TW591083B - Liquid crystal-orienting agent and liquid crystal display element - Google Patents

Abstract

To obtain a liquid crystal-orienting agent that has excellent printability without occurrence of uneven printing and pinholes, when print-coated on a substrate and provide a liquid crystal display element equipped with a liquid crystal orientation film obtained from the liquid crystal orientation agent. The liquid crystal orientation agent comprises (A) a polymer bearing at least one of recurring units selected from an amic acid structure and an imide structure, preferably a polyamic acid and an imide polymer and (B) a silicon-including compound having polyether bonds.

Description

591083 A7 B7 V. Description of the invention (; | [Technical Field of the Invention] The present invention relates to an invention of a liquid crystal alignment agent and a liquid crystal display element. More specifically, it relates to a liquid crystal alignment agent with excellent printability and its application. [Previous technology] At present, it is known that a liquid crystal display element is formed by, for example, forming a liquid crystal alignment film on a surface of a substrate provided with a transparent conductive film as a substrate for the liquid crystal display element, and the substrate is divided into two pieces. In the opposite arrangement method, a nematic liquid crystal layer having a dielectric anisotropy is formed in the gap as a unit cell of a sandwich structure, so that the long axis of the liquid crystal molecules is continuously twisted from one substrate to the other substrate. 90 degrees, that is, a N-type liquid crystal display element having a TN-type (Twisted Nematic) liquid crystal cell. In addition, for example, when a liquid crystal with an optically active substance isomerized is used, the long axis of the liquid crystal molecules can be on the substrate. The STN (Super Twisted Nematic) type liquid crystal display element that achieves a state of continuously reversing 180 degrees or more, and uses the multi-refraction effect produced by this method In addition, for example, an IPS (In-Plane Switiching) type liquid crystal display element having a lower viewing angle dependency than a TN type liquid crystal display element or a vertical alignment type liquid crystal display element has also been developed. The liquid crystal alignment film in the aforementioned liquid crystal display element Among materials, it is known that, for example, conventional polyimide, polyimide, polyester, etc., especially polyimide, because of its excellent heat resistance, affinity with liquid crystals, mechanical strength, etc. Use for display elements. The liquid crystal alignment film formed of polyimide is generally made of polyimide precursor of polyimide or soluble polyimide. The paper size applies to Chinese National Standard (CNS) A4 (210X297 mm). ) (Please read the notes on the back before filling this page)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the Ministry of Economic Affairs of the People's Republic of China-591083 A7 _B7_ V. Description of the Invention (^ The organic solvent solution of imine is coated on the substrate, and then it is made by heating it to imide. To this liquid crystal crystal alignment agent, a silane coupling agent for the purpose of improving the horizontality to the substrate can be added. However, the liquid crystal alignment agent added with the silane coupling agent can improve the horizontality to the substrate, but it is extremely easy to apply. The generation of bubbles, which is the reason for the easy formation of sand holes in the liquid crystal alignment film, will cause the alignment of the liquid crystal and reduce the electrical characteristics of the produced liquid crystal display element. [Objective of the Invention] The present invention The purpose is to provide a liquid crystal alignment agent that does not cause foaming when coated on a substrate and has good coating properties. Other objects and advantages of the present invention will be apparent from the following description. SUMMARY OF THE INVENTION According to the content of the present invention, 'the purpose and advantages of the present invention are to provide a liquid crystal alignment agent', which contains (A) having a weight selected from the following formula (ϊ-1) Unit and polymer of at least one repeating unit in the repeating unit shown in the following formula (I-2), and (B) a silicon-containing compound liquid crystal alignment agent having a polyether bond; This paper size applies to Chinese national standards ( CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page) 丨 Pain ·

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the Ministry of Economic Affairs -5- 591083 A7 B7 V. Description of the invention (HOOC \ COOH / P \ 1 HNOC CONH——Q1 1-1)

Q 1 is a 2-valent organic (1-2) (Please read the notes on the back before filling this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (where P2 is a 4-valent organic base, Q2 is Divalent organic group). [Embodiments of the invention] The present invention will be further described below. (A) Polymer The polymer used in the present invention contains at least one repeating unit selected from the repeating unit represented by the above formula (I -1) and the repeating unit represented by the above formula (I-2). For example, a fluorinated polymer having a structure obtained by dehydration ring closure (fluoridation) of polyfluorinated acid and / or polyfluorinated acid. In the present invention, the "fluorene imidized polymer" includes those in which all of the repeating units are fluorinated and some are fluorinated. Alternatively, a part of the fluorene imine ring is an isofluorene ring. This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -6-591083 A7 B7 V. Description of the invention () 4 (Please read the notes on the back before filling this page) It is better to use in the invention The polymer is a polymer having a repeating unit represented by the above formula (I -1) and a repeating unit represented by the above formula (I-2). The liquid crystal alignment agent having the aforementioned polymer is, for example, a polymer of the following ① to ③. ① Liquid crystal alignment agent having both polyamidic acid and fluorinated imidized polymer. © A block copolymer-containing liquid crystal alignment agent formed from a prepolymer having a polyamidic acid and a prepolymer having a fluorimine structure. ® A liquid crystal alignment agent containing a polyimide polymer obtained by partial dehydration and ring closure. Among them, ① and ② are more preferable, and ① is the best. Polyamic acid The polyamino acid used in the present invention is obtained by reacting a tetracarboxylic dianhydride with a diamine. [Tetracarboxylic dianhydride] The tetracarboxylic dianhydride used in the synthesis of polyamic acid printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, such as butane tetracarboxylic dianhydride, 1, 2, 3, 4 Alkanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4 monocyclobutanetetracarboxylic dianhydride, 1,3_dimethyl-1,2,3,4 monocyclobutanetetra Carboxylic dianhydride, 1,3-dichloro-1,2,3,4 monocyclobutanetetracarboxylic dianhydride, 1,2,3,4 tetramethyl-1,2,3,4-cyclo Butanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4, —The basic paper size of Dicyclohexane is applicable to China National Standard (CNS) A4 (210X297 mm) 591083 A7 B7 V. Description of the invention (^ (Please read the notes on the back before filling this page) Tetracarboxylic dianhydride, 2 , 3,5-tricarboxycyclopentylacetic dianhydride, 3,5,6-tricarboxyoranidine- 2-acetic dianhydride, 2,3,4,5-tetrahydrofuran tetraresidic acid dianhydride, 1,3,3a, 4,5,9b -Hexahydro-5 (tetrahydro-2,5-dioxo-3 -furan Yl) mononaphthalene [1,2-c] -pyran-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5 methyl-5-(tetrahydro-2,5 -Dioxo-3-furyl) -naphthalene [1,2-c] -furan-1,3-dione, 1,3,3 a, 4,5,9b-hexahydro-5-ethyl- 5 (tetrahydro-2,5-dioxo-3-pyranyl) -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, 1,3,3 a, 4,5,9b —Hexahydromonomethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphthalene [1,2, c] —pyran-1,3 —di Ketone, 1,3,3a, 4,5,9b -hexahydro-7-ethyl-5 (tetrahydro-2,5-dioxo-3 -furanyl) -naphthalene [1,2, c]- Furan-1,3-dione, 1, Intellectual Property Bureau of the Ministry of Economic Affairs 0 (printed by the Industrial and Consumer Cooperatives 3 '3a' 4 '5' 9b -hexachloro-8 -methyl-5 (tetraamine-2,5- Dioxo-3-furanyl) -naphthalene [1,2,- c] monofuran-1,3-dione, 1,3,3a, 4,5,9b -hexahydro-8-ethyl-5 (tetrahydro-2,5-dioxo-3 -furanyl) —Naphthalene [1,2, c] -furan-1,3-dione, 1,3,3 a '4' 5 '9b —hexamine-5' 8 — — ^ methyl-5 (tetraammine-2 ， 5-dioxo-3-furanyl) -naphthalene [1,2-c] —The size of fur paper is subject to Chinese National Standard (CNS) A4 (210X297 mm) 591083 A7 B7 V. Description of the invention (g ( Please read the notes on the back before filling in this page.) 1,2,3 -dione, 5-(2,5 -dioxotetrahydrofuranyl) -3 -methyl -3 -cyclohexene -1,2,- Fatty acids such as dicarboxylic dianhydride, bicyclo [2,2,2] -oct-7-ene-1,2,3,5,6-tetracarboxylic dianhydride, compounds represented by the following formulae (I) and (II) Family and alicyclic tetracarboxylic acid anhydrous;

(In the formula, R1 and R3 are divalent organic groups having an aromatic ring, R2 and R4 are hydrogen atoms or alkyl groups, and plural R2 and R4 may be the same or different). Pyromellitic dianhydride printed by employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, such as 3 5 3, 4, 4 ♦ —_. Benzophenone tetracarboxylic dianhydride 3 5 3 4 > 4 — Biphenylsulfonic tetracarboxylic acid Acid dianhydride, 1, 4 5 5 5 8 —naphthalene tetracarboxylic dianhydride \ 2, 3, 6, 7-naphthalene tetracarboxylic dianhydride 3 5 3 j 4, 4, — diphenyl ether tetracarboxylic acid dianhydride Anhydride, * 3, 3 and 5 4 4 —monomethyldiphenylsilane tetracarboxylic dianhydride, '3, 丨 3 9 > 4 4 —tetraphenylsilane tetracarboxylic dianhydride, 1, 2, ， 3, 丨 4 — Furantetracarboxylic dianhydride, 4 4 $ —Bis (3, 4-diresidual phenoxy) diphenyl sulfide dianhydride, this paper size applies to China National Standard (CNS) A4 specifications (210X: Z97 mm) .4 ^ 1083 A7 —— ^ ____ £ Z_ V. Description of the invention (4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfonium dihydrazone, 4 , 4, bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4 'bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3 , 3 ' 4,4 'monoperfluoroisopropylenediphthalic dianhydride, 3,3', 4,4,4-diphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride , P-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4 ' —Diphenyl ether dianhydride, bis (triphenylphthalic acid) —4,4′—diphenylmethane dianhydride, ethylene glycol—bis (anhydrotrimellitic acid ester), propylene glycol—bis (anhydroanhydrobenzene) Triester), 1 '4-Butanediol-bis (anhydrotrimellitic acid ester), 1,6-Hexanediol-anhydrous (anhydrotrimellitic acid ester), 1,8-octanediol an-anhydrous (Dehydrated trimellitate), 2,4-bis (4-hydroxyphenyl) propane-bis (dehydrated trimellitate), aromatic tetracarboxylic compounds such as compounds represented by the following formulae (1) to (4) Acid dianhydride, etc. It can be used alone or in combination of two or more. (Please read the precautions on the back before filling this page) Intellectual Property Bureau of the Ministry of Economic Affairs (printed by the Industrial Cooperative Cooperative) Standard (CNS) A4 specification (210X297 PCT) -10-591083 V. invention is described (o 0

0 A7 B7

.CH3, CH3 (2) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

(Please read the notes on the back before filling this page)

This paper size applies to China National Standard (CNS) A4 (210X 297 mm) ^ -11-591083 A7 __ B7 ____

V. Description of the invention (I (please read the notes on the back before filling out this page) Among them, butane tetracarboxylic dianhydride, 1 '2, 3' 4 monocyclobutane tetracarboxylic dianhydride, 1, 3- Dimethyl-1,2,3,4 monocyclobutanetetracarboxylic dianhydride, 1,2,3,4 monocyclopentanetetracarboxylic dianhydride, 2 '3,5-tricarboxycyclopentylacetic dianhydride , 5- (2,5 -dioxotetrahydrofuryl) -3 -methyl- 3 -cyclohexene-1,2-dicarbic acid dianhydride, 1,3,3a, 4,5,9b -hexahydro —5 — (tetrahydro-2,5-dioxo-3furanyl) —naphthalene [1,2, c] pyran-1,3-dione, 1,3,3 a, 4, 5, 9b -hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3 -pyranyl) -naphthalene [1,2, c] furan-1,3-dione, 1, 3, 3a, 4, 5, 9b —hexahydro-5,8 —dimethyl-5 — (tetrahydro-2,5-dioxo-3 -furyl) —naphthalene [1,2, c] furan —1,3 —dione, bicyclo [2,2,2] —octyl-7, storage one 2,3,5,6-tetracarboxylic dianhydride, trimellitic dianhydride, 3 ′ 3 ′, 4, 4 '— Benzophenonetetracarboxylic dianhydride, 3,3 ', 4, printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Industrial and Commercial Cooperative, 4, 4-biphenylsulfonic tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetra Carboxylic dianhydride, compounds represented by the following formulae (5) to (7) among the compounds represented by the formula (I) above, and compounds represented by the following formula (8) among the compounds represented by the formula (II), because Good liquid crystal alignment, so it is a preferred compound. Especially 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1, 3, 3 a, 4, 5, 9b —hexahydro-5— (tetrahydro-2,5-dioxo-3—furanyl) —naphthalene [1,2, c] furan-1,3-dione 、 1,3,3 a, 4,5,9b —Hexahydro-8—Methyl-1 5 1 Paper size applies to China National Standard (CNS) A4 specification (210X 297 mm) ~ — " -12- 591083 A7 B7 V. Description of the invention (10- (tetrachloro-2'5-monooxo-3-pyranyl) -Cai [1'2-c] furan-1,3-dione, trimellitic dianhydride And compounds represented by the following formula (5) are more preferred.

0 (5)

Ο 0 (6)

(7) (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 〇 0

(8) [Diamine] It can be used to synthesize the diamine of the polyamidic acid described above, such as p-phenylenediamine m-phenylenediamine, 4,4, diaminodiphenylmethane, 4,4, diamine Diphenyl ethane, 4,4'-diaminodiphenyl sulfide, 4 This paper size is applicable to China National Standard (CNS) A4 specifications (210 ×; Z97 mm) -13- 591083 A7 B7_ V. Invention Description (4,4-Diaminodiphenyl master, 3,3'-dimethyl-4,4,1 (Please read the precautions on the back before filling this page) Diaminobiphenyl, 4,4 'Monodiamino N-benzidine aniline, 4' 4, Diamino diphenyl ether '1,5-Diamino naphthalene, 2,2' Monodimethyl-4,4, -Diamine Dibiphenyl, 3 ′ 3-monomethyl-4,4, -diaminobiphenyl, 2,2′-ditrifluoromethyl-4, 4, diaminobiphenyl, 3, 3'-ditrifluoromethyl-4,4'-diaminobiphenyl, 5-amino-1 (4'monoaminophenyl) -1,3,3-trimethylindane, 6-Amine-1 mono (4'-aminophenyl) -1,3,3-trimethylindane, 3,4'-diaminodiphenyl ether 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2'-bis [4 one (4 Monoaminophenoxy) phenyl] propane, 2,2 'monobis [4 mono (4 monoaminophenoxy) phenyl] hexafluoropropane, 2,2' monobis (4 monoaminophenyl) ) Hexafluoropropane, 2,2 'bis [4- (4-aminophenoxy) phenyl], 1,4-bis (4-aminophenoxy) benzene, Intellectual Property Bureau of the Ministry of Economic Affairs 8 Industrial and consumer cooperatives printed 33.1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminoaminobenzene) Radicals) —1 0-hydroanthracene, 2,7-diaminofluorene, 9,9—bis (4-aminophenyl) fluorene, 4,4′-methylene-bis (2-chloroaniline), 2,2 ', 5,5, -tetrachloro-4,4'-diaminobiphenyl, 2,2, -dichloro-4,4'_diamino-5,5'-dimethoxy Phenylbiphenyl, 3,3-monomethoxy-4,4,4-diaminobiphenyl, 1,4,4,-(p-phenylene isopropylidene) bisaniline, 2,2 , -Double [4 one (4 one 2-a-trifluoromethylphenoxy) phenyl] hexafluoro This paper is sized to the Chinese National Standard (CNS) A4 (210X297 mm) -14- 591083 A7 B7 _ 5. Description of the invention (12) (Please Please read the notes on the back before filling in this page) Propane, 4,4 '—diamino-1,2,2′-bis (trifluoromethyl) biphenyl, 4,4′-bis [(4-amino Aromatic diamines such as 1-trifluoromethyl) phenoxy] -octafluorobiphenyl; 1,1-dimethoxymethoxydiamine, 1,3-propanediamine, tetramethyldiamine, penta Methyldiamine, hexamethyldiamine, heptamethyldiamine, octamethyldiamine, nonamethyldiamine, 4,4'-diamino heptamethyldiamine, 1,4-diamine Cyclohexane, isophoronediamine, tetrahydrodicyclopentadienediamine, hexahydro-4,7-methanolylindanediethylenediamine, tricyclic [6. 2.1.〇2'7 ] —Undecenyl dimethyl diamine, 4,4'-methylene bis (cyclohexylamine) and other aliphatic and alicyclic diamines; printed by S Industrial Consumer Cooperative, Bureau of Intellectual Property, Ministry of Economic Affairs, 2, 3 — 2 Aminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine Pyridine, 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) piperazine, 2,4-diamino-6-isopropoxy —1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6—benzyl-1,3, 5-triazine, 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazine, 4,6-diamino-2- Acetyl-s-triazine, 2,4-diamino-5 monophenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5-diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridinyl propionate, 3,8-diamino-6-phenylphenanthrene Pyridine, 1,4 diaminopiperazine, 3, 3¾. This paper size applies to China National Standard (CNS) A4 (210X297 mm) -15- 591083 A7 B7 V. Description of invention j (4

H2N NH2 (V) (wherein R7 is a divalent organic group selected from the group consisting of -CO1-, COCO- ~, -NHCO-, -CO-NH- and -CO-1, R8 is a monovalent organic group or an alkyl group having 6 to 30 carbon atoms having a group selected from a cholesteric skeleton, a trifluoromethyl group and a fluoro group)

H2N + CH R 〇—Si-

R 9 7q CH2j-NH2 (VI) (Please read the notes on the back before filling out this page) (where R9 is a hydrocarbon group with 1 to 12 carbons, and the plural R9 may be the same or different, P is an integer from 1 to 3, and Q is an integer from 1 to 20) The compound printed by employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by the following formulas (9) to (1 3). The diamine may be used alone or in combination of two or more kinds. This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) -17- 591083 A7 B7 V. Description of the invention \ 5 CH3

CH3 H3C CH (CH2) 3 CH

NH2 CH3 (9) CH3 H3C CH (CH2) 3CH CH3 CH3

CH3

H2N

/ —NH2

CH3 I H3c pH (CH2) 3CH CH3 (11) (Please read the precautions on the back before filling this page)

C2H4 NH2V ° O (12)

H2N

s- NH2

(13) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (where y is an integer from 2 to 12 and z is an integer from 1 to 5) where P—phenylenediamine, m—phenylenediamine, 4 4,4-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-di Amino biphenyl, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 2,7-diaminofluorene, 4,4'-diaminodiphenyl ether 2. This paper size is in accordance with the Chinese National Standard (CNS) A4 specification (210X 297 mm) -18- 591083 A7 B7 5. Description of the invention (16) 2, bis [4 one (4 monoaminophenoxy) Phenyl] propane, 9,9-bis (4-aminoaminophenyl) fluorene, 2,2, -bis (4-monoaminophenyl) hexafluoropropane, 4,4 '-(P-phenylene diiso Propylene) bisaniline, 4,4 'mono (m-phenylene diisopropylidene) bisaniline, 1,4 monocyclohexanediamine, 4,4' monomethylbis (cyclohexylamine), 1, 4-bis (4-aminophenoxy) benzene, 4,4,4-bis (4-aminophenoxy) biphenyl Group, the compounds represented by the above formulae (9) to (1 3), 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diamine group Acridine, a compound represented by the following formula (1 4) among the compounds represented by the above formula (III), a compound represented by the following formula (1 5) among the compounds represented by the formula (I v), and the above formula (V) Among the compounds shown, dodecyloxy-2,4-diaminobenzene, pentadecyloxy-2,4-diaminobenzene, hexadecyloxy-2,4-diaminobenzene, octadecane Oxy-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, pentadecyloxy-2,5-diaminobenzene, hexadecyloxy-2 '5-diamine Phenylbenzene, hexadecyloxy-2,5-diaminobenzene, and compounds represented by the following formulae (1 6) to (2 1) are preferred. m I * 丨 i 1 ^ 1 LH ϋ— mi —ml ϋ (Please read the notes on the back before filling out this page) Order P. Intellectual Property Bureau of the Ministry of Economy B (printed by the Industrial and Consumer Cooperatives β74 This paper is applicable to China Standard (CNS) 8 4 specifications (210 X 297 mm) -19- 591083 A7 B7 V. Description of the invention (17 COO —CH2CH2 — (~ yrS N (14) Η2Ν ~ ν ^ ΝΗ2 h2nh〇 ~ nLXcH2VCn ~ 〇 ~ nh2 (15) COO · Η2Ν-^ Χ-ΝΗ2

H3C

CH3 H3C CH (CH2) 3CH CH3 CH3 (16) CH3

H3C CH (CH2) 3CH

H2N

CH3 CH3 (17) CH3 H3C CH (CH2) 3CH = C " < CH3

H3C CH3 H2N-J ^ JLNH2

H3C H2N

CH3 (18) CH3 I 丨 CH (CH2) 3CH = ^ CH3 = C \ ^ CH3 (19) H3C CH3 Printed by COO 00c- rS H2N-X > -NH2 / CF3 V / ( 20) COO -〇00c- H2N -0- NH2 (21) (Please read the precautions on the back before filling this page)

This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) -20-591083 A7 B7 V. Description of the Invention (18) [Synthesis of Polyamic Acid] (Please read the notes on the back before filling this page ) The ratio of tetracarboxylic dianhydride to diamine compound used in the synthesis reaction of polyamic acid is to use 1 equivalent of the amine group contained in the diamine compound and use 0.2 to 2 equivalents of tetracarboxylic dianhydride. The proportion of acid anhydride groups is preferred, and a ratio of 0.3 to 1.2 equivalents is more preferred. The synthesis reaction of the polyamic acid is carried out in an organic solvent, and is generally carried out at a temperature of 20 ° C to 150 t, preferably 0 to 100 t. Among them, the organic solvent is not particularly limited as long as it can dissolve the synthetic polyamino acid, for example, N-methyl-2-pyrrolidone, N, N-dimethylvinylamine, N, N-dimethylformamidine Aprotic polar solvents such as amines, dimethylsulfoxide, r-butyrolactone, tetramethylurea, and hexamethylphosphinetriamine; phenol solvents such as m-cresol, xylenol, phenol, and halogenated phenol Wait. In addition, the amount (a) of the organic solvent is generally used under the total amount of the tetracarboxylic dianhydride and the diamine compound (b), and the total amount (a + b) of the reaction solution is used in the range of 0.1 to 30% by weight. The amount is better. Printed by the 8th Industrial Cooperative Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In the previous organic solvent, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, etc. of the poor solvents of polyamic acid can be used in the organic solvent. It is used in the range that will cause the generated glutamic acid to crystallize. Specific examples of the aforementioned lean solvent include, for example, methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethanol, ethylene glycol monomethyl ether, ethyl lactate, and lactic acid Butyl ester, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate , Diethyl oxalate, Diethyl malonate, Diethyl ether, Glycol methyl ether, Glycol ethyl ether, Glycol — η — Butyl This paper size is applicable to Chinese national standards (CNS> Α4 Specifications (210X297 mm) ~ Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 591083 A7 B7 V. Description of the invention (19) Ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol Alcohol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol mono Ethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, 〇- Chlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, etc. As shown above, the polyamic acid is dissolved to prepare a reaction solution. Subsequently, this reaction solution is injected into a large amount of lean solvent The precipitate is obtained in the middle, and the precipitate is dried under reduced pressure to obtain polyamic acid. In addition, the polyamino acid may be re-dissolved in an organic solvent, and then one or more precipitation steps may be performed with the solvent. The polyimide polymer is used for the purification of polyamidic acid. The polyimide polymer used in the present invention is a polyamidic acid prepared by reacting a tetracarboxylic dianhydride with a diamine. [Tetracarboxylic dianhydride] The tetracarboxylic dianhydride used in the synthesis of fluorinated imidized polymers described above, such as the tetracarboxylic dianhydride used in the synthesis of polyfluorinated amines. Synthesis of the present invention As the tetracarboxylic dianhydride used in the fluorinated polymer, an alicyclic tetracarboxylic dianhydride is preferably used. The best specific examples are 2, 3, 5-tricarboxycyclopentylacetic dianhydride, l, 3,3a, 4,5,9b —hexahydro-5 — (tetrahydro-2,5-dioxo-3 —furanyl) — 〔1,2—c〕 —Furan-1,3-dione, 1,77 This paper size applies to Chinese national standards (CNS> A4 specification (210X297 mm) -22- (Please read the precautions on the back before filling (This page)

591083 A7 _B7 V. Description of the invention (20) 3, 3 a, 4, 5, 9b —Hexahydro-8 —Methyl-5 — (Tetrahydro (Please read the precautions on the back before filling out this page}) ~ 2 , 5-dioxo-3-furanyl) -naphthalene [1,2-c] -buffan-1,3-dione, etc. In addition, alicyclic tetracarboxylic dianhydride can also be used with other tetracarboxylic acids. The dianhydride is used in combination. [Diamine] The diamine used in the synthetic fluorinated imidized polymer described above, such as the diamine used in the synthetic polyfluorinated acid described above. The synthetic fluorinated imidized polymer of the present invention The diamine used can also be used with the diamine represented by the above formula (V) and other diamines. Other diamines are preferred, such as P-phenylenediamine, 4,4'-diaminodiphenylmethane , 4,4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2, 2'-dimethyl-4,4, monodiaminodiphenyl, 2,2, ~ Ditrifluoromethyl-4,4'-diaminobiphenyl, 2,7-diaminofluorene, 4,4'-diaminodiphenyl ether, 2,2, -bis [4 ~ economy Produced by Du Zhizhi Property Bureau, 8 industrial and consumer cooperation Du printed (4 monoaminophenoxy Phenyl] propane, 9,9-bis (4-aminoaminophenyl) fluorene, 2,2-bis [4-mono (4-aminoaminophenoxy) phenyl] hexafluoropropane, 2,2-bis ( 4 monoaminophenyl) hexafluoropropane, 4, 4 'mono (p-phenylene diisopropylidene) bisaniline, 4,4' mono (m-phenylene diisopropylidene) bisaniline , 1,4-cyclohexanediamine, 4,4, -methylenebis (cyclohexylamine), 1,4-bis (4-aminophenoxy) benzene, 4,4, one-bis (4-1 Aminophenoxy) biphenyl 'Compounds represented by the above formulae (9) to (13), 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -23- 591083 A7 B7 V. Description of the invention (21) (锖 Please read the precautions on the back before filling this page) 3,6 —Diamino group Acridine, a compound represented by the above formula (1 4) among the compounds represented by the above formula (III), a compound represented by the above formula (1 5) among the compounds represented by the formula (IV), and the like. In a polymer, a diamine represented by the above formula (V) The total diamine is preferably 0.5% by weight or more, more preferably 1% by weight or more. [Synthesis of fluorene imidized polymer] The fluorene imidized polymer constituting the liquid crystal alignment agent of the present invention may be used. The polyamic acid described above is prepared by dehydration and ring closure. The dehydration and ring closure of the polyamic acid is (i) a method in which the polyamino acid is heated, or (ii) the polyamino acid is dissolved in an organic solvent, A dehydrating agent and a dehydrating closed-loop catalyst are added to the solution, and the heating is performed when necessary. The reaction temperature of the method for heating polyamic acid printed by the Intellectual Property Bureau of the Ministry of Economic Affairs (printed in the above (i) by the Industrial and Consumer Cooperatives) is generally 50 to 200 ° C, preferably 60 to 170 ° C. The reaction temperature is lower than 5 At 0 ° C, the dehydration ring-closing reaction does not proceed sufficiently. When the reaction temperature exceeds 200 ° C, the molecular weight of the fluorene imidized polymer obtained may decrease. Also, the above-mentioned '(ii) In the method of adding a dehydrating agent and a dehydrating closed-loop catalyst to a polyamic acid solution, for example, an acid anhydride such as acetic anhydride, anhydrous acrylic acid, and anhydrous trifluoroacetic acid can be used as the dehydrating agent. The repeating unit of the amino acid is preferably from 0.01 to 20 moles. For the dehydration ring-closing catalyst, for example, tertiary amines such as pyridine, trimethylpyridine, dimethylpyridine, and triethylamine can be used. Here, dehydration closed -24-This paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) 591083 Α7 B7 V. Description of the invention (22) The amount of ring catalyst used, for the use of 1 Moore The dehydrating agent is preferably from 0.01 to 10 moles. Also, dehydration The organic solvent used in the ring-closing reaction can be, for example, an organic solvent exemplified for the synthesis of polyamic acid. The dehydration ring-closing reaction temperature is generally 0 to 180 ° 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 of purifying polyfluorinated acid to purify the fluorinated imidized polymer. The fluorinated imidized polymerization used in the present invention It is also possible to use partially dehydrated and closed-loop fluorene imidization. The fluorene imidization polymer used in the present invention preferably has a fluorene imidization rate of 80% or more, more preferably 85%. Above, the "fluorenimide ratio" refers to the ratio of the total number of repeating units in the polymer to the number of repeating units forming a sulfonimide ring, expressed in%. At this time, a part of the sulfonimide ring It may be an isoamidine ring. The polymer of the terminal modification type may include polyimide acid and amidine polymer, which may be obtained by adjusting the molecular weight of the terminal modification type. The aforementioned terminal modification type is When synthesizing polyamidic acid, the acid monoanhydride and monoamine compound are used. Isocyanate compounds are added to the reaction system to synthesize. Among them, acid monoanhydrides such as maleic anhydride, benzoic anhydride, itaconic anhydride, η-decylsuccinic anhydride, η-dodecylsuccinic anhydride, η-tetradecane Succinic anhydride, η-hexadecyl succinic anhydride, etc. In addition, monoamine compounds such as aniline, cyclohexylamine, η-butylamine, η-pentylamine, η-hexylamine, η-heptylamine, q-octylamine, η-nonylamine, η-decylamine, η—h-alkylamine, η — ten paper sizes are applicable to China National Standard (CNS) M specifications (210 × 297 mm) (please first Read the notes on the back and fill out this page) Order% r. Printed by the 8th Industrial Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -25- _51 59l〇83 A7 V. Description of the invention (23) Dimethylamine, η — 13 Rhodium amine, η-fourteen amine, η--h five (please read the precautions on the back before filling this page) Benzylamine, η-hexadecyl amine, η-heptadecylamine, η-octadecylamine, η-icosylamine and the like. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate. Logarithmic Viscosity of Polymers The polyamidoacid and fluorinated imidized polymers prepared according to the above methods have a logarithmic viscosity of generally 0.05 to 10d Ι / g, preferably 0.05 to 5dl / g. The logarithmic viscosity (7? Ln) of the present invention uses N-methyl-2 ~ pyrrolidone as a solvent, and a solution with a concentration of 0.5 g / 100 ml is used to measure the viscosity at 30 ° C and according to the following formula (I) Those obtained by the calculation formula.

In (solution flow time / solvent flow time) V 1η = (i) (weight concentration of polymer) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Industrial and Consumer Cooperatives (B) Silicon-containing compound The silicon-containing compound used in the present invention is Polyorganosiloxane with polyether bond. The polyorganosiloxane mentioned above is preferably a branch having a polyether bond. The above-mentioned silicon-containing compound and the compound represented by the following formula (I I) are the best compounds. This paper size applies to Chinese National Standards (CNS> 8-4 specifications (2 丨 〇 > < 297 mm) -26- 591083 A7 B7_______ V. Description of the invention (24)

H3C | -fOCmH2 ^ (〇CnH2n ^ -B (Please read the notes on the back before filling out this page) H3C-fsi-〇ysi-〇) ^ s | ^ CH3 ^ (II) ch3 ch3 (where A is Single bond, methyl group or alkylene group with 2 to 5 carbon atoms, B is a hydroxyl group or alkyl group with 1 to 3 carbon atoms, a and 13 are independent numbers from 1 to 100, and c and d are mutually Independent numbers of 1 to 3, m and η are independent numbers of 1 to 6) The alkylene groups of 2 to 5 carbon atoms represented by A in the above formula (II), such as ethylidene, η-propylene Group, η ~ butylene, pentyl and the like. Further, the alkyl group having 1 to 3 carbon atoms represented by B of the above formula (I I) includes, for example, methyl, ethyl, η-propyl, and the like. The a and b of the above-mentioned formula (I I) printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs may be numbers from 1 to 100 independently, preferably from 30 to 80. In addition, c and d are numbers of 1 to 3 independent of each other. In addition, m and η are numbers of 1 to 6 independently of each other, and preferably numbers of 1 to 3. In particular, a combination of m being 1 and η being 2 and a combination of m being 2 and η being 3 are more preferable. These compounds can be used alone or in combination of two or more. In addition, the (B) silicon-containing compound used in the present invention has a molecular weight of generally 500 to 50,000, preferably 1,000 to 10,000. In the liquid crystal alignment agent of the present invention, (B ) The amount of silicon-containing compound added is based on 100 parts by weight of (A) polymer, generally 0. to the paper size. Applicable to China National Standard (CNS) A4 specification (210X297 mm) -27- 591083 A7 B7___ 5 、 Explanation (26) (please read the precautions on the back before filling this page) polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol Diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N,, N, —Tetraglycidyl-m —xylylenediamine, 1,3-bis (N, N — —►glycidylamine methyl) cyclohexane, Ν, Ν, Ν ′, Ν ′ —tetraglycidyl -4,4-diaminodiphenylmethane, etc. The aforementioned epoxy group-containing compound is added in an amount of 100 parts by weight to the polymer, generally 40 parts by weight or less, and preferably 0.1 to 30 parts by weight. Liquid crystal display element The liquid crystal display element of the present invention can be produced, for example, by the following method. The 4th Bureau of the Ministry of Economic Affairs (printed by the Industrial and Consumer Cooperative) (1) The liquid crystal alignment agent of the present invention will be coated on one side of a substrate provided with a patterned transparent conductive film by a suitable printing method, etc. Then, the coating surface is heated to form a coating film. The substrate may be, for example, a wide glass or a soda lime glass, or polyethylene terephthalate, polybutylene terephthalate, poly Transparent substrate made of plastic such as ether mill and polycarbonate index. As for the transparent conductive film provided on one side of the substrate, for example, NES Α film (trademark of American PPG Corporation) composed of tin oxide (S η〇2), It is an IT film composed of indium oxide-tin oxide (In2 03-S η〇2), and the pattern of the transparent conductive film can be formed by etching or using a photomask in advance. 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, a functional silane can be pre-coated on the aforementioned surface of the substrate. The paper size is applicable to China National Standard (CNS) A4 specifications (210X297 mm). ) -29- 59108 3 A7 B7 V. Description of the invention (27) (Please read the notes on the back before filling out this page} compounds, functional titanium compounds, etc. The heating temperature after the liquid crystal alignment agent is applied is 80 to 30CTC, preferably 120 Up to 250 ° C. In addition, the liquid crystal alignment agent of the present invention containing polyamidic acid removes the organic solvent to form a coating film of the alignment film after coating, dehydrates and closes the ring by heating, and then undergoes imidization to It is also possible to form a coating film. The film thickness of the formed coating film is generally from 0. 001 to 1 // m, preferably from 0.005 to 0.5 / zm. (2) On the surface of the formed coating film, it can be A roller that is wrapped with a fabric made of fibers such as nylon, snails, and cotton is rubbed in a certain direction. After this treatment, the coating film can be provided with liquid crystal molecular alignment energy to form a liquid crystal alignment film. Printed by the Consumer Cooperative of the Property Bureau. The liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention is, for example, described in Japanese Patent Application Laid-Open No. 6-222366 or Japanese Patent Application Laid-Open No. 6-28193 7. It can be partially irradiated with ultraviolet rays. Where the pretilt angle changes , Or as described in Japanese Patent Application Laid-Open No. 5-1 0 7 5 4 4, a portion of the photoresist film is formed on the surface of the liquid crystal alignment film obtained after the rubbing treatment, and then the rubbing treatment is used to remove it in a direction different from the previous rubbing treatment. The photoresist film can change the liquid crystal alignment of the liquid crystal alignment film, and can change the viewing angle characteristics of the liquid crystal display element. (3) Make two substrates that form the liquid crystal alignment film according to the method described above, and make the liquid crystal alignment film The rubbing direction is formed at right angles or in the opposite direction. The two substrates are arranged opposite to each other with a gap. The peripheral parts of the two substrates are bonded with a sealant. The liquid crystal is injected into the gap separated by the surface substrate and the sealant. The injection hole is closed to form a liquid crystal cell. Subsequently, on the outer surface of the liquid crystal cell, that is, the other side of the substrate of the liquid crystal cell, the polarizing plate is applied to the Chinese national standard (CNS) A4 specification (210X29 * 7 mm) according to the paper size. -30- 591083 A7 B7 V. Description of the invention (28) The polarization direction and the rubbing direction of the liquid crystal alignment film formed on the other side of the substrate are adhered in the same or right-angled manner to obtain a liquid crystal display element. (Please read the precautions on the back before filling out this page.) Among them, examples of sealants can include hardeners and aluminum oxide epoxy resins for pitch adjustment. 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-type liquid crystals, azo oxide-based liquid crystals, biphenyl-based liquid crystals, phenylcyclohexane-based liquid crystals, and pyrimidines. Based liquid crystal, dioxane based liquid crystal, bicyclooctane based liquid crystal, cube based liquid crystal, and the like. In addition, the liquid crystal may be added with a cholesteric liquid crystal such as cholesteryl chloride, cholesteryl nonyl ester, or cholesteryl carbonate, or trade names [C — 1 5], [c B — 1 5] (Mei Lu Can be made by the company). In addition, for example, a strong dielectric liquid crystal such as P-decoxybenzylidene-P-amino-2-methylbutylstyrene can be used. The polarizing plate attached to the outer surface of the liquid crystal cell, and in the case of using polyethylene glycol to extend the alignment, a polarizing film obtained by adding a polarizing film with a protective film of cellulose acetate and a film of iodine absorbed by iodine, or a The polarizing plate formed by the diaphragm itself. Printed by the Intellectual Property of the Ministry of Economic Affairs ^ Employee Consumer Cooperatives [Embodiments] Hereinafter, the present invention will be described in more detail with examples, but the present invention is not limited by these examples. Synthesis Example 1 The paper size of 109 · 06g (0.5 · mol) of tetracarboxylic dianhydride is benzene. The Chinese paper standard (CNS) A4 specification (210X297 mm) is applied., --31-591083 A7 _B7___ V. Description of the Invention (29) (Please read the precautions on the back before filling out this page) Tetracarboxylic dianhydride, 98.06g (0.5 Moore) 1,2,3,4 Monocyclobutanetetracarboxylic dianhydride, two 200 · 2 g (1-mole) of 4,4-diaminodiphenyl ether of an amine compound was dissolved in 4500 g of N-methyl-2-pyrrolidone, and reacted at 60 ° C for 6 hours. Subsequently, the reaction solution was poured into an excess of methanol to precipitate a reaction product, and the reaction product was washed with methanol and dried at 40 ° C under reduced pressure for 15 hours to obtain a logarithm of viscosity 0 · 88d Ι / g. 290 g of polyamic acid (hereinafter referred to as "polyamino acid (A-1)") at a rate of 0%. Synthesis Example 2 Tetracarboxylic dianhydride of 109.06 g (0.5 mol) of pyromellitic dianhydride and 98.06 g (0.5 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride 198.27g of diamine compound (1 mole) 4,4'-diaminodiphenylmethane was dissolved in 4500 g of N-methyl-2-pyrrolidone printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Reaction at 6 Ot: 6 hours. Subsequently, the reaction solution was poured into excess methanol to cause precipitation of the reaction product, and then washed with methanol, and dried under reduced pressure at 40 t for 15 hours to obtain a logarithm of viscosity 0.992d Ι / g. It was 310 g of polyamidic acid (hereinafter referred to as "polyamidic acid (A-2)"). Synthesis Example 3 196.12 g (1.0 mole) of tetracarboxylic dianhydride, 1, 2, 3, 4-cyclobutane tetracarboxylic dianhydride, 200.2 g (1.0 mole) of diamine compound 4, 4 '—Diaminodiphenyl ether This paper is in accordance with China National Standard (CNS) A4 specification (210X297 mm) ~ 591083 A7 __ _B7_ V. Description of the invention (3〇) (Please read the notes on the back before filling (This page) was dissolved in 4,500 g of N-methyl-2-pyrrolidone, and reacted at 60 ° C for 6 hours. Subsequently, the reaction solution was poured into excess methanol to precipitate the reaction product, and the reaction product was washed with methanol and dried at 40 ° C under reduced pressure for 15 hours to obtain a logarithmic viscosity of 0.90 d 1 / g. Polyamidic acid having an imidization ratio of 0% (hereinafter referred to as "polyamidic acid (A-3)") 290 g Synthesis Example 4 196.12 g (1.0 mole) of tetracarboxylic dianhydride ) 1 '2,3,4 Monocyclobutanetetracarboxylic dianhydride, 2 1 2 g (1.0 mole) of 2, 2'-4,4 '—aminobiphenyl dissolved in 4 5 0 0 In g of N-methyl-2-pyrrolidone, react at 60 ° C for 6 hours. Subsequently, the reaction solution was poured into excess methanol to precipitate the reaction product, and the reaction product was washed with methanol, and dried at 40 ° C under reduced pressure for 15 hours to obtain a logarithm of viscosity 0.99 d 1 / g. 290 g of polyamic acid (hereinafter referred to as "poly (A-4)") having an amination rate of 0%. Bureau of Intellectual Property, Ministry of Economic Affairs: Printed Synthesis Example 5 by Shelley Consumer Cooperative, 224 · 17g (1.0 mole) of tetracarboxylic dianhydride 2 '3,5-tricarboxycyclopentylacetic dianhydride, diamine Of the compound, 200.2 g (1.0 mole) of 4,4'-diaminodiphenyl ether was dissolved in 4,500 g of N-methyl-2-pyrrolidone at 600. (: React for 6 hours. Then, inject the reaction solution into excess methanol to make the paper size applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -33- 591083 A7 B7. V. Description of the invention (31)) (Please First read the precautions on the back and fill in this I) The reaction product precipitates, and then washed with methanol, dried at 40 ° C under reduced pressure for 15 hours to obtain the logarithm of viscosity 0 · 8 7 d 1, / g, 醯Polyamidic acid having an imidization rate of 0% (hereinafter referred to as "polyamidic acid (A-5)") 2 8 0 g ° Synthesis Example 6 224. 17 g of tetracarboxylic dianhydride (0.5 Mo (Ear) 2,3,5-tricarboxycyclopentylacetic dianhydride, 157.14g (0.5 mole) 1,3,3a, 4,5,9b -hexahydro-5 -methyl-5 (tetrahydro-1 94.62g (0.5875 moles) p-phenylene of 2,5-dioxo-3-furyl) -naphthalene [1,2-c] -furan-1,3-dione, diamine compound Diamine, 32.02g (0. 1 mole) 2,2-ditrifluoromethyl-4, 4-diaminobiphenyl, 6.43g (0. 0 1 mole) 3,6-bi (4 monoaminophenylfluorenyloxy) cholestaene (a compound represented by the above formula (9), The same below), 4 · 04g (0 · 015 mole) printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the 18th printed alkoxy-2,5-diaminobenzene dissolved in 4500g of N-methyl-2-pyrrolidone The reaction was carried out at 60 ° C for 6 hours. Subsequently, the reaction solution was poured into excess methanol to precipitate the reaction product, washed with methanol, and dried at 40 ° C for 15 hours under reduced pressure to obtain the viscosity. Logarithm: 0.887 d / g, 410 g of polyamidic acid with a fluorinated imidization rate of 0%. 30 g of the polyamidic acid obtained was re-dissolved in 570 g of N-methyl-2-pyrrolidone, and 23. After 4 g of pyridine and 18.1 g of acetic anhydride, perform dehydration and closed-loop reaction at 110 ° C for 4 hours, and -34- This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 591083 A7 __B7 __ V. Description of the invention (32) (Please read the precautions on the back before filling in this page) After carrying out the same precipitation, washing and decompression as described above, the viscosity logarithm is 0.80 d Ι / g. 100% of fluorene imidized polymer (hereinafter referred to as "fluorene imidized polymer (B-1)") 17. 5 g. Synthesis Example 7 Carboxylic dianhydride: 224 · 17g (0.5 mole) 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 157 · 14g (0 · 5 mole) 1,3,3a, 4,5, 9b —hexahydro-5 —methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphthalene [1,2-c] -furan-1,3-dione, diamine compound 94 · 62g (0 · 875 mol) p-phenylene diamine, 24 · 85g (0 · 1 mol) bisaminopropyltetramethyldisilax Printed alkane, 6.43g (0. 0 1 mol) 3,6-bis (4-aminophenylfluorenyloxy) cholestaene, 4.04g (0.015 mol) octadecyloxy-1 2,5-Diaminobenzene was dissolved in 4500 g of N-methyl-2-pyrrolidone and reacted at 60 ° C for 6 hours. Subsequently, the reaction solution was poured into an excess of methanol to precipitate a reaction product, and the reaction product was washed with methanol, and dried at 40 ° C under reduced pressure for 15 hours to obtain a logarithm of viscosity 0.882d I / g. 370 g of polyamic acid at a rate of 0%. 30 g of the obtained polyamic acid was re-dissolved in 570 g of N-methyl-2-pyrrolidone, and 23.4 g of pyridine and 18.1 lg of acetic anhydride were added, followed by a dehydration ring-closure reaction at 110 ° C for 4 hours. After carrying out the same precipitation, washing, and decompression, the logarithm of viscosity was 0.77 d 1 / g, and the imidization ratio was 100 ° /. Zhiimide polymer (at -35- this paper size applies Chinese National Standard (CNS) A4 specification (210X297mm) 591083 A7 B7_ V. Description of the invention (33) hereinafter referred to as "醯 imide polymer ( B — 2) ") 18 · 5g. (Please read the precautions on the back before filling this page) • Synthesis Example 8 224 · 17g (1 · 0 mole) of tetracarboxylic dianhydride 2, 3, 5-tricarboxycyclopentylacetic dianhydride 107 · 06 g (0 · 99 mole) of P-amine compound, 6 · 43 g (0 · 01 mole) of P-phenylenediamine, 3,6-bis (4-aminophenylphenoxy) cholesterol dissolved In 4 500 g of N-methyl-2-pyrrolidinone, react at 60 ° C for 6 hours. Subsequently, the reaction solution was poured into excess methanol to precipitate the reaction product, and then washed with methanol, and dried under reduced pressure at 40 t for 15 hours to obtain a logarithm of viscosity 0.90 d 1 / g. Polyglycolic acid 4 0 0 g with a chemical conversion rate of 0%. 30 g of the obtained polyamic acid was re-dissolved in 570 g of N-methyl-2-pyrrolidone, and 23.4 g of pyridine and 18.lg of acetic anhydride were added, followed by 4 at 1 10 ° C. Hours of dehydration and closed-loop reaction, and after the same precipitation, washing, and decompression as described above, the viscosity logarithm is 0.85 d 1 / g. The imidization rate printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is 100%. 17.5 g of fluorene imidized polymer (hereinafter referred to as "fluorene imidized polymer (B-3)"). Synthesis Example 9 224 · 17 g (0.5 mole) of tetracarboxylic dianhydride 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 157.1 g (0.5 mole) of 1,3,3a ， 4,5,9b —hexahydro-5 —methyl-5 (tetrahydro-2,5-dioxo-3 —furanyl) -naphthalene [This paper size applies to China National Standard (CNS) A4 specification (210X297 Mm) -36-59l〇83 A7 B7 _________________ V. Description of the invention (34) (Please read the notes on the back before filling out this page) 1,2-c] -furan-1,3-dione, diamine 89. 21g (.825 mol) of P-Phenylenediamine, 32.02g (0.1 mol) of 2'2'-ditrifluoromethyl- Printed by the Industrial Property Cooperative of the Ministry of Economic Affairs 4 4,4-diaminobiphenyl, 25.34g (0.06 mole) 1- (3,5-diaminophenylphenyloxy)-4-(4-trifluoromethylphenyloxy) ) -Cyclohexane (the compound represented by the above formula (20), the same applies hereinafter), 4 · 04 g (0. 15 mol) octadecyloxy-2,5-diaminobenzene was dissolved in 4500 g of N- Methyl-2-pyrrolidone, 6 hours at 60 ° C . Subsequently, the reaction solution was poured into excess methanol to precipitate the reaction product, and the reaction product was washed with methanol and dried at 40 ° C under reduced pressure for 15 hours to obtain a logarithm of viscosity 0.99 d Ι / g. 4 1 0 g of polyamic acid having an amination rate of 0%. 30 g of the obtained polyamic acid was re-dissolved in 570 g of N-methyl-2-pyrrolidone, and after adding 23.4 g of pyridine and 18.lg of acetic anhydride, dehydration and ring closure were performed at 110 ° C for 4 hours. The reaction is carried out by the same precipitation, washing, and decompression as described above to obtain a logarithmic viscosity of 0.83 d 1 / g and a fluorinated imidization polymer having a fluorinated imidization rate of 100% (hereinafter referred to as “fluorene” Aminated polymer (B-4) '') 17.5g. Example 1 100 parts by weight of the fluorene imidized polymer (B-1) obtained in Synthesis Example 6 and SH 3 77 1 (Toray—Dow Corning Corporation) containing a silicon-containing compound represented by the above formula (II) Made) 0 _ 075 parts by weight dissolved in r-butyrolactone / N-methyl-2-pyrrolidone / butyl cellulose solubilizer This paper is applicable to China National Standard (CNS) A4 (210X297 mm) ~ " " 591083 A7 B7 V. Description of the invention (35) (Please read the precautions on the back before filling out this page) In a mixed solvent (71/17/12 (weight ratio)), the solution with a solid content concentration of 4% by weight ' This solution was filtered through a filter with a pore size of 1 // m to make the liquid crystal alignment agent of the present invention. The above-mentioned liquid crystal alignment agent was coated on a transparent electrode surface of a glass substrate with a transparent electrode of IT using a liquid crystal alignment film printer (manufactured by Japan Photo Printing Co., Ltd.), and dried on a hot-pressed plate at 80 t for one minute. And dried on a hot platen at 200 ° C for 10 minutes to form a film with an average thickness of 600 angstroms. When the substrate was observed under a microscope at a magnification of 20 times, printing streaks and sand holes were not found, and it was confirmed that the printability was extremely good. Printed by the Goods and Consumers Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. This film is rolled on a roller with a dragon-proof cloth. Friction machine is used to rotate the roller at 5 0 0 r pm, the platform moving speed is 3 cm / second, and the presser foot length is 0. The rubbing treatment was performed under a condition of 4 mm to form a liquid crystal alignment film. Subsequently, the substrate on which the above-mentioned liquid crystal alignment film was formed was immersed in isopropyl alcohol for 1 minute, and then dried on a hot platen at 100 ° C for 5 minutes. Subsequently, a pair of the substrates with the outer edges of the liquid crystal alignment film are coated with an alumina epoxy resin adhesive with a diameter of 5 · 5 // m, and then the liquid crystal alignment film faces are bonded in an opposite way. Harden the adhesive. Subsequently, a matrix type liquid crystal (MLC-6 2 2 1) was filled between a pair of substrates through the liquid crystal injection hole, and then the liquid crystal injection hole was closed with an acrylic light-curing adhesive, and then the two outer surfaces of the substrate The deflection plate is bonded to the upper surface to complete the liquid crystal display element of the present invention. The obtained liquid crystal display element was subjected to a rectangular wave of 30Hz and 3.0V with alternating AC 6.0V (peak and peak) for 50 hours at an ambient temperature of 70 ° C, and the result was observed visually. I learned that the paper size of this paper is in accordance with the Chinese National Standard (CNS) A4 (210X297 mm) -38- 591083 A7 B7 V. Description of the invention (36) Crystal display elements have not been found to display poorly. Examples 2 to 22, Comparative Examples 1 to 2 The polyimide acids and fluoridimide polymers obtained in Synthesis Examples 1 to 9 and Comparative Examples 1 to 2 were used, except for changing the types and addition amounts of silicon-containing compounds and Except for the drying temperature of the liquid crystal alignment film, a liquid crystal alignment agent was prepared in the same manner as in Example 1, and the film formed on the substrate was observed to see whether it had printed streaks or sand holes, and then the obtained liquid crystal display element was observed. Is there any display failure? Moreover, in Examples 5 to 2, and Comparative Examples 1 to 2, the polyamidic acid and the fluorene imidized polymer system used polyamic acid: fluorene imidized polymer = 4: 1 (weight ratio) ratio . The results are also shown in Table 1. (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 applies the Chinese National Standard (CNS) A4 specification (21 OX 297 mm) -39-591083

AB 5. Description of the invention (37) Table 1 Printed polymer containing silicon compounds (parts by weight) of the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Printability shows poor Example 2 B-2 C-K0.075) Good / γγΓ- IiTF j \ w Example 3 B-3 C-K0.075) Good 4m * 111II y ι Example 4 B-4 Cl (0.075) Good example 5 A-1, B-1 C-K0.075) Good dnL · TTTT1: J \ w Example 6 A-2, B-1 C-K0.075) Good inL ιΓΓΓ Example 7 A-3, B-1 C-K0.075) Good 4rrc. 11111 Example 7 A-4, B-1 Cl (0.080) Good J J \\\\ Example 8 A-5, B-1 Cl (0.080) Good 4cnl lilt J INN Example 9 A-1, B-2 C-K0. 080) Good > frrf 111 rr Example 1 0 A-2, B-2 C-K0.080) Good MJ Example 1 1 A-3, B-2 Cl (0.080) Good J \\\ Example 1 2 A-4, B-2 Cl (0.075) Good 4πΐ. Ill Γ J INN Example 1 3 A-5, B-2 C-K0.075) Good 4nt Π Γ Example 1 4 A-1, B -3 C-K0.075) Good itnt Π MJ l Example 1 5 Α · 2, B-3 C-K0.075) Good M j \\\ Example 1 6 A-3, β-3 Cl (0.075 ) OK / frr r Mil J l \ N Example 1 7 A-4, B-3 Cl (0.075) Good dfral tttr j \\\ Example 1 8 A-5, B-3 C-K0.075) Good > frrr lilt Example 1 9 A-3, B-4 C-K0.075) Good / frrr ΙΠΠΓ J k NN Example 2 0 A-4, B-4 C-K0.075) Good > 6nr Example 2 1 A -1, B-1 Cl (0.075) Good > fnT-II1Γ Example 2 2 Α · 4, B-4 C-K0.075) Good 4ttL tin II J \ w Comparative Example 1 A-1, B-1 _ Speckled MJ i ΛΝ Comparative Example 2 A-3, B-2 Speckled 4rrr / fn-r 1111Γ 111 J \\\ Jv \\ This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ( Please read the precautions on the back before filling this page) -40 591083 A7 B7__ V. Description of the invention (38) C— 1: SH3 77 1 (manufactured by Toray Co., Ltd., a polysilicon company) (Please read the back Please fill in this page again for precautions) C-2: SH190 (manufactured by Toray Co., Ltd. and Polysilicon Co., Ltd.) [Effect of the invention] The liquid crystal alignment agent of the present invention can be obtained when coated on a substrate. LCD with good printability such as printing streaks and sand holes Film. The liquid crystal display element of the present invention is applicable to TN type and STN type liquid crystal display elements. The liquid crystal used can also be selected, and used to obtain SH (Super Homeotropic) type, IPS (In-Plane Switching) type, strong Dielectric and anti-ferroelectric liquid crystal display elements. In addition, the liquid crystal display element of the present invention can be effectively used in various devices, such as display devices such as desktop computers, watches, clocks, number display boards, word processors, personal computers, and LCD televisions. Printed by Xiao Gong Consumer Cooperative, Bureau of Intellectual Property, Ministry of Economic Affairs This paper is sized to the Chinese National Standard (CNS) A4 (210X297 mm) -41-

This paper size is in accordance with Chinese National Standard (CNS) A4 (21 × 297). Binding 591083 A7 B7

V. Description of the invention (13) 6-diaminoacridine, bis (4-aminophenyl) phenylamine and compounds represented by the following formulae (III) to (IV), etc., have two primary amine groups in the molecule A diamine with a nitrogen atom other than the primary amine group;

H2N NH2 (III) I --------- 4 clothing—— (Please read the precautions on the back before filling this page) (where R 5 is a compound with pyridine, pyrimidine, triazine, piperidine A monovalent organic group having a nitrogen atom-containing ring structure selected from piperazine, and X is a divalent organic group)

, 1T 0x_r6'x " 0 (iv) line (where R 6 is a divalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine, and piperazine, and X is Divalent organic group, X in plural may be the same or different) Mono-substituted phenylenediamines represented by the following formula (V); Diamine-based organosiloxanes represented by the following formula (VI); Applicable to China National Standard (CNS) A4 specification (210X297 mm) -16-591083 A7 B7 Zhen "25. Description of the invention (25) 2 parts by weight, preferably 0.05 to 1 part by weight, more preferably 0. 05 to 0 · 5 parts by weight. If it is less than 0 · 0 1 parts by weight, the effect of improving printability may be insufficient, and when it exceeds 10 parts by weight, it may be thickened. Liquid crystal alignment agent In the liquid crystal alignment agent of the present invention, the polymer (A) and the silicon-containing compound (B) described above are generally constituted by being dissolved in 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 200 ° C, and preferably in the range of 20 ° C to 60 °. The organic solvent constituting the liquid crystal alignment agent of the present invention can be, for example, an organic solvent used in the synthesis reaction of poly (fluorinated acid). In addition, a poor solvent that can be used in the synthesis reaction of polyamic acid can also be used after being appropriately selected. The concentration of the solid component in the liquid crystal alignment agent of the present invention is preferably in the range of 1 to 10% by weight in consideration of viscosity, volatility and the like. 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. Therefore, when the solid content is less than 1% by weight, 'the film thickness of the coating film is too thin, so it cannot be used. A good liquid crystal alignment film is obtained, and when the viscosity of the liquid crystal alignment agent is too large, its coating characteristics may also deteriorate. The liquid crystal alignment agent of the present invention is preferably a compound containing an epoxy group in terms of improving the adhesion to the substrate surface. The aforementioned epoxy-containing compounds, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, this paper standard applies to China National Standard (CNS) A4 Specifications (21〇χ297mm) Approved clothing-(Please read the precautions on the back before filling this page) Thread 28-

Claims (1)

591083 A8 B8 C8 D8 r. Attachment of Patent Application Range: Patent Application No. 9 1 1 1 6903 Chinese Application for Patent Scope Amendment October 9, 1992 Amendment 1 · A liquid crystal alignment agent, which contains (A) has 100 parts by weight of a polymer selected from the repeating units represented by the following formula (I-1) and at least one repeating unit represented by the following formula (I-2), and (B) has a polyether bond Liquid crystal alignment agent of 0.0 1 to 2 parts by weight of silicon-containing compound represented by formula (II) below; HOOC COOH HNOC X CONH (1-1)-^-(Please read the notes on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper size applies to China National Standard (CNS) A4 (210 X 297 mm), ιτ silk COOH CONH—Q 591083 A8 B8 C8 D8 VI. Patent application scope (where A is a single bond, a methyl group or an alkyl group having 2 to 5 carbon atoms' B is a hydroxyl group or an alkyl group having 1 to 3 carbon atoms, and a and b are Independent numbers from 1 to 100, c and d are independent numbers from 1 to 3, and m and η are independent numbers from 1 to 6). 2. The liquid crystal alignment agent according to item 1 of the scope of patent application, wherein (A) the polymer is a polymer containing a repeating unit represented by the following formula (I-1) and a repeating unit represented by the following formula (I-2) Property; HOOC, (1-1) (Please read the notes on the back before filling in this page) HNOC (In the formula, P 2 is a tetravalent organic group derived from tetracarboxylic dianhydride, and Q 2 is a divalent organic group derived from diamine.) 3. The liquid crystal alignment agent according to item 1 of the scope of patent application, in which, (B) the silicon-containing compound having a polyether bond is a compound represented by the following formula (II); This paper size applies the Chinese National Standard (CNS) A4 Specifications (210X297 mm) -2-591083 A8 B8 C8 D8 Patent application scope h3? I H3C-4si-〇V (si-〇 OCm H2 ^ (〇CnH2nV " 巳 Si- (CH3) 3 II a, CH3 ch3 ( In the formula, A is a single bond, a methyl group, or an alkyl group having 2 to 5 carbon atoms, B is a hydroxyl group or an alkyl group having 1 to 3 carbon atoms, a and b are independent numbers of 1 to 100, and c and d is an independent number from 1 to 3, and m and η are independent numbers from 1 to 6.) 4 · If applied, the liquid crystal alignment agent of the patent scope item 1 ·, which is used for liquid crystal display elements. € Pack — (Please read the precautions on the back before filling out this page) 4 — The paper printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Silk Economy applies the Chinese National Standard (CNS) Α4 specification (210 × 297 mm) -3-