TW200537180A - Liquid crystal alignment agent - Google Patents

Abstract

The present invention provides a liquid crystal alignment agent for liquid crystal display element and a liquid crystal display element made of the liquid crystal alignment agent. Even under the conditions of that not limited on ITO, and using the reflect electrode, the liquid crystal alignment film with excellent calcining property also could be obtained by using the said liquid crystal alignment agent. The said liquid crystal alignment agent contains 100 part by weight of polymer having repeat units of the amidic acid and imide, the ratio of the said amidic acid repeat units are 40~60% based on the weight of total repeat units, and at least 5 part by weight of a compound comprising at least 2 epoxy inside the molecular.

Description

200537180 • Description of the invention: [Technical field to which the invention belongs] The present invention relates to a liquid crystal alignment agent. More specifically, it is related to a liquid crystal alignment agent having good sintering characteristics regardless of the type of electrodes constituting the liquid crystal display element. [Prior art] In the past, TN type liquid crystal display elements having a TN (Twisted Nematic) type liquid crystal cell are known. In the TN type liquid crystal cell, a transparent conductive film is inserted into two pieces and a liquid crystal is formed on the surface. A nematic liquid crystal layer having a positive dielectric anisotropy is formed between the φ substrates of the alignment film to form a stacked structure. The major axis of the liquid crystal molecules is continuously twisted 90 degrees from one substrate to the other substrate. In addition, there is also a state in which the long axis of the liquid crystal molecules is continuously twisted between the substrates by 180 degrees or more by the addition of a palm agent, and the resulting STN (Super Twisted Nematic) ) Type liquid crystal display element. And recently, a nematic liquid crystal layer having a negative (dielectric isotropy) vertical (h 〇me 〇tr 〇pic) alignment φ state has been developed between the opposing substrates, or the spiral axis is parallel to the substrate normal A cholesterol-type liquid crystal layer in a state in which a gUest_host reflective liquid crystal display element is added to these liquid crystal layers. The liquid crystal alignment of these liquid crystal display elements is usually achieved by a liquid crystal alignment film subjected to a rubbing treatment. Here, as the liquid crystal alignment film material constituting the liquid crystal display element, polyimide, polyimide, polyester, and the like have been conventionally used. In particular, polyimide has excellent heat resistance, affinity with liquid crystals, mechanical strength, and the like, and is therefore used in most liquid crystal display devices. Recently, researches have been focused on high-definition display of liquid crystal display elements. 200537180 The quality improvement and power consumption reduction have been investigated, and the range of use of liquid crystal display elements is also expanding. In particular, reflective or semi-transmissive liquid crystal display elements that can maintain high display quality even when used outdoors are used at the carrying end, and various metal electrodes (hereinafter referred to as reflective electrodes) are used in order to exhibit the function of reflecting external light. . However, if a liquid crystal display element having a reflective electrode is used, an alignment film used in a conventional ITO electrode causes a problem of sintering. [Summary of the Invention] An object of the present invention is to provide a liquid crystal alignment agent for a liquid crystal display element, which can obtain a liquid crystal alignment film having excellent sintering characteristics even when a reflective electrode other than ITO is used. Other objects and advantages of the present invention will be apparent from the following description. According to the present invention, the above objects and advantages of the present invention are achieved by a liquid crystal alignment agent, which is characterized in that the liquid crystal alignment agent contains 100 parts by weight of a repeating unit having the following formula (1-1) and the following formula (1 -2) The polymer represented by the repeating unit and the proportion of the repeating unit represented by formula (1-1) accounts for 40% to 60% of the total repeating unit Φ yuan by weight of the polymer, and at least 5 parts by weight of the molecule Compounds with at least two epoxy groups. [Chemical 1]

(In the formula, P1 is a tetravalent organic group, and Q1 is a divalent organic group.) 200537180 [化 2] 〇 〇

〇〇 (In the formula, P2 is a tetravalent organic group, and Q2 is a divalent organic group) The liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention, even when φ uses a reflective electrode that is not limited to ITO, A liquid crystal alignment film having excellent sintering characteristics can be obtained, and can be suitably used in various liquid crystal display elements such as a TN liquid crystal display element, an S TN liquid crystal display element, a reflective liquid crystal display element, and a transflective liquid crystal display element. The liquid crystal display element of the present invention can be effectively used in various devices. For example, it can be suitably used as a display device such as a desktop computer, a watch, a timer, a mobile phone, a counting display board, a word processor, a personal computer, and an LCD television. Best Mode for Carrying Out the Invention The present invention will be described in detail below. The liquid crystal alignment agent of the present invention contains a polymer (hereinafter referred to as a "specific polymer") having a repeating unit represented by the above formula (B1) and a repeating unit represented by the above formula (1-2). The polymer may be a mixture of (1) a polyamidic acid having a repeating unit represented by the above formula (VII-1) and a polyimide having a repeating unit represented by the above formula (1-2), or may be a mixture of (2) A polymer (hereinafter, referred to as a polymer formed by random or block bonding of the repeating unit represented by the above formula (Bu1) and the repeating unit represented by the above formula (1-2) As "partial fluorene imine 200537180". The polyamidic acid can be obtained by the addition of ring-opening polymerization of a tetracarboxylic dianhydride and a diamine compound. The "polyamidoimine" is generally obtained by dehydrating and closing the polyamido acid. The partially fluorinated imidized polymer is generally obtained by a method of partially dehydrating and closing the polyfluorinated acid, or a method in which a fluorinated acid prepolymer and a fluorinated imine polymer are bonded to form a block copolymer. < Polyamine acid > [Tetracarboxylic acid dianhydride] B Examples of the tetracarboxylic acid dianhydride include butanetetracarboxylic acid dianhydride, 1,2,3,4 · cyclobutanetetracarboxylic acid dianhydride , 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride , 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid Acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-bicyclo Hexanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6-tricarboxylic norbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofuran Tetracarboxylic acid diacid φ anhydride, 1,3,3 &, 4,5,91) -hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [l, 2-c] -furan-1,3-dione, 1,3,3 &, 4,5,91) -hexahydro-5-methyl-5- (tetrahydro-2,5-dioxo- 3-furanyl) -naphtho [1,2 <]-furan-1,3-dione, 1,3,3 a, 4,5,9b-hexahydro-5-ethyl-5- (tetrahydro -2,5-dioxo-3-furyl) -naphtho [l, 2-c] -furan-1,3-dione, 1,3, 3 &, 4,5,913-hexahydro-7-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2 ^]-furan-1,3- Dione, 1,3,3 &, 4,5,91) -hexahydro-7-ethyl-5- (tetrahydro-2,5-dioxo-3-furyl) -naphtho [l, 2-c] -furan-1,3-dione, 1,3,3 &, 4,5,91) -hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo- 3-furanyl) -naphtho [1,2-(:]-furan-1,3-di200537180 ketone, 1,3,3a, 4,5,9b-hexahydro_8_ethyl_5_ (tetra Hydrogen_2,5_dioxo_3_furanyl) -naphtho [l, 2-c] -furan-1,3-monoone, 1,3,3 &, 4,5,91)- Hexahydro_5,8-dimethyl-5- (tetrahydro-2,5-dioxo_3-furylbenzonaphtho [l, 2-c] -furan-1,3-dione, 5 -(2,5-Dioxotetrahydrofurfuryl 3-methyl · 3_cyclohexane-1,2-di-residual acid dianhydride, bis [2,2,2] _ 辛 -7- suspect · 2,3,5,6 -Tetra-residue diacid hydrazone dry, 3-oxo hydrazone ring [3 · 2 · 1] Xinyuan-2,4-一 嗣 -6-spiro-3 '-(four gas Furan_2,5, -dione), aliphatic and alicyclic tetracarboxylic dianhydrides such as compounds represented by the following formulae (1) and (Π); [化 3] 〇〇

〇〇 (II) (wherein R1 and R3 represent a divalent organic group having an aromatic ring 'R2 and R4 represent a hydrogen atom and an alkyl group, and a plurality of r2 and R4 may be the same or different, respectively) Pyromellitic dianhydride, 3,3 ', 4,4, benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylphosphonium tetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride Anhydride, 2,3,6,7-naphthalenetetracarboxylic acid anhydride, 3,3,, 44, diphenyl ether tetracarboxylic acid 200537180 diacid anhydride, 3,3 ', 4,4'-dimethyldibenzene Silyl tetracarboxylic dianhydride, 3,3 ', 4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis ( 3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylphosphonium dianhydride, 4,4'-bis (3 , 4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-Perfluoroisopropylidene diphthalic anhydride, 3,3', 4,4'- Diphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m Phenyl-bis (triphenylphthalic acid) dianhydride, bis (triφphenylphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride, ethylene glycol-bis (anhydrotrimellitic acid ester), propylene glycol-bis (anhydrotrimellitic acid ester), 1,4-butanediol-bis (anhydrous Trimellitate), 1,6-hexanediol-bis (anhydrotrimellitic acid ester), 1,8-octanediol-bis (anhydrotrimellitic acid ester), 2,2-bis (4 -Hydroxyphenyl) propane-bis (anhydrotrimellitic acid esters), aromatic tetracarboxylic acid diacid anhydride compounds such as compounds represented by the following formulae (1) to (4). These can be used individually by 1 type or in combination of at least 2 types. [Chemical 4]

-10200537180

Among these, from the viewpoint of exhibiting good liquid crystal alignment, preferred are butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and 1,2 · dimethyl- 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1 , 2,3,4-cyclobutanetetracarboxylic acid diacid-11- 200537180 wild 'u, 3,4'methyl-1,2,3,4 · cyclobutanetetracarboxylic acid diacid anhydride, cyclopentane Carboxylic acid anhydride, U ,. , Hexatetracarboxylic acid dianhydride, 2,3,5 · tri-residue cyclopentylacetic acid dianhydride, 5- (2,5_dioxotetrahydrofurfurylmethyl-3-cyclohexamethylene dicarboxylic anhydride, ^ Exohexahydro ^ tetrahydro_2,5-dioxoIfuranyl) -naphtho [丨 Shimanfuran],% dione, 1,3,4,5, ~ hexahydro-5_ Methyltetrahydro'5_dioxo | pyranylbenzonaphtho [l, 2-cl · furan ", 3-dione, · hexahydro_7_methyl-5- (tetrahydro_2,5 _Dioxo_3-furanyl) _naphtho [l, 2-c] -panan · L3-diketone, 1,3,3 &, 4,5,91) _hexahydro-8_fluorenyl _5_ (tetrahydro_2,5_dioxo_3_furanyl) -naphtho [l, 2-c] _furan-; 1,3-dione, methyl 5 (tetrahydro_2,5 _Dioxofuranylnaphtho [U_e 卜 furan '0Π sense ring [2,2,2] -oct-7-anil-2,3,5,6 -tetra-octanoic acid dianhydride, 3_ oxobicyclo [ 3 · 2 · η octane 2+ dione + spiro-3, _ (tetrahydrofuran_2,, 5, _one ketone) 'succinic tetracarboxylic dianhydride, 3,3,, 4,4, _diphenyl Methyl ketone tetracarboxylic acid dianhydride 3'3 '4'4. Monophenyl tetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, the following formula in the compound represented by the above formula ⑴ (5) to (7) and the compound represented by the above formula Among the compounds represented by (11), compounds represented by the following formula (8). Particularly preferred compounds include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, dimethyl-1,2 , 3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2, 3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5- Cyclohexatetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,3,3 &, 4,5,913-hexahydro-5- (tetrahydro-2,5-dioxo -3-furanyl) -naphtho [l, 2-c] furan-1,3-dione, 1,3,3 &, 4,5,91 ^ -hexahydro-5-methyl-5- ( Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-〇] -furan-1,3--12-200537180

-13- 200537180

〇 〇 (8) The tetravalent organic group represented by P1 in the repeating unit (fluorenic acid unit) represented by the above formula (1-1), and the repeating unit (醯 亚) represented by the above formula (1-2) The quaternary organic groups represented by P2 in # of amine units) are all derived from tetracarboxylic dianhydride. They can be the same or different. As preferred examples of P 1 in the above formula (I-1), the groups represented by the following formulae (i) and (i,) can be cited, respectively. As a preferable example of ρ 2 in the above formula (I-2), a group having an alicyclic skeleton 'is particularly preferred, and the groups represented by the following formulae (Π) and (ii,) are particularly preferred.

(Where R is a halogen atom, methyl or ethyl, & is an integer of 0 or 丨, b is an integer of 0 to 6, c is an integer of 0 to 4, and d is an integer of 0 to 5) Specific examples of the preferred tetracarboxylic acid dianhydride in the repeating unit. As the tetra-residual acid carboxylic acid field constituting the ammonium acid unit, 1,2,3,4--14-2005-37. Acid anhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dicarboxylic anhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dicarboxylic acid Acid anhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic diacid anhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetra Carboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, pyromellitic dianhydride, etc. In addition, as the tetracarboxylic dianhydride constituting the fluorene imine unit, alicyclic tetracarboxylic acid can be listed. Carboxylic acid anhydrides, in particular, 2,3,5-tricarboxycyclopentylacetic acid anhydride, 1,3,3 &, 4,5,91) -hexahydro-5- (tetrahydro-2,5 -Dioxo-3-furyl) -naphtho [l, 2-c] furan-1,3-dione, 1,3,3 &, 4,5,913-hexahydro • -5 -methyl-5 -(Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [l, 2- c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-methyl-5- (tetrahydro · 2,5-dioxo-3-furanyl ) -Naphtho [l, 2-c] -furan-1,3-dione, 1,3,3 &, 4,5,91) -hexahydro-8-methyl-5 (tetrahydro-2 , 5-dioxo-3-furyl) -naphtho [l, 2-c] -furan-1,3-dione, 1,3,3 &, 4,5,91) -hexahydro-5 , 8-dimethyl-5- (tetrahydro-2,5-dioxo-3-furyl) -naphtho [l, 2-c] -furan-1,3-dione and the like. [Diamine compound] As the diamine compound used in the synthesis of the polyphosphonic acid, for example, φ can be listed. For example, p-phenylenediamine, m-phenylenediamine, 4,4, diaminodiphenylmethane, 4,4 ' -Diaminodiphenylethane, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl ", 3,3'-dimethyl-4,4 ' -Diaminobiphenyl, 4,4 '· diaminobenzidine aniline, 4,4, diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2, -dimethyl- 4,4'-diaminobiphenyl, 5-amino-1- (4-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4'-amine Phenyl) -1,3,3-trimethylpyridine, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4'-diamine Benzophenone, 4,4'-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- ( 4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4--15-200537180

, I Aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] fluorene, 1,4-bis (4-aminophenoxy) benzene, 13 -Bis (4-aminophenoxy) benzene, 丨, 3-bis (3-aminophenoxy) benzene, 9,9 · bis (4-aminophenyl) -10-hydroanthracene, 2 ,, 7-Diaminopyrene '9,9-bis (4-aminophenyl) pyrene, 4,4, -methylene-bis (2-chloroaniline), 2,2', 5,5'-tetra Chloro-4,4, -diaminobiphenyl, 2,2, -dichloro-4,4, -diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy -4,4, · diaminobenzidine, 1,4,4 '-(p-phenylene isopropylidene) benzidine, 4,4'-(m-phenylene isopropylidene) benzidine , 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexa • fluoropropane, 4,4, diamino-2,2, -bis (tri Aromatic diamines such as fluoromethyl) biphenyl, 4,4, -bis [(4-amino-2 -trifluoromethyl) phenoxy] -octafluorobiphenyl; 1,1-m-xylylene Amine, 1,3-propanediamine, butylenediamine, pentanediamine, hexamethylenediamine, heptanediamine, octanediamine, nonanediamine, 4,4-diaminoheptanediamine, 1,4-diamine Aminocyclohexane, isophorone diamine, tetrahydrodicyclopentane Diene diamine, hexahydro-4,7-methyleneindene dimethylene diamine, tricyclic [6.2.1.02,7] -undecene dimethyl diamine, 4,4'-methylene Aliphatic and alicyclic diamines such as bis (cyclohexylamine); φ 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diamine Pyridine, 5,6-diamino-2,3 · dicyanopyridine, 5,6 · diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethyl Amine-1,3,5-triple, 1,4-bis (3-aminopropyl) piperidine, 2,4-diamino-6-isopropoxy-1,3,5-tris Coax, 2,4-diamino-6-methoxy-1,3,5-trigon, 2,4-diamino-6-phenyl-1,3,5-trigon, 2,4 -Diamino-6-methyl-s-triplet, 2,4-diamino-1,3,5-triplet, 4,6 · diamino-2-vinyl-s-triplet, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5-diamino-1 , 2,4-triazole, 6,9-diamino-2-ethoxyacridine lactate, 3,8--16- 200537180 diamino-6-phenylphenanthridine, 1,4- Diaminopiperidine '3,6-diamino group 11 yapidine' bis (4-aminophenyl) aniline and the following formulae (III) to (IV) Compound apos nitrogen atom in the molecule other than the diamine having two primary amine groups and the primary amine group;

[Wherein R5 represents a monovalent organic group having a ring structure containing a nitrogen atom selected from pyridine 'pyrimidine, triple well, piperidine, and piperidine' X represents a divalent organic • group)

(Wherein X represents a divalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triple well, piperidine, and piperidine, and R6 represents a divalent organic group, and a plurality of X may be Same or different) Monosubstituted phenylenediamines represented by the following formula (V);

(Wherein R7 represents a divalent organic group selected from -0-, -COC ^, -〇CO-, -NHCC ^, -CONH- and -CO-, R8 represents a group having a skeleton selected from steroids, Trifluoromethyl and fluoro-based monovalent organic groups or alkyl groups having 6 to 30 carbon atoms) -17- (VI) 200537180 [化 ίο] H2N inch CH2v4 juice 0 fttCH2 ^ NH2 i9 R9 (wherein R9 A hydrocarbon group having a carbon number of 1 to 12 'R9 may be the same or different, and P is an integer of 1 to 3' and q is an integer of 1 to 20) As shown in the following formulae (9) to (13) Compounds etc. These diamine compounds may be used singly or in combination of at least two kinds.

-18- 200537180

(In the formula, y is an integer of 2 to 12, and Z is an integer of 1 to 5.) Among them, p-phenylenediamine, 4,4'-alimyl-benzyl, and 4,4-diamine are preferred. Diphenylsulfide, 丨, 5-diaminonaphthalene, 2,7 · monoaminofluorene, 4,4-monoaminodiphenyl ether, 2,2-bis [4- (4-amino Phenoxy) phenyl] propionate '9,9 · bis (4-aminophenyl) pyrene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropionate, 2,2-Bis (4-aminophenyl) hexafluoropropane '4,4 ** (Paraben-isopropylidene) φbenzidine, 4,4,-(m-phenylenediisopropylidene) Aniline, 丨, 4-cyclohexanediamine, 4,4, methylene bis (cyclohexylamine), 1,4-bis (4-aminophenoxy) benzyl 4,4-bis (4-amine Phenoxy) biphenyl, compounds represented by the above formulae (9) to (13), 2,6-aminopyridine, 3,4-diaminopyridine, 2,4-diaminopyran D It is determined that the compound represented by the following formula (14) among the compounds represented by the above formula (IΠ) is '3,6. Diamino cyanine', and the following formula among the compounds represented by the above formula (IV) ( 15) Any of the following compounds (16) to (21) among the compounds represented by the above formula (V) Of compounds. -19- 200537180

-20- 200537180

[Synthesis reaction of polyamic acid] • The proportion of tetracarboxylic dianhydride and diamine compound used in the synthesis reaction of polyamic acid is relative to the amine group contained in 1 equivalent of diamine compound. The acid anhydride group is preferably 0.2 to 2 equivalents, and more preferably 0 to 12 equivalents. The synthesis reaction of polyamic acid is preferably performed in an organic solvent at a temperature of -20 to 150 ° C, more preferably 0 to 100 ° C. Here, the organic solvent is not particularly limited as long as it can dissolve the synthesized polyamino acid. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, and n, N-diamine can be exemplified. φ Methylformamide, dimethylformamide, γ-butyrolactone, tetramethylurea, hexamethylphosphonium triamine and other aprotic polar solvents; m-cresol, xylenol, phenol, halogenated phenol, etc. Phenol solvents. The amount (a) of the organic solvent is preferably such that the total amount (b) of the tetracarboxylic dianhydride and the diamine compound is 0.1 to 30% by weight based on the amount (a + b) of the entire reaction solution. the amount. [Weak solvent] Among the above organic solvents, a weak solvent of a polyamic acid, alcohols, ketones, esters, ethers, and halogenated hydrocarbons can be used in combination within a range in which the generated polyamic acid does not precipitate, Hydrocarbons and so on. As specific examples of the weak solvent, Examples-21-200537180 For example, methanol, ethanol, isopropanol, cyclic glycol, 1,4-butanediol, triethylene glycol, ethylene glycol butyl monoformate, and acetone can be listed. , Methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, methyl methoxypropionate, diethyl oxalate, diethyl malonate, ethyl g ethylene glycol ethyl ether, ethyl Glycol n-propyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol diethyl ether, diethylene glycol Monomethyl ether acetate, acid ester, tetrahydrofuran, dichloromethane, 1,2-dichloroethylenetrichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptylbenzene, xylene and the like. As described above, polyamic acid is obtained, and then a large amount of a weak solvent is injected into the reaction solution to obtain a polyamic acid by drying the precipitate under reduced pressure. The step of re-dissolving the polyamidic acid in an organic φ agent once or several times to refine the polyamidic acid. [Pyrimidinated polymer] < Pyrimidinated polymer > Phosphonimidation constituting the liquid crystal alignment agent of the present invention, The above-mentioned polyphosphonium acid is dehydrated and closed to produce a ring. The polyfluorene can be, for example, (i) a method in which the polyamino acid is heated by dissolving the polyamino acid in an organic solvent, and the method is convenient in which the ring-closed catalyst is dissolved in the solution and heated as required] (i) the polyamino acid is heated F-hexanol, ethylene glycol, propyl ether, ethyl lactate, milk hexanone, methyl acetate, ester, ethyl ethoxypropyl I, ethylene glycol methyl ether, alcohol isopropyl ether, A reaction solution of ethylene diethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether ethyl ether, 1,4-dichlorobutane, alkane, octane, benzene, and methyl ether. Of course, the precipitate can be closed by dehydrating the polymer in addition to a solvent and then weakly soluble in the solvent, or (ii) by adding a dehydrating agent and dehydrating the poly. Short-term temperature, preferably -22-200537180 50 ~ 200 ° C, more preferably 60 ~ 170 ° C. If the reaction temperature is lower than 50 ° C, it is difficult to carry out the dehydration ring-closing reaction sufficiently. If the reaction temperature exceeds 200 ° C, the molecular weight of the fluorene imine polymer obtained will decrease. On the other hand, in the method of adding a dehydrating agent and a dehydrating ring-closing catalyst to the polyamic acid solution (ii), acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used as the dehydrating agent. The used amount of the dehydrating agent is preferably from 0.001 to 20 mols with respect to 1 mol of the polyamine repeating unit. In addition, as the dehydration ring-closing catalyst, tertiary amines such as pyridine, trimethylpyridine, dimethylpyridine, and triethylamine can be used. However, it is not limited to these. The amount of the dehydration closed-loop catalyst used is preferably 0 · 0 1 to 10 moles relative to the dehydration agent used in 1 mole. Examples of the organic solvent used in the dehydration ring-closure reaction include the same organic solvents as those exemplified as the solvent used in the synthesis of polyamic acid. The reaction temperature of the dehydration ring-closing reaction is preferably 0 to 180 ° C, and more preferably 10 to 150 ° C. The reaction solution thus obtained can be purified by performing the same operation as in the polyamic acid purification method. φ [partial fluorene imine] < polyimide containing imine group> The polyimide containing imine group used in the present invention has a structure obtained by partially imidizing the polyamido acid. . The fluorene imidation rate in the polyimide acid containing an imine group used in the present invention is preferably 10 to 90%, and further preferably 30 to 70%. Here, the "fluorene imidization rate" refers to the ratio of the number of repeating units obtained by forming a fluorene imine ring with respect to the total number of repeating units of the polymer expressed in%. In this case, a part of the fluorene imine may be an isofluorene ring. -23- 200537180 As a method for synthesizing a polyimide acid containing imine groups, for example, (i) a method of partially dehydrating and ring-closing synthesis by heating the polyamidic acid, and (ii) dissolving the polyamidic acid in In an organic solvent, a method of adding a dehydrating agent and a dehydration ring-closing catalyst to the solution and heating as needed to partially synthesize the dehydration and ring closure, or (iii) mixing a tetracarboxylic acid anhydride, a diamine compound, and a diisocyanate compound, A method of heating and condensation synthesis as necessary, (iv) a method of combining a polyamidic acid prepolymer and a polyimide prepolymer to obtain a block copolymer. φ In the above method, the reaction temperature is preferably 300 ° C or lower, and more preferably 100 to 250 ° C. If the reaction temperature exceeds 300 ° C, the molecular weight of the imine-group-containing polyamic acid will decrease. On the other hand, examples of the dehydrating agent used in the method (ii) include acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride. The amount of the dehydrating agent used is preferably 0.2 to 20 moles relative to 1 mole of the polyamine repeating unit. In addition, as the dehydration ring-closure catalyst, for example, tertiary amines such as pyridine, trimethylpyridine, dimethylpyridine, and triethylamine can be used. However, it is not limited to these. The amount of the fluorene imidization catalyst used is preferably from 0.1 to 10 moles per 1 mole of the dehydrating agent used. Examples of the organic solvent used in the dehydration ring-closure reaction include the same organic solvents as those exemplified as the solvent used in the synthesis of polyamic acid. The reaction temperature of the dehydration ring-closing reaction is preferably 0 to 180. (:, More preferably 60 to 150 ° C.) The reaction solution thus obtained can be purified by the same operation as the polyamic acid purification method to purify polyimide containing imine groups. As described above ( iii) Examples of -24-200537180 diisocyanate compounds used in the reaction include aliphatic diisocyanates such as hexamethylene diisocyanate; cyclohexane-1, 2-diisocyanate, 1-methylcyclohexane -2,4-diisocyanate, 1,2: dimethylcyclohexane-ω, ω diisocyanate, 1,4-dimethylcyclohexane-ω, ω'-diisocyanate, isophorone diisocyanate , 1,3,5-trimethyl-2-propylcyclohexane 1ω, 2ω-diisocyanate, alicyclic diisocyanate such as dicyclohexylmethane_4,4'_diisocyanate; diphenylmethane-4 , 4'-diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1-methyl-2,4-phenylene diisocyanate, 1-methyl-2,6 -An aromatic diisocyanate such as phenylene diφ isocyanate, such as a diisocyanate represented by the following formulae (22) to (26).

-25 200537180

Among them, as preferable examples, dicyclohexylmethane-4,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, and 1-methyl-2,4-phenyl diisocyanate , 1-methyl-2,6-phenylene diisocyanate. They can be used alone or in combination of at least two kinds. The reaction catalyst of (iii) is not particularly necessary, and the reaction temperature is preferably 50 to 200 ° C, and more preferably 100 to 160 ° C. In the method (iv) above, the amidine prepolymer can be adjusted to a polymer having an amine group or an acid anhydride group at the terminal by adjusting the ratio of the amount of tetracarboxylic dianhydride and diamine compound used. Obtained by the same method as the synthesis method of amidine. The fluorene imine prepolymer can be dehydrated by the above-mentioned fluorinated acid prepolymer-26-200537180, or the ratio of the diisocyanate compound to the diamine compound can be adjusted to become an amine group or an isocyanate group at the terminal. In addition to the polymer, it can also be obtained by the same method as (in) above. The block copolymer can be synthesized by reacting the amine group and the acid anhydride group at each terminal of these prepolymers or the amine group with an isocyanate group. [ Terminal modification] < End-modified polymer > The polyamino acid and polyimide containing imine group may be terminal-modified polymers having a molecular weight adjusted by φ. By using this terminal-modified polymer, the coating characteristics and the like of the liquid crystal alignment agent can be improved without impairing the effects of the present invention. Such a terminal-modified polymer can be synthesized by adding a monoanhydride, a monoamine compound ', a monoisocyanate compound, and the like to a reaction system when synthesizing a polyamino acid. Here, examples of the monoacid anhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, and n-hexadecyl Succinic anhydride and so on. Examples of the monoamine compound include aniline, Φcyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, and n-undecylamine. N-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-eicosylamine, etc. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate. [Logarithmic viscosity] < Logarithmic viscosity of polymer > The logarithmic viscosity (η1η) of the polyamidic acid and polyimide containing imine groups obtained as above is preferably 0.05 to 10 dl / g, and more preferably 0.05. ~ 5dl / g. -27- 200537180 In the present invention, the logarithmic viscosity (η ln) 値 can be determined using N-methyl-2-pyrrolidone as a solvent, and the viscosity of a solution having a concentration of 0.5 g / 100 ml at 30 ° C can be determined by the following formula ( A) Find it out. ln (solution flow down time / solvent flow down time) η 1 π _-------------- ^ '(weight concentration of polymer) < liquid crystal alignment agent > liquid crystal alignment of the present invention The agent is preferably constituted by dissolving and containing the polymer in an organic solvent. The polymer constituting the liquid crystal alignment agent of the present invention contains a repeating unit represented by the above formula (1-1) in which φ accounts for 40 to 60% of all repeating unit elements. The repeating unit represented by the above formula (1-1): The ratio of the repeating unit represented by the above formula (1-2) is preferably 4: 6 to 6: 4, and more preferably 5: 5. Examples of the organic solvent constituting the liquid crystal alignment agent of the present invention include solvents exemplified as the solvent used in the synthesis of polyamic acid. In addition, it is also possible to appropriately select and use a weak solvent exemplified in combination with a solvent used in the synthesis reaction of polyamic acid. The solid content concentration in the liquid crystal alignment agent of the present invention may be selected in consideration of viscosity, volatility, etc., and is preferably in a range of 1 to 10% by weight. That is, the liquid crystal alignment agent of the present invention is applied on the surface of a substrate to form a coating film that becomes a liquid crystal alignment film. However, when the solid content concentration is less than 1% by weight, the film thickness of the coating film is too small to obtain a good liquid crystal alignment film. . When the solid content concentration exceeds 10% by weight, the film thickness of the coating film is too large to obtain a good liquid crystal alignment film. In addition, the viscosity of the liquid crystal alignment agent increases and the coating characteristics tend to deteriorate. In addition, the temperature when preparing the liquid crystal alignment agent of the present invention is preferably 0 ° C to 200 ° C, and more preferably 20 ° C to 60 ° C. The liquid crystal alignment agent of the present invention contains at least -28 to 200537180 with respect to 100 parts by weight of the polymer. ≪ > A compound having at least two epoxy groups in the molecule at 5 parts by weight (hereinafter referred to as "epoxy-containing compound" "). Examples of the epoxy-containing compound include a compound represented by the following formula (1): [Chem. 14] H2C-CC-〇-R10-Ο-CC-CH2 ηλ \ / Η2 η2 \ / 2 ⑴ ο ο This Where R1 () represents a divalent fatty group, and a compound represented by the following formula (2) [Chem. 15]

/ 0 \ Η ?. -C

H2C -C- Η Η C- N-

-R 11 v • C H2 c H2

/ 0 \ ~ ch2 H 2 H C——CH2 V (2) can be single Here, R11 represents a divalent organic group. The epoxy-containing compound is used alone or in combination of at least two kinds. Preferred examples of the epoxy-containing compound include ethylene glycol φ diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether. Ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 1, 3, 5, Tetraglycidyl-2,4 · hexanediol, N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylamino) (Methyl) cyclohexane, 1 ^ chuanshan ', 1 ^'-tetraglycidyl-4,4, diaminodiphenylmethane, etc. The content of the epoxy-containing compound is preferably 5 to 40 parts by weight, more preferably 10 to 30 parts by weight and 29 to 200537 parts by weight with respect to 100 parts by weight of the specific polymer. It is contained to the extent of the characteristics of the alignment agent. The liquid crystal alignment agent of the present invention may contain a functional silane-containing compound. Examples of the functional silane-containing compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, and 2-amino group. Propyltriethoxysilane, N · (2 · aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3 · aminopropylmethyldi Methoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxy # silane, Ν-ethyl Oxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethylol Oxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6- Diazanonylacetate, 9-triethoxysilyl-3,6-diazanonylacetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl 3-Aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxy Silane, Ν- bis (oxyethylene) _ _ 3-aminopropyl methoxy silane-three Lu, Ν- bis (oxyethylene) -3-aminopropyl triethoxy silane-like. The mixing ratio of these functional silane-containing compounds is preferably not more than 40 parts by weight, and more preferably 0.1 to 30 parts by weight, based on 1,000 parts by weight of the polymer. < Liquid crystal display element > A liquid crystal display element obtained using the liquid crystal alignment agent of the present invention can be produced by, for example, the following method. (1) Applying the liquid -30-200537180 crystal alignment agent to one side of a substrate provided with a patterned transparent conductive film by a method such as a roll coating method, a rotation method, a printing method, an inkjet method, and the like, The coating surface is heated to form a coating film. Here, as the substrate, for example, glass such as float glass and soda glass can be used. The substrate is made of plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether fluorene, and polycarbonate. Transparent substrate. As the transparent conductive film provided on one surface of the substrate, a NESA film (registered trademark of the United States PPG Corporation) formed of tin oxide (registered trademark of American PPG Corporation), and an IT film formed of indium oxide-tin oxide (In203-Sn〇2) can be used Etc. The pattern of these transparent conductive films can be a photo-etching method or a method using a pre-mask. The reflective electrode can be a metal such as A1 or Ag, φ or an alloy containing these metals. As long as it has sufficient reflectivity, When the liquid crystal alignment agent is applied, in order to improve the adhesion between the substrate surface and the transparent conductive film or the reflective electrode and the coating film, the surface of the substrate may be coated with a compound containing a functional silane and a functional titanium Compounds, etc. The heating temperature after the application of the liquid crystal alignment agent is preferably 80 to 300 ° C, more preferably 120 to 250 ° C. The liquid crystal alignment agent of the present invention containing polyamic acid is formed by removing organic solvents by coating. The coating film of the alignment film can be dehydrated and closed-looped by heating to form a further imidized coating film. The thickness of the film to form the coating film is preferably 0.001 to 1 μm, and more preferably 0.005 to 0.5 μιη. (2) The formed coating film surface is rubbed with a roller wound with a cloth made of fibers such as nylon, rayon, cotton, etc., and rubbed in a certain direction to perform a rubbing treatment. The alignment ability of liquid crystal molecules is formed, and a liquid crystal alignment film is formed. In addition, the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention can be partially A process of changing the pretilt angle by irradiating ultraviolet rays, or performing a local protective film formed on the surface of the liquid crystal alignment film subjected to rubbing treatment as described in Japanese Patent Application Laid-Open No. 5-1 07544, different from the previous rubbing treatment. The process of removing the protective film after changing the rubbing treatment to change the liquid crystal alignment ability of the liquid crystal alignment film can improve the visual field characteristics of the liquid crystal display element. (3) Fabricate two substrates forming the liquid crystal alignment film as described above, and make the liquid crystal alignment film respectively. The rubbing direction is vertical or antiparallel. Place the two substrates into the gap (unit interval) to face each other. Place the two substrates around. The part is stuck with a sealant, and the 塡 -filled liquid φ crystal is injected into the gap separated by the substrate surface and the sealant, and the injection hole is sealed to form a liquid crystal cell. Moreover, the outer surface of the liquid crystal cell, that is, the side of the transparent substrate constituting the liquid crystal cell A liquid crystal display element is obtained by arranging a polarizing plate. Here, as the sealant, for example, a curing agent and an epoxy resin containing alumina balls as a gasket can be used. Examples of the liquid crystal include nematic liquid crystal and smectic Among them, nematic liquid crystals are preferred. For example, Schiff base liquid crystals, azo oxide liquid crystals, biphenyl liquid crystals, phenylcyclohexane liquid crystals, ester liquid crystals, and bi-triphenyl liquid crystals can be used. Biphenyl cyclohexane-based liquid crystals, pyrimidine-based liquid crystals, dioxane-based liquid crystals, dicyclooctane-based liquid crystals, cubic liquid crystals, and the like. In addition, to these liquid crystals, for example, cholesterol-type liquid crystals such as cholesterol chloride, cholesterol nonanoate, and cholesterol carbonate may be added, or a pair sold as "C-1 5" and "CB-15" (made by Merck). Hand lotion and so on. Further, a highly conductive liquid crystal such as p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate can also be used. In addition, as the polarizing plate adhered to the outer surface of the liquid crystal cell, for example, cellulose acetate for a polarizing film called -32- 200537180 1 锄 Η film which absorbs iodine while extending the orientation of polyvinyl alcohol can be cited. The polarizing plate sandwiched by the protective film or the polarizing plate formed by the diaphragm itself. [EXAMPLES] The present invention will be specifically described below by way of examples, but the present invention is not limited to these examples. The transparency, voltage retention, and sinterability of Examples and Comparative Examples were evaluated by the following methods. [Transparency] The HITACHI U-2010 spectrophotometer (manufactured by Hitachi, Ltd.) was used as the measuring device. The liquid crystal alignment agent of the present invention prepared as described above was coated on a quartz substrate having a thickness of 1.5 mm with a spinner, and dried at 180 ° C for 1 hour to form a coating film having a dry film thickness of 800A. The transmittance of the produced coating film was measured. The transmittance was measured, and 値 at wavelengths of 700 nm, 600 nm, 500 nm, 450 nm, 400 nm, 3 50 nm, and 300 nm were determined. It was judged as good when the transmittance at any measurement wavelength was 90% or more, and it was judged as bad in other cases. [Voltage holding ratio] φ After applying a voltage of 5 V at an interval of 1,67 milliseconds to the liquid crystal display element at a pressing time of 60 microseconds, the voltage holding ratio was measured after the voltage was released to 1,67 milliseconds. As the measuring device, VHR-1 manufactured by Toyo Technica was used. A voltage holding ratio of 90% or more was judged as good, and otherwise it was judged as bad. [Sintering] Apply an intensive 1.0V DC 30Hz, 2.0V rectangular wave to the liquid crystal display element at an ambient temperature of 70 ° C for 1 hour. The voltage remaining in the liquid crystal cell immediately after the DC voltage is cut off is determined by the flicker elimination method Residual DC voltage. The residual DC 値 is not limited to the type of electrodes constituting the liquid crystal display element. -33- 200537180 is not higher than 2V, and the difference between the residual DC between the electrode types is not higher than 0.5V. The situation was judged to be bad. Synthesis Example 1 2 24.1 7 g (0.5 mole) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride and 157.14 g (0.5 mole) of 1,3,3 &, 4,5,913-hexahydro-8- Methyl-5- (tetrahydro-2,5-dioxo-3-furyl) -naphtho [l, 2-c] -furan-1,3-dione as a tetracarboxylic acid dianhydride, 94.62g (0.875 mol) p-phenylenediamine, 3 2.02 g (0.1 mol) 2,2, -ditrifluoromethyl-4,4, -diaminobiphenyl and 6.43 g (0.01 mol) 3,6 -Bis (4- # aminobenzyloxy) cholesterol as a diamine compound, 10.85g (0.03 mole) of 4-aminophenyloctadecyl ether as a monoamine dissolved in 4,500g of N-methyl In 2-pyrrolidone, react at 6 ° C for 6 hours. Then, pour the reaction solution into a large excess of methanol to precipitate the reaction product. Then, wash with methanol and dry at 40 ° C for 15 hours under reduced pressure to obtain 410 g of logarithm Polyamic acid having a viscosity of 0.87 dl / g. 30 g of the obtained polyamic acid was dissolved in 570 g of N-methyl-2-pyrrolidone, 23.4 g of pyridine and 18.1 g of acetic anhydride were added, and dehydration was performed at i10 ° C for 4 hours to close the ring. Precipitation, washing, and decompression were performed in the same manner as described above to obtain 17.5 g of polyimide having a log viscosity of 0.80 dl / g. (This is called "polyimide, (A-1)). Synthesis Example 2 2 24.1 7 g (0.5 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride and 157.14 § (0.5 Mol) 1,3,3 &, 4,5,91) -hexahydro 1-8-methyl-5- (tetrahydro_2,5_dioxo-3-furanyl) -naphtho [l , 2-c] -furan-1,3-dione as a tetra-residic acid dianhydride, 94.62 g (0.875 mole) p-phenylenediamine, 24.85 g (0.1 mole) bisaminopropyltetramethyl Disoxanes and 6.43 g (0.01 mole) of 3,6-bis (4-aminobenzyloxy) cholesterol as a monoamine compound, 10.85 g (0.33 mole) of 4- Amine-34-200537180 t * phenylphenyloctadecyl ether was dissolved as a monoamine in 4,500 g of N-methyl-2-pyrrolidone and reacted at 60 ° C for 6 hours. Then, the reaction solution was poured into a large amount of excess methanol The reaction product was precipitated. Then, it was washed with methanol and dried at 40 ° C. for 15 hours under reduced pressure to obtain 370 g of polyamic acid having a log viscosity of 0.82 dl / g. 30 g of the obtained polyamino acid was dissolved in 570 g of N-methyl- To 2-pyrrolidone, 23.4 g of pyridine and 18.1 g of acetic anhydride were added, and the mixture was dehydrated and closed for 4 hours at 11 ° C., and precipitation and washing were performed in the same manner as described above. , Under reduced pressure, to obtain polyimide i8.5g logarithmic viscosity 〇.77dl / g, (referred to as "polyimide" Ο (A-2)). Synthesis Example 3 22.22 ^ 0.05 mole) 2,3,5-tricarboxycyclopentylacetic acid dianhydride and 298.57 g (0.95 mole) of 1,3,3a, 4,5,9b-hexahydro-8-formaldehyde 5- (tetrahydro-2,5-dioxo-3-furyl) -naphtho [1,2 · C ^ furan-1,3-dione as a tetracarboxylic acid dianhydride, 83.81 g (0.775 Mol) p-phenylenediamine, 64.04g (0.2 Mol) 2,2 ,. ditrifluoromethyl-4,4, -diaminobiphenyl and 6.43g (0.01 Mol) 3,6-bis ( 4-Aminobenzyloxy) cholesterol as a diamine compound, 2.79g (0.03 mole) q Aniline is dissolved as a monoamine in 4,500g of N-methyl-2 · pyrrolidone at 60 ° C Reaction for 6 hours. Then, the reaction solution was poured into a large amount of excess methanol + to precipitate a reaction product. Then, it was washed with methanol and dried at 40 ° C. for 15 hours under reduced pressure to obtain 410 g of polyamidic acid having a log viscosity of 0.85 dl / g. 30 g of the obtained polyamic acid was dissolved in 570 g of N-methyl-2-pyrrolidone, 23.4 g of pyridine and 18.1 g of acetic anhydride were added, and the mixture was dehydrated and closed at 110 ° C. for 4 hours, and precipitated and washed in the same manner as the above stomach. And reduced pressure to obtain 15.1 g of polyfluorene imine with a log viscosity of 0.83 dl / g (referred to as "polyimide" (A-3)). Synthesis Example 4 -35- 200537180 In Synthesis Example 2, 95.7 g (0.88 mol) of p-phenylenediamine, 24.8 5 g (0.1 mol) of bisaminopropyltetramethyldisilaxane ( The compound represented by the above formula (VI)) and a monoamine other than 809 g (0.03 mol) of n-octadecylamine were used in the same manner as in Synthesis Example 2 to obtain H4g with a log viscosity of 0.65 dl / g. Polyimide (referred to as "polyimide, (A_4)). Synthesis Example 5 196.12 g (1.0 mole) of cyclobutane tetracarboxylic dianhydride was used as tetracarboxylic dianhydride, and 212 g (1.0 mole) 2,2, -dimethyl-4,4, -diaminobiphenyl as 0 is a diamine compound dissolved in 4500g N-methyl-2-pyrrolidone and reacted at 60 ° C 6 Hours. Then, the reaction solution was poured into a large amount of excess methanol to precipitate a reaction product. Then, by washing with methanol and drying under reduced pressure at 4 ° C for 15 hours, 410 g of polyamidine having a log viscosity of 0.90 dl / g was obtained. Acid (referred to as "polyamine" (B-1)). Synthesis Example 6 In Synthesis Example 5, 1 09.06 g (0.5 mole) of pyromellitic dianhydride and 9 8.06 g (0.5 mole) were removed. Ear) Cyclobutanetetracarboxylic dianhydride as tetracarboxylic acid di In the same manner as in Synthesis Example 5 except that 200.2 g (1.0 mol) of 4,4, -diaminodiphenyl ether was used as the diamine compound, 410 g of a polymer having a log viscosity of 0.93 dl / g was obtained. Phosphonic acid (referred to as "polyamidic acid" (B-2)). Synthesis Example 7 In Synthesis Example 5, i.09.06 g (0.5 mole) of pyromellitic dianhydride and 9 8.06 g (0.5 mol) cyclobutane tetracarboxylic dianhydride was used as the tetracarboxylic dianhydride, and 198.3 g (1.0 mol) of 4,4'-diaminodiphenylmethane was used as the diamine compound. Similarly, 410 g of polyamidic acid having a logarithmic viscosity of 0.95 dl / g (referred to as "polyamidic acid" (B-3)) was obtained. -36- 200537180 瓤 Synthesis Example 8 Remove the single An amine compound, 4-aminophenyloctadecyl ether, was synthesized in the same manner as in Synthesis Example 1 except that 96.24 g (0.89 mole) of p-phenylenediamine was used, and then dissolved in N-methyl. -2-Pyrrolidone forms a solution having a solid content concentration of 10% by weight. In addition, the polyamidic acid (B-2) obtained in the above Synthesis Example 6 was used as the amino acid prepolymer and was similarly dissolved in N-methyl -2-pyrrolidone A solution having a component concentration of 10% by weight. Then, 500 g of amidine prepolymer solution and 500 g of amidine prepolymer solution were mixed and stirred for 2 hours, and then the reaction solution was poured into a large amount of excess methanol to precipitate a reaction product. By washing with methanol and drying at 40 ° C for 15 hours under reduced pressure, 100 g of a polymer formed by polyamic acid and polyimide (ratio of polyamic acid) having a log viscosity of 0.95 dl / g was obtained. 50% by weight) (referred to as "Polymer (C-1)"). Synthesis Example 9 Monoamine 4-aminophenyloctadecyl ether was removed in Synthesis Example 2, and fluorene) was prepolymerized in the same manner as in Synthesis Example 2 except that 96.24 g (0.89 mole) of p-phenylenediamine was used. It was dissolved in N-methyl-2-pyrrolidone to form a solution having a solid content concentration of 10% by weight. In addition, the polyamidic acid (B-1) obtained in the above Synthesis Example 5 was used as a pseudomic acid prepolymer, and similarly dissolved in N-methyl-2-pyrrolidone to form a solid content concentration of 10% by weight. The solution. Then, after 500 g of the fluorene imine prepolymer solution and 500 g of the fluorin acid prepolymer were mixed and stirred for 2 hours, the reaction solution was poured into a large excess of methanol to precipitate a reaction product. Then, by washing with methanol and drying at 40 ° C for 15 hours under reduced pressure, 100 g of a polymer formed of polyamic acid and polyimide (ratio of polyamic acid, having a log viscosity of 0.93 dl / g, 50% by weight) (referred to as -37-200537180, μ "Polymer (C-2)). Synthesis Example 10 In Synthesis Example 4, the monoamine 4-aminophenyloctadecyl ether was removed. A fluorene imine prepolymer was synthesized in the same manner as in Synthesis Example 4 with the exception of 9 7.3 2 g (0.90 mole) of p-phenylenediamine, and dissolved in N-methyl-2-pyrrolidone to form a solid component concentration of A 10% by weight solution. In addition, the polyamidic acid (B-3) obtained in the above Synthesis Example 7 was used as the amino acid prepolymer, and was similarly dissolved in N-methyl-2-pyrrolidone to form A solution having a solid content concentration of 10% by weight. Then, after mixing 500 g of amidine prepolymer solution and 500 g of amidine prepolymer solution and stirring for 2 hours, the reaction solution was poured into a large amount of excess methanol to precipitate a reaction product. Then, By washing with methanol and drying at 40 ° C for 15 hours under reduced pressure, 100 g of polyamine and polyfluorene having a log viscosity of 0.97 dl / g were obtained. Amine to form a polymer (the ratio of polyamide acid, 50% by weight) (referred to as "polymer (C-3)). Example 1 The polyamidoimine (A-1) obtained in Synthesis Example 1 and the polyamidoimide (B-1) obtained in Synthesis Example 5 were prepared by polyamidoimide: polyamidoimide = 50: 50 (weight Ratio), dissolved in a mixed solvent of N-methyl-2-pyrrolidone / γ-butyrolactone (weight ratio of 30/70), and 10 parts by weight (Phr) of polyethylene glycol relative to 100 parts by weight of polymer The diglycidyl ether (molecular weight of about 400) forms a solution having a solid content concentration of 4% by weight. After sufficiently stirring, the solution is filtered through a sieve with a pore size of 1 μm to prepare the liquid crystal alignment agent of the present invention. The above-mentioned liquid crystal alignment agent was applied with a spinner (rotation number: 2,000 rpm, coating time: 1 minute) onto a transparent conductive film formed of an ITO film provided on one side of a glass substrate having a thickness of 1 mm, and On the reflective film formed by A1, dry at 200 ° C for 1 hour -38- 200537180

I into a protective film with a dry film thickness of 0.08 μm. A rubbing device having a roller wound with a rayon cloth was used on the protective film, and rubbing treatment was performed at a rotation speed of the roller of 40 (Η · ριη, a table moving speed of 3 cm / sec, and a brush foot of 0.4 mm in length.) After the liquid crystal alignment film-coated substrate was immersed in isopropyl alcohol for 1 minute, it was dried on a hot plate at 100 ° C for 5 minutes. Then, a pair of transparent electrodes / transparent electrode substrates and a pair of transparent electrodes / reflective electrode substrates were dried. The liquid crystal alignment film of the above-mentioned liquid crystal alignment film-coated substrate is coated with an epoxy resin adhesive doped with alumina balls having a diameter of 5.5 μm on the outer periphery, respectively, and then superimposed and pressed against the liquid crystal alignment film surface to cure the adhesive. After filling the nematic liquid crystal (Merck, MLC-622 1) from the liquid crystal injection port to the substrate, the liquid crystal injection port was sealed with an acrylic light-curing adhesive, and polarizers were bonded on both sides of the substrate to produce Liquid crystal display element. The voltage retention and sinterability of the obtained liquid crystal display element were evaluated. On the quartz substrate having a thickness of 1.5 mm, the liquid crystal alignment agent of the present invention prepared as described above was applied with a spinner to communicate with the liquid crystal. A coating film was formed in the same manner when a display element was manufactured. The transparency was evaluated from the transmittance measurement of the manufactured coating film. The results are shown in Table 1. It was confirmed that the voltage retention and flicker characteristics of the liquid crystal alignment agent obtained by the present invention were good. Example 2 ~ 15 According to the scheme described in Table 1 below, polyimide (A-1) to (A-4), polyamic acid (B · 1) to (B-3) obtained in Synthesis Examples 1 to 10, Part of fluorene imine (C-1) ~ (C-3) and epoxy-containing compound are dissolved in a mixed solvent containing γ-butyrolactone as the main component to obtain a solution with a solid content concentration of 4.0%. The liquid crystal alignment agent of the present invention was prepared by filtering through a sieve with a pore size of 1 μm. The liquid crystal alignment agent thus prepared was used. In the same manner as in Example 1, a protective film was formed on the surface of the substrate. Substrate-39- 200537180 »« Production of a liquid crystal display element. Evaluation of transparency, voltage retention, and sinterability was performed. The results are shown in Table 1. Comparative Examples 1 to 5 According to the scheme shown in Table 1 below, the same applies to the examples. A liquid crystal display device was produced in advance, and the transparency and electrical properties were evaluated. Pressure retention rate and sinterability. The results are shown in Table 1. -40- 200537180 »Qin Table 1 Polymer Polymer Mixing Ratio Additive Type Additive Amount (phr) Transparency Voltage Retention Rate Sinterability Transmissive Reflection Type Transmissive Reflection Type Implementation Example 1 A-1 B-1 50/50 polyethylene glycol diglycidyl ether 10 Good Good Good Good Good Example 2 A-2 B-1 40/60 Polyethylene glycol diglycidyl ether 20 Good Good Good Good Good example 3 A-3 B-3 50/50 polyethylene glycol diglycidyl ether 10 good good good good good example 4 A-3 B-3 50/50 1,3,5,6-tetraglycidyl -2,4-hexanediol 10 Good Good Good Good Good Example 5 A-3 B-2 50/50 1,3,5,6-Tetraglycidyl-2,4-hexanediol 10 Good Good Good Good Good Example 6 A-2 B-2 40/60 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane 10 Good Good Good Good Good Example 7 A-4 B -2 50/50 1,3-bis (N, N-diglycidylaminoamido) cyclohexane 10 Good Good Good Good Example 8 A-4 B-3 50/50 N, N, N ', N'-Tetraglycidyl-4,4'-diaminodiphenylmethane 20 Good Good Good Good Good Example 9 A-1 B-1 50/50 Polyethylene glycol diglycidyl ether 5 Good Good Good Good Good Example 10 A-1 B-1 50/50 N, N, N ', N'-Tetraglycidyl-4,4'-m-xylylenediamine 5 Good Good Good Good Good Example 11 A- 2 B-3 45/55 Polyethylene glycol diglycidyl ether 20 Good Good Good Good Good Example 12 A-1 B-3 50/50 Ethylene glycol diglycidyl ether 20 Good Good Good Good Good Example 13 C -1 Polyethylene glycol diglycidyl ether 20 Good Good Good Good Good Example 14 C-2 Glycol diglycidyl ether 20 Good Good Good Good Good Example 15 C-3 N, N, N ', N' -Tetraglycidyl-4,4'-diaminodiphenylmethane 20 Good Good Good Good Good Comparative Example 1 A-1 Polyethylene glycol diglycidyl ether 10 Good Good Good Good Not good Comparative Example 2 A- 1 B-1 50/50 Good Good Good Good Not good Comparative Example 3 B-3 1,3-Bis (N, N-Diminished Hydroglycerylaminomethyl) cyclohexane 10 Good Good Good Good No Good Comparative Example 4 C-1 Good Good Good Good Good No Comparative Example 5 C-3 Good Good Good Good No

Claims (1)

200537180 10. Scope of patent application: 1. A liquid crystal alignment agent, characterized in that the liquid crystal alignment agent contains 100 parts by weight of a repeating unit represented by the following formula (1-1) and represented by the following formula (1-2) A polymer having a repeating unit represented by formula (1-1) in a proportion of 40% to 60% of the total repeating unit by weight, and at least 5 parts by weight of a polymer having at least 2 epoxy groups in the molecule Compound HOOC ΌΟΟΗ HNOC CONH——Q1 (M) (where P1 is a tetravalent organic group and Q1 is a divalent organic group) (In the formula, P2 is a tetravalent organic group, and Q2 is a divalent organic group.) 2. The liquid crystal alignment agent according to item 1 of the application, wherein the compound having at least two epoxy groups in the molecule is at least one selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2) Compounds containing epoxy groups, [Chemical formula 3] h2c ~ —c 0 ίο Η-C-〇-R10——〇——CC——CH; H2 h2 \ / O -42 · 200537180 * ^ (Wherein R1 () represents a divalent aliphatic group) [Chem. 4] (2) (wherein R11 represents a divalent organic group). 3. The liquid crystal alignment agent according to item 1 or 2 of the patent application scope, wherein the polymer has a transmittance of more than 90% in a wavelength range of 300 nm to 700 nm. -43- 200537180 Nose 7. Designated Representative Map: (1) The designated representative map in this case is: None. (II) Brief description of the component symbols in this representative figure: ΙΙΙΓ \ Ν 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: