TWI374928B - - Google Patents

Description

1374928 (1) Technical Field of the Invention The present invention relates to a liquid crystal alignment treatment agent for forming a liquid crystal alignment film of a liquid crystal display element, and a liquid crystal display element produced using the same. [Prior Art] The liquid crystal display element currently in widespread use is a structure in which a liquid crystal substance is filled between two opposing substrates, and the liquid crystal substance maintains an intended initial orientation by the action of a liquid crystal alignment film provided on the surface of the substrate. status. The liquid crystal alignment film is generally widely used by a polyimide film of a polyimide film (flat film). Further, in place of the flat film, a method of irradiating an organic film with a polarized ultraviolet light or the like (photo-alignment film) has been actively studied. The applied voltage-transmittance characteristics of such liquid crystal display elements are generally known to vary with the ambient temperature, and are an obstacle to stable high-grade display. The first reason for this variation in characteristics is the temperature dependence of the liquid crystal characteristics, and there are also reasons for the alignment film from the liquid crystal. For example, if the pretilt angle of the liquid crystal fluctuates with the ambient temperature, the threshold voltage at the time of driving the liquid crystal slips, and as a result, the applied voltage-transmittance of the liquid crystal display element also fluctuates. The change in the pretilt angle due to the ambient temperature is exhibited by a liquid crystal alignment film having a high pretilt angle or, for example, a light alignment film, when the liquid crystal orientation regulating force of the liquid crystal alignment film is weak. In extreme cases, the pretilt angle is greatly reduced at high temperatures, which causes problems such as the fact that the liquid crystal cannot be driven normally. Therefore, the liquid crystal display element which is necessary for a high pretilt angle, and the light orientation (2) (2) 1374928 film which is a method of replacing the flat graining film are particularly important. In general, the liquid crystal pretilt angle of a polysalination liquid crystal alignment film obtained from a simple structure is not too high, and the pretilt angle is increased to any enthalpy. It is known that a long chain alkyl group is introduced into the side chain of the polyimine. And a method of a fluoroalkyl group (refer to, for example, Japanese Patent Laid-Open No. Hei 2-282726). Further, with respect to the above-described improved pretilt angle, the stability of the heat treatment for forming the liquid crystal alignment film is improved by the stability of the heat treatment after the liquid crystal display element is formed, and the side chain structure introduction ring of the polyimine is also known. For example, Japanese Patent Laid-Open Publication No. Hei 9-278724. However, conventional stabilization techniques for pretilt angles are mostly for the stability of the process, stability with respect to durability, and changes in ambient temperature. The pre-tilt stabilization technology has not been reported. Disclosure of the Invention Problems to be Solved by the Invention The present invention has been made in order to solve the problem of stability of a liquid crystal pretilt angle of a change in ambient temperature, particularly a problem of pretilt stability at a high temperature. That is, the object of the present invention is to provide a liquid crystal aligning treatment agent which has a small change in the pretilt angle for a change in ambient temperature and which is stable at a high temperature to impart a high pretilt angle to the liquid crystal, and which can provide a change in ambient temperature. A liquid crystal display element that is stable for high-grade display. Means for Solving the Problem (3) 1374928 The above object of the present invention has been found to be solved by the following liquid crystal aligning agent and display element. Thus, the gist of the present invention is as follows. A liquid crystal aligning agent containing an addition polymer having a structural unit of the following formula (1).

B—X1—X2—R1 (wherein A is a polymer backbone structure obtained by addition polymerization, B is a single bond or a group selected from the group consisting of esters, ethers, guanamines, and urethanes. XI and X2 independently represents an aromatic ring, an alicyclic ring or a heterocyclic ring, an alkyl group having 3 to 18 carbon atoms, an alkoxy group having 3 to 18 carbon atoms, a fluoroalkyl group having 1 to 5 carbon atoms, and 1 carbon atom; a fluoroalkoxy group, a cyano group or a halogen atom to 5). 2. The liquid crystal aligning agent according to the above 1, which further comprises at least a group selected from the group consisting of polylysine, polyimine, polyester, and polyurea. A polymer. 3. The liquid crystal aligning treatment agent according to 2 above, wherein the addition polymer is chemically combined with at least one polymer selected from the group consisting of polylysine, polyimine, polyamine, polyester, and polyurea. The status contains. 4. The liquid crystal aligning agent according to the above 1, 2 or 3, wherein among the polymer components contained in the liquid crystal aligning agent, the structural unit of the formula (1) accounts for 0.01 to 50% by weight. 5. The liquid crystal aligning agent according to any one of the above items 1 to 4, wherein the addition polymerization (4) (4) 1374928 system, the structural unit of the formula (1), contains 50% or more in terms of the number of structural units, and The ratio of the above-mentioned addition polymer in the polymer component is from 1 to 20% by weight. 6. The liquid crystal aligning agent according to any one of the above 1 to 5, wherein the addition polymer system, the structural unit of the formula (1) contains 5% or more in terms of the number of structural units. 7. The liquid crystal aligning agent according to any one of the above 1 to 6, wherein the addition polymer system is a structure of the following formula (2) in the formula (1) of the structural unit.

(wherein R2 represents a hydrogen atom, a methyl group or a halogen atom.) 8. A liquid crystal display element using the liquid crystal alignment treatment agent according to any one of items 1 to 7 above. Advantageous Effects of Invention The liquid crystal alignment film formed by the liquid crystal alignment treatment agent of the present invention has a small change in the liquid crystal pretilt angle for environmental temperature change, and can impart a high pretilt angle to the liquid crystal for thermal stability. Further, the liquid crystal display using the liquid crystal alignment treatment agent of the present invention The component has a small variation in voltage-transmittance characteristics for changes in ambient temperature, and can be stabilized for high-grade display. -9 - (5) 1374928 [Embodiment] Hereinafter, the present invention will be described in detail. The liquid crystal aligning agent of the present invention is a preserving agent for forming a liquid crystal alignment film on a substrate to form a stabilizer, and an addition polymer containing a structural unit of the formula (1).

B—X1—X2—R1 In the formula (1), the polymer backbone structure of the A system is subjected to addition polymerization to form a 'B single bond' or a group selected from the group consisting of esters, ethers, decylamines and urethanes. Binding base. The above polymer obtained by addition polymerization has a polyvinyl group, poly(meth)acrylic acid, polym-butyleneimine or the like. The following is a specific configuration example of a part of A, but is not limited thereto.

(H2, a hydrogen atom such as a hydrogen atom, a methyl group or a fluorine atom in the above formula, a halogen atom such as a chlorine atom). From the viewpoint of easiness of introduction of a polymerizable property or a side chain, an addition polymerization reaction -10 - (6) (6) 1374928 The polymer is preferably poly(meth)acrylic acid. Preferably, the A-B portion of the system U) is of the formula (2).

(In the formula, R2 represents a hydrogen atom, a methyl group or a fluorine atom, or a halogen atom such as a chlorine atom.) In the formula (1), XI and X2 independently represent an aromatic ring, an alicyclic ring or a heterocyclic ring, and R1 represents an alkane having 3 to 18 carbon atoms. a group, an alkoxy group having 3 to 18 carbon atoms, a fluoroalkyl group having 1 to 5 carbon atoms, a fluoroalkoxy group having 1 to 5 carbon atoms, a cyano group or a halogen atom. The portion formed by XI-X2-R1 is preferably a liquid crystal structure. The specifics of XI or X2 are as follows. The aromatic ring has a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, an indoline ring, etc., and the alicyclic ring has a cyclobutyl ring, a cyclopentane ring, a cyclohexane ring, a bicyclooctyl ring, etc., and the heterocyclic ring has a furan ring, a thiophene ring, A thiazole ring, a pyridine ring, a pyrimidine ring, an anthracene quinone ring, an acridine ring, a pyridine ring, a benzothiazole ring, a dioxane ring or the like. The bonding position of these ring structures in the formula (1) is preferably a linearity, and for example, a benzene ring is preferably a para-position. Preferred examples of X 1 or X 2 are shown below, but are not limited thereto. Further, X 1 and X 2 may be different from each other. * 11 - (7) (7) 1374928

In the above structure, any hydrogen atom in the 'ring structure' may be substituted with a halogen atom such as a methyl group, an ethyl group, a fluorine atom or a chlorine atom. The combination of X 1 and X 2 is preferably a combination of a benzene ring, a cyclohexane ring, a pyridine ring and a pyrimidine ring, which is selected from the group consisting of a benzene ring and a cyclohexane ring. Especially good. Specifically, the combination of X 1 and X 2 is preferably a group selected from the group consisting of biphenyl, bicyclohexyl, phenylcyclohexyl and cyclohexylphenyl, and is compatible with the liquid crystal used and the target pretilt angle. The size may be appropriately selected from an alkyl group having 3 to 8 carbon atoms and an alkoxy group having 3 to 8 carbon atoms. (8) (8) 1374928 A fluoroalkyl group having 1 to 5 carbon atoms and a carbon atom. Between 1 and 5 of a fluoroalkoxy group, a cyano group or a halogen atom. Among them, an alkyl group having 5 to 8 carbon atoms and an alkoxy group having 5 to 8 carbon atoms are particularly suitable for a wide range of applications. The following is a part of a specific example of the portion formed by X1-X2-R1, but is not limited thereto. In the following configuration, η is preferably from 3 to 12, particularly preferably from 5 to 10.

The addition polymer of the structural unit containing the formula (]) may be a mono-monomer of the formula (1) or a 13- (9) (9) with other structural units obtained by addition polymerization. 1374928 Random copolymer, alternating copolymer, block copolymer or graft copolymer. These polymers can be synthesized by radical polymerization, cationic polymerization, anionic polymerization or the like. The polymerization means may be any of thermal polymerization, photopolymerization, and the like. The addition polymer of the structural unit containing the formula U) may be a monomer corresponding to the monomer of the formula (1), that is, a vinyl compound having a substituent formed by the above -X b X2-R1 via the above B bond And a maleimide compound, etc., obtained by a general addition polymerization reaction. The following is a configuration of a monomer corresponding to the configuration of the formula (1), but is not limited thereto. However, in the following formula, R, R2, XI, and X2 are as above.

* 14 - (10) 1374928

•X1—X2-R1 R2

R2 Χ1—X2-R1

R2

R2 0——Χ1—X2——R1

ΗΝ——Χ1—X2——R1 (11)1374928

ο

As the above monomer, one type or a plurality of types can be used. Further, the polymer having the structure of the formula (1) controls the solubility of the polymer in an organic solvent to control the solubility of the polymer in an organic solvent, controls the compatibility with other polymers contained in the liquid crystal aligning agent, and enhances the liquid crystal aligning agent. For the purpose of imparting heat resistance to the liquid crystal alignment film, one type of monomer which can be subjected to addition polymerization reaction can be used as a random copolymer, an alternating copolymer, a block copolymer or the like. Specific examples of the other monomer of the polymerization reaction include (meth)acrylic acid methyl ester, ethyl (meth)acrylate, (meth)acrylic acid n-butyl vinegar (isobutyl methacrylate), (methyl) Hexyl acrylate, (meth) propionate, vinegar, (meth)propionic acid 2-methoxyethyl acetate, (methyl) propyl acid 2-ethoxyethyl ester, (meth)acrylic acid 2- Butoxyethyl ester '(methyl) propyl hexanoate, phenyl (meth) acrylate, benzyl methacrylate, glycidyl (meth) acrylate, styrene, hydroxybenzene ,钱-16 - (12) (12)1374928 Styrene, methacrylamide, N-arylmethyl Acrylamide, N-hydroxyethyl-N-methylmethacrylamide, N-methyl-indole-phenylmethacrylamide, acrylamide, fluorene aryl acrylamide, hydrazine, hydrazine Aryl acrylamide, hydrazine-methyl-hydrazine-phenyl acrylamide, hydrazine-vinyl-2-pyrrolidone, fluorenyl-phenyl maleimide, vinyl carbazole, vinyl pyridine; vinyl imidazole Wait. Among them, the polymer of glycidyl methacrylate is particularly effective in improving the solubility and compatibility. As described above, an addition polymer containing a structural unit of the formula (1) is obtained by a radical polymerization method using a monomer corresponding to the structure of the formula (1) and, if necessary, other monomer components capable of addition polymerization. An example of the technique is as follows. The corresponding monomer is dissolved in an organic solvent, and a reaction initiator is added. The above reaction solvent is not particularly limited as long as it can dissolve the obtained polymer. For example, r · butyrolactone, cyclohexanone, dimethyl sulfite, N-methyl-2-pyrrolidone, hydrazine, N-dimethylacetamide, hydrazine, N-dimethylformamide, lactic acid Ethyl ester (EL), methoxypropanol (PGME), propylene glycol-methyl ether acetate (PGMEA) or a mixture of these, the reaction initiator has an azo compound such as AIBN (azobisisobutyronitrile), A peroxide such as an benzoyl sulfonate group. Further, in order to promote the reaction and to complete the reaction, the reaction system may be heated. The polymer thus obtained may be used as it is, or may be used by injecting a weak solvent to recover the target polymer. In the addition polymer of the structural unit containing the formula (1), the content ratio of the structural unit of the formula (1) can be freely set, and it is preferable to convert the pretilt angle to 5% or more in terms of the number of structural units, 30%. The above is better. Further, as will be described later, when the liquid crystal aligning agent of the present invention contains an addition polymer having a structural unit of the formula (1), and a polymer other than the polymer, the structure of the formula (]) -17 - (13) (13) 1374928 The ratio of the unit is preferably 50% or more, more preferably 60% or more, and 70% or more of the polymer having the structure of the formula (1) is not particularly limited, for example, GPC (Gel Permeation Chromatography) The weight average molecular weight measured by the gel permeation chromatography method is preferably from 1,000 to 1,000,000, from 2,000 to 400,000, from 5,000 to 100,000, and the like. The polymer component contained in the liquid crystal aligning agent of the present invention is preferably a polymer containing a liquid crystal alignment regulation for imparting a parallel pattern to the substrate, in addition to the addition polymer containing the structural unit of the formula (1). Such a polymer can be used as a polymer which is generally used in a liquid crystal alignment film, and is preferably a polyamic acid, a polyimide, a polyamine, a polyester, a polyurea or the like. In particular, polyamic acid or polyimine, which is excellent in orientation and heat resistance of liquid crystal, is widely used as a material of a liquid crystal alignment film, and is a preferred polymer component contained in the liquid crystal alignment treatment agent of the present invention. The structure of the above-mentioned polyfluorene. Amine acid or polyimine is not particularly limited, and the liquid crystal aligning agent of the present invention is used for a method of forming an oriented film by irradiation with polarized ultraviolet rays or the like, and a light-oriented film is preferred for the main chain. It contains a cyclobutane ring, a guanamine bond, an olefin structure, and a diphenyl ketone structure which are chemically reactive with light. Usually, polylysine can be obtained by reacting a tetracarboxylic dianhydride with a diamine compound in an organic solvent. Further, polyethylenimine can be obtained by imidization (dehydration ring closure) of polyglycolic acid. Examples of the polyamic acid which may be contained in the liquid crystal aligning agent of the present invention include one selected from the group consisting of tetracarboxylic dianhydride and a diamine compound, one or more kinds of tetracarboxylic dianhydrides, and two or more kinds thereof. The amine compound is reacted to obtain a polyamic acid, but -18 - (14) 1374928 is not limited thereto.

The tetracarboxylic dianhydride used in the synthesis reaction of poly-proline is pyromic acid, 2,3,6,7-naphthalenetetracarboxylic acid ' 1,2,5,6 -catetracarboxylic acid, 1,4 5,8-naphthalenetetracarboxylic acid, 2,3,6,7-decanetetracarboxylic acid, 1,2,4,6-decanetetracarboxylic acid, 3,3% 4,4,biphenyltetracarboxylic acid, 2,3,3 ',4-biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether, 3,3,4,41-diphenyl ketone tetracarboxylic acid, 3,3',4,4, chalcone IV Formic acid, bis(3,4-diphenylene), bis(3,4-dicarboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propane, 1,1,1 ,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)dimethyl decane, bis(3,4-di a dianhydride of an aromatic tetracarboxylic acid such as carboxyphenyl)diphenylnonane, 2,3,4,5-nonylpyridinium tetracarboxylic acid or 2,6-bis(3,4-dicarboxyphenyl)pyridine, 1 , 2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 2,3,5-tricarboxycyclopentyl Alicyclic tetracarboxylic acid such as ester, 3,4-dicarboxy-1, .. 2,3,4-tetrahydro-1-naphthalene succinic acid The aliphatic dianhydride, 1,2,3,4 butane tetracarboxylic acid dianhydride of the tetracarboxylic acid and the like. The diamine compounds used in the synthesis of polylysine are p-phenylenediamine, m-phenylenediamine, N,N-diallyl-1,2,4-benzenetriamine, 2,5-diamine. Benzonitrile, 2,5-diamine toluene, 2,6-diamine toluene, 4,4, diamine biphenyl, 3,3_-dimethyl-4,41-diamine biphenyl, 3,3_-dimethyl Oxygen-4,4'-diamine biphenyl, diamine diphenylmethane, diaminodiphenyl ether, diaminodiphenylamine, 2,2'-diaminodiphenylpropane, bis(3,5-di Ethyl 4-aminophenyl)methane, diaminodiphenyl hydrazine, diaminodiphenyl ketone, 3,3'-diamine chalcone, 4,4'-diamine chalcone, 3,3 1-diamine oxime, 4,41-diamine oxime, diamine naphthalene, 1,4-bis(4-amine-19-(15)(15)1374928 phenoxy)benzene '1,4-double (4 -amine phenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 1,3-bis(4-aminophenoxy)benzene, 4,4.-bis(4-aminephenoxy) Diphenyl milling, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis(4-aminophenyl)hexafluoropropane '2,2-bis[4-( Aromatic diamine such as 4-aminophenoxy)phenyl]hexafluoropropane, 2,6-diamine pyridine, 2,4-diamine pyridine, 2,7-diamine And furan, 2,7-diamine carbazole, 3,7-diamine thiophene, 2,5-diamine-1,3,4-thiadiazole, 2,4*diamine-S-triazine An alicyclic diamine such as a heterocyclic diamine, bis(4-aminecyclohexane)methane or bis(4-amine-3-methylcyclohexyl)methane, and 1,2-diamine ethane, 1,3- Aliphatic diamines such as diamine propane, 1,4-diamine butane, 1,6-diamine hexane, 1,3-diamine-4-octadecyloxybenzene, 1,3-diamine-4 -hexadecane oxybenzene, 1,3-diamine-4-dodecyloxybenzene, 4-[4-(4-trans-n-heptylcyclohexyl)phenoxy]-1,3-diamine benzene a side chain such as (4. trans-n-pentylbicyclohexyl)-3,5-diaminobenzyl ester having an alkyl group similar to a liquid crystal structure of diamine ' 1,3 -bis(3-aminopropyl)-1 , 1,3,3-tetradecanedioxane and the like. The polyamic acid contained in the liquid crystal aligning agent of the present invention preferably has a weight average molecular weight [M w ] of 2,000 to 50,000 as measured by a GPC (Gel Permeation Chromatography) method. When the molecular weight is too small, the strength of the obtained coating film is insufficient, and when the molecular weight is too large, workability is poor when a coating film is formed. The molecular weight control of the poly-proline can be adjusted via the molar ratio of the tetracarboxylic dianhydride to the diamine compound for the synthesis reaction of poly-proline. As with the usual polycondensation reaction, the closer the molar ratio is to 1.0, the greater the degree of polymerization of the polymer produced. The synthesis reaction of polylysine is carried out in an organic solvent, and it is usually carried out at a reaction temperature of from 〇 to -20 - (16) (16) 1374928 ] at 5 ° C for preferably from 0 to 100 °C. The organic solvent in this case is not particularly limited as long as it can dissolve the obtained polyamic acid. Specific examples thereof include N: N-dimethylformamide, N,N-dimethylacetamide, N-methyl.2·d-pyrrolidone, N-methylcaprolactam, and Ayaoshu, tetramethylurea, pyridox, dimethylhydrazine, hexamethylene sulfonium, 7-butyrolactone and the like. These can be used singly or in combination. Further, those which do not dissolve the polylysine may be used in combination with the above solvent insofar as the polyphthalic acid produced by the polymerization does not precipitate. The polylysine which can be contained in the liquid crystal aligning agent of the present invention is, for example, those obtained by imidization (dehydration ring closure) of the above polyamic acid. Here, the poly-proline acid-containing compound is suitable for the liquid crystal directional treatment agent of the present invention, even if it is not all of the repeating units of the poly-proline, and is only a certain degree. The ruthenium imidization (dehydration ring closure) can be carried out in solution. In the method of imidizing polyphosphonium amide in a solution, the reaction temperature is usually from 50 to 200 ° C, preferably from 60 to 170 ° C. When the reaction temperature is lower than 50 °C, the dehydration ring-closure reaction cannot be sufficiently carried out. When the reaction temperature exceeds 200 t, the molecular weight of the ruthenium iodide polymer decreases. In the case of the ruthenium imidization reaction, since the addition of the dehydrating agent and the dehydration ring-closing catalyst is carried out at a relatively low temperature, the molecular weight of the obtained polyglycine is not easily lowered, which is preferable. As the dehydrating agent, a tertiary amine such as pyridine or triethylamine can be used. The amount of the dehydrating agent to be used is preferably 0.01 to 20 moles per mole of the repeating unit of the polyamic acid. Further, as the dehydration ring-closing catalyst, a tertiary amine such as pyridine 'triethylamine can be used. The dehydration ring-closing catalyst is preferably used in an amount of from 0.01 to 10 mol per mol of the dehydrating agent used. The organic solvent used for the dehydration ring-closing reaction is exemplified as an organic solvent which can be used for the synthesis of -21 - (17) (17) 1374928 poly-proline. When a dehydrating agent and a dehydration ring-closing catalyst are added, the reaction temperature is usually from 0 to 180 ° C, preferably from 10 to 150 ° C. The poly-proline or polyimine obtained above may be used as it is, or may be precipitated, separated and recovered by a weak solvent such as methanol or ethanol. In the liquid crystal aligning agent of the present invention, the addition polymer containing the structural unit of the formula (1) may contain other polymer components in a state of being chemically bonded thereto. The method may be, for example, introducing a polymerizable substituent into the polymer side chain of the other polymer component contained, in the solution in which the polymer is present, as described above, using a single structure corresponding to the formula (1) The addition polymerization reaction is carried out on the body and, if necessary, other monomer components of the addition polymerization reaction. In polylysine or polyimine, in order to chemically bond a polymer having the structure of the formula (1), for example, a polyamine can be synthesized using a diamine having a vinyl group or a methacryl fluorenyl group in its side chain. The above reaction is carried out in a solution in which the polyamic acid is present. The diamine having a methyl methacrylate group in its side chain has the following diamine.

Further, 'a hydroxyl group, a carboxyl group, an amine group, an isocyanate group, an anhydride group or the like' may be introduced into each of the polymer having the structure of the formula (1) and a polymer contained as another polymer component, and a hydroxyl group or a carboxyl group and an isocyanate group may be used. The reaction 'amine group is combined with an anhydride group reaction or the like. -22 - (18) (18) 1374928 In the whole of the polymer component contained in the liquid crystal aligning agent of the present invention, the weight ratio of the structural unit of the formula (1) can be arbitrarily set according to the target pretilt angle, and is 0.0. It is preferably 50% by weight, more preferably 0.1 to 20% by weight. The liquid crystal aligning agent of the present invention contains the addition polymer of the structural unit of the formula (1) and the polymer of the formula (1) plus the polymer for the orientation regulation of the liquid crystal in the horizontal direction of the substrate. The content ratio of the polymer to be formed is preferably from 0.1 to 20% by weight, more preferably from 0.3 to 5% by weight, based on the total of the polymer component contained in the liquid crystal alignment treatment agent. The addition polymer having a high content of the structural unit of the formula (1) is less stable than the polymer for regulating the orientation of the liquid crystal in the horizontal direction of the substrate, and the pretilt angle stability can be obtained and the liquid crystal alignment regulation in the horizontal direction of the substrate is also Excellent liquid crystal alignment film. In the above, the content ratio of the structural unit of the formula (1) containing the liquid crystal aligning agent of the present invention is more than 50% in terms of the number of structural units, More preferably, 60% or more, more than 75% by weight, more preferably an addition polymer, and (B) at least one polymer selected from the group consisting of polyamic acid, polyamidiamine, polyamine, polyester or polyurea, The ratio of (A) in the total polymer component is from 0.1 to 20% by weight, preferably from 3% to 5% by weight. The liquid crystal aligning agent of the present invention contains a coating liquid of the above polymer component. The solvent contained in the coating liquid is not particularly limited as long as it can dissolve the above polymer component. Further, these may be used alone or in combination of two or more. The solvent in which the polymer alone cannot be dissolved can also be added in the range in which the polymer component does not precipitate. Specific examples of the solvent component are shown below, but are not limited thereto. N-methyl-2-pyrrolidone, Ν'N-dimethylformamide' N,N-di-23 - (19) (19)1374928 methyl acetamide 'τ-butyrolactone, dimethyl amide Milling, tetramethylurea, hexamethylphosphonium tridecylamine 'm-cresol, methanol, ethanol, diethyl ether, ethylene glycol-methyl ether, ethylene glycol ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, two Glyme, diethylene glycol-methyl ether, diethylene glycol-butyl ether 'cyclohexanone, hexane, heptane, toluene, xylene. The liquid crystal aligning agent of the present invention may contain a functional decane compound in order to impart adhesion to the substrate. For example, Ν-trimethyl decyl acetamide, diethyl methoxy dimethyl decane, tetramethoxy decane, 3-aminopropyl diethoxy carbene, 3-aminopropyl triethoxy decane, 1, 4 _ bis (dimethyl decyl) benzene, bis (dimethylamine) dimethyl decane, bis (ethylamine) dimethyl decane, 1-trimethyl decyl imidazole, methyl triethoxy decane, diethoxy methyl Phenyl decane 'phenyl triethoxy decane, diphenyl decane diol, etc. are not limited thereto. In order to obtain the liquid crystal aligning agent of the present invention, the above components may be mixed to prepare a solution which can be applied to the concentration of the substrate. The concentration of the polymer component of the liquid crystal aligning agent of the present invention may be appropriately changed depending on the thickness of the liquid crystal alignment film to be formed, but it is preferably from 1 to 15% by weight. When it is less than 1% by weight, it is difficult to form a uniform flawless coating film, and when it is more than 15% by weight, the solution storage stability may be poor. The liquid crystal aligning agent of the present invention obtained as described above can be applied to a substrate after filtration, dried, and calcined to form a coating film, and the surface of the coating film is subjected to directional treatment by illuminating the surface of the substrate with polarized ultraviolet rays in a certain direction. It can be used as a liquid crystal alignment film. The coating method of the liquid crystal aligning agent is a spin coating method, a printing method, an inkjet method, etc., and a transfer method widely used in the industry based on productivity, and is also suitable for the liquid crystal of the present invention. Directional treatment agent. The drying process after the application of the liquid crystal aligning agent is not necessary, but the drying process is preferably carried out after the application to the time of calcination is not constant for each of the substrates, or is not immediately calcined after coating. In the drying system, the solvent is evaporated until the shape of the coating film is not deformed by the conveyance of the substrate or the like, and the drying means is not particularly limited. Specific examples are a method of drying on a hot plate at 50 to 150 ° C, preferably 80 to 120 ° C, for 0.5 to 30 minutes, preferably 1 to 5 minutes. The calcination of the liquid crystal aligning agent can be carried out at any temperature of 100 to 350 ° C, preferably 150 ° C to 300 ° C, more preferably 200 ° C to 250 t. When the poly-proline is contained in the liquid crystal aligning agent, the conversion ratio of the polyaminic acid to the polyimine is different depending on the calcining temperature, but the liquid crystal aligning agent of the present invention does not necessarily have to be imidized by 100%. It is preferable to calcine at a temperature higher than the heat treatment temperature of the sealant hardening or the like required for the liquid crystal element process by 10 °C or higher. The thickness of the coating film after calcination is too large, and the power consumption of the liquid crystal display element is unfavorable. If the thickness is too thin, the reliability of the liquid crystal display element is lowered, so that it is preferably 5 to 300 nm, preferably 10 to 100 nm. In the liquid crystal display device of the present invention, the substrate to which the liquid crystal alignment film is attached is obtained by the liquid crystal alignment treatment agent of the present invention, and the liquid crystal element is produced by a conventional method. For the manufacture of liquid crystal elements, a pair of substrates in which a liquid crystal alignment film has been formed is formed with a gap control material of 1 to 30 μm, preferably 2 to 10 μm, and set to a flat grinding direction of 〇 to 2 70 2 5 / / any angle 'around the sealant to fix, inject liquid crystal and seal the general method. The method of encapsulating the liquid crystal is not particularly limited, and for example, a vacuum method in which a liquid crystal element made of -25 - (21) (21) 1374928 is decompressed and then injected into a liquid crystal, a liquid crystal is dropped, and a drop method of encapsulation is performed. The substrate for a liquid crystal display element is not particularly limited as long as it is a substrate having high transparency, and a substrate such as a ITO electrode for driving a liquid crystal can be formed by using a plastic substrate such as a glass substrate, an acrylic substrate or a polycarbonate substrate. A simplified view is preferred. Further, in the reflective liquid crystal display device, an opaque material such as a germanium wafer may be used only for the one-side substrate, and a material such as aluminum which can reflect light may be used as the electrode. The present invention will now be described in more detail by way of examples, but the invention is not limited to the Examples &lt;Synthesis Example 1 &gt; Methyl propylene oxime chloride 5.16 g (49.36 mmo 〇, 4- (4-trans-n-pentylcyclohexyl)酣11.06g (44.87mmo t ) and triethylamine 4.99g (49.36mmo t ) were stirred at room temperature for 30 minutes in tetrahydrofuran 200mL solvent, then stirred at 50 ° C for 1 hour. The reaction solution was cooled to room temperature. After extracting with ethyl acetate, the organic layer was dried over anhydrous sodium sulfate. The organic layer was concentrated and purified by column chromatography (ethyl acetate:hexane = 3:1) 4-(4-trans-n-pentylidene)phenoxy methacrylate 14.15 g. &lt;Synthesis Example 2 &gt; 4-(4-trans-n-pentylcyclohexyl)phenoxy group as in the synthesis example Methyl 26 (22) (22) 1374928 Acetate vinegar 20.10g (0_07mo^) and methacrylic acid propylene vinegar 427g (0.03mo^) dissolved in N-methyl-2-13 than ketone (hereinafter referred to as NMP) 8 7.48g after the flask was replaced with nitrogen, and the temperature was raised to 7 〇乞. After heating, the azoisobutyl hydrazine (hereinafter referred to as AIBN) dissolved in NMP l〇g· was added under nitrogen atmosphere. .2g After reacting for 24 hours, an addition polymer containing a structural unit of the formula (丨) was obtained. The weight average molecular weight of the addition polymer was 28000 ° &lt; Synthesis Example 3 &gt; p-phenylenediamine l〇.81 g (O. lmoO was dissolved in 2.4 g of NMP 17 , and 19.61 g (0.1 mol) of cyclobutane tetracarboxylic dianhydride was added thereto, and reacted at room temperature for 24 hours to obtain polyamic acid. The weight average molecular weight of the obtained polyamic acid {Mw } is 156000. &lt;Example 1 &gt; Ν Μ P was added to the addition polymer reaction solution of Synthesis Example 2 to prepare a solution having an addition polymer concentration of 3 wt%. Further, the polyamine acid of Synthesis Example 3 was obtained. NMP was added to the reaction solution to prepare a solution having a concentration of polyglycine of 3 wt%. 99 g of the 3 wt% solution of the polyaminic acid was added, and a 3 wt% solution of the above-mentioned addition polymer was added, and the mixture was thoroughly stirred to obtain a homogeneous solution. The liquid crystal directional treatment agent of the invention is prepared by pressure filtration of a filter having a pore size of 0.5 μm, and then spin coating on a glass substrate with a transparent electrode. The substrate is dried on a hot plate at 80 ° C for 5 minutes. After that, calcined in a hot air circulating oven at 2 0 ° C for 60 minutes -27 - (23) (23) 1374928 clock 'yuji The coating film having a film thickness of 50 nm was applied, and the coating film surface was flat-grinded by a flat grinding device equipped with a PAYON cloth at a light rotation speed of 300 rpm, a moving speed of 20 mm/s, and a pressing force of .5 mm. A substrate with a liquid crystal alignment film. Two sheets of the above-mentioned substrate with a liquid crystal alignment film were coated, and a gap control material of 6 μm was spread on the liquid crystal alignment film surface of one of the substrates, and then the flat grinding direction was directly applied to the injection of nematic liquid crystal (ZLI-made by MERCK Corporation). 4792) Making liquid crystal components. The liquid crystal cell was treated at 120 ° C for 30 minutes, and then the orientation state of the liquid crystal was observed with a polarizing microscope, and it was confirmed that the liquid crystal was uniformly oriented without missing. The pretilt angle at 23 ° C of the liquid crystal element was measured by a pretilt angle measuring device (PAS-301) manufactured by ELSICON Co., Ltd. to be 22.1 °. Next, the voltage-transparency characteristic (ν-Τ curve) of the liquid crystal cell was measured at 23 ° C and 60 ° C, and the applied voltage (V90) 透射 at a transmittance of 90% was compared to evaluate the thermal stability. As a result, V90 at 23 °C was 0.72 V, and V90 at 60 °C was 0.66 V, and the shift from the temperature characteristic of the liquid crystal to the low voltage side was observed, but there was no shift from the high voltage side from the pretilt angle drop. Observe and confirm that the pretilt angle is not affected by the ambient temperature and is very stable. The measurement of the V-T curve and the calculation of V90 were carried out as follows. (1) Using a polarizing microscope in which the light receiving element is provided in the eye portion, the angle of the polarizer and the analyzer of the polarizing microscope is set to 90 degrees. (2) Set the liquid crystal element so that the orientation processing directions of the upper and lower substrates are consistent with the polarizing direction of the polarizer or the analyzer, and the light transmission is the most when no voltage is applied (24) (24) 1374928 (3) for the liquid crystal element The AC rectangular wave of 30 Hz is applied gradually to 5δ of 5V to 0.0 IV, and the amount of light transmitted by the above-mentioned light-receiving element is recorded by the above-mentioned light-receiving element. (4) The light-transmitting amount when no voltage is applied is 100% transmittance. The amount of light transmission when ±5 V was applied was 0% of the transmittance, and the relationship between the applied voltage and the transmittance was plotted, and the applied voltage 値 at a transmittance of 90%, that is, V90, was read from the graph. (5) The measurement at 23 °C was carried out at room temperature of 23 t, and the measurement at 60 °C was carried out by heating the liquid crystal element on the stage of the polarizing microscope at 60 °C. &lt;Example 2&gt; As in the case of the coating film obtained in Example 1, instead of the flat grinding treatment, the illuminating device 〇pt〇AlignTM (E 3 - UV - 6 0 0 - A) manufactured by ELSICON Co., Ltd. was used, and the angle of the lamp was 0 deg, irradiated with light of 20 Å, and subjected to light orientation treatment to obtain a substrate with a liquid crystal alignment film. Two sheets of the above-mentioned substrate with a liquid crystal alignment film are prepared, and a gap control material of 6 μm is dispersed on a liquid crystal alignment film surface of a substrate, and the light is irradiated in a direct direction to be bonded, and a nematic liquid crystal (ZLI manufactured by MERCK Co., Ltd.) is injected. -4792) Fabricating a liquid crystal element. The liquid crystal element was 1 2 0 . (:, 30 minutes for treatment, the orientation state of the liquid crystal was observed by a polarizing microscope, and it was confirmed that there was no deletion and uniform orientation. The liquid crystal element was measured for the pretilt angle as in Example 1, and the ν_τ curve was measured. 22.5 °. In addition, 23 t of V90 is 0.78 V, 60 V of V90 is 0.66 V, and the temperature characteristic from the liquid crystal is observed to the low voltage -29 - (25) (25) 1374928 pressure side offset 'but no From the observation of the deviation from the pretilt angle to the high voltage side, it was confirmed that the pretilt angle was not affected by the ambient temperature and was very stable. <Comparative Example 1 &gt; p-phenylenediamine 9.73 g (〇jm〇q and 1,3 - 3.77g (0·1 mo &lt;) of diamine-4-octadecyloxybenzene was dissolved in n-methylpyrrolidone (NMP) 187.8 g, and cyclohexanetetracarboxylic dianhydride I9.61 g (0.1 mol) was added thereto. The reaction was carried out at room temperature for 24 hours to obtain a poly-proline. The weight average molecular weight of the obtained poly-proline was {6000. The reaction solution of the poly-proline was added with a solution of NMP to a concentration of 3 wt%. Liquid crystal aligning agent for comparison. A liquid crystal element was produced as in Example 1 using the above liquid crystal aligning agent. The orientation state of the liquid crystal cell was observed by a polarizing microscope, and it was confirmed that there was no deletion and uniform alignment. The liquid crystal cell was measured as the ν-τ curve by measuring the pretilt angle as in Example 1. As a result, the pretilt angle was 6.5 °. The V90 of °C is 0.87V' V90 of 60 t is 1.01V, the shift to the high voltage side due to the decrease of the pretilt angle of 60 r is observed, and the pretilt angle is unstable. &lt;Comparative Example 2&gt; Phenylenediamine 9.3 7g (〇.〇9m〇z) and 4-[4-(4-anti-n-heptylcyclohexyl)phenoxy]·], 3-limb benzene 3.8]g (O.Olmo^ ) dissolved in N -methyl hydrazine ketone (NMP) 1 87.8g 'with cyclobutane tetracarboxylic acid monoanhydride added thereto 9.61 g (26) (26) 1374928 (0.1 mo &lt; ), reacted at room temperature for 24 hours, Polylysine. The weight average molecular weight {Mw} of the obtained polyamic acid is 143000. The reaction solution of the polyphthalic acid is added with a solution of NMP to a concentration of 3 wt%, which is used as a liquid crystal aligning agent for comparison. The alignment treatment agent was used to prepare a liquid crystal element as in Example 1. The orientation state of the liquid crystal element was observed with a polarizing microscope, and it was confirmed that there was no deletion and uniform orientation. The liquid crystal cell was measured for the pretilt angle as in Example 1, and was measured for the VT curve. As a result, the pretilt angle was 20.9 °. Further, the V90 at 23 ° C was 0.63 V '60 ° C and the V90 was 0.76 V, and 60 ° C was observed. The deviation of the pretilt angle from the high voltage side is unstable. <Comparative Example 3> 12.72 g (0.05 m〇i) of n-dodecyl methacrylate and 7.11 g (0.55 mol) of glycidyl methacrylate were dissolved in NMP 69·3 g, and the flask was replaced with nitrogen, and the temperature was raised. Up to 70 °C. After the temperature was raised, 0.2 g of azoisobutyronitrile (AIBN) dissolved in 10 g of NMP was added under a nitrogen atmosphere, and the mixture was reacted for 24 hours to obtain a comparative addition polymer. The weight average molecular weight {Mw} of the addition polymer is 32000 ° p-phenylenediamine 8.65 g (0.8 mol) and 4-[4-(4-trans-n-heptylhexyl)phenoxy]-1,3- 7.61 g (0.2 mol &lt;) of diamine benzene was dissolved in N-methylpyrrolidone (NMP) 2 0 3.3 g, and cyclobutane tetracarboxylic dianhydride was added 19.6 lg (O.lmo"), and reacted at room temperature 24 In hours, poly-proline is obtained. The weight average molecular weight {Mw} of the obtained polyamic acid was 143,000. &quot;31 * (27) (27) 1374928 A reaction solution of the above-mentioned addition polymer was added with NMP to obtain a solution having an addition polymer concentration of 3 wt%. Further, NMP' was added to the reaction solution of the polyamic acid obtained above to obtain a solution having a polyglycine concentration of 3 wt%. 99 g of a 3 wt% solution of the polyamic acid was added to the 3% by weight solution lg of the above-mentioned addition polymer, and the mixture was thoroughly stirred to obtain a homogeneous solution to obtain a liquid crystal aligning agent for comparison. A liquid crystal element was produced as in Example 2 using the above liquid crystal aligning agent. The orientation state of the liquid crystal cell was observed with a polarizing microscope, and it was confirmed that there was no deletion and uniform orientation. The pretilt angle was measured for the liquid crystal element as in the Example, and the V-T curve was measured. As a result, the pretilt angle was 2 2 · 1 °. 2 3 °C V 9 0 is 0.7 Ο V, 6 0 t: V 90 is 1.2 8 V, and a large offset to the high voltage side due to a 60 °C pretilt angle drop is observed. The pretilt angle is very high. stable. <Comparative Example 4 &gt; A 3 wt% solution of polylysine prepared in Comparative Example 3 was used as a liquid crystal directional treatment agent for comparison. Using this liquid crystal alignment treatment agent, a liquid crystal element was produced as in Example 2. The orientation state of the liquid crystal cell was observed with a polarizing microscope, and it was confirmed that there was no uniform orientation of the missing. The liquid crystal element was measured for pretilt angle as in Example 1, and the V-T curve was measured. As a result, the pretilt angle was 15.9°. Further, the V90 at 23 °C is 0.78 V', and the V90 at 60 °C is 1.42 V. A large shift to the high voltage side due to a decrease in the pretilt angle of 60 °C is observed, and the pretilt angle is extremely unstable. -32 - (28) (28) 1374928 &lt;Comparative Example 5 &gt; The 3 w t % solution of the polylysine prepared in Example 1 was used as a liquid crystal aligning agent for comparison. Using this liquid crystal alignment treatment agent, a liquid crystal element was produced as in Example 2. The orientation state of the liquid crystal cell was observed with a polarizing microscope, and it was confirmed that there was no uniform orientation of the missing. The liquid crystal cell was measured for pretilt angle as in Example 1 and the v - T curve was measured. As a result, the pretilt angle is as low as 〇.3°. Further, the V90 at 23 ° C was 1.41 V', and the V90 at 60 ° C was 1.33 V, and the shift from the liquid crystal temperature characteristic to the low voltage side was observed. This table 2 3 . (:There are no pretilt angles in the next few cases, so the temperature is raised to 60 °c and there is no observation of the pretilt angle drop. Table 1

Directional pretilt angle 2 3〇C 60〇C Δ V90 値V90値V90値 (23T: -6(TC) Example 1 Good 22.1. 0.72V 0.66V 0.06V Example 1 Good 22.5. 0.78V 0.66V 0.12V Comparative Example 1 Good 16.5. 0.87V 1.01 V -0· 14V Comparative Example 2 Good 20.9. 0.63V 0.76V -0.13V Comparative Example 3 Good 22. Γ 0.70V 1.28V -0.58V Comparative Example 4 Good 15.9 0.78V 1.42V -0.64V Comparative Example 5 Good 0.3° 1.41 V 1.3 3 V 0.08V (29) 1374928 [Simplified Schematic] Figure 1 shows the v-τ curve of Example 1. Figure 2 compares VT graph of Example 4. [Explanation of main component symbols] V: Applied voltage (V) T: Transmittance (%) 23 °C: V-Τ curve of 23 °C 60 °C: V-Τ of 60 °C curve

Claims (1)

1374928 Patent Application No. 093132263 Patent Application Revision of the Chinese Patent Application No. 1989, the disclosure of which is incorporated herein by reference. An addition polymer of a unit, and at least one polymer selected from the group consisting of polylysine-, polyimine, polyamine, polyester, and polyurea, B—X1—X2—R1 (wherein A is a main chain structure of a polymer obtained by addition polymerization, and b is a single bond or a bond selected from the group consisting of esters, ethers, guanamines, and urethanes; XI and X2 independently represent an aromatic ring, an alicyclic ring or a heterocyclic ring... R1 represents an alkyl group having 3 to 18 carbon atoms, an alkoxy group having 3 to 18 carbon atoms, a fluoroalkyl group having 1 to 5 carbon atoms, and a carbon source. a fluoroalkoxy group, a cyano group or a halogen atom having a number of 1 to 5, wherein the addition polymer is in the formula (1) of the structural unit, and the portion indicated by AB has the following formula (2) The constructor, / R2 \ Ο 〇 (2) 1374928 (wherein R2 represents a hydrogen atom, a methyl group or a halogen atom). 2. The liquid crystal aligning treatment agent according to claim 2, wherein the addition polymer is at least one selected from the group consisting of polyamic acid, polyamidiamine, polyamine, polyester, and polyurea. The state of the chemical combination of the polymer is contained. 3. The liquid crystal directional treatment agent according to the first or second aspect of the patent application, wherein the weight ratio of the structural unit represented by the formula (1) among the polymer components contained in the liquid crystal aligning treatment agent is 〇. 〇丨 to 50% by weight. 4. The liquid crystal aligning agent according to claim 1, wherein the addition polymer contains the structural unit represented by the formula (1), and the number of the structural units is 50% or more' and all of the polymer components are as described above. The ratio of the addition polymer is from 0.1 to 20% by weight. 5. The liquid crystal aligning agent according to the first aspect of the invention, wherein the structural unit of the formula (1) contained in the addition polymer is 5% or more in terms of the number of structural units. A liquid crystal display element characterized by using a liquid crystal aligning agent as claimed in any one of claims 1 to 5. -2-