TW200527081A - Liquid crystal alignment treating agent for vertical alignment and liquid crystal display - Google Patents

Abstract

A liquid crystal alignment treating agent for vertical alignment with which a liquid crystal alignment layer for vertical alignment excelling in aging resistance and voltage retention performance at high temperature can be prepared; and a liquid crystal display capable of high-quality displaying being stable over a prolonged period of time. There is provided a liquid crystal alignment treating agent for vertical alignment, comprising at least either one polymer among a polyamic acid obtained by reaction of a diamine of given structure containing an aromatic ring, a diamine of given structure containing an aromatic ring and a carbon to carbon unsaturated bond and a tetracarboxylic acid dianhydride containing an alicyclic structure and a polymer resulting from dehydration ring closure of the polyamic acid. There is further provided a liquid crystal display obtained with the use of the liquid crystal alignment treating agent.

Description

200527081 (1) IX. Description of the invention [Technical field to which the invention belongs] The present invention relates to a liquid crystal alignment treatment agent for forming a liquid crystal alignment film of a vertical alignment type liquid crystal display element, and a liquid crystal display element produced by using the same. [Prior art] The basic structure of a liquid crystal display element is a structure in which liquid crystal substances are filled between two opposing substrates. The liquid crystal substance is maintained by a liquid crystal alignment film provided on the substrate surface to maintain a desired initial alignment state. The liquid crystal alignment film mainly uses a polyimide resin film with excellent heat resistance, and realizes vertical alignment and horizontal alignment for the substrate. Means for achieving vertical orientation are known as a method of introducing a long-chain alkyl chain into a polyamic acid and a polyimide (refer to, for example, Patent Document j), and a method of introducing a cyclic substituent (see, for example, Patent Documents 2 and 3). ). The vertical alignment type liquid crystal display element has the characteristics of fast response speed, large viewing angle and high contrast, and there are proposals for new vertical alignment type liquid crystal display elements such as MVA, ASV, and PVA. In addition, the driving method of these liquid crystal display elements has conventionally been known as matrix display in which display patterns such as stripes or grids are formed on the substrate by electrodes, and the recent vertical alignment type liquid crystal display elements use high-definition, low-power Thin film transistor (TFT) liquid crystal display element. The use of these vertical alignment type liquid crystal display elements has been expanded from the monitors of computers and portable devices in the past to the TV applications that require long-term reliability recently. TFT liquid crystal display elements have been developed with reliability indicators regardless of the orientation method (2 ) (2) One of 200527081, known characteristics of simple liquid crystal elements with voltage retention. Means for improving the voltage holding characteristic have been known to attempt to use a polyimide-based resin structure, and it is known that a high voltage holding ratio can be obtained by using an dianhydride having an aliphatic ring structure (refer to, for example, Patent Document 4, 5, 6) ° However, these are the methods to improve the voltage retention rate at high temperature. So far, there is no stabilization method for the voltage retention rate at high temperature due to the high voltage retention rate at high temperature and long-term reliability index. Patent Literature 1: Japanese Patent Laid-Open No. 6-3 6 7 8 Patent Literature 2: Japanese Patent Laid-Open No. 9-2 78 724 Patent Literature 3: Japanese Patent Laid-Open No. 200 1 -3 1 1 08 0 Patent Literature 4: Special Kaihei 5 -3 4 1 29 Japanese Patent Publication No. 5: Japanese Patent Laying-Open No. 8- 1 699 54 Japanese Patent Publication No. 6: Japanese Patent Laid-Open No. 1 1 -843 9 Japanese Patent No. 1 [Summary of Invention] (Problems to be Solved by the Invention) The invention provides a liquid crystal alignment treatment agent for vertical alignment, which is capable of forming a vertical alignment liquid crystal alignment film that has excellent voltage holding characteristics at high temperatures and excellent aging resistance at high temperatures, and provides a liquid crystal display element that can be stable for a long time for advanced displays. (Means for Solving the Problems) The problems of the present invention have been found to be solved by the following liquid crystal alignment treatment agents and liquid crystal display elements. -6-(3) 200527081 1 · A diamine component containing a diamine having a structure of the following formula (1) and a diamine having a structure of the following formula (2), and a tetracarboxylic acid dicarboxylic acid having an alicyclic structure A liquid crystal alignment treatment agent for vertical alignment of at least any polymer of polyamic acid obtained from the anhydride reaction or the dehydrated ring-closed material of the polyamino acid.

X factory x2 (in formula (1) \) form bond or a divalent bonding group selected from the group consisting of ether, ester, amidine, and urethane. X2 represents a linear alkyl group having 8 to 20 carbon atoms, Or a monovalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms.)

(In formula (2), 1 represents a linear hydrocarbon group having 1 to 12 carbon atoms or a branched hydrocarbon group having 1 to 12 carbon atoms, and h represents a hydrogen atom 'a linear hydrocarbon group having 1 to 12 carbon atoms, or a carbon atom. A branched hydrocarbon group having a number of 1 to 12. R3 and R4 independently represent a hydrogen atom or a methyl group.) 2. The liquid crystal alignment treatment agent for vertical alignment of the above 1, wherein the diamine component of the structure of the formula (1) accounts for the diamine. 10 to 80 mol%, and the diamine structure of formula (2) accounts for 20 to 90 mol%. (4) 200527081 Bu 1,3-diaminebenzene, and / or (4-trans-n-heptylbicyclohexyl) -3,5-diamine benzoate. 4. The liquid crystal alignment treatment agent for vertical alignment according to any one of 1 to 3 above, wherein the diamine having the structure of the formula (2) is a diamine having the structure of the following formula (3).

(3) 5. A liquid crystal display device using the liquid crystal alignment treatment agent for vertical alignment according to any one of 1 to 4 above. (Effects of the Invention) According to the present invention, a liquid crystal alignment film for vertical alignment, which has excellent voltage holding characteristics at high temperatures and excellent aging resistance at high temperatures, can be formed, and can be used as a liquid crystal display element for advanced display. The present invention is described in detail below. The liquid crystal alignment agent for vertical alignment of the present invention contains a diamine having a structure of the above formula (1) and a diamine component of the diamine having the structure of the formula (2) and a tetracarboxylic dianhydride having an alicyclic structure. A liquid crystal alignment treatment agent for vertical alignment of at least any polymer of the polyamic acid obtained by the reaction or the dehydrated ring-closed product of the polyamic acid. Formula (0 structure of diamine component) -8- (5) (5) 200527081 Formula (1) structure is one of the amines' is used to impart vertical alignment to the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention The amount is preferably 10 mol% or more of the total diamine components used in the reaction to obtain polyamic acid. In order to ensure the stability of vertical orientation, it is preferably 20 mol% or more, and 30 mol% or more is preferred. The relationship between the preferred amount of one of the amines of the formula (2) structure is 80 mol /% or less, more preferably 70 mol% or less. From the viewpoint of printability when the liquid crystal facing treatment agent of the present invention is used as a coating liquid, It is preferably 60% ο 1% or less. In the formula (1), the Xe epitope bond or a divalent bonding group selected from the group consisting of acid, vinegar, amine, and urethane. Among them, ether, ester, or Amidine is preferred. Diamines of different formula (1) may be used. X2 in formula (1) is a straight-chain alkyl group having 8 to 20 carbon atoms, or a lipid having 4 to 40 carbon atoms. The cyclic skeleton is a valence organic group. The linear alkyl group is preferably one having 12 to 18 carbon atoms, more preferably 16 to 18 carbon atoms. The alicyclic skeleton having 4 to 40 carbon atoms is Ring Monocyclic skeletons such as alkane, cyclopentane, cyclohexane, etc. These monocyclic skeletons have a combination of 2 or more, steroid skeletons such as cholesterol, cholesterol and the like. These monovalent organic groups having an alicyclic skeleton have One or more alkyl groups having 5 to 12 carbon atoms are preferred. The preferred positions of the two amine groups in formula (1) are relative to positions 2, 4 and 2, 5 or 3, 3 on the benzene ring of X] system. 5 position. Specific examples of the diamine structure of the formula (1) are given below, but are not limited thereto. 1 '3-monoamine-4-octadecylbenzene, 1,3-diamine-4 -hexadecylbenzene' Diamines having alkyl groups such as 1,3-diamine · 4_ + dioxobenzene. 4- [4- (4-trans-n-heptyl (6) 200527081 hexyl) phenoxy] -1,3-diamine Benzene, (4-trans-n-pentacyclohexyl) -3,5-diaminebenzene and other side chains have diamines similar to liquid crystal structures. Diamines with steroidal structures of the following formulae (4) to (6).

-10- (7) 200527081

Among the diamines mentioned above, 4- [4- (4-trans-n-heptylcyclohexyl) phenoxy] · 1,3-diaminebenzene, (4-trans-n-pentacyclohexyl) -3,5-diamine Diamines such as benzoate have side-chain-like diamines, which provide excellent stability in vertical orientation. < Diamine component of the structure of formula (2) > The diamine of the structure of formula (2) is used to impart stability to aging of the voltage holding ratio, and is characterized by having an N-allylaniline structure. It is preferably used in an amount of 20 mol% or more, and more preferably 30 m ο 1% or more of the total diamine component used in the reaction to obtain polyamic acid. From the relationship with the preferred amount of the diamine structure of the formula (1) described, it is preferably 90 mol% or less, more preferably 80 mol% or less, and even more preferably 70 mol% or less. The preferred positions of the two amine groups in formula (2) are, for N-allyl, the 2, 4 position, 2, 5 position, or 3, 5 position on the benzene ring. -11-(8) 200527081 Ri in the formula (2) is a linear nicotyl group having 1 to 12 carbon atoms or a branched hydrocarbon group having 1 to 12 carbon atoms. The hydrocarbon group preferably has a carbon-carbon double bond. The double bond is more preferably combined between the second carbon and the third carbon from the nitrogen atom. The number of carbon atoms of R 1 is preferably 6 or less, and more preferably 3 or less from the viewpoint of the printability of the liquid crystal alignment treatment agent. R2 in formula (2) represents a hydrogen atom, a linear hydrocarbon group having 1 to 12 carbon atoms, or a branched hydrocarbon group having 1 to 12 carbon atoms. The hydrocarbon group may also contain a carbon-carbon double bond. The number of carbon atoms of R2 is preferably 6 or less, and more preferably 3 or less. R2 is more preferably a hydrogen atom. In formula (2), R3 and R4 independently represent a hydrogen atom or a methyl group, and a hydrogen atom is preferred. A preferable example of the diamine having the structure of the formula (2) is a structure having the following formula (3).

(3) A specific example of a diamine having the structure of the following formula (2), but is not limited thereto.

-12- (9) 200527081

⑻

(9)

(10)

(ID Among the above diamines, the diamine of (7) or (8) is particularly preferred. ≪ Other diamine components > The diamine having the structure of the above formula (1) and the diamine having the structure of the above formula (2) are required. The diamine component of the present invention is used to control the printing characteristics of liquid crystal alignment treatment agents. (13) (10) (10) 200527081, various characteristics of residual DC voltage characteristics of liquid crystal elements, and may also contain other diamines. The amount of amine is preferably 70 mol% or less, more preferably 60 mol% or less, and 40 to 10 m ο 1% of the total diamine component used in the reaction to obtain polyamic acid. Special restrictions, specific examples include p-phenylenediamine, m-phenylenediamine, 2,5-diamine benzonitrile, 2,5-diamine toluene, 2,6-diamine toluene, 4,4'-diamine Benzene, 3,3, -dimethyl-4,4, -diamine biphenyl, 3,3, -dimethoxy-4 '4'-diamine biphenyl, diaminodiphenylmethane, diaminediphenyl Phenyl ether, diaminodiphenylamine, 2,2'-diaminodiphenylpropane, bis (3,5-diethyl-4-aminophenyl) methane, diaminodiphenylsulfone, diaminodiphenyl Methyl ketone, 3, 3'-diamine chalcone, 4,4 '· diamine chalcone, 3, 3, Amine] g, 4, 4'-diamine stilbene, diamine naphthalene, 1,4-bis (4-aminephenoxy) benzene, 1,4-bis (4-aminophenyl) benzene, 9,10- Bis (4-aminophenyl) anthracene, 1,3 · bis (4_aminophenoxy) benzene, 4,4, bis (4-aminephenoxy) diphenyl master, 2,2, -bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2 '2-bis [4- (4-aminephenoxy) phenyl] hexafluoro Aromatic diamines such as propane, 2,6-diamine pyridine, 2,4-diamine pyridine, 2,7-diamine benzofuran, 2,7-diamine carbazole, 3,7-diamine coffee Thien, 2,5-diamine-1, 3,4-thiadiazole, 2,4-diamine-S-tripyrene and other heterocyclic diamines, bis (4-aminecyclohexyl) methane, bis (4-Amine-3-methylcyclohexyl) methane and other alicyclic diamines and 1,2-diamineethane, 1,3-diaminepropane, 1,4-diaminebutane, 1,6-diamine Aliphatic diamines such as amine hexane, silicon diamines such as 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane, etc. (11) (11) 200527081 < Tetracarboxylic acid dianhydride with alicyclic structure > tetracarboxylic dianhydride with alicyclic structure has 1,2,3,4-cyclobutanetetracarboxylic acid 1 '2,3' 4 · cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 2,3,5-tricarboxycyclopentylacetic acid, 3,4-dicarboxy-1, 2,3,4-tetrahydro-1-naphthalenesuccinic acid, bicyclic [3,3,0] octane-2,4,6,8-tetracarboxylic acid, etc. but not limited thereto. Two or more of these tetracarboxylic acids are used Copolymerization of acid dianhydride is also possible. From the viewpoint of the polymerization reactivity with the diamine component, 1,2,3,4-cyclobutane tetracarboxylic acid is preferred. < Synthesis reaction of polyamidic acid > The polyamidic acid in the present invention is a diamine component containing a diamine of the formula (1) structure and a diamine of the formula (2) structure, and a polyamine structure having an alicyclic structure. The tetracarboxylic dianhydride component is obtained by reaction. The diamine component and the tetracarboxylic dianhydride component are reacted at a ratio of 0.9 to 1.1 mol for the former 1 mol, preferably the latter, especially 0.95 to 1.05 mol. The synthesis reaction of polyamic acid is in an organic solvent, usually at a reaction temperature of 0 ~ 150 ° C, preferably 0 ~ 100 t. If the organic solvent in this case can dissolve the obtained polyamic acid, there is no particular limitation. Specific examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N.methyl-2-pyrrolidone, N-methylcaprolactam, dimethylasyl, Methylurea, pyridine, dimethylformamide, hexamethylasyl, 7-butyrolactone and the like. These can be used alone or in combination. The solvent which does not dissolve the polyamic acid can also be used in the range where the polyamino acid produced by the polymerization reaction does not precipitate, and is mixed with the above-mentioned solvent. Polyamic acid used in the liquid crystal alignment treatment agent of the present invention is GPC (Gel (12) 200527081

The weight-average molecular weight {Mw} measured by the Permeation Chromatography) method is preferably 2,000 to 500,000, and especially 5,000 to 200,000. When the molecular weight is too small, the strength of the obtained coating film is insufficient, and when the molecular weight is too large, the workability during film formation or deteriorates. The molecular weight control of polydonkey acid can be mistakenly adjusted by the molar ratio of the diamine component and the tetracarboxylic dianhydride used in the synthesis reaction of polyamic acid. As with the usual polycondensation. Reaction, the closer the Mohr ratio is to 1.0, the greater the degree of polymerization of the resulting polymer. &lt; Dehydration ring closure of polyamic acid &gt; Dehydration ring closure of polyamic acid is polyimide. The so-called dehydration ring-closing system of polyamines is not limited to the dehydration ring-closing units of the polyamines, and all are suitable for the liquid crystal alignment treatment agent of the present invention. In general, polyimidation (dehydration ring closure) of polyamic acid can be performed in solution. In the method for polyimidating ammonium sulfonium in a solution, the reaction temperature is usually 50 to 2 0 ° C, preferably 60 to 17 0 ° C. If the reaction temperature is lower than 50 ° C, the dehydration and ring-closing reaction will not proceed sufficiently. If the reaction temperature exceeds 200 ° C, the molecular weight of the imidized polymer will decrease. In the fluorene imidization reaction, the addition of a dehydrating agent and / or a dehydration ring-closing catalyst is preferred because the molecular weight of the polyfluorene imine obtained by the fluorene imidization reaction at a relatively low temperature is unlikely to decrease. As the dehydrating agent, for example, anhydrides such as acetic anhydride and propionic anhydride can be used. The amount of the dehydrating agent is preferably 1 mol to 0.1 to 20 mol of the repeating unit of the polyamic acid. For dehydration ring-closing catalysts, tertiary amines such as pyridine and triethylamine can be used. The amount of dehydration closed-loop catalyst is preferably 1 mol to 1 mol. Organic solvents used for dehydration and ring closure are exemplified by those used for the synthesis of polyamic acid. The reaction temperature when adding a dehydrating agent and / or dehydrating -16- (13) (13) 200527081 ring catalyst is usually 0 ~ 180 ° C, preferably 10 ~ 150 ° C. The polyamic acid or polyimide obtained as above can be used directly, or it can be recovered by precipitation, separation, and use of weak solvents such as methanol and ethanol. &lt; The liquid crystal aligning agent of the present invention &gt; The liquid crystal aligning agent of the present invention must contain a polyamic acid of the above-mentioned specific structure, or at least one of the polymers in the dehydrated closed-loop of the polyamino acid, usually based on Use in coating liquid form. The solvent contained in the coating liquid is not particularly limited as long as it can dissolve the polymer components described above. These solvents may be used alone or in combination of two or more. Solvents that do not dissolve the polymer alone can be added in a range where the polymer components do not precipitate. The solid content concentration of the coating liquid can be set according to the coating device used, and the thickness of the obtained liquid crystal alignment film can be set to any value. Generally, the coating method used and the thickness of the liquid crystal alignment film are preferably about 1 to 10% by weight. Specific examples of the solvent components contained in the coating liquid are as follows, but are not limited thereto: 0N-methyl-2-D-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamidine Amine, 7-butyrolactone, dimethyl arsenol, tetramethylurea, hexamethylphosphonium trimethylamine, m-cresol, methanol, ethanol, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol ether, ethylene glycol n Butyl ether, ethylene glycol dimethyl ether, diglyme, diglyme, diglyme, etc. The polymer component contained in the liquid crystal alignment treatment agent of the present invention, in order to control the printing characteristics of the alignment treatment agent, various characteristics of the residual DC voltage characteristics of the liquid crystal element, can also be described in the specific structure of the polyamic acid and / or its In addition to dehydrated ring-closing compounds, the polymer structure of these polymers differs from these specific structures. 17- (14) (14) 200527081. The polymer having another structure is preferably 95% by weight or less of the entire polymer component contained in the liquid crystal aligning agent of the present invention, and is more preferably 90 to 10% by weight. Examples of the polymer having another structure are selected from the following tetracarboxylic dianhydrides and diamine compounds, one or more tetracarboxylic dianhydrides, and polyamines obtained by reacting with one or more diamine compounds, and The dehydrated closed-loop is not limited thereto. Tetracarboxylic dianhydride: pyromelic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3 , 6,7-anthracene tetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic acid, 3,3,, 4,4'-biphenyltetracarboxylic acid, 2,3 '3', 4-biphenyltetracarboxylic acid, Bis (3,4-dicarboxyphenyl) ether, 3,3,, 4,4'-benzophenone tetracarboxylic acid, 3,3,4,4'-chalcone tetracarboxylic acid, bis (3, 4-dicarboxyphenyl) 5, bis (3,4-dicarboxyphenyl) methane, 2 '2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3, 3-Hexafluoro-2,2-bis (3,4-di-residual phenyl) propanone, bis (3,4-di-residual phenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) di Aromatic tetracarboxylic dianhydrides such as phenylsilane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis (3,4-dicarboxyphenyl) pyridine, 1,2,3,4 · ring Ding Yuan. Tetracarboxylic acid ,! , 2,3,4-Cyclopentane tetracarboxylic acid, 1,2,4,5-cyclohexanecote tetracarboxylic acid, 2,3,5-tricarboxycyclopentylacetic acid, 3,4-dicarboxyl · 1,2 , 3,4-tetrahydro-1-naphthalene succinic acid, bicyclo [3 · 3 · 0] xinyuan_2,4,6,8-tetracarboxylic acid, dianhydride of alicyclic tetraresidual acid, 1 '2, Dianhydrides of aliphatic tetracarboxylic acids such as 3,4 · butanetetracarboxylic acid; diamine compounds: p-phenylenediamine, m-phenylenediamine, 2,4-diamine_N, diallylaniline, 2,5- Diamine benzonitrile, 2,5-diamine toluene, 2,6--18- (15) (15) 200527081 diamine toluene, 4,4'-diamine biphenyl, 3,3'-dimethyl- 4,4'-diamine biphenyl, 3,3'-dimethoxy-4,4'-diamine biphenyl, diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenylamine, 2 2,2 diaminodiphenylpropane, bis (3,5-diethyl-4-aminophenyl) methane, diaminodiphenylamine, diaminobenzophenone, 3,3, diamine Ketone, 4,4'-diamine chalcone, 3,3, diamine M, 4,4, -diamine; g, diamine naphthalene, 1,4-bis (4-aminephenoxy) benzene, 1,4-bis (4-aminophenyl) benzene, 9,1 0-bis (4-aminophenyl) anthracene, 1, 3 -Bis (4-aminephenoxy) benzene, 4,4'-bis (4-aminephenoxy) diphenylhydrazone, 2,2-bis [4- (4-aminephenoxy) phenyl] propane , 2,2-bis (4-aminephenoxy) hexafluoropropane, 2,2-bis [4- (4-aminephenoxy) phenyl] hexafluoropropane and other aromatic diamines, 2,6-di Aminopyridine, 2,4-diaminepyridine, 2,7-diaminebenzofuran, 2,7-diaminecarbazole, 3,7-diamine phenothiazine, 2,5-diamine-1,3 Heterocyclic diamines such as 4,4-thiadiazole, 2,4-diamine-S-trioxine, lipids such as bis (4-aminecyclohexyl) methane, bis (4-amine-3-methylcyclohexyl) methane Cyclic diamines and 1,2-diamineethane'1,3-diaminepropane, 1,4-diaminebutane, aliphatic diamines such as 1,6-diaminehexane, 1,3- Diamine-4-octadecylbenzene, 1,3-diamine-4-hexadecylbenzene, 1,3-diamine-4-dodecylbenzene, 4- [4- (trans-n-heptylcyclohexyl) ) Phenoxy] -1,3-diamine benzene, (4-trans-n-pentylbicyclohexyl) -3,5-diamine benzoate and other side chains with alkyl groups, diamines similar to liquid crystal structures, 1 Silanediamines such as 3, bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane, etc. The liquid crystal aligning agent of the present invention may contain a compound containing a functional silane to impart adhesion to a substrate. There are, for example, N-trimethylsilylacetamidamine, diethylacetoxydimethylsilane, tetramethoxysilane, 3-aminopropyldiethyl-19- (16) (16) 200527081 oxysilane, 3-amine Propyl triethoxysilane, 1,4-bis (dimethylsaminyl) benzene, bis (dimethylamino) dimethylsilane, bis (ethylamino) dimethylsilane, 1-trimethylsilimidazole, methyl Triethoxysilane, diethoxymethyl benzene sand institute, phenyl diethoxy sand institute, monophenyl sand institute glycol, and the like are not limited thereto. &lt; Liquid crystal alignment film &gt; The liquid crystal alignment film of the present invention is applied to a substrate and then dried. • The liquid crystal alignment film for vertical alignment can be obtained by firing. The coating method of the liquid crystal alignment treatment agent includes a spin coating method, a printing method, an inkjet method, and the like. The transfer printing method is widely used industrially in terms of productivity. The liquid crystal alignment treatment agent of the present invention is also applicable. The drying step after the application of the liquid crystal alignment treatment agent is not necessary, and the time from the application to the calcination may vary from substrate to substrate, and it is preferable that the substrate is not calcined immediately after coating, and the drying step is preferred. The shape of the drying coating film does not need to be able to evaporate due to the degree of deformation of the substrate during transportation, and the drying means is not particularly limited. A specific example is 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 alignment treatment agent can be performed at any temperature from 00 to 350 ° C, preferably 150 ° C to 300 ° C, and more preferably 200 ° C to 25 0 ° C. When the liquid crystal aligning agent contains polyamidic acid, the conversion ratio of the polyamidic acid to the polyamidoimine changes with the calcination temperature, and the liquid crystal aligning agent of the present invention does not necessarily need to be 100% polyimide. Regardless of whether it contains polyamic acid or not, it is preferred that the heat treatment such as hardening of the sealant necessary for the process of manufacturing the liquid crystal element be performed at a temperature of 10 ° C or higher. -20- (17) 200527081 If the thickness of the coating film after calcination is too thick, it is disadvantageous to the power consumption of the liquid crystal display element. If it is too thin, the reliability of the liquid crystal display element may decrease, so it is 5 ~ 300nm, 10 ~ 10. nm is preferred. <Liquid crystal display element> The liquid crystal display element of the present invention is obtained by the liquid crystal alignment treatment agent of the present invention with a substrate with a liquid crystal alignment film in accordance with the above-mentioned method, and then a liquid crystal element is produced by a conventional method as a liquid crystal Display component. An example of the production of a liquid crystal element is a general method in which a pair of substrates on which a liquid crystal alignment film has been formed is sandwiched with a gap of 1 to 30 μm, preferably 2 to 10 μm, fixed with a sealing agent, injected into a liquid crystal, and encapsulated. The method of sealing the liquid crystal is not particularly limited, and there are, for example, a vacuum method of injecting liquid crystal into a produced liquid crystal element and depressurizing the liquid crystal, and a dropping method of sealing after dropping the liquid crystal. The substrate used for the liquid crystal display element is not particularly limited if it is a substrate having a higher transparency, and a glass substrate, an acrylic substrate, a polycarbonate substrate, or a plastic substrate can be used. Among them, the use of a substrate for driving the ITO electrode of the liquid crystal has been formed, which is preferable in terms of simplifying the manufacturing process. Reflective liquid crystal display elements can have opaque objects such as silicon wafers if they have a substrate on one side. At this time, electrodes such as aluminum can reflect light. The following examples illustrate the present invention in more detail, but the present invention is not limited to this. [Embodiments] Examples-21-(18) (18) 200527081 &lt; Example 1 &gt; Amine-N, N-diallylaniline 12.20g (0.06mol) and 4- [4- (4-trans-n-heptylcyclohexyl) phenoxy] -1,3-diaminebenzene 15.22g (0.04mol) Dissolved in 187.3 g of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), and added 1,2,3,4-cyclobutanetetracarboxylic dianhydride 19.4 1 g (〇 · 09 9 m ο 1 ) And react at room temperature for 24 hours to obtain a polyamidic acid solution. The weight average molecular weight {Mw} of the obtained polyamic acid was 40,000. 30 g of this solution was added with 50 g of NMP and 20 g of ethylene glycol n-butyl ether, and the mixture was thoroughly stirred to obtain a uniform solution to obtain a liquid crystal alignment treatment agent of the present invention having a concentration of 6 wt%. The liquid crystal alignment treatment agent was pressure-filtered through a filter membrane having a pore size of 0.5 μm, and then spin-coated on a glass substrate with a transparent electrode. The substrate was placed on a hot plate at 80 ° C and dried for 5 minutes, and then fired in a hot air circulation oven at 210 ° C for 60 minutes to obtain a liquid crystal alignment film with a thickness of 100 nm on the substrate. Two substrates with the above-mentioned liquid crystal alignment film were prepared, and a 6 μm spacer was spread on the liquid crystal alignment film surface of one of the substrates, followed by lamination, and injection of a negative nematic liquid crystal for vertical alignment (MLC-6608 by MERCK) Production of liquid crystal elements. The alignment state of the liquid crystal was observed with a polarizing microscope, and it was confirmed that there was no defect in the uniform vertical alignment. This liquid crystal element was placed in a thermostatic bath, and a voltage holding ratio measuring device {VHR-1 manufactured by Toyo Technica Co., Ltd.) was used, with a voltage of ± 4V, a pulse width of 0.06 m seconds, and a frame period of 16.6 7 m seconds. Measure the voltage retention ratio from the voltage ratio. As a result, the voltage retention rate at 80 ° C was 9 7.9 ° /. It's very high. After the liquid crystal element was subjected to an aging treatment at 120 ° C for one week, the voltage retention rate at 80 ° c was also measured again, and it remained very high at 94.1%. The aged state of the liquid crystal-22- (19) (19) 200527081 was observed with a polarizing microscope, and it was confirmed that there were no defects and uniform vertical orientation. <Example 2> 19.83 g of 4,4'-diaminediphenylmethane .im〇i) was dissolved in 228.6 g of NNP, and 10.9 lg (0.05 mol) of pyromelite dianhydride and 9.61 g of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (0.0%) were added thereto. 49 mol), and reacted at room temperature for 24 hours to obtain a polyamic acid solution. The weight average molecular weight {Mw} of the obtained polyamic acid was 65,000. 40 g of this solution was added with 40 g of NMP and 20 g of ethylene glycol n-butyl ether, and the mixture was thoroughly stirred to form a uniform solution having a concentration of 6 wt%. Next, 40 g of the polyamic acid solution having a concentration of 6 wt% and 10 g of the liquid crystal alignment treatment agent prepared in Example 1 were mixed, and then thoroughly stirred to obtain a uniform solution to obtain the liquid crystal alignment treatment agent of the present invention. Using this liquid crystal alignment treatment agent, the same treatment as in Example 1 was performed to prepare a liquid crystal element. The alignment state of the liquid crystal was observed with a polarizing microscope ', and it was confirmed that there were no defects and uniform vertical alignment. With respect to this liquid crystal element, the voltage retention rate was evaluated as in the examples. As a result, the voltage retention rate at 80 ° C before aging was very high of 97.7%. Even after 120 weeks of aging treatment, the voltage retention rate of the 80 series remained very high at 96.1%. The alignment state of the liquid crystal after aging was observed with a polarized light microscope to confirm that it was defect-free and uniformly oriented vertically. &lt; Example 3 &gt;

20.02 g (0.1 mol) of 4,4, diamine diphenyl ether was dissolved in NMP -23 · (20) (20) 200527081 253.8 g, and bicyclo [3.3.0] octane-2,4 was added thereto. 2,4.7 7 g (0.099 mol) of 6,8-tetracarboxylic dianhydride was reacted at room temperature for 24 hours to obtain a polyamidic acid solution. The weight average molecular weight {Mw} of the obtained polyamic acid was 36000 °. 30 g of the solution was added with 50 g of NMP and 20 g of ethylene glycol n-butyl ether to form a solution having a concentration of 6 wt%, and the solution was thoroughly stirred to form a homogeneous solution. Next, 40 g of the polyfluorenic acid. Solution with a concentration of 6 wt% and 10 g of the liquid crystal aligning agent obtained in Example 1 were mixed, and then thoroughly stirred to form a uniform solution to obtain the liquid crystal aligning agent of the present invention. The liquid crystal alignment treatment agent was treated in the same manner as in Example 1 to produce a liquid crystal element. Observe the alignment state of the liquid crystal with a polarizing microscope, and confirm that there are no defects and uniform vertical alignment. This liquid crystal element was evaluated for the voltage holding ratio as in Example 1. As a result, the voltage retention rate at 80 ° C before aging was very high at 97.9%. After aging at 120 ° C for 1 week, the voltage retention rate at 80 ° C remained very high at 95.5%. The alignment state of the liquid crystal after aging was observed with a polarizing microscope, and it was confirmed that there was no defect and the orientation was uniform and vertical. &lt; Example 4 &gt; 12.20 g (0.06 mol) of 2,4-diamine-N, N-diallylaniline and 15.07 g of 1,3-diamine-4-octadecylbenzene were used in the above formula (7). (0.04 mol) was dissolved in 186.7 g of NMP, 9.4,1 g (0.0 9 9 m ο 1) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was added thereto, and reacted at room temperature for 2 4 hours to obtain Polyamic acid solution. The weight average molecular weight {Mw} of the obtained polyamic acid was 44,000. 30 g of the solution was added with 50 g of NMP and 20 g of ethylene glycol n-butyl ether, and the mixture was thoroughly stirred to obtain a uniform solution to obtain a liquid crystal alignment treatment agent of the present invention having a concentration of 6 wt%. -24- (21) (21) 200527081 This liquid crystal alignment treatment agent was treated in the same manner as in Example 1 to produce a liquid crystal element. Observe the alignment state of the liquid crystal with a polarizing microscope and confirm that there is a uniform vertical alignment without defects. This liquid crystal element was evaluated for the voltage holding ratio as in Example 1. # As a result, the voltage retention rate at 80 ° C before aging is very high at 96.4%. After aging treatment at 120 ° C for 1 week, the voltage retention rate at 80 ° C remained very high at 9 2.2%. The orientation state of the liquid crystal after aging was observed with a polarizing microscope, and it was confirmed that there was a uniform vertical orientation without defects. &lt; Example 5 &gt; 12.20 g (0.06 mol) of 2,4-diamine-N, N-diallyl aniline of formula (7) and 4- [4- (4-trans-n-heptylcyclohexyl) ) Phenoxy] -1 'diaminebenzene 15.22 g (0.04 mol) was dissolved in NMP 187.3 g, and 1' 2,3,4-cyclobutanetetracarboxylic dianhydride was added thereto] 9.41 g (0.099 mol) in The reaction was carried out at room temperature for 24 hours to obtain a polyamic acid solution. Next, the solution was diluted with 1.26 g of NMP 3 5, 0.50 g of acetic anhydride 3 and 1 3.0 0 g of pyridine were added, and the mixture was reacted at 30 ° C for 4 hours. The reaction solution was cooled to about room temperature, and then poured into methanol, and the precipitated solid matter was recovered. The solid was washed several times with methanol and dried under reduced pressure at 80 ° C to obtain a white polyimide powder. The weight average molecular weight of the obtained polyimide was {Mw} 35000. The polyimide has an imidization rate (dehydration ring closure rate) of 59%. The hydrazone imidization ratio was confirmed by 1H-NMR measurement, and was calculated from the integral ratio of the protons derived from the remaining fluorenamine groups and the protons derived from a methyl group. 6 g of the polyfluorene imide powder obtained above was dissolved in 74 g of NMP, 20 g of ethylenedi-25- (22) (22) 200527081 alcohol n-butyl ether was added, and the solution was thoroughly stirred to obtain a liquid crystal alignment treatment agent of the present invention at a concentration of 6 wt% . The liquid crystal alignment treatment agent was subjected to the same treatment as in Example 1 to produce a liquid crystal element. The alignment state of the liquid crystal was observed with a polarizing microscope ', and it was confirmed that there were no defects, and the orientation was uniform and vertical. As for this liquid crystal element, the voltage holding ratio was evaluated as in Example 1. As a result, the voltage retention rate at 80 ° C before aging was very high of 97.9%. Furthermore, after the aging treatment at 120 ° C for 1 week, the voltage retention rate of 80 ° C maintained a very high value of 93.0. The orientation state of the liquid crystal after aging was observed with a polarizing microscope ', which is a uniform vertical orientation without defects. &lt; Example 6 &gt; In Example 5, the polyimide powder was obtained in the same manner from 30 ° C / 4 hours to 40 ° C / 4 hours. The weight average molecular weight {Mw} of the obtained polyfluorene imine was 35,000, and the ratio of fluorene imine was 87%. 6 g of the polyfluorene imide powder obtained above was dissolved in 74 g of NMP and 20 g of ethylene glycol n-butyl ether. The mixture was thoroughly stirred to obtain a uniform solution to obtain a liquid crystal alignment treatment agent of the present invention having a concentration of 6 wt%. The liquid crystal alignment treatment agent was subjected to the same treatment as in Example 1 to produce a liquid crystal element. The orientation of the liquid crystal is observed by polarized light, and the observation is a uniform vertical orientation without defects. This liquid crystal element was evaluated for the voltage holding ratio as in Example 1. As a result, the voltage retention rate at 80 ° C before aging was very high of 97 · 8%. After 1 week of aging treatment at 120 ° C, the voltage retention rate at 80 ° C remained very high -26- (23) 200527081 9 5.5%. The orientation state of the liquid crystal after aging was observed with a polarizing microscope, and it was confirmed that there was a uniform vertical orientation without defects. &lt; Example 7> 25 g of the liquid crystal alignment treatment agent prepared in Example 6 was mixed with 25 g of a polyamic acid solution having a concentration of 6 wt% prepared in Example 2 and thoroughly stirred to obtain a uniform solution to obtain the liquid crystal alignment treatment agent of the present invention. The liquid crystal alignment treatment agent was treated in the same manner as in Example 1 to produce a liquid crystal element. Observe the alignment state of the liquid crystal with a polarizing microscope and confirm that there is a uniform vertical alignment without defects. This liquid crystal element was evaluated for the voltage holding ratio as in Example 1. As a result, the voltage retention rate at 80 ° C before aging was very high of 9 7.2%. More than 12 ° C, after 1 week of aging treatment, the voltage retention rate at 80 ° C maintained a very high value of 96.8%. The orientation state of the liquid crystal after aging was observed with a polarizing microscope to confirm a uniform vertical orientation without defects. &Lt; Implementation Example 8 &gt; In Example 5, the polyimide conditions of the polyamidic acid solution were changed from 30 ° C / 4 hours to 5 (TC / 4 hours. Polyimide powder was obtained in the same manner. The obtained polyimide powder was obtained. The weight-average molecular weight {Mw} is 35000, and the imidization ratio is 97%. 6 g of the polyimide powder obtained above is dissolved in 74 g of NMP, 20 g of ethylene glycol n-butyl ether is added, and the solution is thoroughly stirred to obtain a concentration of 6 wt. % Of the liquid crystal alignment treatment agent of the present invention. The liquid crystal alignment treatment agent was treated in the same manner as in Example 1 to produce a liquid crystal element »27- (24) (24) 200527081. The orientation state of the liquid crystal was observed with a polarizing microscope to confirm that there were no defects. Uniform vertical orientation. The voltage retention rate of this liquid crystal device was evaluated as in Example 1. As a result, the voltage retention rate before aging was 80.8%, which was very high. It was more than 120 ° C for 1 week. After aging treatment, the voltage retention rate at 80 ° C remains at 98.1% Very high 値. The orientation state of the liquid crystal after aging was observed with a polarizing microscope, and it was confirmed that there was no defect in the uniform vertical orientation. &Lt; Comparative Example 1 &gt; 2,4-diamine-N'N · diene of the above formula (7) Propylaniline I2.20g (0.06mol) and 4- [4- (4-trans-n-heptylcyclohexyl) phenoxyb 1,3-diaminebenzene 15.22g (0.04mol) was dissolved in NMP 196.0g, in which Add pyromellitic dianhydride 2 1 · 5 9 g (0.0 9 9 m ο 1), and react at room temperature for 2 4 hours to obtain a polyamic acid solution. The weight average molecular weight of the obtained polyamic acid {Mw} is 44000. 30 g of NMP50 g of the solution and 20 g of ethylene glycol n-butyl ether were fully stirred to obtain a uniform solution to obtain a liquid crystal alignment treatment agent having a concentration of 6 wt% for comparison. The liquid crystal alignment treatment agent was treated as in Example 1. The liquid crystal element was made. Observe the orientation state of the liquid crystal with a polarizing microscope to confirm uniform vertical alignment without defects. The liquid crystal element was evaluated for the voltage holding ratio as in Example 1. As a result, the voltage holding ratio at 80 ° C was determined before aging. Very high 74.0%. More than 120. (: The voltage retention rate at 80 ° C is maintained after one week of aging treatment. It is 10.0%, which is significantly lower than the original. The orientation state of the liquid crystal after aging is observed with a polarizing microscope. -28- (25) (25) 200527081 is confirmed to be a uniform vertical orientation without defects. &Lt; Comparative Example 2 &gt; 7) 12.20 g (0.06111〇1) of 2,4-diamine-N, N-diallylaniline and 4- [4- (4-trans-n-heptylcyclohexyl) phenoxy] _1,3-di 15.22 g (0.04 mol) of amine benzene was dissolved in 237.3 g of NMP, 31.9 g (0.099 mol) of 3,3, '4,4'-benzophenone tetracarboxylic dianhydride was added thereto, and reacted at room temperature 2 4 hours' to obtain a polyamine solution. The weight average molecular weight {Mw} of the obtained polyamic acid was 48,000. 30 g of this solution was added with 50 g of NMP and 20 g of ethylene glycol n-butyl ether, and the mixture was sufficiently stirred to obtain a uniform solution having a concentration of 6 wt% for a liquid crystal alignment treatment agent. The liquid crystal alignment treatment agent was treated in the same manner as in Example 1 to prepare a liquid crystal element. The alignment state of the liquid crystal was observed with a polarizing microscope, and it was confirmed that there was a uniform vertical alignment without defects. The voltage retention of the liquid crystal element was evaluated as in Example 1. As a result, the voltage retention rate at 80 ° C before aging was as low as 8 9.3%. The voltage retention rate at 80 ° C after 1 week at 120 ° C was maintained at 62 · 1%, which was a significant decrease from the original. The orientation state of the liquid crystal after aging was observed with a polarizing microscope, and it was confirmed that there was a uniform vertical orientation without defects. &lt; Comparative example 3 &gt; p-phenylenediamine 6.49 g (0.06 mol) and 4- [4- (4-trans-n-heptylcyclohexyl) phenoxy] -1,3. diamine benzene 15.22 g (. (4.04 mol) was dissolved in 233.0 g of NMP, and 1,2,3,4-cyclobutanetetracarboxylic dianhydride-29- (26) 200527081 19.41 g (0.09 9 mol) was added thereto, and reacted at room temperature for 24 hours To obtain a polyamic acid solution. The weight average molecular weight {Mw} of the obtained polyamic acid was 48,000. 40 g of this solution was added with 40 g of NMP and 20 g of ethylene glycol n-butyl ether, and the mixture was thoroughly stirred to obtain a uniform solution to obtain a comparative liquid crystal alignment treatment agent having a concentration of 6%. This liquid crystal aligning agent was treated in the same manner as in Example 1 to prepare a liquid crystal element. Observe the alignment state of the liquid crystal with a polarizing microscope and confirm that there is uniform vertical alignment without defects. This liquid crystal element was evaluated for the voltage holding ratio as in Example 1. Results The voltage retention rate at 80 ° C before aging was as high as 97.3. After the aging treatment at 120 ° C for one week, the voltage retention rate at 80 ° C was maintained at 87.9%, which was lower than the original. The orientation state of the liquid crystal after aging was observed with a polarizing microscope 'to confirm that the S-based system had a uniform vertical orientation without defects. Hereinafter, the measurement results of the voltage holding ratios of Examples 1 to 8 and Comparative Examples 1 to 3 are shown in the table. -30- (27) 200527081 Table 1 At 8 (voltage retention rate of TC (%) before aging after aging Example 1 97.9 94.9 Example 2 97.7 96.1 Example 3 97.9 95.5 Example 4 96.4 92.2 Example 5 97.9 93.0 Example 6 97.8 95.5 Example 7 97.2 96.8 Example 8 98.1 98.1 Comparative Example 1 74.0 10.0 Comparative Example 2 89.3 62.1 Comparative Example 3 97.3 87.9

Claims (1)

200527081 (1) X. Patent application scope 1. A liquid crystal alignment treatment agent for vertical alignment, characterized in that it contains a diamine having a structure of the following formula (1) and a diamine having a structure of the following formula (2) Component, at least any polymer of polyamic acid obtained by reaction with tetracarboxylic dianhydride having an alicyclic structure, or at least one polymer of dehydrated ring-closure of the polyamino acid, Χι—X2 (X1 form bond in formula (1), or a divalent bonding group selected from the group consisting of ether, ester, amidine, and urethane; X2 represents a linear alkyl group having 8 to 20 carbon atoms, or has a Monovalent organic group of alicyclic skeleton with 4 to 40 carbon atoms (In formula (2), R! Represents a linear hydrocarbon group having 1 to 12 carbon atoms, or a branched hydrocarbon group having 1 to 12 carbon atoms, and R2 represents 1 atom of hydrogen, and the number of carbon atoms is from 〖to I〗. Hydrocarbyl group 'or branched hydrocarbon group with carbon number η; R3'L independently represents hydrogen atom or methyl group). 2. The liquid crystal alignment treatment agent for vertical alignment according to item 1 of the patent application scope, in which among the diamine components, one of the amines having the structure of formula (1) accounts for 10 ~ 80m〇1 / ° -32- 200527081 (2) And the diamine structure of the formula (2) accounts for 20 to 90 mol%. 3. The liquid crystal alignment treatment agent for vertical alignment as described in the first or second item of the patent application, wherein the diamine structure of the formula (1) is 4- [4- (4-trans-n-heptylcyclohexyl) phenoxy]- 1,3-diaminebenzene, and / or (4-trans-n-heptylbicyclohexyl) -3,5-diaminebenzoate. .4. The liquid crystal aligning agent for vertical alignment according to any one of claims 1 to 3, wherein the diamine having the formula (2) structure is a diamine having the structure of the following formula (3). 5. A liquid crystal display element characterized by using a liquid crystal alignment treatment agent for vertical alignment as described in any one of claims 1 to 4 of the patent application scope. -33- 200527081 VII. (1) The designated representative map in this case is: None. (2) Brief description of the component representative symbols in this representative map: 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: -4-