TWI359189B - Liquid crystal alignment agent, liquid crystal ali - Google Patents

Description

1359189 IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element. More specifically, the liquid crystal alignment agent which can obtain the following liquid crystal alignment film, and the liquid crystal alignment film and the above liquid crystal display element using the alignment film, which have reliability, low afterimage resistance, abrasion resistance and liquid crystal It is excellent in the alignment property, and can be applied to a large substrate in particular, and it can be easily peeled off by any one of commercially available water-based or organic-based liquid crystal alignment film peeling liquids for the recovery of the substrate. [Prior Art] In the past, there has been known a TN type liquid crystal display element having a TN (Twisted Nematic) type liquid crystal cell, which is inserted into a transparent conductive film and formed a liquid crystal on the surface. Between the substrates of the alignment film, a nematic liquid crystal layer having positive dielectric anisotropy is formed to form a laminated structure, and the long axis of the liquid crystal molecules is continuously twisted by 90 degrees from one substrate toward the other substrate.

In addition, there is also a STN (Super Twisted Nematic) type liquid crystal display element. In the STN type liquid crystal display element, the long axis of the liquid crystal molecule is achieved at 180 degrees or 1 between the substrates by the addition of the palm powder. The state of continuous twisting of 80 degrees or more utilizes the birefringence effect thus produced. Further, recently, a nematic liquid crystal layer in which a homeotropic alignment state having a negative dielectric anisotropy is formed between opposite substrates, or a cholesteric liquid crystal layer in which a spiral axis is parallel to a substrate normal is developed. A guest-host type reflective liquid crystal display element in which a coloring matter is added to a liquid crystal layer. Here, as a liquid crystal alignment film material which constitutes a liquid crystal display element of 1359189, polyimides, polyamines, polyesters and the like are known in the past. In particular, polyimine is used in many liquid crystal display elements because of its excellent heat resistance, affinity with liquid crystals, and mechanical strength. However, recently, liquid crystal display elements have been increased in size, light weight, and low in power consumption. In view of the fact that the high-performance display elements have been significantly developed, the performance requirements for liquid crystal alignment films have become increasingly stringent. In particular, the process improvement and cost reduction requirements associated with the enlargement of the substrate are also stricter. However, an alignment film formed of a polyimine precursor which is known in the prior art, or a quinone imine polymer having a structure obtained by dehydration and ring closure, has high reliability and high alignment quantitative force. The high abrasion resistance imparts high adhesion to the substrate and coating properties. As a result, in order to reduce the cost, the large-sized substrate is recovered, that is, the commercially available water-based and organic-based liquid crystal alignment film peeling liquid peeling off the alignment film cannot be sufficiently peeled off. On the other hand, an alignment film which is easily peeled off by a commercially available liquid crystal alignment film peeling liquid can be used, and has problems of reliability, alignment quantitative force, and abrasion resistance.

An object of the present invention is to provide a liquid crystal alignment agent which can provide a liquid crystal alignment film which can achieve good reliability, alignment characteristics, and abrasion resistance, and can be easily peeled off with a commercially available water-based and organic release liquid. Another object of the present invention is to provide a liquid crystal alignment film having various excellent properties as described above. Still another object of the present invention is to provide a liquid crystal display element comprising the liquid crystal alignment film of the present invention. 1359189 In addition to TN type and STN type liquid crystal display elements, it can also be applied to SH (Super Vertical) type, IPS (In-Plane Switching) type. , ferroelectric and antiferroelectric liquid crystal display elements, and the like. Further, the liquid crystal display element of the present invention can be effectively used in various devices, for example, in a display device such as a desktop computer such as a watch, a timer, a parameter display panel, a word processor, a personal computer, or a liquid crystal television. detailed description

Hereinafter, the present invention will be described in detail. The liquid crystal alignment film of the present invention can be usually formed by applying the liquid crystal alignment agent of the present invention to a transparent electrode plate, followed by drying (generally, heat drying), and performing rubbing or the like on the surface of the film. The liquid crystal alignment agent of the present invention is composed of a polymer having at least one bonding unit of a quinone imine bonding unit and a proline bonding unit formed by a reaction of a tetracarboxylic dianhydride and a diamine, or a mixture thereof. . In the case where the liquid crystal alignment agent contains both bonding units, it may contain a mixture of polyimine and polylysine, or may contain a polymer having a quinone bond unit and a hydrazine bond unit. In the polymer, the oxime bond unit and the guanamine bond unit may be contained in any of random or block states. In the liquid crystal alignment film of the present invention, when the liquid crystal alignment agent is applied onto a substrate and dried, the film may be dried by heating and drying, and the unit of the liquid phase alignment agent may be dehydrated and closed to form a quinone imine bond unit. <Polyamic acid> The polylysine used in the present invention can be subjected to ring-opening polymerization of a tetracarboxylic acid dianhydride and a diamine compound to obtain an acid anhydride, I, 2, 3, 4 -furan tetracarboxylic acid dianhydride, 4,4, bis(3,4-dimercaptophenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4.dicarboxyphenoxy) Diphenyl sulfide dianhydride '4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane diacid, 3,3',4,4'-perfluoroisopropylidene Phthalic acid dianhydride, 3,3,4,4,biphenyltetracarboxylic acid dianhydride, bis(phthalic acid)phenylphosphine hydride dianhydride, phenyl-bis(triphenylene) Terephthalic acid, phenyl-bis(triphenylphthalic acid) dianhydride bis(triphenylphthalic acid) _4,4,-diphenyl dianhydride, double (three Phenylphthalic acid)·4,4,-diphenylmethane diacid oxime, ethylene glycol-bis(dehydrated trimellitic acid vinegar), propylene glycol-bis(dehydrated trimellitic acid vinegar), 1,4 - Butanediol - bis (dehydrated trimellitate), iota, hexamethylene glycol - bis (dehydrated trimellitate), 1,8- Octanediol-bis(dehydrated trimellitate), 2,2-bis(4-hydroxyphenyl)propanoid-bis(anhydrophthalic acid ester)' represented by the following formulas (1) to (4) An aromatic tetracarboxylic dianhydride compound such as a compound. They may be used singly or in combination of at least two.

-12- 1359189

For the above polytetracarboxylic dianhydride used in the present invention, it is preferred to use 50 to 0.1, particularly preferably 25 to 0.1 mol%, to make some other tetracarboxylic acid dianhydride compound or a mixture thereof, relative to All mole%, more preferably 30~0.1 mole%. [Diamine compound] As the diamine compound, p-phenylenediamine, bisaminopropyltetramethyl-13-1359189 methylphenoxy)phenyl]hexafluoropropane, 4,4,-diamino group- An aromatic diamine such as 2,2'-bis(trifluoromethyl)biphenyl, 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl; p-Benzyldiamine, 1,3-propanediamine, butanediamine, pentanediamine, hexamethylenediamine, heptanediamine, octanediamine, decanediamine, heptanediamine, 1,4-diamine Cyclohexane 'isophorone diamine, tetrahydrodicyclopentadiene diamine, hexahydro-4,7-methylene dimethylene diamine, tricyclo[6,2,1,02· 7]-undecene dimethyl diamine, 4,4'-methylene bis(cyclohexylamine) and other aliphatic and alicyclic diamine;

a monosubstituted phenylenediamine represented by the following formula (III); a diamine organooxime represented by the following formula (IV) (except for bisaminopropyltetramethyldioxane) ; [化3]

(III)

(IV) wherein X represents a divalent organic group selected from the group consisting of -0-, -COO-, -OCO-, -NHCO-, -CONH- and -CO-, and R5 represents a steroid-like skeleton or trifluoro a monovalent organic group of a methyl group. R9 represents a hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R9 groups may be the same or different, p is an integer of 1 to 3, and q is an integer of 1 to 20) -15 - 1359189 The compounds represented by the following formulas (5) to (8) and the like. These diamine compounds may be used singly or in combination of at least two. [Chemical 4]

H2N

(7)

(8) (wherein, y is an integer of 2 to 12, and Z is an integer of 1 to 5) These other diamine compounds, for the above-mentioned polymer or a mixture thereof used in the present invention, relative to all diamine compounds, It is preferably used in an amount of from 0.5 to 0.1 mol%, more preferably from 50 to 0.1 mol%. Tetracarboxylic acid dianhydride and diamine compound for polyamic acid synthesis reaction @ -16- 1359189 • The ratio of use, relative to 1 equivalent of the amine group contained in the diamine compound, the anhydride group contained in the tetracarboxylic acid dianhydride It is preferably 2 to 2 equivalents, and more preferably 0 to 3 to 1.4 equivalents. When the ratio of the acid anhydride group contained in the tetracarboxylic acid dianhydride is less than 0.2 equivalents and in the case of more than 2 equivalents, the molecular weight of the obtained polymer may become too small, and the coatability of the liquid crystal alignment agent may be deteriorated. Happening. The polyaminic acid constituting the liquid crystal alignment agent of the present invention is synthesized by reacting the above tetracarboxylic acid dianhydride with the above diamine compound. The synthesis reaction of polylysine, f is usually carried out in an organic solvent at a temperature of from 0 to 150 ° C, more preferably from 〇 to 10 ° C. When the reaction temperature is below 0 °C, the solubility of the compound in the solvent may be deteriorated. If it exceeds 150 °C, the amount of the obtained polymer molecule may be lowered. The organic solvent to be used in the synthesis of the poly-proline is not particularly limited as long as it can dissolve the polyamic acid formed by the reaction of the dicarboxylic acid dianhydride and the diamine compound. For example, γ-butyrolactone, N- Methyl-2-pyrrolidone, hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine-dimethylacetamide, dimethyl hydrazine, tetramethylammonium, hexamethylphosphonium triamine, 1, An aprotic polar solvent such as 3-dimethyl-2-imidazolidinone; a phenolic solvent such as m-cresol, xylenol, phenol or halogenated phenol. The amount of the organic solvent used is preferably 0.1 to 30% by weight based on the total amount (Β + Β) of the reaction raw material tetracarboxylic acid dianhydride and the diamine compound (Α + Β). the amount. Further, in the above organic solvent, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons of a weak solvent of polyproline may be used in combination within a range in which the produced polyamine does not precipitate. Classes, etc. As a specific example of the weak solvent, -17- 1359189

For example, methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetic acid can be mentioned. Ester, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethyl Glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, Ethylene glycol methyl ether acetate, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol dimethyl ether , dipropylene glycol diethyl ether, ethylene glycol ethyl ether acetate, 4-hydroxy-4-methyl-2-pentane, ethyl 2-hydroxyacetonate, ethyl lactate, methyl lactate, lactic acid Ester, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethyl oxygen Methyl propionate, 3-methyl-3-methoxybutanol, 3-ethyl-3-methoxybutanol, 2-methyl-2-methoxybutanol, 2-ethyl- 2-methoxybutanol, 3-methyl-3-ethoxybutanol, 3-ethyl-3-ethoxybutanol, 2-methyl-2-ethoxybutanol, 2-B Ethyl-2-ethoxybutanol, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, Heptane, octane, benzene, toluene, xylene, and the like. They may be used singly or in combination of at least two kinds. By the above synthesis, a polymer solution in which polylysine is dissolved can be obtained. Then, the reaction solution is poured into a large amount of a weak solvent to obtain a precipitate, and the precipitate is dried under reduced pressure to obtain a polyamic acid. Further, the polyaminic acid can be purified by performing a process in which the polyamic acid is redissolved in an organic solvent once and then precipitated in a weak solvent. -18-1359189 - <Polyimine> The polyimine of the liquid crystal alignment agent of the present invention can be produced by the following methods (1) to (2). Further, a polymer in which a part of the repeating unit of polylysine is dehydrated and closed, and the so-called oxime imidization ratio is less than 100% is also applicable to the liquid crystal alignment agent of the present invention. Method (1): A method in which polylysine is heated to dehydrate and ring. The reaction temperature of the method is preferably 60 to 300 ° C, more preferably 120 to 250 ° C. When the reaction temperature is lower than 60 ° C, the ruthenium imidization reaction is not sufficiently carried out, and the reaction temperature exceeds 25 ° C, and the molecular weight of the obtained polyimine is lowered. Method (2): Dissolving polylysine in an organic solvent, adding a dehydrating agent and a hydrazine imidization catalyst to the solvent, and heating may be carried out as needed. In the method, as the dehydrating agent, for example, acetic anhydride, propionic anhydride, or the like can be used.

Anhydride such as trifluoroacetic anhydride. The amount of the dehydrating agent to be used is preferably 1.6 to 20 moles per 1 mole of the polyamido acid repeating unit. Further, as the ruthenium amide catalyst, a tertiary amine such as pyridine, trimethylpyridine, lutidine or triethylamine can be used. However, it is not limited to the use amount of these ruthenium imidization catalysts, and it is preferably 0.5 to 10 moles with respect to the dehydrating agent used for 1 mole. In addition, examples of the organic solvent used in the ruthenium imidization reaction include the same organic solvents as those exemplified as the solvent used for the synthesis of polyamic acid. Further, the reaction temperature of the hydrazine imidization reaction is preferably from 0 to 180 ° C, more preferably from 60 to 150 ° C. ·<Intrinsic viscosity of polyaminic acid and polyimine> Intrinsic viscosity of polylysine and polyimine obtained as above (30 ° C, in N-methyl-2-indole The measurement is the same as the above, preferably from -19 to 1359189, 0.05 to 10 dl/g, more preferably from 0.05 to 5 dl/g. <Terminal-Modified Polymer> The poly-proline and the polyimine used in forming the liquid crystal alignment agent of the liquid crystal alignment film of the present invention may be terminal-modified polymers. The terminal modified polymer has a molecular weight which can be adjusted to improve the coating properties of the liquid crystal alignment agent without impairing the effects of the present invention. The terminal-modified polymer can be synthesized by adding an acid anhydride, a monoamine compound, or a monoisocyanate compound to the reaction system when synthesizing polyglycolic acid.

Examples of the acid anhydride added to the reaction system in order to obtain the terminal modified polymer in the synthesis of polyamic acid include maleic anhydride, phthalic anhydride, isoconic anhydride, n-decyl succinic anhydride, and n-dodecyl group. Succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl succinic anhydride, and the like. Further, as the monoamine to be added to the reaction system, for example, aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, and n- Amine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecaneamine, n-octadecylamine, n-dodecylamine and other alkylamines: 3- Aminopropylmethyldiethoxydecane, 3-[N-allyl-N-(2-aminoethyl)]aminopropyltrimethoxydecane, N-(2-aminoethyl , 3-aminopropylmethyldimethoxydecane, N-[(3-trimethoxydecyl)propyl]diethylenetriamine, and the like. Further, examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate. <Liquid crystal alignment agent> The liquid crystal alignment film of the present invention is usually formed by dissolving a liquid crystal alignment agent containing the above polyimine and/or polyamic acid in an organic solvent. -20- 1359189 - The organic solvent constituting the liquid crystal alignment agent of the present invention may, for example, be the same solvent as exemplified as the solvent used in the synthesis reaction of polylysine. Further, a weak solvent exemplified as a solvent to be used in combination in the polyamic acid synthesis reaction may be appropriately selected and used in combination. The solid content concentration in the liquid crystal alignment agent forming the liquid crystal alignment film of the present invention can be selected in consideration of viscosity, volatility, etc., preferably in the range of 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 which is a liquid crystal alignment film. However, when the solid content concentration is less than 1% by weight, the film thickness of the coating film is too small and it is difficult to obtain a good film. Liquid crystal alignment film. When the solid content concentration is more than 10% by weight, the film thickness of the coating film is too large to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent is increased, and the coating property is liable to be deteriorated. Further, the temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably from 0 ° C to 200 ° C, more preferably from 20 ° C to 60 ° C. <Epoxy group-containing compound> The liquid crystal alignment agent which forms the liquid crystal alignment film of the present invention may optionally contain a compound having at least one epoxy group in the molecule. Examples of the compound having at least one epoxy group in the molecule include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol. Diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6·hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2'-dibromo neopentyl glycol diglycidyl ether, 1, 3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylenediamine, 1,3-bis(Ν,Ν· Diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, etc. are preferred as the epoxy-containing The mixing ratio of the compound of the base-21 to 1359189 w is preferably not more than 40 parts by weight, more preferably 0.1 to 30 parts by weight, per 100 parts by weight of the polymer. The liquid crystal alignment agent which forms the liquid crystal alignment film of the present invention may further contain a compound containing a functional decane from the viewpoint of improving the adhesion of the substrate surface. Examples of the functional decane-containing compound include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, and 2-amino group. Propyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldi Φ methoxy decane, 3-ureidopropyl trimethoxy decane, 3-ureidopropyl triethoxy decane, N-ethoxycarbonyl-3-aminopropyl trimethoxy decane, N-B Oxycarbonyl-3-aminopropyltriethoxydecane, N-triethoxydecylpropyltriamine, N-trimethoxydecylpropyltriamine, 10-trimethyl Oxidylalkyl-1,4,7-triazadecane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6- Diazepine acetate, 9-triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl Alkyl-3-aminopropyltriethoxydecane, N-% phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N- double( Ethylene) -3-aminopropyl trimethoxy Silane, N- bis (ethylene oxide) - 3-amino propyl triethoxy silane-like. The mixing ratio of the functional decane-containing compound is preferably not more than 4 parts by weight, more preferably 0.1 to 30 parts by weight, per 100 parts by weight of the polymer. <Liquid crystal display element> The liquid crystal display element obtained by using the liquid crystal alignment film of the present invention can be produced, for example, by the following method. -22- 1359189

(1) A liquid crystal alignment agent which forms the liquid crystal alignment film of the present invention is coated on one surface of a substrate on which a patterned transparent conductive film is provided by, for example, a roll coating method, a spin method, a printing method, or the like, and then the coated surface is heated. A coating film is formed. Here, as the substrate, for example, glass such as float glass or soda glass can be used: it is formed of plastic such as polyethylene terephthalate, polybutylene terephthalate or polyether milled polycarbonate. Transparent substrate. As the transparent conductive film provided on one surface of the substrate, NESA formed of tin oxide (Sn〇2) can be used.

A film (registered trademark of PPG, USA), an ITO film formed of indium oxide-tin oxide (In2〇3_Sn〇2), or the like. The pattern of these transparent conductive films may be a photolithography method or a pre-mask method. In the application of the liquid crystal alignment agent, a functional decane-containing compound, a functional titanium-containing compound, or the like may be applied to the surface of the substrate in order to improve the adhesion between the substrate surface and the transparent conductive film and the coating film. The heating temperature after application of the liquid crystal alignment agent is preferably 80 to 300 ° C, more preferably 12 0 to 2 50 ° C. Further, the liquid crystal alignment agent of the present invention containing polyglycolic acid is formed into a coating film which becomes an alignment film by coating, and then dehydrated and closed by heating, whereby a coating film which is further imidized can be obtained. The film thickness of the coating film is preferably 〇·〇〇1 to 1 μmη, more preferably 0.005 to 0.5 μmη. (2) A rubbing treatment is performed on the formed coating film surface by a roll wound with a cloth formed of fibers such as nylon, rayon, cotton or the like in a predetermined direction. Thus, liquid crystal molecular alignment ability is provided on the coating film to form a liquid crystal alignment film. In addition, the liquid crystal alignment film which is formed by the liquid crystal alignment agent of the present invention is subjected to a treatment for changing the pretilt angle by locally irradiating ultraviolet rays, as shown in Japanese Laid-Open Patent Publication No. Hei. 6-222366 or Japanese Patent Application Laid-Open No. Hei No. Hei. -23- 1359189 - A protective film is partially formed on the surface of the liquid crystal alignment film subjected to the rubbing treatment as disclosed in Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei. In order to change the liquid crystal alignment ability of the liquid crystal alignment film, the field of view characteristics of the liquid crystal display element can be improved. (3) fabricating two substrates on which the liquid crystal alignment film is formed as described above, inserting the two substrates into the gap (unit spacing), and arranging the peripheral portions of the two substrates with a sealant, and distinguishing them by the surface of the substrate and the sealant. In the cell gap, φ is implanted into the liquid crystal to seal the injection hole and constitute a liquid crystal cell. Further, the outer surface of the liquid crystal cell, i.e., the other side of the transparent substrate constituting the liquid crystal cell, was adhered to the polarizing plate to obtain a liquid crystal display element. Here, as the sealant, for example, a curing agent and an epoxy resin containing an alumina ball as a gasket may be used as the liquid crystal, and a nematic liquid crystal may be mentioned. For example, you can use Schiff City.

Liquid crystal, oxidized azo liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal 'dioxane liquid crystal , bicyclooctane liquid crystal, cubic liquid crystal liquid crystal, and the like. In addition, in these liquid crystals, a cholesteric liquid crystal such as cholesterol chloride, cholesterol phthalate cholesteryl carbonate, or the like, which is sold under the trade name "C-15" and "CB-15" (made by Merck) can be added. Used in the case of agents. In addition, as a polarizing plate which is adhered to the outer surface of the liquid crystal cell, for example, a polarizing film called a ruthenium film which absorbs iodine while stretching and dispersing polyvinyl alcohol is sandwiched by a cellulose acetate protective film. A polarizer or a polarizing film formed by the ruthenium film itself. -24- 1359189 - <Liquid crystal alignment film peeling liquid> The peeling liquid used for peeling the liquid crystal alignment film of the present invention from the substrate may, for example, contain an ethylene glycol solvent and a basic compound and/or a nonionic An aqueous solution-based stripping solution of a surfactant or an organic solvent-based stripping liquid containing N-methylpyrrolidone or γ-butyrolactone. Examples of the ethylene glycol-based solvent contained in the aqueous solution-based stripping solution include ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monoisopropyl ether, and diethylene glycol monobutyl ether acetate. Wait.

Further, examples of the basic compound include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, ammonium dihydrogen phosphate, and potassium dihydrogen phosphate. , sodium dihydrogen phosphate, lithium niobate, sodium citrate, potassium citrate, lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate, ammonia, tetramethylammonium hydroxide, dihydroxyethyl hydroxide Trimethylammonium, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, ethanolamine, hydrazine-methyl Piperidine, trimethylhydroxyethylammonium hydroxide, and the like. Further, examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene allyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene derivative, and ethylene oxide/propylene oxide block copolymerization. , sorbitol fatty acid ester 'polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine

Further, the above-mentioned organic solvent-based peeling liquid may, for example, be formed of yttrium-methylpyrrolidinium or γ-butyrolactone or may contain not less than 20% of the above solvent -25-

Claims (1)

1359189 f t Amendment Patent No. 094100689 "Liquid Crystal Alignment Agent, Liquid Crystal Alignment Film and Liquid Crystal Display Element" (Revised on July 4, 2011) X. Patent Application: a liquid crystal alignment agent which is a polymer having at least one bonding unit formed by reacting a tetracarboxylic dianhydride with a diamine, and at least one bonding unit of a proline bonding unit or The mixture is characterized in that the tetracarboxylic dianhydride of the polymer or a mixture thereof contains three kinds of tetracarboxylic dianhydrides, which are 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, l ,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-di-oxo-3-furanyl)naphtho[l,2-c]furan-1 , 3-dione and pyromellitic dianhydride; and the diamine contains a selected from the group consisting of p-phenylenediamine, bisaminopropyltetramethyldioxane, 4,4'-diaminodiphenyl At least three of methane, 2,2'-dimethyl-4,4'-diaminobiphenyl and 3,6-bis(4-aminobenzylideneoxy)cholestane Patent application of the liquid crystal alignment agent of item 1, wherein the above three tetracarboxylic acids The composition of the acid dianhydride contains at least 3 mole % of pyromellitic diacid anhydride. 3. The liquid crystal alignment agent of claim 1 or 2, which further comprises a compound having at least one epoxy group in the molecule. A liquid crystal alignment film formed by the liquid crystal alignment agent according to any one of claims 1 to 3. A liquid crystal display element comprising a liquid crystal alignment film according to item 4 of the patent application.