TW200530375A - Liquid crystal alignment agent and liquid crystal display element - Google Patents

Abstract

The present invention provides a liquid crystal alignment agent used for liquid crystal membrane of the liquid crystal display element having high reliability as not as necessary to follow the step conditions of membrane's thickness and rubbing condition etc. The present application relates to a liquid crystal alignment agent produced form the polyamic acid imidization polymer is characterized in that the said imidization polymer satisfy the conditions [a] and [b] as below: [a] such as the main chain of the imidization polymer has the unit represented as [formulas 1], [b] such as the side chain of the imidization polymer has alkyl which the carbon number of the main chain are more than 8, or the main chain of the imidization polymer has 1,1-cycloalkylene which the carbon number are more than 6.

Description

200530375 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a liquid crystal alignment agent used for forming a liquid crystal alignment film of a liquid crystal display element. More specifically, it relates to a liquid crystal alignment agent that imparts a liquid crystal alignment film that has excellent coating properties, good liquid crystal alignment, and excellent long-term stability of a liquid crystal display element. [Prior art] Now, it is known that a liquid crystal display element is formed on a substrate surface of a transparent conductive film to form a liquid crystal alignment film made of polyamic acid, polyimide, or the like as a substrate for a liquid crystal display element. The two cells are arranged opposite to each other, and a nematic liquid crystal layer with positive dielectric anisotropy is formed in the gap as a unit cell of a sandwich structure. The long axis of the liquid crystal molecules is from one substrate to the other substrate. A TN-type liquid crystal display element that is continuously twisted at 90 degrees and has a so-called TN-type (Twisted Nematic) liquid crystal cell. In addition, STN (Super Twisted Nematic) type liquid crystal display elements have been developed which have higher contrast than TN type liquid crystal display elements and have less viewing angle dependence. This STN type liquid crystal display element uses a pair of optical active materials in a nematic liquid crystal as a liquid crystal. The long axis of the liquid crystal molecules is produced by continuously twisting the substrates at 180 degrees or more between the substrates. Birefringence effect. It is known that two electrodes for driving liquid crystals are arranged in a comb-tooth shape on a substrate on one side, and a parallel electric field is generated on the substrate surface to control liquid crystal molecules in a lateral electric field mode. The liquid crystal alignment in these liquid crystal display elements is usually found by a liquid crystal alignment film subjected to a rubbing treatment. 200530375 A liquid crystal display element different from the above is known as a liquid crystal display element including a vertical alignment type liquid crystal cell formed by vertically aligning liquid crystal molecules having negative dielectric anisotropy on a substrate. In such a liquid crystal display element, the alignment control of liquid crystal is usually controlled by a liquid crystal alignment film formed by a liquid crystal alignment agent containing a polymer such as polyamic acid, polyimide, or the like. Recently, for the purpose of reducing the weight of a liquid crystal display element, it has been attempted to replace a conventionally used glass substrate with a resin substrate. In order to reduce the heat-resistant temperature of the resin substrate, the calcination treatment when forming the liquid crystal alignment film must be performed at a low temperature of 0. The calcination treatment of a soluble polyfluorene imine liquid crystal alignment agent containing an unnecessary thermal fluorination reaction is appropriate. However, soluble polyfluorene imine has a lower affinity with a solvent than polyamic acid, so film thickness spots in printing tend to cause poor coating, such as pinholes. Therefore, the development of a liquid crystal alignment agent which is excellent in coating properties and can be calcined at a low temperature is desirable. [Summary of the Invention] [Problems to be Solved by the Invention] In view of the above, the present invention provides a first object of the present invention to provide an alignment ability that can reliably impart liquid crystal molecules through rubbing treatment, and to provide excellent liquid crystal alignment. Liquid crystal alignment agent for liquid crystal display element of liquid crystal alignment film. A second object of the present invention is to provide a liquid crystal alignment agent capable of producing a liquid crystal display element including a liquid crystal alignment film having excellent coating properties. A third object of the present invention is to provide a liquid crystal alignment agent capable of constituting a liquid 200530375 crystal display element with excellent reliability. Other objects and advantages of the present invention will be apparent from the following description. [Means for Solving the Problems] According to the above-mentioned object and advantages of the present invention, if the first feature of the present invention includes a liquid crystal alignment agent composed of a polyimide-fluorinated imidized polymer, the above-mentioned fluorinated imidized polymer is A liquid crystal alignment agent that completely satisfies the following conditions [A] and [B]. [A] The main chain of the fluorene imidized polymer contains at least one of the units shown in the following formulae (1) and (2), respectively. [Chemical 1]

In the formula, Ri to R6 each independently represent hydrogen, a halogen atom, or a monovalent organic group, and P, q, and r each independently represent an integer of 1 to 20. [B] In the main chain of the fluorene imidized polymer, there is at least one group selected from the groups shown in A to D below, respectively, or this group is used as a side chain. A. · The main chain is an alkyl group having 8 or more carbon atoms, the main chain is a perfluoroalkyl group having 3 or more carbon atoms, or a 1,1-cycloalkylene group having 6 or more carbon atoms that can be substituted, 200530375 B: A base of a polycyclic structure with a ring number of 3 or more,

The group represented by Cz-RX-A1. Here, R represents a hydrocarbon group having 3 or more carbon atoms, and X represents a single bond, -0-, -CO-, -COO_, _0C0_, _NH_, -NHCO-, -CONH. -Or -S- is a bonding group, then A1 represents a halogen atom, a cyano group, a fluoroalkyl group, or a substituted benzodihydropyranyl group. The bases shown here, 'R1 ~ R3 represent independently independently substituted hydrocarbon groups having 3 or more carbon atoms,-(Si-0-) n (n is an integer of 5 or more), and χι and X2 are Table Lu It shows a single bond, a bond group represented by -0-, -CO-, -COO-, -OCO-, -NΗ-, -NHCO ·, -CONH-, or -S- each independently. The above-mentioned objects and advantages of the present invention can be achieved by a liquid crystal display element if the liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention is provided according to the second feature of the present invention. [Effects of the Invention] When the liquid crystal alignment agent according to the present invention is used as a liquid crystal alignment film, it is possible to obtain an appropriate liquid crystal alignment film as a liquid crystal display element without high compliance with step conditions such as film thickness and friction conditions. In addition, a liquid crystal display element having an alignment film formed using the liquid crystal alignment agent of the present invention is an excellent alignment and reliability of liquid crystals, and can be effectively used in various devices. Coefficient display board, mobile phone, automatic sensor, personal computer, LCD data projector, LCD TV and other display devices. [Best Mode for Carrying Out the Invention] 200530375 Hereinafter, the present invention will be described in detail. The fluorene imidized polymer used in the present invention is obtained by dehydration and ring closure of a polyfluorine acid synthesized by reacting a tetracarboxylic dianhydride with a diamine compound in an organic solvent. These polymers may be used in combination of two or more. In the main chain of the amidine polymer, a unit represented by any of formulas (1) and (2) shown in the condition [A] is introduced, and at least one of the diamine compounds may be used as formula (1). And a diamine compound in the unit represented by any of (2). The condition [A] improves the coatability of the liquid crystal alignment agent, and also improves the reliability and alignment of the liquid crystal display element, and has the effect of improving the electrical stability and display quality of the liquid crystal display element. In addition, in the main chain or side chain of the fluorene imidized polymer, a group shown in any of A to D shown in the condition [B] is introduced, and at least any one having a tetracarboxylic dianhydride and a diamine compound can be used. One of the compounds is a group represented by any of A to D. Condition [B] is effective when a pretilt angle is found in the liquid crystal display element. The content ratio of the group represented by the condition [A] in the fluorene imidized polymer used in the present invention is preferably 1 to 95 mole%, more preferably 5 to 5% of the total repeating unit of the entire polymer. 50 mole%, particularly preferably 10 to 50 mole%. The content ratio of the group represented by the condition [B] in the fluorene imidized polymer used in the present invention varies depending on the type of the liquid crystal display element for which it is intended, such as TN type, S TN type, and transverse electric field. In the liquid crystal display element, it is preferably from 0.1 to 50 mol%, more preferably from 0.1 to 20 mol%, and particularly preferably from 0.5 to 10 mol% relative to the full repeating unit of the entire polymer. . In the vertical alignment type liquid crystal display element, it is preferably 5 to 80 mole%, more preferably 5 to 50 mole%, and particularly preferably 5 to 30 mole%. -10-200530375 For the production of a perylene imidized polymer, it is preferred that at least one part of the tetracarboxylic dianhydride is a tetracarboxylic dianhydride represented by the following formula (91). [Chemical 2]

(91)

In the formula, R is a tetravalent organic group having an alicyclic structure. The structure derived from the tetracarboxylic dianhydride represented by the formula (9 1), which is unstable and unstable during storage of a solution-like substance, gives a solvent solubility to the fluorinated polymer obtained by dehydration and ring closure. Relationship, so it can be stored in a stable state. In the fluorene imidized polymer, the proportion of the structure derived from the compound represented by the formula (91) is preferably 0.1 to 50 mole%, more preferably 1 to the total repeating unit of the entire polymer. 〇 ~ 50 mole%, particularly preferably 30 ~ 50 mole%. [Tetracarboxylic dianhydride] Examples of the tetracarboxylic dianhydride having a group represented by the condition [B] include compounds represented by the following formulae (82) to (90). -11-200530375 【Chemical 3】 < | H3

/ CH3, C \ ^ CH3 (84)

(82) CHS I / CH3

CH3

By using this tetracarboxylic dianhydride, the sulfonium imidized polymer of the present invention can introduce the bases (&), (0, (magic and (§)) described in the second patent application range. Formula (91 Examples of the tetracarboxylic dianhydride represented by) include: 3,5,6-tricarboxynorbornane-2-acetic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,2, 3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, -12-200530375 anhydride, 1,3-dimethyl- 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetracarboxylic Methyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5- ^ S alkanetetracarboxylic acid Acid dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-dicarboxycyclopentylacetic dianhydride, 3,5,6-tricarboxynorbornane- 2-acetic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5 (0 hydrogen-2,5-dioxy-3 -Furanyl) -naphtho [1,2-〇] -furan-1,3-di-, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5 (tetrahydro-2 , 5-dioxy-3-furan hydrazone) mononaphtho [l, 2_c] -Furan-1,3-dione, 1,3,3 &, 4,5,91 ^ -hexahydro-5-ethyl-5 (tetrahydro-2,5-dioxy-3-furanyl) -Naphtho [1,2-〇] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-methyl-5 (tetrahydro-2,5-di Oxy-3-furanyl) -naphtho [l, 2-c] -furan-1,3-dione, 1,3,3 &, 4,5,91) -hexahydro-7-acetamidine- 5 (tetrahydro-2,5-dioxy-3-furanyl) -naphthalenepyrene [1,2-〇] -furan-1,3-isopropyl, 1,3,3 & 4,5,91 ) -Hexahydro-8-methyl-5 (tetrachloro-2,5-dioxy-3-pyranyl) -naphtho [l, 2-c] -furan-1,3-dione, 1 , 3,3 &, 4,5,91) -Hexahydro-8-ethyl-5 (tetrahydro-2,5-dioxy-3-furanyl) -naphthalene [1, 2_〇]- Furan-1,3-ketone, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5 (tetrahydro-2,5-dioxo-3 -furanyl) -Naphtho [l, 2-c] -furan-1,3-dione, 5- (2,5_dioxytetrahydrofuran) -3 -methyl-3 -cyclohexyl-1,2-dicarboxylic acid di Wild, bicyclo [2,2,2] -octadin-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo [3 · 21] xinyuan-2, ketodione -6-spiro-3 '-(tetrakitofuran · 2'5'-dione |), (4arH, 8arH) -tenki-lt, 4t: 5c, 8c · dimethanol naphthalene · 21 31 :, 6〇, 7 (^ tetracarboxylic acid dianhydride. In addition, tetracarboxylic dianhydride other than the tetracarboxylic acid dianhydride represented by the formula (91) may be used. The other tetracarboxylic dianhydride is a compound represented by the following formulae (I) and (11) 13-200530375, for example, [Chem. 4]

(In the formula, R1 and R3 represent a divalent organic group having an aromatic ring, R2 and R4 represent a hydrogen atom or an alkyl group, and plural R2 and R4 may be the same or different.) For example, the following formulae (III) to ( V) Compounds represented by -14-200530375

-15-200530375 Glycol-bis (trimellitic acid ester), 1,4-butanediol-bis (trimellitic acid ester), 1,6-hexanediol-bis (trimellitic acid ester) ), 1,8-octanediol-bis (trimellitate), 2,2-bis (4-hydroxyphenyl) propane · bis (trimellitate), etc. anhydride. They can be used alone or in combination of two or more. [Diamine compound] Among the diamine compounds used in the synthesis of polyamidic acid, the diamine compound having a group represented by the condition [A] may be, for example, bisaminopropyltetramethyldisilazane, 4 4,4'-hydroxydiphenylamine, 3,4'-hydroxydiphenylamine, 1,4-bis (amino · phenoxy) benzene, bis (4- (4-aminophenoxy) phenyl) ether, and the like. By using the above diamine compound, the group represented by the above formula (1) or (2) can be introduced into the amidine polymer. The diamine compound having a group represented by the condition [B] may be, for example, a diamine compound represented by any one of the formulae (3) to (8 1) described in item 3 of the scope of patent application. Since the diamine compound represented by any one of the formulae (3) to (81) is used, the formula (10, ((1), (0)) shown in item 2 of the patent application scope can be introduced into the amidine polymer. (11), (0) to (2). Any of the diamine compounds other than the diamine compound having a specific structure as described above may be used in the present invention. Examples of other diamine compounds are exemplified. Such as P-dextylene limbs, π-dextylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diamine Diphenylsulfide, 4,4'-diaminodiphenylhydrazone, 4,4, -diaminophenamidobenzene, 5-amino-1- (4'-aminophenyl) -1,3, 3-trimethylindane, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 3,3, diaminobenzophenone, 3 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl-16-200530375 ketone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane , 2,2, _bis [4- (4_amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 2,2_bis [4- (4-aminophenoxy) benzene Radical], 1,4-bis (4-aminophenoxy) benzene, i, 3-bis (4- Aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 4,4, -methylene-bis (2-chloroaniline), 1,4,4 '-(p -Phenylene isopropylidene) bisaniline, 4,4, _ (m-phenylene isopropylidene) bisaniline, 2,2'-dimethyl-4,4, -diaminobiphenyl Group, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl aromatic diamine; such as 1,1-m-xylylenediamine, i, 3-propanedi Amine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diamine Heptamethylene diamine, 1,4-diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentadiene diamine, hexahydro-4,7-methanolindane Methyldiamine, tricyclic [6.2.1.02,7] -undecene dimethyldiamine, 4,4'-methylenebis (cyclohexylamine) aliphatic and alicyclic diamine; 2 , 3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2.4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyridine, 5,6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-three 1,4-bis (3-aminopropyl) piperidyl, 2,4-diamino-6-isopropoxy-1,3,5-tris, 2,4-diamino-6 -Methoxy-1,3,5-triple, 2,4-diamino-6-phenyl_1,3,5-triple, 2,4-diamino-6-methyl triple trap , 2,4-diamino-1,3,5-triple, 4,6-diamino-2_vinyl-s-triple, 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-diamino-6-phenylphenanthridine, 1,4-diaminopiperidyl, 3,6-diaminoacyl-17-200530375 , Bis (4-aminophenyl) phenylamine, and compounds represented by the following formulae (VI) to (VIII), which have two primary amine groups in the molecule and nitrogen other than the primary amine group Atomic diamine

(In the formula, R5 represents a divalent organic group, and R6 represents a monovalent organic group including a ring structure selected from a nitrogen atom selected from pyridine, pyrimidine, triple well, piperidinyl, and piperidinyl). 7]

(In the formula, R7 represents a divalent organic group having a ring structure containing a nitrogen atom selected from pyridin, pyridin, trigen, piperidinyl, and piperidinyl. 'R8 represents a divalent organic group. The plural R8 may be the same or different.) Monosubstituted phenylenediamines represented by the following formula (VIII); [Chem. 8] -18-(VIII) 200530375

H2N NH2 • R10 (wherein R9 represents a divalent organic group selected from -〇-, -COO-, -OCO-, -NHCO-, -CONH-, and -CO-, and R1G represents the number of carbon atoms Alkyl 6 to 30) [Synthesis of polyamic acid] The proportion of tetracarboxylic dianhydride and diamine used in the synthesis reaction of polyamino acid is equal to 1 equivalent of the diamine's amine group. The ratio of the acid anhydride group of the carboxylic dianhydride is 0.2 to 2 equivalents, and more preferably, the ratio is 0.3 to 1.2 equivalents. The synthesis reaction of the polyamic acid is carried out in an organic solvent, preferably at a temperature of -20 ° C to 150 ° C, more preferably 0 to 100 ° C. The organic solvent is not particularly limited as long as it can dissolve the synthesized polyamidic acid. Examples include 1-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylarylene, γ-butyrolactone, tetramethylurea Non-protonic polar solvents of hexamethylphosphotriamidine; phenolic solvents of m-cresol, xylenol, phenol, and halogenated phenol. In addition, the amount (α) of the organic solvent is usually preferably 0.1 to 30% by weight based on the total amount (β) of the tetracarboxylic dianhydride and the diamine compound with respect to the total amount (α + β) of the reaction solution. Among the above-mentioned organic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, etc. of the polyamic acid weak solvent can be used in a range in which the polyamic acid is not formed. Specific examples of the weak solvent include, for example, methanol, ethanol, isopropanol, cyclohexanol, 4-hydroxy-4-methyl-2-pentanol, ethylene glycol, -19-200530375 propylene glycol, and 1,4- Butanediol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, acetic acid Ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxy propionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether , Ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether B Acid ester, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate , Diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o- Dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, etc. As described above, a reaction solution obtained by dissolving polyamidic acid can be obtained. Then, the reaction solution is poured into a large amount of a weak solvent to obtain a precipitate, and the precipitate is dried under reduced pressure to obtain polyamic acid. In addition, the polyamidic acid is dissolved in an organic solvent, and then the polyamic acid is purified one or more times by precipitating with a weak solvent. @ [Synthesis of fluorenimide polymer] The sulfonimide polymer constituting the liquid crystal alignment agent of the present invention can be synthesized by dehydrating and closing the polyfluorinated acid. The dehydration ring closure of polyamic acid is by (i) heating the polyamic acid, or by (II) dissolving the polyamic acid in an organic solvent, and adding a dehydrating agent and a dehydration ring-closing catalyst to the solution. Depending on the method of heating necessary. The reaction temperature in the method of heating the (i) polyamic acid is preferably 50 -20-200530375 to 20CTC, and more preferably 60 to 170 ° C. When the reaction temperature is lower than 50 ° C, the dehydration ring-closing reaction system cannot proceed sufficiently, and the molecular weight of the fluorene imidized polymer obtained when the reaction temperature exceeds 200 ° C decreases. On the other hand, in the method of adding a dehydrating agent and a dehydrating ring-closing catalyst to the solution of the (Π) polyamic acid, an acid anhydride such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent to be used is preferably 0.01 to 20 mols relative to 1 mol of the repeating unit of the polyamic acid according to the desired rate of imidization. For the dehydration ring-closing catalyst system, tertiary amines such as pyridine, trimethylpyridine, dimethylpyridine, and triethylamine can be used. However, # is not limited by these. The amount of dehydration closed-loop catalyst used is preferably 0.0 1 to 10 moles relative to 1 mole of the dehydrating agent used.醯 The imidization rate can be higher than when the above-mentioned dehydrating agent and dehydrating ring-closing agent are used in a large amount. The fluorenimide ratio (the ratio of the amine unit to the fluorenim unit) is preferably 40% or more from the viewpoint of the erasure rate of the afterimage of the liquid crystal display element. The organic solvent used in the dehydration ring-closing reaction may be, for example, an organic solvent exemplified for those used in the synthesis of polyamic acid. Then, the reaction temperature of the dehydration ring-closing reaction is preferably 0 to 180 ° C, and more preferably 10 to 15 ° C. Further, the reaction solution obtained in this way is subjected to polyamic acid In the same manner as in the purification method, the fluorene imidized polymer can be purified. [End-modified polymer] The polyfluorinated acid and fluorinated polymer used in the present invention can be terminal-modified with a molecular weight adjusted. By using the terminally modified polymer, the coating characteristics of the liquid crystal alignment agent can be improved without impairing the effect of the present invention. When such a terminally modified polymer synthesizes polyamic acid, Example- 21-200530375 For example, it can be synthesized by adding monofunctional compounds such as acid anhydrides, monoamine compounds, and monoisocyanate compounds to the reaction system. Examples of the acid anhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, and n-deca succinic acid. Acid anhydride, n-undecyl succinic anhydride, n-tridecyl succinic anhydride, n-hexadecyl succinic anhydride, etc. In addition, examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine , N-octylamine, N-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetraamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-diamine Decaamine, etc. In addition, monoisocyanate compounds can be exemplified by benzene isocyanate, naphthalene isocyanate, etc. [Logarithmic viscosity of polymer] As the polyamic acid and fluorenimide polymer obtained above, the logarithmic viscosity (ηΐη) It is preferably from 0.05 to 10 dl / g, and more preferably from 0.05 to 5 dl / g. The above log viscosity (η 黏, N-methyl · 2-pyrrolidone is used as a solvent at a concentration of 0.5 The viscosity is measured at 30 ° C in a solution of g / 100 ml according to the following formula (i). [Equation 1] 1 n (solution run time / solvent run time) 7} "= --- -(i) (weight concentration of polymer) [liquid crystal alignment agent] The liquid crystal alignment agent of the present invention is generally formed by dissolving and containing the polyamidoacid and / or fluorinated polymer in an organic solvent. The temperature of the liquid crystal alignment agent of the present invention is preferably 0 ° to 200 ° C, and more preferably 2 ° C to 60 ° C. 200530375 The above organic solvent may For example, 1-methyl-2 -P-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, 4 -Hydroxy-4-methyl-2-pentanol, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol Methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether , Ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Alcohol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and the like. _ The solid content concentration in the liquid crystal alignment agent of the present invention is selected in consideration of viscosity, volatility, etc., and is preferably in a range of 1 to 10% by weight. That is, when the liquid crystal alignment agent of the present invention is applied to the surface of a substrate to form a coating film of a liquid crystal alignment film, the solid content concentration is less than 1% by weight. When the film thickness of the coating film becomes 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 becomes too large to obtain a good liquid crystal alignment film, and the liquid crystal alignment The viscosity of the agent is increased and the coating characteristics are deteriorated. The liquid crystal alignment agent of the present invention may be a compound containing a functional silane or an epoxy compound from the viewpoint of improving the adhesion to the substrate surface within a range that does not impair the physical properties of the object. Examples of the functional silane-containing compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, and 2-aminopropyl Triethoxysilane, n- (2-aminoethyl) -3-aminopropyltrimethoxysilane, n- (2-aminoethyl) -3-aminopropylmethyldimethoxy Silane, 3-Ureapropyltrimethoxysilane, 3-Ureapropyltriethoxysilane, n-ethoxycarbonyl-3-aminopropyltri-23-200530375 methoxysilane, n-ethoxycarbonyl -3-aminopropyltriethoxysilane, n-, triethoxysilylpropyltriethylenetriamine, n-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1 , 4,7-triazinedecane, 10-triethoxysilyl-1,4,7-triazinedecane, 9-trimethoxysilyl-3,6-diazinyl acetate, 9-triethoxysilyl-3,6-diazinyl acetate, n-benzyl-3-aminopropyltrimethoxysilane, n-benzyl-3-aminopropyltriethyl Oxysilane, n-phenyl-3-aminopropyltrimethoxysilane, n-phenyl-3-aminopropyltriethoxysilane, n-bis Hydroxy stretch ethyl) -3-aminopropyl trimethoxy Silane, n-bis (hydroxy extending aminoethyl) -3-aminopropyl triethoxysilane Silane-like. Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and neopentyl glycol diglycidyl. Glyceryl 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-diglycidylaminomethyl) Cyclohexane, N, N, N ', N',-tetraglycidyl-4,4'-diaminodiphenylmethane, 3- (N-allyl-N-glycidyl) amine® Propane Trimethoxysilane, 3- (N, N-diglycidyl) aminopropyltrimethoxysilane and the like. [Liquid crystal display element] The liquid crystal display element of the present invention can be produced by, for example, the following method. (1) On one side of a substrate on which a patterned transparent conductive film is provided, the liquid crystal alignment agent of the present invention is applied by a method such as a roll coating method, a spin coating method, a printing method, or the like, and then formed by heating the coated surface. Coating film. The substrate can be -24-200530375. It is made of glass such as float glass, sodium carbonate glass, etc .; plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether, polycarbonate, etc. Transparent substrate. As the transparent conductive film provided on one surface of the substrate, a NESA film (registered trademark of PPG, USA) made of tin oxide (Sn02), an ITO film made of indium tin oxide (In203-Sn02), or the like can be used. These transparent conductive films are patterned by a photo-etching method or a method 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 transparent conductive film and the coating film, the surface of the substrate may be previously coated with a compound containing a functional silane or a compound containing a functional titanium. The heating temperature of the liquid crystal and the alignment agent after coating is preferably 80 to 3 00 ° C, and more preferably 1 20 to 2 50 ° C. In addition, the liquid crystal alignment agent of the present invention containing polyamic acid can form an enhanced coating by removing the organic solvent after coating to form a coating film as an alignment film, and then dehydrating and closing the film by heating. membrane. The thickness of the coating film to be formed is preferably 0.001 to 1 μm, and more preferably 0.005 to 0.5 μm. (2) The surface of the coating film to be formed is rubbed in a certain direction with a roll wrapped with a nylon cloth such as nylon, rayon, cotton, etc., to perform a rubbing treatment. Thereby, the alignment energy of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film. Xin also "liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention, for example, as shown in Japanese Patent Application Laid-Open No. 6-222366 or Japanese Patent Application Laid-Open No. 6-28 1 93 7", and changes in the pretilt angle by irradiation of ultraviolet rays Treatment, or as shown in Japanese Patent Application Laid-Open No. 5- 1 07 5 44, by forming a photoresist film on the surface portion of the liquid crystal alignment film to which rubbing treatment is applied, and removing the photoresist after rubbing treatment in a direction different from the previous rubbing treatment. The film can be processed to change the liquid crystal alignment ability of the liquid crystal alignment film, which can improve the visual field characteristics of the liquid crystal display element. -25-200530375 (3) As mentioned above, one substrate is used to form the liquid crystal alignment film, and one substrate is formed without the transparent guide and the electrical film pattern is formed. The direction of friction in each liquid crystal alignment film is orthogonal or antiparallel, 2 The sheet substrates are arranged facing each other through the gap (cell gap), and the peripheral parts of the two substrates are bonded with a sealant, and the liquid crystal is injected into the cell gap between the substrate surface and the area divided by the sealant. The injection hole is sealed to form a liquid crystal cell. Then, on the outer surface of the liquid crystal cell, that is, on the other surface side of each substrate constituting the liquid crystal cell, the polarizing plate is bonded by the polarization direction of the liquid crystal alignment film formed on one side of the substrate being aligned or orthogonal to the friction direction To obtain a liquid crystal display element. # In this case, the sealant may be, for example, a hardener and an epoxy resin containing alumina balls as a spacer. Examples of the liquid crystal include a nematic liquid crystal and a disc-shaped liquid crystal. Among them, a nematic liquid crystal is particularly preferable. For example, a shifted base liquid crystal, an azo oxide liquid crystal, a biphenyl liquid crystal, and a phenyl group can be used. Cyclohexane-based liquid crystals, ester-based liquid crystals, bitriphenyl-based liquid crystals, biphenylcyclohexane-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 sold under the trade names "C-15" and "CB-15" (Merck). It is used in the palm of hand. Alternatively, a strong dielectric liquid crystal such as p-desoxyalkylbenzylidene-P-amino-2-methylbutylacetophenate may be used. In addition, the polarizing plate attached to the outer surface of the liquid crystal cell may be, for example, a polarizing plate or a diaphragm thereof sandwiching a polarizing film called holmium film that absorbs iodine while extending the alignment of polyvinyl alcohol. Of the polarizer. -26-200530375 [Examples] Hereinafter, the present invention is further specifically described by way of examples, but the present invention is not limited by these examples. The evaluation methods in each liquid crystal display element produced according to the following examples and comparative examples are as follows. [Perylene imidization ratio of polymer · Average fluorination ratio of liquid crystal alignment agent] The polymer or liquid crystal alignment agent is dried under reduced pressure at room temperature and dissolved in deuterated dimethylimide. Silane was used as a reference substance to measure 1H-NMR at room temperature, and was obtained from the formula shown in the following formula (II). % 醯 imidization rate r / cOWl-AVA ^ cOxlOO · · · (II) A 値 NΗ The origin of the peak area of the matrix proton (10 ppm) A2: The area of the peak origin of other protons α: The precursor of the polymer (poly Sulfamic acid), the ratio of the number of other protons to one NH group proton [Solidity of imidized polymer and liquid crystal alignment agent] The polymer or liquid crystal alignment agent is dried under reduced pressure at room temperature After that, a solution having a solid content concentration of 10% by weight is dissolved in γ-butyrolactone for one hour at room temperature to dissolve it, and it is visually confirmed whether there is an undissolved residual portion, and a completely dissolved person is ΟΚ, an undissolved residue For NG. [Printability test of imidized polymer and liquid crystal alignment agent] The polymer or liquid crystal alignment agent is dissolved in γ-butyrolactone / N-methylpyrrolidone / butyl cellosolve (77/3/20 (weight (Ratio)) A mixed solvent is used as a solution having a solid content concentration of 4% by weight, and the solution is filtered by using a filter with a pore size of 1 μm and 200530375 to prepare a liquid crystal alignment agent of the present invention. The above-mentioned liquid crystal alignment agent is applied on a glass substrate with a transparent electrode formed of an ITO film by a liquid crystal alignment film printer (manufactured by Japan Photographic Press Co., Ltd.), and dried on a hot plate at 80 ° C for 1 minute. After that, it was dried on a hot plate at 180 ° C. for 20 minutes to form a film having an average film thickness of 600 A. The substrate was observed under a microscope with a magnification of 20 times, and the printability was judged based on the presence of print spots and pinholes. [Liquid crystal display element reliability test] In a high temperature and high humidity environment (temperature 70 ° C, relative humidity 80%), the liquid crystal display element is driven by a rectangular wave of 5V, 60Hz, and after 1,500 hours Use a microscope to see if there are white pollution-like display defects. [Voltage holding ratio of liquid crystal display element] After applying a 5V voltage of 60 microseconds to the liquid crystal display element at a pitch of 167 milliseconds, the voltage holding rate was measured from the time when the voltage was released to 167 milliseconds. The measuring device used VHR-1 manufactured by Toyo Technology Co., Ltd. Synthesis Examples 1 to 9 and Comparative Synthesis Examples 1 to 2 In N-methyl-2-pyrrolidone, the composition shown in Table 1 is represented by diamine and tetracarboxylic dianhydride ("anhydride" in the table) ) Was added in the order of 15% by weight as a solid content and reacted at 60 ° C. for 6 hours to obtain a polyamic acid having a logarithmic viscosity as shown in Table 1. In the obtained polyamic acid, 5 mol% of pyridine and 3 mol% of acetic anhydride were added to the total amount of tetracarboxylic dianhydride and diamine used, followed by heating at 110 ° C for 4 hours. Dehydration closed-loop reaction. After the resulting solution was re-sinked with diethyl ether, it was recovered and dried to obtain fluorinated polymers B1 to B9, bl, and b2 having logarithmic viscosity and fluorinated ratio shown in Table 1. -28-200530375 [Table 1]

Synthetic Example Diamine compound (millimol) Acid anhydride (millimol) Polyamidoamino acid log viscosity (dl / g) 醯 Iminated polymer polymer solubility 醯 Iminization ratio (%) Log viscosity (% ) 1 Dl (38), D-2 (10), D-6 (2) Tl (50) 0.4 89 0.5 B1 OK 2 Dl (38), D-2 (10), D-8 (2) Tl ( 50) 0.5 91 0.7 B2 OK 3 Dl (38), D-2 (10), D-9 (2) Τ-1 (50) 0.5 89 0.7 B3 OK 4 Dl (24), D-2 (24), D-6 (2) Τ-1 (50) 0.4 90 0.5 B4 OK 5 Dl (38), D-3 (10), D-6 (2) Τ-1 (50) 0.7 91 0.9 B5 OK 6 D- 1 (38), D-4 (10), D-6 (2) T-1 (50) 0.8 89 0.9 B6 OK 7 Dl (38), D-5 (10), D-6 (2) T- 1 (50) 0.7 88 0.7 B7 OK 8 D-2 (24), D-3 (24), D-6 (2) Τ-1 (50) 0.4 89 0.5 B8 OK 9 D-10 (33), D -2 (15), D-6 (2) T-1 (50) 0.6 90 0.8 B9 OK Comparative Synthesis Example 1 Dl (38), D-6 (2), D-7 (10) T-1 (50 ) 0.6 91 0.7 bl OK 2 Dl (40), D-6 (2), D-7 (8) Τ-2 (50) 0.7 醯 imide does not dissolve b2 NG The diamine compounds in Table 1 The carboxylic dianhydride is as follows. < Diamine compound > Dl: p-phenylenediamine D-2: bisaminopropyltetramethyldisilazane D-3: 4,4'-hydroxydiphenylamine D-4: 1, 4 -Bis (aminophenoxy) benzene D-5: bis (4- (4-aminophenoxy) phenyl) ether D-6: diamine-29 represented by the above formula (13)-200530375 D_7 : 4,4'-methylene diphenylamine D-8: diamine D-9 represented by the above formula (15): diamine D-10 represented by the above formula (21): 2,2'-dimethylformamide -4,4'-diaminobiphenyl < tetracarboxylic dianhydride > T-1: 2,3,5-tricarboxycyclopentylacetic dianhydride T-2: pyromellitic dianhydride [Embodiment] Example 1 It is called to dissolve 2 g of fluorene imidized polymer (B 1) obtained in Synthesis Example 1 in γ-butyrolactone as a solution having a solid content concentration of 4% by weight. The solution has a pore size of 1 A μm filter is used to prepare the liquid crystal alignment agent of the present invention. The liquid crystal alignment agent is a liquid crystal alignment film coating printer and is applied to a transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film, and dried on a hot plate at 180 ° C for 20 minutes to form a dry film thickness of 0.05. μιη coating film to evaluate the printability. This coating film was subjected to a rubbing process with a friction machine having a roll wound with a rayon cloth, a φ revolution of the roll of 500 rpm, a moving speed of a stage of 1 cm / sec, and a gross indentation length of 0.4 mm. Next, on a pair of friction-treated liquid crystal substrates each having a liquid crystal alignment film, screen-printed and coated with a resin resin doped with alumina balls with a diameter of 17 μm. It is opposite to the liquid crystal alignment film surface, but the rubbing direction is overlapped and pressed in antiparallel to harden the adhesive. -30-200530375 Next, from the liquid crystal injection port to a pair of substrates, the nematic liquid crystal (Merck, MLC-5 08 1) is filled, and then the liquid crystal injection port is sealed with an epoxy-based adhesive. The polarizing plates on the two outer sides are bonded together with the polarizing direction of the polarizing plate as the rubbing direction of the liquid crystal alignment film of the substrate, respectively, so as to produce the liquid crystal display element of the present invention. The reliability and voltage retention of the obtained liquid crystal display element were evaluated. The results of the printability test at the same time are shown in Table 2 below. Examples 2 to 9, Comparative Example 1

A liquid crystal alignment agent was prepared in the same manner as in Example 1 except that the polymers shown in Table 1 were used. A liquid crystal display element was prepared using this liquid crystal alignment agent and evaluated. The evaluation results are shown in Table 2. [Table 2] Example polymer printing reliability reliability voltage retention [%] Kind 1 B1 Good Good ^ 98 2 B2 Good Good ^ 98 3 B3 Good Good ^ 98 4 B4 Good Good ^ 98 5 B5 Good Good ^ 98 6 B6 Good Good ^ 98 7 B7 Good Good ^ 98 8 B8 Good Good ^ 98 9 B9 Good Good ^ 98 Comparative Example 1 B1 Needle-eye white dirt ^ 98

[Schematic description] -31-

Claims (1)

200530375 10. Scope of patent application: 1. A liquid crystal alignment agent, which is a liquid crystal alignment agent made of polyimide-fluorinated imidized polymer, characterized in that the above-mentioned imidized polymer meets the following conditions [ A] and [B], [A] contains at least one of the units represented by the following formulae (0 and (1), respectively, in the main chain of the imidized polymer, [Chem. 1] ⑴ -32-1 In the formula, R! ~ R6 each independently represent hydrogen, a halogen atom, or a monovalent organic group, P, q, and r each independently represent an integer of 1 to 20, [B] is in 醯 亚The main chain of the aminated polymer contains at least one group selected from the groups shown in the following A to D, or the group is a side chain. A: The main chain is an alkyl group having 8 or more carbon atoms. The main chain is a perfluoroalkyl group having 3 or more carbon atoms or a 1,1-cycloalkane group having 6 or more carbon atoms that can be substituted, B: a group having a polycyclic structure with 3 or more rings, Ci-RX A group represented by -A1, where R is a hydrocarbon group having 3 or more carbon atoms, and X is a single bond, -0-, 200530375 -CO-, _COO ·, -OCO-, -NH-, _NHCO_, -CONH The bonding group represented by-or -S- 'A1 represents a halogen atom, a cyano group, a fluoroalkyl group, or a substituted benzodihydropyranyl group. Di-RlX ^ W-XlR3, where R1 to R3 each independently represent a hydrocarbon group having 3 or more carbon atoms and-(Si-O-) η (where η is an integer of 5 or more) ), X1 and X2 each independently represent a single bond, · 0-, -CO-, -COO-, -OCO-, -NΗ-, -NHCO-, -CONH- or -S- . 2 · The liquid crystal alignment agent according to item 1 of the scope of patent application, wherein the base represented by the condition [B] is at least one selected from the group consisting of the following formulae (a) to (z) ' -33-200530375 【Chemical 2】 34 200530375 [Chemical 3] 35 200530375 -36-200530375 (where A is a phenyl group or a single bond, X, Y, and P are independently selected from -0, -CO-, -COO_, -oco-, -NHCO-,- CONH-, -S-, -Ar-Ar-CH2- (where Ar is a phenylene group), a methylene group, an alkylene group having 2 to 6 carbon atoms, and a divalent group of a phenylene group, Z is It is a monovalent organic group selected from -CF3, -CN, -COCH3, -COOH, -N02, -SOCH3, -S02CH3, -F, -CM, -OCF3. R1 to R9, R11 to R19, R21, R23 , R24, R25, R27 ~ R33 each independently represent a halogen atom or a monovalent organic group, R2C, R22, and R26 are divalent organic groups, R1G is a trivalent organic group, and Q is 6 to 1 carbon atoms 6 alkyl groups, and m and n are each an integer of 1 or more). 3. The liquid crystal alignment agent according to item 1 of the scope of patent application, wherein the group represented by the condition [B] is derived from one of the amine compounds 75 in the following formulas (3) to (8 1) ' -37-200530375 Hua5] H2N- < —coo ΪΗ3 ^ CH3 H3CCH (CH2) 3CH ^ ch3 (3) ° ~ 〇-_ H2it—COO NH2 / CH3 CH3 H3C H (CH2) 3CH: xCH3, CH3 (4) H2W-〇- NH2 H3C l (CH2) 3CH H3C H (CH2) 3CH: ίΗ3 / CH3 H3C CH (CH2) 3CH ^, CH3 (5) H2N coo NH2 ^ CH3, XH3 (6) H2W—j ^ | —coo (7) CH3 H3 (? CH (CH2) 3CH NH2 CH3, CH3 (8) 38 200530375 [Chem. 6] / CH3 CH3 (14) -39-200530375 [Chem. 7] -40-200530375 [chemical 8] (37) (38) -41-200530375 Chemical 9] XX ^ cc Η〆—, NH2 tCH 2 seven CH3 XXH H2N nh2 tCH; 2 seven CH3 (40) XX: 〇Kch2Vo_0 " hO (41) (43) N 2 (45) ΑίΗ: H2N room 2 (44) 4 ° ~ 0 ~ 0 ~ (46) OCH3 ^ ch2V ° ~ 0 ~ 0 ^ 'ocf3 (47) (48) XXNH H2N nh2 L〇 ~ (cH as xc, c- h2n ▼ nnh2 (50) ch, -o- (ch2 ^ cf2-^-f h2n nh2 GH 「〇- (〇Λ N NH2 (51) r〇 ^ CH2 ^ -Si- CH (52) o—ch2— (cf2) ^ h H2N nh2 (53) -chsHcf2) ^ H2N NH2 (55) H2N NH2 (54) XXNH H2N nh2 -42-200530375 [Chemical 10, 0 " (cH VII CH3 h2n…, nh2 ja: (57) 〇V ^ CH2fcCH3 H2N nh2 (63) -43-200530375 h2n nh2 ch3 (73) H2N SprW 〇 ^ C, 〇- (cH2 known * CH3 nh2 H2N (75) nh2 yc, cH yCT (77) NH2 C2H4 6 · — (80) H2N NH2 S- ^} (81) (where y is an integer of 2 to 12 and z is an integer of 1 to 5). 4. The liquid crystal alignment agent according to item 1 of the scope of patent application, wherein the base represented by the condition [B] is derived from the tetracarboxylic dianhydride represented by the following formulae (82) to (90), -44-200530375 [Chemical 1 2] 5. The liquid crystal alignment agent according to any one of claims 1 to 4, in which at least one part of the tetracarboxylic dianhydride is a polyfluorene obtained by using the tetracarboxylic dianhydride represented by the following formula (91) Composed of urethane and imidized polymer, [Chem. 1 3] -45-(91) 200530375 In the formula, R represents a tetravalent organic group having an alicyclic structure. 6. The liquid crystal alignment agent according to item 1 of the scope of patent application, wherein the tetracarboxylic dianhydride represented by the formula (9 1) is 2,3,5-tricarboxycyclopentylacetic dianhydride. 7. A liquid crystal display element characterized by having a liquid crystal alignment film obtained from a liquid crystal alignment agent according to any one of claims 1H to 6. -46-200530375 7. Designated Representative Map: (1) The designated representative map in this case is: None. (2) Brief description of the component symbols of this representative figure: 〇 8. If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: 〇H3 (pH3 ch3 ch3