following compounds of the formula (I) The compounds represented by formulas (5) to (7) and the compounds represented by formula (8) below among the compounds represented by formula (II) above are preferred compounds because they have good liquid crystal alignment. In particular, 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid are applicable to Chinese national standards on the paper scale ( CNS) A4 specification (210X297 mm) -13-583426 A7 B7 V. Description of the invention (1) dianhydride, 2, 3, 5-tricarboxycyclopentylacetic dianhydride, 1, 3, 3 a, 4, 5 , 9 b —hexahydro-5 — (tetrahydro-2,5-dioxo-3-furanyl) -naphthalene [1,2, c] furan-1,3-dione, cis-3,7-di Butylcyclooctyl-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 3,5,6-tricarbonyl-1 2-carboxyorthospinane-2: 3,5: 6 —Dianhydride, 1,3,3a, 4,5,9b —hexahydro-8-methyl-5 — (tetrahydro-2,5-dioxo-3 —furanyl) -naphthalene [1, 2 — c] furan-1,3-dione, 3-oxabicyclo [3,2,1] octane-2,4-dione-6-spiro-1 '(tetrahydrofuran-2', 5'-1 A diketone) and a compound represented by the following formula (5) are more preferred. (Please read the notes on the back before filling this page)

This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) -14-583426 Α7 Β7 V. Description of the invention (for ο π

The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the better of other tetracarboxylic dianhydrides, such as butanetetracarboxylic dianhydride and pyromellitic dianhydride, such as 3,3, '4,4' —diphenyl Methyl ketone tetracarboxylic dianhydride, 3,3, '4,4, -biphenyl tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride and the like. Among the aforementioned tetracarboxylic dianhydrides, an alicyclic tetracarboxylic dianhydride accounts for more than 50% of the total tetracarboxylic dianhydride. < Diamine > The group represented by the above formula (Q-1) and the above formula (Q-2) is a group that generates a diamine in the synthesis of a polyamino acid. Hereinafter, a diamine having a group represented by the above formula (Q-1) and the above formula (Q-2) is also referred to as a "specific diamine". In the above formula (Q-1), R1 is an alkyl group having 10 to 20 carbon atoms, for example, η-decyl, η-twelve-base, η-fifteen-base, η--16-base, η- Eighteen 垸 ji, η-twenty Yuanji and so on. In addition, R1 in the above-mentioned formula (Q-1) and the above-mentioned formula (Q-2) (please read the precautions on the back before filling in this page)-Binding and binding paper size Common Chinese National Standard (CNS) A4 Specifications (210 × 297 mm) -15- 583426 A7 B7 V. Description of the invention (as a monovalent organic group having an alicyclic skeleton having a carbon number of 4 to 40 as shown by R2, such as cyclobutane, cyclopentane, ring Cycloalkanes such as hexane and cyclodecane have alicyclic skeletons; Cholesterol and dihydrocholesterol have steroid skeletons; Protospines and adamantanes have bridging alicyclic skeletons. The best is η-octadecyl and cyclohexyl to generate a base having only an alicyclic skeleton and a base having a steroid skeleton. The organic group having the above-mentioned alicyclic skeleton may be a halogen atom, preferably a fluorine atom. Substituted groups are preferred. In addition, R1 in the above formula (Q-1) is a group having a fluorine atom of 6 or more, such as η-hexyl, η-octyl, η-decyl, and the like. Above linear alkyl groups; cyclohexyl, cyclooctyl and other alicyclic hydrocarbon groups having 6 or more carbon atoms; phenyl, biphenyl Organic groups such as aromatic hydrocarbon groups having a carbon number of 6 or more are substituted by a part or all of the worn atoms or oxygen groups. The above formula (Q-1) and the above formula (Q-2 ) 2 in X) "For example," Organic radicals "such as 101, -001, -101, -NHCO-, -CONH-, -C0-, methyl group, carbon number The alkylene and phenylene groups of 2 to 6, etc., among which are the groups represented by 10-, -c001, and 10c01. Diamines having a group represented by the above formula (Q-1) Specific examples, such as undecyloxy-2,4-diaminobenzene, fifteenrinoxy-2,4-0 female basic, hexadecyloxy-2,4-diaminobenzene, Eighteen-house oxy-2,4-diaminobenzene, compounds represented by the following formulae (9) to (16) are preferred. This paper size applies to China National Standard (CNS) A4 specification (210 X 297) Mm) (Please read the notes on the back before filling this page)

Printed by 1T Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs -16-583426 A7 B7 V. Description of Invention

This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -17- 583426 A7 B7 V. Description of the invention (for CH3 H2N 〇 C00

CH3 CH3 (17) CH3

^ CH3, CH3 (18) CH3 H2N — <> ~

/ CH3, CH3 (19) (Please read the precautions on the back before filling this page) • Installed-Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs H2N — <> — O-C4H8—0 — <> — NH2 (20) H2N O-C12H24—ο ο ΝΗ2 (21) In the synthesis of the polyamic acid used in the present invention, the Chinese paper standard (CNS) A4 specification (210 ×: 297) applicable to the paper size of the present invention is not damaged. (%) -18- 583426 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (# To the extent of the effect, other diamine compounds can be used. Other diamine compounds such as P-phenylenediamine, m- Phenylenediamine, 4,4'-diaminodiphenylphosphonium, 4,4'-diaminodiphenylethane, 4,4'-diaminomonophenylsulfide, 4 '4' — Monoamino-phenylphenyl, 3,3'-methyl-4,4'-diaminobiphenyl, 4,4, -diamino N-phenylanilide, 4,4'- Diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 5-monoamino-1 (4'-amine Phenyl) -1, 3,3-trimethylbenzyl, 6-amino-1 1- (4 'monoaminophenyl) -1,3,3-trimethylindane, 3,4'-diaminodiphenyl Ether, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2 'one pair [4— (4-monoaminophenoxy) phenyl] propane, 2,2'-bis [4- — (4-monoaminophenoxy) phenyl] hexafluoropropane, 2,2'-bis (4-amino Phenyl) hexafluoropropane, 2,2'-bis [4-mono (4-aminoaminophenoxy) phenyl], 1,4-bis (4-aminoaminophenoxy) benzene, 1,3- Bis (4-monoaminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-monoaminophenyl) -10-hydroanthracene, 2,7 -Diaminofluorene, 9,9 bis (4-aminophenyl) fluorene, 4,4 'methylidene-bis (2-chloroaniline), 2,2', 5,5'-tetrachloro- 4, 4, 1- ^ aminobiphenyl, 2,2 — — ^ chloro-4,4 — — * amino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy -4., 4'-diamino Biphenyl, 1, 4, 4 '— (p —phenylene isopropylidene) bisaniline, 2, 2' one double [4 one (4 one amino group — one paper size applies to Chinese National Standard (CNS) A4 size (210X297mm) (Please read the precautions on the back before filling this page)

1T -19-583426 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (for 2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-diamino Aromatic dimers such as 2,2 'bis (trifluoromethyl) biphenyl, 4,4' bis [(4-monoamino-difluoromethyl) phenoxy] -octachlorobiphenyl Amines; 1,1,1-dioxooxydiamine, 1,3-propanediamine, tetramethyldiamine, pentamethyldiamine, hexamethyldiamine, heptamethyldiamine, octamethyldiamine , Nonamethyldiamine, 4,4'-diaminoheptamethyldiamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienediamine, hexamethylene Hydrogen-4,7-methanolylindanedimethylenediamine, tricyclo [6.2.1.202'7] undecenedimethyldiamine, 4,4'-methylenedibis ( Cyclohexylamine) and other aliphatic and alicyclic diamines; 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyridine, 5,6-diamino-2,3-diaminopyrazine, 5,6-diamino-2,4-dihydropyrimidine, 2 4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis (3-aminopropyl) piperidine, 2,4-diamino-6-isopropyl Oxy-1,3,5-triamidine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-phenyl-1, 3,5-triazine, 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazine, 4,6-diamine 2-ethenyl-s-triazine, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethylurea Pyrimidine, 3,5-diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridine propionate, 3,8 (Please read the notes on the back first (Fill in this page again) • Packing · This paper size applies to China National Standard (CNS) Α4 size (210X297 mm) 20- 583426 A7 B7

V. Description of the invention (1) B monoamino-6-phenylphenanthridine, 1,4-diaminopiperazine, 3,6-diaminodine, bis (4-aminophenyl) phenyl Amines, etc. have two 1-based amine groups in the molecule and the diamines of the following formula (III) so the external nitrogen atom; amine organic sand oxygen institute; R7 R7 H2N-f CH2) — Si ^ 〇- Λ 'R R7 (III) (wherein R7 is a hydrocarbon group having 1 to 12 carbons, and R7 in the plural exists each may be the same or different, P is an integer of 1 to 3, and Q is an integer of 1 to 20) The aforementioned = amine 'may be used alone or in combination of two or more. Among them, P-phenylenediamine, 4,4, -diaminodiphenylmethane, 4 '4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 7-di Amine hydrazone, 4,4,4-diphenyl ether, 2,2'-bis [4-((4-aminoaminophenoxy) phenyl] propane, 9,9- (Please read the precautions on the back before (Fill in this page)

, 1T Printed bis (4-aminoaminophenyl) pyrene, 2,2 'bis [4-mono (4-monoaminophenoxy) hexafluoropropane, 4phenyl] hexafluoro Propane, 2,2'-bis (4-aminophenoxy) alkane, 4,4 '-(p-phenylene diisopropylidene) bisaniline 4'-(m-phenylene diisopropylidene) Group) bisaniline, 1,4-monocyclohexanediamine, 4,4'-methylenebis (cyclohexylamine), 1,4-bis (4-aminophenoxy) benzene, 4,4'-double (4-monoaminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine This paper is sized to the Chinese National Standard (CNS) A4 (210 X 297 mm)- 21-583426 A7 B7 V. Description of the invention (It is better to show the compounds shown as pyridine, 2,4-diaminopyrimidine and 3,6-diaminoacridine. (Please read the precautions on the back before filling this page) The proportion of the specific diamine component to the total diamine component in the total polymer contained in the liquid crystal alignment agent of the present invention is preferably 5 mol% or more for the total amount of the diamine component. More preferably 10 Moore %, If the proportion is less than 5 mol%, it will be difficult to obtain a sufficient vertical alignment effect. &Lt; Synthesis of polyamic acid &gt; Tetracarboxylic dianhydride and dicarboxylic acid The proportion of the amine compound to be used is preferably 1 equivalent to the amine group contained in the diamine compound, and 0.2 to 2 equivalents of the anhydride group of the tetracarboxylic dianhydride, and more preferably 0.3 to 1.2 equivalents. The synthesis reaction of ammonium acid is carried out in an organic solvent, and is generally carried out at a temperature of 20 t: to 150 t, preferably 0 to 100 t. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Among them, the organic solvent is not particularly limited as long as it can dissolve the synthetic polyamidonic acid, for example, 1-methyl-2-D-bivaloxone, N, N-dimethylvinylamine, N, N- Aprotic polar solvents such as dimethylformamide, dimethylsulfoxide, r-butyrolactone, tetramethylurea, hexamethylphosphinetriamine; m-cresol, bisphenol, phenol, halogenated Phenol-based solvents such as phenol, etc. The amount of organic solvent used (^) is generally the compound of tetracarboxylic dianhydride and diamine. The total amount of the substances is preferably 0.1 to 30% by weight based on the total amount of the reaction solution (α + / 3). In addition, in the organic solvent described above, Alcohols in lean solvents This paper applies Chinese National Standard (CNS) A4 specifications (210 X 297 mm) -22-583426 Α7 B7 V. Description of the invention (, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons It can be used in a range that does not cause crystallization of the produced glutamic acid. Specific examples of the aforementioned poor solvent, such as methanol, ethanol, isopropanol, cyclohexanol, 4-hydroxyl-4-fluorenyl-1 2 —Mitanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl Isobutanone, cyclohexanone, methyl 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-i-propyl 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 Ethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1, 2-dichloroethane, 1, 4 Dichlorobutane, trichloroethane, chlorobenzene, 0-chlorobenzene, Jiyuan, Gengyuan, Xinyuan, benzene, toluene, xylene, etc. As shown above, the reaction solution can be prepared by dissolving the polyamic acid. Subsequently, the reaction solution was poured into a large amount of a lean solvent to obtain a precipitate, and the precipitate was dried under reduced pressure to obtain a polyamic acid. In addition, the polyfluorene I can be re-dissolved in an organic solvent, followed by one or more precipitation steps with the solvent to refine the polyphosphonic acid. [Dehydration and Closed-loop Reaction] The specific polymer constituting the liquid crystal alignment agent of the present invention can be used for: upper | heteropoly This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the precautions on the back first) (Fill in this page) • Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -23-583426 A7 B7 Printed by the Employee Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (2) 1 Part or all of amino acids Synthesized via dehydration ring-closing reaction. The proportion of the specific polymer used in the present invention 'with respect to the repeating unit having a fluorene imine ring in all the repeating units (hereinafter also referred to as "fluorine imidization") is 40 mol% or more, preferably 50 mol. Those with ears above. When a polymer having an imidization ratio of 40 mol% or more is used, a liquid crystal alignment agent capable of producing a liquid crystal alignment film having a short afterimage erasing time can be obtained. The dehydration ring closure of polyamic acid is (i) heating the polyamic acid by heating, or (ii) dissolving the polyamic acid in an organic solvent, and then adding a dehydrating agent and a dehydrating closed-loop catalyst to this solution. And, if necessary, by heating. The reaction temperature of the method for heating polyamic acid according to (i) above is generally 50 to 200 ° C, preferably 60 to 170 ° C. When the reaction temperature is lower than 50 ° C, the dehydration ring-closing reaction does not sufficiently proceed. When the reaction temperature exceeds 200 ° C, the molecular weight of the obtained fluorinated imidized polymer may decrease. In addition, in the method of adding a dehydrating agent and a dehydrating closed-loop catalyst to the polyamic acid solution described in (ii) above, for example, acetic anhydride, anhydrous acrylic acid, and anhydrous trifluoroacetic acid can be used as the dehydrating agent, and the amount of the dehydrating agent used, It is preferred to use 0.01 to 20 moles for 1 mole of polyamic acid repeat unit. As the dehydration ring-closing catalyst, for example, tertiary amines such as pyridine, trimethylpyridine, dimethylpyridine, and triethylamine can be used. But it is not limited to this. The amount of dehydrated closed-loop catalyst used is preferably from 0.01 to 10 mol for 1 mol of dehydrating agent used. The hydrazone imidization rate is higher when the dehydrating agent and dehydrating ring-closing agent described above are used. In addition, the size of the organic solvent paper used in the dehydration closed-loop reaction applies to the Chinese National Standard (CNS) A4 specification (210X297mm) &quot; -24- (Please read the precautions on the back before filling this page) • Binding and ordering i # 583426 Α7 Β7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention. ° C, preferably 10 to 150 ° C. In addition, the reaction solution prepared by the method of the present invention can be subjected to the same operation as the method for purifying polyamic acid to purify specific polymers. Terminal-modified polymer The specific polymer used in the present invention may be a terminal-modified type obtained by adjusting the molecular weight. The use of this terminal-modified polymer does not necessarily impair the effect of the present invention, but may Coating properties that improve the alignment of liquid crystals. This terminal-modified polymer refers to those synthesized by adding acid monoanhydride, monoamine compound, and monoisocyanate compound to the reaction system when synthesizing polyamic acid. Among them, the acid monoanhydride is, for example, maleic anhydride, benzoic anhydride, itaconic anhydride, η-decylsuccinic anhydride, η-dodecylsuccinic anhydride, η-tetradecylsuccinic anhydride, η-hexadecyl Succinic anhydride, etc. In addition, monoamine compounds such as aniline, cyclohexylamine, η-butylamine, η-pentylamine, η-hexylamine, η-heptylamine, η-octylamine, η-nonylamine , Η-decylamine, η-undecylamine, η-dodecylamine, η-tridecylamine, η-tetradecylamine, η-pentadecylamine, η-ten Hexaalkylamine, η- 17-membered amine, η- 18-membered amine, η-20-membered amine, etc. Also, monoisocyanate compounds such as phenyl isocyanate, naphthyl isocyanate, etc. &lt; Polymer Logarithmic viscosity &gt; (Please read the notes on the back before filling this page)-Binding_ The size of the paper is applicable to Chinese National Standard (CNS) A4 (210X297mm) -25- 583426 A7. ^ 一 _ B7__ 5 2. Description of the invention ((Please read the precautions on the back before filling this page) The polyamic acid prepared according to the above method has better logarithmic viscosity (77 in). 0.05 to 10 d 1 / g, more preferably ο · 05 to 5 d 1 / g. The log viscosity (7? I η) of the present invention uses N-methyl-2-pyrrolidone as the Solvent was measured at a concentration of 0.5 g / 100 ml ^ solution at 30 ° C, and the viscosity was calculated according to the following formula (i): = M solution flow time / solvent flow time)

1 η (weight concentration of polymer) U [liquid crystal alignment agent] In the liquid crystal alignment agent of the present invention, the above-mentioned specific polymer dissolving angle is constituted by using an organic solvent. The temperature when manufacturing the liquid crystal alignment agent of the present invention is generally in the range of 0 ° C to 20 CTC, preferably in the range of 20 ° C to 60 ° C. An organic solvent constituting the liquid crystal alignment agent of the present invention is printed by the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, such as 1-methyl-2-pyrrolidone, r-butyrolactone, r-butyrolactam, N, n-dimethylamine Methylformamide, N, N-dimethylacetamide, 4-monohydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy Methyl propionate, ethyl ethoxybutyrate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol mono-propyl ether, ethylene glycol ~ i monopropyl ether, ethylene glycol Alcohol-n-butyl ether (butyl lysin) ethylene glycol dimethyl_, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl ether Glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene paper This paper is applicable to the Chinese National Standard (CNS) A4 specification (210x297 mm) -26- 583426 A7 B7 V. Description of the invention (Alcohol monomethyl ether) Ether ether acetate, diethylene glycol monoethyl ether acetate, etc. The concentration of the solid component in the liquid crystal alignment agent of the present invention is preferably 1 to 1 in consideration of viscosity, volatility, and the like. The range of 0% by weight. That is, the liquid crystal alignment agent of the present invention is formed on the substrate surface to form a coating film as a liquid crystal alignment film. When the solid content is less than 1% by weight, If the thickness is too thin, a good liquid crystal alignment film cannot be obtained. In addition, when the viscosity of the liquid crystal alignment agent is too large, the coating characteristics may also be deteriorated. The liquid crystal alignment agent of the present invention is within a range that does not damage the objective physical properties. From the viewpoint of improving the adhesion to the substrate surface, a functional silane compound or an epoxy compound may be used. The functional silane-containing compound such as 3-aminopropyltrimethoxysilane and 3-aminopropyl Triethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N-(2 —Amineethyl) —3—Aminopropylmethyldimethoxysilane, 3-Ureapropyltrimethoxysilane, 3-Ureapropyltriethoxysilane, N-Ethoxycarbonyl-3-amine Propyltrimethoxysilane, N-triethoxy stilbene propyl diethylene diamine, N- Dimethoxyethoxypropyldiethylene triamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl1,4,7 -Triazadecane, 9-trimethoxysilane-3,6-diazanonylacetate, 9-triethoxysilyl-3,6-diazanonylacetate, N -Benzyl-1 -aminopropyltrimethoxysilane, N -benzyl-3 -aminopropyltriethoxyshiyin, N -phenyl-1 -aminopropyldimethylaminosand , N -benzyl-3 -aminopropyltriethoxysilane, N -bis (oxaethylene)-This paper size is applicable to China National Standard (CNS) A4 size (210X297 mm) (Please read the back Please fill in this page for further information.) • Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -27-583426 A7 _B7 V. Description of the invention (3-aminopropyltrimethoxysilane, N- (oxaethylene) -1 3-aminopropyltriethoxysilane and the like. So-called epoxy compounds such as ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether Ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 1, 3, 5, 6-tetraglycidyl-1 2,4 monohexanediol, N, N, N,, N '—tetraglycidyl — m —xylylenediamine, 1, 3 —bis (N, N-diglycidylamine methyl) cyclohexane , N, N, N ', N'-tetraglycidyl-4,4-diaminodiphenylmethane, 3- (N-allyl-N-glycidyl) aminopropyltrimethoxy Silane, 3-(N, N-diglycidyl) aminopropyltrimethoxy sand, etc. Liquid crystal display element The liquid crystal display element of the present invention can be produced, for example, by the following method. (1) A liquid crystal alignment agent of the present invention is coated on one side of a substrate provided with a patterned transparent conductive film by a method such as a roller coating method, a spin coating method, a printing method, and the like. The coated surface is heated to form a coating film. Among them, the substrate can be, for example, a wide substrate or a soda-lime glass, or a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether master, and polycarbonate resin. . As for the transparent conductive film provided on one side of the substrate, for example, a NESA film (trademark of the United States PPG company) composed of tin oxide (s η 0 2), indium tin oxide (the paper size applies to the Chinese National Standard (CNS)) A4 specification (210X297 mm) (Please read the notes on the back before filling out this page) Binding and printing Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -28- 583426 A7 B7 ___ 5. Description of the invention (I n2〇3 — Sn 〇2) IT film, etc., the pattern of the transparent conductive film can be formed by etching or using a photomask in advance. In addition, the alignment direction of the liquid crystal is formed on the substrate surface in a specific direction. Liquid crystal display elements that can improve viewing angle dependence can also be obtained by methods such as forming electrode gaps. When the liquid crystal alignment agent is applied, in order to improve the adhesion between the substrate surface and the coating film of the transparent conductive film, it can be applied to the aforementioned surface of the substrate. On the surface, a functional silane compound, a functional titanium compound, etc. are coated in advance. The heating temperature after coating of the liquid crystal alignment agent is 80 to 250 t, preferably 120 to 2 0 0 ° C. The film thickness of the formed coating film is generally from 0.001 to 1 // m, preferably from 0.005 to 0.55 // m. In addition, the liquid crystal alignment agent of the present invention can be applied to the coating. After that, the organic solvent is removed to form a coating film of the liquid crystal alignment film, or dehydration and closed-loop heating is performed to form a partially or completely imidized coating film. (2) Making the formed coating film It has liquid crystal alignment. This method can be used, for example, to roll a cloth roller made of nylon, snails, cotton, and other fibers to perform rubbing treatment in a certain direction, or use polarized ultraviolet rays, ion beams, and electron beams on the film surface. Irradiation is a better method to give its alignment energy, etc. In addition, a method of forming a coating film using a uniaxial stretching method or a Lamir method can be used to obtain a liquid crystal alignment film. In addition, to remove fine powder particles (foreign matter) generated by rubbing treatment It is preferable to make the surface clean, and it is preferable to wash the formed liquid crystal alignment film with isopropyl alcohol, etc. In addition, the surface of the formed liquid crystal alignment film is partially irradiated with ultraviolet rays, ion beams, electron beams, etc., so that Dealing with changes in pretilt angle (for example For example, Japanese Unexamined Patent Publication No. 6-2 2 2 3 6 and Japanese Unexamined Patent Publication No. 6-28 1 937 are applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). -29- (Please read the back first Please pay attention to this page and fill in this page). Binding and printing 583426 A7 _ B7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Description of the invention (, Japanese Patent Publication No. 7 — 1 6 8 1 8 7 and Japanese Patent Publication No. 8-234207 Publication No.), for the formation of a photoresist film on the surface of the liquid crystal alignment film, and then applying a rubbing treatment with a direction different from the previous rubbing treatment, the photoresist film is removed to change the alignment film of the liquid crystal alignment film. Treatment (for example, Japanese Patent Application Laid-Open No. 5-1 0 7 5 4 4) can improve the viewing angle characteristics of the liquid crystal display element obtained. (3) Make two substrates forming the liquid crystal alignment film according to the method described above, and arrange them in a manner with gaps facing each other. Adhere the peripheral parts of the two substrates with a sealant, and separate the surface substrate from the sealant. Liquid crystal is injected into the gap, and the injection hole is closed to form a liquid crystal cell. Subsequently, a polarizing plate is bonded to the outer surface of the liquid crystal cell, that is, the other side constituting the substrate of the liquid crystal cell, to prepare a liquid crystal display element. Among them, examples of the sealant include an epoxy resin containing a hardening agent and an alumina ball containing a pitch, and the like. Liquid crystal forms include, for example, matrix-type liquid crystals and twisted-matrix-type liquid crystals. Among them, matrix-type liquid crystals are preferred, such as Schiff-based liquid crystals, azo oxide-based liquid crystals, biphenyl-based liquid crystals, and phenylcyclohexane-based liquid crystals. Pyrimidine-based liquid crystals, dioxane-based liquid crystals, bicyclooctane-based liquid crystals, cubic-based liquid crystals, and the like. In addition, the liquid crystal may be added with cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonyl ester, and cholesteryl carbonate, or trade names [C-15], [CB-15] (manufactured by Melco). ) Selling mirror. A polarizing plate attached to the outer surface of the liquid crystal cell. In the alignment using polyvinyl alcohol, a polarizing film obtained by adding a polarizing film with a protective film of cellulose acetate and a film of iodine absorbed by iodine may be added, or η The polarizing plate composed of the film itself is applicable to the Chinese National Standard (CNS) Α4 size (210X297 mm) (please read the precautions on the back before filling out this page)-installed, printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Consumption Cooperative Manufacturing -30-583426 A7 B7 V. Description of the invention (etc.) The liquid crystal alignment agent of the present invention is very suitable for use in EVA liquid crystal display elements. The EVA mode is like "liquid crystal" vol. 3 No. 4 272 (1 999 As disclosed in the year, the electrode structure is accurately spaced to control the vertical pattern of the alignment direction. The space structure can be formed on the TFT substrate side and the color filter side respectively. The liquid crystal alignment agent of the present invention is extremely suitable for use Vertical alignment type liquid crystal display elements such as a light alignment method irradiated with polarized ultraviolet light as disclosed in "jpn Appl. Phys." Vol 36 428 (1979). Used in this liquid crystal display element Polarized ultraviolet light is preferably linearly polarized ultraviolet light. [Examples] Hereinafter, the present invention will be described in more detail with examples, but the present invention is not limited by these examples. Method for measuring the conversion rate] The polymer was dried under reduced pressure at room temperature, and then dissolved in deuterated dimethyl sulfoxide. Tetramethylsilane was used as a reference substance at room temperature for 1 NMR measurement. Calculated by the formula shown in the following formula (ii): 醯 imidization rate (% Xl-AVA ^ oOxlOO (ii) A1: the area of the peak generated by the NH-based proton. (1 〇p pm This paper scale is applicable to China National Standard (CNS) A4 specification (21 OX297 mm) --------- • -installation-(Please read the precautions on the back before filling out this page), 11 Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs Printed -31-583426 A7 B7 V. Description of the invention (2 &amp; A2: Peak area generated by other protons α: Other protons of the polymer precursor (polyamic acid) for 1 NH group Number ratio [production method of liquid crystal display element] liquid crystal display element Production: (1) Ε V Α unit cell is shown as 1 in Figure 1. Corresponding to the sample elements of EVA mode, for example, two glass substrates with I but 0 pattern are printed on the liquid crystal alignment agent, and 80 ° C for 1 minute, followed by drying at 180 ° C for 1 hour to obtain a dry film with a thickness of 60 angstroms. Then, the screen was printed on the outer edge of one side plate by screen printing. After applying an epoxy resin adhesive containing alumina balls with a particle diameter of 3.5 m, two substrates were bonded together at a staggered positional relationship as shown in FIG. 1. The negative cell MLC-6 2 2 1 made by Melco is injected into the unit cell where the surface of the substrate and the outer edge are separated by an adhesive, and then the injection hole is closed with an epoxy-based adhesive, and The vertical alignment type liquid crystal display element of the present invention was obtained. The obtained liquid crystal display element was subjected to a rectangular wave of 30 Hz and 3.0 V with an alternating frequency of 6.0 V (peak and peak) at 70 t: ambient temperature. After 500 hours of downward application, the results were observed visually and it was found that the liquid crystal display element did not find any poor display. (1) Photo-alignment type unit cell corresponding to the vertical light-alignment method of the sample element, for example, 2 sheets with this paper size applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) --------- Equipment-(Please read the precautions on the back before filling out this page) Order printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-32-583426 A7 ____B7 V. Description of the invention (ice (please read the precautions on the back before filling in this Page) IT 〇 glass substrates, respectively printed liquid crystal alignment agent, and 80 ℃, 1 minute, and then dried at 180 ° C, 1 hour to obtain a dry film thickness of 60 angstrom coating film Then, a mercury lamp was applied to each substrate at a wavelength of 3 65 nm, and linearly polarized ultraviolet rays were used to irradiate the film surface at a direction of 45 degrees with an irradiation intensity of 1 · 0 J / cm 2 for 3 minutes. On the outer edge part, an epoxy resin adhesive containing alumina balls having a particle diameter of 3 · 5 // m was applied by screen printing, and then each substrate was formed at 180 ° (antiparallel) in the direction of light irradiation. After laminating, and injecting MLC-6 2 2 1 in the same way as the ev A-type cell, then, A vertical alignment type liquid crystal display element was obtained by closing the injection hole. [Vertical Alignment] At a voltage of 0FF, the liquid crystal display element under AC 12 V (peak and peak) was observed using a cross-section. [Voltage hold Rate] Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs to measure the voltage retention rate of the liquid crystal display element after applying a voltage of 5 V for 60 microseconds, 167 milliseconds after plating, and 167 milliseconds after releasing the applied state. The measuring device was VHR-1 manufactured by Toyo Tiekeni Co., Ltd. [Elapsed time of residual image of liquid crystal display element] The liquid crystal display element was superimposed by DC 3 · Ο V and AC 6. 〇 V (peak and peak) 3 〇矩形 z, 3. 0 V rectangular wave is applied at an ambient temperature of 70 ° C for 20 hours, and then the voltage is 0FF. The Chinese national standard (CNS) Α4 specification (210 X 297 mm) is applied to the paper standard. ) -33- 583426 A7 B7 V. Explanation of the invention (3) Observation and measurement of the time required for the afterimage to elapse. [Synthesis of specific polymer] Synthesis examples 1 to 7 In 1-methyl-2-pyrrolidone, according to the table Composition shown in 1 Diamine and tetracarboxylic dianhydride were added sequentially, so that the solid concentration was 20%, and after reacting at 60 ° C for 6 hours, a polyamic acid having the log viscosity shown in Table 1 was obtained. (Please first Read the notes on the back and fill in this page) The paper size printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs applies to Chinese National Standards (CNS) A4 (210X297 mm) -34- 583426 A7 B7 I. Description of the Invention (Concluded) Synthetic anhydride diamine logarithmic viscosity (dL / g) TCAAH (50), PDA (25) / diamine 0 (25) 0.7 TCAAH (50) 〇 octa (37.5) / diamine 0 (12.5) 0.8 3 — TCAAH ( 50) PDA (37.5) / diamine① (12.5) 0.7 ._ ^ TCAAH (50) PDA (37.5) / diamine③ (12_5) 0.7 TCAAH (50) PDA (37.5) / ODA (12.5) 0.7 6 TCAAH ( 45) / CB (5) PDA (37.5) / diamine② (12.5) 0.8 7 TCAAH (37.5) / PDA (37.5) / diamine② (12.5) 0.6 MTDA (12.5) (Please read the precautions on the back before (Fill in this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (the number in parentheses is Moore% TCAAH: 2,3,5-tricarboxycyclopentylacetic dianhydride CB: 1, 2, 3, 4 a cyclodine MTDA: 1, 3, 3 a, 4,5,9b —Hexahydro — 5 — 8 —methyl — (tetrahydro-2,5 -dioxo-3 —furanyl) —naphthalene [1,2, C] 1-Aran-1 , 3-dione PDA: p-phenylenediamine ODA: octadecyloxy-2,4-diaminophenylenediamine ①: diamine diamine represented by formula (9) ②: represented by formula (1 0) Diamine diamine ③: The diamine represented by formula (1 3) The paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) -35- 583426 A7

7 B V. Description of the invention (3 $ Synthesis Examples 8 to 1 7 Polyamines obtained in Synthesis Examples 1 to 7 were diluted with 1-methyl-2-pyrrolidone to a solid concentration of 5%, and then added to Table 2 A specific polymer was synthesized after the catalyst piridine and acetic anhydride 'were stirred at 110 ° C for 4 hours. This polymer solution was reprecipitated with diethyl ether to obtain a polymer Polymer) white powder. The specific imidization rate of the specific polymer obtained is described in Table 2. Also, in Table 2, pyridine / anhydride (bemol) = 1.0 / 1 _ 〇 , Refers to the addition of 1.0 mole to the polyamic acid bond 1.0 mole mole pyridine, 1.0 mole mole acetic anhydride (please read the precautions on the back before filling this page) Bureau of Intellectual Property, Ministry of Economic Affairs Printed by employee consumer cooperatives [Table 2] Synthesis example Polyamic acid pyridine / acetic anhydride (Bemol) 耳 Imidization rate (%) 8 Synthesis example 1 1.0 / 1.0 70 9 Synthesis example 2 1.0 / 1.0 70 10 Synthesis Example 2 1.5 / 1.5 80 11 Synthesis example 2 2.0 / 2.0 90 12 Synthesis example 2 5.0 / 3.0 100 13 Synthesis example 3 1.5 / 1.5 80 14 Synthesis example 4 1.5 / 1.5 80 15 Synthesis example 5 1.0 /1.0 70 16 Synthesis Example 6 1.0 / 1.0 70 17 Synthesis Example 7 1.0 / 1.0 70 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -36- 583426 A7 B7 V. Description of the invention (Coated Synthesis Example 1 8 to 2 7 In 1-methyl-2 -pyrrolidone, according to the composition shown in Table 2, sequentially add diamine and tetracarboxylic dianhydride so that the solid concentration is 20%, at 60 After 6 hours of reaction at t, a polyamic acid with a logarithmic viscosity as shown in Table 3 was obtained. (Please read the precautions on the back before filling this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Employees' Cooperatives. Standard A age (-Xjing ^ _37_ 583426 A7

Produced by the Intellectual Property Bureau of the Ministry of Economic Affairs for consumer cooperation DU Inventory ^ Description of the invention (male 3) Synthesis !!!! The anhydride diamine log viscosity (dL / g) TDA (50) PDA (20) / 〇DA (30) 0.6 19 ^ TNA (50) PDA (15) / ODA (35) 0.4 TCAAH (25) / TNA (25) PDA (37.5) / diamine ⑥ (12.5) 0.7 TCAAH (50) PDA (45) / diamine ② (5) 1.5 22 TCAAH (50) diamine④ (37.5) / diamine② (12.5) 1.7.23 CB (45) / TNA (5) PDA (37.5) / diamine② (12.5) 0.8 _24 CB (50) diamine③ (50) 0.3 .25 TCAAH (50) PDA (25) / diamine 0 (25) 0.9 26 TCAAH (40) / CHA (IO) DDM (50) 1.4 27 TCAAH (50) diamine ④ (37 · 5) / Diamine ⑤ (12 · 5 1.6 28 CB (50) DDE (50) 1.3 (Please read the precautions on the back before filling out this page) () The numbers in parentheses are mole% TDA: 1 '3, 3a, 4 , 5,9b —Hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) —naphthalene [1,2 ~ C] —furan-1,3-dione TNA: 3,5 , 6-tricarbonyl- 2 -carbonyl orthospinane-2: 3,5 ·· 6-dianhydride C Η A: Anhydride DDE of formula (1) DDE: 4, 4, diaminodiphenyl ether- Amine ②: Diamine monoamine represented by formula (1 0) ·· Diamine shown in formula (2 1) | Andanediamine ⑤: Two teams of diamine shown in formula (17) ⑥: Two paper sizes shown in formula (16) apply Chinese National Standard (CNS) A4 specification (210 X297 Gongchu) -38- 583426 A7 B7 V. Description of the Invention (Synthesis Examples 2 9 to 3 4 (Please read the notes on the back before filling out this page) The polyamino acid obtained in the Synthesis Example is 1-methyl-2 -After diluting pyrrolidone to a solid concentration of 5%, add batch B of the catalyst shown in Table 4 and acetic anhydride, and stir at 110 ° C for 4 hours to synthesize a specific polymer. Diethyl ether was reprecipitated to obtain a white powder of a polymer (fluorenimidized polymer). The fluorination rate of the specific polymer obtained is described in Table 4. Also, in Table 4, pyridine / Anhydride (bemol) = 1. 0 / 1.0, refers to the addition of 1.0 mol pyridine, 1.0 mol acetic anhydride to the polyamic acid bond [Table] 4] Synthesis example Polypyridine / acetic anhydride (Bemol) 醯 Imidization ratio (%) 29 Synthesis example 2 0.8 / 0.8 50 30 Synthesis example 2 0.2 / 0.2 20 31 Synthesis example 1 1.2 / 1.2 60 32 Synthesis example 1 9 1.2 / 1.2 43 33 Synthesis example 21 1.0 / 1.0 48 34 Synthesis example 22 0.5 / 0.5 30 Synthetic example printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 3 5 to 3 9 In 1 -methyl-2- In pyrrolidone, diamine and tetrakisuccinic acid dianhydride were sequentially added according to the composition shown in Table 5 so that the solid concentration was 20%. After reacting at 60 for 6 hours, the composition shown in Table 5 was obtained. Log viscosity polyamic acid. This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm) ——-~ -39 · 583426 A7 B7 V. Description of the invention (Table 5) Example of logarithmic viscosity of synthetic anhydride diamine (dL / g) 35 TCAAH (37.5) / PDA (37.5) / diamine 0 (12.5) 0.9 PMDA (12.5) 36 TCAAH (50) PDA (17.5) / diamine 0 (32.5) 0.7 37 TCAAH (50) PDA (12.5) / diamine 0 (37 · 5) 0.6 38 TCAAH (50) diamine ② (50) 0 · 5 39 TCAAH (50) PDA (40) / diamine 0 (10) 0.8 () Numbers in parentheses are mole% PMDA: both Pyromellitic dianhydride (please read the precautions on the back before filling this page) Binding and Ordering Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economy 4 Synthesis Example 4 -2 -pyrrolidone was diluted to a solid concentration of 5%, and then added as a catalyst to the polyamino acid-bonded 1.0 moles of pyridine, 1.0 moles of pyridine, and 1.0 moles of acetic anhydride. After stirring at 110 ° C for 4 hours, a specific polymer was synthesized. This polymer solution was reprecipitated with diethyl ether to obtain a white powder of the polymer (fluorinated polymer). The obtained specific polymer The ratio of imidization was 50%. Examples 1 to 10 The specific polymers shown in Table 6 were prepared using N-methyl-2-11 than melanones (NMP): butylcellosolve (BC). 2 6: 4 (weight ratio of this paper applies Chinese National Standard (CNS) A4 specification (210X297 mm) &quot; 1 ~ • 40-583426 Α7 Β7 V. Description of invention (3 ^) mixed solvent is made as solid A solvent with a concentration of 6.0% was used as the vertical alignment type liquid crystal alignment agent of the present invention. A liquid crystal display element was produced using this liquid crystal alignment agent and various evaluations were performed. The results are shown in Table 6. [Table 6] Example specific Polymer Vertical Alignment Voltage Retention Rate Elapsed Time (%) Interval (seconds) _ 1 Synthesis Example 8 Good 99.1 60 2 Synthesis Example 9 Good 99.2 60 3 Synthesis Example 10 Good 99.2 50 4 Synthesis Example 11 Good 99.2 40 5 Synthesis Example 12 Good 99.1 30 6 Synthesis Example 1 3 Good 99.0 80 — 7 Synthesis Example 14 Good 98.2 90 8 Synthesis Example 1 5 Good 99.2 60 9 Synthesis Example 1 6 Good 99.1 50 10 Synthesis Example 17 Good 99.1 40 Examples 1 to 2 7. Comparative Example 1 Example 11 is a special 5 g of polymer (Synthesis Example 2 9) and 5 g of the additive (N, N, N,, N'-tetraglycidyl-4, 4'-diaminodiphenylmethane hereinafter referred to as EP) were dissolved in Ν Μ P: BC = 5: 5 (weight ratio) in a mixed solvent, and a solvent with a solid concentration of 6.0% is prepared as the vertical alignment of the present invention. This paper is a common Chinese national standard (CNS) A4. Specifications (210X297mm) Packing-(Please read the notes on the back before filling this page), 1Τ i # Printed by the Consumer Consumption Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -41-583426 A7 _B7_ V. Description of the Invention (3) &amp; type liquid crystal alignment agent. The liquid crystal alignment agent was used to produce the above-mentioned E V A type liquid crystal display element, and various evaluations were performed. The results are shown in Table 7. According to the same content as in Example 11 and according to the proportions shown in Tables 7 to 8, specific polymers, additives and solvents were mixed to make liquid crystal alignment agents, and their characteristics were evaluated separately. The results are summarized in Tables 7 to 8. (Please read the notes on the back before filling out this page) The paper size printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs applies to the Chinese National Standard (CNS) A4 (210X25) 7 mm) -42- 583426 A7 B7 Description of the invention (4 [Table 7] Examples of solid materials (0 is parts by weight) printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Solvent (0 is parts by weight) Liquid crystal display characteristics Specific polymer additives Vertical alignment voltage retention rate ( %) Afterimage elapsed time (seconds) 11 Synthesis Example 29 (95) EP (5) NMP (5) / BC (5) Good 99.2 60 12 Synthesis Example 29 (91) EP (9) NMP (5) / BC ( 5) Good 99.5 40 13 Synthesis Example 29 (91) Silane① (9) NMP (5) / BC (5) Good 99.4 40 14 Synthesis Example 30 (91) EP (9) NMP (5) / BC (5) Good 99.1 60 15 Synthesis Example 31 (91) EP (9) NMP (5) / BC (5) Good 99.0 80 16 Synthesis Example 31 (16) Synthesis Example 28 (67) Silane① (17) NMP (1) / BC ( 1) / BL (8) Good 99.2 30 17 Synthesis example 32 (91) EP (9) NMP (5) / BC (5) Good 99.0 50 18 Synthesis example 33 (91) EP (9) NMP (5) / BC (5) Good 99.0 30 19 Synthesis Example 34 (91) EP (9) NMP (5) / BC (5) Good 99.5 10 20 Synthesis Example 19 (91) EP (9) NMP (3) / BC (7) Good 98.7 70 21 Synthesis Example 9 (4) Synthesis Example 28 (79) EP (17) NMP (1) / BC (1) / BL (8) Good 98.2 10 22 Synthesis Example 22 (91) EP (9) NMP (5) / BC (5) Good 99.1 10 23 Synthesis Example 24 (9) Synthesis Example 25 (91)-NMP (5) / BC (5) Good 97.1 90 24 Synthesis Example 23 (8) Synthesis Example 28 (75) EP (17) NMP (5) / BC (5) Good 97.1 90 25 Synthesis Example 26 (91) EP (9) NMP (5) / BC (5) Good 99.1 50 26 Synthesis Example 27 (99) EP⑴ NMP (5) / BC (5) Good 99.1 50 27 Synthesis Example 1 (83.3) E〇 (16.7) NMP (5) / BC (5) Good 99.1 60 Silane①: N- Glycidyl-N, N-bis [3 · (methyldimethoxysilyl) propyl] amine BL: r -butyrolactone This paper is sized for China National Standard (CNS) A4 (210X 297 male) Li) (Please read the notes on the back before filling in this page)

1T.b. -43- 583426 A7 B7 V. Description of the invention (41 [Table 8] Specific solids (0 is parts by weight) Solvent liquid crystal display characteristics are better than specific polymer additives (0 is parts by weight) Vertical alignment voltage Example of retention time after image elapsed (%) (seconds) 1 Synthesis example 2 8 (100) NMP (5) / BC (5) No vertical 89.1 120 (Please read the precautions on the back before filling this page) Economy The paper size printed by the Ministry of Intellectual Property Bureau's Consumer Cooperatives applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -44- 583426 A7 ___B7 V. Description of the invention (: 42 Example 2 8 (Please read the note on the back first) Please fill in this page again for the matter) Prepare a specific polymer solution and make an EVA-type cell in the same way as in Example 11. The EVA-type cell has good liquid crystal alignment and operates according to the voltage 0N and 0FF. There was no abnormal alignment in the magnetic domain. In addition, the voltage retention of the unit cell was 99 · 3%, and the afterimage elapsed time was 40 seconds. Example 2 9 A specific polymerization was made in the same manner as in Example 11 1 And a photo-aligned cell. The prepared photo-alignment type unit cell has good liquid crystal alignment, and operates according to voltages of 0N and 0FF, and no abnormality of alignment occurs in the magnetic domain. In addition, the voltage retention rate of the unit cell is 98.3% The afterimage elapsed time was 95 seconds. Examples 30 to 34, Comparative Example 1 In Example 30, a specific polymer (Synthesis Example 3 5) was printed with 85g of a consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In addition, EP 1 5g of the additive is dissolved in a mixed solvent of NMP: BC = 3: 7 (weight ratio) to obtain a solvent having a solid concentration of 6.0%, which is used as the vertical liquid crystal alignment agent of the present invention. The sub-liquid crystal alignment agent was used to make the above-mentioned EVA type liquid crystal display element, and various evaluations were performed. The results are shown in Table 9. In the content of Example 30, specific polymers, additives and solvents were mixed in the proportion shown in Table 9 to produce Liquid crystal alignment agent, and various characteristics are evaluated. The results are all summarized in Table 9. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -45- Example solids (0 is part by weight) ) Solvent (0 parts by weight) Crystal Display Characteristics Specific Polymer Additives Vertical Alignment Voltage Retention Rate (%) Afterimage Elapsed Time (seconds) 30 Synthesis Example 35 (85) EP (15) NMP (3) / BC (7) Good 98.9 60 31 Synthesis Example 36 (85) EP (15) NMP (3) / BC (7) Good 99.2 40 32 Synthesis Example 37 (85) EP (15) NMP (3) / BC (7) Good 99.1 50 33 Synthesis Example 38 (85) EP (15) NMP (3) / BC (7) Good 99.1 60 34 Synthesis example 40 (85) EP (51) NMP (5) / BC (5) Good 99.4 60 583426 A7 B7 V. Description of the invention (43 [Table 9 ] (Please read the notes on the back before filling out this page)-装-

， 1T Printed by the Intellectual Property Bureau of the Ministry of Economy ’s Consumer Cooperatives This paper is printed in accordance with the Chinese National Standard (CNS) A4 specification (210X297 mm) -46- Printed by the Intellectual Property Bureau of the Ministry of Economy ’s Consumer Cooperatives 583426 A7 __B7 __ V. Description (44 [Effects of the invention] According to the content of the present invention, an excellent liquid crystal alignment agent and liquid crystal display element with good vertical alignment and extremely short afterimage elapsed time (EVA, light alignment, etc.) can be obtained. A liquid crystal display element having a liquid crystal alignment film formed by using the liquid crystal alignment agent of the present invention can effectively use various devices, such as a direct-view personal computer monitor, and a liquid crystal television, such as a projection-type transmissive and reflective display. Device, etc. [Simplified description of the diagram] Figure 1 ······································ Description of the main element symbols 1 Color filter side electrode 2 Liquid crystal alignment film 3 Pixel electrode (IT〇) 4 Liquid crystal molecules 5 Alignment control method (interval) This paper size is applicable to Chinese national standards (CNS) A4 size (210 'Yi in 297 mm) (Please read the back of the precautions to fill out this page) - installation - set -47-

Claims (1)

583426 A8 B8 C8 D8 r, patent application scope 1 -............ 9 1 1 1 7 0 5 3 patent application, public ' Volume-.: KI Chinese Patent Application Scope Amendment '&quot; ι ---------------------- Revised July 31, 1992 1 · A vertical alignment Type liquid crystal alignment agent, which contains a polymer having a repeating unit represented by the following formula (I-1) and at least one repeating unit of the following formula (I — repeating unit; HOOC COOH / P \, HNOC CONH —Ql (I-1) (Please read the precautions on the back before filling out this page} Q type is recorded as the Q base machine is available} Price base 4 is shown as 1 and P), 2 of the I type Q (or economic Printed by the Ministry of Intellectual Property Bureau's Consumer Cooperative Q2- -QN 2 Q χί \ is written as 2 Q base machine has} valence base 4 is shown as 2 P) ， 2 I type Q Γν / 1 \ or this paper size applies Chinese National Standard (CNS) A4 specification (21 OX297 mm) 583426 A8 B8 C8 D8 6. Scope of patent application 2 C 0 I, C0 (Q-1) (where X is 10110C01, 1 NHC0, 1 CON—, —s —, methyl group, number of carbons A bivalent group selected from 2 to 6 alkylene groups and phenylene groups' R1 is an alkyl group having 10 to 20 carbon atoms, and a monovalent organic group having an alicyclic skeleton or carbon having 4 to 40 carbon atoms. Monovalent organic group with a fluorine atom from 6 to 12)-(Please read the precautions on the back before filling out this page) 〇fl 2 〇 (Q-2), tr Printed by the Intellectual Property Office of the Ministry of Economic Affairs, Consumer Consumption Cooperative (In the formula, X is 101, one c01, one c001, 100c01, one NHCO-, one CONH-, one S-, methylene, from 2 to 6 carbons The divalent group selected from the alkylene and phenyl groups, and R2 is a divalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms). 2 · For example, the vertical alignment type liquid crystal alignment agent in the scope of patent application, it is used for liquid crystal alignment film of liquid crystal display elements. This paper size applies to China National Standard (CMS) A4 (210X297 mm) -2-