TW201241088A - Liquid crystal aligning agent - Google Patents

Abstract

A liquid crystal aligning agent has properties of stable pre-tilt angle and excellent adhesion and can eliminate deficient display caused by image sticking. The liquid crystal aligning agent includes a polymer (A) and a polymer (B). The polymer (A) is_polyimide-polyamide acid having diamine in a side chain, and the polymer (B) is polyamide acid having diamine in a side chain.

Description

201241088 DX101202 37328twf.doc/n VI. Description of the Invention: [Technical Field] The present invention relates to a liquid crystal alignment agent, and more particularly to a polyimine-polyamide having a side chain diamine A liquid crystal alignment agent of an acid and a polyamic acid having a side-bonded diamine. ^ [Prior Art] Liquid crystal display is a display that utilizes photoelectric change of liquid crystal. It has the advantages of small size, light weight, low power consumption, and good quality. Therefore, it has become a flat in recent years. The development of the main LCD display with the expansion of the kneading size, high saturation of color, high contrast and anti-neutrality requirements, by twisted nematic (TN) liquid crystal display, super twisted nematic (5 twisted nematic, STN) liquid crystal display, until now developed into a thin filmed transistor (TFT) TFT liquid crystal display. In recent years, the driving method of the TFT type liquid crystal display has been continuously improved. For example, in terms of improving the viewing angle, a vertical alignment (VA) mode or a coplanar conversion (m pi (four) switchmg' IPS) method has been developed. In addition, an optical compensation bend (4) can be developed to improve the response speed of the corresponding moving cymbal. (5). In the liquid crystal display, a typical twisted nematic (TN) electric field effect type liquid crystal display has a positive system. Dielectric anisotropic nematic liquid crystal... In general, 201241088 0X101202 37328twf.doc/n liquid crystal molecules are placed between a pair of substrates containing electrodes, and the alignment directions of the two substrates are perpendicular to each other' and the liquid crystal molecules can be controlled via a control electric field. For this type of liquid crystal display, it is important to make the long axis direction of the liquid crystal molecules and the substrate surface have a uniform tilt angle. The liquid crystal molecules are arranged in a uniform pre-tilt angle alignment material. It is called an alignment film. There are two typical methods for preparing an alignment film in the industry. The first method is to form an inorganic film into an inorganic film by vapor deposition. For example, the cerium oxide is vapor-deposited on a substrate. The film is formed, and the liquid crystal molecules are aligned in the vapor deposition direction. However, although the above method can obtain a uniform alignment, The second method is to apply an organic film on the surface of the substrate, and then rub it with a soft cloth of cotton, nylon or polyester to orient the surface of the organic film so that the liquid crystal molecules are rubbed. The direction is aligned. Since this method is 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 (polyvinylalcoho PVA), polyoxyethylene (polyethylene 〇xide, PE0). ), polyfluorene (PA) or polyimine, in which polyimine is most commonly used as an alignment film material because of its chemical stability and thermal stability. When a voltage is applied to the display device, the generated ionic charge is adsorbed by the liquid crystal alignment film, and even after the applied voltage is released, it is difficult to cause the ionic charge to be detached from the liquid crystal alignment film, thereby causing residual image on the screen. Therefore, the development of the recent alignment film materials is mainly to improve the afterimage problem. 4 201241088 DX101202 37328twf.doc/n [Invention The present invention provides a liquid crystal alignment agent capable of obtaining a liquid crystal display element having stable pretilt property, excellent adhesion, and improved image sticking problem. The present invention provides a liquid crystal alignment agent comprising a polymer (A) and polymerization. The polymer (A) is a polyimine acid having a side chain diamine represented by the following formula (1). The polymer (B) is represented by the following formula (2) Also, a poly-proline acid having a side chain diamine. The weight ratio (A) / (B) of the polymer (A) to the polymer (B) is, for example, 5/95 to 95/5.

In formula (1) and formula (2), Tl, T2 and T3 are respectively represented as tetravalent organic groups of tetracarboxylic dianhydride monomers, m+n=p η$〇.5, Pi or D2 At least a portion is a divalent organic group selected from the group consisting of a diamine compound represented by formula (3) or formula (4), and at least a portion of A is a divalent organic group derived from a diamine compound represented by formula (4) And the remaining part of Di, 1) 2 and D3 is a divalent compound having a bivalent amount of 201241088 37328 twf.doc/n, and (3)

In the formula (3), R!, R2, R3, R5 and R6 are each independently represented by hydrogen or a carbon group having a carbon number of 1 to 5, and R4 represents a carbon group having a carbon number of 4 to 2 Å, CO2R22, CONR22 or ( CH2) pCF3'p is an integer of 1 to 5, R22 represents an alkyl group having a carbon number of 4 to 20, and in the formula (4), either of R7 to Rn is a hydrazine-based amine group, and the others are each independently a gas atom or The monovalent organic groups 'R7~丨 other than the primary amine group may be the same or different, and X! and χ2 are represented as a single bond or selected from the group consisting of ethers, esters, ketones, decylamines and secondary amines. The valence bond group, Χι and X2 can be the same or different, 乂3 and & expressed as carbon number 3 and the Χ4 can be the same or different, Rl2 is expressed as carbon® number 6~carbon number One of the alicyclic skeletons of 3 to 40 is an organic group or a carbon organic group. a valence of an organic group or a heterocyclic skeleton of a family skeleton 6 201241088 DX101202 37328 twf.doc/n According to an embodiment of the present invention, in the liquid crystal alignment agent of the present invention, D1, 〇2 and D3 are selected from In addition to the portion of the divalent organic group of the diamine compound represented by the formula (4), the remainder of the above q^ may also be selected from the group consisting of the formulae (5) to (10), 13

X-R X-R

Wherein R. (12) a divalent aromatic or carbon number long-chain aliphatic prevalent organic group or a carbon number R15 is a carbon number of 4 to 4 U. The base 14 is a dentate atom or a monovalent organic group; An alicyclic divalent organic group; R16 is a divalent alicyclic group, a long chain fat carrier of 1 to 8; χ and γ 201241088

Vm.^j2 37328twf.doc/n is a divalent group selected from the group consisting of mud %〇-NHCO-, -CONH-; z is, -CF3, -CN, C0CH, widely C00H, 2, s〇 CH3 s〇 Free - the monovalent organic group of the group consisting of OCF3, -F and -Cl. 1 3, according to the embodiment of the present invention, the polymer (A) towel from the amine compound of the two price, such as containing f, (tetra) compound (4) bis ~ base D ^ D2 total amount of 〇 "mole% to 5 〇 Mo %. 1 Organic According to the embodiment of the present invention, the content of the divalent organic group of the amine compound of the formula (3) in the polymer (B) is based on the total weight of the polymer (B) D3. .1 mole % to 5 % mole %. According to the present invention, the polymer (A) towel (tetra)-amine compound has a two-filament content, (10) compound (A) all = base D! and E > 2 total amount is 5 mol% to 5 〇 耳 %. According to an embodiment of the present invention, the content of the divalent organic group of the amine compound represented by the formula (4) in the polymer (B) is 5 mol% based on the total amount of the polymer A of the polymer (B). 1〇〇% by mole. . The monovalent organic group is based on the above, since the liquid crystal alignment agent of the present invention comprises a polyamidimide having a side chain diamine as shown in the formula (1), and a polyaminic acid, and having a side chain of two The amine ugly acid, so the liquid crystal alignment film formed by the liquid crystal alignment agent can have the effect of stabilizing the pretilt angle, and the liquid/alignment film can be improved and the image sticking problem can be improved, thereby turning the display element The above features and advantages of the present invention will become more apparent and obvious. The following detailed description of the embodiments and the accompanying drawings will be described in detail below. 8 201241088 DX101202 37328twf.doc/n [Embodiment] The liquid crystal alignment agent of the invention comprises a polymer (A) and a polymer (B). The polymer (A) is a polyimine-polyamide having a side chain diamine represented by the following formula (1). The polymer (B) is a polyamic acid having a side chain diamine structure represented by the following formula (2). Formula (1) 〇〇

Ο 〇 N-

D2- (7) 0 0

Ο 0 In formula (1) and formula (2), 1, T2 and T3 are respectively represented as tetravalent organic groups, and m+n=l, nS0.5, D! or D2 are at least one selected from the group consisting of (3) or a divalent organic group of the diamine compound represented by the formula (4), at least a part of D3 is a divalent organic group of the diamine compound represented by the formula (4), and in Di, D2 and D3 The remainder is the divalent organic group of the diamine compound. Equation (3) 201241088 DX101202 37328twf.doc/n

In the formula (3), 'R1, R2, R3, 5 and R6 are each independently represented by hydrogen or an alkyl group having a carbon number of 1 to 5, and R4 represents an alkyl group having a carbon number of 4 to 2 Å, c〇2R22, and CONR2. ^(CH2)pCF3, p is an integer of Bu 5, and R22 represents a burning group having a carbon number of 4 to 2 Å. Formula (4)

Re, X3,

Ri

Χι~"—N ,X2——R12 ‘11

R In the formula (4), any of R7 to R11 is a primary amine group, and the others are each independently a hydrogen atom or a monovalent organic group other than the primary amino group, and each of R7 to Rn may be different or different from each other. Χ2 is represented as a single bond or a divalent binding group selected from the group consisting of shouting, vinegar, residual, = and secondary amines, && each of the two orders may also be different 'X3 and X4 are expressed as carbon* 1 〜3 t直键状伸Λ 3 f X4 each may be the same or different, Rn is a valence ring skeleton having a carbon number of 1 to 2 之一, an organic group having a carbon number of 6 to 51, or a valence organic group or The heterocyclic skeleton is a valence organic group. The weight ratio of the substance (VIII) to the polymer (9) (4) / _ is 5/95 to 201241088 DX101202 37328twf.doc / n 95/5. Further, in the liquid crystal alignment agent of the present invention, in the Di, D2 and D3, in addition to the portion selected from the divalent organic group of the diamine compound represented by the formula (3) or the formula (4), the above D!, The rest of 02 and D3 can also be selected from the group consisting of free (5) to (12), X-Rl3 W〇—

_Y

•R 13

(5)

Wherein Ri3 is an alicyclic monovalent organic group having a carbon number of 4 to 40 or a long-chain aliphatic monovalent organic group having a carbon number of 8 to 20; R14 is a halogen atom or a monovalent organic group; and R15 is an alicyclic group having a carbon number of 4 to 40. Divalent organic group; R16 is a divalent alicyclic group, 11 201241088 ι^Λΐυι^.υ2 37328twf.doc/n a long-chain aliphatic divalent organic group of 1 to 8; χ and γ are selected from -〇 -, ΝΗ·, each, C0 c〇〇〇c〇=HCO _CONH_ and the divalent group of the scale formed by z is selected from F3 CN COCH3 ' -COOH ' -N〇2 &gt; SOCH3 ' -SO2CH3 '-OCT3' The monovalent organic group of the group consisting of -F and -ci. The preparation method of the polymer (A) synthesized by the present invention is that the polymerization reaction is carried out by spraying the tetracarboxylic acid mono- and diamine compounds in a timely manner, and a partial ring-closing reaction is carried out by a dehydration reaction to obtain a side. The polydiimine-polylactoic acid product of a chain diamine. The tetracarboxylic dianhydride used to synthesize the polymer (A) may be selected from the compounds shown in the table. The diamine compound for synthesizing the polymer (A) may be selected from the group consisting of the diamine compound represented by the formula (3) and the formula (4) as shown in Table 2; From the formula (3) and the diamine compound represented by the formula (4). At least one of the diamine compounds used to synthesize the polymer (A) is selected from the compounds shown in Table 1. Table 1 NO. Four resorcinic dianhydride NO. —-------- Tetracarboxylic dianhydride 1-1 0 0 Ho 0 0 1-2 -------------____ 0 0 &gt;ττΛ 〇, /° r^( 0 0 1-3 0 0 0 0 1-4 Pull Of ___—---° 12 201241088 DX101202 37328twf.doc/n Ο 1-5 0 0 .(9) 0 0 1-6 Table II NO. Diamine NO. Diamine 2-1 h2n^o-^^-〇c8h17 h2n 2-2 H2' /〇~<〉-OC12H25 h2n 2-3 η2' ο-〈〉—〇 C16h33 h2n 2-4 Η^Νγ^γΝΗ2 oo 2-5 u M NH2 XXn W^\ 2-6 HZN\^\^NH2 XT 2-7 η2ν^^^νη2. Work p Table III NO. Diamine NO . Diamine 13 201241088 37328twf.d〇c/n

Further, the tetracarboxylic dianhydride used in the synthesis of the polymer (A) of the present invention may be an isomer of the compound shown in the above Table 1 or a mixture of such isomers. The diamine compound for synthesizing the polymer (A) of the present invention may be an isomer of the compound shown in the above Table 2 or Table 3, or a mixture of such isomers. The present invention is not limited to the above examples, and the tetra-hypo-acid dianhydride and the diamine compound to be used may be compounds other than the above compounds. In particular, it is desirable to have a liquid crystal display element having a high voltage holding ratio 'a compound having an alicyclic structure such as NO·1-2, 1-3, 1-4, 1-5, 1-6 in Table 1. Choose at least one of them to achieve. Further, the pretilt angle of the liquid crystal in the liquid crystal alignment agent of the present invention can be adjusted by changing the size of the side chain on the polyimine-polyglycolic acid, for example, by changing the size of the side chain group on the diamine compound. This is carried out, so that at least one of the diamine compounds represented by N0.2-1 to 2-3 in Table 2 can provide an appropriate pretilt angle. Further, at least one of the diamine compounds represented by NO. 2-4 to 2-7 in Table 2 may be selected to obtain a liquid crystal alignment agent having excellent adhesion characteristics. 201241088 DX101202 37328twf.doc/n, the polymer (B) synthesized by the invention is prepared by polymerizing a tetracarboxylic dianhydride and a diamine compound in an organic solvent to obtain a side chain diamine. Poly-proline product. The tetraphthalic acid dianhydride used to synthesize the polymer (B) may be selected from the compounds as shown in Table 1. The diamine compound for synthesizing the polymer may be selected from the group consisting of the diamine compound represented by the formula (3) and the formula (4) as shown in Table 1, or may be selected from the formula (Table 3). 3) and a diamine compound represented by the formula. At least one of the diamine compounds used to synthesize the polymer (B) is selected from the compounds represented by Tables N0.2-4 to 2-7. Further, the present invention; the tetracarboxylic acid dianhydride used for the synthesis of the polymer (B) may be an isomer of the compound shown in the above Table i, or a mixture of such isomers. The diamine compound for synthesizing the polymer (8) of the present invention may be an isomer of the compound shown in the above Table 2 or Table 3, or a mixture of such foreign matters. The present invention is not limited to the above examples, and the use of the acid dianhydride and the diamine compound (IV) may be a compound of the above compound material. The divalent organic group represented by the formula (3) has an extremely stable alignment effect and an extremely stable liquid crystal display element. f Inclination effect (3) The content of the divalent organic group of the diamine compound shown in (3) is: (4) The total amount of all the divalent organic groups D1 and D2 of the formula (A) is Q 丨 as the polymer %. The amount of 二/° to 5 〇 of the diamine compound represented by the formula (3) in the polymer (B) is preferably such that the polymer (B) is a divalent organic group D = the organic group contains the ear % to 50% Mohr % 3, and the amount of the nucleus is 0.1. The divalent organic group represented by the formula (4) has an extremely stable alignment effect and makes the liquid crystal display element extremely stable. The content of the divalent organic group of the diamine compound represented by the group of people (2012, guojin 15 201241088 DX101202 37328twf.doc/n (4) is preferably 5 moles based on the total amount of all divalent organic groups of the polymer (A). % to 5〇% of the ear. The content of the divalent organic group of the diamine compound represented by the formula (4) in the polymer (B) is preferably calculated based on the total amount of all the divalent organic groups D3 of the polymer (B).摩尔% to 100 mol. / 〇. The ratio of tetradecanoic acid to p-diamine compound used in the synthesis reaction of the polymer (A) of the present invention, the anhydride group content of the tetracarboxylic dianhydride is The amount of the amine compound of the diamine compound is from 0.5 equivalents to 2 equivalents, and the amine group content of the amine compound is preferably from 0.7 equivalents to 1.5 equivalents. The synthesis of the polymer (A) is carried out in an organic solvent. Completed, and the organic solvent used is divided into an organic solvent having a better solubility for polyimine and polyamide and a poor solubility for polyimine-polyamide. For polyimine-polyamide solubility Preferred organic solvents are, for example, N-burnone, n,N-dimethylamine, N,N_:methylacetamide, dimethyl sulfoxide, Sulfhydryl urea, hexamethylphosphonium, butyl vinegar, K, etc., and the above solvents can be used in combination on two (four). For solvents with poor solubility of polyimine _ poly-acid, it can also be used with The organic solvent with good solubility of amine and poly-acid is mixed." The limited polyimine. Polypyrene # is separated into two; the solvent with poor resolution includes methanol, ethanol, isopropanol, n-butanol, alcohol Monobutyl _, B-^ ethylene glycol monoethyl amide, ethylene bismuth, ^ methyl sulphate, ethylene glycol diethyl ether, diethyl tetra η 咕 、, t ethyl epoxide, cyclohexyl hydrazine, acetic acid Vinegar, ethyl acetate, chlorodecane, tri-methane, 1,2, dichloroethane, benzene, A 201241088 DX101202 37328twf.doc/n Benzene, diterpene benzene, hexaburn, Zheng Gengxuan, Zhengxin, etc. The formation of the polymer (A) requires a dehydration ring closure reaction. The dehydration ring closure reaction can be carried out by direct heating dehydration ring closure or addition of a dehydrating agent and a catalyst. (1) Direct heating dehydration ring closure: The reaction temperature is, for example, between 50 ° C and 300 Between °C and '100 ° C to 250 ° C. When the reaction temperature is lower than 50 ° C, the dehydration ring closure reaction will not proceed (2) Adding a dehydrating agent and a catalyst: The reaction temperature is, for example, between -20 ° C and 150 ° C, preferably 〇 ° C to 120 ° C. The dehydrating agent may use an acid anhydride such as acetic anhydride, propionic anhydride, or the like. Fluorine anhydride, etc. The amount of the dehydrating agent depends on the desired closed-loop ratio, and is used in a reproducing unit per 1 mole of polyimine-polyamide. The dehydrating agent is preferred. The catalyst may use a tertiary amine such as triethylamine, butyl ratio, dimercaptopyridine, etc. The amount of the catalyst is from 0.01 mol to 1 mol per 1 mol of dehydrating agent. good. The polymer (A) is purified by first pouring a reaction solvent of polyimine-polyglycine into a solvent having a poor solubility to obtain a precipitate. Then, drying is carried out under reduced pressure to obtain polyimine-polylysine. Thereafter, the polyimine-polyamide acid is dissolved in an organic solvent, and the solubility is poor/mixture into the sputum. This step can be carried out one or more times to purify the polyamidene-polyglycine. Finally, the purified (tetra) compound (A) was obtained by carrying out the above procedure after the above-mentioned step. The viscosity (β in) of the liquid crystal alignment agent of the present invention can be obtained by the formula (1). η]η — j_n (solution flow time/solvent flow time) η weight concentration of polymer (Ι) 17 201241088 37328twf.doc/n The liquid crystal alignment agent of the present invention has a solid content of 1% by weight according to viscosity and volatility It is preferably 10% by weight. The liquid crystal alignment agent of the present invention is applied onto a substrate to form a film, i.e., a liquid crystal alignment film is formed. When the solid content of the liquid crystal alignment agent is less than 丨% by weight, the thickness of the applied alignment film becomes too thin, thereby lowering the liquid crystal alignment; when the liquid of the liquid alignment agent contains 5: still 1% by weight At the time, the coating quality will be affected. ‘, 曰. Further, the temperature at which the liquid crystal alignment agent of the present invention is prepared is 〇. (3 to 150 ° C is preferred, preferably 20: (: to 50 ° C.) The organic solvent of the liquid crystal alignment agent of the present invention includes N-mercapto-2-pyrrole, N,N-diindenyl hydrazine. Indoleamine, hydrazine, hydrazine, decyl acetamide, N-methylhexanide, decylamine, dipyridamole, butane vinegar, butane amide, ethylene glycol, methyl hydrazine Monoethyl _, ethylene glycol mono-n-propyl (tetra), ethylene glycol single-butyl test, etc., and the above solvents may be used in combination of two or more. In addition to the above solvents, as long as it can dissolve polyimine poly The organic solvent of the proline may be used. The liquid crystal alignment agent of the present invention may also contain an organic oxime (oxy) alkane compound, such as aminopropyldimethoxy-11, aminopropyltriethylsulfonate, ethylene. Methyl wei, Ν · (2-aminoethyl) _3 · aminopropyl f quinodimethoxy oxalate, Ν · (2_aminoethyl) _3_aminopropyl tridecyloxy Hetero, ethylene triethoxy alcohol, 3_mercapto propylene methoxy propyl trimethoxy wei, 3 _ ring propyloxypropyl trimethoxy decane, 3-glycidoxypropyl Methyl dimethyl _ base: 2-(3,4-epoxycyclohexyl)ethyltrimethoxy , I-ureidopropyltrimethoxywei, 3-propionic triethoxy hetero, oxime ethoxylate 18 201241088 DX101202 37328twf.doc/n -3-aminopropyltrimethoxydecane, N_ Ethoxycarbonyl amidopropyltriethoxyamine decane, N-triethoxycarbenylpropyltrisethyltriamine, N-dimethoxymethoxymethylalkylpropyltriethylamine N_bis(oxyethylidene=3-aminopropyltrimethoxydecane, N-bis(oxyethylidene)_3-aminopropyltriethyldecane, etc. The above organoindole (oxy)alkane compound is The content of the liquid crystal alignment agent can improve the adhesion of the liquid crystal alignment film to the surface of the substrate under the condition that the liquid crystal alignment agent does not affect the characteristics required for the liquid crystal alignment film. If the liquid crystal alignment agent is organic stone (oxygen) When the content of the fired compound is too large, the formed liquid crystal alignment film is liable to cause poor alignment; and if the content of the organic germanium (oxy) alkane compound in the liquid crystal alignment agent is too small, the formed liquid crystal alignment film may cause poor brushing ( Rubbing mum) and excessive phenomenon of particles. Therefore, the liquid crystal alignment agent of the present invention contains The concentration of the organic (oxy)ane compound, the organic oxirane compound is preferably from 0.01% by weight to 5% by weight based on the weight of the polymer in the liquid crystal alignment agent, and particularly preferably from 3% by weight to 3% by weight. Further, the liquid crystal alignment agent of the present invention may further contain an epoxy compound such as ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, hydrazine, 6 _hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexane 2 Alcohol, N, -tetraglycidyl-m-phenylenedibenzene, 1,3-bis(N,N-diglycidylamino)cyclohexane, hydrazine, hydrazine, hydrazine, &gt; Tetraglycidyl-4,4'diaminodicarbylmethyl, 3-(N-allyl-N-glycidyl)aminopropyltrimethoxy aspartate, 3-(N,N- Diglycidyl)aminopropyltrimethoxylate. The above-mentioned % oxygen compound described in 201241088 ^iyizv/2 37328twf.d〇c/n can improve the density of the liquid crystal alignment film on the substrate surface under the condition that the content thereof does not affect the characteristics of the liquid crystal alignment film in the liquid crystal alignment agent. Sexuality. When the content of the epoxy compound in the liquid crystal alignment agent is too large, the formed liquid crystal alignment film is liable to cause poor alignment; if the content of the epoxy compound in the liquid crystal alignment agent is too small, the formed liquid crystal alignment chess may generate a brush. Poor and excessive dusting. Therefore, if the liquid crystal alignment agent of the present invention contains an epoxy compound, the concentration of the epoxy compound is preferably from 0.01% by weight to 3% by weight based on the total weight of the liquid crystal alignment agent, and is preferably from 重量% to 2% by weight. good. Hereinafter, a liquid crystal display panel produced by using the liquid crystal alignment agent of the present invention, which can be obtained by the following steps, will be described. (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, heating is performed for baking to remove the organic solvent in the liquid crystal alignment agent and to promote dehydration/ring closure reaction of the uncyclized polyamic acid to form a polyimide film. The above heat baking temperature is between 80 ° C and 300 ° C and is 100. (: to 240 ° C is optimal. The thickness of the film formed is preferably from 0.005 μm to 0.5 μm. (2) The formed film is subjected to directional rubbing by a roller wound with a nylon or cotton cloth. In order to make the liquid crystal molecules have an orientation. (3) coating the sealant on the substrate having the liquid crystal alignment film, and spraying the spacer on the substrate having the liquid crystal alignment film, and then brushing the two substrates to each other The motor is vertically 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 panel. Generally, the following characteristics are used as the evaluation index (1) Pretilt amount. The liquid crystal display panel that has been injected into the liquid crystal is measured by the crystal rotation method. (2) Pretilt angle variation measurement and measurement LCD cell _ nine her, recording Heterogeneity evaluation, the smaller the pretilt variability is, the better the stability is as the change (3) The voltage retention rate is 侔ί: At ambient temperature, '3V DC is applied to the liquid crystal display retention rate. Z ' _ 宽卿咖' To measure What is the electric power in the crystal display element? (4) The image sticking phenomenon determines the disc electric power! ^, measuring the transmittance of the liquid crystal display element at a specific position _ ' 'When the above liquid crystal display element is subjected to direct current 30V η translation t' then discharge for a while Then, in the same position: the measurement of the amount of change of the tooth = voltage. The voltage of the penetration of 5〇% is based on the measured value of the change before and after the reference voltage, and divided by the original &gt;5^ ^杨 Yang, the amount of change before and after the penetration is judged to be excellent, &gt;5/〇 is 中, and greater than 1〇% is judged to be poor. (4) Cyclization rate (醯imination ratio) Or the liquid crystal alignment agent is dried under reduced pressure at room temperature, and then the solid after the dissolution is dissolved in the chaotic dimethyl sapite, using four 曱21 201241088 ι^Λΐυι^υ2 37328twf.d〇c/ N-based Wei as a reference (four), such as 1H_NMR measured f, from the mail) to obtain the brewing imidization ratio.醯imination _(%H"AVA2xa)X10G (Π) 2 The proton-derived sharpening area from the _ group (l〇ppm) The peak area derived from other protons a. Other protons relative to the polymer precursor ( The number ratio of protons of one of the NH groups in polyglycolic acid is (5). The liquid crystal alignment agent is coated on the ITO substrate, and the ITO substrate is at 100 CX , , , , 1 J later 3M tape test (cr〇ss cUt method) ° The synthesis method of synthetic polymers A1_A7, B1B6 and al, bl~b3 is described below. The diamine compound and tetracarboxylic dianhydride are sequentially added to N•methyl group. _2_pyridone ketone (for example, as shown in Table 4 and Table 5), a solution having a solid content of 25% by weight is prepared, and reacted at 50t: to 6 (TC temperature for 4 hours to 5 hours). Poly-proline. Add bite and acetic acid liver to the obtained poly-aramidic acid (the amount of which must be added according to the polyamidation ratio), at 1 〇〇. (: to u (rc) dehydration / ring closure reaction 3 to 4 hours. The obtained solution was immersed in methanol and purified with methanol. Finally, it was collected and dried under reduced pressure to obtain The polymers αι_Α7, Β1·Β6, al and Μ~b, which have the intrinsic viscosity and the ruthenium iodide ratio shown in Tables and Table 5, which have no formulas of + al and bl 〜 b3 (3) and the diamine compound represented by the two (4). 22 201241088 L) X101202 37328twf.doc/n Table 4 Synthesis Example Diamine Compound (10) Molar Number Diacid Anhydride (10) Molar Number 醯 Iridization Ratio (%) Intrinsic Viscosity (dl/g) Polymer 1 2-1(30) ' 3-1 (70) 1-6(100) 75 ----- 0.4 ------ A1 2 2-2(10), 3-1 (90) 1-6(100) 85 0.5 A2 3 2-3(5) ' 3-1 (95) 1-6(100) 90 0.6 —-—— A3 4 2-1(30), 2-4(5), 3-1(65) 1-6(100) 76 0.4 A4 5 2-1(30), 2-4(20), 3-1(50) 1-6(100) 74 0.3 ----- A5 6 2-1(30), 2-5(20), 3-1(50) 1-6(100) 75 0.3 A6 7 2-4(50), 3-1 (50 ) 1-6(100) 75 0.4 A7 8 3-1(100) 1-6(100) 95 0^8 Ί al Table 5 Synthesis Example Diamine Oxide tK Millol Number) Diacid anhydride Viscosity (dl/s) Polymer 9 2-4(100) 1-2 (100) 0.75 B1 10 2-4(50) 3-3(50) 1-2 (50), 1-5(50) 0.80 "B2 11 2-4(50) 3-2(50) 1-2 (50), 1-5(50) 0.79 B3 12 2-4(50) 3- 5(50) 1-2 (70) ' 1-5(50) 0.81 B4 13 2-4(100) 1-3 (100) 0.65 B5 14 2-4(100) 1-1 (100) 0.52 B6 15 3-5(100) 1-2(50), 1-5(50) 0.89 Μ 16 3-2(50) 3-3(50) 1-2(50), 1-5(50) 0.78 b2 17 3-2(100) 1-2(50) '1-5(50) 0.86 b3 Experimental method of the examples and the comparative examples Dissolving a fixed ratio of the solid polymer (A) and the solid polymer (B) in the T- In a mixed solvent of butyrolactone and N-mercapto-2-pyrrolidone, a solution having a solid content of 6% by weight was prepared and filtered through a filter having a diameter of 1 μm. The filtrate collected is the liquid crystal alignment agent of the present invention. The liquid crystal alignment agent of the present invention was applied to a glass substrate by a roll press and dried by a hot plate at a temperature of 200 ° C for 20 minutes to form a film having a thickness of 0.08 μm. The film was subjected to directional rubbing at a roller rotation speed of 1000 (rev / 23 201241088 υΛΐυιζυ2 37328 twf.doc/n), a platform moving speed of 6 〇 (mm/sec), and a press-in amount of 0.4 μm. A sealant is applied to the substrate, and the spacer is sprayed on the other substrate. Then, the two substrates are combined in such a manner that the rubbing directions of each other are perpendicular to each other, and liquid crystal (ZLI-4792) is injected into the gap between the two substrates to seal the injection holes to form a liquid crystal display element. The obtained liquid crystal display element was evaluated for pretilt angle, voltage holding ratio, residual characteristics, and adhesion. The evaluation results are shown in Table 6. Table 6 Example Poly-W (weight ratio) Pre-tilt pre-tilt variability Voltage retention (%) Image-resistance Adhesiveness 1 Α1(1)+Β1(4) 4.0 0.2 99 Youyou 2 Al ( l)+B2(4) 4.5 0.3 97 Medium 3 Al(l)+B3(4) 4.5 0.3 98 Zhongzhongyou 4 Al(l)+B4 (4) 4.4 0.3 96 Medium 1 with 5 Al(l)+B5 (4) 4.1 0.3 89 Excellent φ 6 Al(l)+B6(4) 4.1 0.3 88 Excellent 1 and excellent φ 7 Α2(1)+Β1(4) 3.5 0.4 99 优ΐίΆ. m 卞一_ 8 Α3 (1)+Β1(4) 5.1 0.6 99 中丨和优9 Α4(1)+Β1(4) 3.9 0.3 99 Medium 1 'Go image 1Α5(1)+Β1(4) 3.6 0.3 98 -I^L υ 优 ί 11 11 Α 6 (1) + Β 1 (4) 1.2 0.2 98 excellent IssL injury control mixed species (weight β ratio) pretilt pre-tilt variability voltage retention rate (%) afterimage characteristics - L and adhesion Sexual brushing property 1 al(l), bl(4) 1.2 1 85 difference Φ 2 al(l), b2(4) 1.5 1 88 difference—^ 卞-zhong” 3 al(l) , b3(4) 1.3 1 89 ---::--- Poor - In summary, since the liquid crystal alignment agent of the present invention comprises a polyazide having a side chain diamine as shown in the formula (j) 24 201241088 DX101202 37328twf.doc/n _ Polyproline and a poly-proline having a side chain diamine as shown in the formula (2), so that the liquid crystal alignment film formed by the liquid crystal alignment agent can have a function of stabilizing a pretilt angle, and the liquid crystal alignment film The adhesion and the improvement of the film property can also improve the image sticking problem, 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 description of the diagram] * »&gt;\ [Description of main component symbols]

Claims (1)

201241088 DX101202 37328twf.doc/n VII. Patent Application Range: 1. A liquid crystal alignment agent comprising: a polymer (A) which is a polyimine-polymer having a side chain diamine represented by formula (1) a proline acid; and a polymer (B), which is a poly-proline acid having a side chain diamine represented by the formula (2), wherein the weight ratio of the polymer (A) to the polymer (B) ( A) / (B) is 5/95 to 95/5, Equation (1) 0 0 0 0 Ο 〇 ”m L ό Ο ” η (2) Ο ο • OH Η Ν-D3—— Ο Ο In equations (1) and (2), TVT2 and Τ3 are respectively tetravalent organic groups; n/(m+n) S0.5; Di, D2 and D3 are divalent An organic group, and at least a part of Di or D2 is selected from a divalent organic group of the diamine monomer represented by formula (3) or formula (4), and at least a part of D3 is a diamine monomer represented by formula (4) Divalent organic radical, 26 201241088 DX101202 37328twf.doc/n In the formula (3), Ri, R2, 3, Rs and R6 are each independently represented by hydrogen or an alkyl group having 1 to 5 carbon atoms; privately, an alkyl group having 4 to 20 carbon atoms, C02R22, CONR22 or (CH2) PCF3, wherein P is an integer of Bu 5, R22 represents an alkyl group having a carbon number of 4 to 20, and (4) is only 8 - NN - X2 - R12 R, ^ In the formula (4), R7 to Ri 1 &gt; is a primary amine group 'the rest of each is independently a monovalent organic group other than a 1 atom or a primary amine group 'R7 to R11' and the same may be different; X, and x2 are represented as a single bond or selected from an ether The divalent binding group of the group consisting of ester, ketone, decylamine and secondary amine, X丨 and X2 are each the same or different; X3 and X4 are represented by a linear one with a carbon number of 1 to 3. 'X3 and X4 each may be the same or different; Ri2 is represented by an alkyl group having a carbon number of U0, an alicyclic organic group having a carbon number of 3 to 4, and an aromatic skeleton having a carbon number of 6 to 51. a valence organic group or a valence organic group of a heterocyclic skeleton. 2. The liquid crystal alignment agent according to claim 1, wherein the remaining part of Di, 02 and D3 is selected from the formula (5) to the formula (12). The group formed, X-Rl3 prA' χ ^ R13 ^ kx (5) (6) kx (7) Wherein R13 is an alicyclic monovalent organic group having a carbon number of 4 to 40 or a long-chain aliphatic monovalent organic group having a carbon number of 8 to 20; R14 is a halogen atom or a monovalent organic group; and Ri5 is an alicyclic group having a carbon number of 4 to 40. a divalent organic group; R16 is a divalent alicyclic group, a divalent aromatic group or a long-chain aliphatic divalent organic group having a carbon number of 1 to 8; X and Y are respectively selected from -0-, -NH-, -S a divalent group of a group consisting of -, -CO-, -COO-, -OCO-, -NHCO-, -CONH-; Z is selected from 28 201241088 DX101202 37328twf.doc/n -CF3, -CN, COCH3, a monovalent organic group of a group consisting of -COOH, -no2, soch3, -so2ch3, -OCF3, -F, and -Cl. 3. The liquid crystal alignment agent according to claim 1, wherein the content of the divalent organic group of the diamine monomer represented by the formula (3) in the polymer (A) is the polymer (A) The total amount of all divalent organic groups Di and D2 is from 0.1 mol% to 50 mol. /. . 4. The liquid crystal alignment agent according to claim 2, wherein the content of the divalent organic group of the diamine monomer represented by the formula (3) in the polymer (B) is the polymer (_ The liquid crystal alignment agent of the first aspect of the invention, wherein the towel is composed of the diamine monomer represented by the formula (4), wherein the total amount of the d3 is from 2% to 50% by mole. The content of the valence organic group, = Mo field: The price base D1 total amount is 5 mol%. The liquid crystal alignment agent according to item 1 of the poly profit range, wherein the polymerization W Mo % is. - The total amount of mussel organic D3 is 5 mol% to 1〇〇29 201241088 DX101202 37328twf.doc/n IV. Designation of representative drawings: (1) Designated representative figure of the case: None (2) Components of the representative figure Brief description of the symbol: No. 5. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: (1) Ο 0 Ο 0 -OH Η Ν一 D2—— -J η (2) 〇 〇 2