TWI356934B - Liquid crystal alignment agent and liquid crystal - Google Patents

Description

1356934 浐 < IX. Description of the Invention: [Technical Field] 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, the present invention relates to a liquid crystal alignment agent which is excellent in storage stability and which is capable of forming a liquid crystal alignment film which is excellent in coatability and which gives an excellent alignment property to a liquid crystal display element. [Prior Art] At present, as a liquid crystal display element, there is known a ΤΝ-type liquid crystal display element having a so-called ΤΝ-type (twisted nematic) liquid crystal cell which forms polylysine on a surface of a substrate on which a transparent conductive film is provided. A liquid crystal alignment film such as a quinone imine is used as a substrate of a liquid crystal display device, and two substrates are arranged to face each other, and a nematic liquid crystal layer having positive dielectric anisotropy is formed in the gap to form a sandwich structure, liquid crystal molecules. The long axis is continuously twisted by 90 degrees from one substrate to the other. Further, an STN (Super Torsional Nematic) type liquid crystal display element having higher contrast and less viewing angle dependency than a ΤΝ-type liquid crystal display element is being developed. The S-type liquid crystal display element is used in a nematic liquid crystal in which an optically active substance is used as a liquid crystal, and a double layer is produced by causing a long axis of liquid crystal molecules to be continuously twisted by 180 degrees or more between substrates. Refraction effect. Further, a horizontal electric field type liquid crystal display element is known in which two electrodes for driving liquid crystals are provided in a comb shape on one side substrate, and an electric field parallel to the substrate surface is generated to control liquid crystal molecules. The alignment of the liquid crystals in these liquid crystal display elements is usually exhibited by a liquid crystal alignment film subjected to a rubbing treatment. As a liquid crystal display element other than the above, a liquid crystal display element having a vertical alignment 1356934 vertical liquid crystal cell in which liquid crystal molecules having negative dielectric anisotropy is vertically disposed on the substrate is known. In the element, the control of the liquid crystal alignment is usually carried out by forming a alignment film from a liquid crystal alignment agent of a polymer such as an amine acid or a soluble polyimine. [Inventive] A first object of the present invention is to provide a liquid crystal alignment agent, which is produced. A liquid crystal display element having a liquid crystal alignment film which can surely generate liquid crystal molecular alignment energy and has excellent crystal alignment. A second object of the present invention is to provide a liquid crystal alignment agent which is a liquid crystal display element having a liquid crystal alignment film having excellent coatability. Other objects and advantages of the present invention will be apparent from the following description. The above objects and advantages of the present invention, first, are achieved by a liquid agent characterized by comprising a polyimine having both repeating units of the following formulas (A) and (B), and the following formula (A) and B) The total amount of each unit represented is 50 mol or more of all repeating units in the polyimine, and the liquid crystal cell is oriented. In a liquid crystal containing polyfluorene, it is able to pass a different liquid through the liquid, which can be seen from the crystal to the repeat of the self-representation % or 1356934

(wherein R is a tetravalent organic group p. The above objects and advantages of the present invention, and the second 'through liquid crystal display element realization' is characterized by having a liquid crystal alignment film produced by the liquid crystal alignment agent of the present invention. When the liquid crystal alignment agent of the present invention is used as a liquid crystal alignment film, a liquid crystal alignment film which is highly reliable and suitable for use in a liquid crystal display element can be obtained without depending on process conditions such as polishing conditions. The liquid crystal alignment element of the liquid crystal alignment film formed is excellent in liquid crystal alignment and can be effectively used in various devices', for example, for desktop computers, watches, desk clocks, coefficient display screens, mobile phones, word processors, personal computers, and liquid crystals. The present invention will be described in detail below. The polyimine used in the present invention can be reacted by reacting a tetracarboxylic dianhydride with a diamine compound in an organic solvent. The obtained polylysine is obtained by dehydration and ring closure. These polyimines may also be used in combination of two or more.

<Polyuric acid and polyimine]> [Tetracarboxylic dianhydride] The tetracarboxylic anhydride used in the synthesis of polylysine as a polyimine precursor may, for example, be butane tetracarboxylic acid Anhydride, 1,2,3,4-cyclobutanin dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3 yl-1,2 , 3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanecarboxylic dianhydride, 1,2,3,4-tetramethyl-1, 2,3,4-cyclobutane tetracarboxylic acid di 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid di 3,3' 4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentanoic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3, 4,5 furan tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxafuryl)-naphthalene [l,2-c]- Furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2 -(:]-furan-1 ketone, 1,3,33,4,5,91)-hexahydro-5-ethyl-5-(tetrahydro-2,5-dioxo-3.yl)- Naphthalene [1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7--5-(tetrahydro-2,5-dioxo- 3-furyl)-naphthalene [l,2-c]-furan-1,3-di 1,3 ,33,4,5,91)-hexahydro-7-ethyl-5-(tetrahydro-2,5-dioxo-3-furohnaphthalene[1,2-c]-furan-1,3 -dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-hydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-c]-furan -1,3-di 1,3,33,4,5,91?-hexahydro-8-ethyl-5-(tetrahydro-2,5-dioxo-3-furanylnaphthalene [1,2 -c]-furan-1,3-dione, 1,3,33,4,5,91)-hexahydro-5,8-di-5-(tetrahydro-2,5-dioxo-3 -furyl)-naphthalene [1,2-c]-furan-1,3-di-5-(2,5-dioxotetrahydrofuranmethylene)-3-methyl-3-cyclohexene-1, 2_ acid dianhydride, bicyclo[2,2,2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3,bicyclo[3.2.1]octane-2,4-di Keto-6-spiro-3'-(tetrahydrofuran-2',5' carboxylic acid: tetracarboxylic-dimethanetetrahydride, anhydride, vinegar-tetrahydro-3--5-methyl, 3-di-furan Aliphatic and alicyclic groups such as the compound represented by the following formulas (I) and (II); Tetracarboxylic dianhydride,

(wherein R1 and R3 represent a divalent organic group having an aromatic ring, R2 and R4 represent a hydrogen atom or an alkyl group, and a plurality of R2 and R4 present may be the same or different); pyromellitic dianhydride , 3,3',4,4'-benzophenonetetracarboxylic dianhydride '3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 1,4,5,8-naphthalene Carboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4' - Dimethyldiphenylnonanetetracarboxylic dianhydride, 3,3',4,4'-tetraphenylnonanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4, 4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsebacic anhydride, 4,4 '-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-homofluoroisopropylidene dicarboxylic acid di 1359934 anhydride, 3,3',4 , 4'-biphenyltetracarboxylic dianhydride, di(decanoic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphosphonate) dianhydride, m-phenylene-di(three) Phenyl phthalic acid) dianhydride, di(triphenylphosphonic acid)-4 , 4'-diphenyl ether dianhydride, bis(triphenylphosphonic acid)-4,4'-diphenylmethane dianhydride, ethylene glycol bis(hydrogen trimellitate), propylene glycol-di (dehydration) Trimellitic acid ester), 1,4-butanediol-di(hydroper trimellitate), 1,6-hexanediol-di(hydroper trimellitate), 1,8-octanediol - aryl (dehydrated trimellitate), 2,2-bis(4-hydroxyphenyl)propane-di(hydrogen trimellitate), a compound represented by the following formulas (1) to (4), etc. Group tetracarboxylic dianhydride. They may be used alone or in combination of two or more.

^CH3, CH3 (2)

-10- 1356934 ο

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Among them, preferred is φ -1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3 -di: tetramethyl-1,2,3,4-ring: dianhydride, 1, 2,4,5-cyclohexanecarboxylic acid dianhydride, 2,3,5-triferrane-2 -acetic acid di 1,3,3a,4,5,9b-hexanitro[1,2-c]-furan -1,3-diφ-2,5-dioxo-3-indole l,3,3a,4,5,9b-hexahydro-naphthalene[1,2 - c ]-furan-1, 3 hydrogen -2,5-dioxo-3-l,3,3a,4,5,9b-hexahydro-naphthalene [l,2-c]-furan-1,3 hydrogen-2,5-dioxo- 3-l,3,3a,4,5,9b-hexahydro-naphthalene [l,2-c]-furan·1,3 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1, 2-Dimethyldecanoic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetra-amp;-1,2,3,4-cyclobutane tetracarboxylic dianhydride 1,2,3,4-"alkane tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid alkyltetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyl Tetra-L-carboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarboxylic anhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, -5-(tetrahydro-2,5-dioxo -3-furanyl)-naphthone, 1,3,3&,4,5,91)-hexahydro-5-methyl-5-(tetrahydro:anyl)-naphthalene [l,2-c] -furan-1,3-diketone, 5-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-dione, 1,3,3 3,4,5,91)-hexahydro-7-methyl-5-(tetrafuranyl)-naphthalene [l,2-c]-furan-1,3-dione, 7-ethyl-5- (tetrahydro-2,5-dioxo-3-furoyl)-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrafuranyl)· Naphthalene [1,2-c]-furan-1,3-dione, 8-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-dione, l,3 ,3a,4,5,9b-hexahydro-5,8-dimethyl-11 - 1356934 -5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2- c]-furan-1,3-dione, 5-(2,5-dioxotetrahydrofuranmethylene)-3·methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, double ring [2,2,2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride '3-oxabicyclo[3.2.1]octane-2,4-dione-6- a compound represented by the following formulas (5) to (7) and a compound represented by the above formula (II) in the compound represented by the above formula (I), spiro-3'-(tetrahydrofuran-2·,5'-dione) The compound represented by the following formula (8), etc., is particularly preferably 2,3,5-tricarboxycyclopentyl acetic acid dianhydride. ό OL. ό

c\/ H

o""o

ΟΜΗΛ /1UO / 6 5 〇= -12- 1356934

[Diamine compound] The diamine compound used in the synthesis of the polyimine of the above polyimine is 4,4'-diamino-2,2'-dimethylbiphenyl, 4 , 4'-diamino-2,3'-dimethylbiphenyl, 4,4'-diamino-3,3'-dimethylbiphenyl, 1,2-cyclohexanedi(methylamine ) '1,3-cyclohexanedi(methylamine) and 1,4-cyclohexanedi(methylamine). The ratio of use is such that the total amount of the repeating units represented by the above formulas (A) and (B) is 50 mol% or more with respect to all the repeating units in the polymer. The diamine compound may be used alone or in combination of two or more. Further, 'optionally, the total amount of the repeating unit represented by each of the above formulas (A) and (B) may be used in combination with the above diamine compound in a ratio of 50 mol% or less of all repeating units in the polymer. Examples of the diamine compound include p-phenylenediamine, m-phenylenediamine, 4,4,-diaminobenzophenone, 4,4'-diaminodiphenylethane, 4, 4, -diaminodiphenyl sulfide, 4,4'-diaminodiphenyl maple, 4,4'-diaminobenzamide, 4,4,-diamino-phenyl ether, 1,5 -diaminonaphthalene, 5-amino-1-(4,-aminophenyl)-1,3,3-trimethyl-free, 6-amino-indole-(4'-aminophenyl) -1,3,3 -trimethylmethane, 3,4-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4,-diaminobenzophenone, 4 , 4'-diaminobenzophenone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy) Phenyl]hexafluoropropane, 2,2-13- 1356934 bis[4-aminophenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]indole, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroquinone, 2,7-diaminopurine, 9,9-di ( 4-aminophenyl)anthracene, 4,4'-methylene-bis(2-chloroaniline), 2,2',5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 1,4,4'-(p-phenylene isopropylidene)bis(aniline), 4,4'-(m-phenylene isopropylidene)bis(aniline), 2,2'-di [4-(4-Amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, An aromatic diamine such as 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl; 1,3-propanediamine, butanediamine, pentamethylenediamine , hexamethylenediamine, heptanediamine, octanediamine, decanediamine, 4,4-diaminoheptyldiamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrobicyclo Pentadiene diamine, hexahydro-4,7-methyleneindanylene dimethylene diamine, tricyclo[6.2.1.02,7]-undecene dimethyldiamine, 4,4' -methylene bis(cyclohexylamine), 2, Aliphatic and alicyclic diamines such as 5-norbornane bis(methylamine), 2,6-norbornane (methylamine), 2,7-norbornane (methylamine); 2,3-diamine Pyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyridinium, 5, 6-Diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-tri-trap, 1,4-bis(3-aminopropyl) Piper, 2,4-diamino-6-isopropoxy-1,3,5-tri-trap, 2,4-diamino-6-methoxy-1,3,5-three tillage 2,4-Diamino-6-phenyl-1,3,5-tri-trap, 2,4-diamino-6-methyl-s-trin, 2,4-diamino-1 , 3,5-three tillage, 4,6-diamino-2-vinyl-s-tripper, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5 ,6-Diamino-1,3-dimethyluracil, 3,5-diamino-1,2,4- -14- 1356934 triazole, 6,9-diamino-2-ethoxy Acridine lactate, 3,8-diamino-6-phenylphenanthridine, 1,4-diaminopiperazine, 3,6-diaminoacridine, bis(4-aminophenyl) a phenylamine and a compound represented by the following formulas (III) to (IV) having a two-stage amine group in the molecule and a nitrogen other than the amine group of the same Amine diamine,

(wherein R5 represents a monovalent organic group having a cyclic structure containing a nitrogen atom selected from the group consisting of pyridine, pyrimidine, triple trap, piperidine and piperazine, and X represents a divalent organic group),

(wherein, X represents a divalent organic group having a cyclic structure containing a nitrogen atom selected from the group consisting of pyridine, pyrimidine, tri-till, piperidine, and pipe trap, and R6 represents a divalent organic group, and a plurality of X present may be The same may be different); a monosubstituted phenylenediamine represented by the following formula (V); a diamine organophosphonane represented by the following formula (VI); -15-(V) 1356934

H2N

Rf—R8 (wherein R7 represents a divalent organic group selected from the group consisting of -〇-, -C〇0_, _〇C〇-, -NHCO-, -CONH-, and -CO-, and R8 represents a steroid selected from the group consisting of steroids a monovalent organic group of a skeleton, a trifluoromethyl group, and a fluorine group; or an alkyl group having 6 to 30 carbon atoms),

(wherein R9 represents a hydrocarbon group having 1 to 12 carbon atoms, and a plurality of Rs present may be the same or different, p is an integer of 1 to 3, and q is an integer of i to 20); (9) A compound represented by (21) or the like. These diamine compounds may be used singly or in combination of two or more. Yan /CH3 H3C CH(CH2)3CH. i ^CH3

-16 - 1356934

COO~CH2CH2—^ H2N-I〇LnH2 N (14) η2ν-〇^ν^Χ°Η2^~^ν~〇·νΗ2 (15 >

CH3 H3C CH (CH2)3CH: coo- -CH3 CH3 (16) ίΗ3 /CH3

H3C CH(CH2)3ChCT u , CH3 H3C Γ ^ (17) coo

A H2N-k^>-NH2 -17- 1356934

(wherein y is an integer of 2 to 12' z is an integer of 1 to 5). [Synthesis of Polylysine] The yield of the tetracarboxylic dianhydride and the diamine supplied to the polyaminic acid synthesis reaction is preferably one based on the amine group of one equivalent of the diamine, and the tetracarboxylic dianhydride group is The reaction of 0.2 to 2 equivalents, more preferably 0.3 to 1.2 equivalents of t-polyglycine, is preferably -20 ° C, more preferably 0 to 00 ° C in an organic solvent. Go on. The organic solvent is not particularly limited as long as it can dissolve the synthesized polyamic acid. For example, 1-methyl-2-pyrrolidone, dimethylacetamide 'N,N-dimethylformamide, dimethyl hydrazine, r. ester, tetramethyl urea, hexamethylphosphoric acid An aprotic polar agent such as tridecylamine; an anthraquinone such as m-methylphenol, xylenol, phenol or halogenated phenol. Further, the amount of the organic solvent (α) is preferably such that the total amount (Θ) of the tetradecanoic acid diamine compound is relative to the total enthalpy of the reaction solution (α + ratio of acid: rate. - butyl lysine and ?) are from -18 to 1356934 in an amount of from 0.1 to 30% by weight. Further, in combination with a polyglycine which does not cause the formation of poly-proline Solvent esters, ethers, halogenated hydrocarbons, hydrocarbons, etc. Examples of such a body include methanol, ethanol, isopropanol hydroxy-4-methyl-2-pentanone, ethylene glycol, propylene glycol, 1,4 diol, ethylene glycol monomethyl ether, ethyl lactate, butyl ketone ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate butyl acetate, methyl methoxypropionate Ethyl ethoxypropionate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether ether, ethylene glycol ethyl ether acetate, Diethylene glycol dimethyl ether diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran π 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorotrihexane, heptane, octane, benzene, toluene, xylene, etc. As described above, the dissolved poly is obtained. The reaction of proline is carried out by pouring the reaction solution into a large amount of a poor solvent, and the precipitate is obtained by drying the precipitate under reduced pressure to obtain a polyamic acid. Further, the amine acid is dissolved in an organic solvent, and then precipitated once or several times with a poor solvent. In the next step, the poly-proline can be purified. [Synthesis of Polyimine] The polyimine constituting the liquid crystal alignment agent of the present invention can be synthesized by dehydration of lysine. The dehydration of poly-proline is lysine. Method, or (Π) dissolving polylysine in the ash, the above alcohol, ketone, poor solvent, cyclohexanol, 4-butanediol, triethyl, acetone, methyl, acetic acid Ester, ester, diethylene glycol diethyl ether, ethylene glycol, ethylene glycol diethylene glycol diethylene glycol monomethyl I, dichloromethane, €, o-dichlorobenzene, solution. Then, to the precipitate The polyp is again taken out by passing the above poly ring through (i) heating in the 'organic solvent, -1 9- 1356934 A dehydrating agent and a dehydration ring-closing catalyst are added to the solution, and heating is carried out as needed. The above (i) heating method of poly-proline is preferably carried out at a temperature of 50 to 200 ° C, more preferably 60 to 170 ° C. When the reaction temperature is less than 50 ° C, the dehydration ring-closure reaction cannot be completed completely, and if the reaction temperature exceeds 200 ° C, the molecular weight of the obtained polyimine will decrease. On the other hand, in the above ( Ii) In the method of adding a dehydrating agent and a dehydration ring-closing catalyst to a polyaminic acid solution, as the dehydrating agent, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride may be used. The amount of the dehydrating agent is preferably required. The ruthenium amination rate is 0.01 to 20 moles relative to the 1 molar polylysine repeat unit. Further, as the dehydration ring-closure catalyst, a tertiary amine such as pyridine, trimethylpyridine, lutidine or triethylamine can be used. However, it is not limited to these. The amount of the dehydration ring-closing catalyst used is preferably 0.01 to 10 moles per 1 mole of the dehydrating agent. The larger the amount of the above dehydrating agent or dehydrated closed-loop catalyst, the higher the yield of ruthenium. As an organic solvent used in the dehydration ring closure reaction, it can be exemplified as polylysine synthesis.

An organic solvent exemplified as the solvent used. Further, the reaction temperature of the dehydration ring closure reaction is preferably from 0 to 180 ° C, more preferably from 10 to 1 501. Further, the polyimine can be purified by the same operation as the polyamic acid purification method of the reaction solution thus obtained. In the polyimine of the present invention, the total amount of the repeating units represented by the above formulas (A) and (B) is 50 mol% or more of all the repeating units. The entire repeating unit, the repeating unit represented by each of the above formulas (A) and (B) and the quinone imine repeating unit (diamine compound and tetracarboxylic dianhydride which are different from each other) and It is composed of 醯-20-1356934 amino acid repeating units of these repeating units. [Terminal modified polymer] The polyimine used in the present invention may also be a terminal modified polymer having a molecular weight adjusted. By using the terminal-modified polymer, the coating properties and the like of the liquid crystal alignment agent can be improved without impairing the effects of the present invention. Such a terminally modified polymer can be synthesized by adding a monofunctional compound such as a monoanhydride, a monoamine compound or a monoisocyanate compound to a reaction system during the synthesis of polyamic acid. As the monoanhydride, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl succinic anhydride or the like can be enumerated. Further, examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-undecylamine, and Dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecaneamine, n-octadecylamine, n-icosylamine, and the like. Further, examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate. 0 [logarithmic viscosity of polymer] The polyamic acid and polyimine obtained as above have a logarithmic viscosity (7 In) 値 of preferably 0.05 to 10 dl/g, more preferably 0.05 to 5 dl/g. The above logarithmic viscosity (7? In) is determined by the following formula (i) by using N-methyl-2-pyrrolidone as a solvent and measuring the viscosity of a solution having a concentration of 0.5 g/100 ml at 30 ° C. value.

In (solution flow time / solvent flow time) 7? m = ------ ~~ (weight concentration of polymer) -21 - 1356934 [Liquid crystal alignment agent] The liquid crystal alignment agent of the present invention is usually composed of the above poly The amine is dissolved in an organic solvent to form. The temperature at which the liquid crystal alignment agent of the present invention is formulated is preferably from 0 ° C to 200 ° C, more preferably from 20 ° C to 60 ° C.

The organic solvent may, for example, be 1 - methyl-2-pyrrolidone 'r-butyrolactone, r-butyrolactam, ν, ν·dimethylformamide, ν, ν-dimethylacetamidine. Amine, 4-hydroxy 4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol Ether, ethylene glycol 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, two Ethylene 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, etc. . The solid content concentration in the liquid crystal alignment agent of the present invention is selected in consideration of viscosity and volatility, and is preferably from 1 to 10% by weight. In other words, the liquid crystal alignment agent of the present invention is applied to the surface of the substrate to form a coating film as a liquid crystal alignment film. When the solid content concentration is less than 1% by weight, the thickness of the coating film is too small, and a satisfactory liquid crystal alignment film cannot be obtained. When the solid content concentration exceeds 1% by weight, the thickness of the coating film is too thick, 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. In the liquid crystal alignment agent of the present invention, a compound having a functional oxime or an epoxy compound may be optionally contained from the viewpoint of improving the adhesion to the surface of the substrate insofar as the physical properties of the object are not impaired. As such a compound having a functional oxime, for example, 3·aminopropyltrimethoxyindole-22-1356934 alkane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxy group Decane, 2-aminopropyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-amine Propyl propyl dimethoxy decane, 3-ureidopropyl trimethoxy decane, 3-ureidopropyl triethoxy decane, N-ethoxycarbonyl-3-aminopropyl trimethoxy decane , N-ethoxycarbonyl-3,aminopropyltriethoxydecane, N-triethoxydecylpropyltriethylethylamine, N-trimethoxydecylpropyltriethylethyl Amine, ίο-trimethoxydecane-1,4,7-triazadecane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl- 3,6-diazaindolyl acetate, 9-triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane , N·benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxysulfoniumAlkyl, N-bis(hydroxyethyl)-3-aminopropyltrimethoxydecane, N-bis(hydroxyethyl)-3-aminopropyltriethoxydecane, and the like. Examples of such an epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and tripropylene glycol diglycidyl ether.

Polypropylene glycol dimethyl sulphate, neopentyl glycol dimethyl sulphate, hydrazine, 6-hexanediol condensed ethylene dioleate, ethylene dihydrate dimethyl ether, 2,2-dibromo Neopentyl glycol condensed ethylene dioleate, 1,3,5,6-tetrahydroethylenedioleyl-2,4-hexanediol 'Ν,Ν,Ν',Ν'-tetrahydroethylenediyl -m_xylylenediamine, 1,3 -di(anthracene, fluorene-dihydroethylenedioleylaminomethyl)cyclohexane, ν,Ν,Ν', N'-tetrahydroethylenediyl- 4,4'-diaminodiphenylmethane, 3-(anthene-allyl-N-diethylidene)aminopropyltrimethoxydecane, 3-(anthracene, fluorene-dihydrate Oil based) Aminopropyltrimethoxydecane, and the like. [Liquid Crystal Display Element] -23-

1356934 The liquid crystal display element of the present invention can be produced, for example, by the following. (1) The liquid crystal alignment agent of the present invention is applied to one surface of a substrate through which a pattern is formed by, for example, a roll coater method, a spin coater method, or a printing method, and then, by heating the coated surface into a substrate, for example, for example, Ethyl phthalate such as float glass, soda lime glass, polybutylene terephthalate, polyether mill, plastic transparent substrate. As the transparent surface provided on one side of the substrate, a NESA film made of tin oxide (Sn02) (American PPG ) standard) or indium tin oxide (In203~Sn02) can be used. Photolithography and pre-fabrication. In the application of the liquid crystal alignment agent, in order to further improve the adhesion between the transparent conductive film and the coating film, it is also possible to apply a functional decane-containing compound or a functional titanium-containing dabbin liquid crystal alignment agent to the substrate. The heating temperature is preferably from 80 to 30,000 ° C and from 120 to 250 ° C. The thickness of the formed coating film is preferably 0.001 to 1 and preferably 0.005 to 0.5/m. (2) the surface of the formed coating film is rubbed with a roll of a cloth made of a fiber such as nylon or cotton, and rubbed in a predetermined direction to form a liquid crystal which imparts alignment energy to the liquid crystal molecules of the coating film. By the film formed by the liquid crystal alignment agent of the present invention, a process of changing the pretilt angle by, for example, a partial illumination as shown in Japanese Patent Laid-Open Publication No. Hei 6-222366, or the like, or In the method of making a grinding method as shown in Japanese Laid-Open Patent Publication No. 5-1 07 5 44, a coating film of a conductive film of tantalum is used. Work: glass: poly-ply phthalate, etc. 丨 conductive film, 〖 registrar 〖 and so on. The faces of these 1 masks: the surface of the board and the surface of the object. The coating is more preferably // m, more, fiber-making, and grinding. To the membrane. The liquid crystal alignment 丨 或 或 日 日 或 或 或 或 或 或 或 或 或 或 或 或 或 -24 -24 -24 -24 -24 -24 -24 -24 -24 -24 -24 -24 -24 -24 -24 -24 -24 -24 -24 -24 -24 -24 -24 -24 -24 -24 -24 -24 -24 -24 -24 -24 -24 -24 -24 -24 -24 The processing in which the liquid crystal alignment can be changed can improve the field of view characteristics of the liquid crystal display element. (3) Each of the substrate on which the liquid crystal alignment film is formed and the substrate on which the transparent conductive film pattern is not formed are each fabricated, and the rubbing directions in the respective liquid crystal alignment films are perpendicular or antiparallel to each other, and the two substrates are placed oppositely through the gap (box gap). The peripheral portions of the two substrates are bonded together with a sealant, and the liquid crystal is injected into the cell gap separated from the surface of the substrate and the sealant, and the φ hole is closed and injected to form a liquid crystal cell. Then, a polarizing plate is bonded to the outer surface of the liquid crystal cell, that is, the other side surface of each of the substrates constituting the liquid crystal cell, such that the polarization direction thereof is uniform or perpendicular to the rubbing direction of the liquid crystal alignment film formed on one side of the substrate, thereby obtaining a liquid crystal. Display component. Here, as the sealant, for example, an alumina ball-containing epoxy resin or the like as a curing agent and a spacer can be used. Examples of the liquid crystal include nematic liquid crystals and dish-shaped liquid crystals. Among them, a nematic liquid crystal is preferable, and for example, a Schiff's-type liquid crystal, an oxidized mono-nitrogen-based liquid crystal, a biphenyl liquid crystal, or a phenyl ring can be used. Alkane liquid crystal, ester liquid crystal, diphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal 'cubic liquid crystal, and the like. Further, in these liquid crystals, a bile-type liquid crystal such as chlorinated cholesterol, cholesterol phthalate or cholesterol carbonate may be added and sold under the trade name "c _丨5,' '"CB-15" (manufactured by Merck). It is used for the palm reagent, and 'you can also use a strong dielectric liquid crystal such as p-nonoxybenzylidene·imino-2-methylbutyl cinnamic acid.” In addition, it is attached to the outer surface of the liquid crystal cell. For the polarizing plate, a polarizing plate made of a polarizing plate or a ruthenium film which is obtained by stretching a polyvinyl alcohol and simultaneously absorbing iodine, which is obtained by sandwiching a polyvinyl alcohol film into a protective film of acetate, can be cited. The present invention will be more specifically described, and it is not limited to these examples. The examples of the present specification and the ratio of the oxime imidization ratio of the polymer, the storage stability of the liquid crystal alignment agent, the transparency of the alignment film, and the friction resistance. The liquid crystal display and the residual voltage ratio of the liquid crystal display were evaluated by the following methods. [醯imination rate] The polyimide was dried under reduced pressure at room temperature, and then dissolved in a bismuth telluride. Methyl hydrazine As a reference substance, the room temperature measurement 1 Η is obtained by the formula represented by the following formula (II). The oxime imidization ratio (%) = (1-Α1/Α2χ α )xlOO (II) Α1: from the ruthenium matrix Peak area (10 ppm) A2: Peak area α from other protons: The ratio of the number of other protons in the polymer precursor (polyproline) relative to one NH. [Storage stability of liquid crystal alignment agent] The liquid crystal alignment agent prepared by the predetermined composition was stored at 40 ° C for one month. If the alignment agent was uniformly dissolved after one month, it was recorded as unevenly dissolved, and it was designated as X. [Printing of liquid crystal alignment agent Performance test] The polymer was dissolved in a mixed solvent of r-butyrolactone/N-methylpyrrolidone/butyrate (77/3/20 (weight ratio)) to prepare a solid content by weight% solution, and the solution was prepared. The polarization is filtered by a filter with a pore size of 1 // m. However, in the present example, the dimethyl-NMR > matrix storage of the liquid crystal device is 〇, the base solubility is 4, and the preparation is -26-1356934. The liquid crystal alignment agent of the present invention, which is obtained by using a liquid crystal alignment film printing machine (manufactured by Japan Photographic Printing Co., Ltd.) The agent was coated on the transparent electrode surface of the glass substrate with the ITO film transparent electrode, dried on a hot plate at 80 ° C for 1 minute, and then dried on a hot plate at 180 ° C for 20 minutes to form an average film thickness of 600 Å of the coating film. The substrate was observed under a microscope at a magnification of 20, and the printing performance was judged by the unevenness of printing and the presence or absence of the pinhole. [Orientation of liquid crystal] Voltage opening of the liquid crystal display element. When it was released, the presence or absence of an abnormal region was observed under a φ polarizing microscope, and it was evaluated as “good” when there was no abnormal region. [Voltage residual ratio of liquid crystal display element] A voltage of 5 V was applied to the liquid crystal display element over a time span of 16.7 msec. The voltage application time was 60 microseconds, and the voltage residual ratio after the voltage was released to 16.7 milliseconds was measured. The measurement apparatus was VHR-1 manufactured by Dongyang Technology Co., Ltd. Synthesis Example 1 224.17 g (1 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 2,2'-dimethyl-4 as a diamine compound, 4,-Diaminobiphenyl 106.15 g (0.5 mol) was dissolved in 4500 g of N-methyl-2-pyrrolidone' reaction at 60 ° C for 6 hours. Next, the reaction solution was poured into a large excess of methanol to precipitate a reaction product, which was then washed with methanol, and dried at 40 ° C for 15 hours under reduced pressure to obtain 360 g of a polydecylamine having a logarithmic viscosity of 0.75 dl/g. Acid (which is called "polyproline (A丨)).) 3 〇g of polylysine was dissolved in 570 g of N-methyl·2·pyrrolidone, and 23.4 g of pyridine and 1 8 ·1 were added. g acetic anhydride' dehydration ring closure at 1 1 〇t: for 4 hours, the same -27-1356934 as above, washing, drying under reduced pressure, to obtain 18.0 g logarithmic viscosity of 〇.80 (11 / £, yttrium The polyamidene having a conversion rate of 88% (this is called polyimine (B1)). Synthesis Examples 2 to 10 and Comparative Examples 1 to 3 except that the tetracarboxylic dianhydride and the diamine were replaced with Table 1. In the same manner as in Synthesis Example 1, the logarithmic viscosity and the oxime imidization ratio were as shown in Table 1 as B2 to B10 and bl~b2». Table 1 Synthesis Example Diamine Compound (mol) Anhydride (mol) Polylysine (dl/g) Polyimine Polyimine Iridium Amination Rate (%) Logarithmic Viscosity (dl/g) 2 Dl (0.15), D3 (0.05), D6 (0.8) Tl ( lO) 0.7 90 0.8 B2 3 D 1(0.3) ' D3(0.05) ' D6(0.65) Tl(lO) 0.6 88 0.7 B3 4 Dl(0.15), D3(0.03), D6(0.82) Tl(lO) 0.7 89 0.8 B4 5 D 1( 0.3) ' D3(0.03) ' D6(0.67) Tl(1.0) 0.6 88 0.7 B5 6 Dl(0.15)' D6(0.85) Tl(1.0) 0.7 87 0.7 B6 7 D 1(0.3) ' D6(0.7) Tl (1.0) 0.6 86 0.7 B7 8 D2(0.15)' D4(0.05), D5(0.8) Tl(1.0) 0.8 88 0.9 B8 9 D2(0.3) ' D5(0.7) Tl(1.0) 0.7 86 0.9 B9 10 D2 (0.3), D4 (0.05), D6 (0.6) D7 (0.05) Tl (1.0) 0.9 88 0.9 B10 Comparative Synthesis Example 1 D3 (0.04), D7 (0.76), D8 (0.2) Tl (lO) 0.6 91 0.7 Bl 2 D7(1.0) T2(1.0) 0.6 85 0.7 b2

The diamine compound and the tetracarboxylic dianhydride in Table 1 are as follows: <Diamine compound> D1: 1,3-cyclohexanedi(methylamine) D2: 1,4·cyclohexanedi(methylamine) -28- 1356934 D3: Diamine D4 represented by the above formula (16): diamine D5 represented by the above formula (17): 3,3'-dimethyl-4,4'-diaminobiphenyl D6: 2,2'-Dimethyl-4,4,-diaminobiphenyl D7: p-phenylenediamine D8: 4,4'-methylenediphenylamine <tetracarboxylic dianhydride> T1: 2 , 3,5-tricarboxycyclopentyl acetic acid dianhydride T2: 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3 -• furyl)-naphthalene [l,2_c]-furan-1,3-dione Example 1 2 g of the polyimine (B1) obtained in Synthesis Example 1 was dissolved in 7-butyrolactone. A solution having a solid concentration of 4% by weight was used, and the solution was filtered through a filter having a pore size of 1 /zm to prepare a liquid crystal alignment agent of the present invention. The storage stability and printing performance of the obtained liquid crystal alignment agent were evaluated. The results are shown in Table 2 °. The above liquid crystal alignment agent was applied onto a transparent conductive film made of an ITO film provided on one side of a 1 mm thick glass substrate by a spin coater (rotation speed: Φ 2000 rpm, coating time: 1 minute), after passing through The film was dried at 200 ° C for 1 hour to form a coating film having a dry film thickness of 0.05 / / m. The coating film was polished by a sander equipped with a roller wound with a rayon cloth at a roller rotation speed of 400 rpm, a section moving speed of 3 cm/sec, and a pile intrusion length of 0.4 mm. The substrate coated with the liquid crystal alignment film was immersed in isopropyl alcohol for 1 minute, and then dried on a hot plate of 10 ° for 5 minutes. Then, the liquid crystal alignment film substrate coated with the liquid crystal on the pair of transparent electrode substrates was provided with liquid crystal. On each outer edge of the alignment film, an epoxy resin binder coated with alumina balls having a diameter of 5.5 μm is applied, and then the liquid crystal alignment film faces are relatively superposed and pressed to cure the adhesive -29-1356934 mixture. Then, a nematic liquid crystal (MLC-6221, manufactured by Merck Co., Ltd.) was filled between the substrates through a liquid crystal injection port, and then the liquid crystal injection port was closed with a acrylic acid-based photocurable adhesive, and the two sides of the substrate were attached. The polarizing plate was used to form a liquid crystal display element, and the voltage residual ratio and the alignment property of the obtained liquid crystal display element were evaluated. The results are shown in Table 2. Examples 2 to 1 0, Comparative Examples 1 to 2 Except for using Table 2 A liquid crystal alignment agent was prepared and treated in the same manner as in Example 1 except that the polyimine or polyamic acid was used, and the liquid crystal display element was produced and evaluated. The evaluation results are shown in Table 2.

Table 2 Example Polymer Storage Stability Printability Alignment Voltage Residual Rate (%) 1 B1 〇 Good Good 98 or more 2 B2 〇 Good Good 98 or more 3 B3 〇 Good Good 98 or more 4 B4 〇 Good Good 98 or more 5 B5 〇 Good good 98 or more 6 B6 〇 Good good 98 or more 7 B7 〇 Good good 98 or more 8 B8 〇 Good good 98 or more 9 B9 〇 Good good 98 or more 10 B10 〇 Good good 98 or more Comparative example 1 Μ 〇 Good pinhole 98 or more 2 B2 X - - - -30-

Claims (1)

1356934 X. Patent Application Range: 1. A liquid crystal alignment agent characterized by comprising a polyimine having both repeating units represented by the following formulas (A) and (B), and formulas (A) and (B) The total amount of repeating units represented by each represents 50% or more of all repeating units in the polyimine. In the formula, r is a tetravalent organic group. 2, as in the liquid crystal alignment agent of claim 1, wherein R is represented by the following formula (C). Ch2-3. The liquid crystal alignment agent according to claim 1 or 2 wherein the repeating unit represented by the above formula (A) accounts for 50 to 95 mol% of the total repeating unit of the polymer '31- 1356934 and the above formula ( The repeating unit represented by B) accounts for 5 to 50 mol% of all repeating units of the polymer. A liquid crystal display element comprising a liquid crystal alignment film formed by the liquid crystal alignment agent according to any one of claims 1 to 3. -32-