TW201204766A - Aromatic diamine compound, polyamic acid and polyimide prepared using the same and liquid crystal alignment agent - Google Patents

Abstract

A liquid crystal alignment agent suitable for a display is provided. The liquid crystal alignment agent includes a polyimide obtained by polymerizing a diamine compound and a tetracarboxylic acid or a dianhydride compound thereof. The diamine compound contains an aromatic diamine represented by formula (I), wherein any two of R1 to R5 are primary amino group, and others are each independently hydrogen atom or monovalent substituent except primary amino group; R6 is C1 to C20 alkyl group, C3 to C40 monovalent alicyclic substituent, C6 to C51 monovalent aromatic substituent or monovalent heterocyclic substituent; X1 and X2 are each independently single bond or divalent binding group selected from the group consisting of ether group, ketone group, ester group, amido group and secondary amino group; X3 and X4 are each independently C1 to C3 straight-chain alkylene group.

Description

201204766 A "v / v, 34008twf.doc / n VI. Description of the invention: [Technical field of the invention] The present invention relates to an aromatic diamine compound, polyglycine prepared using the aromatic diamine compound ( P〇lyamic acid) with polyimide (PI) and liquid crystal alignment agent', and particularly relates to an aromatic diamine compound which can improve the performance of a liquid crystal display element, and a polyglycol prepared using the aromatic diamine compound Proline and polyimine and liquid crystal alignment agent. [Previous technology] Liquid crystal display is a display that utilizes photoelectric change of liquid crystal, which has the advantages of small size, light weight, low power consumption and good display quality. Therefore, it has become the mainstream of flat panel displays in recent years. The development of liquid crystal displays is required by the expansion of the size of the kneading surface, the high saturation of color, the high contrast and the increase of the reaction speed, by twisted nematic (TN) liquid crystal. Display, super twisted nematic (such as (4) twisted nematic 'STN) liquid crystal display, until now developed to each pixel TFT type liquid crystal riding, which is equipped with thin-film transistors (thin tansist〇r, TfT), has been continuously improved in recent years for the driving method of the TFT Weiri day display. For example, in the improvement of the viewing angle, vertical alignment has been developed. VA) mode or in piane switching (IPS) mode. In addition, optical compensation f (QptieaUy(3) _心_, 〇 mode) which can improve the response speed of the corresponding animation is also developed. 201204766 -^—03 34008twf.doc /n crystal display; ί steering column (four) electric field effect type liquid crystal liquid distribution early Λ a 4KI · human W electricity "square linear nematic liquid crystal. In general, the direction of the mutual ^ h between the electrodes with the substrate, and the two substrates The formula 弋]j (4) control the arrangement of the electro-radiation-controlled coronal molecules 3 US =, for the display, the alignment of the long axis of the liquid crystal molecules ": β with a uniform tilt angle is quite important

The ancestors are arranged in a uniform pretilt angle (clear reading a_). The aligning material is called an alignment film. At present, there are two typical methods for preparing alignment films in the industry. The first method is to form the inorganic substance f into an inorganic film by the deposition. For example, a thin film is vapor-deposited on a substrate to form a thin film, and the scattered molecules are aligned in the vapor deposition direction. However, although the above method achieves uniform alignment, it is less industrially advantageous. In the second method, an organic film is coated on the surface of the substrate, and then rubbed with a soft cloth of cotton, nylon or polyester to orient the surface of the organic film so that the liquid crystal molecules are aligned in the rubbing direction. Since this method is relatively simple and relatively easy to obtain uniform alignment, it is generally applied on an industrial scale. The polymer which can form an organic film is, for example, polyvinyl alcohol (PVA), polyethylene oxide (PEO), polyamide 'Pa or polyimine, wherein the polyimine has Chemical stability and thermal stability are the most commonly used as alignment film materials. In the prior art, when a voltage is applied to the liquid crystal display, the generated ionic charge is adsorbed by the liquid crystal alignment film, and even after the applied voltage is released, it is difficult to separate the ionic charge from the liquid crystal alignment film. , 5 201204766 UAuyuyuj 34008twf.doc/n This causes a problem of residual images on the screen. Therefore, the development of recent alignment film materials has been the primary issue of improving afterimage problems. SUMMARY OF THE INVENTION The present invention provides a liquid crystal alignment agent which forms a liquid crystal alignment film having an effect of improving a pretilt angle. The present invention further provides an aromatic diamine compound which can improve the performance of a liquid crystal display element. Displaying the display element The present invention further proposes a poly-proline which enhances the performance of the liquid crystal device. The present invention further provides a polyimine which enhances the performance of a liquid crystal device. The present invention & a liquid crystal alignment agent suitable for use in displays. The liquid crystal alignment agent includes a polyimine obtained by polymerizing a diamine compound and a tetracarboxylic acid or a dianhydride compound thereof. The diamine compound contains an aromatic diamine compound represented by Formula 1, μ

Any one of the center-to-heart of the formula (I) is a primary amine group, and the others are each independently a hydrogen atom or a monovalent substituent other than the primary amine group; and R6 is a monovalent alicyclic group of C1 to C20 from C3 to C40. a substituent, a C- to C51-valent aromatic substituent or a monovalent heterocyclic substituent; & and X2 are each independently a single bond or a free ether group, a keto group, an ester group, a decyl group and a secondary amine group Group of constituents = 201204766 u^vy\jy〇3 34008twf.doc/n Binary binding group; X3 and X4 are each independently a linear alkyl group of ci to C3. In the liquid crystal alignment agent according to the embodiment of the present invention, the content of the aromatic diamine compound used in the polymerization of the polyimine is, for example, at least 1 mol% based on the total amount of the diamine compound. The liquid crystal alignment agent according to the embodiment of the present invention has, for example, at least 10 mol% of the aromatic diamine compound used in the polymerization of the polyimine in terms of the total amount of the diamine compound. The liquid crystal alignment agent according to the embodiment of the present invention, wherein the content of the aromatic diamine compound used in the polymerization of the polyimine is, for example, at least 50 mol% based on the total amount of the diamine compound. The liquid crystal alignment agent according to the embodiment of the present invention may further comprise a polylysine obtained by polymerizing a diamine compound and a tetracarboxylic acid or a dianhydride compound thereof. Further, the liquid crystal alignment agent according to the embodiment of the present invention has a content of the aromatic diamine 彳 匕 φ φ 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合Moor. /〇. According to the liquid crystal alignment agent of the embodiment of the present invention, the content of the aromatic diester used in the polymerization of the polyamic acid is, for example, at least 10 mol% based on the total amount of the diamine compound. a sigma 2 according to the liquid crystal alignment agent of the embodiment of the present invention, wherein the content of the aromatic diamined person used in the polymerization of the polyaminic acid is, for example, at least 50 mol%. . σ The liquid crystal alignment agent according to the embodiment of the invention may further comprise a solvent of 34008 twf.doc/n 201204766. The present invention further provides an aromatic diamine compound represented by the formula (1).

Wherein 1 to Rs are both a primary amine group, and the others are each independently a hydrogen atom or a monovalent substituent other than the primary amine group; Re is a C1 to C20 alkyl group, and a C3 to C40 monovalent alicyclic substituent a monovalent aromatic substituent or a monovalent heterocyclic substituent of C6 to C51; a group consisting of oxime and & each independently a single bond or an ether group, a keto group, an ester group, a guanamine group, and a secondary amine group A monovalent binding group; X3 and X4 are each independently a linear alkyl group of C1 to (7). The present invention further provides a polyaminic acid obtained by polymerization of a tetracarboxylic acid or a dianhydride compound thereof and a diamine compound, wherein the diamine compound contains the above aromatic aryl diamine compound ό θ The poly-aracine acid described in the examples is a core of a diamine compound. The content of the above aromatic diamine compound is, for example, at least 1 mole. The polyamic acid according to the embodiment of the present invention, the content of the above aromatic diamine compound is, for example, based on the diamine compound. 〇 耳 %. The poly-proline acid according to the embodiment of the present invention, wherein the content of the above aromatic diamine compound in the diamine compound is, for example, at least 50 201204766 to sand 03 34008 twf.doc/n Moer%. The present invention further provides a polyimine which is obtained by polymerization of a tetradecanoic acid or a dianhydride compound thereof and a diamine compound, wherein the diamine compound contains the above aromatic diamine compound. The polyimine according to the embodiment of the present invention has a content of the above aromatic diamine compound of, for example, at least 1 mol% based on the total amount of the diamine compound. ,

The polyiminoimine according to the embodiment of the present invention has a content of the above aromatic diamine compound of, for example, at least 1 mol% based on the total amount of the diamine compound. According to the polyimine of the embodiment of the present invention, the content of the above aromatic diamine compound is, for example, to mol% based on the total amount of the diamine compound. Based on the above, since the liquid crystal alignment agent contains the aromatic compound of the present invention and the acid reading or the dibric compound thereof to obtain 2 = J or polyimine and polylysine, the liquid crystal is formed. The film has the effect of increasing the face angle, and allows the liquid crystal display element to have a residual DC charge of a relatively good value to improve the performance of the liquid crystal display element. The following sections (4) are more obvious and easy to understand, and the _® style is described in detail below. [Embodiment] The present invention provides a liquid crystal alignment agent, which is suitable for use in displays. The liquid crystal alignment agent comprises a polystyrene compound obtained by polymerization of a diamine compound and 201204766 v-/ 34008 twf.doc/n or a bis-compound thereof, which comprises the formula (1). An aromatic diamine compound represented.

The center to r5 is either a primary amine group, and the others are independently a monovalent group other than a gas atom or a primary amine group; R6 is a C1 to C2 anthracene, and a C3 to C40 monovalent alicyclic group a substituent, a monovalent aromatic substituent or a monovalent heterocyclic substituent of C6 to C51; 乂1 and 乂2 are each independently a single bond or are selected from the group consisting of an ether group, a ketone group, an ester group, a decyl group and a secondary group. a divalent binding group of a group consisting of an amine group; X3 and X4 are each independently a C1 to C3 linear chain. In the embodiment of the present invention, the aromatic diamine compound represented by the formula (I) may be 1-(2,4-diaminophenyl)·4·ethyl·Brigade ^ (1 - (2) , 4-diaminopheny l)-4-ethy Ι-piperazine), 1-(3,5-diaminophenyl)-4-..ethyl_ _ . ° Chen. Qin (l-(3,5 -diaminobenzoyl)_4-ethyl-piperazine), 1·(2,4-diaminophenyl)·4-phenyl-α- per (嘻-(2,4-diaminophenyl)-4-phenyl-piperazine), 1 -(3,5-Diaminobenzimidazole)-4-phenyl-peptone (l-p'S-diaminobenzoyl^-phenyl-piperazine) and the like. The aromatic diamine compound represented by the formula (1) can be synthesized by the following steps: First, in the presence of a base and an organic solvent, 201204766 UX〇y〇903 34008twf.doc/n dinitrate represented by the formula (II) The benzene compound is reacted with a piperazine compound represented by the formula (III) to obtain a compound represented by the formula (IV), wherein Y is -F, -Cb-Br, -COC1, -COOH and many more.

Then, the compound represented by the formula (IV) is subjected to a hydrogenation reaction to obtain an aromatic diamine compound compound represented by the formula (1).

In the above synthesis method, a substitution reaction is carried out mainly in the presence of a dinitrobenzene represented by the formula (II) in the presence of a base and an organic solvent, followed by a reduction reaction (hydrogenation reaction) to obtain A spent aromatic diamine compound represented by the formula (1). The test added has the effect of a catalyst which increases the speed of the synthesis reaction and lowers the reaction temperature. The base compound which is suitable for use in the synthesis process may be selected from the group consisting of Group IA and Group IIA metals. The salt is preferably a carbonate selected from the group consisting of Group IA and Group IIA metals. Alternatively, the base suitable for use in this synthetic method may be a tertiary amine (e.g., trimethylamine, triethylamine, triisopropylethylenediamine, etc.). The organic solvent suitable for use in the synthesis method may be an alkyl halide (such as 201204766 34008twf.doc/n dichloromethane, di-ethane, gas, etc.), a ketone (such as acetone, methyl ethyl ketone, etc.), N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl alum, and the like. In the above reduction reaction (hydrogenation reaction), it can be carried out by a generally known hydrogenation reaction method. For example, a metal catalyst such as platinum (pt), palladium (Pd) or Raney-Ni (Niney) can be used in the form of hydrogen or Yijin (tetra) at an appropriate pressure and temperature. Alternatively, a reducing agent such as dicarbazide 12) or iron (Fe) is subjected to a reduction reaction with concentrated hydrochloric acid. Alternatively, the reaction is carried out in an aprotic solvent using a reducing agent such as LiAlH4. Further, the liquid crystal alignment agent of the present invention may contain, in addition to the above-mentioned diamined character and the tetrakid or its two-ride compound, a reaction of a diamine, and may also contain a polymerization reaction of the above diamine compound and tetra::= anhydride compound. The polylysine obtained is also containing a solvent. The above polyimine and polylysine can be dissolved in an organic polar solvent (such as Ν-methyl 2_* each fine, Ν, Ν: methyl methamine, hydrazine, hydrazine _ dimethyl hydrazine The amine, Ν-methyl caprolactam, dimercapto, hard, vinegar, etc.) are then applied to a substrate or a plate having a transparent electrode. At a temperature of from 3 to 3 thieves, the solution was subjected to heat treatment to evaporate to form a film. After the film is subjected to directional rubbing treatment, the liquid helium alignment film can be obtained, which can provide liquid crystal molecules with stable _ ^ voltage holding ratio. , the male thief mentioned above is usually not particularly limited, it can be aromatic tetrazoic acid (such as U, 4,5-benzene tetrazoic acid, 3,3,, 4,4l diphenyl four test, 2 3 3,4_ diphenyltetradecanoic acid, bis(3,4-dicarboxyphenyl)ether, 3,3,44,_benzophenone 12 201204766 υΑυ^υ^03 34008twf.doc/n tetracarboxylic acid , bis(3,4-dicarboxyphenyl)anthracene, bis(3,4-ditrophenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propene, 1, U,3,3,3_six rustic _2 soil 2 雔 (3,4-dibuylphenyl)propane, bis (3,4-disyl), dimethyl sulphur, two pairs (10) - 二二基基基^Phenshixi^(4)"Comparatively sulphuric acid, ^-bis(3,4_di-n-phenyl)K, dianhydride and di-nuclear compound derived from the upper surface Etc.), an aliphatic cyclic four-core (such as cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, hydrazine 3 hydrazine, a cyclopentyl acetic acid, 3, 4 - 2 -year base _1,2,3,4_tetrahydronaphthylbutylate: acid liver has been derived from the above-mentioned lipid-bearing ring four-fold two- and two-acid bis-compounds, etc.) or aliphatic tetracarboxylic acid (such as Alkanetetracarboxylic acid and its derived diacid di- and di-restroginium bismuth compounds). The above-mentioned four-core and its diacid liver and di-acid diterpenoid halogen compounds may be used singly or in combination of two or two. ° In addition, the above diamine compound and tetrazoic acid or its diacid are carried out. In the polymerization reaction of the needle-forming compound, the diamine compound may contain other diamine compounds in addition to the aromatic diamine compound represented by (4) (1). The other diamine compound described above is a -diamined product. It may be a scented diamine compound (such as p-phenylenediamine, diamine dipyridyl methane, diamine j-based m-polyamine phenylpropanol, bis(3,5-diethylylaminophenyl) Monoamine monophenyl sulfone, diamino dioxolanone, diamino naphthalene, I#·aminophenoxy)benzene, U_bis(4-aminophenyloxy)benzene, 4,4 _ bis (4 _ base cone oxy): phenyl m bis (4,4-aminosilylphenyl) propyl, _:: (aminophenyl) hexafluoro and 2, 2 bis ( 4,4-Aminophenoxyphenyl) ', murine propylene), an aliphatic cyclic diamine compound (such as bis(4-aminocyclohexane 13 34008twf.doc/n 201204766) decane , bis(4-amino-3-methylcyclohexyl)decane, etc.) or aliphatic diamine a compound such as butanediamine or hexamethylenediamine. The other diamine compounds described above may be used singly or in combination of two or more. In the examples of the present invention, the diamine used is used. The content of the above aromatic diamine compound is at least 1 mol%, preferably at least 10 mol%, more preferably at least 50 mol%, based on the total amount of the compound. The above-mentioned _amine compound and tetradecanoic acid are carried out. In the polymerization of the diacid liver compound or the diacid liver compound, the degree of polymerization of the product is preferably between 〇·〇5 dl/g to 3 〇dl/g. The above specific viscosity was measured at a concentration of 0.5 g/dl of N-methyl-2-pyrrolidone at a temperature of 30 C. & J | For the polymerization method of the diamine compound and the tetrazoic acid or its diacid compound, there is no __ ‘ For example, 'the first diamine compound will be transferred to an organic polar solvent (such as Ami 2, N, N• dimethylidene _, N, N dimethyl _, 1 A wind Ϊ Ϊ J, will The acid or its dianhydride compound is added to the solvent to carry out the polymerization of the lamp to entangle the filament of the copolymer of the ruthenium amide. The polymerization is carried out at a temperature of, for example, between 150 C, preferably _5 t to just c. The polymerization clock is up to 24 hours, preferably between 1 and 8 hours. "In addition to the 5 knives, the complex content of the copolymer of polyamine and poly-proline is compared. Should be between 10% by weight and 3% by weight. (4) Libai knife in order to make polyimine or polyimine and poly-_ copolymer have 201204766 DX090903 34008twf.doc / n appropriate molecular weight, tetracarboxylic The molar ratio of the acid or its dianhydride compound to the diamine compound is, for example, between 0.8 and 1.2. The closer the molar ratio of the tetracarboxylic acid or its dianhydride compound to the diamine compound is, the larger the molecular weight is. And the higher the viscosity. When the molar ratio of the tetracarboxylic acid or its dianhydride compound to the diamine compound is less than 1, an appropriate amount of terminal closure can be added. End cap functional group ' to reduce the oxidation of terminal functional groups caused by the molar ratio not equal to i. Suitable terminally-closed functional groups are, for example, phthalic anhydride, maleic anhydride, aniline, cyclohexaneamine Etc. * After the polymerization reaction, the copolymerization degree of the copolymer of the obtained polyfluorene or polyimine and poly-proline is, for example, 1 to 5 Torr (preferably 16 to 250). Further, the weight average molecular weight is, for example, 5 Å to 25 Å (preferably 8,000 to 125,000). Further, in order to increase the degree of polymerization of the above polymerization reaction and to reduce the reaction time, a catalyst may be added during the reaction. The catalyst is, for example, triethylamine, diethylamine, n-butylamine, pyridine, etc. The above catalyst also has a function of adjusting the pH of the solution. # In addition, in other embodiments, the liquid crystal alignment agent may further contain An organic oxime (oxy) alkane compound which may be aminopropyltrimethoxydecane, aminopropyltriethyldecane, vinylmercaptodecane, N-(2-aminoethyl)-3-aminopropyl Base quinone methoxy decane, N-(2-amino group 3-aminopropyltrimethoxy decane, vinyltriethoxydecane, 3-mercaptopropenyloxypropyldimethoxyxanthine, 3-glycidoxypropyltrimethyl Oxyzepine, 3_glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, 3-ureidopropyl three曱oxydecane, 3-ureidopropyl three 15 34008twf.doc/n 201204766 ethoxy oxime, N-ethoxycarbonyl_3_aminopropyltrimethoxy decane, N-ethoxycarbonyl-3- Aminopropyltriethoxyamine decane, N-triethoxydecylpropyltrisethyltriamine, N-trisethoxydecylpropyltriethylamine, N-double (oxyethyl) 3-aminopropyltrimethoxydecane, N-bis(oxyethyl)-3-aminopropyltriethyldecane, and the like. The content of the organic oxime (oxy) alkane compound does not affect the desired characteristics of the liquid crystal alignment film and can improve the adhesion of the liquid crystal alignment film to the surface of the substrate. When the content of the organic sulfonium (oxy) alkane compound is too high, the formed liquid crystal alignment film is liable to cause poor alignment; if the content of the organic sulfonium (oxy) alkane compound is too low, the formed liquid crystal alignment film is likely to be generated. Poor brushing and excessive powder cutting. Therefore, the content of the organic oxime (oxy)alkyl compound is, for example, 0.01% by weight to 5% by weight, preferably 0.1% by weight to 3% by weight based on the total weight of all the polymers in the liquid crystal aligning agent. Furthermore, 'in other embodiments, the liquid crystal alignment agent may further contain an epoxy compound' which may be ethylene glycol diglycidyl hydrazine, propylene glycol diglycidyl hydrazine, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl glycerol. Ether, 1,6-disalone monoglycidyl diglycidyl ether, glycerol diglycidyl hydrazine, 2,2-di-di, pentaerythritol diglycidyl _, 1,3,5,6-tetraglycidyl-2 , 4-carbolyzed diol, N,N,N',N'-tetraglycidyl-m-phenylene, 1,3-bis(n,N-diglycidylamino)cyclohexane , N,N,N',N,-tetraglycidyl·4,4,-diaminodiphenylnonane, 3—(;Ν-allyl-indole-glycidyl)aminopropyl three Alkoxy decane, 3-(anthracene, fluorene-diglycidyl) aminopropyltrimethoxy zeoxime. The content of the epoxy compound is such that the desired characteristics of the liquid crystal alignment film are not affected and the adhesion of the liquid crystal alignment film to the surface of the substrate can be improved. If the content of the epoxy compound 201204766 DX09〇y〇3 34008twf.doc/n is too high, the formed liquid crystal alignment film is liable to cause poor alignment, and if the content of the oxygen compound is too low, the formed liquid crystal alignment film It is easy to produce poor brushing and excessive powder cutting. Therefore, the content of the epoxy compound is, for example, from 1% by weight to 3% by weight based on the total weight of the alignment film material, preferably from 9% by weight to 2% by weight. In order to match the processability of the liquid crystal alignment film, the solid content of the formed polyimine or the copolymer of polyimine and polyglycolic acid can be adjusted to 3 wt% to wt% in an organic solvent to adjust the viscosity. The film thickness and coating properties are controlled, and the subsequent alignment film processing process is facilitated. Suitable organic solvents are, for example, N-mercapto-2-° ratio brewing J, meta-salt, γ-butyrolactone, n,n-dimethylacetamide, N,N-monomethylformamidine Amine or a mixture thereof. Alternatively, a solvent which does not have the ability to dissolve polyimine may be added as long as it does not cause poor solubility of the polyimine in other solvents. Such a solvent is, for example, ethylene glycol monoethyl ether, ethylene glycol monobuthyl ether, diethylene glycol monobuthyl ether, Diethylene glycol monoethyl ether, butyi carbitol, ethyl carbitol acetate, ethylene glycol or a mixture thereof. The content of such a solvent is preferably controlled to be 90% or less of the total weight of the solvent. The method of synthesizing the brewed imine is, for example, heating the polyamic acid to carry out dehydration ring closure to form a polyimine. The heating temperature is, for example, between 10 ° C and 350 ° C, preferably between 120 ° C and 320 ° C. The reaction time is, for example, from 3 minutes to 6 hours. 17 201204766 u^.\jy\jyy}^ 34008twf.d〇c/n There are two main methods for the synthesis of copolymers of polyimine and poly-proline. The first method is to obtain a copolymer by controlling the ratio of the number of dehydrated moles. In the second method, a part of the diamine compound and the diacid-reducing person are subjected to dehydration cyclization at a specific ratio, and then the remaining diamine compound and the dianhydride compound are added at room temperature to carry out polymerization. The liquid 曰a display can be obtained by the following steps. (1) The liquid crystal alignment agent of the present invention is applied onto a glass substrate by a roll coating method, a spin coating method or a printing coating method. This glass substrate has a patterned transparent conductive film. After coating the liquid crystal alignment agent, heat baking is performed to remove the organic solvent in the liquid crystal alignment agent and to promote the dehydration/ring closure reaction of the uncircularized polyamic acid to form a polyimide film. The above heat baking temperature is between 80 and 30 (TC, preferably 100 to 24 Torr). The film thickness is preferably from 0.005 to 0.5 μm. (2) The formed film is used. A roller wound with a nylon or cotton fiber cloth is subjected to directional rubbing to make the liquid crystal molecules have an alignment property. (3) coating a sealant on a substrate having the above liquid crystal alignment film, and applying the above liquid crystal to another tamping device The spacer is sprayed on the substrate of the south film, and then the two substrates are combined with each other in a direction perpendicular to each other or parallel to each other, and liquid crystal is injected into the gap between the two substrates to seal the injection hole, thereby forming a liquid crystal display element. For the liquid crystal display element, the following characteristics are generally used as the evaluation index. (1) Pretilt angle The liquid crystal display element that has been injected into the liquid crystal (ZLI_4792) is crystallized by the crystallization method 18 201204766 UA〇yw03 34008tw£doc/n (2) Brushing property The liquid crystal alignment agent was applied by spin coating to an indium tmoxide (ITO) substrate and baked through an oven at a rate of 1 rpm. , 60 mm / sec platform movement The directional brushing was performed 1 time, and the surface after brushing was visually observed by a polarizing microscope. (3) The voltage holding ratio was applied to the liquid crystal display at 60 Hz in an ambient temperature of 90 C. The pulse width is 60 pSec to measure the voltage holding ratio in the liquid crystal display element. (4) Residual DC charge - 5 V DC is applied to the liquid crystal display element for 1 hour at an ambient temperature of 6 ° C, and then the DC current is cut off. The residual DC voltage in the liquid crystal display element is measured. (5) Cyclization ratio (imidization ratio) The liquid crystal alignment agent is dried under reduced pressure at room temperature, and then the dried solid is dissolved in the deuterated diterpene group. In the Aamu, 'Using tetradecyldecane as a reference substance' is measured by 1H-NMR, and the imidization ratio is obtained by the following formula. The imidization ratio (%) = (1 - A1/A2 X X1 〇〇

Aj: Proton-derived spike area of self-deuterated group (1〇ppm) A. Peak area derived from other protons α: Number of protons of other protons relative to polyamine/NH group *201204766 34008twf.doc /n (6) Adhesion ^. The liquid crystal alignment agent was coated on the ITO substrate, and the IT crucible substrate was boiled at 100 C for 1 hour, and then subjected to 31 V [package test for 100% test (cr〇ss cut method) (7) reliability to the temperature rlT In the house environment (temperature 5 〇. 〇, relative humidity 9 〇 RH), the liquid crystal display element was driven at 60 Hz / 5 V for 5 hours, and then observed through a polarizing microscope. The invention will be described below by way of experimental examples. Synthesis of Aromatic Diamine Compounds Example 1 Synthesis of 1-(2,4-diaminophenyl)ethyl-α-endopurine (1-(2,4-diaminophenyl)-4-ethyl-piperazine) at 2 liters In the reaction flask, 2,4-dinitrofluorobenzene (67 g, 360 mM), dimethylacetamide (500 g) and carbonate (potassium) were added. Carbonate) (72, 5 g, 525 mmol), stirred for 5 minutes. Then, will N-ethyl mother. N-ethylpiperazine (40 g, 350 mmol) was slowly dropped into the reaction flask. After all the drops have been completed, the temperature is raised to 80. (:, the reaction was carried out for 48 hours, and then returned to room temperature. Then, the reactant was poured into ice pure water (2000 g) to precipitate a shoal. Then, a pumping transition was carried out, and the obtained cake was a product 20 201204766 DX090903 34008twf.doc/n 1-(2,4-Dinitrophenyl)-4-ethyl-piperazine (70.6 g, 252 mmol), The yield was 72%. Spectral data: 1H NMR (400 MHz, CDC13) δ 8.6 (1 Η), 8.2 (1H), 7.1 (1H), 3.3 (4H), 2.6 (4H), 2.5 (2H), 1.1 (3H) In a 1 liter reaction flask, add 1-(2,4-dinitrophenyl)-4-ethyl-piperazine (56.07 g '200 mmol), tetrahydroanthracene plus 11741'〇 £11 melon 11) (400 g), 10% palladium-on-carbon (2.05 g), and 攒: mix for 10 minutes. Then, 80% aqueous hydrazine hydrate (30 ml) was slowly added dropwise. After the completion of the dropwise addition, the temperature was raised to 40 ° C, and 80% aqueous hydrazine (30 ml) was slowly added dropwise. Stirring was continued for 24 hours after all the drops were completed. Next, the reaction temperature was lowered back to room temperature. Then, suction filtration was carried out to obtain a filtrate. Thereafter, the solvent was removed by concentration under reduced pressure, and the residue was recrystallized from ethyl acetate and hexane to give the product 1-(2,4-diaminobenzene)-4. Ethyl-piperazine (39.6 g, 180 mmol) in 90% yield. Spectral data: 1H NMR (400MHz, CDC13) δ 6.81-6.85 (1Η), 6.04-6.10 (2H), 3.4-4.1 (4H), 2.85-2.87 (4H), 2.40-2.55 (2H), 1.08-1.12 (3H ) ppm. Experimental Example 2 Synthesis of 1-(3,5-diaminobenzimidyl)-4-ethyl-piperazine (1 -(3,5-diaminobenzoyl)-4-ethyl-piperazine) 21 201204766 UASjyyjyyj^ 34008twf. Doc/n

Ον Add 3,5-dinitrobenzoyl chloride (115.3 g, 500 mmol), anhydrous tetrahydrofuran (500 g) and potassium carbonate (103.7 g) in a 2 liter reaction flask. , 750 millimoles), and after 10 C, mix for 5 minutes. Then, N-Ethyl Brigade (74.2 g, 65 Torr) was slowly dropped into the reaction flask. After all the drops were completed, return to room temperature and allow for 4 hours. The tetrahydrofuran was removed by concentration under reduced pressure, and the residue was poured into purified water (2000 g) to be precipitated. Next, suction filtration is performed. Then take out the cake and force it into methanol (l〇〇). Then, heating and refluxing were carried out for 1 hour. Then, return to room temperature. Thereafter, it was subjected to suction filtration and washed with decyl alcohol to obtain the product 1-(3,5-dinitro-p-carbamoylethyl-α-endazine (1-(3,5-dinitrobenzoyl)-4-ethyl-piperazine (126.4 g, 410 mmol), yield 82%. Spectral data: lHNMR (400 MHz, CDC13) δ 9.04-9.05 (1 Η), 8.55-8.56 (2H), 3.42-3.81 (4H), 2.43- 2.55 (6H), 1.06-1.09 (3H)ppm. In a 500 ml reaction flask, 力·(3,5-dinitrobenzhydrazide)_4_ethyl-piperazine (24.9 g '81 m) Mole), tetrahydrofuran (200 g), palladium on carbon catalyst (0.43 g), and stirred for 1 min. Then, 80% aqueous hydrazine (15 ml) was slowly added dropwise. The temperature was raised to 4 ° C, and 80% aqueous hydrazine (15 ml) was slowly added dropwise. The whole batch was continuously mixed for 24 hours. Then the reaction temperature was lowered back to room temperature. Then, suction filtration was carried out, 22 201204766 UXl)yW〇3 34008twf.d〇c/n to take the filtrate. Thereafter, the solvent was removed by concentration under reduced pressure and concentrated under reduced pressure, and the residue was recrystallized from ethyl acetate and n-hexane to give the product 1-(3,5-diaminophenylhydrazineethyl- Piperazine (17.7 g, 71 mmol), yield 88%. Spectroscopic data · 1H NMR (400 MHz, CDC13) δ 6.0-6.01 (3H), 3.5-3.8 (4H), 2.4-2.5 (6H), 1.1 (3H) ppm. Experimental Example 3 Synthesis of l-(2,4-diaminophenyl)_4-phenyl-piperazine (1-(2,4-diaminophenyl)-4-phenyl-piperazine)

X) Add μ-phenylpiperaZiiie (56.74 g, 350 mM) in a 2 liter reaction flask, Ν-曱 砒嗓

N-methyl-2-pyrrolidone (700 g) and potassium carbonate (72.5 g, 525 mmol) were stirred at room temperature for 20 minutes and then warmed to 7 Torr. (:. Then, a mixed solution of 2,4-dinitrofluorobenzene (67.1 g, 360 mmol) and N-methyl ketone (175 g) was slowly dropped into the reaction flask. After that, the mixture was stirred for 6 hours. Then, the temperature of the reaction flask was returned to room temperature, and the solution was poured into pure water (2625 g) to be precipitated. Then, suction filtration was performed to obtain a filter cake. The filter cake was added with methanol (525 g) and heated to reflux for 1 hour. After cooling, suction filtration was carried out, and the obtained product was washed with methanol to give 1-(2,4-dinitrophenyl)-4-phenyl·piperidin.嗓23 201204766 UAuyuyu^ 34008twf.doc/n (l-(2,4-dinitrophenyl)-4-phenyl-piperazme) (91.9 g, 280 mmol), yield 80%. Spectroscopic data: 1H NMR (400 MHz, d-DMSO) 68.60 (1H), 8.30 (1H), 8.30 (1H), 7.30-7.50 (1H), 7.20-7.30 (2H), 6.90 (2H), 6.8-6.9 (1H), 3.4-3.5 (4H), 3.30(4H) ppm. In a 2 liter reaction flask, put i_(2,4-dinitrophenyl)-4-phenyl-piperazine (40 g '121 mmol) and Ethanol (200 ml) and stirred at 5 ° C for 10 minutes. Then, slowly add in the vaporized stannous chloride (tin chlori a mixture of de) (202 g, 784 mmol), hydrochloric chloride (l32 ml), water (26 ml), ethanol (200 ml). After the completion of the number of drops, the temperature was raised to 75 ° C. After stirring for 3 hours, it was returned to room temperature. Then, the solution was poured into pure water (1500 g), and potassium hydroxide (100 g) was slowly added to precipitate, and then evacuated. Filtration and washing with pure water gave solid 1-(2,4-diaminophenyl)-4, phenyl-piperazine (25 g, 84 mmol), yield 70%. Spectrometry: 1H NMR (400 MHz, CDC13) 57.26-7.30 (2H), 6.96-6.98 (d, 2H), 6.85-6.89 (2H), 6.09-6.12 (2H), 3·30-4.02 (8Η), 2.98-3.00 (4Η ) ppm. Experimental Example 4 Synthesis of 1-(3,5-diaminobenzonitrile)-4-benzol-pyr. Qin (l'(3,5-diaminobenzoyl)-4_phenyl-piperazine) 24 201204766 DX090903 34008twf .doc/n

In a 2 liter reaction flask, add 1-phenyl 11 henazine (48 6 g, 300 mM), Ν-曱 base 嗔 ) (600 g) and pyridine (35 6 g), It was stirred at room temperature for 20 minutes and then warmed to 7 Torr. Hey. Then, a mixture of 3,5_ • dinitromethane (71.2 g, 309 mmol) and 1^-methyl carbitol (150 g) was slowly dropped into the reaction flask. After all the dropwise drops, the mixture was stirred for 6 hours' and the reaction temperature was lowered back to room temperature, and poured into pure water (2250 g). Then, suction filtration was carried out to obtain a filter cake. Next, the filter cake was taken out and sterol (450 g) was added. Then, heating and refluxing were carried out for 1 hour. Thereafter, suction filtration was carried out and washed with methanol to obtain the product 1 - (3,5-dinitro adeno)-4-phenyl-pyr. (1-(3,5-dinitrobenzoyl)-4-phenyl-piperazine) (85·5 g, 24 〇 mA | Mo), yield 80%. Spectral Data·· 1H NMR (400 MHz, CDC13) 59.07-9.08 (1H), 8.59-8.60 (2H), 7.24-7.29 (2H), 6.89-6.93 (3H), 3.58-3.96 (4H), 3.16-3.2 (4H) ppm. In a 2 liter reaction flask, put i_(3,5-dinitrophenylhydrazine)_4_phenyl-p-pyrazine (l-(3,5-dinitrobenzoyl)-4-phenyl-piperazine) (40 g) '112 mmol, stannous chloride (2 〇 1 g, 784 mmol) and ethanol (800 ml) and stirred at 5 ° C for 10 minutes. Then, a mixture of hydrochloric acid (132 ml) and pure water (26 ml) was slowly added dropwise. After all the drops were completed, the temperature of the reaction flask was raised to 75 ° C, stirred for 3 hours, and then returned to room temperature. Next, the solution 25 201204766 34008twf.doc/n was poured into pure water (2 gram) and slowly added to the hydrazine clock (touch gram) to be precipitated. Then, it was subjected to suction filtration and washed with pure water to obtain a solid 1-(3,5--amine basic toluene)-4-phenyl-π-henazine (25 g, 84 mmol) in a yield of 75%. Spectroscopic data: 1H NMR (400 MHz, d_DMS0) 57.20-7.24 (2H), 6.93-6.95 (2H), 6.79-6.82 (2H), 5.80- 5.88 (3H), 4.96 (4H), 3.52-3.66 (4H) , 3.10 (4H) ppm. Synthesis of Polyimine and Preparation of Liquid Crystal Alignment Membrane (1) 1-(2,4-Aminophenyl)-4-ethyl-Phenanthine (1-(2,4-diaminophenyl)-4-ethyl- Piperazine), referred to as DPEP. (2) 1-(3,5-Diaminobenzoyl)_4-ethylamino-piperazine, abbreviated as DBEP. 1-(2,4-Diaminophenyl)-4-phenyl-α-Phenazine (l-(2,4-diaminophenyl)-4-phenyΙ-piperazine), abbreviated as DPPP. (4) 1-(3) ,5-Diaminobenzoyl-4-phenyl-piperazine, abbreviated as DBPP ° (5) 4,4'-diamine Dibenzophenan (4,4'-11^1^161^(^1^1^^), abbreviated as MDA. (6) 1,2,3,4-cyclobutane tetracarboxylic dianhydride (cyclobutane) -1,2,3,4-tetracarboxylic dianhydride), abbreviated as CBDA. Experimental Example 5 26 201204766 UAuyuy〇3 34008twf.doc/n 11 g (0.05 mol) of DPEP and 9.8 g (0.05 m) of CBDA The reaction was carried out at room temperature for 12 hours in 83.2 g of N_曱 based stone, and then diluted with 312 g of NMP to obtain a polyamic acid solution (specific viscosity of 0.6 dl/g). The polyamic acid solution was spin-coated on a glass substrate having a transparent electrode at 3000 rpm, followed by heating at 200 C for 30 minutes to form a polyimide film, and using a 40 micrometer spacer. , assembled into a liquid crystal box assembled in parallel direction. Filled into the liquid crystal (for example, model: ZLI-4792, manufactured by Merck), the liquid crystal cell is in the right parent Nicholas Ling (cr〇ssed nic〇is Rotate and present a full dark edge. The value of the pretilt angle obtained by using the Hit Angie tester (tba) is 90. Experimental Example 6 12.4 g (0.05 m) DBEP and 9.8 g The CBDA of (0·05 mol) was reacted in 88.8 g of hydrazine at room temperature for 12 hours, and then 333 g of hydrazine was added for dilution to obtain a polyamidonic acid solution (specific viscosity: 〇·55 dl/g). Then, the polyaragic acid solution was spin-coated on a glass substrate having a transparent electrode at 3 rpm, and then heated at 200 ° for 30 minutes to form a polyimide film. And using a 40 micron spacer, assembled into a liquid crystal cell assembled in parallel. After filling the liquid crystal (for example, model: ZLI-4792, manufactured by Merck), the liquid crystal cell is in crossed Nicole Rotating between and showing a full dark state, the pretilt angle obtained by the pretilt measuring machine is 90°27 201204766 34008twf.doc/n Experimental Example 7 13.4 g (0.05 mol) DPPP was reacted with 9.8 g (0.05 mol) of CBDA in 92.8 g of NMP at room temperature for 12 hours, then 348 g was added. The NMP was diluted to obtain a poly-proline solution (specific viscosity of 0.57 dl/g). Then, the polyamic acid solution was spin-coated at 3000 卬m on a glass substrate having a transparent electrode. Then, at 2〇〇. (: Heat down for 30 minutes to form a polyimide film, and assemble it into a liquid crystal cell assembled in parallel directions using a 4 μm spacer. Fill the liquid crystal (for example, model. ZLI-4792 ' by Merck After the company manufactures, the liquid crystal cell rotates between the crossed Nicoles and presents a full dark state, and the pretilt angle value obtained by the pretilt angle measuring machine is 90°. Experimental Example 8 14.8 g (0.05 m) DBPP and 9 8 g (〇〇5 mol) of CBDA were reacted in 98.4 g of NMP at room temperature for 2 hours, and then 369 g of NMP was added for dilution to obtain a poly-proline solution (specific viscosity). It was 0.52 dl/g. Then, this polyamic acid solution was spin-coated on a glass substrate having a transparent electrode at 3 rpm, and then heated at 2003⁄4 for 30 minutes to form a poly An amine film, which is assembled into a liquid crystal cell assembled in parallel directions using a 4 μm spacer. After filling the liquid crystal (for example, Model No. ZLI-4792 'Merck), the cell is in crossed Nico The ear is rotated between the crystals and presents a full dark state, which is obtained by using a pretilt measuring machine. The pretilt angle value is 90° ^ 28 201204766 UAuyuv03 34008twf.doc/n Experimental Example 9 2.2 g (〇·〇ι莫耳) of DpEp, 14 8 g (〇〇4 Mo MDA and (9) g (1) Milk Mox (10) Eight and two grams of Li^ were reacted at room temperature for 12 hours, and then diluted with 4 〇 2 g of NMp to obtain a polyaminic acid solution (specific viscosity 〇86 dl/g). Then, The polyaminic acid solution was spin-coated on a glass substrate having a transparent electrode at 3000 rpm, followed by 'heating at 200 ° C for 30 minutes to form a polyimide film. This polyimine was cooled. After that, the bristles were subjected to directional rubbing, and f was assembled into a liquid crystal cell in a parallel direction by using a 40 micrometer spacer. After the liquid crystal (for example, model: ZLI_4792, manufactured by Merck) was used, the pretilt amount was utilized. The pretilt value obtained by the tester was 5 〇. Experimental Example 10 2.48 g (0.01 mol) of DBEP, 14 8 g (〇〇4 mol) of MDA and 9.8 g (0.05 m) of CBDA were placed at 1. 〇 8.3 g of NMp was reacted at room temperature for 12 hours, and then 406.2 g of NMP was added for dilution to obtain a poly-proline solution (ratio The degree was 0.73 dl/g. Then, the poly-aracine solution was spin-coated on a glass substrate having a transparent electrode at 3000 rpm, and then heated at 2 Torr for 30 minutes to form a polyfluorene. The imine film. After cooling the polyimide film, it was directionally rubbed with bristles and assembled into a liquid crystal cell assembled in parallel directions using a 40 micrometer spacer. After pouring the liquid crystal (for example, model: ZLi_4792, manufactured by Merck), the pretilt angle value obtained by the pretilt angle measuring machine was 5 3 . . 29 ------- 34008tw£doc/n Experimental Example 11 2.68 g (0.01 mol) of DPPP, 14 8 g (〇〇4 mol) of MDA and 9.8 g (0.05 m) The CBDA was reacted in a 1 〇 9 gram NMI> at room temperature for 12 hours' and then 409.2 g of NMP was added for dilution to obtain a polyaminic acid solution (specific viscosity 〇·80 dl/g). Then, this polyaminic acid solution was spin-coated on a glass substrate having a transparent electrode at 3000 rpm. Next, at 200. (: heating for 30 minutes to form a polyimide film. After cooling the polyimide film, the bristles were directionally rubbed, and assembled into parallel liquid crystal cells by using a 40 micrometer spacer. After pouring the liquid crystal (for example, model: ZLI_4792, manufactured by Merck), the pretilt angle value obtained by using the pretilt angle measuring machine is as follows. Experimental Example 12 2.96 g (〇.〇1 mol) DBPP, 14.8 g MDA of (〇.〇4mol) and 9.8 g (0.05 mol) of CBDA were reacted in 11〇2 g of NMp at room temperature for 12 hours, and then 413.4 g of NMP was added for dilution to obtain polylysine. Solution (specific viscosity: 0.72 dl/g). Then, the polyaminic acid solution was spin-coated on a glass substrate having a transparent electrode at 3000 rpm. Then, it was heated at 20 (TC for 3 minutes to Forming a polyimide film. After cooling the polyimide film, it is directionally rubbed with bristles, and assembled into a liquid crystal cell assembled in parallel directions by using a spacer of 40 micrometers. Model: zu_4792, manufactured by Merck) After using 'pretilt angle measurement The pretilt angle value obtained was 5 5. 201204766 UAUyuy〇3 34008twf.doc/n Comparative Example 1 9.7 g (0.05 mol) of MDA and 9.8 g (0.05 mol) of CBDA were placed in 78 g of NMP. The reaction was carried out for 12 hours under temperature, and then added with 292.5 g of NMP for dilution to obtain a polyaminic acid solution (specific viscosity of 0.81 dl/g). Then, the polyamic acid solution was spin-coated at 3 〇〇〇Γριη. The film was coated on a glass substrate having a transparent electrode, and then heated under a crucible for 30 minutes to form a polyimide film. After the polyimide film was cooled, it was subjected to directional rubbing with bristles and utilized. A 4 μm spacer was assembled into a liquid crystal cell assembled in parallel. After filling the liquid crystal (for example, model ΖΠ-4792, manufactured by Merck), the pretilt angle obtained by the pretilt angle measuring machine was 2.1. For the comparison of the pretilt angle between the embodiment and the comparative example, please refer to Table 1. Table 1

31 201204766 34008twf.doc/n Experimental Example 11 20 80 100 5.2 Experimental Example 12 20 80 100 5.5 Ratio Comparative Example 1 100 100 2.1 As shown in Table 1, the aromatic diamine of the present invention was added in the preparation of the liquid crystal alignment agent. Compound (Experimental Examples 5-12), and thus the formed liquid crystal alignment film can have an effect of increasing the pretilt angle. Table 2 compares the residual DC charges of the examples and comparative examples. Please refer to Table 2. Table II Diamines (mol%) Tetracarboxylic dianhydride (mol%) Residual direct current (mV) DPEP DBEP DPPP DBPP MDA CBDA Experimental Example 5 100 100 63.9 Experimental Example 6 100 100 101 Experimental Example 7 100 100 97.2 Experimental Example 8 100 100 131 Experimental Example 9 20 80 100 221 Experimental Example 10 20 80 100 302 Experimental Example 11 20 80 100 268 Experimental Example 12 20 80 100 341 Comparative Example 1 100 100 533 32 201204766 iJAuyuy〇3 34008twf.doc/ n As apparent from Table 2, since the aromatic diamine compound of the present invention (Experimental Examples 5 to 12) was added at the time of preparation of the liquid crystal alignment agent, the liquid crystal display element was allowed to have a low residual DC charge. As described above, since the liquid crystal alignment agent contains a polyimine or a polyimine obtained by polymerization of the aromatic diamine compound of the present invention and a tetracarboxylic acid or a dianhydride compound thereof, The liquid crystal alignment film formed by the liquid crystal alignment agent can have the effect of increasing the pretilt angle, and enables the liquid crystal display element to have a lower residual DC charge, thereby achieving the purpose of improving the performance of the liquid crystal display element. Although the present invention has been disclosed in the above embodiments, it is not intended to limit the invention, and any one of ordinary skill in the art can make some modifications and refinements without departing from the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims. [Simple diagram description] None [Main component symbol description] None 33

Claims (1)

34008twf.doc/n 201204766 VII. Patent application: 1. A liquid crystal alignment agent suitable for display. The liquid crystal alignment agent comprises: polyimine, which is polymerized from a diamine compound and a tetracarboxylic acid or a dianhydride compound thereof. Obtained by the reaction, wherein the diamine compound contains an aromatic diamine compound represented by the formula (1), Wherein R to Rs are both primary amine groups, and the others are each independently a hydrogen atom or a monovalent substituent other than the primary amine group; the rule 6 is a Ci to C20 alkyl group, and a C3 to C4 oxime monovalent alicyclic ring. a substituent of a group, a monovalent aromatic substituent of C6 to C51 or a monovalent heterocyclic substituent; & and X2 are each independently a single bond or an ether group, a ketone group, an ester group, a decyl group and a secondary group A divalent binding group of a group consisting of an amine group; X3 and X4 are each independently a linear alkylene group of C1 to C3. 2. The liquid crystal alignment agent according to claim 1, wherein the content of the aromatic diamine compound used in polymerizing the polyimine is at least 丨 mol% based on the total amount of the diamine compound. . 3. The liquid crystal alignment agent according to claim 1, wherein the aromatic diamine compound is used in an amount of at least 10 moles based on the total amount of the diamine compound. %. 4. The liquid crystal alignment agent according to claim 1, wherein the aromatic 34 is used in the polymerization of the polyimine, and the aromatic diamine used in the polymerization of the polyimine is 201204766 34008twf.doc/n The amount of the compound is at least 50 mol%. 5. The liquid crystal alignment agent according to claim 1, further comprising poly-proline, which is obtained by polymerization of the diamine compound and the tetracarboxylic acid or a dianhydride compound thereof. 6. The liquid crystal alignment agent according to claim 5, wherein the aromatic diamine compound is used in an amount of at least 1 mol based on the total amount of the diamine compound. %. 7. The liquid crystal alignment agent according to claim 5, wherein the aromatic diamine compound is used in an amount of at least 1 mole based on the total amount of the diamine compound. ear%. 8. The liquid crystal alignment agent according to claim 5, wherein the polydiamine compound is used in an amount of at least 50 moles based on the total amount of the diamine compound. %. 9. The liquid crystal alignment agent according to claim 1, further comprising a solvent. 10. An aromatic diamine compound represented by formula (1), ^The center to Rs is either a primary amine group, and the others are each independently a hydrogen atom c or a valence substituent other than the primary amine group; a Re A C1 to C2G theater group, a 3 to C40 valence alicyclic group substitution a monovalent aromatic or monovalent heterocyclic substituent of c6 to C5i; Χι and & each independently a single bond or selected from a base steel group, a vine group, a guanamine group and a secondary amine group. Group 35 201204766 34008twf.doc/n Divalent binding group; X3 and X4 are each independently a linear stretching group of Cl to C3. 11. The poly-acid is synthesized from the tetra-nucleus or its dianhydride compound and the di-compound. The diamine compound contains the aromatic diamine compound as described in claim 10 of the patent target. . 12. The poly-araminic acid according to claim 5, wherein the aromatic diamine compound is present in an amount of at least 1 mol% based on the total of the diamine compound. 13. If the patent claims the poly-proline as described in item u, The diamine compound is used in an amount of at least 10 mol%. 14. The polyaminic acid according to the scope of the patent application, wherein the content of the aromatic diamine compound is at least 50 mol% based on the total amount of the diamine compound. A polyimine imine is obtained by polymerization of a tetra- or a di-branched compound thereof with a diamine compound, wherein the diamine compound contains the aromatic diamine compound as described in claim 10 of the patent application. 16. The polyimine of claim 1, wherein the amount of the diamine compound is at least 1 mole based on the total amount of the amine compound. /. . 17. The polyamidiamine according to claim 15 wherein the content of the aromatic diamine compound is at least 10 mol% based on the total of the far-amine compound. 18. The polyimine according to claim 15 wherein the content of the aromatic diamine compound is at least 50 mol% based on the total f of the a-amine compound. 36 201204766 L>Auyuy〇3 34008twf.doc/n IV. Designation of representative drawings: (1) Representative representative of the case: None (2) Simple description of the symbol of the representative figure: No. 5. If there is a chemical formula in this case, please Reveal the chemical formula that best shows the characteristics of the invention: Formula (I)