TW201237068A - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element, and polyamic acid and polyimide for producing thereof - Google Patents

Abstract

The present invention provides a liquid crystal alignment agent for obtaining a liquid crystal display element having excellent residual image characteristics. The liquid crystal alignment agent comprises at least one polymer selected from the group consisting of a polyamic acid produced by reacting a tetracarboxylic acid dianhydride with a diamine and an imidized polymer thereof. The tetracarboxylic acid dianhydride comprises aromatic tetracarboxylic acid dianhydrides. The diamine comprises a compound represented by the following formula (1).

Description

201237068 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a liquid crystal alignment member and a substrate for use in the above-described manufacturing. [Prior Art] In order to cause a liquid crystal to be applied to a film in a liquid crystal display element. As a material of the liquid crystal alignment film, it has various properties such as liquid crystal compatibility and affinity with liquid crystal, and heat resistance, mechanical strength, and polyimide. ...usually using polyacrylic acid, it is necessary to obtain a sufficiency such as the following: 缓 缓 施加 施加 施加 施加 施加 施加 施加 施加 施加 缓 缓 缓 缓 缓 缓 缓 缓 缓 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了In order to improve the above-described afterimage characteristics, the liquid crystal alignment film has at least one of a low charge and a DC voltage. 1 P is a kind of day-to-day alignment gland, y·h*, μ. Patent Document 1 discloses a liquid crystal alignment agent containing a ruthenium imine, which is used by a sub-monthly female. The amine of the alkanol skeleton is obtained. Further, in Japanese Patent Laid-Open No. 2, a liquid crystal alignment agent containing no polyamine or the like is used, and the polyamine is used for the use of a diamine having an acridine structure. In the above-mentioned Patent Documents 1 and 2, the Rasch production-point 曰τ improves the afterimage characteristics by containing the polyimine or the polyamine of the above structure in the night crystal alignment agent. [PRIOR ART DOCUMENT] [Patent Document 1] JP-A-H09-241646 (Patent Document 2) Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. Problem] Here, the liquid crystal display element is suitable for a high-quality monitor such as a liquid crystal television. For such a high-quality monitor, it is required that the image sticking property is good even after continuous use for a long period of time (for example, one day). On the other hand, the liquid crystal alignment agent described in the above-mentioned Patent Document 1 and the liquid crystal alignment agent described in Patent Document 2 do not consider the afterimage characteristics after continuous use for a long period of time. The present invention has been made in view of the above circumstances, and a main object thereof is to provide a liquid crystal alignment agent for obtaining a liquid crystal display element having excellent afterimage characteristics, a poly-proline and a polyimide which can be used as a component of the liquid crystal alignment agent, And a liquid crystal alignment film and a liquid crystal display element produced using the above. [Means for Solving the Problem] The present inventors have conducted intensive studies to solve the problems in the prior art as described above, and as a result, have found that the above problem can be solved by including a polymer in a liquid crystal alignment agent to complete the present invention. The product is obtained by using an aromatic tetracarboxylic dianhydride and a specific structure of a diamine having a tertiary nitrogen atom. The present invention specifically provides the following liquid crystal alignment agents, liquid crystal alignment films, liquid crystal display elements, polylysine and polyimine. The present invention provides a liquid crystal alignment agent characterized by comprising at least one selected from the group consisting of polylysine obtained by reacting a tetracarboxylic dianhydride with a diamine and a ruthenium imidized polymer thereof. The tetracarboxylic dianhydride contains an aromatic tetracarboxylic dianhydride containing a compound represented by the following formula (1). (1) H2N-ANA--NH. 201237068 (In the formula (1), 'A each independently is a phenylene group, a naphthyl group, and an extension. It is more than a bite base, a stretch, a bite base or a sleeve 2 ^ ^ ^ well And the substituents may have a substituent. B is a monovalent alicyclic group having a valent group, a valence group of a carbon atom, or a monovalent alicyclic ring having a carbon number of 3 to 3 G. Nicotinyl, and the chain hydrocarbyl or alicyclic hydrocarbon may have a substituent, and a part of the mercapto group may be substituted by an oxygen atom, a carbonyl group or a -(3)〇_ wherein the 'in 8' is bonded to the nitrogen atom in the formula (1) It is an anthracene group, a carbon atom forming an alicyclic structure or a carbon atom forming an aromatic ring structure.) The liquid crystal alignment agent according to the present invention can be formed to exhibit good even after continuous use for a long period of time, for example, 1 day. A liquid crystal alignment film having excellent afterimage characteristics, whereby a liquid crystal display element having excellent afterimage characteristics can be obtained, and the stability of the pretilt angle can be improved, and the rate of change of the voltage holding ratio (hereinafter also referred to as reliability) can be improved. The control is very low. In addition, the above-mentioned afterimage characteristics, stability of pretilt angle, and sinfulness are made better. The above B is preferably an alkyl group having a carbon number of 丨 1-6 (the alkyl group may have a substituent, and a part of the methylene group may be substituted by an oxygen atom, a carbonyl group or a -COO-), or an aromatic group which may have a substituent Further, the above A is preferably a stretched phenyl group which may have a substituent. The present invention provides a liquid crystal alignment film formed by the liquid crystal alignment agent described above, and a liquid crystal display element including the liquid crystal alignment film. Provided is a polyaminic acid characterized by comprising a polyamic acid obtained by reacting a tetrazoic acid with a monoamine, wherein the tetrazoic acid dicarboxylic acid comprises an aromatic tetracarboxylic dianhydride, and the diamine comprises A compound of the above formula, further comprising a polyimine which is obtained by dehydration ring closure of the polyamic acid. 201237068 In addition, in the present specification, the "hydrocarbon group" may be a saturated hydrocarbon group or an unsaturated group. Hydrocarbyl group. Further, the "chain hydrocarbon group" means a hydrocarbon group composed only of a structure, and may be linear or branched. The lipid oxime hydrocarbon group means a hydrocarbon group which contains only an alicyclic structure as a ring structure and does not contain a fragrant ring structure. And it is not necessary to be composed only of an alicyclic structure, and a chain structure may be included in the portion thereof. The "aromatic hydrocarbon group" means a hydrocarbon group having an aromatic ring structure as a ring structure. And no need to be only aromatic, '. The constitution of the structure may include a chain structure or an alicyclic structure in a part thereof. [Embodiment] The liquid crystal alignment agent of the present invention contains a tetracarboxylic dianhydride and a dihydrazide. Any of the obtained polyaminic acids and their quinone imidized polymers. Hereinafter, the liquid crystal alignment agent of the present invention will be described in detail. <Polyuric acid> [tetrazoic acid] The tetradecanoic acid dianhydride of polyglycine used in the invention is aromatic. Tetracarboxylic dianhydride. Here, the aromatic tetracarboxylic dianhydride is an aromatic tetracarboxylic dianhydride which is obtained by binding to at least one carboxyl group of the aromatic two and having four carboxyl groups dehydrated in the molecule, preferably bonded to the aromatic tetracarboxylic dianhydride. The acid two needles obtained by intramolecular dehydration of the four carboxyl groups of the same or non-swallowing ring. The number of clothes is preferably 丨~4. In this case, if the aromatic ring is a chain of 5 cyclic amines to a fine ring of cyclic acid, 201237068, it is preferably an acid obtained by intramolecular dehydration of 4 carboxyl groups bonded to the aromatic ring. anhydride. Further, if the aromatic ring is two or more, it is preferred that the acid dianhydride obtained by intramolecular dehydration of two carboxyl groups bonded to one aromatic ring and intramolecular dehydration of the other aromatic ring, Or a carboxyl group bonded to one of the adjacent two aromatic rings and the carboxyl group bonded to the other aromatic ring, and bonded to the carboxyl group of one of the adjacent two aromatic rings An acid dianhydride obtained by intramolecular dehydration with a carboxyl group bonded to another aromatic ring. Specific examples of such an acid dianhydride include those represented by the following formula (Ar-1). 〇 〇 (Ar-1) 〇 Ar 〇 Ο 0 In the formula (Ar-1), Ar is an aromatic group derived from the following structures. 201237068

(In the above formula (Ar-1), *1 is a bonding bond bonded to one acid anhydride group, and *2 is a bonding bond bonded to another acid anhydride group) at least at least one of the hydrogen atoms of the carbon atom in the above Ar. One may be substituted with a halogen atom or an alkyl group having 1 to 6 carbon atoms or a fluoroalkyl group or the like. The halogen atom exemplifies a fluorine atom, a chlorine atom, a bromine atom, an argon atom or the like. The alkyl group having 1 to 6 carbon atoms may be linear or branched, and specifically 'exemplifies a mercapto group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, and a second-order butyl group. Base, tertiary butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl and the like. In addition, as the fluoroalkyl group having 1 to 6 carbon atoms, the 201237068 group obtained by substituting at least one hydrogen atom of the group exemplified as the above-mentioned alkyl group having 1 to 6 carbon atoms with a fluorine atom is exemplified. Further, Ar may have only one or more of the above-mentioned groups, or may have two or more types. Preferred examples of the aromatic tetrazoic acid dibasic liver include pyromellitic dianhydride, hydrazine, 4-difluoro-benzenetetracarboxylic dianhydride, and 2,5-trifluorobenzenetetracarboxylic dianhydride. Trifluoromethylbenzenetetracarboxylic dianhydride, 3,3,,4,4,_ fluorenone tetraacid dianhydride, 3,3,4,4,-biphenyltetracarboxylic dianhydride, oxygen _4,4 , dioxalic acid dianhydride, 2,2_bis[4_(3,4-dicarboxyphenyloxy)phenyl]propanol, naphthalene-1,4,5,8-tetracarboxylic dianhydride, ethylene glycol Benzoic acid tetraacid 3'3 '4,4'-diphenyl term (tetracarboxylic acid two-pin, benzene-i,4-diyl bis(1 oxo-1,3-dihydro-2-benzo) The furan-5-carboxylate), etc., and the aromatic tetra-two-pins described in JP-A-20 10-97 188, and the aromatic tetracarboxylic acid di-xanthene other than the above. Among them, pyromellitic dianhydride, 1,4-difluoro-benzoic acid bis- 2,5-trifluoromethylbenzenetetracarboxylic dianhydride, 3,3', 4, 4,- are preferred. Dibasic tetraacid dianhydride, benzo-anthracene, 4_diyl bis(1,3-di- oxodihydro-2·°f--5-buffer acid ester), or ethylene glycol dibenzoate tetra Acid dianhydride. The above aromatic tetracarboxylic dianhydride can be used alone - Two or more types can be used together. By using aromatic tetradecanoic acid dianhydride, the residual density of the produced display element after continuous use for a long period of time (for example, one day) is good. In addition, the stability of the pretilt angle can be improved. And the rate of change of the compressible retention rate is suppressed to be low. Further, as the tetradecanoic acid, only the above aromatic tetrabasic acid dianhydride may be used, and the aliphatic tetrahydro acid dianhydride may also be used as the aliphatic four. At least one of carboxylic acid dianhydride and fat] tetrabasic acid. Substituting: fluorenyl diphenyl phthalate di dianhydride, 3 - 2 externally tempering acid tetraphenyl benzo or group liquid crystal Sf > 埃四覆式-10- 201237068 Aliphatic tetracarboxylic acid liver, refers to the acid dianhydride obtained by intramolecular dehydration of four rebel groups bonded to a chain hydrocarbon structure. However, it is not necessary to only use the bond. The hydrocarbon structure may have an alicyclic structure or an aromatic ring structure in a part thereof. The alicyclic tetracarboxylic dianhydride refers to a plurality of groups including four groups bonded to the alicyclic structure. An acid dianhydride obtained by intramolecular dehydration. The four carboxyl groups are not bonded to the aromatic ring. Further, it is not required to be composed only of a lipid raft structure, and may have a chain hydrocarbon structure or an aromatic ring structure in a part thereof. As an aliphatic tetracarboxylic dianhydride, for example, 1,2,3,4-butane, four, and other, as the lipid bismuth carboxylic acid dianhydride, for example, i,2,3,4-anthracene tetracarboxylic dianhydride , 2,3,5-tricarboxycyclopentyl acetic acid II, 1 3 3 /\ ' ' a,,5,9b_hexahydro-5-(tetrahydro-2,5-di-oxo-3-furanyl )-naphtho[1,2 - c 1 4, J-nan-1,3-dione, 1,3,3 mad, 4,5,913-hexahydro-8-methyl-5- (four gas-2 s - ' _ side oxy-3-furanyl)-naphtho[i,2-c]furan-1,3-dioxin, 3 -oxaxan ”"[3·2_1]octane- 2,4-dione-6-spiro-3,-(tetrahydrofuran-2',5 bis) (2,5--one oxo-tetrazol-3-0f0-northyl)-3-fluorenyl -3 - cyclohexene-丨2-private 3 ^ '- slow anhydride, 3,5,6-tricarboxy-2-carboxydecylnorbornane-2 _ '6' one field, 2,4,6 , 8-tetracarboxybicyclo[3.3.0]octane-2: 3,5 • 6 _ — Sf· \ 4 q _ 'dioxatricyclo[5.3.1.02'6]undecane-3,5, 8,10-tetraone and the like. In addition, the aliphatic tetramine _ <-anhydride and alicyclic tetracarboxylic dianhydride described in JP-A-2010-97188 can be used, and a fat other than the above, such as an aliphatic tetracarboxylic dianhydride, can be used. The alicyclic tetracarboxylic dianhydride oxime is a four-percent _ 夂%-anhydride, among the aliphatic tetracarboxylic dianhydride and the alicyclic -11-201237068 tetracarboxylic dianhydride, from the viewpoint of solubility, the ring The formula is four acid-lowering needles, more preferably comprising a W-cyclopentane needle or a 1,2,3,4-cyclobutane-tetracarboxylic dianhydride, preferably comprising 2,3,5_:= cyclodecyl acetic acid dianhydride . In the case of the aliphatic or alicyclic tetracarboxylic acid dianhydride as described above, these aliphatic or alicyclic tetracarboxylic dianhydrides may be used singly or in combination of two or more. As a tetracarboxylic dianhydride, in the case of containing not only aromatic tetracarboxylic dianhydride but also aliphatic or alicyclic tetracarboxylic dianhydride, aromatic four relative to the total amount of tetracarboxylic dianhydride The ratio of the phthalic acid dianhydride is preferably 0.1 to 90 mol%, more preferably 5 to 8 mol%, more preferably 1 to 7 mol%, and particularly preferably 2 to 50 mol%. By setting it as such a range, the afterimage characteristics after continuous use for a long time can be made better. In addition, it can be: The stability of the pretilt angle, and the rate of change of the voltage holding ratio can be controlled to be very low. [Diamine] The diamine used for the poly-proline in the δ-cost description includes a compound represented by the following formula (1) (hereinafter also referred to as diamine (D1)). ~NA ——NH2 (1) (In the formula (1), A each independently is a phenylene group or an extended naphthyl group. These may have a substituent such as a pyridine, a pyrimidyl group or a trisyl group. a monovalent chain hydrocarbon group having a monovalent chain structure, a monovalent chain hydrocarbon group having 1 to 3 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 30 carbon atoms, and a chain hydrocarbon group or an alicyclic hydrocarbon group may have a substituent, A part of the methyl group may be substituted with an oxygen atom, a carbonyl group or -12-201237068 -COO-. Among them, in B, a nitrogen atom bonded to the nitrogen atom in the formula (1) is a sub-f group' forming a carbon atom of an alicyclic structure. Or a broken atom forming an aromatic ring structure). In the above-mentioned formula (1), examples of the pendant phenyl group include an anthracene, a 3-phenylene group, a 1,4-phenylene group, and the like; and as an anthranyl group, a 1,4-naphthyl group is exemplified. a 1,5-anthranyl group, etc.; as a pyridyl group, a 2,4-extended pyridyl group, a 2,5-extended pyridyl group, etc.; as a pyrimidyl group, a 2,5-pyrimidine group is mentioned. Examples of the substituents include a 2,4-extended trisyl group, and the like; and examples of the substituent which the group may have include a _- atom atom or an alkyl group having 1 to 6 carbon atoms, an alkoxy group. Or fluoroalkyl and the like. In the above-mentioned, the ketone atom, the alkyl group having an atomic number of 1 to 6 and the gas-burning group having 1 to 6 carbon atoms are exemplified as the substituent of the above-mentioned Ar, and as a carbon atom. Examples of the alkoxy group having a number of from 1 to 6 are an alkoxy group which is bonded to an oxygen atom as a group of the above-mentioned group having an anthracen number of from 1 to 6 in the above-mentioned spoon, and specific examples thereof include a decyloxy group. Ethoxylate and the like. In the case of 'Hai et al., A is preferably a phenyl group which may have a substituent. That is, the diamine in the present invention preferably contains a compound represented by the following formula (2) (hereinafter referred to as a diamine (D small oxime). It is presumed that the formed liquid CT ° film In the case where an amine moiety (donor) and an acid anhydride moiety (acceptor) interact with each other to produce photoelectricity, the occurrence of unevenness of ions or the polarization of the alignment film itself is suppressed. Make liquid day-13- (2) 201237068

(弋(), 玟3 are each independently a calcination group, an alkoxy group, or a ruthenium, an atom, or a slave atom number of 1 to 6. The definition of B is + 土 土 k is independently 〇~4 The integer is the same as the above formula (1). Specific examples of Ra of the above formula (2) include the same substituents as those of the above-mentioned fAn ancient substituents, and the above-mentioned A may be mentioned. In the above cut, the base is k, preferably 0 to 2, more preferably 0: fixed; b):: the binding position of the '1 amine group in the benzene ring is not particularly limited relative to the formula (2) Gas or 4-bit, more preferably 4_ bit. Quan Jia is 3-bit i 3. := The mussel chain tobacco group of the carbon number H0 in the formula (1) and the B in the above formula (2) is preferably a ruthenium group having a carbon number of Μ and having 1 to 12 carbon atoms; Gossip is considered to be linear or branched, for example

For example, thiol, ethyl, 屯# J ethyl, n-propyl, isopropyl, n-butyl, secondary butyl, secondary T group, n-pentyl, isopentyl, neopentyl, Isoisohexyl 3, 3-methylpentyl, 2, dimethylbutanedimethylbutyl, n-heptyl, n-octyl ' |1: abundance 1 fluorenyl, n-decyl, n-undecyl , n-dodecyl and the like. In addition, if it is a methylene group bonded to the nitrogen atom in the above formula (u), the above formula (the above formula (a part of the methylene group shown in Ο can also be In addition, carbon 痔 痔 ^ _ _ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少a ruthenium atom or the like, a hydroxy group, a cyano group or the like. In the case where ruthenium is a chain hydrocarbon group, 'may have a substituent, preferably a part of a methylene group, a carbon atom substituted by an oxygen atom, a few groups or a -coo- Number-14- 201237068 1 to 6 of the alkyl group is more preferably a carbon atom number of 1 to 6 or a fluoroalkyl group, particularly preferably a sintered atomic number of 1 to 6. The above carbon number of B is 3~ The 30-valent monovalent alicyclic hydrocarbon group may be composed only of an alicyclic structure, and may also include a chain structure in a part thereof. As the alicyclic structure, cyclopentane, cyclohexane, cycloheptane, and cyclooctane are listed. Burning, norbornane, adamantane, etc. On the other hand, in the case where a part has a chain structure, the chain structure can have the above formula (1) The nitrogen atom in the above formula (2) may be bonded to the chain structure, or may be omitted. The alicyclic hydrocarbon group may include the linked chain structure and the unlinked structure. In the above-mentioned monovalent alicyclic hydrocarbon group, if a nitrogen group is bonded to the nitrogen atom in the above formula (1) or the above formula (2), a methylene group or a carbonogen+ which forms an alicyclic structure is obtained. Then, a partial methylene group as shown in the above formula (1) may be substituted. Further, it may have a substituent which is the same as the above-mentioned chain hydrocarbon group. The above monovalent alicyclic hydrocarbon group may have a carbon number of 17 a group having a skeleton of a retention type, the skeleton of the retention type, which means a cyclopentane hydrogenated phenanthrenequinone, or a single bond between carbon atoms of the skeleton, such that one or more single bonds become double bonds The obtained bones are obtained as rabbits, and y] moon wood is a group having such a skeleton of the retention type, and examples thereof include a cholesteryl group, a cholestyl group, and the like. The above-mentioned B has an aromatic ring structure of the soldier L 11 The base may be composed only of an aromatic ring structure 'and may also contain a chain to a part thereof (9) The structure and the alicyclic structure may also be a naphthalene ring, an onion, or a thiophenan ring as an aromatic ring structure, and may be a stupid ring, a ring, a phenanthrene ring, an anthracene ring, an anthracene ring, etc. Ring-15- 201237068, pyrrole ring aroma ring. As a bicycloalkane, alkane, cyclooctane carbon atom structure, -COO- the above structure, also aroma ring structure, terphenyl type existent chain, these structural hydrocarbon groups are the same The above formula (1) and the ring structure have a group of an aromatic ring, wherein a stable monovalent group of the dip angle, a 吱 ring, a ° bite ring, a 01 0 ring, a three ring, etc. Examples of the heteroaromatic ring structure include a monocycloalkane or a tricycloalkane having 3 to 12 carbon atoms, and specific examples thereof include cyclopentane, cyclohexane, cycloheptane, norbornane, and adamantane. As the chain structure, a number of saturated hydrocarbons or unsaturated hydrocarbons of 3 to 12 are listed. Further, these alicyclic chains may have at least one of -0-, a carbonyl group and a part thereof. The monovalent group having an aromatic ring structure may have only one aromatic ring and may have plural. In the case of a plurality of aryl groups, these multiple aryl groups may be bonded by a single bond, and in this case, biphenyl or the like is specifically enumerated. Further, it may be in the form of a square structure or an alicyclic structure in which a plurality of aromatic ring structures are linked. The aromatic ring structure, the chain structure, and the alicyclic structure may have at least a substituent. As the substituent, a substituent similar to the above-mentioned bond is listed. In the case of the monovalent group having an aromatic ring structure, if the atom bonded to the nitrogen atom in the above formula (2) is a methylene group, a carbon atom forming a fat or a carbon atom forming an aromatic ring structure, the structure is The monovalent group may be an aromatic ring structure bonded to the gas source or may be a long time in which the nitrogen atom and the aromatic ring structure are connected in at least one of a chain structure and an alicyclic structure. The image retention property, pre-tanning property and reliability after continuous use are good, and have an aromatic ring structure (preferably, the aromatic ring structure is bonded to the above nitrogen atom and has -16-

201237068 The i-valent base of the aromatic ring structure. Further, it is more preferably an aromatic cyclic benzene ring, or a naphthyl group having an aromatic ring structure such as a naphthalene ring, an anthracene ring, a phenanthrene ring, an anthracene ring or an anthracene ring. That is, it can have a square base. Further, a structure represented by the following formula (3) is particularly preferable. (in the formula (3), 'the number of carbon atoms of the atomic number is 丨~", the monovalent alicyclic hydrocarbon group having an atomic number of 3 to 30, or the valent group having an aromatic ring number of 6 to 30, and the alkyl group Or the alicyclic hydrocarbon group may have a part of the methylene group which may be substituted by an oxygen atom, a carbonyl group or a -COO-, and the integer 'm is 2 to 4, and each of the plurality of Rbs independently has an upper "*" indicating a combination with the above formula ( 1), the nitrogen bond in the above formula (2)). The halogen atom of Rb is preferably a fluorine atom, a gas atom, an iodine atom or the like. The alkyl group having 1 to 30 carbon atoms of Rb is preferably a group of 1 to 12, and specifically, a group exemplified as the monovalent chain group of 1 to 30 in the above b. . Further, the alkyl group may be substituted 'specifically, including alkoxy group, _ -C00-R31. _〇C〇-Ral> .Ra2_〇_Ral_Ra2_c〇_Ral_ V1 ' ja2-〇CO_Rd(R "Alkanediyl group having a substituent of an alkyl group which may have a substituent." The monovalent alicyclic hydrocarbon group having 3 to 30 carbon atoms as Rb is a monovalent fat having 碳% to % of carbon atoms in the above B. In addition, in the case where a part has a chain structure, the structure is a condensed group of a fused benzene substituent, and a carbon-based carbon substituent, and 111 is defined as 0 to 4. The partial sub-CO-Ral, Ra2-COO-, and Ra2 of the number of carbon atoms of the bromo or the bromo atom are exemplified, and the chain -17-201237068, the structure can be the above formula (3) The benzene ring and the alicyclic structure may be bonded to each other or may be unbonded. The alicyclic group may also include the linked chain structure and the unlinked chain structure. And, as an alicyclic hydrocarbon group, preferably having a carbon atom number of from 7 to 30, having a sulfhydryl shell. Specifically, a decyl group, a cholesteryl group, a fluorenyl group, a cholestyl group, a cholyloxy group, a cholestyloxy group, etc. In the case of a monovalent group having an aromatic ring structure in the above B, a group having a chain-like structure or an alicyclic structure is exemplified. The lower chain structure and the alicyclic structure may exist in a manner in which the benzene ring and the aromatic ring structure in the above formula (3) are linked, or may be present in a non-linked manner. In addition, the Hf group may be the same At least one of the linkage-form, the chain structure, the structure, and the % structure, and at least one of the unbonded bond structure and the alicyclic structure are included. Examples of the substituent which the Rb may have include a substituent which may be a monovalent chain hydrocarbon group having 1 to 30 carbon atoms in the above B. The Rb' is preferably a fluorine atom or a carbon atom. The alkyl group, the alkoxy group or the fluoroalkyl group of i to 9 is more preferably an alkyl group having 1 to 9 carbon atoms. m is preferably 0 to 2 'better 0 or 1. When m is 1, the bonding position of Rb is not particularly limited, but is preferably 3-position or 4-position, more preferably 4-position relative to the above formula (丨), the nitrogen atom in the above formula. As the diamine (D-oxime), 3 in the above formula (2) is preferably a group having a carbon number of -18 to 201237068 1 to 6, or a group represented by the above formula (3). , may, for example, be: N,N-bis(4-aminophenyl)-decylamine, N,N-bis(4-aminophenyl)-propylamine, hydrazine, hydrazine-bis(4-amine Phenyl)-hexylamine, N,N-bis(4-aminophenyl)-aniline, N,N-bis(4-aminophenyl)-p-nonylaniline, N,N-bis (4 -aminophenyl)-p-hexylaniline, N,N-bis(4-aminophenyl)-p-octylaniline, N,N-bis(4-aminophenyl)-p-(1-methyl Tetradecyl)aniline, N,N-bis(4-aminophenyl)-p-(cholestyloxycarbonyl)aniline, anthracene, fluorene-bis(4-aminophenyl)-pair (cholesteryl) Alkenyloxycarbonyl)aniline, anthracene, fluorene-bis(4-aminophenyl)-p-(cholestyloxy)aniline, anthracene, fluorene-bis(4-aminophenyl)-pair (biliary Retaining alkenyloxy) aniline and the like. By using at least one of these compounds together with the above aromatic tetracarboxylic dianhydride, three or more benzene rings are introduced into the main chain of the polyamic acid, and three benzene rings bonded to at least two benzene rings are introduced. Grade nitrogen atom. As a result, the residual image characteristics of the produced liquid crystal display element after continuous use for a long period of time can be made good. In addition, the stability of the pretilt angle can be improved, and the rate of change of the voltage holding ratio can be suppressed to be low. As the diamine for synthesizing the polyglycolic acid in the present invention, only the above diamine (D-1) may be used, or the diamine (D-1) may be used together with other diamines. Examples of the other diamine which can be used herein include an aliphatic diamine, an alicyclic diamine, an aromatic diamine, a diamine organooxane, and the like shown below. Specific examples of such an aliphatic diamine include m-xylylenediamine, 1,3-propylenediamine, tetradecyldiamine, pentamethylenediamine, and hexamethylenediamine. And as an alicyclic diamine, for example, 1,4-diaminocyclohexane-19-201237068, 4,4'-methylenebis(cyclohexylamine), 丨'夂 bis (amino group) Examples of the aromatic diamine include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4,-diaminodiphenylmethane, and 4,4. _Diaminodiphenyl stearnes, 1,5-diaminone, 2,2'-dimercapto-4,4,-diaminobiphenyl, 4,4'-diamino-2, 2,-bis(trifluoromethyl)biphenyl, 2,7-diaminostilbene, 4,4,diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy) Phenyl]propane, 9, 9 bis(4-aminophenyl), 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2 - bis(4-aminophenyl)hexafluoropropane, 4,4,-(p-phenylenediphenylene)bis(aniline), 4,4,-(inter)phenyldiisopropylidene ) bis(stupylamine), 1,4-bis(4-aminophenoxy)benzene, 4,4'- (4-amino stupid yloxy) biphenyl stupid, 2,6-aminopyridine, 3,4-aminopyridine, 2,4-diamino mouth. '3,6-Diamino acridine, 3,6-diaminocarbazole, N-mercapto-3,6.diamine-based samarium, oxime-ethyl-3,6-diamino Carbazole, fluorene-phenyl __3,6-diamino hydrazine. Sit, Ν,Ν'-bis(4-aminophenyl)-benzidine, anthracene, fluorene,-bis(4-aminophenyl)-indole, Ν'-dimethylbenzidine, bis-(4 -aminophenyl)-piperazine, 3,5-diaminobenzoic acid, dodecyloxy-2,4-diaminobenzene, tetradecyloxy 2'4-aminobenzene, ten Penta-oxy-2,4-diaminobenzene, hexadecyloxydiamine, octadecyloxy-2,4-diaminobenzene, dodecyloxy-2,5-di Aminobenzene, tetradecyloxy-2,5-diamino stupid, pentadecyloxy, 5-diamino stupid, cetyloxy-2,5-diamine stupid, octadecane Oxylate, 5-diamino stupid, cholestyloxy-3,5-diaminobenzene, cholestyloxy, 5-diaminobenzene, cholestyloxy-2,4-diamine Benzobenzene, cholestyloxy 2,4-diamino stupid, choline alkyl 3,5-diaminobenzoic acid, cholesteryl 3,5-diaminobenzoic acid, 3,5 -1,5-bis(4-aminobenzylideneoxy)cholane, 3,6-bis(4-aminophenoxy)choline-20-201237068 Sterred, 4-(4'-trifluoromethoxyphenylhydrazo)cyclohexyl-3,5-diaminobenzoic acid, 4-(4,·trifluoromethyl) Methoxycarbonyl)cyclohexyl-3,5-diaminobenzoic acid, 1,1-bis(4-((aminophenyl)indenyl)phenyl)-4-4-butylcyclohexane, 1, 1-bis(4-((aminophenyl)indenyl)phenyl)·4-heptylcyclohexane, 1,1-bis(4-((amino)oxy)indolyl) _4_heptylcyclohexane, bis(4-((aminophenyl)indenyl)phenyl)_4_(4-heptylcyclohexyl)cyclohexane, 2,4-diamino-N,N- Diallyl aniline, 4-aminobenzylamine, 3-aminobenzyl benzylidene, 1-(2,4-diaminophenyl)piperazin-4-carboxylic acid, 4-(i-phenyl-4-yl) Benzene '1'3 bis(N-(4-aminophenyl)α-bottom)propane, α-aminoaminophenyl olefin, propynyloxy) 2,4-phenylenediamine 4_Aminophenyl 4-aminobenzoic acid vinegar, 4,4.-[4,4,-propanol- 4,4-propanyldiylbis(piperidine-1,4-diyl)] An aniline or the like; as the monoamine-based organic oxime, for example, 1,3 bis(3-aminopropyl)-tetradecyldioxane may be mentioned, and in addition, 曰bente may be used. The diamine described in JP-A No. Hei-971 88 is opened. In addition to the compounds, the compounds represented by the formula (Α'υ) are listed by the following.

(AD or -COO-, R丨 is carbon #子D is an integer of 栌_ which is independently a single bond, 吟 stone anti-atomic number 1~3, but a&b is not π 凡一基, a is 〇 or 丨, b is (a and b do not need to be simultaneously or 1). — ' , ^ 1 to 20 integer, τι; as the two-valent base-21-201237068 represented by the above formula (Α)) It is a divalent base of 1 to 3 atoms, * - Ο -, * - C Ο Ο - or * -0-CH2CH2-0- (with a "*" linkage and a diaminophenyl group) Specific examples of the group CcH2c+1- include a mercapto group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, an n-heptyl group, an n-octyl group, and a n-decyl group. N-decyl group, n-dodecyl group, n-tride-burning group, n-tetradecyl group, positive fifteen-burning group, positive sixteen-burning base, positive seventeen-burning base, positive eight-burning base, positive nineteen burning a base, a decyl group, etc. The two primary amine groups in the diaminophenyl group are preferably at the 2,4-position or the 3,5-position relative to the other groups. Specific examples of the compound shown in 1) include, for example, each of the following formulas (d2-l) to (d2-6). And the like.

CjH,, H2N h2n ΝΗο (d2-2) nh2 (d2-3) h2n 0^coo-c2h4-o^0M^)-&lt;^- C5Hh (d2-4) h2n H2NH^^-0—C2H4—( D2-5) nh2 h2n (d2-6) h2n In the case of synthesizing polyamic acid, the ratio of the above diamine (D-1) is preferably 0.1 mol% or more based on the total amount of the diamine. Better for the package -22- 201237068 containing 0.5 to 80 m. /. More preferably, it contains i~7〇mole%, 2~50 m. /. . By setting it as such a range, it is possible to make it easier to include the afterimage characteristics after continuous use. In addition, it can be mentioned: long-term stability, and the rate of change of voltage retention rate = [molecular weight regulator] &amp; low * ° in the synthesis of poly-proline, can also be used with diamine The molecular weight regulator is a polymer of Carbohydrate. Further improving the coating of the liquid crystal alignment agent by the effect of forming the terminal-modified polymer end: the type of the decoration::) (4), for example, an amine compound, a monoisocyanate Compounds, etc. For example, as a S-saponic anhydride, for example, a maleic acid of a maleic acid, a methic acid, a fluorene anhydride, a n-decyl succinic anhydride, or a n-dodecyl group can be mentioned. Succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl succinic anhydride, etc.; long-term, as a monoamine compound, for example, streptoamine, cyclohexylamine, N-butylamine, N-pentyl The monoamine, N-hexylamine, N-heptylamine, N-octylamine, etc. Examples of the monoisophytic acid vinegar compound include phenylisoindol* S曰 and 4-isoisocyanate g. The use ratio of the molecular weight modifier is preferably 20 parts by weight or less, more preferably 1 part by weight or less, based on the total amount of the tetracarboxylic dianhydride and the diamine to be used. <Synthesis of Monoamine (D-1)> The diamine (D-1)' represented by the above formula (1) can be suitably produced by a conventional method of organic chemistry. Specifically, in the above formula, B is a group represented by the above formula (3) in -23 to 201237068, for example, 'Firstly, the compound (M-1) and the compound (M_2) represented by the following formula are used. The reaction is carried out to obtain an intermediate (M-3) (refer to the following reaction formula (1)). In the above formula (1), when B is a monovalent chain hydrocarbon group or a monovalent alicyclic group (hereinafter referred to as B1) ', for example, first, a compound represented by the following formula (M_4) is used. The reaction with the compound (M-5) gives the intermediate (M_6) (refer to the following reaction formula (II)).

Rb and m are the same as defined in the above formula (3)) K Bi 02N—A—Y + N—A—N〇2 _► i H 〇2n-a^ \A-no2 (wherein Y is a halogen atom, A is the same as defined in the above formula (M-6) (Μ*4) (M-5) (wherein Y is a halogen atom, and B1 is an i-valent oxime hydrocarbon group having a carbon number of ^30 or a carbon number of 3~ a monovalent alicyclic hydrocarbon group of 30, and these may have a substituent 'partial fluorenylene group which may be substituted by an oxygen atom, a prison group or _c 〇◦_. wherein 'B is bonded to a secondary nitrogen atom is Aa A group or a carbon atom which forms an alicyclic type or a civic structure. A is the same as defined in the above (1). As a Y atom, a bromine atom, a gas atom, an iodine atom, a fluorine atom, etc. are listed. Among them, a fluorine atom is preferred from the viewpoint of reactivity. The reaction of the reaction formulae (I) and (II) is preferably carried out in the presence of a base. As the base of the-24-201237068, for example, a fluorinated planer or a fluorine is used. Potassium, sodium fluoride, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium ethoxide, sodium butoxide, sodium acetate, etc. Reaction formula (I) and (II Reaction temperature according to The method can be appropriately set, but it is preferably 0 to 15 (rc, more preferably 80 to 15 (rc.) as an organic solvent used in the reaction, for example, dimethyl hydrazine, dimethyl acetamide, etc. Next, if it is after the above reaction formula (I), the intermediate (M_3) is subjected to reduction of a nitro group and reduction of a hydroxyl group under catalytic reduction conditions, if after the above reaction formula (11) The intermediate (M-6) is subjected to reduction of a nitro group and reduction of a hydroxyl group under catalytic reduction conditions, whereby a diamine (D-1-a) and a diamine contained in the diamine (D-1) can be obtained. Amine (Hb) (refer to the following reaction formula (III) and the following reaction formula (IV)) °

02N~A〆 \α—Ν02 (M-3)

Rb and m are the same as the above formula (wherein A is the same as defined in the above formula (1), and the definition of (3) is the same).

(wherein A is the same as defined in the above formula (1); and B 1 is the same as defined in the above formula (II)).

Pt〇2 The reaction of the formulae (III) and (IV) uses a nickel, palladium-broken-25-201237068 pd(〇H)4 catalyst, preferably at -2〇~i5〇〇c for more preferably 0. ~120. . get on. As the solvent to be used in the reaction, for example, tetrahydroethylene, ethanol, toluene, N,N-dimethylformamidine, N,N-dimethylacetamide, 1-methyl-2-pyrene More than π. Set _ and so on. &lt;Synthesis of Polylysine&gt; The polylysine in the present invention can be obtained by reacting tetrahydro acid di-anthracene containing an aromatic tetracarboxylic dianhydride with a diamine containing The compound represented by the above formula (1) preferably contains a compound represented by the above formula (7). Regarding the use ratio of the tetracarboxylic dianhydride to the diamine supplied to the polyamine acid, the acid anhydride group of the tetracarboxylic dianhydride is preferably 〇2 to 2 with respect to the amine oxime equivalent of the diamine. The ratio of the equivalent is further preferably from 0 to 3 to 1.2 equivalents. The synthesis reaction of polylysine is preferably carried out in an organic solvent. The reaction temperature at this time is preferably _2 (TC to 150 ° C, more preferably 0 to 10 (rc ^ additionally, the reaction time is preferably from 0.1 to 24 hours, more preferably from 5 to 12 hours. Here, Examples of the organic solvent include an aprotic polar solvent, a phenol and a derivative thereof, an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, and a hydrocarbon. Specific examples of these organic solvents include the above-mentioned aprotic polar solvent. 'For example, N-methyl-2-pyrrole, n, n-dimethylacetamide, N,N-didecylguanamine, dimethyl sulfoxide, γ-butyrolactone may be mentioned. And tetramethyl urea, hexamethylenephosphonium triamide, etc., and examples of the phenol derivative include m-cresol, xylene oxime, and dentate benzene; and examples of the alcohol include methanol and ethanol. , isopropyl alcohol, -26-.201237068 cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol glycol monoterpene ether, etc.; examples of the ketone include acetone and hydrazine; Ethyl ketone, butyl ketone, cyclohexanone, etc.; examples of the ester include ethyl lactate, methyl butyrate acetate, ethyl acetate, and acetic acid. Ethyl ester, decyloxypropionic acid ethyl propionate, diethyl oxalate, diethyl malonate, etc.; as the ether, for example, diethyl ether, ethylene glycol thioglycol B Ether, ethylene glycol n-propyl ether, ethylene glycol-isopropyl ether glycol-n-butyl ether, ethylene glycol diterpene ether, ethylene glycol ethyl ether diethylene glycol diethylene ether diethylene ether Glycol diethyl ether, diethylene glycol monoterpene diethylene glycol monoethyl ether, diethylene glycol monoterpene ether acetate, diethyl ether acetate, tetrahydrofuran, etc.; as the halogenated hydrocarbon, for example, two Examples of the hydrocarbons include methane, 1,2-ethane, 1,4-di-butane, tri-ethane, benzene, o-dichlorobenzene, etc., and examples thereof include hexane, heptane, octane, and toluene. , dinonylbenzene, isoamyl propionate, isoamyl isobutyrate isoamyl ether, etc. Among these organic solvents, it is preferred to use a solvent selected from the group consisting of an aprotic solvent and a phenol and a derivative thereof. One or more of the groups (solvents of the first group); or preferably one or more selected from the group consisting of the first group of organic solvents, and selected from the group consisting of alcohols, _, and S a mixture of etherified hydrocarbons and hydrocarbons (group 2 of organic solvents). In the latter case, relative to the total of the first group of agents and the second group of organic solvents, The second group of organic, ethyl isophthalate, ethyl ether, ethyl acetate, ether, alcohol monodichloro», benzene, - polar organic group, halogen, an organic solvent

The use ratio of S -27- 201237068 is preferably 50% by weight or less, more preferably 4 〇 by weight. Further, it is preferably more than 30% by weight. The amount (a) of the organic solvent is preferably such an amount as the total amount (b) of the tetracarboxylic dianhydride and the diamine relative to the (a + b) ' of the reaction solution. As described above, the reaction solution obtained by dissolving the poly-proline can be directly supplied to the preparation of the liquid crystal alignment agent, or the poly-proline contained in the reaction solution can be separately separated and supplied. The preparation of the alignment agent or the preparation of the liquid crystal alignment agent can also be carried out on the basis of refining the separately separated polyfluorene. When polypyridic acid is subjected to ring closure to form a polyimine, the above reaction solution may be supplied to a dehydration ring closure reaction, or may be provided for dehydration ring closure on the basis of separately separating the polyamic acid in the reaction solution. The reaction, or the separate separation and purification of the dehydrated closed-loop poly-plysine based on the separately separated polyamic acid can be carried out according to a known method. &lt;Synthesis of a ruthenium-imiding polymer&gt; The ruthenium iodide polymer (polyimine) in the present invention can be obtained by dehydration ring closure and deuteration by the polylysine synthesized by the above operation. The polyimine in the present invention may be a complete ruthenium imide, and the ruthenium imide may be obtained by dehydration ring closure of the chiral acid structure of all polyamic acids as a precursor thereof; A part of the acid structure is subjected to dehydration ring closure, and a partial quinone imide compound in which a proline structure and an anthracene ring structure coexist. The polyamidation rate in the present invention is preferably 3% or more, more preferably 35 to 99%, and further, a total amount of 50 parts by weight. In the single liquid crystal amino acid dehydration directly contained in the purification should be. For example, the imine has a guanamine imine amine. • 28- 201237068

The way to proceed. Where ' is preferably based on the post-method. In the method of adding a dehydrating agent and a dehydration ring-closure catalyst to the solution of the above polyamic acid, as the dehydrating agent, for example, an acid anhydride such as an acetic acid needle, propionic anhydride or trifluoroacetic anhydride can be used. The dehydrating agent is preferably used in an amount of from 1 to 2 moles per mole of the glycine structure of the polyaminic acid. As the dehydration ring-closing catalyst, for example, pyridine, tridecylpyridine or dimercaptopyridyl can be used. A tertiary amine such as triethylamine or the like. The amount of the water closed-loop catalyst is preferably 〇.〇1~1〇 丨 相对 relative to the dehydrating agent used. The organic solvent used in the dehydration ring-closing reaction is exemplified as an organic solvent exemplified as the organic solvent used in the synthesis of polyglycine. The reaction temperature of the dehydration ring closure reaction is preferably 〇 18 (rc, more preferably 1 〇 to l5 (rc. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours). a reaction solution containing polyamidiamine.

Polyimine is based on the preparation of a liquid crystal alignment agent. . These refining reaction solutions can be directly supplied to the preparation of the liquid crystal alignment agent, or the dehydrating agent can be removed from the reaction &gt; the liquid and the capsule can be used to assist the children, and the β α crystal supply -29-201237068 can be used. A known method is carried out. &lt;Solid viscosity of the polymer&gt; The polyamine or the hydrazine of the present invention obtained by the imine-like operation; hereinafter referred to as a specific polymer; preferably made into a hard 10 weight The solution has a solution viscosity of 10 to 800 mPa.s and preferably has a solution viscosity of 15 to 500 mPa.s. Cold J, £ type: The solution viscosity (mpa.s) of the Korean polymer is: at 25.值 A value obtained by measuring a concentration of 10% by weight of a δ solution prepared using a good solvent (for example, γ_ of γ 比 定 定 等 等 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 &lt;Additive Additives&gt; The liquid crystal alignment film of the present invention contains the specific polymer as described above as an essential component, but may contain other components as necessary. Examples of the other components include other polymers, compounds having at least one epoxy group in the molecule (hereinafter referred to as "epoxy compounds"), and functional decane compounds. [Other polymers] The above other polymers can be used to improve solution characteristics and electrical properties. The above other polymer is a polymer other than the specific polymer, for example, a tetracarboxylic dianhydride containing no aromatic tetracarboxylic dianhydride and a diamine containing a diamine (D-1) are reacted. The obtained polyaminic acid (hereinafter referred to as "other poly-proline (")"), which is obtained by dehydration ring-closure of the poly-proline (hereinafter referred to as "other poly" Amine (1)"), a polylysine obtained by reacting a diamine containing no diamine (D-1) with a tetracarboxylic dianhydride (hereinafter referred to as "other polylysine (2)" -30- 201237068 Polyacrylamide (hereinafter referred to as "other polyimine (2)"), polyglycolate, polyester, polyamide, poly a siloxane, a cellulose derivative, a polyacetal, a polystyrene derivative, a poly(phenylethene-phenylmaleimide) derivative, a poly(indenyl) acrylate, etc. Preferred are other polylysines (1), other polylysines (2), other polyimines (1) or other polyimines (2), more preferably other poly Amine acid (1) or other poly-proline (2). As a fourth of the above-mentioned polylysine (1), (2) or other polyglycolide (丨), (2) Examples of the slow acid dianhydride include tetracarboxylic acid dianhydride similar to the tetracarboxylic dianhydride described above as a tetracarboxylic dianhydride for synthesizing a specific polymer. Preferably, 12, 3, and 4 are used. • cyclobutane tetracarboxylic dianhydride, perylene tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid 1,3,3,4,5,91)-hexahydro-5-(tetrahydrogen) At least one selected from the group consisting of _2,5-di-oxo_3_furanyl)-naphtho[12-c]furan-1,3-dione. The use of a polyfluorene polymer is selected from the group consisting of 4,4'-diaminodiphenylmethane, 2,2,-dimethyl-4,4,diamine-based curtain, cholestyloxy- 2,4-Diaminobenzene and 3,5-diaminobenzoic acid as two of the other polyamines (1), (2) or other indoleamines (1), (2) for synthesizing the above The amine may, for example, be the same diamine as the diamine described above for synthesis. Preferably, it is at least one of a group consisting of 1,4-bis-(4-aminophenylpolypiperidinium. In the case of an alignment agent, the ratio of the rubbing ratio is preferably 95 or more. Preferably, the amount of the other polymer added to the liquid crystal in the liquid crystal alignment agent is less than or equal to 0.1% by weight, more preferably from 0. 1 to 9% by weight, %. -31 - 201237068 [Ring The oxygen compound 彳 is used as the above p #. hydroglycerin scale, and the milk compound 'is, for example, ethylene glycol di-terminated ether, tripropylene di: ethylene glycol diglycidyl shunt, propylene glycol diglycidyl neodecanediol纩'&amp;glycidyl ether, polypropylene glycol diglycidyl hydrazine, ,, _ ^ , , , § glyceryl ether, hydrazine, 6-hexanediol diglycidyl bond, oil-shrinking sweet, Yigan, 趑 'three Hydroxymethylpropane triglycidyl ether, 2 bromo neopentadiene 醆 ^ ^, 2, 2% ~ hydrazine glyceryl ether, ν, ν, ν, ν, - tetraglycidyl, 1 221 Amine, i, 1-bis(indole, fluorene-diglycidylaminomethyl) Yan, 兀, 'Ν, Ν', Ν,, glycidyl _4,4'-diaminodiphenyl A Ν, Ν-diglycidyl _ 胺 Ν, Ν, Ν • diglycidyl-amine = its cyclohexene, p, NT τ 暴 '一 &amp; glyceryl-3⁄4 hexylamine, etc. as preferred Cyclohexane composition. In the case where these epoxy compounds are added to the liquid crystal alignment agent, the blending ratio is preferably 1 part by weight relative to the total amount of the polymer contained in the /crystal former. It is 4 parts by weight or less, and more preferably 〇丨3 parts by weight. [Functional decane compound] The above-mentioned functional decane compound 'is, for example, 3-aminopropyldimethoxy oxacyclohexane, 3 -Aminopropyltriethoxydecane, 2-aminopropyldimethoxydecane, 2-aminopropyltriethoxydecane, N-(2-Monthylethyl)-3-amine Propyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxyoxydecane, 3-ureidopropyltrimethoxydecane, -32-1 _ gland Propyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxysulfanyl, N-ethoxycarbonyl-3-aminopropyltriethoxydecane, N-di Ethoxy decyl propyl triethylene triamine, N_ trimethyl Methyl propyl propyl triethylene triamine, 10-trimethoxy decyl hydrazine, hydrazine, 7-three 201237068 azadecane, 10-triethylene sulfonyl-I, 4, 7- Triazanonane, 9-trimethoxydecyl-3,6-diazaindolyl acetate, 9-trimethoxymethoxycarbamido-3,6-diazaindolyl acetate , 9-triethoxydecyl-3,6-diazaindolyl acetate, 9-trimethoxydecyl-3,6-diazadecanoic acid decyl ester, 9-triethyl Methyl oxoalkyl-3,6-diazanonanoate, N-benzyl-3-aminopropyltrimethoxy decane, N-benzyl-3-aminopropyltriethoxy Baseline, N-phenyl-3-aminopropyltrimethoxy oxetine, N-phenyl-3-aminopropyltriethoxydecane, glycidoxymethyltrimethoxydecane, Glycidoxymethyltriethoxydecane, 2_glycidoxyethyltrimethoxydecane, 2_glycidoxyethyltriethoxydecane, 3-epoxypropoxypropane Trimethoxy decane, 3 epoxy propoxy propyl propylene diethoxy oxime, and the like. In the case where the soil is added to the liquid crystal alignment agent, the blending ratio is preferably in parts by weight. Under these functional decane compounds, the total amount i of the polymer is less than 2% by weight, more preferably 0.02 to 0.2. <Organic solvent> Regarding the liquid helium of the present invention, it is a stalk. The nightingale aligning agent is constituted by allowing a specific polymer to be arbitrarily blended in a pot and an organic solvent as needed. The ruthenium addition agent, preferably dissolved in the (4) (tetra) crystal alignment agent, may be exemplified by N-methyl 2 - pyrrolidine _, ^ 2 of the &amp; machine solvent, for example, N, N-dimethyl A Indoleamine, N, N_: internal 曰, butane 醯 安 基 -2- 2-pentanone, ethylene glycol monomethyl ether, lactic acid;: decylamine, 4-hydroxy_4_methylmethoxypropionic acid vinegar, Ethyl ethoxypropyl hydrazine, butyl acetate, methyl glycol ethyl ether, ethylene glycol n-propyl ether, / L - alcohol decyl ether, hexylene glycol - isopropionyl ether, ethylene di-33 - 201237068 Alcohol-n-butyl ether (butyl cyproterone), ethylene glycol dimethyl ether, ethylene glycol ethyl acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl Glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoterpene ether acetate, monoethylene glycol monoethyl acetate, diisobutyl ketone, isoamyl propionic acid, isoamyl Isobutyrate, diisoamyl ether, ethylene carbonate, carbonic acid, propylene, etc. These may be used singly or in combination of two or more. The solid content concentration in the liquid crystal alignment agent of the present invention (the ratio of the total weight of the components other than the solvent of the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) is appropriately selected in consideration of viscosity, volatility, and the like. It is preferably in the range of 1 to 1% by weight. In other words, the liquid crystal alignment agent of the present invention is applied to the surface of the substrate as described later, and it is preferred to form a coating film as a liquid crystal alignment film or a coating film to be a liquid crystal alignment film by heating, but the solid content concentration is insufficient. In the case of %, the film thickness of the coating film is too small to obtain a good liquid crystal alignment film. On the other hand, when the body content concentration exceeds 10% by weight, the film thickness of the coating becomes too large: a good liquid crystal is obtained by the method. The alignment film...the liquid crystal alignment agent has a large viscosity θ and the coating property is deteriorated. The range of the particularly preferable solid content concentration differs depending on the method used for coating the liquid crystal on the substrate. For example, in the case of solid scorpion gossip, white* 扪 特 特 特 特 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于The viscosity of the solution is in the range of 12 to 5 〇 mpa.s. In the case of the case, it is particularly preferable to make the sinister summer; the scent of the mouth ink method makes the solid content concentration i~5 wt%, so that the solution viscosity is in the range of 3 to 15 mPa. The temperature of the liquid crystal alignment agent of the present invention is 0. &lt;Liquid crystal alignment film and liquid crystal display element&gt; The liquid crystal alignment layer of the present invention is formed of the above liquid crystal alignment agent. Further, the liquid crystal display element of the present invention comprises the liquid crystal alignment film. About liquid

The operation mode in the crystal display element can be applied to a horizontal alignment type such as an ips type, a tn type, or an STN type, and can also be applied to a vertical alignment type such as a VA type. Hereinafter, a method for producing a liquid crystal display device of the present invention will be described, and a method for producing a liquid crystal alignment film of the present invention will be described. In the liquid crystal display device of the present invention, for example, the following (p 1 ) to (p 3 ) can be used. Step of Manufacturing] [Step (P1): Formation of Coating Film] First, the liquid crystal alignment agent of the present invention is applied onto a substrate, and then the coated surface is heated to form a coating film on the substrate. (The corpse dip) manufactures TN-type soil, and the habit of not being used for the next day: Next, two substrates provided with a patterned transparent conductive film are used as one or two's on the surface of each of the transparent conductive films. Preferably, the liquid helium alignment yoke of the present invention is applied by an offset printing, a tantalum roll coating method or an inkjet printing method, and each coated surface is heated (relatively heated (prebaked) and fired (post) Bake) two steps of force / town heating) to form a coating. Here, in the liquid crystal alignment agent of the present invention, since the offset printing method is used as the coating method, it is preferable to use the viewpoint of excellent effects of the invention: for example, glass of float glass or soda glass can be used. Substrate 4 Na-formic acid glycol, cellulose triacetate (TAC) -35- 201237068, polyethylene terephthalate, polybutylene phthalate, polyether sulfone, A transparent substrate formed of a plastic such as polyamine, polyimine, decyl acrylate, polycarbonate, or poly(alicyclic olefin). As the transparent conductive film provided on one surface of the substrate, a NESA film (registered trademark of pPG, Inc., USA) formed of tin oxide (Sn〇2) can be used. ITO film formed of indium oxide-tin oxide (In2〇3_Sn〇2) Etc., in order to obtain a patterned transparent conductive film ' may be based, for example, on a method of forming a pattern without a pattern: a pattern of a transparent conductive film by photolithography, and a mask having a desired pattern when forming a transparent V film Method etc. When the liquid crystal alignment agent is applied, in order to further improve the adhesion between the substrate surface and the transparent conductive film:coat film, the pretreatment may be carried out by pre-coating the surface on the surface of the substrate: the surface on which the coating film is to be formed. Pretreatment of Sexual Stones, S-energy Titanium Compounds, etc. For the liquid crystal alignment 杳丨丨, cold too hot (pre-baking), the coated surface after the burrs are placed, and then the pre-bake temperature is preferably post-baked to form a coating film. Pre-supplied °C. When pre-baking, the door is more preferably 40 to 150 ° C, and particularly preferably 40 to 100. Choice: 1 is 〇·25~10 minutes, more preferably 5·5~5 minutes

{, the roasting degree is preferably 80 to 300 ° C, more preferably 120 250 〇 c. The post-baking time is preferably 5 or more preferably 120 to 250 C. By this operation, the formed knife clock is more preferably 〇~100 minutes. Borrowed as 〇.0〇5~G.5_. (4) The film thickness is preferably (4), and more preferably, the film forming surface and the substrate not provided with the transparent conductive film in the case where the comb-type liquid crystal display element is provided. Conductive cloth The liquid crystal alignment agent of the present invention is connected to the surface of the board to heat the coated surfaces to form a coating layer. 36-.201237068. The material f used in the substrate and the transparent conductive film used at this time, the coating method, the heating conditions after coating, the patterning method of the transparent conductive film, the pretreatment of the US plate, and the formed coating film are preferably: (P1-1 )the same. In the case of any of the above (P1-1) and (P1-2), it is applied to the right side. The α丞 plate is coated with a liquid helium alignment agent|, and the organic solvent is removed to form a film of the film. In this case, after the formation of the coating film, further: :: thus performing a dehydration ring-closing reaction, a coating which can be made more imidized [step (Ρ2): rubbing treatment] in the production of ΤΝ type, STN type or IPS type The liquid helium Ss _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ΓΓ The rubbing treatment is performed, whereby the liquid crystal molecules are applied to the coating film to form a liquid crystal alignment film. Further, the above-mentioned liquid crystal A green "7" alignment film is irradiated with ultraviolet rays. ", the treatment of a pre-tilt angle of a portion of the knives of a portion of the eight Ft X liquid crystal alignment film that is incident on the liquid crystal alignment film or the formation of an anti-friction film on a blade of the liquid-aligning film surface.盥古 AL 〃, 摩擦 刖 刖 刖 摩擦 摩擦 摩擦 摩擦 摩擦After the treatment, the anti-friction film treatment is made to make the liquid corrugated alignment film have a liquid crystal alignment function of % ¥ + gate in each region, thereby obtaining the viewing property of the liquid crystal display element. In addition, the VA type is manufactured. In the case where the liquid crystal gg - _ makeup is displayed on a daily basis, the coating film formed by the above step (1) can be directly used as a liquid crystal alignment film, and the above-described rubbing treatment can be carried out. 201237068 [Step (P3): Construction of Liquid Crystal Cell] In order to arrange liquid crystal between substrates, the following two methods are exemplified. The first method is a conventionally known method. First, each liquid crystal alignment film is opposed to each other. In the method, the two substrates are opposed to each other via a gap (cell gap), and the peripheral portions of the two substrates are bonded together using a sealant, and the filling liquid is injected into the interstitial space of the substrate surface and the sealant region, and the injection hole is sealed. Thus, a liquid crystal cell can be manufactured. The second method is a technique called an ODF (Liquid Crystal Dropping) method in which a predetermined portion on one of the two substrates forming the liquid crystal alignment film is coated, for example. In the external light-curable sealing material, liquid crystal is further dropped on the liquid crystal alignment film surface, and then another substrate is bonded in such a manner that the liquid crystal alignment film is opposed to each other, and then the entire surface of the substrate is irradiated with ultraviolet light to harden the sealing agent. Thus, a liquid crystal cell can be produced. In the case of any of the methods, it is preferred that the liquid crystal cell produced as described above is further heated to a temperature at which the liquid crystal used becomes an isotropic phase, and then slowly cooled to the chamber. In the case of the sealing agent, for example, an epoxy resin containing a curing agent and an alumina ball as a spacer can be used. Examples of the liquid crystal include nematic liquid crystal and smectic liquid crystal. Among them, a nematic liquid crystal is preferable, and for example, a Schiff base liquid crystal, an oxidized azo liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal, a diphenyl liquid crystal, or a biphenyl group can be used. Extremely burned liquid crystal,. A dense sigma type liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a cubic liquid crystal, or the like. In addition, it is also possible to add, for example, gasified cholesteric alcohol, cholesteric 201237068 alcoholic acid s, and (4) alcoholic carbonic acid type "c-15" and "cb_15" to these liquid crystals (Merc 乍 is a commercial mouth) j I) is a chiral agent that is sold; it is used for ferroelectric liquid crystals such as decyloxy-pyrudodomide-p-amino-2-indole butyl cinnamate. The liquid crystal display element of the present invention can be obtained by attaching a human sigma polarizing plate to the outer surface of the liquid crystal cell. As a polarizing plate, a polarizing plate obtained by sandwiching a cellulose acetate protective film with a polarizing film called a 4-film obtained by stretching and orienting a polyvinyl alcohol while absorbing the enthalpy of the polyvinyl alcohol can be formed by a polarizing plate. Polarizer. The liquid crystal display element of the invention can be effectively applied to various devices, for example, can be used for watches, portable game machines, word processors, notebook computers, car navigation systems, camcorders, pDAs, digital cameras, mobile phones, various monitors. , display devices such as LCD TVs. [Examples] Hereinafter, the present invention will be more specifically illustrated by the examples, but the present invention is not limited to the examples. &lt;Synthesis of Diamine&gt; First, Synthesis Examples 1 to 4 of various diamine compounds (D-1) will be described below. Further, the synthesis was carried out repeatedly as needed on the following scale, thereby ensuring the necessary amount in the subsequent synthesis example of the polyimine. [Synthesis Example 1]: Synthesis of N,N-bis(4-aminophenyl)-p-methylaniline N,N-bis(4-aminophenyl)-p-A was synthesized according to the following synthesis scheme Aniline (hereinafter referred to as compound (d-Ι)). -39- 201237068

2 02N-^^-F h3c-^^- nh2

CsF, DMSO ~110°C *

N02

Pd/C, N2H4EH2〇 THF/EtOH, 70°C^

NH2 In a 300 ml three-necked flask, 21.2 fluoronitrobenzene 21.2 g (0.15 mol), fluorinated planer 27.4 g (0.18 mol), 4-mercaptoaniline 8.0 § (0.0745 mol) were mixed under a nitrogen atmosphere. , dimethyl sulfoxide 75111 is at 110. (The reaction was stirred for 6 hours. Thereafter, the reaction solution was mixed with 800 ml of ethanol and stirred for 1 hour. The precipitate was filtered and dried to obtain an intermediate 1 2 2 g. Next, in a 300 ml three-necked flask, under a nitrogen atmosphere The intermediates 11.2 § (〇 〇 25 mol), Pd/C 9.1 g, and tetrahydrofuran (50 ml) synthesized by the above were mixed and heated and stirred at 701 for 1 hour, after which 15 ml of hydrazine monohydrate was added. The reaction was stirred at 8 (rc) for 3 hours under a nitrogen atmosphere. Thereafter, the catalyst was removed by filtration, and the filtrate was concentrated and dried. The obtained product was obtained by column chromatography (methanol / acetone = 1 / / 1). After the viscous liquid is purified, it is concentrated and dried to obtain the compound (d_1) 4. 〇g. [Synthesis Example 2] : Synthesis of N,N-bis(4-aminophenyl-octylaniline according to the following synthesis scheme, N,N-bis(4-aminophenyl-octylaniline (hereinafter referred to as compound (d_2)) was synthesized. -40- 201237068

In a 300 ml three-necked flask, 4_fluoronitrobenzene 21_2 g (0.15 mol), fluorinated planer 27.4 g (0.18 mol), 4-octylaniline 15.3 g (0.0745 mol) were mixed under a nitrogen atmosphere. Dimethylhydrazine 75 ml 'mixed reaction at ll ° ° C for 6 hours. Thereafter, the reaction solution was mixed with ethanol 8 〇〇mi and stirred for 1 hour. The precipitate was filtered and dried to obtain an intermediate i i 2 g. Then, in a 300 ml three-necked flask, the intermediate 11.2 § (〇_025 mol), 1) (1/(:: 91 §, tetrahydrofuran) 50 ml, which was synthesized by the above, was mixed under a nitrogen atmosphere. At 70 ((: heating and stirring for 1 hour. Thereafter, after adding 15 ml of hydrazine monohydrate), the reaction was stirred at 8 for 8 hours under a nitrogen atmosphere. Thereafter, the catalyst was removed by filtration, and the filtrate was concentrated and dried. The obtained viscous liquid was purified by column chromatography (gas imitation/acetone = 1 〇/1), concentrated, and dried to obtain 5 3 g of the compound (d_2). [Synthesis Example 3] : N, N- Synthesis of bis(4-aminophenyl)-aniline According to the following synthesis scheme, bis(mono)-aminophenyl)-aniline (hereinafter referred to as compound (d _ 3)) was synthesized. -41 - 201237068 2 〇2n-Qf + (y nh2

P

Pd/C, n2h4eh2o THF/EtOH, 70°C

In a 300 ml three-necked flask, 40.6 g (0.288 mol) of 4-fluoronitrobenzene, 2.8 g (0.137 mol) of aniline, 50.0 g (0.329 mol) of fluorinated, and dimethyl group were mixed under a nitrogen atmosphere. Sulfoxide i00in is in 1 1〇. The reaction was stirred for 3 days. Thereafter, water was poured into the reaction liquid to precipitate a precipitate, which was washed with water and ethanol, and dried to obtain 34.5 g of an intermediate. Then, in an 300 ml three-necked flask, 34.1 g (0.102 mol) of the intermediate synthesized by the above, Pd/C 2.54 g of tetrahydrofuran 200 ml, ethanol 200 ml, and 25.4 ml of hydrazine monohydrate were added under a nitrogen atmosphere. The reaction was stirred at 70 ° C for 2 days at room temperature for 1 hour. Thereafter, the catalyst was removed by filtration, and 500 ml of ethyl acetate was added thereto, and the mixture was washed four times with 300 ml of distilled water and concentrated. The obtained powder was refined by recrystallization (after dissolving in 270 ml of ethyl acetate in 190 ml, and 150 ml of hexane was added and allowed to cool), and the filtrate was further concentrated. Recrystallization was carried out after dissolving in 60 ml of ethyl acetate at 80 ° C. Hexane 4 〇ml and allowed to cool), thereby finally obtaining 23.5 g of the compound (d-3). [Synthesis Example 4]: Synthesis of N,N-bis(4-aminophenyl)-fluorenylamine N,N-bis(4-aminophenyl)-decylamine was synthesized according to the following synthesis scheme (hereinafter referred to as compound (d-4)). -42 - 201237068

K2C〇3, DMAc ~~-M〇°C~**

〇2n_〇~f +〇2n^^_n" In a 300 ml three-necked flask, mixed with 4_fluoronitrobenzene, 18.6 g (0.132 mol), N-mercapto-4-nitroaniline in a nitrogen atmosphere I8.3g (0.12 mol), potassium carbonate 18_2g (0.132 mol), and dimethylacetamide i2〇m b were mixed for 3 days at 11 ° C. Thereafter, water was poured into the reaction solution, and the precipitate was filtered. The product was washed with water and ethanol, and dried to obtain intermediate 2: 4 g. Then 'in a 300 ml three-necked flask, under the nitrogen atmosphere, the intermediate synthesized by the above was 28.1 g (0.1 〇 3 mo Ear), Pd/C 3.08g, tetrahydrofuran 200m, ethanol 2〇〇m Bu, add 3〇8ml of hydrazine monohydrate, stir the reaction at room temperature for 3〇, at 7〇t: stir the reaction for 3 days (on the way) Pd/C lg + 2g, 肼1〇ml+1〇ml) was added. Thereafter, the catalyst was removed by filtration, and 5 μl of ethyl acetate was added thereto, and the obtained powder was dried by 4 liters of distilled water. Further, 21.3 g of the compound was washed and concentrated. (d - 4) 合成 < Synthesis of I-imine> The oxime imidization ratio and solution viscosity of the polyimine in the following synthesis examples are as follows Assay. [Method for determination of the imine XI]

(available from the subsidiary company)), and the resonance device (product name: jNM_ECX4〇〇) is measured at room temperature as a reference material dissolved in the sputum of the sputum, and the sputum is based on the formula shown in the following formula (1). -43- 201237068 醯 imidization rate (%) = (i-aVa2x, ^α) χΐ〇 0 (i) A. The peak area of the protons derived from the NH group (lOppm) A. The peak area of other protons α: the ratio of the number of protons in protonic acid relative to the proton of a sulfhydryl group [solution viscosity] The solution viscosity of the polymer (mPa w &quot;) is from 25 ° C Use the E-spin

The transadhesive meter measures a solution which is diluted to a prescribed solid content concentration using a prescribed solvent. Degree [Synthesis Example 5] As a diamine compound, bis(4-aminophenyl)-p-octylaniline U8g (4.58 mmol), 4,4, _:aminodiphenylmethyl 82 § (4 η 亳 Mo Er), 4-aminophenyl 4-aminophenyl phthalate 丨 57 g (6 87 mmol) — (2 propynyloxy) 2, 4-phenylenediamine 〇 74 g (458 mmol), fourteen = oxy-2,4-diaminophenyl hydrazine. 73 g (2 29 mM), 3,6-bis (4 amino benzyloxy) cholestane 29.29g (〇.46 mmol) dissolved in N_mercapto_2_. After 44 g of pyridone, 4.57 g (20-4 mmol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride was added, and the reaction was carried out at 6 Torr for 3 hours. Thereafter, 49 g (2 27 mmol) of pyromellitic dianhydride was added, and after reacting at room temperature for 1 N··, N 5 -methyl-2-pyrrolidone 5 5 g was added for dilution to obtain a mouth plate. 3 A solution of 1 〇% solution having a viscosity of 3 〇 mPa.s of polylysine solution of about 110 g 〇 followed by 'addition of pyridine 9. 〇g and acetic anhydride 6.9 g and dehydration at n 〇 °% for 4 hours. After the imidization reaction, the solvent of the a agent in the system is replaced with a new γ-butyrolactone (in this operation, the pyridine and acetic anhydride of -44- •201237068 are removed from the oxime imidization reaction to the outside of the system). A solution containing about 1 〇〇g solid content concentration of 1% by weight, a solution viscosity of 33 mPa s, and a ruthenium iodide ratio of 83% was obtained. [Synthesis Examples 6 to 21, Comparative Synthesis Example 2 2] For Synthesis Examples 6 to 2 1 and Comparative Synthesis Example 2, the types and composition ratios of the monomers to be used were set as described below in Table 1 and below. A polyimide-containing solution was prepared in the same manner as in Synthesis Example 5 except for (1) and (2). Further, in Table 1, [m〇l%] of each tetracarboxylic dianhydride indicates the content of the total amount of the tetracarboxylic dianhydride, and [m〇l%] of each diamine indicates the total amount of the diamine. content. (1) The solvent for the various diamines in the glutamic acid solution is 760 g of N-methyl-2-pyrrolidone and 760 g of γ-butyrolactone in Synthesis Example 16, and N-methyl-2 in Synthesis Example 17. - ° ratio &quot; each biting ketone 2 2 g and γ _ butyl vinegar 2 2 g. Further, the amount of N-methyl-2-pyrrole which was added for dilution after the preparation of the polyaminic acid solution was 190 g in Synthesis Example 16. (2) The amount of addition of pyridine and acetic anhydride was 9.3 g and 7.2 g in Synthesis Example 1 and Comparative Synthesis Example 2, and 9.5 g and 7.4 g in Synthesis Examples 1 and 12; 9.4 g and 7.2 g in 15, 31 l.lg and 240.9 g in Synthesis Example 16, 9.0 g and 6.9e in Synthesis Example 17, and 8.9 g and 6-9 g in Synthesis Examples 18 and 21; In Examples 19 and 2, 8.5 g and 6.6 g; in Comparative Synthesis Example 1, 10 g and 7.7 g. -45- 201237068 [Table i] Tetracarboxylic dianhydride diamine oxime imidization ratio (%) Solution viscosity (mPa-s) Aromatic alicyclic Dl Other diamines tl Other t-5 d-5 d- 6 d-7 d-8 d-9 d-10 d-11 d-12 Synthesis Example 5 0.49 g lOmol% 4.57 g 90 mol% d-2 I.78 g 20 mol°/〇〇.82 g 18 mol% 1.57 g 30 mol% 〇 .74g 20mol% 〇.73g lOmol% 0.29g 2mol% 83 33 Synthesis Example 6 25.25g 5mol°/〇4.83g 95mol% d-2 1.78g 20mol% 0.82g 18mol% 1.57g 30mol% 〇.74g 20mol% 〇 .73g lOmol0/. 29.29g 2mol% 83 35 Synthesis Example 7 0.099g 2mol% 4.98g 98moI% d-2 1.78g 20mol% 〇.82g I8mol% l_57g 30mol% 〇.74g 20mol% 〇-73g lOmol% 〇.29g 2mol% 83 35 Synthesis Example 8 0.99 g 20 mol% 4,07 g 80 mol% d-2 1.78 g 20 mol% 0.82 g 18 mol% 1.57 g 30 mol% 〇.74 g 20 mol% 〇.73 g lOmol% 0.29 g 2 mol% 78 33 Synthesis Example 9 2.48 g 50 mol % 2.55 g 50 mol% d-2 3.95 g 50 mol% 1.40 g 30 mol% / 〇 0.26 g 8 mol% 〇. 65 g lOmol% 0.26 g 2 mol% 45 60 Synthesis Example 10 51.51 g lOmol% 4.76 g 90 mol% d-2 〇. 92 g lOmol% 1.32 g 28 mol% 163 g 30 mol% 〇.77 g 20 mol% 〇.76 g lOmol% 0.3 lg 2mo1% 80 40 Synthesis Example 11 53.53g lOmol% 4.86g 90mol°/〇d-2 〇.47g 5mol% 1.59g 33 mol%% 1.67 g 30 mol% 〇.79 g 20 mol%/〇〇-78 g lOmol% 0.31 g 2 mol% 45 55 Synthesis Example 12 53.53 g lOmol% 4.92 g 90 mol% d-2 0.19 g 2 mol% 1.76 g 36 mol% l-69 g 3〇mol% 0.80g 20mol% 〇-79g lOmol% 0.32g 2mol% 45 65 Synthesis Example 13 0.53g lOmol% 4.77g 90mol% dl 1.38g 20mol% 〇.85g 18m〇1% l-63g 30mol% 〇-77g 20 mol% 〇-77 g lOmol% 0.3 lg 2 mol% 83 35 Synthesis Example 14 〇.53g lOm Oll% 4.80g 90mol°/〇d-3 1.32g 20m〇l% 〇-86g 18mol% 1.64g 30mol% 〇.78g 20mol% 〇.77g IOmol% 0.3 lg 2mol% 80 35 Synthesis Example 15 0.53g lOmol% 4.91 g 90 mol% d-4 l.llg 20 mol% 0.88 g 18 mol% 1.68 g 30 mol% 0,80 g 20 mol% 〇-79 g IOmol% 〇.32 g 2 mol% 80 36 Synthesis Example 16 17.16 g lOmol% 158.7 g 90 mol% dl 47.42 g 20 mol% 56.11 g 30 mol% 26.26 g IOmol% 10.54 g 2 mol% 25.74 g 8 mol% 17.73 g 20 mol% 20.36 g 1 O mol% 80 50 Synthesis Example 17 0.49 g 10 mol% 4.57 g 90 mol ° / 〇 dl 1.32 g 20 mol% 1.57 g 30 mol % 〇.74g 20mol% 〇.73g I Omol% 〇.29g 2mol% 〇-72g 8mol% 〇.57g 1 Omol% 80 20 Synthesis Example 18 t-2 〇.63g lOmol% 4.52g 90mol°/〇d-2 L_75g 20 mol% 〇.81g 18 mol% 1.55 g 30 mol ° / 〇 0.73 g 20 mol% 〇. 72 g IO mol % 〇. 29 g 2 mol% 83 38 Synthesis Example 19 t-3 0.99 g lOmol% 4.36 g 90 mol ° / 〇d-2 1.69 g 20 mol% 0.78 g 18 mol% 1.49 g 30 mol% 〇, 71 g 20 mol% 0.70 g IOmol% 〇.28 g 2 mol% 83 40 Synthesis Example 20 29.29 g 5 mol ° / 〇 4.36 g 95 mol ° / 〇 dl 1.58 g 20 mol % 〇. 62 g lOmol% 0.88 g IOmol% 〇.12 g 2 mol% 〇.21 g 2 mol ° / 〇 1.70 g 57. 3 mol% 83 44 Synthesis Example 21 t-4 〇.89g lOmol% 4.58g 90mol°/〇d-2 1.71g 20mol% 〇.79g 18moI% 1.5Ig 30mol% 0.71g 20mol% 〇, 71g IOmol% 〇.28g 2mol % 82 20 Comparative Synthesis Example 1 t-4 2.06 g 20 mol% 4.51 g 80 mol% 3.43 g 68 mol% 〇, 82 g 20 mol% 〇-81 g IOmol% 〇.33 g 2 mol% 84 120 Comparative Synthesis Example 2 5.29 g 100 mol% dl 1.38 g 20 moi% 〇.85 g 18 mol% i.63 g 30 mol% 〇.77 g 20 mol% 〇. 76 g IOmol% 〇-31 g 2 mol% 90 33 In Table 1, the abbreviations of the respective compounds are as follows. [tetracarboxylic dianhydride] tl : pyromellitic dianhydride t-2: 2,5-trifluoromethylbenzenetetracarboxylic dianhydride-46- 201237068 t-3 . Benzene-1,4-diyl double (1,3-di-oxo-1,3-diaza-2-benzoa-pentan-5-carboxylate) t-4: ethylene glycol dibenzoate tetraacid dianhydride t-5 : 2,3,5-tricarboxycyclopentyl acetic acid dianhydride [diamine] d-1 : N,N-bis(4-aminophenyl)-p-nonylaniline d-2 : N,N-double ( 4-aminophenyl)-p-octylaniline d-3 : N,N-bis(4-aminophenyl)-aniline d_4 : N,N-bis(4-aminophenyl)-methylamine d -5 : 4,4'-diaminodiphenylmethane d-6 : 4-aminophenyl 4-aminophenyl phthalate d-7 · 1-(2-propionyl lactyl)-2 , 4-phenylenediamine (1-8: tetradecyloxy-2,4-diaminobenzene d-9 : 3,6-bis(4-aminophenyl fluorenyloxy) cholestane dl〇 : 4,4'-[4,4'-propane-4,4-propane-1,3-diylbis(piperidine-1,4-diyl)]diphenylamine d-1 1 : p-phenylenediamine D-12: bisaminopropyltetramethyldioxane &lt;synthesis of poly-proline&gt; [Synthesis Example 22] 1,2,3,4-cyclobutane as tetracarboxylic dianhydride Tetraic acid dianhydride 200g (1.0m), 2,2'-dimercapto-4,4'- as diamine 210 g (1·0 mol) of diaminobiphenyl was dissolved in 370 g of N-mercapto-2-pyrrolidone and 3300 g of γ-butyrolactone, and reacted at 40 ° C for 3 hours to obtain a solid content concentration of 10% by weight. %, a poly-linic acid solution having a solution viscosity of 1 600 m P a · s - 47 - 201237068 &lt;Preparation of liquid crystal alignment agent &gt; [Example 1] Polyimide-containing solution obtained in the above Synthesis Example 5 Adding γ-butyrolactone (BL), Ν-methyl-2-oxaridone (ΝΜΡ) and butyl cyanidin (BC), further added to 100 parts by weight of the total amount of the polymer. 2 parts by weight of N,N,N ',N '-tetraglycidyl-4,4,-diaminodiphenyl decane as an epoxy compound, and sufficiently stirred to prepare a solvent composition of BL: NMP: BC = 75: 10: 15 (by weight), a solution having a solid content concentration of 5% by weight. This solution was filtered using a filter having a pore size of 1 μm to prepare a liquid crystal alignment agent. [Examples 2 to 19. Examples 1 to 2] Liquid crystal alignment agents of Preparation Examples 2 to 19 and Comparative Example were treated in the same manner as in Example 除了 except that the polymer described in Table 2 was used. [Production and Evaluation of Display Element] [Evaluation of Printability] Using the liquid crystal alignment film printer (manufactured by 写本写真印刷), the prepared Examples 1 to 19 and Comparative Examples were prepared! Each of the liquid crystal alignment agents of ～2 was applied to the transparent electrode surface of the glass substrate with the transparent electrode formed of the ITO film, and heated (prebaked) for 1 minute on a hot plate at 80° C. to remove the solvent, and then at 200. The hot plate of °C was heated for 1 minute (post-baking) to form a coating film having an average film thickness of 600A. The coating film was observed with a microscope having a magnification of 2 times and the unevenness of printing and the presence or absence of small holes were investigated. The case where there is no shrinkage or uneven coating is "good", and the other cases are "poor". [Evaluation of film thickness uniformity of coating film] -48-.201237068 For the above Examples 1 to 19 and comparison In each of the coating films of Examples 1 to 2, the film thickness at the center portion of the substrate and the film thickness at a position 5 mm from the outer end of the substrate were measured using a needle-type film thickness meter (manufactured by KLA-Tencor Co., Ltd.). . When the film thickness difference between the two is 20 A or less, the film thickness uniformity r is good, and when the film thickness difference exceeds 20 A, the film thickness uniformity is evaluated as "poor J ° [manufacture of liquid crystal display element]. Each of the coating films of Examples 丨 to 丨9 and Comparative Examples 1 to 2 was subjected to a friction machine having a roller for winding a rayon cloth at a roller rotation speed of 400 rpm, a stage moving speed of 3 cm/sec, and a pile extrusion length of 〇5 mm. The rubbing treatment is performed to impart a liquid crystal alignment function. Thereafter, for each of the respective coating films, ultrasonic cleaning is performed for 1 minute in ultrapure water, followed by drying in a 100 C clean oven for 1 〇 minute, thereby obtaining The substrate of the liquid crystal alignment film was further subjected to this operation, and a pair of (two) substrates having a liquid crystal alignment film were obtained. Next, for each of the examples obtained in the above, 丨~丨9 and Comparative Examples 1 to 2 Applying an epoxy resin adhesive containing an alumina ball having a diameter of 3.5 μπ 1 to the outer edge of any one of the pair of substrates having a liquid crystal alignment film on the substrate, and then facing the liquid crystal alignment film surface in a relative manner weight And crimping the 'attachment agent to harden. Then, a nematic liquid crystal (MLC-622 1 manufactured by Merck) is filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal is sealed with an acrylic photocurable adhesive. Liquid crystal display element was produced by the main inlet. [Evaluation of liquid crystal alignment] When the liquid crystal display elements of Comparative Examples 1 to 2 and the examples 1 to 2 manufactured as described above were observed by an optical microscope, The case where the bubble leakage was not observed was evaluated as "good" liquid crystal alignment, and the case where light leakage was observed was evaluated as "poor" liquid crystal alignment. [DC image retention characteristic (residual dc relaxation measurement)] For each of the liquid crystal display elements of Examples 1 to 19 and Comparative Examples 1 to 2 manufactured as described above, DC 1 V was used in a high temperature environment (60 ° C). After 10 days of driving with a 10 Hz triangular wave, the residual DC value was measured by a flicker elimination method. The measurement was performed on the relaxation rate (mV/sec) associated with the initial residual DC value immediately after the stop of driving and the inclination of the residual DC value with time. When the initial residual DC value is moderated at 1000 mV or less, the DC residual image characteristics are good, and the case where the DC residual is not relaxed is poor. [AC image retention characteristics (Evaluation of pretilt stability for each of the liquid crystal display elements of Examples 丨1 to 19 and Comparative Examples 1 to 2 manufactured as described above) was carried out in accordance with "T. j. Scheffei^j. Αρρΐ· Phys. The method described in Volume 48 'Page 1783 (1977) and "F. Nakano et al., JPN. J. Appl. Phys. Vol. 19, p. 2013 (1980)" by using He-Ne Ray The pre-tilt angle after driving for 13 hours at room temperature (pre-tilt angle 0ac after driving) was measured by a crystal rotation method of light emission, and the pretilt angle change rate α [%] was calculated according to the following formula (u). The case where the rate of change is less than 3〇/〇 is evaluated as “good”, and the case where the above is evaluated as “poor”. The above evaluation is evaluated as the characteristic of AC afterimage. a = (0ac-eini)/0inixl〇〇[〇 /o] (1)) [Reliability] For each of the liquid crystal display elements of Examples 丨 to 19 and Comparative Example manufactured as described above, the voltage after the application of stress for 1〇〇-50-201237068 hours under the backlight lamp was measured. Rate of change of retention rate (AVtiR). Regarding the voltage level u, the holding rate, with a application time of 60 microseconds and a pitch of 1 670 milliseconds, after applying a voltage of 1 V to the liquid component, the measurement is performed after the application is released. After the voltage retention rate. The measuring device was manufactured using TOYO Technica Co., Ltd. When the rate of change (ΔνΗΙΙ) is within 2%, it is judged to be a good one. The evaluation results of Examples 1 to 19 and Comparative Examples 1 and 2 are shown in Table 2 below together with each of #έ and 成. [Table 2] Polyimine Polyamide Printed Film Thickness Uniformity Liquid Crystal Alignment C Shadow D Residue Good Good Good Good Good Initial Residual DC Value (mV) 180 700 750 180

Hi pretilt stability evaluation change rate (%)

Reliability L Good 1.2 Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Synthesis Example 5 Synthesis Example 6 Synthesis Example 7 Synthesis Example 8 Example 1 Example 2 Example 3 Example 4

-51-.201237068 As shown in Table 2, both the film thickness uniformity and the liquid crystal alignment property of any of Example 丨~丨9 and Comparative Example ^ were good. In addition, the DC afterimage characteristics, ac afterimage characteristics, and reliability of any of Embodiments 1 19 are also good, and the DC residual image characteristics, AC residual image characteristics, and sinfulness of the 'Comparative Example 1' are good. Any of them was bad; the aC afterimage characteristic of Comparative Example 2 was good', but the DC residual image characteristics and reliability were poor. Further, regarding the embodiment 19, the total amount of the aromatic tetracarboxylic dianhydride relative to the tetracarboxylic dianhydride is 2% and 2 moles per kg of the molar ratio of the molars. Example 3' and Example 2 with respect to two molar ratios of 5 and 2 g of the monoamine (1)-1) and ,1J / and 2 mol% of Example 8 compared to 5 'Either molar ratio is 丨〇Mo Q, and the relaxation rate of the residual DC value of the first, fourth, sixth, and ninth steps on the 1/°U is a particularly preferable value. [Simple diagram description] fe 〇 [Main component symbol description] fe·- 〇 #»*&gt; -52-

Claims (1)

201237068 VII. Patent application scope: 1. A liquid crystal alignment agent characterized by: comprising a group consisting of polyamic acid obtained by reacting tetracarboxylic dianhydride with diamine and ruthenium imidized polymer thereof At least one polymer in the group, the tetracarboxylic dianhydride comprising an aromatic tetracarboxylic dianhydride, the diamine comprising a compound represented by the following formula (1), B H2N--A-1-A-NH2 (1) (In the formula (1), A each independently represents a phenylene group, an anthranyl group, an aziridine group, a pyrimidinyl group or a decyl group, and these may have a substituent; B has an aromatic ring structure. a monovalent chain, a monovalent chain hydrocarbon group having 10 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 30 carbon atoms, and the chain hydrocarbon group or the alicyclic hydrocarbon group may have a substituent, and a part of the fluorenylene group may be An oxygen atom, a carbonyl group or a -COO-substitution; wherein 'in B, a nitrogen atom is bonded to a nitrogen atom in the formula (丨), a carbon atom forming an alicyclic structure or a carbon atom forming a bad aromatic structure). 2. The liquid crystal alignment agent according to claim 1, wherein the b is an alkyl group having 1 to 6 carbon atoms or an aryl group which may have a substituent, the alkyl group may have a substituent, and a part of the fluorenylene group The liquid crystal alignment agent of the above-mentioned item of the invention, wherein the octa- phenyl group having a substituent is a phenyl group which is substituted by an oxygen atom, a carbonyl group or a carbonyl group. A liquid crystal alignment film which is formed, for example, by a liquid crystal alignment agent according to any one of the first to third aspects of the invention. -53- 201237068 . Seed liquid ^ crystal j. a , &quot; cattle, /, with the liquid crystal alignment as in the fourth paragraph of the patent application. Polylysine characterized in that it is a polyamic acid obtained by reacting a tetracarboxylic dianhydride with a diamine, and the amine is composed of a compound represented by the following formula (1). The dianhydride comprises an aromatic tetracarboxylic dianhydride η2ν~α-Ν-Α一Νη2 (1) (in the formula (1), each of the oximes is independently a phenylene group, an anthranyl group, a stilbene group, or a thiophene group. Trimorphin' and these may have a substituent; β is a valence group having an aromatic ring structure, a fluorene chain hydrocarbon group having a carbon number of 丨 ” or a monovalent alicyclic ring having a carbon number of 3 to 30 , 日技山 I, and the chain hydrocarbon or alicyclic hydrocarbon group may have a substituent 'partial methylene group may be substituted by a gas atom, a few groups or -COO-, wherein 'in B, and the formula benefits' Α 7 "The nitrogen atom binds to a methylene group, a magnetic precursor that forms an alicyclic structure, or a carbon atom that forms an aromatic ring structure." It is made by dehydration and ring closure of the patented vanillic acid. -54- 201237068 IV. Designated representative map: (1) The representative representative of the case is: (2) A brief description of the symbol of the representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: