TW593602B - A liquid crystal orientated solvent varnish and a liquid crystal display element - Google Patents

Abstract

In an orientated process by rubbing, a scar of an orientated film surface is common orientated defects. Because the orientated film be cut, this cutting scum is a cause of display defects. Further, for using plastic plate recently, because the forming temperature is lower, a polyamide film has question that hardness hasn't enough. In the present invention, a liquid crystal orientated solvent varnish is including a polyorganosilsesquioxane and a condensation polymer. The polyorganosilsesquioxane is polyorganosilsesquioxane that having a functional group, and the functional group is including epoxy group, carboxyl group, hydroxyl group, amino group, acryloyl oxy group, or methacryloyl oxy group. The condensation polymer is including polyamide acid, solubility polyimide, polyamide, or over two kind of the compound. In the present invention, a liquid crystal display element has a orientated film that forming from the varnish. The ratio of polyorganosilsesquioxane is 0.01 weight % to 50 weight % of total contents of non-volatile constituents of the varnish. At the same time, the ratio of the condensation polymer is 50 weight % to 99.9 weight % of total contents of non-volatile constituents of the varnish. When using the varnish of the present invention, the liquid crystal orientated film has stronger resistance to friction for rubbing and better hardness of surface.

Description

8804pif1 发明, Description of the invention: Field of the invention The present invention relates to a liquid crystal alignment agent varnish, and more particularly to a liquid crystal display element with higher display quality and better reliability. BACKGROUND OF THE INVENTION Liquid crystal display elements are mainly used for nematic liquid crystal display elements. Proposals in this regard include TN-type liquid crystal display elements that are rotated by 90 °, and STN-type liquid crystals that are usually rotated by more than 180 °. A display element and a so-called TFT-type liquid crystal display element using a thin film transistor. Recently, in-plane switching (hereinafter referred to as "IPS") type liquid crystal display elements with improved horizontal visual field characteristics and vertical alignment (Vertical Alignment) (hereinafter referred to as "VA") ) Type liquid crystal display elements, or optically compensated birefringence (Optically Compensated Birefringence) (hereinafter referred to as "0CB") type liquid crystal display elements with extremely fast response speed and wide viewing angle. In such a liquid crystal display element, it is important whether the alignment system of the long axis direction of the liquid crystal molecules is uniform. An industrially representative method for uniformly aligning liquid crystal molecules is a rubbing method described below, that is, an alignment film formed of an organic coating film is provided on a substrate surface, and the surface is A method of rubbing a cloth such as cotton, nylon, polyester, or the like in a certain direction to align liquid crystal molecules in the rubbing direction. This friction method can relatively easily obtain a uniform orientation 'and at the same time has better productivity, thus becoming the mainstream on the industrial 8804pifl. The material of the alignment film is, for example, polyvinyl alcohol, polyoxy ethylene, polyamide, polyimide, polyamide-imide, etc. Polymer. Among them, polyimide is most used. The reason is that it has better chemical and thermal stability and can withstand industrial mass production. The alignment treatment method for forming an alignment film by rubbing can obtain better productivity in a simple manner, and is an industrially useful method. However, when the liquid crystal display element is used in various fields, although the performance of the liquid crystal display element can be improved, various problems can be pointed out. For example, during rubbing, when the alignment film is peeled off, the scum after removal thereof becomes a cause of display defects. In STN type elements, in order to obtain a high contrast, it is not desirable to see alignment defects caused by scratches on the surface of the alignment film due to friction. Furthermore, in a TFT type element, the mechanical force used for friction has the effect of damaging the transfer element. What's more, in recent years, in order to reduce the manufacturing cost or light weight, when plastic substrates are used instead of glass substrates, liquid crystal alignment agent varnishes have been tried at temperatures as low as 200 degrees Celsius. Sintered. However, when polyamine is coated on the substrate under the precursor of polyimide, and it is fired at a low temperature, the dehydration ring closure (imidization) reaction of polyamine cannot be performed completely. The deep problem of the scar of the alignment film caused by insufficient hardness of the polyimide. The above-mentioned problems of the friction method are caused by the use of polymers in the alignment film. For example, when the cause is insufficient surface hardness, the 8804pif1 should be rubbed to cause damage to the alignment film. Furthermore, when the cause is insufficient adhesion of a glass substrate or the like, the alignment film may be cut. Therefore, it is preferable to develop an alignment film in order to improve the above problems. For insufficient surface hardness, the molecular structure of the alignment film can be improved to some extent. However, it is difficult to simultaneously improve the electrical characteristics of the alignment film or the pre-tilt angle of the liquid crystal in the obtained pricing. Moreover, the adhesion to the glass substrate can be improved to some extent by using a coupling agent. However, because the coupling agent is affected by hydrolysis, there is a problem in the preservation stability of the alignment agent lacquer. Furthermore, when too much coupling agent is used to prevent peeling, there is a problem that the performance of the liquid crystal display element is lowered. SUMMARY OF THE INVENTION The present inventors have proposed a liquid crystal alignment agent varnish containing polyorganosilsesquioxane (polyorganosilsesquioxane is represented by PSQ in the following description), which has solved the aforementioned problems. Because PSQ is a highly bridged crosslinked body, it does not easily undergo hydrolytic reaction. For this reason, compared with the case of using a coupling agent, there is no problem of storage stability of the alignment agent paint. Furthermore, when the amount is excessive, it will not adversely affect the display performance of the liquid crystal display element. When the amount is small, a highly reliable liquid crystal alignment film can also be formed. Moreover, although there are examples of the disclosure of a resin composition using an organic oligomeric silsesquioxane oligomer as an ingredient, it is a technique different from the object of the present invention. For example, in the technology disclosed in Japanese Patent Laid-Open No. 8 ^ 59895, the main purpose is to use a liquid crystal 8804pif1 display element as a protective film such as a transparent substrate or a color filter. Furthermore, the technology disclosed in Japanese Patent Laid-Open No. 6-186570 aims to improve the zigzag defects of the dual-stable ferroelectric liquid crystal display device. To date, there has been no literature on improving the problems caused by the alignment process. The present invention has the following structures Π] to [7]. [1] A liquid crystal alignment agent lacquer, comprising a polymer component and a solvent formed by a polyorganosilsesquioxane and a polycondensed polymer, wherein the ratio of the polyorganosilsesquioxane in the polymer component is 〇01% to 50% by weight and the ratio of the polymer component is about 0.1% to 40% by weight of the total amount of the liquid crystal alignment agent lacquer, and the ratio of the solvent accounts for the entire amount of the liquid crystal aligning agent lacquer 60% to 99.9% by weight. [2] The liquid crystal alignment agent paint according to [1], wherein the polycondensation polymer is selected from the group consisting of polyamic acid, soluble polyimide, polyamidine, or a mixture of any two or more of the foregoing. One of the ethnic groups. [3] The liquid crystal alignment agent lacquer according to [1], wherein the polycondensation polymer is selected from the group consisting of polyamic acid, soluble polyimide, polyamidine, or a mixture of any two or more of the foregoing. In the case of one of the constituent groups, the polyorganosilsesquioxane is a polyorganosilsesquioxane containing a functional unit having a repeating unit which is not included in the formula (1). 8804pif1

CH2CH2 —R10—Y

Rl_Si ^) _ si _R ^ (〇_R4) m〇 (3 nm) / 2 (1) R3 (where R1, R2, and R3 are each a linear, branched, independent carbon number of 1 to 18 Shaped or cyclic saturated hydrocarbon group, or linear, branched or cyclic unsaturated hydrocarbon group having 2 to 6 carbon atoms, or aryl group having 10 or less carbon atoms; R4 series It is a linear or branched saturated hydrocarbon group having 1 to 4 carbon atoms, CH3CO—, CH2 = CHCO—, or Ch2 = C (CH3) CO—; m is 0 or 0.05 to 2.0 Number 値; η number 値 When m is 0, η is 0.1 ~ 2.0, and when m is not 0 and is 0.05 ~ 2.0, the sum of f] n + m is 0.1 ~ 3.0; R1Q is an alkylene group having 1 to 8 carbon atoms, and one of the alkene groups or two CH2 which are not adjacent to each other can also be replaced with one 10 or one NH—; Y series It is epoxy, carboxyl, hydroxyl, amino, amino, acrylyloxy (methacryloyloxy), or methacrylyloxy (methacryloyloxy). It is a functional group formed by mixing two or more of the foregoing.) [4] The liquid crystal alignment agent varnish according to [3], wherein the polyorganosilsesquioxane system is (1) Polyorganosilicon silsesquioxane containing functional groups with repeating units of m 0 and η from 0.1 to 2.0 shown in (1) [5] The liquid crystal alignment agent lacquer as described in [3], wherein The organic sand silsesquioxane is a polyorganic sand silsesquioxane represented by the formula (1) and having a functional unit having a repeating unit of m of 0.05 to 2 and 11 of 0.05 to 2.0. [6] The liquid crystal alignment agent lacquer as described in [3], wherein the polyorganic chossesquioxane is 593602 8804pifl to the functional group by the reaction path shown in the following steps (a) to (d). Polysilsesquioxane. (a) An organotrichlorosilane represented by the formula (2) and an organomonochlorosilane represented by the formula (3) in an amount of η times the mole are mixed. (b) The mixture obtained in (a) is reacted with at least one compound represented by the formula (4) in m times the molar amount of the organotrichlorosilane. (c) By reacting the reaction product obtained in (b) with water at a molar amount of [(3 + nm) / 2] times the organic trichlorosilane, a repeating unit represented by formula (5) can be obtained and Polyorganosilsesquioxane compounds having a number average molecular weight of 500 to 5000. (d) The polyorganosilsesquioxane compound obtained in (c) is reacted with a compound represented by the above formula (6). π 593602 8804pif1

Cl R1

I (2) (3) (4)

Si-Cl

I

Cl R3

I

Si-H

I

Cl

R4—OH

(3-nm) / 2 (5) ⑹ ch2 = CH—R10 —γ (R1 to R4, R1G, Y, m, and n in the above formulae have the same meanings as described in [3].) [ 7] A liquid crystal display device having an alignment film formed using the liquid crystal alignment agent varnish according to any one of [1] to [6]. In order to make the above and other objects, features, and advantages of the present invention more comprehensible, the preferred embodiments are described below in detail as follows: Detailed description of the preferred embodiments The PSQ used in the present invention is, for example, PSQ consists of trifunctional silicon with organic functional groups. Examples of this organo-containing official 12 593602 8804pifl energy group are, for example, alkyl and phenyl. Examples of this PSQ are, for example, polymethylsilsesquioxane, polypropylsilsesquioxane, and polyphenylsilsesquioxane. The aforementioned compound is synthesized, for example, by referring to the method described in Chemical Reviews 1995, vol. 95? No. 5? 1409-1430. The PSQ is not limited to containing only one type of organic group, and may include two or more types of organic group. For example, polyphenyly-methyl-silsesquioxane, polyphenyl-propyl-silsesquioxane, polymethyl-propyl-silsesquioxane, polymethyl-propyl-silsesquioxane Hospital (polymethyl-propylsilsesquioxane). In this way, when there is a case where the organic groups are different from each other, they can be synthesized by co-hydrolysis of two types of trichlorosilanes. In the present invention, although examples of several types of PSQ containing organic functional groups will be described, it is not limited thereto. A next example of a PSQ used in the present invention is a PSQ containing a functional base. This functional group is, for example, a polymerizable unsaturated azido group, a maleamide group, an epoxy group, a 2-cinnamic acid group, or a hydroxyl group. , Thiol, formyl, acetal, isocyanate, cyano, amino, amido, ester, carboxyl, sulfur Sulfonyl, aldehydo, oxime, meixapto. Among them, among the functional groups used above, it is preferably 13 $ 93602 88〇4Pif1 dual combination of epoxy group, carboxyl group, hydroxyl group, amino group and polymerizability. Furthermore, the PSQ used in the present invention may contain a single functional group or two or more functional groups. Alternatively, two or more kinds of PSQs having different kinds of functional groups may be used. In short, in the present invention, psQ is preferably a PSQ containing a functional group with a repeating unit shown in the following formula (1) ° ch2ch2 —r10—y

I R1—Si p —Si —R2) n (〇—R4) m〇 (3.nm) / 2 ⑴ R3 In this formula, R1, 1 ^ 2, and r3 are each independent carbon numbers of 1 to 18 Straight chain, branched or cyclic saturated hydrocarbon group, or straight chain, branched or cyclic unsaturated hydrocarbon group with 2 to 6 carbon atoms, or aromatic group with 10 or less carbon atoms base. Preferable examples of R1 to R3 are a linear or branched alkyl group having 1 to 4 carbon atoms, a vinyl group, a vinyl group, an allyl group, a cyclohexyl group, and a phenyl group. R4 is a linear or branched saturated hydrocarbon group having 1 to 4 carbon atoms, CH3CO—, CH2 = CHCO—, or CH2 = C (CH3) CO—-. m is a number of 0 or 0.05 to 2.0, and η is a number of 0.1 to 2.0 when m is 0, and a sum of n + m when m is not 0 and 0 to 0 5 to 2.0 The range is 0.1 to 3.0. R1 () is an olefin group having 1 to 8 carbon atoms, and one of the olefin groups or two CH2 which are not adjacent to each other may also be replaced with one 0—or one NH—. Y is preferably an epoxy group, a carboxyl group, a hydroxyl group, an amino group, a propoxyfluorenyl group, or an isobutoxyfluorenyl group, and may be a functional group obtained by mixing two or more of the foregoing. 14 593602 8804pif1 —CH2CH2 —R1G—Y, which is a compound of formula (6) described later, is a group bonded to Si by a hydrosilylation reaction. Preferred examples of this group are 3-aminopropyl, 4-aminobutyl, N- (2-aminoethyl) -3-aminopropyl, 3 -3-glycidoxy propyl, acryloyloxy ethyl, acryloyloxy propyl, metharyloyloxy ethyl, isobutyl Methacryloyloxy propyl, a hydroxy alkyl group having 3 to 10 carbon atoms, and a carboxyl alkyl group having 4 to 11 carbon atoms. The compound of formula (6) is preferably a compound having an unsaturated bond at the terminal on the opposite side of the functional group of the aforementioned group. This PSQ can be manufactured not only by the method described above, but also by the manufacturing method described in the specification of Japanese Patent Application No. 2000-64498. That is, PSQ containing a functional group can be obtained by the reaction paths shown in the following (a) to (d). (A) The organic trichlorosilane represented by formula (2) and η-beamole ( The organic monochlorosilane shown in formula (3) was mixed in an amount of mole). (b) The mixture obtained in (a) is reacted with at least one compound represented by the formula (4) in m times the molar amount of the organotrichlorosilane. (c) By reacting the reaction product obtained in (b) with water with a molar amount of [(3 + nm) / 2] times the organic trichlorosilane, a repeating unit represented by formula (5) can be obtained and PSQ having a number average molecular weight of 500 to 5000 015 593602 8804pifl (d) The PSQ obtained in (c) is reacted with one or more compounds represented by the formula (6). C1

I R1— Si—C1 (2)

I

Cl R3

I R *-Si—H (3)

I

Cl R4—OH (4)

(5) CH2 = CH—R10—Y (6) (The meanings of R1 to R4, R1G, Y, m, and n in the formulas above are the same as above.) The liquid crystal alignment agent lacquer of the present invention is A paint composition having a polymer component formed of PSQ and a polycondensation polymer dissolved in a solvent state. Among them, in the content of PSQ in this composition, the weight percentage of the polymer component is 0.01 to 50.0% by weight, the preferred weight percentage is 0.1 to 10.0% by weight, and the more preferred weight percentage is 0.3 to 3.0% by weight. %. When this content is too large, PSQ may precipitate on the surface of the alignment film, and it may become a cause of poor liquid crystal alignment 16 593602 8804pif1. Furthermore, when the content is too low, the effect of increasing the hardness of the alignment film tends to decrease. The content of the polycondensed polymer in the liquid crystal alignment agent paint of the present invention is 50 to 99.9% by weight of the polymer component. The polycondensation polymer may be a copolymer such as a random copolymer or a block copolymer. Furthermore, a plurality of polycondensation polymers may be used simultaneously. The polycondensation polymer is preferably a polyamic acid obtained by reacting a tetracarboxylic acid dianhydride with a diamine, and a soluble polyimide obtained from the dehydration reaction of the polyamino acid. Ammonium amine, polyamine and the like obtained by reacting dicarboxylic acid or dihalide with diamine. In addition, the hydrogen atom of the fluorene bond (CONH) of this polyamine may be replaced with another group. The above-mentioned selection conditions of the tetracarboxylic acid dianhydrous are that they can react with diamines to form polyphosphonic acid, and the selection conditions of dicarboxylic acids or dicarboxylic acid dihalides are that they can react with diamines to form Polyamine is sufficient, and there are no other restrictions on the two. For diamines, the selection conditions are the same as those described above, as long as they can react with tetracarboxylic acid dianhydrous to form polyamines and can react with dicarboxylic acids or dicarboxylic dihalides to form polyamines. There are no other restrictions. In addition, two or more of the above-mentioned tetracarboxylic acid dianhydrous, dicarboxylic acid or dicarboxylic acid dihalide, and diamine may be used, respectively, and all of them are not limited. Among the acids or diamines used for the polyamic acid or polyamine raw materials, specific examples of the tetracarboxylic acid dianhydride and the diamine are, for example, arbitrary

The compounds described in this publication such as WO 98 / 31725A1, WO 99 / 33902A1, WO 17 593602 8804pif1 99 / 33923A1, WO 99 / 34252A1, and WO 01 / 00732A1 are selected for use. In addition, specific examples of the dicarboxylic acid include, for example, the compounds described in WO 01 / 14457A1 and the dihalides of the compounds. In addition, in the aforementioned partial polyamidic acid or raw material of polyamidoamine, a monoamine compound, a monocarboxylic acid anhydrous substance to stop the end of the polymer can also be used, or the foregoing can be used simultaneously. Both. Furthermore, in order to increase the adhesion with the substrate, an amino silicon compound may be used. Specific examples of the ammonium compounds include para-aminophenyl trimethoxy silane, para-aminophenyl triethoxy silane, and meta-aminotrimethoxysilane. (Meta-aminophenyl trimethoxy silane), meta-aminophenyl triethoxy silane, aminopropyl trimethoxy silane, aminopropyl trimethoxy silane, aminopropyl triethoxy silane) and the like. The concentration of the polymer component in the liquid crystal alignment agent paint of the present invention is preferably from 0.1 to 40% by weight. When the concentration of the polymer component exceeds 40% by weight, the viscosity of the liquid crystal alignment agent lacquer will increase. When dilute varnishes are used to adjust the film thickness, it is common to tend to mix solvents into varnishes. When a spinner method or a printing method is used, it is usually 10% by weight or less in order to maintain a good film thickness. Other coating methods, such as the tipping method, require a low concentration. On the other hand, when the concentration of the polymer component is less than 0.1% by weight, the problem of excessively thin film thickness of the obtained alignment film of 18 593602 8804 pif1 easily occurs. Therefore, the concentration of the polymer component is 0.1% by weight or more when a conventional spin coating method or printing method is used, and preferably 0.5 to 10% by weight. % However, in the coating method of the liquid crystal alignment agent varnish, a thinner concentration may be used. The selection conditions of the solvent used in the liquid crystal alignment agent lacquer solvent of the present invention are not limited as long as it has the ability to dissolve the polymer component. Therefore, when manufacturing or using polyamic acid, soluble polyimide, polyamidine, etc., the solvent used is a general solvent, and it is only necessary to appropriately select the purpose of use. For the total amount of lacquer, the solvent ratio is 60 to 99.9% by weight. For ammonium acid, soluble polyimide, and polyamine, the closest solvents are polar organic solvents that are proton-free. The solvent is, for example, N-methyl-2_pyrrolidone, dimethyl-imidazolidinone, N-methyl caprolactam, N-methyl propionamide, N, N-dimethyl acetamide, dimethyl sulfo oxide, N, N-dimethyl N, N-dimethyl formamide, N, N-diethyl formamide, diethyl acetamide, and γ-butyrolactone (Γ-butyrolactone). In addition, when the purpose is to improve the coating property, other solvents may be used instead. In this case, the solvents are, for example, alkyl lactic acid and 3-methyl-3-methoxy butanol. , Tetraline, isophorone, ethylene glycol monoalkyl 19 593602 8804pifl ether, diethylene glycol monoalkyl ether, propylene glycol first hospital Propylene glycol monoalkyl ether, malonic acid dialkyl, dipropylene glycol monoalkyl ether, and triethylene glycol monoalkyl ether. It is also possible to use the above-mentioned organic acid ester. For example, it is an ester compound solvent such as acetate. The ethylene glycol monoalkyl ether is, for example, ethylene glycol monobutyl ether. Diethylene glycol monoethyl ether is, for example, diethylene glycol monoethyl ether. The propylene glycol monoalkyl ether is, for example, propylene glycol monobutyl ether. The dihomonyl malonic acid is, for example, malonic acid diethyl. The dipropylene glycol monoalkyl ether is, for example, dipropylene glycol monomethyl ether. The liquid crystal alignment agent varnish of the present invention may contain various additives if necessary. For example, when it is desired to improve the coating property, a surfactant may be mixed, and when it is necessary to improve the prevention of electricity, a charge preventing agent may be mixed. The substrate on which the liquid crystal alignment film is formed using the liquid crystal alignment agent of the present invention and the substrate on which the same or different liquid crystal alignment film is formed are overlapped with each other. When the two liquid crystals are held, the substrate becomes a liquid crystal holding substrate . A liquid crystal display element can be obtained on this liquid crystal holding substrate by a known method. The operation mode (mode) of the liquid crystal display device includes TN type, STN type, IPS type, VA type, 0CB type, ferroelectric type, and anti-ferroelectric type. The liquid crystal display element using the alignment agent varnish of the present invention is a liquid crystal display element in which liquid crystal molecules are aligned by a liquid crystal alignment film. 20 593602 8804pifl changes the arrangement state of liquid crystal molecules used. Other than that, there are no other restrictions on the liquid crystal display element. The alignment film is formed by a process of applying a liquid crystal alignment agent to a substrate, and then continuing a process of sintering and forming. The substrate is, for example, a glass substrate or a plastic substrate. In addition, the plastic substrate is preferably in the shape of a film. The coating method is a conventionally known method such as a spin coating method, a printing method, a dye tip method, or a dropping method, and can be applied to the present invention. In addition, the method of firing the liquid crystal alignment agent lacquer is generally known methods such as a method of performing a heat treatment in an oven or an infrared oven or a method of performing a heat treatment on a hot plate. It can also be applied to the present invention. In addition, usually, the heat treatment process is preferably performed in a temperature range of about 120 ° C to about 300 ° C. When using a plastic substrate, it is necessary to consider the heat-resistant temperature of the substrate. Therefore, it is preferable to perform it at a low temperature of about 120 ° C to 160 ° C. Examples of the liquid crystal composition that can be used with the present invention include Japanese Patent Laid-Open No. 8-157828, Japanese Patent Laid-Open No. 8431960, Japanese Patent Laid-Open No. 9-241644 (EP 885272A1), and Japanese Patent Japanese Patent Laid-Open No. 9-302346 (EP 806466A1), Japanese Patent Laid-Open No. 8-199168 (EP 722998A1), Japanese Patent Laid-Open No. 9-235552, Japanese Patent Laid-Open No. 9-241643 (EP 885271A1), The liquid crystal group 21 disclosed in Japanese Patent Laid-Open No. 10_20401 (EP 844229A1), Japanese Patent Laid-Open No. 10-204436, Japanese Patent Laid-Open No. 10-231482, and Japanese Patent Laid-Open No. 2000-087040. 593602 8804pif1. [Best Method for Carrying Out the Invention] Although the present invention is described below by way of example, the present invention is not limited to this example. (Manufacturing example 1) < Production of liquid crystal alignment agent lacquer A > In a 200 ml four-necked flask having a mounting port for a thermometer, a stirrer, raw material input, and the like, and a nitrogen pouring port, 0.3215 g of 4,4 was added. '· Aminodiphenylmethane (4,4'-diaminodiphenylmethane), 3-91〇lg of 1,1-bis (4- (4-aminophenoxy) phenyl) -4_ (trans-4 -Pentylcyclohexyl) cyclohexane (1,1-bis (4- (4-aminophenoxy) pheny 1) -4- (trans-4-pentyl cyclohexyl) cyclohexane), and 54.00g of dehydrated N-methyl- 2-% pyrrolidone (hereinafter referred to as "NMP"), and dissolve by stirring under a dry nitrogen atmosphere. The temperature of the reaction system was maintained at 5 degrees Celsius, and 1.7684 g of pyromellitic acid dihydrate (hereinafter referred to as "PMDA") was added, and then the temperature was controlled to react at a specific temperature for 30 hours. . Finally, 40.00 g of butyl celluiose (hereinafter referred to as "BC") was added to produce a polyamic acid lacquer having a polymer content concentration of 6% by weight. This varnish is referred to as varnish A for liquid crystal alignment agent. Moreover, in the example of the present invention, the reaction is performed by checking the viscosity in the reaction, that is, the viscosity of the liquid crystal alignment agent lacquer A after adding butyl cellulose is 55 ~ 65mpa * s (using E Type viscometer, 22 593602 8804pifl, and the measurement temperature is 25 degrees Celsius) at the time point, the reaction is completed and stored at low temperature. (Manufacturing example 2) < Production of liquid crystal alignment agent lacquer B> In addition to using a diamine compound instead of 0.8118 g of 4,4'-diamino-phenyl ethyl compound (4,4 '-(1 丨 & 111 丨 11〇 (101101161116111 & 1 ^), and 2.51-2008 of 1,1-bis (4- (4-aminophenoxy) phenyl) -4- (2- (trans- In addition to 4-pentylcyclohexyl) ethyl) cyclohexane (1,1-bis (4- (4_aminophenoxy) phenyl) _4- (2- (trans-4_pentyl cyclohexyl) ethyl) cyclohexane), other steps are the same as In the same manner as in Production Example 1, a liquid crystal alignment agent lacquer B was produced. (Production example 3) < Production of a liquid crystal alignment agent lacquer C > Formula-4- (trans-4-pentylcyclohexyl) cyclohexyl) phenyl) methyl-l, 3-diaminobenzene (5_ (4- (trans-4- (trans-4-pentyl cyclohexyl) cyclohexyl ) Except for phenyl) methyl-1,3-diaminobenzene), the other steps were the same as those in Production Example 1 to obtain a liquid crystal alignment agent lacquer C. (Production example 4) < Production of liquid crystal alignment agent lacquer D & gt In addition to changing the diamine compound to 1.4514g of 4,45-diaminodiphenyl formaldehyde In addition to using 1.4357 g of cyclobutane tetracarboxylic acid dianhydride instead of PMDA, the other steps were the same as those in Manufacturing Example 1 to obtain a liquid crystal alignment agent lacquer D. 23 593602 8804pifl (mixed Preparation of lacquer) Mixing liquid crystal alignment agent lacquer A and liquid crystal alignment agent lacquer D to obtain mixed lacquer AD, mixing liquid crystal alignment agent lacquer B and liquid crystal alignment agent lacquer D to obtain mixed lacquer BD, and mixing liquid crystal alignment The lacquer C and the liquid crystal alignment agent lacquer D obtain a mixed lacquer CD. In the aforementioned mixed lacquer, the ratio of the liquid crystal alignment agent lacquer D is 90% by weight. (Example 1) Japanese Patent Application No. 2001-64498 The method described in the preferred embodiment of the publication No. is to quasi-synthesize PSQ (carboxyl decyl) with a number average molecular weight of 2300 and a carboxyl content of 178 millimole / g. PSQ is mixed with the liquid crystal alignment agent lacquer A obtained in Manufacturing 1, wherein the ratio of the total amount of polymer components to PSQ is 3% by weight. That is, this mixture uses a mixed solvent of NMP-BC (weight ratio 1/1) Dilute to adjust The concentration of the whole polymer component was 3% by weight. This dilute lacquer is applied on a substrate with transparent electrodes by spin coating method 'and then sintered for about 5 minutes at 80 ° C. Next, it is sintered at 140 ° C for about 12 minutes to form an alignment film with a film thickness of 60 nm. Then, the entire surface is aligned by friction. Make a piece of the same substrate as above, spread a gap material of 20 // m on the alignment film surface of one substrate, and then use the epoxy hardener on the surface of the other substrate facing the alignment film surface to overlap Seal to make an anti-paraUel cell with a gap of 20 // m. Then, the following liquid crystal composition is injected into this unit, and after completion, the injection port is closed with a photohardener. After that, a heating process of 24 593602 8804pifl for about 30 minutes at 110 degrees Celsius is performed to produce a homogeneous alignment unit. Under the rotation observation of a cross Nicol, this unit cannot confirm the spiral-like traces obtained by friction. Since the obvious light and dark can be uniformly confirmed, it can be confirmed that it has a good alignment in the rubbing direction. 25 593602 8804pif1 C2H5OCH2

5wt .-% c3h7och2

15wt .-% c4h9och2

13wt .-% C5HuOCH2

13wt .-%

c3h7 ch3 8wt .-% c3h7 OCH3 4wt .-% c2h5

F

CN 15wt .-% c3h7

CN 15wt .-%

c3h7

c3h7

c3h7

4wt .-% 4wt .-% 4wt .-% 26 593602 8804pif1 (Example 2 to Example 10) The functional group and organic group of PSQ were changed according to the description in Table 1, and the aforementioned Japanese Patent No. 2001-64498 The method described in the publication was synthesized on the basis of the method, except that the addition amount was changed, and adjusted to the same dilute lacquer as in Example 1. Furthermore, the same unit as in Example 1 was produced. This unit could not be confirmed to have spiral traces due to rubbing under the rotation observation of a crossed Nicols polarizer. Since the obvious brightness and darkness can be uniformly confirmed, it can be confirmed that it has a good orientation in the rubbing direction. The results of Examples 2 to 10 are shown in Table 1 as τκ. (Example 11 to Example 14) Except using polymethyl-silsesquioxane or polyphenyl-silsesquioxane, the same unit as in Example 1 was produced, and it was confirmed that there were scratches or nicks after rubbing . The point of difference from Example 1 is that several spiral traces were confirmed in the rubbing direction, and some alignments were observed to have disordered portions, which indicates that the liquid crystal display element has insufficient resistance to full use. The results of Examples 11 to 14 are shown in Table 1. (Comparative Example 1) The same unit as in Example 1 was produced except that PSQ was not added to the liquid crystal alignment agent varnish A. Under the observation of the rotation of a crossed Nicols polarizer, this unit was confirmed to have a significant spiral wound in the rubbing direction. And observing its disordered alignment. The results of Comparative Example 1 are shown in Table 1. 27 7 [\ ° 593602 ΓΗΜ-Ι-Hd inch 〇88 1 «^ srlf (gEffi / p)

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镒 Ή 省略 Inch ei (NI IIοι 6 00 L 593602 8804pif1 In Table 1, the meanings of the omitted codes, symbols, etc. are as follows. Omitted codes: PSQ: polyorganosilicon silsesquioxane Me: methyl Ph: phenyl Π-Ργ · Ι Ί · • Internal PSQ added amount:% by weight relative to the total polymer Molecular weight of PSQ: Number of PSQ used Average molecular weight PSQ Functional group content unit: millimoles / g Indicates whether there is damage Meaning of symbols: ◎: No damage. 0: Some damage. Χ: Damage. Display unevenness. It is used to observe and evaluate the display unevenness immediately after writing. The meaning of the symbol is shown below. : ◎: No display unevenness 0: Some display unevenness x: Some display unevenness (Example 15 to Example 18) The same liquid crystal alignment agent paint for coating as in Example 1 was prepared, except that The same unit as in Example 丨 was prepared separately for the 30 kinds of sintering temperatures shown in Table 2 except for about 30 minutes of heat treatment. This unit could not be confirmed due to friction under the rotation observation of an orthogonal ^ Kohler polarizer. Spiral shape Traces. Since the obvious brightness and darkness can be confirmed evenly and uniformly, 29 593602 8804pifl can be confirmed to have a good orientation in the rubbing direction. The results are shown in Table 2. (Comparative Example 2 to Comparative Example 5) Except for use The same units as in Examples 15 to 18 were made separately without adding the PSQ liquid crystal alignment agent varnish. This unit was observed under the rotation of a crossed Nicols polarizer, at this time, it was confirmed that it had a significant difference in the rubbing direction. Spiral flaws. Observed alignment disorder. The results of Comparative Examples 2 to 5 are shown in Table 2. (Examples 19 to 25 and Comparative Examples 6 to 12) Seven types of varnishes shown in Table 2 were used. At this time, the PSQ containing the carboxyl group described in Example 1 is added, and each is prepared into a coating liquid crystal alignment agent paint. Thereafter, this coating paint is used to make the same unit as in Example 1. Observe this The damage caused by the friction of the alignment film is shown in Table 2 together with the comparative example, and the results obtained by measuring the rake angle by the crystal rotation method are shown in Table 2.

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VVVVVVVV Two one eat ugly 001 bu one 91 ◎ ◎ ◎ ◎ ◎ ◎ `` o / olCN 『0 / 0I (N 100/013 2 / ol (N loo / ol < N 5/013『 0 / 0I < N 50 / 013 ro / OICN 2 / oi (n ”0 / 0I < N 2 / ol (N 2/01 (n Γ0 / 0 ΙΙΟ oo 卜 I ΟΟΓΠIZ £ jj-u HOOu. ^ Hu; KH ^ ffiuI 00 卜 I 00s £ ά £ ά ΗΟΟυ. ^ Ηονβκ ^ κυ3S οοζ, ι—ηοοΓΟίΝ £ έ JPH-U ΗΟΟυ- ^ Ηυνκυκυi ΟΟΔΙ 00S £ ά ΗΟΟυ- ^ Ηο ^ ΗοMΗυI οοζ.1—ηooroCN £ οο κ ^ κυI 00 卜 I ooroCN £ ά ffiooo— ^ HuHKyHuI 00 卜 一 oorn (N £ ά HOOu- ^ Huvffi ^ Hum ie ρύ αώ α-ν α υ e ν ρύ αώ α_ν α υ PQ ν ^ siοι uang KΉ 6 crown The meaning of the omission code, symbol, etc. in Table 2 is the same as that shown in Table 1. From Table 2, it can be seen that the LCD with a forward tilt of 1.1 ° to 89.3 ° The effect of PSQ on friction scars and nicks has been confirmed in the alignment agent lacquer. Therefore, the TN type liquid crystal display element, the STN liquid crystal display element, the TFT liquid crystal display element, the IPS liquid crystal display element, and the VA liquid crystal display element For various types of liquid crystal display elements such as glass, OCB-type liquid crystal display elements, ferroelectric liquid crystal display elements, and anti-ferroelectric liquid crystal display elements, the effects of the present invention can be fully recognized. [Industrial use is possible [Properties] The use of PSQ-containing liquid crystal alignment agent varnish can increase the hardness of the alignment film and prevent the effect of spiral wounds on the alignment film during the rubbing operation. That is, using the present invention, the TN liquid crystal Display elements, STN liquid crystal display elements, TFT type liquid crystal display elements, IPS type liquid crystal display elements, VA type liquid crystal display elements, OCB type liquid crystal display elements, ferroelectric liquid crystal display elements, anti-ferroelectric liquid crystal display elements, etc. In other words, higher performance can be achieved.

Claims (1)

593602 8804pif1 Scope of patent application: L-type liquid crystal alignment agent lacquer, including a polymer component and a solvent formed by a polyorganosilsesquioxane and a polycondensation polymer, wherein the polymer component is The ratio of the polyorganosilsesquioxane is about 0.01% to 50% by weight, and the ratio of the polymer component is about 0.1% to 40% by weight of the total amount of the liquid crystal alignment agent lacquer, and at the same time The ratio of the solvent accounts for about 60% to 99.9% by weight of the total amount of the liquid crystal alignment agent lacquer. 2. The liquid crystal alignment agent paint according to item 1 of the scope of the patent application, wherein the polycondensation polymer is selected from the group consisting of polyamic acid, soluble polyimide, polyamidine, or a mixture of any two or more of the foregoing. Among them, the group consisting of -03. The liquid crystal alignment agent paint as described in item 1 of the scope of application for patent, wherein when the polycondensation polymer is selected from polyamic acid, soluble polyimide, polyimide In the case of one of the groups consisting of amidine or a mixture of any two or more of the foregoing, the polyorganosilsesquioxane is a polyorganosilsesquioxane having a functional unit containing a repeating unit represented by formula (1) Oxane. CH2CH2 —Ri〇—YR ^ Si () -Si _R2) n (〇-R4) m〇 (3n_m) / 2 (1) R3 (where R1, R2, and R3 are each independent carbon numbers from 1 to 18 linear, branched or cyclic saturated hydrocarbon groups, or linear, branched or cyclic unsaturated hydrocarbon groups having 2 to 6 carbon atoms, or carbon atoms of 10 or less Aryl; R4 is a linear or branched saturated hydrocarbon with 1 to 4 carbon atoms 33 593602 8804pif1, CH3CO—, CH2 = CHCO—, or CH2 = C (CH3) CO—; m is 〇 or 〇 · 〇5 ~ 2.0 number 値; when the number of n is 0, n is 0.1 ~ 2.0, and when m is not 〇 and is ~ 2.0, then the sum of n + m is 0.1 ~ 3.0; It is an alkene group having 1 to 8 carbon atoms, and one of the olefin groups or two of the non-adjacent two-CH2- can also be replaced with one 10- or one NH-; Y is Epoxy group, residue, hydroxyl group, amino group, propoxycannyl group, or isobutoxyacid group 'in addition' may be a functional group composed of two or more types) 4. If the scope of patent application The liquid crystal alignment agent paint according to item 3, wherein the polyorganosilsesquioxane is represented by formula (1) Is 0 and η ηι containing functional group is a repeating unit of poly silicones 0.1~2.0 silsesquioxane. 5. The liquid crystal alignment agent lacquer as described in item 3 of the scope of the patent application, wherein the polyorganic sand silsesquioxane system is not included in formula (1) and contains π of 0.05 to .2.0 and η of 0.05 to 2.0. Polyorganosilsesquioxane with repeating functional groups. 6. The liquid crystal alignment agent paint according to item 3 of the scope of patent application, wherein the polyorganosilsesquioxane is obtained through the reaction path shown in the following steps (a) to (d). Based polyorganosilsesquioxane, (a) organic trichlorosilane shown in formula (2) and organic- * chlorocholine shown in formula (3) in the amount of n-fold mole are mixed; (b) reacting the mixture obtained in (a) with at least one compound represented by formula (4) in m times the molar amount of organotrichlorosilane; (c) reacting the reaction product obtained in (b) with [( 3 + n_m) / 2] times the molar amount of organic trichlorosilane and react with it to obtain a polyorganic silicon having a weight 34 593602 8804pif1 complex unit with a number average molecular weight of 500 to 5000 as shown in formula (5). Silsesquioxane compound; (d) reacting the polyorganosilsesquioxane compound obtained in (c) with one or more compounds represented by formula (6). C1 I R1— Si—Cl (2) I Cl R3 I R2— Si—H (3) I Cl R4—OH (4) (5) CH2 = CH—R10—Y (6) (The meanings of R1 to R4, R1G, Y, m, and n in the formulas above are the same as those described in item 3 of the scope of patent application) 7. A type of liquid crystal The display element has an alignment film formed using the liquid crystal alignment agent varnish as described in any one of claims 1 to 6 of the patent application scope. 35 Date of amendment: April 29, 1993 593602 Description of invention patent (The format, order and boldface of this specification, please do not change it arbitrarily, ※ Please do not fill in the marked part) ※ Application number: V, ※ Application date: Λ 3. I. Name of the invention: (Chinese / English) Liquid crystal alignment agent varnish and liquid crystal display element A LIQUID CRYSTAL ORIENTATED SOLVENT VARNISH AND A LIQUID CRYSTAL DISPLAY ELEMENT, Applicant: (2 persons in total) Name or Name Chinese / English Co., Ltd./CHISSO CORPORATION 2. Representative of CHISSO PETROCHEMICAL CORPORATION · (Chinese / English) 1. Goto Shunji / GOTO, SHUNKICHI 2. Takeno Shupin / KASENO, SHUHEI Address of residence or business office : (Chinese / English) h Yueben 6-6 32, Nakanoshima 3-chome, Kita-ku, Osaka-shi, Osaka, Japan 2 · 32, Chiyoda-ku, Tokyo Marunouchi 2-chome 7 Ban 3-7- 3, Marunouchi 2-choume, Chiyoda, ku, Tokyo, Japan Nationality ·· (Chinese / English) 1 ~ 2, Japanese JP Participants and inventors: (Total 3 persons) Name: (Total 3 persons) Chinese / English) 1. Hirai Jiji / HIRAI, YOSHIHARU 2. Tanioka Satoshi / TANIOKA, SATOSHI 3. Murata Town Man / MURATA, SHIZUO Address: (Chinese / English)