TW200538827A - Method of evaluating polymer for liquid crystal alignment agent and liquid crystal alignment agent - Google Patents

Abstract

The present invention is to provide a method for determining the possibility of the occurrence of undue coating of a liquid crystal alignment agent before the coating and to provide a liquid crystal alignment agent without the occurrence of such undue coating by using the method. The dynamic light scattering of an organic high-molecular polymer solution is determined, and the maximum size of an aggregate of the organic high-molecular polymer component and the position of the peak top are obtained from the determined light scattering, whereby the printability of using the organic high-molecular polymer solution as a liquid crystal alignment agent is evaluated. In the evaluation method of the organic high-molecular polymer solution and in the determination of the of the dynamic light scattering of the organic high-molecular polymer solution, the determined fluid dynamics radius (RH) of the peak-top of the maximun peak of the aggregate derived form the organic high-molecular polymer component or the fluid dynamics radius (RH) of the maximun peak of the liqud alignment agent has an average value of 20 μm or less.

Description

200538827 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to an evaluation method for a liquid crystal aligning agent and a liquid crystal aligning agent which is less likely to cause poor coating during flexographic printing and coating using the evaluation method. [Prior art] Today, a liquid crystal alignment film made of an organic polymer or the like is formed on the surface of a substrate on which a transparent conductive film is mounted. As a substrate for a liquid crystal display element, two substrates are placed opposite each other, and A liquid crystal layer is formed in the gap to obtain a cell having a sandwich structure. A so-called TFT liquid crystal panel that operates the liquid crystal display element by TFT driving is generally replacing a current cathode ray tube monitor. As a liquid crystal display element, it is known to use a nematic liquid crystal having a positive dielectric anisotropy as a liquid crystal. The long axis of the liquid crystal molecules is continuously twisted by 90 degrees from one substrate to the other substrate. TN type liquid crystal display element of twisted nematic) type liquid crystal. Furthermore, STN (Super Twisted Nematic) type liquid crystal display elements and vertical alignment type liquid crystal display elements, which have higher contrast than TN type liquid crystal display elements and have a small viewing angle dependency, are being developed. This STN type liquid crystal display element uses a chiral reagent in which a nematic liquid crystal is mixed with an optically active substance as a liquid crystal, and uses a long axis of the liquid crystal molecules to continuously generate a birefringence between the substrates by 180 degrees or more. Furthermore, IPS (in-panel power distribution) type liquid crystal display elements and vertical alignment type liquid crystal display elements that are less dependent on viewing angles than TN type liquid crystal display elements are being developed. The liquid crystal alignment film has a function of controlling liquid crystal alignment in these liquid crystal display elements. A liquid crystal alignment agent containing a liquid crystal alignment film material composed of an organic polymer and a solvent is applied to a base plate by a method such as aniline printing, and is fired to It was obtained by forming a resin 200538827 film and giving it liquid crystal alignment energy. As the organic polymer used as the material for the liquid crystal alignment film, polyimide polymers such as polyamic acid described in Patent Documents 1 and 2 can be used, and polyamino acids described in Patent Document 3, such as Patent Documents. A mixture of the polyfluorenic acid and / or the fluorene imidized polymer described in 4, and the partially fluorinated imine polymer described in Patent Document 5, and the like. For the formation of the liquid crystal alignment film, an aniline printing method capable of forming a film with a small amount of a coating liquid is widely used. However, the organic high-molecule φ used as an alignment film material has a chemical structure composition distribution and molecular weight distribution in one polymer chain, and the distribution of two kinds of components will produce a small amount of flocculating components, which will be affected during aniline printing. Problems such as pinhole defects occur. The pinhole-like defects are caused by the alignment state of the liquid crystal molecules being different from the surroundings when the liquid crystal display element is driven, and are the cause of poor display such as bright spots. As a liquid crystal aligning agent that is unlikely to cause poor coating, a liquid crystal aligning agent containing an auxiliary component selected from homopolymers and copolymers of acrylates and methacrylates in Patent Document 6 can be disclosed. Also disclosed is a liquid crystal aligning agent composed of a mixture of polyamic acids derived from a specific component and reducing viscosity in a certain range in Patent Document 70. In addition, as a method for treating a substrate which is less likely to cause poor coating, there is a method disclosed in Patent Document 8 for cleaning the substrate before the formation of the alignment film with a city aqueous solution. In Patent Document 9, the surface of the substrate is cleaned and immersed in a storage solution. In order to maintain a clean state, in Patent Document 10, a method of irradiating ultraviolet rays on the surface of the bottom plate to improve the wettability of the liquid crystal aligning agent is adopted. In Patent Document 11, the intensity of the anions after the bottom plate is washed is controlled to a certain concentration or less. To prevent poor coating. In Patent Document 12, the method of applying a glow discharge treatment to the base plate to decompose impurities 200538827, thereby making it difficult to cause poor coating. However, as described in Patent Literature 6 and Patent Literature 7, in the design of an alignment film whose one of the main purposes is to prevent the occurrence of poor coating, it is difficult to consider the display characteristics of the liquid crystal panel as the original purpose of the alignment film. The selection range becomes narrower. In addition, as described in Patent Document 8, Patent Document 9, Patent Document 10, Patent Document 11 and Patent Document 12, processing of the substrate through the manufacturing process of the liquid crystal panel adds necessary steps, and as a result, the manufacturing of the liquid crystal panel is increased. This is not expected. Patent Document 1 JP 05-60565 Patent Document 2 Patent 2 8 9 3 6 7 Specification 1 Patent Document 3 Patent 260033 8 Specification Patent Document 4 JP 1 0-1 83 1 Patent Document 5 Japanese Patent Application Laid-Open No. 05-2 1 6044 Patent Literature 6 Japanese Patent Application Laid-open No. 6-2567 1 Japanese Patent Application Laid-Open No. 6 2002_ 8 824 Japanese Patent Publication No. 1 φ Patent Literature No. 8 Japanese Patent Laid-Open No. 6- 1 865 64 Patent Literature No. 9 Patent Publication No. 200 1 -300454 Patent Document 10 Japanese Unexamined Publication No. 2002-1 96337 Patent Document No. 11 Patent Unexamined Publication No. 2002-35 562 Patent Publication No. 12 Patent Publication No. 2003- 1 40 1 55 [Summary of the Invention] According to the above situation, An object of the present invention is to provide a liquid crystal aligning agent which can use various liquid crystal aligning materials and does not cause poor coating even if a special substrate surface treatment is unnecessary. 200538827 Another object of the present invention is to provide an evaluation of a liquid crystal aligning agent that may cause poor coating. Other objects and advantages of the present invention are described below. According to the present invention, the above objects and advantages of the present invention are as follows. The maximum size or peak position derived from the organic polymer is obtained by dynamic light scattering measurement of the molecular polymer solution. Based on this, the printable polymer solution when the organic polymer solution is used as an agent is evaluated. Evaluation method. According to the present invention, the above-mentioned objects and advantages of the present invention are as follows. The dynamic peak of the organic polymer polymer component derived from the organic polymer polymer component is measured at the peak of the hydrodynamic radius (Rh) or the fluid force of the maximum peak. Both are below 20 μm. However, when a plurality of components are contained, at least one of them satisfies the above-mentioned relationship. The liquid crystal aligning agent is composed of a polymer solution. Furthermore, according to the present invention, the above-mentioned object of the present invention has the following characteristics. The peak derived from the maximum peak of the organic polymer measured in the measurement of the organic polymer is measured by the hydrodynamic radius (RH) or the maximum peak ( Rh) has an average 値 of less than 20 μm, and its maximum peak [0.20 or less. However, under the condition that it contains a plurality of components, at least one of them satisfies the above-mentioned relationship, so that the liquid crystal aligning agent is composed of a polymer solution. The evaluation method of the present invention is characterized by the method of determining the orientation of the liquid crystal first.丨 became apparent. The first lies in the fact that it has dynamic light scattering and uses the condensation of polymer components as liquid crystal orientation to achieve organic. The second lies in the flat-bed polymer polymerization with the maximum radius of the polymer (Rh) in the state light scattering measurement. In this way, the Z_mean fraction of the hydrodynamic radius of the agglomerates of the agglomerates of the dynamic light scattering components of the third solution is completed in the case of molecular polymers. Scattering, and evaluate the printability of the liquid crystal aligning agent based on the average of the 'maximum hydrodynamic radius (Rh) of the largest agglomerates or the maximum hydrodynamic radius (Rh) of the maximum agglomeration at the prescribed concentration of the solution in the solution . Here, printability refers to a state where no pinhole-like defects are recognized during flexographic printing. Here, the mean value of the peak hydrodynamic radius (Rh) and the maximum hydrodynamic radius (Rh) of the largest peak are roughly the same when the Rh distribution is symmetrical, but they are different when they are asymmetrical. . Because pinhole defects are prone to occur when the size of the aggregate is large, in the present invention, a larger hydrodynamic radius (Rh) of φ is used as a specific parameter. In the polymer solution, concentration fluctuations occur due to the diffusion movement caused by the thermal movement of the polymer. In Dynamic Light Scattering (DLS), the fluctuation of the scattered light intensity obtained by injecting laser light into a polymer solution, that is, by calculating the self-time correlation function of the concentration fluctuation, the diffusion coefficient of the polymer can be determined. The diffusion coefficient in the finite concentration obtained here is based on the Einstein-Stokes formula and the hydrodynamic radius (Rh) in the finite concentration. The so-called hydrodynamic radius (Rh) corresponds to the radius when the width of a polymer chain is represented by an imaginary hard φ sphere in a solution with a limited concentration. In polymer solutions, due to the influence of molecular weight distribution, the reunion of molecular chains, the formation of network knots, etc., the diffusion coefficient obtained from the time-dependent function of concentration fluctuations, that is, the hydrodynamic radius (Rh) is difficult to specify with a unitary radius. Generally has a certain degree of distribution width. In order to obtain the diffusion coefficient obtained from the time correlation function of concentration fluctuations, that is, the distribution of the hydrodynamic radius (Rh), there are several analysis methods. For example, perform a cumulative number analysis on a polymer solution with a narrow diffusion coefficient distribution. In this method, a diffusion coefficient as an average chirp and a parameter representing the width of its distribution are obtained. On the other hand, in a system where the molecular chains are agglomerated with each other in a 200538827 solution, the histogram method and the CONTIN method are often used for analysis. Use the histogram method and the CONTIN method to obtain the diffusion coefficient, which is the z-mean fraction of the hydrodynamic radius (Rh) distribution. In general, the diffusion coefficient, the average 値 of the hydrodynamic radius (Rh), and the distribution shape change with the polymer concentration in the solution. The concentration when the concentration of the solution changes can be assumed to be the concentration change when the liquid crystal alignment agent as the product is printed on the substrate. In this way, the hydrodynamic radius (Rh) obtained in a certain concentration can be used as the polymer component generated in the printed film The condensate size is indirectly expressed by φ. When the concentration of the polymer solution for many alignment films is about 1% by weight or less, each molecular chain can be dissolved as one chain. However, as the concentration increases, because of poor solubility in the solvent of the polymer, agglomeration occurs between the molecular chains to form aggregates. In the worst case, tens of μχη aggregates are formed, and printability is extremely deteriorated, and pinhole-like defects are formed when an alignment film is printed on the substrate. Using the DLS measurement and the CONTIN analysis method, the 2-mean distribution of the hydrodynamic radius (RH) was obtained, and the φ agglomerate size and Z-average fraction 値 in the polymer solution for an oriented film were obtained. The dispersion of the hydrodynamic radius (RH) of the aggregate of the polymer component is reflected in the thickness dispersion of the orientation film printed on the base plate. It is found that the absence of the orientation film is related to the pinhole defects that occur. Therefore, by using DLS to measure the z-average distribution of the hydrodynamic radius (Rh), it is possible to evaluate and screen a polymer solution for an orientation agent at the raw material stage. The present invention is based on such knowledge. The polymer solution for an alignment film of the present invention is characterized by being a composition containing an organic polymer and a solvent. The solid content of the polymer is in the range of 1 to 10% by weight. Scattering measurement-10- 2005.38827, the peak of the hydrodynamic radius (Rh) or the average hydrodynamics of the maximum peak that represents the size of the hydrodynamic radius (Rh) of the agglomerate size in the orientation film resin solution at a specified concentration. The radius (Rh) is below 20 μηι, preferably below 15 μηΐ, more preferably below 10 μιη, and the 2_average fraction of the maximum peak is below 0.20, preferably below 0. 15 and more preferably below 0 · ΐ〇, containing a variety of polymer components In the case, at least one of them satisfies the above range. The evaluation method of the present invention is to measure the dynamic light scattering (DLS) of a polymer solution for an article and an oriented film, and to evaluate the orientation agent printing at a finite concentration by indicating the hydrodynamic radius (Rh) of a dissolution unit in the polymer solution for an oriented film. Pinhole defects at this time. In this way, firstly, it can minimize the decrease in yield caused by poor coating of the directional agent during coating on the substrate. Secondly, it can improve pinhole defects caused by the cluster size distribution of the polymer formed, and make the alignment film. Evaluation and screening of polymers are easy, and it is expected that the yield will be improved in the future, and it can be used very suitably in the production of expected liquid crystal display devices. [Embodiment] [Dynamic light scattering measurement device] φ The present invention will be described in detail below. In order to measure the diffusion coefficient obtained by fluctuating the scattered light intensity of the polymer solution for an orientation film, that is, a dynamic light scattering measurement device for the hydrodynamic radius (Rh), a light scattering device manufactured by ALV, Germany was used. The description of this device uses ALV / DLS / SLS-5022F (with Attenuator) as a direction finder, a He-Ne laser with a wavelength of 632.8nm and 22mW as the laser source, and a dual ion avalanche radiating diode (ALV-High QE APDx2) and beam splitter are used as scattered light detectors. ALV-5000 / EPP and ALV-60 1 0/1 60 are used for fast measurement as the correlation function analyzer. The control and analysis program uses ALV-5000E / WIN (ver.3). In addition, as a radium-11- 200538827 source, it is possible to use Ar laser (wavelength 4 8 8nm), solid-state semiconductor laser (yag 2 wave, 532nm) in scattered light detectors such as photomultiplier tubes, photodiodes, etc. Wait. [Composition for liquid crystal aligning agent] The liquid crystal aligning agent of the present invention is constituted by dissolving a polymer such as polyamic acid in a solvent. The polymer component of the present invention is preferably a polyfluorenic acid having a repeating unit represented by the above formula, a fluorenimide polymer having a repeating unit represented by the following formula (1-2), and a polymer having the following formula (1-1): A block copolymer of a fluorenic acid prepolymer # having a repeating unit and a fluorenimine prepolymer having a repeating unit represented by the following formula (1-2), and the like.

/ HOOC \ / COOH 冬 脑 〆 \ C0NH—Ql In the formula, P1 is a tetravalent organic group, and Q1 is a divalent organic group.

In the formula, P2 is a tetravalent organic group, and Q2 is a divalent organic group. They can be used alone or in combination of two or more. When two or more of them are used in combination, it is preferred to use a mixture of polyamidonic acid and amidine polymer. In the above formula (1-1), the polyfluorinated acid is a 'fluorinated polymer obtained by reacting a tetracarboxylic dianhydride and a diamine, which is obtained by dehydrating and closing the polyfluorinated acid. In addition, the fluorene imidization polymer does not need to dehydrate and close 100% of the repeating units, and the ratio of the repeating units having a fluorene imine ring in all the repeating units (hereinafter referred to as "fluorinated imidization rate") may be sufficient. Less than 100%. (Tetracarboxylic acid dianhydride) -12-200538827 Specific examples of the tetracarboxylic acid dianhydride used in the synthesis of polyamic acid are, for example, 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2 -Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3 -Dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4' · dicyclohexyltetracarboxylic acid Diacid anhydride, cis-3,7-dibutylcycloocta-1,5-diene-1,2,5,6-tetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride , 3,5,6-tricarbonyl-2-carboxynorbornane-2: 3,5: 6-dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic diacid • anhydride, 1,3,3 &, 4,5,91) -hexahydro-5 (tetrahydro-2,5-dioxo-3-furyl) -naphtha n, 2-c] -furan-1,3-dione, 1 , 3,3 &, 4,5,91) -hexahydro-5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -Petroleum [1,2-c] -furan -1,3-dione, 1,3,3 &, 4,5,91) -hexahydro-5-ethyl-5 ( Hydrogen-2,5-dioxo-3-furyl) -Petroleum [l, 2-c] -furan-1,3-dione, 1,3,3 &, 4,5,91} -hexahydro -7-methyl-5 (tetrahydro_2,5-dioxo-3-furyl) -petroleum [1,2, <]-furan-1,3-dione, 1,3,3 &, 4 , 5,91 ^ -hexahydro-7-ethyl-5 (tetrahydro-2,5-monooxy-3-furyl) -petroleum [l, 2-c] -furan-1,3-dione , 1,3,3 &, 4,5,91) -hexahydro-8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -petroleum [1,2, c] -Furan-1,3 · dione, φ1,3,3 &, 4,5,91) -hexahydro-8-ethyl-5 (tetrahydro-2,5-dioxo-3-furyl) -Petroleum [l, 2-c] · furan-1,3-dione, 1,3,3 &, 4,5,91) -hexahydro-5,8-dimethyl-5 (tetrahydro- 2,5 -dioxo-3_furanyl) -Petroleum [1,2-c] -furan-1,3--one, 5- (2,5 -dioxotetrahydrofuran) -3 -methyl-3 -Cyclohexene-1,2 · dicarboxylic acid anhydride, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic acid anhydride, 3-oxabicyclo [3.2. 1] Octane-2,4-dione-6-spiral · 3 ′ · (tetrahydrofuran-2 ′, 5, dione), alicyclic tetracarboxylic acid diacid anhydrides represented by the following formulae (I) and (II) ; 200538827

In the formula, R3 and R6 represent a divalent organic group having an aromatic ring, R4 and R5 represent a hydrogen atom or an alkyl group, and when a plurality of R4 and R5 are present, they may be the same or different. Aliphatic tetracarboxylic dianhydrides such as butane tetracarboxylic dianhydride; pyromellitic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3', 4, 4'-biphenylmethylenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4 '-Biphenyl ether tetracarboxylic dianhydride, 3,3', 4,4'-dimethylbiphenylsilane tetracarboxylic dianhydride, 3,3 ', 4,4'-tetraphenylsilane tetracarboxylic acid Dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) biphenylsulfide dianhydride, 4,4'-bis (3 , 4-dicarboxyphenoxy) biphenylarsuccinic anhydride, 4,4'-bis (3,4-dicarboxyphenoxy) biphenylpropanedioic anhydride, 3,3 ', 4,4'-perfluoro Isopropylene diterephthalic acid dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride, bis (terephthalate) phenylphosphine oxide dianhydride, P-phenylene- Bis (triphenylterephthalic acid) diacid anhydride, m-phenylene-bis (triphenylterephthalic acid) dianhydride, bis (triphenylterephthalic acid) -4,4'_diphenyl Methane dianhydride, ethylene glycol-bis (anhydrotrimellitic acid Ester), butanediol-bis (anhydrotrimellitic acid ester), 1,4-butanediol-bis (anhydrotrimellitic acid ester), 1,6-hexanediol-bis (anhydrotrimellitic acid) Esters), 1,8-octanediol-bis (anhydrotrimellitic acid esters), 2,2 · bis (4- • 14- 200538827 hydroxyphenyl) propane-bis (anhydrotrimellitic acid esters), used Carboxylic acid anhydrides such as aromatic tetracarboxylic acid anhydrides having a steroid skeleton represented by the following formula (1). These can be used alone or in combination of two or more. (4) Respectively aromatic four kinds of combinations

⑴

(2) -15- 200538827

/ CH3 \ ch3 (3)

⑷ Among them, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2, 3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxyl Cyclopentylacetic dianhydride, 5- (2,5-dioxotetrahydrofuran) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, cis-3,7-dibutyl ring Octa-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 3,5,6-tricarbonyl-2-carboxynorbornane_2: 3,5: 6-dianhydride, 1,3,3 &, 4,5,91) -hexahydro-5- (tetrahydro-2,5-dioxo-3-furyl) -petroleum [l, 2-c] · furan-1, 3-dione, 1,3,3 &, 4,5,91) -hexahydro-8-methyl-5 (tetrahydro-2,5-dioxo-3-furyl) -petroleum [l , 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b -hexahydro-5,8-dimethyl- 5- (tetrahydro-2,5 -dioxy -3-furan-16- 200538827 uranyl) -Petroleum [l, 2-c] -furan-1,3-dione, bicyclo [2.2.2] -oct-7-anthyl-2,3,5, 6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiral-3 '-(tetrahydrofuran-2,5'-monoone), the above formula Compound represented by (I) Among the compounds represented by the following formulae (5) to (7), among the compounds represented by the above formula (π), the compounds represented by the following formula (8), Dingyuan tetracarboxylic acid diacid, 1, pyromellitic acid di Anhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalene Tetracarboxylic dianhydride and the like are preferred from the viewpoint of finding good liquid crystal alignment and electrical characteristics, and they can be used alone or in combination of two or more.

⑻ -17- 200538827 (diamine) The diamine used in the synthesis of polyamic acid is, for example, P-phenylenediamine, m-phenylenediamine, 4,4, diaminodiphenylmethane, 4,4 , Diaminodiphenylethane, 4,4'-diaminodiphenylsulfide, 4,4, diaminodiphenylmaple, 2,2'-monomethyl-4,4,- Diaminobiphenyl, 3,3, -dimethyl-4,4, -diaminobiphenyl, 4,4, diaminobenzene (methyl) aniline, 4,4, -diaminobiphenyl Ether, 1,5-diaminocae, 3,3-dimethyl-4,4, -diaminobiphenyl, 5-amino-phenylaminophenyl) -1,3,3-trimethyl Dihydroindene, 6.aminoaminophenylphenyl 1,3,% trimethylindane, 3,4, -diaminodiphenyl ether, 3,3, -diaminodiphenylbenzene • Ketone, 3,4'-diaminobenzophenone, 4,4, -diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4 -(4 aminophenoxy) phenyl] pyrene, 1,4 · bis (4-aminophenoxy) benzene, 1,3 · bis (4-aminophenoxy) benzene, 1,3- Bis (3-amine Phenylphenoxy) benzene, 9,9-bis (cardioaminophenyl) -10-hydroanthracene, 2,7-diaminobenzylmethane, 9,9-bis (4-aminophenyl) Diphenylmethane, 4,4, -methylene-bis (2-chloroaniline), 2,2,5,5, -tetrachloro • 4,4, -diaminobiphenyl, 2,2, -Dichloro-4,4, -diamino-5,5, -dimethoxybiphenyl, 3,3, -dimethoxy-4,4, -diaminobiphenyl, phenylene isopropyl Pyridyl) bisaniline, 4,4,-(m-phenylene isopropylidene) bisaniline, 2,2, bis [4- (4-amino · 2-trifluoromethylphenoxy) phenyl] hexa Fluoropropane, 4,4, · diamino-2,2, -bis (trifluoromethyl) biphenyl, 4,4, -bis [(4 · amino-2-trifluoromethyl) phenoxy ] -Aromatic diamines such as octafluorobiphenyl; 1,1-m-xylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine Amine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, 4,4-diamino heptamethylene diamine, 丨, 4- diamino cyclohexane, isophor Ketone diamine, tetrahydrodicyclopentadiene diyl diamine, hexahydro-4,7- bridgemethylene dihydroindenylene dimethylene diamine, tricyclic [6.2.1.0 2,7]-~ 1-- Aliphatic and alicyclic carbons such as carbodimethyldiamine, 4,4'-methylenebis (cyclohexylamine) -18-200538827 family of pyridines, amines, and hydrazines > 3,5. 1,2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine 2,4-diaminopyrimidine, 5,6-diamino group_2 , 3_dicyanopyridine trap, 5,6_ -2,4-Dimethynamine, 2,4-diaminopyrene dimethylamine], 3, coke, 1,4-bis (3 -Aminopropyl), 2,4-diamino-6-isopropoxy ^ amino group 6 phenyl-1,3,5-triazine, 2,4-diamino-6 -Methyl-s-triazine, 2,4-yl-5-phenylthiazole, 2,6-diaminopurine, 5,6-diaminoacridine, 2,4-diamino-6 · Methoxy- ^, Hongsan acryl trap, 2,4 pyrimidine, 3,5-diamino-1,2,4-triazacene, 6,9-diamino_2_ethoxy 3,8 -Diamino-6-phenylphenanthridine, ι, 4 · diaminopyridine, pyridyl lactate amine_acrylic_3,6-diaminoacridine, bis (4-aminophenyl) aniline And other diamines having two primary amine groups and nitrogen atoms other than the primary amine group in the molecule; a monoamine organic chemical oxygen institute represented by the following formula (III); These diamines can be used alone or in combination of two or more.

η2ν4〇η2 ^ sH-〇— (HI) In the formula, R7 represents a hydrocarbon group having 1 to 12 carbon atoms. When there are multiple R7, they may be the same as or different from each other. P is an integer of 1 to 3, and q is 1 to 20. Integer. Of these, P-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 2,2, dimethyl-4,4, Aminobiphenyl, 1,5-diaminonaphthalene, 2,7-diaminobiphenylmethane, 4,4, -diaminodiphenyl ether, 2,2-bis [4- (4-_amine Phenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) biphenylmethane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoro Propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-(p-phenylene isopropylidene) diphenylamine, 4,4'-(m-phenylene diphenylene Isopropyl) diphenylamine, 1,4-cyclohexanediamine, 4,4 '-19-200538827 Methylenebis (cyclohexylamine), 1,4-bis (4-aminophenoxy) Benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6 -Diaminoacridine and the like are preferred. In the case where the liquid crystal aligning agent of the present invention has a pretilt angle expression, part or all of Q1 and Q2 in the above formula (1-1) is preferably the following formula ( Q-1) and at least one of the groups represented by the following formula (Q-2). That is, it is preferable to use a diamine (hereinafter referred to as a "specific diamine") having a group represented by the following formula (Q-1) or (Q-2), respectively. These can be used individually by 1 type or in combination of 2 or more types.

(Q-1) In the formula, X is a single bond, -〇_, · (: 〇 ·, _c〇〇 ·, _〇c〇_, _NHC〇_, -C〇NH-, -S- or Shenfang R1 is an alkyl group having i0 to 20 carbons, a monovalent organic group having an alicyclic skeleton of 4 to 40 carbons, or a monovalent organic group having a fluorine atom of 6 to 20 carbons.

(Q-2) In the formula, X is a single bond, -〇_, -C〇_, _C〇〇_, _〇C〇_, _NHC〇_, -CONH-, or arylene, and R2 has a carbon A bivalent organic group having a ring group skeleton of 4 to 40 in number. The alkyl group having 10 to 20 carbon atoms represented by R1 in the above formula (Q-1) is, for example, n-decyl, n-dodecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl , N-eicosyl, etc. Further, as a monovalent or -20-200538827 divalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms represented by R1 in the above formula (Q-1) and R2 in the above formula (Q-2), for example, Cyclobutane, cyclopentane, cyclohexane, cyclodecane and other groups derived from alkane having an alicyclic skeleton; cholesterol, cholestanol and other groups having a steroid skeleton; norbornene , Adamantane and other groups having a bridged alicyclic skeleton. Among these, a group that resides in a steroid skeleton is particularly preferable. The organic group having an alicyclic skeleton is a halogen atom, preferably a fluorine atom and a fluoroalkyl group, and preferably a group substituted with a trifluoromethyl group. Further, as the monovalent organic group having a fluorine atom having 6 to 20 carbon atoms represented by R1 in the above formula (Q-1), for example, a straight group having 6 or more carbon atoms such as n-hexyl, n-octyl, and n-decyl Alkyl groups; cyclohexyl, cyclooctyl and other alicyclic hydrocarbon groups having 6 or more φ carbon; organic groups such as phenyl and biphenyls having aromatic carbons of 6 or more, in which part of their hydrogen atoms or All groups substituted with a fluorine atom or a fluoroalkyl group such as a trifluoromethyl group. In addition, X in the above formula (Q-1) and (Q-2) is a single bond, · 〇-, -C〇-, -C〇〇-, -〇C〇-, -NHC〇-, -CONH-, -S- or arylene. Examples of the arylene group include phenylene, benzyl, biphenyl, and naphthyl. Among these, groups represented by -0-, -COO-, and -OCO- are particularly preferred. Specific examples of the diamine having a group represented by the above formula (Q-1) are dodecyloxy-2,4-diaminobenzene, pentadecyl-2,4-diaminobenzene, hexadecyl As the alkoxy-2,4-diaminobenzene and heptadecoxy-2,4-diaminobenzene, compounds represented by the following formulae (9) to (14) can be mentioned as preferable examples.

-21- 200538827 CH〇

(10) (11) Ref.

, Ch3 (12) coo

-ooc

V cf3 H2N —nh2 -22- (13) (14) 200538827

A specific example of the diamine having a group represented by the formula (Q-2) is preferably

(15)

(16) -23- 200538827

Among these, compounds represented by the above formulae (9), (10), (1 3), (1 4), and (1 5) are particularly preferable. The proportion of specific diamines used relative to the total amount of diamines varies according to the size of the pretilt angle found, but it is preferably 0 to 5 mol% for TN and S TN liquid crystal display elements, and for vertical alignment liquid crystals. The display element is preferably 5 to 100 mole%. (Synthesis of polyamic acid) The use ratio of tetracarboxylic dianhydride and diamine provided in the synthesis reaction of polyamic acid is that the ratio of the tetracarboxylic dianhydride to the equivalent of 1 equivalent of the diamine amine group is The acid anhydride group is preferably 0.2 to 2 equivalents, and more preferably 0.3 to 1.2 equivalents. The synthesis reaction of the polyamic acid is preferably performed in an organic solvent at a temperature of -20 ° C to 150 ° C, and more preferably at a temperature of 0 to 100 ° C. Here, the organic solvent is a solvent capable of dissolving the synthesized polyamino acid, and is not particularly limited, and examples thereof include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, and N, N-dimethyl Aprotic polar solvents such as formamidine, dimethylmethane, 7-butyrolactone, tetramethylurea, and hexamethylphosphonium amine; m-toluene, xylene fluorene, phenol, halogenated phenol, etc. Department of solvents. Moreover, the amount of the organic solvent (α) -24-200538827 is preferably the total amount (/ 3) of tetracarboxylic dianhydride and diamine compound, relative to the total amount of the reaction solution (α + / 3). Such an amount is 1 to 30% by weight. The above organic solvents can be used in combination with alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like as poor solvents of the polyamic acid within a range in which the generated polyamic acid does not precipitate. Specific examples of the poor solvent include methanol, ethanol, isopropanol, cyclohexanol, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethylene glycol, propylene glycol, and 1,4- Butanediol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactic acid, butyl lactic acid, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexyl alcohol, methyl acetate, ethyl acetate, butyl acetate , Methylmethoxypropionate, ethylethoxypropionate, diethyloxalic acid, diethylmalonic acid, diethyl ether, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol-n Propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl ether Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 2-dichloroethane, 1, 4 -Dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, etc. The polyamic acid was dissolved as described above to obtain a reaction solution. Next, the reaction solution was added to a large amount of a poor solvent to obtain a precipitate, and the precipitate was dried under reduced pressure to obtain polyamic acid. Then, the polyamic acid can be purified again by dissolving the polyamino acid in an organic solvent and then subjecting the polyamino acid to precipitation in a poor solvent one or more times. (Synthesis of fluorinated imidized polymer) Fluorinated imidized polymer can be synthesized by dehydrating and closing a part or all of the above-mentioned polymerase amino acid. The hydrazone imidization rate is preferably 40 mol% or more, and particularly preferably -25-200538827 70 mol% or more. By using a polymer having an imidization ratio of 40 mol% or more, it is possible to obtain such a liquid crystal aligning agent ', which can form a liquid crystal aligning film having a short afterimage blanking time. The dehydration ring closure of the polyamic acid is (i) a method of heating the polyamic acid 'or (ii) the polyamic acid is dissolved in an organic solvent, and a dehydrating agent and a dehydration ring-closing catalyst are added to the solution as needed. Method of heating. The reaction temperature of the aforementioned method of heating polyamic acid is preferably 50 to 200 ° C, and more preferably 60 to 170 ° C. If the reaction temperature is lower than 5 ° C, the dehydration ring-closing reaction proceeds without sufficient B content. If the reaction temperature exceeds 200 ° C, the molecular weight of the fluorene imidized polymer obtained is low. On the other hand, the polyamine in (ii) In the method of adding a dehydrating agent and a dehydrating ring-closing catalyst to an acid solution, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent to be used depends on the desired rate of imidization. Regarding the adjustment, the repeating unit with respect to 1 mole of polyamic acid is preferably from 0.001 to 20 moles. Further, as the dehydration ring-closing catalyst, for example, pyridine, trimethylpyridine, dimethylpyridine, and triethylamine can be used. Tertiary amines such as I. However, it is not limited to this. The amount of dehydration ring-closing catalyst used is preferably 0.01 to 10 moles relative to the use of 1 mole dehydrating agent. The use of the above-mentioned dehydrating agent and dehydration ring-closure agent can be increased by using a large amount率 Imidation rate. As the organic solvent used in the dehydration ring-closing reaction, the same examples as the organic solvents used in the synthesis of polyphosphonic acid. The reaction temperature of the dehydration ring-closing reaction is preferably 0 to 180 ° C, more The temperature is selected from 10 to 150 ° C. The reaction solution thus obtained is subjected to the same operation as the method for purifying polyamic acid, whereby the obtained fluorene imidized polymer can be purified. (End-modified polymerization) The polymer used in the present invention may also be a terminally modified polymer having a molecular weight adjustment. By using the terminally modified polymer, the effect of the present invention is not impaired, and the liquid crystal aligning agent can be improved. Coating properties, etc. Such a terminally modified polymer can be synthesized by adding an acid monoanhydride, a monoamine compound, a monoisocyanate compound, and the like to a reaction system when synthesizing polyamino acid. Here, the acid monoanhydride is, for example, Malay. Acid anhydride, terephthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, n-hexadecylsuccinic anhydride, etc. In addition, monoamines are aniline, cyclohexylamine, etc. , Φ n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecane Alkylamine, n-pentadecane , N-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-eicosylamine, etc. In addition, the monoisocyanate compound is, for example, phenyl isocyanate, naphthyl isocyanate, etc. (shear viscosity of polymer) When the polymer obtained as described above is measured at a solid content of 4% by weight, its shear viscosity 値 is preferably in the range of 10 to 100 mPa * s, and more preferably • 20 to 60 m P a · s. Shear If the cutting viscosity is too low, it is difficult to hold the liquid on the substrate when applying to the substrate because the liquidity of the liquid crystal aligning agent is too high. If the shear viscosity is too high, the cohesiveness of the liquid crystal aligning agent is increased, and needles are likely to be generated during coating. Pore-like defects, etc. The shear viscosity of the present invention uses N-methyl-2-pyrrolidone as a solvent with a solid content of 4.0% by weight in a polymer-dissolved solution, and is manufactured by Toki Sangyo Co., Ltd. Viscometer RE 100RL. (Block copolymer) In the case of using the block copolymer described above, the polymer component used in the present invention is prepared by synthesizing amidine prepolymer having an amine group or an acid anhydride group at the terminal. 27-200538827 and an acid anhydride at the terminal. A block copolymer can be obtained by combining a sulfonated imidized prepolymer with an amino group or an amine group and combining an amine group and an acid anhydride group at the end of each prepolymer. The method for synthesizing the fluorenic acid prepolymer is the same as the method for synthesizing the polyfluorinated acid. The method for synthesizing the fluorenimine prepolymer is the same as the method for synthesizing the fluorinated polymer. The selection of the functional group at the terminal can be adjusted in accordance with the amounts of tetracarboxylic dianhydride and diamine during the synthesis of the polyamic acid. (Liquid crystal aligning agent) The liquid crystal aligning agent of the present invention is constituted by dissolving the polymer component contained in the solvent. As the solvent, an organic solvent is used. The temperature when preparing the liquid crystal aligning agent of the present invention is preferably 0 ° C to 200 ° C, and more preferably 20 ° C to 60 ° C. As the organic solvent constituting the liquid crystal aligning agent of the present invention, the same solvent can be used as an example in the polyamine synthesis reaction, and the poor solvent used as an example in combination during the polyamine synthesis reaction can also be appropriately selected. To use in combination. An organic solvent selected from at least one of γ-butyrolactone and / or N-methyl-2-pyrrolidone and a poor solvent butyl cellosolve are preferred. 'The two are particularly preferably used in combination. When 醯 φ imidized polymer and / or block copolymer is used as the polymer component, the total content of γ-butyrolactone and / or N-methyl-2-pyrrolidone and butyl cellosolve relative to the total The solvent is preferably 80% by weight or more, and particularly preferably 85% by weight or more. When the two are used in combination, the mixing ratio is the total of γ-butyrolactone and / or N-methylpyrrolidone relative to γ-butyrolactone and / or N-methylpyrrolidone and butyl cellosolve. The amount is preferably 50 to 100% by weight, and particularly preferably 80 to 100% by weight. When γ-butyrolactone and N-methylpyrrolidone are used in combination, the mixing ratio is such that N-methyl is relative to the total amount of the mixed solvent of γ-butyrolactone and N-methylpyrrolidone. The 2-pyrrolidinone is preferably -28-200538827 in an amount of 0.1 to 50% by weight, and more preferably 0.1 to 30% by weight. When using polyamic acid as a polymer component, the total content of γ-butyrolactone and / or N-methyl-2-pyrrolidone and butyl cellosolve is also preferably 80% by weight or more with respect to the entire solvent, and particularly preferably 85% by weight or more. When the two are used in combination, the mixing ratio of γ-butyrolactone and / or N-methylpyrrolidone to γ-butyrolactone and / or N-methylpyrrolidone and butyl cellosolve The total amount is preferably 30 to 80% by weight, and particularly preferably 30 to 50% by weight. When γ-butyrolactone and N-methylpyrrolidone are used in combination, the mixing ratio of φ is such that N-methyl- is relative to the total amount of the mixed solvent of γ-butyrolactone and N-methylpyrrolidone. The 2-pyrrolidone is preferably 30 to 100% by weight, and more preferably 50 to 100% by weight. The solid content of the liquid crystal aligning agent of the present invention can be selected in consideration of viscosity, volatility, and the like, but is in a range of 1 to 7 wt%, preferably 2 to 7 wt%. That is, the liquid crystal aligning agent of the present invention is coated on the substrate surface to form a coating film made of a liquid crystal aligning film. However, when the solid content is less than 1% by weight, the film thickness of the coating film is too small to obtain a good liquid crystal. Orientation film. When the solid content exceeds 7% by weight, the film thickness of the coating film is too large to obtain a good liquid crystal alignment film. In addition, the viscosity of the liquid crystal alignment agent increases, coating characteristics become poor, and the liquid crystal alignment becomes poor. The cohesiveness of the agent is increased, and pinhole-like defects are liable to occur. (Adhesion aid) The liquid crystal aligning agent of the present invention may contain a functional silane-containing compound or an epoxy-containing compound from the viewpoint of improving the adhesion to the surface of the substrate. The functional silane-containing compound is, for example, 3-aminopropyltrimethoxylithium, 3-aminopropyltriethoxy sand, 2-aminodimethoxytrimethoxylithium, or 2-amino Propyltriethoxysilane, N- (2 · aminoethyl) _3_aminopropyl-29- 200538827 trimethoxysilane, N- (2-aminoethyl) -3-aminopropyl Methyldimethoxysilane, 3 -fluorenylpropyltrimethoxysilane, 3 -fluorenylpropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazine Heterodecane, ίο-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-tri Ethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-φaminopropyltriethoxy Silane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxoethylene) -3-aminopropyl Trimethoxy Silane, N - bis (ethylene-oxo) -3 - aminopropyl alkoxy silane-triethylammonium and the like. Further, the epoxy group-containing compound is preferably, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, or polypropylene glycol diglycidyl. Propyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 1 , 3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4, -diaminodiphenylmethane and the like. The mixing ratio of these functional silane-containing compounds and epoxy-containing compounds is preferably 40 parts by weight or less, and more preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the polymer. (Liquid crystal display element) A liquid crystal display element obtained by using the liquid crystal aligning agent of the present invention can be produced, for example, by the following method. (1) On one side of a base plate on which a patterned transparent conductive film is mounted, a liquid crystal aligning agent is applied by an aniline printing method, and then a coating film is formed by heating the coated surface. The bottom plate here can use glass such as float glass, soda lime glass; polyethylene terephthalate, polybutylene terephthalate, polyether, polycarbonate, etc. made of plastic Transparent bottom plate. As the transparent conductive film mounted on one side of the bottom plate, for example, a NESA film (registered trademark of the United States PPG Corporation) made of tin oxide (S η 0 2), and ITO made of indium oxide-tin oxide (In2〇3-SnCh) can be used. Film, etc. When these transparent conductive films are patterned, for example, a photolithography method and a pre-lithographic mask method can be used. When the liquid crystal orientation agent is applied, in order to improve the adhesion between the surface of the substrate and the transparent conductive film and the coating film, the surface of the substrate can be previously coated with a compound containing a functional silane, a compound containing a functional titanium, and the like. The heating temperature after the liquid crystal aligning agent is applied is preferably 80 to 300 ° C, and more preferably 120 to 250 ° C. The liquid crystal aligning agent of the present invention containing a polyamic acid forms a coating film obtained from an alignment film by removing an organic solvent after coating. However, dehydration and ring closure can be performed by heating again to form a more imidized coating film. The film thickness of the formed coating film is preferably 0.001 to 1 / zm, and more preferably 0.005 to 0.5 / zm. 0 (2) A coating film surface formed by rubbing a roll shaft wound with a cloth made of fibers such as nylon, rayon, and cotton in a certain direction. According to this, the alignment energy of the liquid crystal molecules is imparted to the coating film, thereby producing a liquid crystal alignment film. Further, the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention is, for example, as shown in Japanese Patent Application Laid-Open No. 6-222 3 66 and Japanese Patent Application Laid-Open No. 6-28 1 937, in which the pretilt angle is changed by partially irradiating ultraviolet rays. Treatment, or forming a partial protective film on the surface of the liquid crystal alignment film subjected to rubbing treatment as shown in JP-A No. 5-1 0 7 5 4 4 and removing the protective film after rubbing treatment in a direction different from the previous rubbing treatment The process of changing the liquid crystal alignment film liquid-31-200538827 crystal orientation energy like this can improve the visual field characteristics of the liquid crystal display element. (3) Make two substrates forming the liquid crystal alignment film as described above, and place the two substrates facing each other through a gap (box gap) in such a manner that the rubbing directions of the liquid crystal alignment films are perpendicular or antiparallel to each other, and use a sealant to adhere The peripheral part of the two base plates is filled with liquid crystal in the cell gap divided by the bottom surface and the sealant, and the filled holes are sealed to form a liquid crystal cell. Next, a polarizer is adhered on the outer surface of the liquid crystal cell, that is, on the other surface of each bottom plate constituting the liquid crystal cell, in such a manner that the polarization direction of the liquid crystal alignment film formed on the one surface of the bottom plate is the same or perpendicular to the rubbing direction of the liquid crystal alignment film. Thus, a liquid crystal display element is obtained. Here, as the sealant, for example, a hardener and an epoxy resin containing alumina balls as a positioning device can be used. Examples of the liquid crystal include a nematic liquid crystal and a smectic liquid crystal. Among these, a nematic liquid crystal is preferably used, such as a Schiff-type city liquid crystal, an azo oxide liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, and a biphenyl liquid. Cyclohexane-based liquid crystals, pyrimidine-based liquid crystals, dioxane-based liquid crystals, dicyclooctane-based liquid crystals, cubic courtyard-type liquid crystals, and the like. In addition, these liquid crystals can be added with cholesteric liquid crystals such as cholestyryl chloride, cholesteryl nonanoate, and cholesteric carbonate, and trade names such as "C-15" and "CB-15" (manufactured by Miruko Corporation). ) Use of chiral reagents sold. Furthermore, a ferroelectric liquid crystal such as p-decoxybenzylidene-p_amino-2 -methylbutylstyrene can also be used. Moreover, as the polarizers adhered on the outer surface of the liquid crystal cell, for example, while stretching the oriented polyvinyl alcohol, a polarizing film called a rubidium film that absorbs iodine is sandwiched by a protective film of cellulose acetate, or The diaphragm is a polarizer made by itself. [Examples] The following is a more specific description of the present invention through examples, but the present invention is not limited to these examples. The measurement and evaluation methods of the examples and comparative examples were performed as follows. [Hydrodynamic radius (Rh) of agglomerates] The polymers obtained in the following Synthesis Examples 1 to 2 and Comparative Synthesis Example 1 were formulated into a solution at a predetermined concentration of 7.3% by weight, and then thoroughly stirred to obtain a homogeneous solution. The mixing ratio of the solvent used herein was r-butyrolactone / N -methyl-2-mouth ratio. Pyrrolidone = 81.3 / 11.4 (% by weight). The resin solution was filtered using a screening program (for polar solvents) with a pore size of 0 to 45 μm, washed in a methanol reflux cleaner for φ 2 hours or more, and placed in a quartz glass box with a diameter of 20 mm. Because the viscosity of the solution depends on the temperature, it is necessary to precisely control the dynamic light scattering measurement at 2 3 · 0 0 ± 0 · 〇 2 ° C. Through the CONTIN analysis, a z-average distribution of the diffusion coefficient, ie, the hydrodynamic radius (Rh), is obtained. From the obtained distribution chart, the peak crest of the largest peak was obtained. [Printability test of liquid crystal aligning agent] Using a liquid crystal aligning film printer (manufactured by Nippon Photo Printing Press Co., Ltd.), a liquid crystal aligning agent was coated on the transparent electrode surface φ of a glass substrate on which a transparent electrode was mounted made of ITO film. After drying on a hot plate at 80 ° C for 1 minute, it was dried on a hot plate at 180 ° C for 20 minutes to form a coating with an average film thickness of 600 angstroms. Under a microscope at 20 times, the presence or absence of printing unevenness and pinhole-like defects on the base plate was observed to determine whether the printability was good or not. [Orientation of liquid crystal display element] Observe whether a liquid crystal display element has bright spots when a voltage is applied or released under a polarizing microscope, and it is judged as "good" if there are no bright spots. Synthesis Example 1 2,3,5-tricarboxycyclopentylacetic acid dianhydride, which is a tetracarboxylic dianhydride, 33-200538827, 219.69 g (0.98 mole), and p-phenylenediamine, which is a diamine compound. 6.52 g (0.985 mole) and 7.81 g (0.015 mole) of the diamine represented by the above formula (9) were dissolved in 4500 g of N-methyl-2-pyrrolidone and reacted at 60 ° C for 6 hours. Next, the reaction solution was added to a large excess of methanol to precipitate a reaction product. Then, it was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain 280 g of polyamic acid having a shear viscosity of 13 mPa.s and a solid content of 4% by weight. 30 g of the obtained polyamic acid was dissolved in 570 g of N-methyl-2-pyrrolidone, 23.4 g of pyridine and 18.1 g of acetic anhydride were added, and the φ ring was closed by dehydration at 110 ° C for 4 hours, and precipitation was performed in the same manner as above. , Washing, and decompression to obtain 17.8 g of polyfluorene imine with a solid content of 4% by weight and a shear viscosity of 23 mPa.s (referred to as "polyfluorene (A-1)). Synthesis Example 2 As a tetracarboxylic acid 2,3,5-tricarboxycyclopentylacetic acid dianhydride 22 of diacid anhydride 1.93 g (0.99 mol), p-phenylenediamine 1 06.52 g (0.985 mol) as a diamine compound, according to the above formula ( 9) 7.81 g (0.015 mol) of the diamine shown is dissolved in 4500 g of N-methyl-2-pyrrolidone and reacted at 60 ° C for 6 φ hours. Next, the reaction solution is added to a large excess of methanol to precipitate the reaction product. Then, it was washed with methanol and dried under reduced pressure at 40 ° C for 15 hours to obtain 290 g of polyamic acid having a solid content of 4% by weight and a shear viscosity of 34 mPa.s. 30 g of the obtained polyamic acid was dissolved in 570 g of N -Methyl-2-pyrrolidone was added with 2 · 4 g of pyridine and 18.1 g of acetic anhydride, and the mixture was dehydrated and closed at 110 ° C for 4 hours. Precipitation, washing, and decompression were performed in the same manner to obtain 18.3 g of polyfluorene imine (referred to as "polyfluorene (A-2)) having a shear viscosity of 56 mPa.s and a solid content of 4% by weight. Comparative Synthesis Example 1 -34-200538827 Tetracarboxylic dianhydride 2,3,5-tricarboxycyclopentylacetic acid dianhydride 224.1 7 g (1.0 mol) as diamine compound 10.65 g (0.985 mole) of diamine and 7.81 g (0.015 mole) of diamine represented by the above formula (9) were dissolved in 4500 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. 6 hours. Next, the reaction solution was added to a large excess of methanol to precipitate a reaction product. Then, it was washed with methanol and dried under reduced pressure at 4 ° C. for 15 hours to obtain 260 g of a polyamic acid having a shear viscosity of 52 mpa.s at a solid content of 4% by weight. 30 g of the obtained polyamic acid was dissolved in 570 g of N- To methyl-2-pyrrolidine φ ketone, 23.4 g of pyridine and 18.1 g of acetic anhydride were added, and the mixture was dehydrated and closed at 110 ° C for 4 hours. Precipitation, washing, and decompression were performed in the same manner as above to obtain a solid content of 4 weight. 19.0 g of polyfluorene imine with a shear viscosity of 7 4 m P a · s (referred to as “polyimide (A-3)). Examples were obtained in Synthesis Examples 1 to 2 and Comparative Synthesis Example 1. The z-average distribution of the hydrodynamic radius (Rh) of the fluorene imidized polymer. The results obtained are shown in Figures 1 to 3. In the figure, the distribution peak with the smallest hydrodynamic radius 値 considers 0 to be from Single molecules, such a large distribution is thought to come from agglomerates. The peak of the largest peak is shown in Table 1. -35- 200538827 Table 1 Synthesis Example 醯 The peak of the largest peak of the hydrodynamic radius (Rh) of the imidized polymer値 // zm 1 A-1 4 2 A-2 10 3 A-3 30 The fluorinated polymers obtained in Synthesis Examples 1 to 2 and Comparative Synthesis Example 1 are shown in Table 2 below. The weight ratio shown is r-butyrolactone / N-methylpyrrolidone / butyl cellosolve = 77/1 3/10 (wt%) dissolved in a mixed solvent, and the solid content Φ (TSC) of the solution is adjusted to 8 % By weight, 5% by weight, 4% by weight, 3% by weight, and 1% by weight. These solutions were separately filtered using a screening program with a pore size of 1 # m to prepare the liquid crystal aligning agent of the invention. Each of the obtained liquid crystal aligning agents was printed The results are shown in Table 2. A pair of coating film-formed substrates obtained in the printability experiment were made using a friction machine wound with rayon cloth. The number of revolutions of the roller was 400 rpm and the stage The rubbing treatment was performed under the conditions of a movement speed of 3 cm / s and a hair length of 0.4 mm. After immersing the above-mentioned base plate in ultrapure water for 1 minute, drying on a hot plate at 100 ° C for 5 minutes, and obtaining a pair of φ clips After the periphery of the substrate holding the liquid crystal is coated with an alumina ball epoxy adhesive with a diameter of 5.5 // m, a pair of substrates holding the liquid crystal is laminated with the liquid crystal alignment films facing each other to harden the adhesive. The liquid crystal injection port will be a nematic liquid crystal MLC-622 1) After filling between a pair of base plates, the liquid crystal injection port is sealed with an acrylic light hardening adhesive, and polarizers are coated on both sides of the base plate to produce a liquid crystal display element. The obtained liquid crystal display element is confirmed. The results are shown in Table 2. -36- 200538827

Table 2 Example Polymer composition mixing ratio (% by weight) TSC (%) Printability Orientation 1 A-1 100 5 Good Good 2 A-2 100 5 Good Good 3 A-1 100 4 Good Good 4 A-2 100 4 Good Good 5 A-1 100 3 Good Good 6 A-2 100 3 Good Good 7 A-1 / A-2 80/20 5 Good Good 8 A-1 / A-2 80/20 4 Good Good 9 A- 1 / A-2 80/20 3 Good Good 10 A-1 / A-3 80/20 5 Good Good 11 A-1 / A-3 80/20 4 Good Good 12 A-1 / A-3 80/20 3 Good Good Comparative Example Polymer composition mixing ratio (% by weight) TSC (%) Printability Orientation 1 A-1 100 8 Pinholes with bright spots 2 A-2 100 8 Pinholes with bright spots 3 A-1 100 1 No coating — 4 A-2 100 1 No coating — 5 A-3 100 8 Pinholes with bright spots 6 A-3 100 5 Pinholes with bright spots 7 A-3 100 4 Pinholes with bright spots 8 A-3 100 1 Cannot be coated — 9 A-1 / A-2 80/20 8 Pinholes with bright spots 10 A-1 / A-2 80/20 1 Cannot be coated-11 A-1 / A-3 80/20 8 With pinholes and bright spots 12 A-1 / A-3 80/20 1 Cannot be applied — -37- 200538827 Using the evaluation method of the present invention ' The average hydrodynamic radius distribution of the film aggregate material (Rh) with a polymer solution of Z-. When using a directing agent with a small peak-to-peak hydrodynamic radius (Rh) of the largest peak of the condensate or an average hydrodynamic radius (Rh) of the largest peak and a small Z-average fraction of the largest peak, because of good printability, liquid crystal panels are produced during production. The yield is good because the film quality of the alignment film is uniform and the display quality of the liquid crystal panel is good. The liquid crystal display element having the liquid crystal alignment film of the present invention can suitably use TN-type, STN-type, and VA-type liquid crystal display elements, and can also suitably use SH (super-isotropic) type, IPS by selecting the liquid φ crystal used. (Distribution in the panel) type, ferroelectric and antiferroelectric liquid crystal display elements, etc. Further, the liquid crystal display element having the liquid crystal alignment film of the present invention can be effectively used in various devices, such as desktop computers, watches, desktop clocks, mobile phones, coefficient display boards, word processors, personal computers, liquid crystal televisions, Used in display devices such as liquid crystal digital projectors. [Schematic description] Figure 1 shows the results of dynamic light scattering measurement of polymer A-1. φ Figure 2 shows the results of dynamic light scattering measurement of polymer A-2. Figure 3 shows the results of dynamic light scattering measurement of polymer A-3. -38-

Claims (1)

200538827 10. Application Patent Scope · 1 · An evaluation method of organic polymer polymer solution, characterized by measuring the dynamic light scattering of the organic polymer polymer solution, and obtaining the organic polymer originating from the measured dynamic light scattering. The maximum size or the position of the peaks of the aggregate of the polymer component was evaluated based on the printability when the organic polymer solution was used as a liquid crystal aligning agent. 2. A liquid crystal aligning agent composed of an organic polymer polymer solution having a solid content in the range of 2 to 7% by weight, characterized in that the liquid crystal aligning agent is derived from the organic polymer measured in a dynamic light scattering measurement of the organic polymer polymer solution. The peak of the largest peak of the aggregate of the polymer component, the hydrodynamic radius (Rh), or the average of the largest peak of the hydrodynamic radius (Rh), is 20 μm or less, but when the organic polymer contains a plurality of components At least one of them satisfies the above relationship. 3. A liquid crystal aligning agent composed of an organic polymer polymer solution, characterized in that the maximum value of the aggregates derived from the organic polymer polymer component measured in the dynamic light scattering measurement of the organic polymer polymer solution is The peak 値 average 値 of the hydrodynamic radius (Rh) or the maximum 的 mechanical radius (Rh) of the largest peak is below 20 μπι, and the Z_ average fraction of its maximum peak is below 0.20, but it is polymerized in organic polymers containing multiple components. In the case of a substance, at least one of them satisfies the above relationship. 4. The liquid crystal aligning agent according to item 2 or 3 of the scope of patent application, wherein the organic high molecular polymer has at least one kind of repeating unit selected from the repeating unit represented by the following formula (1-1) and the repeating unit represented by the following formula (1-2) Unit of polymer, also contains solvents: HOOCn ^ ΗΝΟ (: // COOH ^ CONH— Q1 (Μ) In the formula, P1 is a tetravalent organic group, and Q1 is a divalent organic group; -39- 200538827 (1-2) In the formula, P2 is a tetravalent organic group, and Q2 is a divalent organic group 5 · 70% by weight or more of the organic high molecular polymer in the liquid as in any one of claims 2 to 4 of the patent application scope The shear viscosity at% is usually in the range of 20 ~ 60mPa * s. 6 · The liquid organic polymer as described in any one of claims 2 to 5 in the liquid contains a total of 90 moles of 1,3,5-tricarboxycyclopentylacetic dianhydride and ρ · benzene. Fluorene imidized polymer. Crystal directing agent with a solid content of 4 wt. Crystal directing agent with 1:% or more repeating monoamine of diamine -40-