TW201120099A - Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display device, polyamic acid and compound - Google Patents

Abstract

A liquid crystal alignment agent comprises at least one kind of polymer selected form a group consisted of a polyamic acid obtained from reacting a tetracarboxylic acid dianhydride and a diamine comprising compounds represented by formula (A-1) below, and a polyimide formed by dehydration cyclization of polyamic acid. In the formula (A-1), R represents an organic group with steroid skeleton and carbon number 17-30, or may also be a halide atom-replaced alkyl group with carbon number more than 1.

Description

201120099 VI. Description of the Invention: [Technical Field] The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, a liquid crystal display element, a polylysine, and a compound. More specifically, the present invention relates to a liquid crystal alignment agent which can provide the following liquid crystal alignment film and which is excellent in printability. The liquid crystal alignment film exhibits good vertical alignment and high voltage retention, and can be high. The present invention also relates to a liquid crystal display element having the liquid crystal alignment film and having high display quality and excellent afterimage characteristics. [Prior Art] The liquid crystal display element has a liquid crystal alignment film for aligning liquid crystal molecules. As the material of the liquid crystal alignment film, polylysine or polyimine which is excellent in various properties such as heat resistance, mechanical strength, and affinity with liquid crystal is suitable for use in many liquid crystal display elements. As one type of liquid crystal display element, a VA (Vertical Alignment) type liquid crystal display element in which liquid crystal molecules having negative dielectric anisotropy are vertically aligned on a substrate is known. However, if a liquid crystal alignment film composed of polyamic acid or polyimine which is currently known is directly applied to a VA type liquid crystal display element, the vertical alignment control force of the liquid crystal molecules is insufficient. In order to solve this problem, various studies have been conducted all the time. For example, in Patent Documents 1 and 2, it is proposed to use, as a liquid crystal alignment film material, a polyimine which is obtained using a diamine containing a high proportion of a hydrophobic functional group having a long-chain alkyl group or the like. This technique is a technique which can be considered to have a high vertical alignment control force in the obtained liquid crystal alignment film of 201120099, but it is pointed out that it is possible to impair the printability of the liquid crystal alignment agent, so that further improvement is required. In addition, as a result of the liquid crystal display element, it has been found that when the cumulative driving time is long, an afterimage (so-called "branding") or the like can be found. In order to improve the image of the afterimage, several current methods have been tried. Most of these methods focus on the relationship between "burning, and the unevenness and accumulation of the DC voltage component (residual DC voltage) applied when driving the liquid crystal display element", which attempts to improve the "burning" by reducing the residual DC voltage. For example, in Patent Document 3, it has been attempted to form a liquid crystal alignment film from a specific polyimine synthesized using a specific diamine having a fluorene structure, which can effectively reduce the residual DC voltage, thereby improving the imprint. However, the liquid crystal alignment film of Patent Document 3 has not sufficiently verified the effect of improving the afterimage in the embodiment, and has not considered the afterimage which occurs when the cumulative driving time becomes long. [Patent Document 1] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei 9-241646 (Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. [Patent Document 4] JP-A-2010-97188 SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object thereof is to provide a liquid crystal alignment agent which can provide excellent vertical display Match

201120099 is a directionality, and even if the cumulative driving time is long, the afterimage film is not generated, and the printability is excellent, and a liquid crystal display element having excellent display quality and excellent afterimage characteristics is provided. Other objects and advantages of the present invention will be apparent from the following description. According to the present invention, in the above object of the present invention, the first object of the present invention is that the liquid crystal alignment agent contains a group consisting of polyamidene formed by dehydration ring closure of poly-proline polyglycine. a polymer in which polylysine is obtained by reacting a tetracarboxylic dianhydride with a diamine containing a compound represented by _

R—X1—{-R1—X11-^—N In the formula (A), R is a group having a carbon number of 17 to 30 having an anthracene skeleton or an alkane X1 having a carbon number of 1 or more which may be substituted by a halogen atom. And X11 are a single bond, *-0-, *-CO-, *-COO- or *- respectively. In the above, the connection key of the belt is the R side. R1 is a phenyl or cyclohexyl group: X111 is a single bond or -CO-, and η is an integer of 0 to 2; wherein, each of R1 and X11 may be the same or different. The above object of the present invention, the second object, is achieved by a liquid crystal display element having a liquid crystal alignment film formed of the above liquid. The liquid crystal accumulates a liquid and the at least one c-type (Α) (A) organic group, OCO-, and the respective crystals are aligned to 201120099. The liquid crystal alignment agent of the present invention can exhibit excellent printability and can exhibit excellent performance. The liquid crystal alignment film in which the liquid crystal alignment film formed by the liquid crystal alignment agent has a high liquid crystal display quality, even when the cumulative driving time is long, Therefore, the liquid crystal display element of the present invention can be effectively adapted, for example, in a timepiece, a portable game machine, a text-based computer, a navigation system, a video camera, a portable information terminal, a Pong mobile phone, and various types of surveillance. Further, in the display device such as a liquid crystal television or the like, the liquid crystal alignment agent of the present invention can also be used as an insulating composition, and a film formed of the composition is also suitable as an electrical insulating film. [Embodiment] Hereinafter, the present invention will be described in detail. The liquid crystal aligning agent of the present invention contains a conjugate (hereinafter, also referred to as "specific polymer") selected from the group consisting of poly phthalimides formed by dehydration ring closure of polyamic acid and aminic acid, wherein polyamine Reaction of a carboxylic acid dianhydride with a diamine containing a compound represented by the above formula (A) <tetracarboxylic dianhydride> As a tetracarboxylic acid for synthesizing the polyglycolic acid in the present invention, for example, an aliphatic group is exemplified. Tetracarboxylic dianhydride, alicyclic tetracarboxylic acid, aromatic tetracarboxylic dianhydride, and the like. Specific examples of these may be aliphatic tetracarboxylic dianhydrides, and examples thereof include butane tetracarboxylic acid II, and the display element i of the present invention is produced by the product. Used for various machines, pens, camera, use. The film forming material is obtained by using the polyacrylic acid as one of four. a dianhydride, a dianhydride, an aromatic: as a fatty anhydride, etc.; as an alicyclic tetracarboxylic dianhydride in 201120099, for example, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 2, 3 , 5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-di-oxo-3-furanyl)-naphthalene n, 2_c]furan-1,3·dione, 1,3,3&,4,5,91>-hexahydro-8-methyl-5-(tetrahydro-2,5-di-oxo-3-furan -Naphthalene [1,2-indolyl]furan-1,3-dione, 3-oxabicyclo[3.2.1]octyl-2,4-dione-6-spiro-3'-(tetrahydrofuran-2 ,, 5'-dione), 5-(2,5-di-side oxytetrahydro-3-furanylmethyl-3-cyclohexene-1,2-dicarboxylic anhydride' 3,5,6-three Carboxy-2-carboxymethylnorbornane-2:3,5:6-dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]oct-2:4,6:8-dianhydride 4,9-dioxatricyclo[5.3.1.02,6]undec-3,5,8,10-tetraketone, etc.; as the aromatic tetracarboxylic dianhydride, for example, pyromellitic acid II And the tetracarboxylic dianhydride described in the patent document 4 (JP-A-2010-97188). The tetracarboxylic dianhydride used for the synthesis of the poly-proline is preferably used. Containing fat Those of the cyclic tetracarboxylic dianhydride, particularly preferably those containing 2,3,5-tricarboxycyclopentyl acetic acid dianhydride. The tetracarboxylic dianhydride used for the synthesis of the aforementioned polyamic acid, relative to all The tetracarboxylic dianhydride preferably contains 10 mol% or more, more preferably 2 mol% or more of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride. The tetracarboxylic acid used for synthesizing the aforementioned polylysine. Acid dianhydride, preferably composed of only 2,3,5-tricarboxycyclopentyl acetic acid dianhydride or only 2,3,5-trisylcyclopentyl acetic acid dianhydride and 1,2,3 And 4-cyclobutane tetracarboxylic dianhydride. 201120099 <Diamine> The diamine used for synthesizing the poly-aracine in the present invention is a compound represented by the above formula (A) (hereinafter, also The diamine which is called "the compound (A),") is an alkyl group having 1 or more carbon atoms of R in the above formula (A), preferably an alkyl group having 1 to 30 carbon atoms, more preferably carbon. The linear alkyl group having a number of 3 to 20, and specific examples thereof include n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, and n-decyl group. , n-undecyl, n-dodecyl, Tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl, etc. these alkanes The organic group having a carbon number of 17 to 30 having a fluorene skeleton which may be substituted by a halogen atom, preferably a fluorine atom, may be a cholesteryl group, a cholesteryl group, a lanthanyl group or the like. Particularly preferred R is a linear alkyl group having a carbon number of 5 to 12, a cholesteryl group, a cholesteryl group or a lanthanyl group. Specific examples of the RI include a 1,4-phenylene group and a 1,4-cyclohexylene group, and among them, a 1,4-phenylene group is preferable. Preferably, X1 is a single bond, *-〇- or *-CO- (the connection key with "*', the R side); X11 is a single bond. X111 is preferably a single bond or *-C 〇-(the bond of the band is the R side); more preferably a single bond. As η, preferably 〇 or 1. The two amine groups attached to the benzene ring are 2,4-position relative to the other groups. 201120099

Examples of the compound (A) having such a structure include compounds represented by the following formulas (A-1) to (A-5), and the like.

R-N

(A-3)

(A-5) In the above formula, R is the same as defined in the above formula (A). Specific examples of R in the above formulas (A-1) to (A-5) include, for example, n-pentyl group and positive Heptyl's ruthenium and the like. The compound represented by the above formula (A) can be synthesized by a conventional method in which an organic compound is appropriately combined. -10- 201120099 For example, a compound represented by the above formula (A-3) can be formed by, for example, reacting 2,4-dinitrobenzene and piperidine, preferably in the presence of a fluorinated planer. The 2,4-dinitropiperidinylbenzene is obtained by reacting the intermediate with a compound R-Br having the desired group R, and converting the nitro group to an amine group using an appropriate reduction system. The compound represented by the above formula (A-4) can be, for example, an intermediate 2,4-dinitro(piperidinyl)benzene obtained in the same manner as above, and a compound R having a desired group R. After the COC1 reaction, a suitable reduction system is used to convert the nitro group to an amine group. The compound represented by the above formula (A-5) can be formed by, for example, reacting 2,4-dinitrofluorobenzene and 4-piperidinylbenzene, preferably in the presence of sodium hydrogencarbonate. N-(4-hydroxyphenyl)-N'-(2,4-dinitrophenyl)piped, the intermediate and the compound R-Br' having the desired group R are preferably After the reaction in the presence of potassium carbonate, a suitable reduction system is used to convert the nitro group to an amine group. The diamine used for the synthesis of the poly-proline in the present invention may be used alone or in combination of the compound (A) and other diamines. Other diamines which may be used herein include, for example, an aliphatic diamine 'alicyclic diamine, an aromatic diamine, a diamine organodecane, and the like. Specific examples thereof include, as the aliphatic diamine, for example, 1,1-m-xylenediamine, U-propylenediamine, anthracene, tetrabutylamine, hydrazine, and 5-pentanediamine. 1,6-hexanediamine, etc.; -11 - 201120099 Examples of the alicyclic diamine include 1,4-diaminocyclohexane and 4,4'-methylenebis(cyclohexylamine). 1,3-bis(aminomethyl)cyclohexane; etc.; as the aromatic diamine, for example, p-phenylenediamine, 4,4 '-diaminodiphenylmethane, 4,4'- Diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2 '-Bis(trifluoromethyl)biphenyl, 2,7-diaminostilbene '4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy) Phenyl]propane, 9,9-bis(4-aminophenyl)anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-double (4-Aminophenyl)hexafluoropropane, 4,4'-(p-phenylenediphenylene)bis(aniline), 4,4'-(meta-phenylphenylene) (aniline), 1,4-bis(4-aminophenoxy)benzene, 4,4' - bis(4-aminophenoxy)biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine , 3,6 · Diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6- Diaminocarbazole, N,N'-bis(4-aminophenyl)-benzidine, N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine, Dodecyloxy-2,4-diaminobenzene, pentadecyloxy-2,4-diaminobenzene, cetyloxy-2,4-diaminobenzene, octadecyloxy -2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, pentadecyloxy-2,5-diaminobenzene, hexadecyloxy-2,5- Diaminobenzene, octadecyloxy-2,5-diaminobenzene, cholestyloxy-3,5-diaminobenzene, cholestyloxy-3, 5-diaminobenzene, Cholesteryloxy-2,4-diaminobenzene, cholesteneoxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholesteryl ester, 3,5-diamine Cholesteryl benzoate, lanostane 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 1,4-bis(4- Aminophenyl) piperazine Well, etc.; -12- 201120099 As the diamine-based organic decane, for example, 1,3-bis(3-aminopropyl)-tetramethyldioxane or the like can be exemplified, and Patent Document 4 can be used. The diamine described in Japanese Laid-Open Patent Publication No. 2010-97188. The diamine used for the synthesis of the polyamic acid preferably contains 0.1 m ο 1 % or more, more preferably 〇 1 to 5 0 m ο 1 %, more preferably more than all diamines. It contains 〜·1 to 30 mol%, particularly preferably 1 to 20 mol% of the compound (A). <Molecular weight modifier> In the synthesis of the above polyamic acid, an end-modified polymer can also be synthesized by using an appropriate molecular weight regulator ‘and the above-described tetracarboxylic dianhydride and a diamine. By forming a specific polymer into the terminal-modified polymer', the coating property (printability) of the liquid crystal alignment agent can be further improved without impairing the effects of the present invention. The molecular weight modifier may, for example, be an acid monoanhydride, a monoamine compound or a monoisocyanate compound. Specific examples thereof are as acid monoanhydride, and examples thereof include maleic acid: 'phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecane a succinic anhydride, n-hexadecyl succinic anhydride or the like; examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine 'n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine and the like; The isocyanate compound may, for example, be phenyl isocyanate or naphthyl isocyanate. -13· 201120099 The use ratio of the molecular weight modifier is preferably 20 parts by weight or less and more preferably 10 parts by weight or less based on 100 parts by weight of the total of the tetracarboxylic acid and the diamine used. <Synthesis of Polylysine> The tetracarboxylic dianhydride used in the synthesis reaction of polyglycine is preferably used in an amount of 1 equivalent of the amine group of the diamine. The synthesis reaction of 0.2 to 2 equivalents, more preferably 0.3 to 1.2 equivalents of lysine, is preferably carried out in an organic solvent at -20 to 150 ° C, more preferably 0 to 100 °. In C, it is preferably carried out for 0 hours, more preferably for 0.5 to 12 hours. Here, examples of the organic solvent include aprotic polar phenol and a derivative thereof, an alcohol, a ketone, an ester 'ether, a halogenated hydrocarbon, a hydrocarbon, and the like. Specific examples of the organic solvent include, as the above-mentioned amorphous polar solvent, for example, N-methyl-2-pyrrolidone, N,N-methylacetamide, hydrazine, hydrazine dimethylformamide And dimethyl sulfite, γ-butytetramethyl urea, hexamethylphosphonium triamide, etc., and examples of the phenol derivative include m-cresol, phenol, halogenated phenol, and the like; For example, methanol, ethanol, isopropylcyclohexanol, ethylene glycol 'propylene glycol' 1,4-butanediol, triethylene glycol, ethylene monomethyl ether or the like is exemplified; and examples of the ketone include acetone and methyl ethyl ketone. Methyl butyl ketone, cyclohexanone, etc.; dianhydride is preferably an acid of a diamine: an example. Preferably, the solvent is 1 to 24, the dimethyl ester, the dimethanol, and the diol isomer-14-201120099 The ester may, for example, be ethyl lactate, butyl lactate, methyl acetate, ethyl acetate or butyl acetate. Ester, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, etc.: Examples of the ether include diethyl ether and ethylene glycol methyl ether. , ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol oxime ether acetate, diethyl 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, etc.; as the halogenated hydrocarbon, for example, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, O-dichlorobenzene or the like; examples of the hydrocarbon include hexane, heptane, octane, benzene, toluene, xylene, isoamyl propionate, isoamyl isobutyrate, and the like. Isoamyl ether and the like. Among these solvents, it is preferred to use one or more selected from the group consisting of an aprotic polar solvent and a phenol and a derivative thereof (the first group of organic solvents), or an organic selected from the first group described above. One or more solvents selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons (the second group of organic solvents). In the latter case, the proportion of the organic solvent used in the second group is preferably 50% by weight or less with respect to the total amount of the organic solvent of the first group and the organic solvent of the second group. It is 40% by weight or less, and further more preferably 30% by weight or less. -15- 201120099 The amount of the organic solvent (a) is preferably the total amount of the tetracarboxylic dianhydride and the diamine (b) relative to the total amount of the reaction solution (a + b) is 〇 1 to 50% by weight . As described above, a reaction solution formed by dissolving polylysine can be obtained. The reaction solution can be directly used for preparing a liquid crystal alignment agent, or can be used for preparing a liquid crystal alignment agent after separating the polyamic acid contained in the reaction solution, or purifying the separated polyamic acid to prepare a liquid crystal alignment. Agent. When polypyridic acid is dehydrated and closed to form a polyimine, the above reaction solution can be directly used for the dehydration ring closure reaction; the polylysine contained in the reaction solution can be separated and used for the dehydration ring closure reaction; or the separation can be carried out. After the polyamic acid is refined, it is used for the dehydration ring closure reaction. The separation and purification of polylysine can be carried out by a conventional method. <Synthesis of Polyimine> The above polyimine can be obtained by hydrazine hydrazide by dehydration of the polylysine synthesized as above. The polyimine in the present invention may be a complete hydrazine imide of a glycine structure having a glycine structure as a precursor of polyproline, or a part of the structure of a proline which is dehydrated and closed, and a guanamine A partial quinone imide that has an acid structure and a quinone ring structure. The ruthenium imidization ratio of the polyimine in the present invention is preferably at least 30%, more preferably from 50 to 99%, still more preferably from 65 to 99%. The ruthenium imidization ratio is a ratio indicating the number of the quinone ring structure in the percentage of the amount of the guanine structure of the polyimine and the total amount of the quinone ring structure. Here, a part of the quinone ring may also be an isoindole ring. -16- 201120099 The dehydration ring closure of polylysine is preferably a method of heating poly-proline, or by dissolving poly-proline in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution, as needed The heating method is carried out. Among them, it is preferred to carry out the latter method. In the method of adding a dehydrating agent and a dehydration ring-closure catalyst to the polyamic acid solution, the dehydrating agent may, for example, be an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride. The amount of the dehydrating agent is preferably 0.01 to 20 m Torr based on the structure of the lysine of 1 mol of polyamic acid. As the dehydration ring-closing catalyst, a tertiary amine such as pyridine, trimethylpyridine, lutidine or triethylamine can be used. The amount of the dehydration ring-closing catalyst is preferably from 0.0 1 to 10 m Torr based on 1 mol of the dehydrating agent used. The organic solvent used in the dehydration ring-closure reaction may, for example, be an organic solvent exemplified as a solvent used for the synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably 〇 18 (TC, more preferably 10 to 150 ° C. The reaction time is preferably 1. 〇 1 to 20 hours, more preferably 2.0 to 30 hours. a reaction solution of quinone imine. The reaction solution can be directly used for preparing a liquid crystal alignment agent, or can be used for preparing a liquid crystal alignment agent after removing a dehydrating agent and a dehydration ring-closing catalyst from the reaction solution; For preparing a liquid crystal alignment agent; or after purifying the separated polyimine, for preparing a liquid crystal alignment agent. These purification operations can be carried out according to a conventional method. -17- 201120099 <Solution viscosity of polymer> '-Solid viscosity - The specific polymer obtained as above is preferably having a solution viscosity of 20 to 800 mp a and a solution viscosity of 30 to 500 mPa_s when it is formed into a concentration of 10 Torr. The solution viscosity of the above polymer ( mPa_s) is a polymer solution obtained by using the polysolvent (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) in a weight %, and using a Ε-type rotational viscometer to measure the enthalpy. ;Other additives &g t The liquid crystal alignment film of the present invention contains the specific polymer component as described above, and may contain other components as needed. Examples thereof include other polymers and compounds having at least a group in the molecule (hereinafter referred to as "epoxy". Compound "), functional hydrazine, etc. [Other polymers] The above other polymers can be used to improve solution properties and electricity. Other polymers are polymers other than specific polymers, and can be classified as tetracarboxylic dianhydride and without compounds ( A) obtained by a diamine reaction (hereinafter referred to as "other poly-proline"), a polyamidene obtained by depolymerizing the polyamine (hereinafter referred to as "other polyimine"), and poly量 Polyester, polyamine, polyoxyalkylene 'cellulose derivative, polyethylene derivative, poly(styrene-phenylmaleimide) derivative A good concentration of 1 〇 2 5 ° C as an essential component, an alkylene oxide compound characteristic. For example, poly-proline water closed-loop glutamate, aldehyde, polyphenyl, poly (methyl) - 18 - 201120099 Acrylate, etc. It Among them, other poly-proline and other polyimine, more preferably other poly-proline. The tetracarboxylic acid used for the synthesis of the above other poly-proline or other polyimine - liver can be enumerated The same tetracarboxylic dianhydride as the above-mentioned tetracarboxylic acid dianhydride for synthesizing a specific polymer is preferably selected from the group consisting of ruthenium, 2,3,4-cyclobutanetetracarboxylic dianhydride Medic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dihydro- At least one of the group consisting of 3-furan)-naphthalene [1,2 - c ]furan-1,3 -dione. The diamine used for the synthesis of the above other polyaminic acid or other polyimine, preferably at least one of the above-exemplified ones selected from the other diamines which can also be used in the synthesis of a specific polymer. One. A diamine for synthesizing other polyaminic acid or other polyimine, preferably selected from the group consisting of 4,4,-diaminodiphenylmethane, 2,2,-dimethyl-4,4' -diaminobiphenyl, cholestyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid and iota,4-bis(4-aminophenyl)piped At least one of the groups. The ratio of use of other polymers is preferably 50% by weight or less, more preferably 0.1 to 40% by weight, based on the total amount of the polymer (refer to the total amount of the above specific polymer and other polymers, the same applies hereinafter). Further preferably, it is 0.1 to 30% by weight. [Epoxy compound] Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol. Diglycidyl ether, neopentyl glycol diglycidyl ether ' -19· 201120099 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, trimethylol triepoxypropyl ether 2,2-dibromoneopentyl glycol diglycidyl ether, N,N,N tetraepoxypropyl-m-xylylenediamine, 1,3-bis(indole, fluorene-diepoxypropylamino group ) cyclohexane, hydrazine, hydrazine, hydrazine, Ν'-tetraepoxypropyl-4,4'-diaminodiphenyl, hydrazine, hydrazine, -dipropylenepropyl-benzylamine, hydrazine, Preferred are hydrazine-diepoxypropyl-aminocyclohexane, hydrazine, hydrazine-diepoxypropyl-cyclohexylamine, and the like. The ratio of these epoxy compounds is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight, based on the total amount of the polymer, based on the functional decane compound. For example, 3-aminotrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropylmethoxydecane, 2-aminopropyltriethoxydecane, oxime-(2-amine Ethylethylaminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropyldimethoxydecane, 3-ureidopropyltrimethoxydecane, 3-ureido Propyl ethoxy decane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane ethoxycarbonyl-3-aminopropyltriethoxy decane, N-triethoxy fluorenylpropyl Ethyltriamine, N-trimethoxydecylpropyltriethylamine, 10-trimethoxydecyl-1,4,7-trioxane, 10-triethoxyalkyl-1,4 , 7-trioxane, 9-trimethoxydecyl-3,6-didecanoate, 9-triethoxydecyl-3,6-dimercaptoacetate, 9-three Base alkyl alkyl-3,6-dicarboxylate, 9-triethoxydecyl-3,6. methyl decanoate, N- 3-aminopropyltrimethoxydecane, N-benzyl: aminopropyltriethoxydecane, N-phenyl-3-aminopropanetrimethoxypropane, N,-ylmethylmethyl Methyl-doped propyl 3-()-3-methyl-tris-, N-in-situ-based triyl fluorenyl methoxy, dimethyl 3-yl hydrazine-20- 201120099 Alkane, N-phenyl 3-aminopropyltriethoxydecane, glycidoxymethyltrimethoxydecane, glycidoxymethyltriethoxydecane, 2-glycidoxyethyltrimethoxy Decane, 2-glycidoxyethyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, and the like. The mixing ratio of these functional decane compounds is preferably 2 parts by weight or less, more preferably 0.02 to 0.2 parts by weight, based on 100 parts by weight of the total of the polymer. <Liquid crystal alignment agent> The liquid crystal alignment agent of the present invention is preferably obtained by dissolving and containing the above specific polymer and any other additives which are optionally mixed as needed in an organic solvent. The organic solvent used in the liquid crystal alignment agent of the present invention may, for example, be N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butylide or N,N-dimethylformamide. Ν, Ν-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy propionate, Ethyl ethoxy propionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cerulerus) ), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene Alcohol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl acetonate, two Isovaleric acid, ethylene carbonate acetonate, propylene carbonate, and the like. They may be used singly or in combination of two or more. -21 - 201120099 The solid content concentration in the liquid crystal alignment agent of the present invention (the ratio of the total weight of the components other than the solvent of the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) is appropriately selected in consideration of viscosity, volatility, and the like. A range of 1% to 1% by weight. That is, the liquid crystal alignment agent of the present invention is applied to the surface of the substrate as described later, preferably by heating to form a coating film which is a liquid crystal alignment film or a coating film which becomes a liquid crystal alignment film, but has a solid concentration of less than 1 When the weight is %, the film thickness of the coating film is too small to obtain a good liquid crystal alignment film; on the other hand, the solid content concentration exceeds 10% by weight. When the film thickness of the coating film is too large, a good liquid crystal alignment film cannot be obtained, and the viscosity of the liquid crystal alignment agent increases, and the coating property is deteriorated. The range of the particularly preferable solid content concentration varies depending on the method employed in coating the liquid crystal alignment agent on the substrate. For example, when the spin coating method is used, the solid content concentration is particularly preferably in the range of 1.5 to 4.5% by weight. When the printing method is used, the solid content concentration is in the range of 3 to 9 % by weight, whereby the solution viscosity is particularly preferably in the range of 12 to 50 mPa*s. When the inkjet method is used, the solid content concentration is in the range of 1 to 5% by weight, whereby the solution viscosity is particularly preferably in the range of 3 to 15 mPa*s. The temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably from 10 to 50 ° C', more preferably from 20 to 30 ° C. <Liquid Crystal Display Element> The liquid crystal display element of the present invention has a liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention as described above. The liquid crystal display element of the present invention is preferably a VA type liquid crystal display element. -22· 201120099 The liquid crystal display element of the present invention can be produced, for example, by the following steps (丨) and (2). U) First, the liquid crystal alignment agent of the present invention is applied onto a substrate, and then a coating film is formed on the substrate by heating the coated surface. The two substrates on which the patterned transparent conductive film is provided are formed in a pair, and the liquid crystal of the present invention is preferably coated on each of the transparent conductive film forming surfaces by offset printing, spin coating or inkjet printing. The alignment agent is then formed by heating each coated surface to form a coating film. Here, the liquid crystal display element of the present invention is excellent in printability, and therefore, from the viewpoint of maximizing the excellent effects of the present invention, it is preferable to use an offset printing method as a coating method. At this time, the substrate can be made of glass such as float glass "sodium glass"; polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, poly (aliphatic) A transparent substrate made of plastic such as olefin). The transparent conductive film provided on one surface of the substrate may be an ITO film composed of a NES A film (registered trademark of PPG, USA) composed of tin oxide (Sn〇2), or indium oxide-tin oxide (In203-SnO 2 ). Wait. In order to obtain a patterned transparent conductive film, for example, a pattern can be formed by photolithography after forming a pattern-free transparent conductive film, and a method of forming a transparent conductive film using a mask having a desired pattern can be obtained. . When the liquid crystal alignment agent is applied, in order to make the adhesion between the surface of the substrate and the transparent conductive film and the coating film better, a functional decane compound or a functional titanium compound may be previously coated on the surface of the substrate on which the coating film should be formed. Wait for pre-processing. -23- 201120099 After the liquid crystal alignment agent is applied, it is preferably preheated (prebaked) for the purpose of preventing the flow of the coated alignment agent droplets. The prebaking temperature is preferably from 30 to 200 ° C', more preferably from 40 to 150. (:, particularly preferably 40 to 100. (: The prebaking time is preferably 0.25 to 1 minute, more preferably 5 to 5 minutes. Thereafter, the solvent is completely removed) based on the content contained in the polymer. The purpose of the hydrazine imidization unit is to perform a firing (post-baking) step. The firing (post-baking) temperature is preferably 80 to 300 t', more preferably 120 to 250. (:. Post-baking time) Preferably, it is 5 to 200 minutes', more preferably 1 Torr to 1 Torr. Thus, the film thickness of the formed film is preferably 0.001 to Ιμηη, more preferably 0.005 to 0.5 μm. The film formed as described above can be used. It is used as a liquid crystal alignment film as it is, and it can be used after rubbing treatment as needed. (2) Two substrates in which the liquid crystal alignment film is formed as described above are prepared, and liquid crystal cells are produced by disposing liquid crystal between the two substrates arranged in the opposite direction. Here, when the coating film is subjected to the rubbing treatment, the two substrates are disposed to face each other such that the rubbing directions of the respective coating films are at a predetermined angle to each other, for example, perpendicular or antiparallel. The liquid crystal is disposed between the substrates, for example, the following Two methods. The first method It is a method currently known. First, in order to arrange the liquid crystal alignment films in the opposite direction, the two substrates are placed facing each other with a gap (cell gap), and the peripheral portions of the two substrates are bonded together by using a sealant. The liquid crystal cell can be manufactured by injecting the liquid crystal into the cell gap divided by the surface of the substrate and the sealant, and sealing the injection hole. The second method is a method called 〇DF (dropping injection method), in which liquid crystal is formed. a predetermined position on one of the two substrates of the alignment film. 24-201120099 'Applying, for example, an ultraviolet curable sealing material, and then dropping the liquid crystal on the liquid crystal alignment film surface, 'fitting another substrate and aligning the liquid crystal The film is opposed to each other, and then the liquid crystal cell is produced by irradiating ultraviolet light on the entire surface of the substrate to cure the sealing agent. In the case of any method, the liquid crystal cell produced as above is heated to the liquid crystal used. After the temperature to the same temperature, it is slowly cooled to room temperature, and it is desirable to remove the liquid alignment during liquid crystal injection. Then, by bonding the polarizing plate to the outer surface of the liquid crystal cell, In the liquid crystal display device of the present invention, for example, an epoxy resin containing a curing agent and an alumina ball as a spacer can be used. For example, a nematic liquid crystal, a smectic liquid crystal, or the like can be used as the liquid crystal. Among them, nematic liquid crystal having negative dielectric anisotropy is preferably used, and for example, dicyanobenzene liquid crystal, xenon liquid crystal, Schiff base liquid crystal, oxynitride liquid crystal, biphenyl may be used. A liquid crystal, a phenylcyclohexane liquid crystal, etc. As a polarizing plate bonded to the outer surface of a liquid crystal, it is called the extension of the polyvinyl alcohol, and the iodine absorption by the cellulose acetate protective film is called. A polarizing plate composed of a polarizing film of "H film" or a polarizing plate composed of a ruthenium film itself. The liquid crystal alignment film of the present invention is further applicable to a PSA (Polymer Continuous Alignment) type liquid crystal display device. [Examples] Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited by the examples. Each of the polymerizations in the polymerization example -25·201120099 The solution viscosity of the solution and the sulfhydrylation ratio of the polyimine were measured by the following methods. [Solid viscosity of the polymer solution] The solution viscosity (mPa*s) of the polymer was measured by adjusting the polymer concentration to 10% by weight using a predetermined solvent, and measuring at 25 ° C using an E-type rotational viscometer. [rhodium imidization ratio of polyimine] The solution of polyimine is put into pure water, and the obtained precipitate is sufficiently dried under reduced pressure at room temperature, and then dissolved in dimethyl hydrazine. Tetramethyl decane was used as a reference material, and iH-NMR was measured at room temperature. From the obtained 1 H-NMR spectrum, the oxime imidization ratio was determined from the formula represented by the following formula (1).醯 imidization ratio (%) = (1-AVa^oOx 1 00 (1) (In the mathematical formula (1), A1 is the peak area of the proton from the NH group which appears near the chemical shift of 1 Oppm, and A2 is The peak area from other protons, α is the ratio of the number of other protons to the proton of the sulfhydryl group in the precursor of one polymer (polyproline). <Synthesis Example of Compound (Α)> In the synthesis example, the amount required in the following polymerization examples was ensured by repeating the operation as needed. Synthesis Example 1 According to the following scheme 1, a compound (Α-3-1) was synthesized. • 26- 201120099

CsF NO.

CsF 〇ί〇Η2ί~Βγ

N〇2 (A-3-1a) C10H2i

(A-3-1b) SnCI2 C10H21

(A-3-1) Scheme 1 In a 1 L three with a stirrer, a nitrogen inlet tube and a thermometer, 46 g of 2,4-dinitrofluorobenzene, 42 g of fluorinated planer, dimethyl hydrazine and 6 5 g of the pipe trap was stirred at 80 ° C for 4 hours. After the reaction was completed, the reaction mixture was poured into 3 L of water, and 400 mL of a reflux flask was collected by filtration. The precipitation of -27-201120099 was generated. The organic layer obtained by dissolving the precipitate in ethyl acetate was washed with water and dried over magnesium sulfate. The solid was recrystallized from ethanol to obtain crystals of 43 g of the compound (A-3-la). Next, 25 g of the compound (A-3-la) obtained above, 1 mL of dimethyl sulfonium 15 g of cesium fluoride and 22 g were placed in a 300 mL three-necked flask equipped with a reflux tube, a nitrogen introduction tube, and a thermometer. 1-Bromo-n-decane was stirred at 80 ° C for 48 hours to carry out a reaction. After the reaction was completed, 500 ml of ethyl acetate was added to the mixture, and the obtained organic layer was washed with water and dried over magnesium sulfate. This solid was purified by a column using a mixed solvent of hexane and ethyl acetate, and the solvent was removed from the obtained fraction under reduced pressure to obtain 20 g of compound (A - 3 -1 b). Next, 2 ng of the compound (A_3-lb) obtained above, 141 g of tin(II) chloride dihydrate were added to a 500 m L three-necked flask equipped with a reflux tube, a nitrogen introduction tube, and a thermometer, and 750 mL of acetic acid was added. The ethyl ester was refluxed for 4.5 hours to carry out the reaction. After completion of the reaction, 300 mL of a 2 mol/L potassium fluoride aqueous solution was added to the reaction mixture, and the precipitated tin salt was removed by filtration. The obtained organic layer was washed successively with a 2 m 〇l/L aqueous potassium fluoride solution and water, and the solvent was removed under reduced pressure to give 6.7 g of Compound (A - 3 -1). Synthesis Example 2 According to the following Scheme 2, the compound (a-4_1) was synthesized. •28- 201120099

(A-3-1a)

Ci〇H2i*CO Cl

(Α-Φ1) In the same manner as in the above Synthesis Example 1, 42 g of a compound crystal was obtained. 2 L of 3 [25 g of the above compound (A-3-la), 100 mL of tetrahydrofuran with a nitrogen introduction tube and a thermometer and ice-cooled. At this time, a solution of 20 g of up to 40 mL of tetrahydrofuran was added dropwise over 30 minutes, and the reaction was carried out at room temperature. After completion of the reaction, ethyl acetate was added to the reaction mixture, and the obtained organic layer was washed with water, and the solvent was evaporated under reduced pressure over magnesium sulfate. ϋ (A-3-1 a) in the flask, add 11 1 g of triethylamine, and dissolve in eleven hydrazine chloride for 2 hours, add to OOxnL acetic acid, and then crystallize to obtain -29- 201120099. Next, in a three-necked flask equipped with a reflux tube, a nitrogen introduction tube, and a temperature, 21 g of the compound (A·" tin(II) chloride dihydrate described above was added to 750 mL of ethyl acetate to carry out a reaction. After completion, a 2 m ol/L potassium fluoride aqueous solution was added to the reaction mixture, and the precipitated organic layer was removed by filtration, followed by 2 m ο 1 /1 potassium fluoride aqueous solution and solvent under reduced pressure. , 7 2 g of compound (a - 4 -1 ) was synthesized. Synthesis Example 3 According to the following scheme 3 'synthesis of the compound (500 mM L l · -1 a of Α_5_υ❶) and 1 1 3 g of I flow for 4.5 hours 3 0 m L of I tin salt. After washing with water, -30- 201120099

HO

(A-5-1a)

N〇2

NaHC03

HO

—N02 (A-5-1b) K2C03 C5HirBr

(A-5-1) Scheme 3 In a 500 mL three-necked flask equipped with a stirrer, a nitrogen inlet tube, and a thermometer, 5.8 g of the compound (A-5-la) and 5.1 g of 2,4-dinitro group were mixed. Fluorobenzene and 2.1 g of sodium hydrogencarbonate were added, and 300 mL of hydrazine, hydrazine-dimethylacetamide was added thereto, and the mixture was stirred at 20 ° C for 12 hours to carry out a reaction. After completion of the reaction, 600 mL of ethyl acetate was added to the reaction mixture of -31 - 201120099, and the obtained organic layer was washed with water. The solid was purified by column chromatography (stationary phase: grit-developing solvent: chloroform), and the solvent was removed from the obtained residue under reduced pressure. The obtained solid was treated with a mixed solvent of ethanol and tetrahydrofuran. Crystallization 'a yellow crystal of 8.3 g of compound (A-5-lb) was obtained. Next, 8.3 g of the compound (A_5_lb) obtained above, 3.8 g of 1-bromo-n-heptane and 1.0 g of potassium carbonate were mixed in a 5 mL flask equipped with a stirrer, a nitrogen introduction tube and a thermometer. The reaction was carried out by adding 3 mL of N,N-dimethylacetamide to the mixture at 80 ° C for 8 hours. After completion of the reaction, 600 mL of ethyl acetate was added to the reaction mixture, and the obtained organic layer was washed with water, and the solvent was removed under reduced pressure to give a solid. This solid was purified by column chromatography (stationary phase: vermiculite developing solvent: chloroform), and solvent was removed from the obtained fraction under reduced pressure to obtain 8.3 g of a yellow powder compound (A-5-1c). Next, 8.3 g of the compound (A-5-lc) obtained above and 45. g of tin (II) chloride dihydrate were mixed in a 500 mL three-necked flask equipped with a reflux tube, a nitrogen introduction tube, and a thermometer, and 300 mL of acetic acid was added thereto. The ethyl ester was refluxed for 4.5 hours to carry out the reaction. After completion of the reaction, 200 ml of a 2 m ol/L potassium fluoride aqueous solution was added to the reaction mixture, and the precipitated tin salt was removed by filtration. The obtained organic layer was washed successively with a 2 m ol / L aqueous potassium chloride solution and water, and the solvent was removed under reduced pressure to give 1. 8 g of Compound (A-5-1). -32-201120099 Synthesis Example 4 In the same manner as in Synthesis Example 3 except that 5.5 g of 1-bromo-n-decane was used instead of 1-bromo-n-heptane in the above Synthesis Example 3, 2 g of the following formula was obtained. Compound (A-5-2) shown in (A-5-2).

(A-5-2) <Polymerization Example of Specific Polymer> [Polymer Example of Polyimine] Polymerization Example 1 8.3 g of 2,3,5-tricarboxycyclopentyl acetic acid as a tetracarboxylic anhydride The dianhydride (TCA) and 2.5 g of the compound obtained in the above Synthesis Example 1 (A-3-1H with respect to 1 mol of TCA, corresponding to 0.2 mol) and 3.2 g of p-phenylenediamine dissolved in 56 g of diamine The reaction was carried out at 60 ° C for 6 hours in N-methyl-2-pyrrolidone to obtain a solution containing 20% by weight of polyglycine. The solution was added in small portions, and N-methyl-2-pyrrolidone was added to form a solution having a polyglycine concentration of 10% by weight, and the solution viscosity measured at 25 ° C was 82 mPa»s. Next, 130 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 4.4 g of pyridine and 5.7 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system is subjected to solvent replacement with a new N-methyl-2-pyrrolidone (by the solvent replacement operation, the pyridine and acetic anhydride used in the dehydration ring closure reaction are removed to the system. Further, in the same manner as below, a solution containing 20% by weight of a ruthenium iodide polymer (P 1-1) having a ruthenium iodide ratio of 70% was obtained. A small amount of the solution was added to '-33-201120099 N-methyl-2-pyrrolidone to form a solution of the concentration of the ruthenium iodide polymer, and the solution viscosity measured at 25 ° C was 48 mPa.s. . Polymerization Examples 2 to 15 The types and amounts of diamine and tetracarboxylic dianhydride shown in Table 1 were mixed with N-methyl-2-pyrrolidone to dissolve, and the amounts of diamine and tetracarboxylic dianhydride were reacted with respect to the reaction. The total weight of the solution was 20% by weight. At 60 t 6 hours, a solution containing 20% by weight of polyglycolic acid was separately obtained, and these solutions were added in small portions, and N-methyl-2-pyrrolidone was added to form an acid concentration of 1 The solution viscosity of the 〇% by weight solution is measured at 25 ° C and is shown in Table 1. Next, 'N- y-pyrrolidone was added to each of the obtained polyaminic acid solutions so that the concentration of poly-proline was 7 wt%, and the number of valinate units per mol of each poly-proline was added. The amounts are pyridine and acetic anhydride, respectively, and dehydration should be carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl. ketone solvent to obtain a solution containing 20% by weight of each of poly(PI-2) to (PI-15). A small amount of these solutions were added, and N_pyrrolidone was added to form a solution having a polyamidene concentration of 1% by weight, which was shown in the form of the measured solution viscosity. <Synthesis of Other Polymers> [Polymerization Examples of Other Polylysine] Polymerization Examples 1 6 and 1 7 The types and amounts of diamines and tetradecanoic acid dianhydrides shown in Table 2 were mixed in N-methyl group- 2 - Pyrrole H ketal was dissolved so that the amount of diamine and tetradecanoic acid dilute was 20% by weight based on the total weight of the reaction solution, and the reaction was carried out at 60 Ό 10 in total weight. Each of the polyamines was similarly Yin- 2 - relative to the closed-loop anti-2-pyrrolidinomethyl-2-2 5 ° C shown in I, and the total weight was added to react -34-201120099 6 hours, A solution each containing 20% by weight of poly B (PA-1 7) was obtained. The solution viscosity of each of these solutions, pyrrolidone, and polypyridic acid concentration of 1 〇% by weight was similarly combined and shown in Table 2 [polymerization example of other polyimine] Polymerization Example _ 18~ 21 ^ The kinds and amounts of the diamines and tetracarboxylic acids shown in Table 2 were dissolved in N-methyl-2-pyrrolidone, and the total weight of the diamine was 20 reactions with respect to the total weight of the reaction solution. In the hour, a solution containing 20% by weight of each of each of the polyethers was separately obtained, and a solution of 10% by weight of N-methyl-2-® glutamic acid was added, and the samples were combined at 25 ° C in Table 2. Said. Next, in each of the obtained polyaminic acid solutions, the pyrrolidone is pyridine and acetic anhydride in an amount such that the concentration of the poly-proline is 7 mol of the number of valeric acid units per polyglycolic acid. , 4 should be performed at 1 1 〇 °C. After the dehydration ring closure reaction, the solvent in the system was replaced with a fresh hexanone solvent to obtain a solution each containing 20 weights (PI-18) to (PI-21). A small amount of these Soluben-2-pyrrolidone was obtained, and the solution viscosity measured at a concentration of 10% by weight of polyimine was similarly combined with the I-amino acid (PA-1) and the addition of N- in Table 2. Methyl-2-solution, mixed with acid dianhydride at 25 ° C, and added to the tetracarboxylic dianhydride [% by weight, a solution of proline at 60 ° C. , the hexanone, the viscosity of the solution formed by the addition of N-methyl-2-t%, added to the polyhydric ring-closing 5 N -methyl-2-pyrrole amount. The ruthenium is a good solution, and a solution of N-methyl% is added, which is represented by 2 5 . -35- 201120099

Polyimine name PI-1 ΡΙ-2 ΡΙ-3 ΡΙ-4 ΡΙ-5 ΡΙ-6 ΡΙ-7 ΡΙ-8 PI-9 PI-10 PI-11 PI-12 PI-13 PI-14 PI-15 Solution viscosity (mPa.s) ν〇V5 ο 00 On v〇fN o Ό VO % 醯 imidization rate (%) 〇00 νο Ο Ον Ο C\ o fN oo v〇On VO \n ro Dehydration closed loop reaction B Anhydride (Morby) wi Ο ρ v*> 1/Ί 〇p pyridine (Morby) in ^Η «ο ρ ο >〇i〇pp Polyacrylic acid solution viscosity (mPas) (N 00 〇\ 00 CN Os Ο Ό 00 00 Os Ο fN 〇\ y-^ o 00 00 v〇On g oo Tetracarboxylic dianhydride _ (Morby) P ο ρ ρ ρ ^Η ο ρ ο ^Η Ο po 00 d (N d On ddoo 3 m 〇6 fN οό ΟΟ οό <Ν 〇6 \〇οό ν〇ΟΟ Ον 卜^ 〇\ (Ν ΟΟ <N t» o oo 卜'O Vi cn 卜d oo 〇 \ vd W *TMΗ rH ι-Η »—Η i—H cs II<N According to other diamines _ (Morbi) oo ο 00 ο σ ο 00 ο σ ο Ο Ο Ο 00 00 00 00 00 ο OO d 〇〇o ϊ-Η oo oo oo O r—N oo 3 (Ν ... Ν Ν ΓΟ CN ... CC ... ΟΟ ΓΟ ro CN ΓΛ (N rn r n ΓΛ ΓΛ rS cs cn ΓΟ cn r-; Category Τ3 -ώ *ό 1-Η Τ3 τΪ3 Τ3 TJ TJ Τ) T3 inch T5 -ό T Ό r-^ *T3 inch T3 T3 inch T3 *— TJ f—^ -ύ II Compound (A) _ (Morbi) (Ν rs rs ο ο (Ν Ο ο fN Ο (Ν dd r-^ moo 3 (Ν' (Ν ··Ο (Ν νο ν〇Ο rn ο ( Ν i〇CN »0 卜(N «η m flsIS i1rm1 waist 1 Α-3-1 Α-4-1 Α-5-1 Α-5-1 Α-5-2 Α-5-2 Α-5- 2 Α-5-2 Α-3-1 I A-5-1 A-5-2 A-3-1 A-5-2 A-3-1 A-5-1 Polymerization example (Ν 寸 〇 ν〇 00 σ o o (N -9ε- 201120099 ^4π^^} κμ^ The name of the polymer ΡΑ-16 ΡΑ-17 PI-18 PI-19 PI-20 PI-21 Polyimine solution viscosity (mPas) 1 I On v〇CN in in r- 醯imination rate (%) 1 1 C\ v〇»n 00 Ό dehydration ring closure reaction acetic anhydride (mole ratio) 1 1 o 1-H pyridine (mole ratio) _ί 1 1 1-H o in Polyacrylic acid solution viscosity (mPa.s) (Ν <Ν o CN 〇\ Os Tetracarboxylic dianhydride*1 (Morby) 〇ΓΟ ο 0.75 0.25 o 1-H Op 1-H o 3 m uS ο CS inch 00 Γ ΟΟ s (N 00 type_1 (Ν Τ-Η rn TH other diamine _ (mole ) o o o On o TH 00 d CN 〇OO o (N 〇00 o CN o 3 00 00 VD oo ro <N ro t- CN CN ro r- CN (N ΓΛ r— (N type (Ν 1 Ό m 1 T3 in T3 ί—H X5 inch T3 polymerization example \〇 oo σ\ _ζε- 201120099 In addition, the abbreviations of the diamine and tetracarboxylic dianhydride in Tables 1 and 2 respectively have the following meanings. [Diamine] A-3-1: Compound (α-π) A-4-1 synthesized in the above Synthesis Example 1: Compound (A-4-1) synthesized in the above Synthesis Example 2 A-5-1 : Synthesis as described above Compound 3 synthesized in Example 3 (A-5-1) A-5-2: Compound synthesized in the above Synthesis Example 4 (Α·5_2) d-1 : p-phenylenediamine d-2 : 4,4'-diamino group Diphenylmethane <1-3:2,2'-dimethyl-4,4'-diaminobiphenyl d-4: 3,5-diaminobenzoic acid cholesteryl ester d-5: 2,4-diamino-(n-octadecyloxy)benzene [tetracarboxylic dianhydride] t-1: 2,3,5-tricarboxycyclopentyl acetic acid dianhydride t-2 : 1,2, 3,4·cyclobutane tetracarboxylic dianhydride t-3 : pyromellitic dianhydride <preparation and evaluation of liquid crystal alignment agent> Example 1 [Preparation of liquid crystal alignment agent for printability evaluation and liquid crystal display element (Preparation of liquid crystal alignment agent) (1) Preparation of liquid crystal alignment agent for evaluation of printing property In a solution containing 100 parts by weight of the polyacid (p 1-1) obtained in the above Polymerization Example 1, 10 parts by weight was added as Epoxy-Mili CJ-38-201120099 义;^,:^,:^'-tetraepoxypropyl-4,4'-diaminodiphenylmethane' then N-methyl- 2-pyrrolidone (NMP) and butyl race Su (BC) 'solvent composition NMP: BC = 60:40 (weight ratio), solid content concentration of 6.5% by weight of the solution. This solution was filtered using a filter having a pore size of 1 μm to prepare a liquid crystal alignment agent (Ρ-1) for evaluation of printability. (2) Preparation of liquid crystal alignment agent for liquid crystal display element production In the preparation of the liquid crystal alignment agent for evaluation of the above-mentioned printability, liquid crystal alignment was prepared in the same manner as described above except that the solid content concentration of the solution before filtration was 4.0% by weight. Agent (S-1). [Evaluation of Liquid Crystal Aligning Agent] The two kinds of the alignment agents prepared above were each evaluated by the following methods. The evaluation results are shown in Table 3. (1) Evaluation of printability Using a liquid crystal alignment film printer (manufactured by Japan Photo Printing Co., Ltd., Angstromer S 4 0 L - 5 3 2 ), a droplet of a liquid crystal alignment agent on an anil roller (ani 1 ο x roll) The liquid crystal alignment agent (P-1) for the printability evaluation prepared above was applied to a transparent electrode of a glass substrate having a transparent electrode composed of an IT tantalum film under the conditions of a drop of 20 drops (about 0.2 g). On the surface. Here, the amount of the liquid crystal alignment agent to be dropped is smaller than that of the same type of printing machine (30 drops to about 3 g), which is a stricter printing condition. The substrate coated with the liquid crystal alignment agent was heated at 8 Torr for 1 minute (prebaking), and after removing the solvent, it was heated at 1 80 for 1 Torr (post-39-201120099 baking) to form a coating film having a film thickness of 80 nm. The coating film was observed under a microscope with a magnification of 20 times, and the presence or absence of dents and coating unevenness was observed. When neither of these was observed, the coating property was evaluated as "good", and when any one was observed, it was evaluated as coating. Sex is not good. In addition, the film thickness of the center of the substrate and the film thickness at a position 15 mm from the outer end portion of the coating film were measured using a stylus type film thickness meter (manufactured by KLA TENCOR Co., Ltd.). The difference in film thickness between the two. When the film thickness difference is 30 A or less, the film thickness uniformity is said to be good. (2) Production of Liquid Crystal Display Element The liquid crystal alignment agent (S-1) prepared above was applied onto a transparent conductive film made of an ITO film on one surface of a glass substrate having a thickness of 1 mm using a spin coater, and heated. The plate was prebaked at 80 ° C for 1 minute, and then heated at 230 ° C for 30 minutes to form a coating film (liquid crystal alignment film) having a film thickness of 80 nm. This operation was repeated to fabricate two (a pair of) substrates having a liquid crystal alignment film. The respective outer edges of the liquid crystal alignment films of the pair of substrates are coated with an epoxy resin binder of alumina particles having a diameter of 3·5 μm, and then laminated and crimped so that the liquid crystal alignment films are opposed to each other, and the adhesive is applied. hardening. The receiver's sealed liquid crystal injection port from the liquid crystal injection port between the substrates and filled with negative liquid crystal (MLC-6608 manufactured by Merck), and sealed on both sides of the substrate. A polarizing plate is used to manufacture a vertical alignment type liquid crystal display element. -40-201120099 (3) Evaluation of the vertical alignment property When the voltage is not applied to the liquid crystal display element manufactured as described above and when an AC voltage (peak-peak) of 8 V is applied, the liquid crystal display element is visually observed from the direction perpendicular to the liquid crystal display element. It was observed that light leakage or the like was poorly displayed, and when no voltage was applied, it was displayed as uniform black, and when a voltage was applied, it was uniformly white, and the vertical alignment was considered to be "good". (4) Evaluation of voltage holding ratio The liquid crystal display element manufactured above was subjected to application of a voltage of 5 V at an application temperature of 60 μsec and an interval of 167 ms at an ambient temperature of 60 ° C. The voltage holding ratio after 1 67 ms. The measuring device used the trade name "VHR-1" manufactured by Toyo Technica Co., Ltd. (5) Evaluation of image sticking characteristics Two liquid crystal display elements manufactured in the same manner as described above were applied to each of them at room temperature, and an IV voltage was applied to one of them, and the other was applied with a DC voltage of 5 V for 24 hours. Thereafter, when the applied voltage of the liquid crystal display element is 2.5 V, the luminances of the two elements are respectively expressed in 256 steps, and the luminance difference (level difference) at this time is considered. When the 値 is 15 or less, the afterimage characteristics are good. Examples 2 to 30 and Comparative Examples 1 to 1 1 Except that the polymer-containing solution shown in Table 3 was used as the polymer-containing solution, and the types and amounts of the epoxy compounds shown in Table 3 were used, and Example 1 was used. A liquid crystal alignment agent was prepared in the same manner and evaluated. The evaluation results are shown in Table 3. -41-201120099 Further, in each of Examples 24 to 28, each of the two polymer-containing solutions was used. Table 3. Evaluation results Liquid crystal alignment agent liquid crystal display element polymer β parts by weight) Epoxy compound (parts by weight) E 卩 brushing vertical alignment voltage retention ratio (%) Image retention level difference coating film thickness uniformity (A Example 1 PI-1 (100) Gl (10) Good 19 Good 99 10 Example 2 ΡΙ-2(100) Gl(lO) Good 8 Good 99 13 Example 3 ΡΙ-3Π00) Gl(10) Good 10 Good 99 12 Example 4 ΡΙ-4(100) Gl(10) Good 18 Good 99 14 Example 5 ΡΙ-4(100) G-2(10) Good 18 Good 99 15 Example 6 ΡΙ-5(100) Gl (10) Good Π Good 99 12 Example 7 ΡΙ-5(100) G-2(10) Good 12 Good 99 11 Example 8 ΡΙ-6(100) Gl(10) Good 20 Good 99 14 Example 9 ΡΙ-6(100) G-2(10) Good 21 Good 99 10 Example 10 ΡΙ-7(100) Gl(10) Good 22 Good 99 10 Example 11 ΡΙ-7(100) G-2(10) Good 18 Good 99 11 Example 12 ΡΙ-8(100) Good 19 Good 98 9 Example 13 ΡΙ-8(100) Gl(3) Good 18 Good 99 11 Example 14 ΡΙ-8(100) Gl(10) Good 12 Good 99 12 Example 15 ΡΙ-8(100) G-2 Good 11 Good 99 13 Example 16 ΡΙ-8(100) G-2(10) Good 15 Good 99 12 Example 17 ΡΙ-9(100) Gl(10) Good 22 Good 99 10 Example 18 ΡΙ-ΙΟ( ΙΟΟ) Gl(10) Good 20 Good 99 11 Example 19 ΡΙ-11(100) Good 26 Good 98 10 Example 20 ΡΙ-11(100) Gl(10) Good 27 Good 99 14 -42- 201120099 Table 3 · Evaluation result (continued) Liquid crystal alignment agent liquid crystal display element f epoxidation printing vertical polymer film thickness uniform alignment voltage retention residual weight (parts by weight) (parts by weight) Coating property (A) Property rate (%) Sex-level difference Example 21 ΡΙ-12(100) G-2(10) Good 19 Good 99 14 Example 22 ΡΙ-13(100) Gl(10) Good 22 Good 99 12 Example 23 PI-13(100) G-2 (10) Good 17 Good 99 11 Example 24 PI-11(80)+PA- 16(20) Gl(10) Good 18 Good 99 10 Example 25 PI-11(50)+PA- 17( 50) Gl(10) Good 23 Good 99 9 Example 26 PI-13(80)+PA- 16(20) - Good 27 Good 98 9 Example TJ PI-13(80)+PA- 16(20) G -2(10) Good 15 Good 99 11 Example 28 ΡΙ· 13(60)+ΡΑ- 17(40) G-2(10) Good 25 Good 98 9 Example 29 PI-14(100) G-2(10) Good 19 Good 99 16 Example 30 PI-15(100 G-2(10) Good 20 Good 99 20 Comparative Example 1 PI-18(100) - Good 10 Bad 96 22 Comparative Example 2 PI-18(100) Gl(10) Good 17 Good 97 33 Comparative Example 3 PI -18(100) G-2(10) Good 18 Good 97 30 Comparative Example 4 PI-19(100) - Good 10 Bad 97 21 Comparative Example 5 PI-19(100) Gl(10) Good 19 Good 97 29 Comparative Example ό PI-19(100) G-2(10) Good 21 Good 97 27 Comparative Example 7 PI-20(100) - Good 15 Bad 96 37 Comparative Example 8 PI-20(100) Gl(10) Good 24 Good 97 40 Comparative Example 9 PI-20(100) G-2(10) Good 25 Good 98 47 Comparative Example 10 PI-21(100) - Bad 42 Good 97 33 Comparative Example 11 PI-21(100) G -2 (10) Bad 49 Good 99 46 -43- 201120099 In Table 3, the number of the polymer in the back bracket is the amount (parts by weight) of the polymer contained in the polymer solution used. The number of oximes in the parentheses after the epoxy compound is the proportion (parts by weight) of each epoxy compound used. Further, the abbreviations of the 'epoxy compounds' are as follows. Gl: N,N,N,'N'-tetraepoxypropyl-4,4'-diaminodiphenylmethane G-2 : N,N,N,'N'-tetraepoxypropyl- m-Xylylenediamine [Simple description of the diagram] None. [Main component symbol description] 4nt pick 0 -44-

Claims (1)

201120099 VII. Patent application scope: 1. A liquid crystal alignment agent characterized in that it contains at least one polymer selected from the group consisting of polylysine and polyimine formed by dehydration of the polyamic acid. Wherein the polyamic acid is obtained by reacting a tetracarboxylic dianhydride with a diamine containing a compound represented by the following formula (A), In the formula (A), R is an organic group having a fluorene skeleton having a carbon number of 17 to 30, or an alkyl group having a carbon number of 1 or more which may be substituted by a halogen atom, and X1 and X11 are each a single bond, *- 0-, *-CO-, *-CO〇· or *-OCO·, in the above, the connection key with "*,' is the R side, R1 is a phenyl or a cyclohexyl group; xni is a single bond or -co-, η is an integer of 0 to 2; wherein each of R1 and each of X11 in the presence of a plurality of R1 and X11 may be the same or different. 2. The liquid crystal alignment agent of claim 1, wherein X111 is a single bond. The liquid crystal alignment agent of claim 1 or 2, wherein the above tetracarboxylic dianhydride is four containing 2,3,5-tricarboxycyclopentyl acetic acid dianhydride. A liquid crystal alignment film, which is formed by a liquid crystal alignment agent according to any one of claims 1 to 3. -45- 201120099 5 - Liquid crystal display element, The liquid crystal alignment agent having any one of the narrowest circumferences of the first to third embodiments forms a poly-proline acid obtained by reacting a tetracarboxylic dianhydride with a diamine of a coating compound. 7. A polyimine, which is a polyamic acid obtained by reacting a tetracarboxylic dianhydride with a diamine of a compound. 8. A compound represented by the above formula (Α). Liquid crystal alignment film. Contains the above formula (Α) containing the above formula (Α) 7^ Dehydration closed and formed -46- 201120099 IV. Designated representative map: (1) The representative representative of the case is: No. (2) The simple description of the symbol of the representative figure: None 0. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: