TWI375096B - - Google Patents

Description

1375096 (1) IX. Description of the Invention [Technical Fields of the Invention] The present invention relates to a liquid crystal alignment agent used in a vertical alignment type liquid crystal display element, and a liquid crystal alignment film and liquid using the liquid crystal alignment agent. • Crystal display components. [Prior Art] The liquid crystal display device is characterized by the use of electro-optical display elements for changing the liquid crystal. The device is small and lightweight, and consumes a small amount of power. In recent years, it has been an impressive development as a display device for various displays. Wherein the nematic liquid crystal having positive dielectric anisotropy is used, and the liquid crystal molecules are arranged in parallel with respect to the substrate at a position opposite to the opposite electrode substrate, and the alignment directions of the liquid crystal molecules are orthogonal to each other. A combination, twisted nematic (TN type) electric field effect type liquid crystal display element is a representative thereof. In such a TN-type liquid crystal display device, it is important that the long-axis directions of the liquid crystal molecules are uniformly aligned to the surface of the substrate, and the liquid crystal molecules are aligned with respect to the substrate so as to have a certain oblique alignment angle. Such a representative method for aligning liquid crystal molecules is to provide a polyimide film on the surface of the substrate, and the surface is honed in a certain direction by cotton, nylon, polyester, etc., and the liquid crystal molecules are made in the honing direction. A method of aligning (for example, refer to Patent Document 1.2). On the other hand, a nematic liquid crystal having negative dielectric anisotropy is vertically aligned with respect to a substrate, and a voltage is applied to an electrode formed on the substrate, and application is performed. The vertical alignment mode of the birefringence change of the liquid crystal layer at the time of voltage -4- (2) 1375096 shows a high contrast compared with the liquid crystal display element of the conventional TN type. However, the liquid crystal alignment film used in such a vertical alignment method is difficult to perform uniform alignment processing by honing treatment as in the past. Therefore, in order to form a protrusion on a substrate, to change the structure of the electrode, to control the direction of the electric field, and to perform the honing process, the vertical alignment mode of the alignment direction of the liquid crystal when the voltage is applied has been actively developed in recent years. These vertical alignment modes can achieve high contrast and at the same time obtain a wide viewing angle characteristic φ, which can be a liquid crystal display element of high display quality. These vertical alignment liquid crystal display elements are used for efficient driving using a thin film crystal (TFT), and not only the vertical alignment of the liquid crystal in the liquid crystal alignment film but also the minimum sintering. The liquid crystal alignment agent used in such a vertical alignment method is a liquid crystal alignment agent using a polymer obtained from an alicyclic acid dianhydride and a diamine (see, for example, Patent Document 3). In recent years, with the increase in size of liquid crystal display elements, display instability that greatly affects the quality of display elements has become a serious problem. Therefore, in order to obtain the performance of the liquid crystal alignment film, not only the vertical alignment of the liquid crystal is good, but also the sintering is extremely small, and display instability is not required in the surface of the display element. Patent Document 1: Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. 3-1 793. Problem to be Solved The object of the present invention is to provide a display having superior printability, which can make a liquid crystal molecule of -5-(3) (3)1375096 aligned vertically and stably, without display instability or display defects, plus A liquid crystal alignment agent for a vertical alignment of a vertical alignment type liquid crystal display element which is hard to cause sintering, a liquid crystal alignment film, and a liquid crystal display element using the same (solution of the subject) The work of the present invention is intensively discussed in order to achieve the above object. As a result of the study, the present invention has been completed. That is, the present invention contains the gist of the following features. </ RTI> a liquid crystal alignment agent for vertical alignment, which comprises at least one of polylysine and a polyimine which is subjected to dehydration ring closure, and a liquid crystal alignment agent with a solvent; The polyamic acid is a diamine component containing a diamine represented by the formula (1) in an amount of from 2 to 80 mol%, and a four-carbonyl group having 20 to 100 mol% directly linked to the aromatic ring structure. The tetracarboxylic dianhydride component of the carboxylic acid dianhydride is obtained by carrying out a reaction. [Chemical 1]

In the formula, R1 is a divalent organic group selected from the group consisting of -0- and -CH20-; and R2 is a linear alkyl group having 1 or more and 8 or less carbon atoms. [2] The liquid crystal alignment agent for vertical alignment according to the above [1], wherein, in the liquid crystal alignment agent, the total concentration of the polylysine and the polyimine which dehydrates the polyamic acid is 2 to 1 0% by weight. [3] The liquid crystal according to the above [1] or [2], wherein the diamine represented by the formula (1) is a formula (6) or a formula (7). Or a diamine represented by the formula (8). [4] The liquid crystal alignment agent for vertical alignment according to any one of the above [1], wherein the diamine component contains at least one selected from the group consisting of a diamine represented by the formula (1). Phenylenediamine, 1,4-bis(4-aminophenyl)benzene, 1,5-naphthyldiamine, 4,4'-diaminobiphenyl, 3,3, dimethyl-4,4 Grouping of '-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, and φ 3,3 dihydroxy-4,4'-diaminobiphenyl Diamine. [5] The liquid crystal alignment agent for vertical alignment according to any one of the above aspects, wherein the solvent contains at least N-methylpyrrolidone and r-butane vinegar. [6] The liquid crystal alignment agent for vertical alignment according to the above [5], wherein the solvent oxime contains at least one of butyl cellosolve and dipropylene glycol monomethyl ether, and a liquid crystal alignment film, which is characterized by using the above [ The liquid crystal alignment agent for vertical alignment according to any one of the items [1] to [6]. [8] A liquid crystal display device characterized by using the liquid crystal alignment film of the above [7]. [Effect of the Invention] The liquid crystal alignment agent for vertical alignment of the present invention can provide printability, uniform coating film uniformity, and excellent liquid crystal alignment property, which is difficult to cause sintering, has no display instability or display defects, and has a good display. Performance vertical alignment type liquid crystal display element. (5) 1375096 [Embodiment of the Invention] The present invention will be described in detail below. The liquid crystal alignment agent for vertical alignment of the present invention comprises at least one of a polyamic acid and a polyimine which is subjected to dehydration ring closure of the polyamic acid, and a solvent. Further, the polyamic acid is a diamine component containing a diamine represented by the formula (1) in an amount of 20 to 80 mol%, and a tetraamine having a content of 20 to 100 m%. The carbonyl group is directly bonded to a tetracarboxylic dianhydride component of a tetracarboxylic dianhydride having an aromatic ring structure, and is obtained by a reaction. The above-mentioned four-hydroxy dianhydride in which the four carbonyl groups are directly bonded to the aromatic ring structure means four carbonyl groups which constitute the four carbonyl groups of the two anhydride rings, and are directly bonded to a benzene ring or a benzene ring condensed structure such as naphthalene or anthracene. Acid dianhydride. In the present invention, a tetracarboxylic dianhydride component containing at least 20 mol% or more of the above four carbonyl groups directly bonded to an aromatic ring structure of a tetracarboxylic dianhydride can be obtained, which is less likely to cause sintering of a liquid crystal display element. This point is preferably more than 50% by mole. # The above four carbonyl groups are directly bonded to the aromatic ring structure. Four specific examples are: pyromellitic acid;: anhydride, 2,3,6,7-naphthalene tetrakis 1, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid di-field, 2,3,6,7*惠. Tetracarboxylic dianhydride, 1 , 2,5,6-nonanedicarboxylic dianhydride, 3,3'4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4,-biphenyltetracarboxylic dianhydride , bis(3,4-di residue phenyl) ether dianhydride, 3,3,,4,4,-benzophenone tetracarboxylic acid di-hepatic, bis(3'4-dicarboxyphenyl)ruthenic anhydride , bis(3,4-dicarboxyphenyl)methine diterpene '2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, hydrazine, I,3,3,3·hexafluoro- 2,2* bis(3,4-dicarboxyphenyl)propane dianhydride, bis(3,dinyl decylphenyl) 1375096 (6) dimethyl decane dianhydride, bis(3,4-dicarboxyphenyl) Diphenylnonane dianhydride, 2,3,4,5-pyridinetetracarboxylic dianhydride, 2,6-bis(3,4-dicarboxyphenyl)pyridine dianhydride, 2,2-bis[4-( An aromatic tetracarboxylic dianhydride such as 3,4-dicarboxyphenoxy)phenyl]propane dianhydride. Among these, 'the effect of having a tetracarboxylic dianhydride having one or two benzene rings and having four carbonyl groups directly bonded to the benzene ring' is difficult to cause sintering of the vertical alignment type liquid crystal display element.

The above tetracarboxylic dianhydride is preferably a tetracarboxylic dianhydride represented by the formula (2) or (3). [Chemical 2]

In the above formulas (2) and (3), X is a single bond or a divalent group containing a stupid ring. Preferably, X has a single bond, -0-, -SO-, -CONH-, -CO-, a divalent aliphatic organic group, a divalent aliphatic organic group substituted by fluorine, or a divalent Si-containing group. Wait. Specific examples of the above tetracarboxylic dianhydride having one or two benzene rings and having four carbonyl groups directly bonded to the benzene ring are pyromellitic dianhydride. 3,3',4,4'-biphenyl Tetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 3,3',4,4'- Benzophenone tetra(8)1375096 [Chemical 3]

(wherein 'W is a divalent organic group selected from the group consisting of -0- and -CH2〇; and r2 is a linear alkyl group having 1 or more and 8 or less carbon atoms). The content of the diamine which is not in the formula (1) is 20 mol/. As described above, good liquid crystal alignment property can be obtained, and is preferably 25 mol% or more, more preferably 3 mol% or more. Further, the content of the diamine represented by the formula (1) is 80 mol% or less, and good printability of the liquid crystal alignment agent can be obtained, and is preferably 70 mol% or less, more preferably 50 mol% or less. R1 in the formula (1) is a divalent organic group selected from the group consisting of -0 and -CH20_; and R2 is preferably a linear alkyl group having 1 or more and 8 or less carbon atoms. When the carbon number of R2 is preferably 4 or more and 8 or less, and more preferably 5 or more and 8 or less linear alkyl groups, a more excellent liquid crystal vertical alignment property can be obtained, which is extremely suitable. Specific examples of the above diamine include diamines represented by the following formulas (4) to (12). Among them, a diamine of the formula (6), the formula (7) or the formula (8) is more preferable. -11 - (4) (9) 1375096 [Chem. 4]

C3H7 H2N\ /NH2

° C4Hs (5)

H2N. MH

°-o-

C5H11 (6) H2N, /NH2

(7) H2N, /NH2

r^\ r~\ (8) -12- (10) 1375096 [5]

When the diamine component used in the present invention is within the above-defined range of two φ shown by the formula (I), it may be used in combination of plural kinds. Further, 20 to 80 mol% of the diamine shown in 1) may be used in combination with other diamines 80 to 20, and may be used in combination with a plurality of other diamines. For example, p-phenylenediamine, 4-, 4-bis(4-phenyl)benzene, 1,5-naphthyldiamine, 4,4'-diaminobiphenyl, 3,3'-yl-4, 4. Diaminobiphenyl, 3,3'-dimethoxy-4,4'-diamine-linked 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3 , dichloro-4,4'-diamine benzene, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 4,4'-bis(4-amino)biphenyl, diamine Diphenylmethane, diaminodiphenyl ether, 2: amine in the formula (; ear % decyl xylene, bisphenoxy, 2-di-13- (11) 1375096 aminodiphenylpropane 4τ4'·diaminodiphenyl selenide, diaminobenzophenone, 1,3-bis(4-aminophenoxy)benzene, 14-bis(4·aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)diphenyl selenide, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 151,1,3,3, 3-hexafluoro: an aromatic diamine such as 2,2-bis[4-(4-aminophenoxy)phenyl]propane; diamine An alicyclic diamine such as dicyclohexylmethane, diaminodicyclohexyl ether or diaminocyclohexane; and 1,2-diaminoethane, 1,3-diaminopropane, I,4 An aliphatic diamine such as diaminobutane or 1,6-diaminohexane, etc., which has a diamine-based oxime represented by the formula (13) or the formula (14), etc. [Chem. 6] /CH3 \ ch3 (13) H2N—(CH2)3rSi—〇Vsi—(CH2)3- NH2 \CH3/PCH3

Ch3\ ch3 Si-OfSi CH3/qCH3

(14) (wherein P and q are each an integer of 1 to 1). Wherein selected from p-phenylenediamine, 1,4-bis(4-aminophenyl)benzene, 1,5-naphthyldiamine, 4,4'-diaminobiphenyl, 3,3, dimethyl Base-4,4,-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, and 3,3'-dihydroxy-4,4'.diamine At least one of the group of bis-phenyl groups has higher polymerization reactivity with the tetra-residual acid dianhydride component, and is more suitable for the poly-proline acid used in the present invention and the polyazide which dehydrates the poly-proline At least one of the amines can be obtained by reacting a tetracarboxylic dianhydride component with a diamine component, and the method is not particularly limited. In general, by mixing in an organic solvent, the reaction is carried out to obtain a poly-proline, and by dehydrating and ring-closing the polyfluorene-14-(12)(12)1375096. amine. a method of mixing a tetracarboxylic dianhydride component and a diamine component in an organic solvent, stirring a solution in which the diamine component is dispersed or dissolved in an organic solvent, and directly dispersing or dissolving the tetracarboxylic dianhydride component. a method of adding an organic solvent; conversely, a method of adding a diamine component in a solution in which a tetracarboxylic dianhydride component is dispersed or dissolved in an organic solvent; a method of alternately adding a tetracarboxylic dianhydride component and a diamine component, etc. . Further, when the tetracarboxylic dianhydride component or the diamine component is formed of a plurality of compounds, the components may be reacted in a predetermined mixed state, or may be reacted in sequence. The temperature at which the tetracarboxylic dianhydride component and the diamine component are reacted in an organic solvent is 〇 150 150 ° C, preferably a temperature selected from 5 toloo. The higher the temperature, the earlier the reaction is completed, but when it is too high, there is a case where a polymer having a high molecular weight cannot be obtained. Further, the reaction can be carried out at a random concentration. However, when the concentration is too low, it is difficult to obtain a polymer having a high molecular weight. When the concentration is too high, the viscosity of the reaction liquid is excessively increased, and it is difficult to perform uniform stirring, and it is preferably 1 ～50% by weight, more preferably 5 to 30% by weight. It can also be carried out at a high concentration in the initial stage of the reaction, and thereafter, an organic solvent is added. The organic solvent used in the above reaction is not particularly limited as long as the produced polylysine is dissolved. Specific examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethyl alum , polar solvents such as tetramethyl urea, pyridine, dimethyl selenium, hexamethyl ferrous, 7-butyrolactone. These can be used singly or in combination. Further, even a solvent in which polylysine cannot be dissolved can be used in the above solvent in a range in which the produced polyamine acid is not precipitated. -15- (13) (13) 1375096 Further, the water in the organic solvent hinders the polymerization reaction, and further causes the hydrolysis of the produced polylysine. The organic solvent is preferably dried by dehydration as much as possible. The ratio of the tetracarboxylic dianhydride component to the diamine component used in the polymerization of polyamic acid is preferably 1:0.8 to 1:1.2 in terms of molar ratio, and the molar ratio is closer to 1:1. The molecular weight of the obtained polyproline is larger. When the molecular weight of the poly-proline is too small, the strength of the obtained coating film is insufficient. When the molecular weight of the poly-proline is too large, the viscosity of the produced liquid crystal alignment agent is too high, and the workability when forming a coating film is The uniformity of the coating film is deteriorated. Therefore, the polyaminic acid used in the liquid crystal alignment agent of the present invention is converted to N-methyl-2-pyrrolidone at a temperature of 30 ° C in terms of reducing viscosity of the polyamidic acid solution. Preferably, the concentration is 0.5 g/d 丨), more preferably 0.5 to 2·0 dl/g. The polyamic acid obtained as described above can be used as it is in the liquid crystal alignment agent for vertical alignment of the present invention, or can be used as a polyimine by dehydration ring closure. At this time, the polyamidimide is preferably 0.05 to 5.0 dl/g (concentration of 0.5 g/dl in N-methyl-2-pyrrolidone at a temperature of 30 ° C) in terms of reducing viscosity of the polyimide solution. More preferably, it is 0.5 to 2.0 dl/g. However, depending on the structure of the polydecanoic acid, it is difficult to use the liquid crystal alignment agent which is insolubilized by the ruthenium imidization reaction, and it is impossible to imidize all of the proline groups in the polyamic acid. A ruthenium iodide may be included in the range of maintaining moderate solubility. The polyamido acid is subjected to dehydration ring closure of the ruthenium imidization reaction. Generally, the polylysine solution is directly heated to be thermally imidized in a polyfluorene-16-(14) 1375096 amine acid solution. The addition of a catalyst for chemical ruthenium iodization; the ruthenium imidization of a ruthenium imidization at a lower temperature is less likely to cause a decrease in the molecular weight of the obtained polyimine, which is suitable. * The above hydrazine imidization reaction allows polylysine to be carried out in an organic solvent by stirring in the presence of a basic catalyst and an acid anhydride. The reaction temperature at this time is -20 to 25 (rc, preferably 0 to 180 ° C, and the reaction time can be carried out in the range of from 1 to 100 hours. The amount of the basic catalyst is 0.5 φ to 30 of the amidate group. The ear is preferably 2 to 20 moles; the amount of the anhydride is 1 to 50 moles, preferably 3 to 30 moles, of the prolyl group. The amount of the basic catalyst or anhydride is too small. When the reaction is not sufficiently carried out, if it is too much, it is difficult to completely remove the reaction after completion of the reaction. The above basic catalysts include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc., wherein pyridine is reacted. It has a moderate alkalinity and is suitable. Further, the acid anhydride includes acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, when acetic anhydride is used, the purification after the completion of the reaction is more convenient and suitable. The solvent used in the polymerization of the above polyamic acid can be used. The chemical imidization ratio of the ruthenium iodide can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time. Amine solution, because the added catalyst remains in the _ solution Therefore, in order to use the liquid crystal alignment agent for vertical alignment of the present invention, it is preferred to use the polyimine solution to be stirred into a weak solvent for precipitation recovery. The weak solvent used for the precipitation of polyimine is not particularly special. Restricted, there are methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, etc. by adding a weak solvent, precipitated poly 醯-17- (15) 1375096 After the amine is filtered, washed and recovered, it is subjected to normal temperature or heat drying under normal pressure or reduced pressure to obtain a powder. The powder is dissolved in a good solvent and repeated for 2 to 10 times to reprecipitate. Polyimine refining. When the precipitation recovery operation cannot remove the impurities, it is preferable to repeat the refining step. In this case, the weak solvent used is, for example, three or more kinds of alcohols, ketones, and hydrocarbons. In the case of a weak solvent, the efficiency of refining can be further improved. #又的聚胺胺酸 can also be subjected to the same operation for precipitation recovery and purification. The liquid crystal alignment agent of the present invention does not want to contain polyglycolic acid polymerization. Used at the time In the case of a solvent or the presence of unreacted monomer components or impurities in the reaction solution, it is preferred to carry out the precipitation recovery and purification. The liquid crystal alignment agent for vertical alignment of the present invention contains the above-mentioned polyfluorene. At least one of an amine acid and a polyamidene which is subjected to dehydration ring closure (hereinafter referred to as a polymer component) and a polymer solution of a solvent to produce polyglycine or polyimine When the organic solvent is appropriate, the reaction solution may be used as the liquid crystal alignment agent for vertical alignment of the present invention, or may be diluted and used. Further, the polymer component precipitated and recovered from the reaction solution may be redissolved in an organic solvent. The liquid crystal alignment agent may be used as the vertical alignment of the present invention. The total concentration of the polymer components in the liquid crystal alignment agent for vertical alignment of the present invention is not particularly limited, but is preferably 2 to 1% by weight. ~ 7 wt%. When the concentration of the polymer component is too small, it is difficult to obtain a film which is uniform and free from defects, and when it is too large, it is difficult to obtain a film having a suitable thickness as the liquid crystal alignment film. The solvent used in the present invention is not particularly limited insofar as the above polymer component is dissolved (16) 1375096 己 基 基 及 及 及 及 80 80 80 80 80 80 80 80 80 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Preferred examples thereof are hydrazine, hydrazine-dimethylmethylamine, hydrazine, hydrazine-dimethylacetamide, hydrazine-methyl-2-pyrrolidone, hydrazine-methyl decylamine, 2-pyrrolidone, Ν-Ethylpyrrolidone, Ν·vinylpyrrole, ketone, dimethyl arylene I, tetramethyl urea, pyridine, dimethyl milling, hexamethyl, fluorene, r · butyrolactone,], 3-dimethyl The group-imidazolinone or the like may be used in combination of one or two or more. Among them, at least one of methyl-2-pyrrolidone 7-butyrolactone is preferred. Further, when the total amount of these preferred φ agents is used alone or in combination, when the total amount of the solvent is 20% by weight, the liquid crystal alignment agent is easily printed uniformly, which is preferably suitable. 70% by weight. Further, the solvent in which the polymer component cannot be dissolved alone can be used in combination in a range which does not impair the solubility of the component. In particular, by appropriate combination of ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethyl-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propanediacetate, propylene glycol diacetate, propylene glycol-1- Monomethyl ether-2-acetic acid, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, 2-(2·butoxypropoxy) Propanol, dipropylene glycol, methyl ether, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, etc., having a low surface tension, which improves the uniformity of the coating film on the substrate. . Among them, at least one of butyl cellosolve and dipropylene glycol methyl ether is preferred. The total amount of these preferred solvents when used alone or in combination is preferably from 20 to 80% by weight, more preferably from 30 to 60% by weight, based on the total amount of the solvent. -19- (17) (17) 1375096 The preferred solvent contained in the present invention contains at least one of N-methyl-2-pyrrolidone and r-butyrolactone, and butyl cellosolve and dipropylene glycol monomethyl ether. The solvent of at least one of them is preferred. Further, 0 to 60% of the total solvent amount may be other solvents than N-methyl-2-pyrrolidone, r·butyrolactone, butyl cellosolve, and dipropylene glycol monomethyl ether. Preferably, the total amount of solvent is 〇~40%. Further, the liquid crystal alignment agent for vertical alignment of the present invention may contain an additive such as a coupling agent in order to improve the adhesion between the liquid crystal alignment film obtained by using the liquid crystal alignment film and the substrate. Specific examples thereof include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, and 2-aminopropyltriethoxydecane. , N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, '3 -ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-amine Propyltriethoxydecane, N-triethoxycarbenylpropyltriethylenetriamine, N-trimethoxycarbamidopropyltriethylenetriamine, 10-trimethoxycarbamido-1 ,4,7-trioxane, 10-triethoxycarbamido-1,4,7-triazane, 9-trimethoxycarbamido-3,6-diazadecylethyl , 9-triethoxycarbamido-3,6-diazadecyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyl Triethoxy decane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, bismuth-bis(hydroxyethylene)-3-amine Propyl trimethoxy矽, Ν-bis(hydroxyethylene)-3-aminopropyltriethoxy decane, ethylene glycol diepoxypropyl ether, polyethylene glycol diepoxypropyl ether, propylene glycol diepoxy-20- (19) (19) 1375096 The power consumption of the element is a disadvantage. When the thickness of the liquid crystal display element is too thin, the reliability of the liquid crystal display element is lowered, preferably 50 to 3000 A, more preferably 1 to 1 5000 A. The liquid crystal element can be produced by a usual method, and the production method thereof is not particularly limited. In general, a sealant is applied to a glass substrate on which a liquid crystal alignment film is formed on at least one of the substrates, and two substrates which are transmitted through a distance-regulating spacer which can maintain a certain gap are bonded to each other to cure the sealant. P liquid crystal injection port is injected into the liquid crystal injection port to close the injection port, and can be made into a liquid crystal element. As the liquid crystal to be used, a fluorine-based liquid crystal or a cyanide liquid crystal having a negative permittivity anisotropy can be used. The liquid crystal alignment agent for vertical alignment of the present invention can form a liquid crystal alignment film having excellent printing properties, no exclusion or uneven film thickness. Further, the vertical alignment type liquid crystal display element using the liquid crystal alignment agent has a superior vertical alignment property of liquid crystal, is difficult to cause sintering, and has display characteristics of no display instability or display defects, and is suitable for a vertical alignment type liquid crystal display element. It is also suitable for use in an MVA type vertical alignment type liquid crystal display element which is not required to be honed. [Embodiment] [Embodiment] The present invention will be described in more detail by way of examples, and the invention is not limited thereto. [Example 1] -22- (20) 1375096

8.724 g of pyromellitic dianhydride (0.04 mol (hereinafter referred to as P-PD) 2.8 77 g (0.0266 mol-re-n-heptylcyclohexyl)phenoxy]-1,3-di and '0.012 mol) was added. N-methyl-2-pyrrolidone (J '9 1 .6g, reacted at room temperature for 3 hours, prepared to reduce the viscosity of the obtained polyaminic acid solution to 〇·7 dl/g, concentration 〇·5 g/ D1).

φ Into 25 g of the polyamic acid solution, 30 g of a NMP agent (hereinafter referred to as B C ) was added to prepare a solid solution of the acid solution, which was used as a liquid crystal alignment agent. The liquid crystal alignment agent was printed on a clean chromium evaporation to obtain a uniform coating film with no exclusion or uneven film thickness, and the liquid crystal alignment agent was spin-coated on the glass substrate at 2,000 rpm by a temperature of 210 ° C. A polyimide film having a film thickness of 1,000 A was fired. After attaching the φ scatter 6; am of the distiller, the other coated splicing is an empty component, and a liquid crystal having a negative permittivity (MLC-6608 manufactured by Meruku) is injected therein. The result of observing this liquid crystal element by a microscope was observed in the iso-rotation (Isogyre) crystal element which was not observed in the center of the field of view, and the liquid crystal was uniformly perpendicularly aligned. Further, in this liquid crystal element, the result of observation of D C 3 V was applied at A C ± 3 V at a frequency of 23 ° C, and the observation was unstable. Ear) p-phenylenediamine), and 4-[4-(amphetamine 4.567g (hereinafter referred to as NMP) polyaminic acid solution. (20g of NMP in 30°C and butyl fibrid! As a result of the ruthenium substrate, the transparent glass was applied for 60 minutes, and the glass substrate of the film on the glass substrate of the film was attached to the anisotropic nematic liquid crystal element. The alignment defect was confirmed, and the liquid was confirmed. The i-rate 30 Hz rectangular wave is less than the display defect or -23- (21) 1375096. Further, the sintering evaluation is performed by the following method. First, the liquid crystal element is fixed under a cross polarizer by a polarizing microscope at a magnification of 40 times in a dark room. The black-and-white sensor for the light-shielded tube brightness meter (model 3298) manufactured by Yokogawa Electric Co., Ltd. is sent to the oscilloscope (model DL7440) manufactured by Yokogawa Electric Co., Ltd. on a range of 400 cd/m2. As a result, it was 2.5 mV, and a DC voltage of 10 V was applied to the liquid crystal element for 3 hours. As a result of measuring the black display state after the applied voltage was removed by the same luminance meter, it was 2.5 mV, and the luminance did not change as compared with before the voltage was applied. [Example 2] 3, 3' , 4,4'-benzophenone tetracarboxylic dianhydride 12.89g (0.04 moles), p-PD 2.877g (0.02 66 moles), and 4-[4-(4-trans-n-heptyl rings) 4.567 g (0.012 mol) of hexyl)phenoxy]-1,3-diaminobenzene was added to 15.2 g of NMP 1 and reacted at room temperature for 3 hours to prepare a polyaminic acid solution. The reducing viscosity of the solution is 0.7 dl/g (concentration of 0.5 g/dl in NMP at 30 φ °C). Add 20 g of NMP and 30,000 g of BC to 25 g of the polyaminic acid solution to prepare a solid concentration of 5%. The polyaminic acid solution is used as a liquid crystal alignment agent. As a result of printing the liquid crystal alignment agent on a clean chromium vapor-deposited substrate, a uniform coating film having no discharge or uneven film thickness can be obtained. The liquid crystal element was produced in the same manner as in Example 1, and the liquid crystal element was observed by a polarizing microscope. No alignment defect was observed, and the rotation was observed at the center of the field of view. Uniform vertical alignment. -24- (22) 1375096 In addition, the results of the evaluation of the liquid crystal element in the same manner as in the first embodiment were not observed to show defects or The display was unstable; in the evaluation by the luminance meter, the applied voltage was 2.5 mV before and after, and no sintering was caused. • [Example 3] 2,3,3:,4'-biphenyltetracarboxylic dianhydride n .77g (0.04 mol), p-PD 2.877g (0.0266 mol) and 4-[4-(4-trans-n-heptylcycloφhexyl)phenoxy]-1,3-diaminobenzene 4.567 g (〇.〇l2 mol) was added to 108.9 g of NMP, and reacted at room temperature for 3 hours to prepare a polyaminic acid solution. The reduced viscosity of the obtained polyaminic acid solution was 0.7 dl/g (3 (concentration of 0.5 g/dl in NMP of TC). 20 g of NMP and BC 30 g were added to 25 g of the polyaminic acid solution to prepare a solid fraction. A polyamine acid solution having a concentration of 5% is used as a liquid crystal alignment agent. As a result of printing the liquid crystal alignment agent on a clean chromium vapor-deposited substrate, a uniform coating film having no discharge or uneven film thickness can be obtained. Using this liquid crystal alignment agent, a liquid crystal element was produced in the same manner as in Example 1. The result of observing the liquid crystal element by a polarizing microscope was observed, and no alignment defect was observed, and the liquid crystal element was observed at the center of the field of view. In the liquid crystal element, the liquid crystal element was evaluated in the same manner as in Example 1. As a result, no display defect or display instability was observed; in the evaluation by the luminance meter, both voltages were applied before and after the voltage was applied. It was 2.5 mV and did not cause sintering. [Example 4] -25- (23) 1375096 Bis(3,4-dicarboxyphenyl)ether dianhydride 12.418 (0. 〇4 mo, p-PD 2.877 g (0.0266) Mohr) and 4·[4-(4-trans-n-heptylhexyl)phenoxy]·1,3-diamine Benzene 4.567g (0.012 mole) was added to 112.5g of NMP and reacted at room temperature for 3 hours to prepare a polyacid solution. The reduced viscosity of the obtained polyaminic acid solution was 0.7 dl/g (in NMP, concentration 〇) .5g/dI) In this polylysine solution, 25g of NMP 20g and BC 30g, prepared into a solution of 5% of the solid concentration of φ φ as a liquid crystal alignment agent. The liquid crystal alignment agent is printed on the clean A uniform coating film having no repulsion or uneven film thickness was obtained on the chrome-vapor-deposited substrate. Using this liquid crystal alignment agent, a liquid crystal was produced in the same manner as in Example 1, and the result of observing the liquid crystal element by a polarizing microscope was observed. It was confirmed that the liquid crystal was in a uniform vertical alignment in the liquid crystal, and the liquid crystal element was evaluated in the same manner as in the first embodiment, and the display was not observed. The defect or the display was unstable; on the evaluation by the luminance meter, both were applied before and after the voltage was 2.5 mV, and no sintering was caused. [Example 5] 1,1,1,3,3,3-hexafluoro-2,2- Bis(3,4-dicarboxyphenyl)propanhydride 1 7_77g (0.04 mol), p-PD 2.877g (0.0266 4. 4g [4-(4·trans-n-heptylcyclohexyl)phenoxy]-1,3-diamine 4.567g (0.012 mole) was added to 142.9g of NMP, and it was prepared at room temperature for 3 hours. Polylysine solution. The ear of the obtained polyaminic acid solution) The base ring, the amine added to the amine at 30 ° C, the component to the missing component, the alkane di) and the benzene reaction to reduce -26- (24) 1375096 Viscosity is 0.7 dl/g (concentration 〇·5 g/dl in NMP at 30 °C). To 25 g of the polyamic acid solution, 20 g of NMP and 30 g of BC were added to prepare a polyamic acid solution having a solid concentration of 5%, which was used as a liquid crystal alignment agent. ' As a result of printing this liquid crystal alignment agent on a clean chromium-deposited substrate, a uniform coating film with no exclusion or uneven film thickness can be obtained. Using this liquid crystal alignment agent, a liquid crystal element was produced in the same manner as in Example 1, and the result of observing the liquid crystal element by a polarizing microscope was observed. The alignment defect was not observed, and the rotation was observed at the center of the field of view. In the component, the liquid crystal is uniformly aligned vertically. Further, in the liquid crystal device, as in the evaluation of the same manner as in the first embodiment, no display defects or display instability were observed. In the evaluation by the luminance meter, the applied voltage was 2.5 mV before and after the application, and no sintering was caused. [Example 6]

4.36 g of pyromellitic dianhydride (〇_〇2 mol), P-PD • 3.028 g (0.028 mol) and 4-[4-(4-re-n-heptylcyclohexyl)phenoxy] 4.567 g (0.012 mol) of 1,3-diaminobenzene was added to NMP 43.8 8 g, and after reacting for 3 hours at room temperature, 1,2,3,4·cyclobutane tetracarboxylic dianhydride was simultaneously added. 3.53 g (0.018 mol) and NMP 87.76 g were reacted for 3 hours to prepare a polyaminic acid solution. The reduced viscosity of the obtained polyaminic acid solution is 0.6 dl/g (3 (in NMP of TC, concentration 0.5 g/dl). Add 20 g of NMP and 30 g of BC to 25 g of this polyaminic acid solution to prepare a solid form. A polyamine solvent solution having a concentration of 5% is used as a liquid crystal alignment agent. The result of printing the liquid crystal alignment agent on a clean chromium-deposited substrate is -27-(25) 1375096, and no discharge or film thickness can be obtained. A uniform coating film was obtained. Using this liquid crystal alignment agent, a liquid crystal element was produced in the same manner as in the example, and the result of observing the liquid crystal element by a polarizing microscope was that 'the alignment defect was not observed, and the rotation was observed at the center of the field of view. Therefore, it was confirmed that the liquid crystal element was uniformly aligned in the liquid crystal element. Further, as the liquid crystal element was evaluated in the same manner as in Example 1, no display defect or display instability was observed; in the evaluation by the luminance meter, application was performed. The voltage was 2.5 mV before and after, and no sintering was caused. [Comparative Example 1] 1,824 g (0.04 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and 2.877 g (0.0266 m) of p-PD. And 4-[4-(4-trans-n-heptylcyclohexyl)phenoxy]-1,3-diamine Benzene 4.567g (0_012 mol), added to NMP 8 6.6g, reacted at room temperature for 3 hours to prepare a polyaminic acid solution. The obtained polyglycine solution has a reducing viscosity of 0.7 dl / g ( 30 ° C In the φ NMP, the concentration is 0.5 g/dl. To 25 g of the polyaminic acid solution, 20 g of NMP and 30 g of BC are added to prepare a polyamic acid solution having a solid concentration of 5%, which is used as a liquid crystal alignment agent. As a result of the alignment agent being printed on the cleaned chromium-deposited substrate, a uniform coating film having no unevenness or uneven film thickness was obtained. Using this liquid crystal alignment agent, a liquid crystal element* was produced in the same manner as in Example 1 to polarize light. As a result of observing the liquid crystal element by a microscope, no alignment defect was observed, and an equal rotation was observed at the center of the field of view, and it was confirmed that the liquid crystal was uniformly aligned in the liquid crystal element. -28- (26) (26) 1375096 In the evaluation of the liquid crystal element and the same results as in the first embodiment, no display instability was observed. Further, in the evaluation by the luminance meter, the liquid crystal element was applied at a voltage of 2.5 mV before the application of a voltage, and a DC voltage of 0 V was applied. Hour, observed at 7.8mV after the voltage is applied The unevenness of the brightness caused sintering. [Comparative Example 2] 8.724 g (0.04 mol) of isophthalic acid dianhydride, 2.877 g (0.0266 mol) of p-PD, and 1,3-diamino group 4- (18) alkoxybenzene 4: 52g (0.012 mole), added to NMP 91.4g, reacted at room temperature for 3 hours, and adjusted to poly-proline solution. The reduced viscosity of the obtained poly-proline solution is 0_7 dl/g (concentration 0.5 g/dl in NMP at 30 °C). To 25 g of the polyamic acid solution, 20 g of NMP and 30 g of BC were added to prepare a polyamine solution having a solid concentration of 5%, which was used as a liquid crystal alignment agent. As a result of printing this liquid crystal alignment agent on a clean chromium-deposited substrate, a uniform coating film having no discharge or uneven film thickness can be obtained. Using this solution, a liquid crystal element was produced in the same manner as in Example 1, and the crucible of the liquid crystal element was observed by a polarizing microscope, and no alignment defect was observed: the rotation was observed at the center of the field of view, and it was confirmed that the liquid crystal element was in the liquid crystal element. The liquid crystal is a uniform vertical alignment. With this liquid crystal element, display defects can be observed when driving. [Comparative Example 3] 8.724 g (0.04 mol) of pyromellitic dianhydride and 4-[4-(4- -29-(27) 1375096 anti-n-heptylcyclohexyl)phenoxy]-1; 3. Diamine benzene i5.22 g of molar was added to 135.7 g of NMP, and reacted at room temperature for 3 hours to form a polyaminic acid solution. The reduced viscosity of the obtained polyaminic acid solution | * dl / g (concentration of 0.5 g / dl in NMP at 30 ° C). To 25 g of this solution, 20 g of NMP and 30 g of BC were added to prepare a polyamic acid solution having a solid content. As a result of printing this solution on a clean chromium-deposited substrate, φ; φ has no uniform coating film with uniform rejection or uneven film thickness. Using this solution, a liquid crystal element was produced in the same manner as in Example 1. As a result of observing the liquid crystal element by a light microscope, it was observed that the alignment defect was not observed and the like, and it was confirmed that the liquid crystal was vertically aligned in the liquid crystal element. [Industrial Applicability] The liquid crystal alignment agent for vertical alignment of the present invention has superior Ef φ and uniformity of coating film, and allows liquid crystal molecules to be vertically and stably aligned with the substrate without display defects or display instability, and is difficult to cause sintering. For the sake of effect, it is used in the vertical alignment type LCD. Further, the disclosure of the application No. 5, patent application No. 2004-3 785 5, filed on Dec. 28, 2004, the entire contents of the entire disclosure, and the entire contents of the present disclosure are hereby incorporated by reference. (0.04 Modulation I 0.7 ? Acid solubility 5% 『According to the bias and i uniform brushability, and the appropriate transcript and pick -30-

Claims (1)

1375096 Patent Application No. 094147028 Revision of Chinese Patent Application Scope Amendment of July 30, 101 of the Republic of China, Application for Patent Scope 1. A liquid crystal alignment agent for vertical alignment, which contains poly-proline and a liquid crystal alignment agent of at least one of a dehydration ring-closed polyimine and a solvent; wherein the polyamine acid is a diamine of the formula (1) containing 20 to 80 mol% The diamine component and the tetracarbonyl dianhydride component of the tetracarboxylic dianhydride of the aromatic ring structure are directly linked to the tetracarbonyl group represented by the formula (2) containing 20 to φ 100 mol%, and are reacted. 1] Wherein R1 is a divalent organic group selected from the group consisting of -〇- and -CH20-; and R2 is a linear alkyl group having 1 or more and 8 or less carbon atoms; 2. The liquid crystal alignment agent for vertical alignment according to the first aspect of the patent application, wherein in the liquid crystal alignment agent, the total concentration of the polyamido acid which is subjected to dehydration ring closure of the polyamido acid is 2~ 10 weight. . 3. The liquid crystal alignment agent for vertical alignment according to claim 1, wherein the diamine represented by the formula (1) is a diamine represented by the formula (6), the formula (7) or the formula (8), (6) (7) 4. The liquid crystal alignment agent for vertical alignment according to item 2 of the patent application, wherein the diamine represented by the formula (1) is a diamine represented by the formula (6), the formula (7) or the formula (8), [ 2]. -2- 1375096 pieces of 曰 modified replacement 3 amine, 4,4,-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy a diamine in the group of 4,4'-diaminobiphenyl and 3,3'-dihydroxy-4,4,-diaminobiphenyl. 6. The liquid crystal alignment agent for vertical alignment according to item 3 of the patent application, wherein the diamine component 'containing at least one other than the diamine represented by the formula (1) Species selected from p-phenylenediamine, anthracene, 4-bis(4-aminophenyl)benzene, 1,5-naphthyldiamine, 4,4,-diaminobiphenyl, 3,3'-dimethyl Base-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, and 3,3'-dihydroxy-4,4,-diamine A diamine of a group of phenyl groups. 7. The liquid crystal alignment agent for vertical alignment according to claim 1, wherein the solvent contains at least one of fluorene-methyl-2-pyrrolidone and r-butyrolactone. 8. The liquid crystal alignment agent for vertical alignment according to claim 4, wherein the solvent contains at least one of N-methyl-2-pyrrolidone and butyrolactone. 9. The liquid crystal alignment agent for vertical alignment according to claim 7, wherein the solvent contains at least one of butyl cellosolve and dipropylene glycol monomethyl ether. 10. The liquid crystal alignment agent for vertical alignment according to item 8 of the patent application, wherein the solvent contains at least one of butyl cellosolve and dipropylene glycol monomethyl ether. A liquid crystal alignment film which is obtained by applying a liquid crystal alignment agent for vertical alignment according to any one of claims 1 to 10 to a substrate and firing it. -3- 1375096_ | 〇 1 year y 曰 曰 correction replacement page 12. A liquid crystal display element, which is characterized by having a substrate having a liquid crystal alignment film which has been formed in the scope of the patent application. -4-