TW201235386A - Liquid crystal aligning agent and liquid crystal alignment film - Google Patents

Abstract

Provided are: a liquid crystal aligning agent for obtaining a liquid crystal display element that has a high stable pretilt angle and is reduced in accumulation of residual charge; and a liquid crystal alignment film which is obtained from the liquid crystal aligning agent. The liquid crystal aligning agent is characterized by containing a polyamic acid ester that has a structural unit represented by general formula (1), a polyamic acid that has a structural unit represented by general formula (2) and an organic solvent, and the liquid crystal aligning agent is also characterized in that the polyamic acid ester has a side chain structure that has a pretilt angle-providing ability. (In the formulae, X1 and X2 each represents a tetravalent organic group; Y1 and Y2 each represents a divalent organic group; R1 represents an alkyl group having 1-5 carbon atoms; and A1 and A2 each independently represents a hydrogen atom, or an optionally substituted alkyl group, alkenyl group or alkynyl group having 1-10 carbon atoms.)

Description

201235386 VI. [Technical Field] The present invention relates to a liquid crystal alignment agent for a liquid crystal display element which exhibits a high pre-tilt angle and a small residual charge accumulation, and a liquid crystal alignment film obtained from the liquid crystal alignment agent. [Prior Art] A liquid crystal display element used for a liquid crystal television, a liquid crystal display or the like is usually provided with a liquid crystal alignment film for controlling a liquid crystal alignment state in the element. As a liquid crystal alignment film, a liquid crystal alignment agent containing a solution of a polyamidene precursor such as polyamic acid or a soluble polyimine is mainly applied to a glass substrate or the like and fired. The polyimine-based liquid crystal alignment film is accompanied by high definition of the liquid crystal display element, and it is required to suppress the contrast of the liquid crystal display element to reduce or reduce the image sticking phenomenon, and in the liquid crystal alignment film, in addition to the excellent liquid crystal alignment property or stability preheating In addition to the tilt angle, it is increasingly important to have a high voltage holding ratio, a small residual charge when a DC voltage is applied, and/or a characteristic that the accumulated residual charge due to a DC voltage is quickly relaxed. In the polyimine-based liquid crystal alignment film, in order to achieve the above-mentioned general requirements, a liquid crystal alignment agent of two or more kinds of polyaminic acid or a quinone imidized polymer having different mixing characteristics is known. For example, a liquid crystal alignment agent containing two or more kinds of polyaminic acid and two or more kinds of polymers having different surface tensions (Patent Document 1 and Patent Document 2), and a polymer having a maximum selectivity selected from the group consisting of ruthenium iodide A liquid crystal alignment agent of a polymer having at least two types of soluble polyimine and polyamic acid having a difference in oxime imidization ratio of a polymer having a minimum conversion ratio of quinone imine-5-201235386 (Patent Document 3) A liquid crystal alignment agent containing a low-polarity side chain polyamine resin and a polyamine having a specific structure (Patent Document 4). [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei 8- No. Hei 8- No. 8-325573 (Patent Document 3) Japanese Patent Laid-Open No. Hei 9-297312 [Patent Document 4] JP-A-2006-124626 [Summary of the Invention] [Problems to be Solved by the Invention] However, in recent years, large-screen and high-definition liquid crystal televisions have become the main body, and the demand for afterimages has become increasingly demanding. Features that require long-term use in harsh environments. In addition, as for the characteristics of the liquid crystal alignment film to be used, it is necessary to have more excellent characteristics and higher reliability, and the above-mentioned two or more kinds of polylysine having different properties or the polylysine Liquid crystal alignment agents of ruthenium imidized polymers are also not able to achieve this requirement. That is, the formation reaction of the polyamic acid used for the formation of the liquid crystal alignment agent is an equilibrium reaction, and the indole exchange reaction is carried out in the solution. Therefore, even if a liquid crystal alignment agent having a composition of two or more types of polyamic acid having different mixing characteristics is subjected to a guanamine exchange reaction in the preparation, storage, coating, and firing, the polymer composition is averaged. As a result, in the case of -6-201235386 containing a side chain component alone, the pretilt angle becomes lower, and the ratio of the side chain component does not increase, and the desired pretilt angle cannot be expressed. However, when the ratio of the side chain component is increased, there is a problem that the DC charge accumulation becomes large. Therefore, it is difficult to solve the above problems in the case of polyphosphonic acid or a liquid crystal alignment agent in which a soluble polyimine and a polyaminic acid are mixed, and on the other hand, it is imidized with 100% of the respective polyamines. The liquid crystal alignment agent of polyimine does not produce the above guanamine exchange. However, in the case of using a liquid crystal alignment agent of a polyimide having a ruthenium iodide ratio of 1% by weight, there is a problem of solubility of polyimide, and deterioration of printability when a liquid crystal alignment agent is formed on a substrate to form a liquid crystal alignment film. The characteristics of the deterioration deteriorated. The present invention provides a high voltage maintenance ratio, a small residual charge when a DC voltage is applied, and/or a residual residue due to a DC voltage, in addition to the above-described general problem, and a pretilt angle which is excellent in liquid crystal alignment or stability. In order to achieve the above object, the present inventors have made efforts to achieve the above object, and have focused on converting a free acid structure of polypergic acid into an ester structure. The polyglycolate does not produce a polyamidamine-like indoleamine exchange reaction because it is esterified to a non-reversible reaction. Then, as a constituent component of the liquid crystal alignment agent, it was found that a polyprene which exhibits a pretilt angle component and exhibits a precharge angle component by exhibiting a pretilt angle component in a polyglycolate which does not produce a guanamine exchange reaction, and which is excellent in suppressing charge accumulation function Acid 201235386 A liquid crystal alignment agent that suppresses charge accumulation components can solve the above problems. The present invention has been developed based on the above knowledge, and the gist thereof is as follows. 1. A liquid crystal alignment agent characterized by comprising a polyphthalate having a structural unit of the following formula (1), a polyamic acid having a structural unit of the following formula (2), and an organic solvent, and Polyglycolate has a side chain structure with pretilt performance, [Chemical 1] [COOR! ) 2 N—C—X^C—N—Yj —Ν—ΟΙ II A! Ο II I o a2 (COOH }2 -X2-CN-Y2-〇A2 (i) (2) (wherein, X! and X2 are tetravalent organic groups, Y丨 and Y2 are divalent organic groups, and Ri is a carbon number of 1 to 5 And a liquid crystal alignment agent according to claim 1, wherein the foregoing is a hydrogen atom, an alkyl group having a carbon number of 1 to 10, or an alkenyl group or an alkynyl group having a carbon number of 2 to 10. The content of the polyamidomate and the content of the polyamic acid are in the range of (the content of the polyamidite/the content of the polyamic acid) is W9 to 9/1. 3. As in claim 1 or The liquid crystal alignment agent according to the above, wherein the total content of the polyamic acid ester and the polyamic acid is 5% to 15% by mass based on the organic solvent. 4. The method according to any one of claims 1 to 3 Liquid crystal alignment agent 'which' has -8- 201235386 Angle configuration of the side chain performance ability by the following formula (3), (4) and (5) into a group of at least one kind selected from,

(In the formula (3), Z3 is a bond group, and each of them is independently a single bond or at least one selected from the group consisting of the following formulas (B-1) to (B-16), and Z2 is a single bond, Or at least one selected from the group consisting of an alkylene group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, and an exoaryl group which may have a substituent, Z4 At least one divalent cyclic group selected from the group consisting of an aliphatic ring having 3 to 20 carbon atoms, an aromatic ring having 6 to 30 carbon atoms, and a heterocyclic ring having 1 to 20 carbon atoms, which may have a substituent, Or a divalent organic group having a carbon number of 12 to 25 having a steroid skeleton, Z5 being an aliphatic ring having 3 to 20 carbon atoms which may have a substituent, an aromatic ring having 6 to 30 carbon atoms, and a carbon number of 1 to 20 At least one divalent cyclic group selected from the group consisting of a ring, a is an integer of 0 to 4, and Z6 is a C1-C18 alkyl group having a substituent and a C1-C18 fluorinated alkane At least one selected from the group consisting of an alkoxy group having 1 to 18 carbon atoms and a fluorine-containing alkoxy group having 1 to 18 carbon atoms, and b is an integer of 1 to 4, and 201235386 is a formula (4). An aromatic ring having a carbon number of 3 to 20 rings, a carbon number of 6 to 30, and a carbon number of 1 to 20 At least one selected trivalent cyclic group or a trivalent organic group having a steroid of 12 to 25, and W2 and Z5 of the formula (3) have an integer of 〇~4, and W3 and Z2 of the formula (3) 26 having the same definition (3) has the same definition, e is an integer of 1 to 4, E in the formula (5), and 2 of the formula (3), and Z3 have the same alkyl group having a carbon number of 4 to 30 or Fluorinated alkyl group, f is a whole of 1 to 4 [3] Ο 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一— Η3 〇10ch3 ch3 NN-r2 (B-9) (B-10) (B-11) -0-^0- 〇II —s— II 〇—CH: II 0 (B-14) (B-15) (B-16) —N — I R2 (B-5) 1N a r2 (B-6) —Ν—^·~ I R2 (B-7) Aliphatic! The carbon number of the rack is the same as defined, C ' w4 and the formula ^ E 2 is the number). *~-NuN— R2 R2 (B-8) -(CH2)n- n=1~10 (B-12) (In the formula (Bl) to (B-16), R2 is independently a hydrogen atom having a substituent A combination of an alkyl group, an alkenyl group, an alkynyl group, a protrusion or the like having a carbon number of 1 to 10). 5. The liquid crystal alignment agent according to any one of claims 1 to 4, wherein, in the formula (1), one or all of Y! has a structure of at least one type selected from the above (5). The base (Yl,)^, or may have: a base, or a part thereof, the above formula (3) to -10- 201235386 6. The liquid crystal alignment agent as described in claim 5, wherein the ratio of the above-mentioned Υ, ' relative to Υι In terms of 1 to 50 mol%. 7. The liquid crystal alignment agent according to claim 5, wherein the structure of the above Y1' is selected from at least one type of structure of the following formulas Π-1] to [1-3],

[1-3] (In the formula [1-1] to [1·3], 'A3 and A4 are each independently a single bond or an alkyl group having 1 to 10 carbon atoms, and As is a single bond or a carbon number of 1 to 2 a divalent organic group of argon, a hexavalent organic group of 8 to 6 or a trivalent organic group having a carbon number of 1 to 30. A7 and a8 are each independently a divalent organic group having a carbon number of 1 to 30. 'Z is the above formula (3) or The side chain structure 'W represented by the above formula (5) is a side chain structure represented by the above formula (4)), and the liquid crystal alignment agent according to any one of claims 1 to 7 wherein the above formula ( X1 and X2 in 1) and (2) are each independently at least one type selected from the structures represented by the following formulas. -11 - 201235386 [化5]

H3c ch3 CH3 h3c ch3 m xx

CH3

TC

The liquid crystal alignment agent according to any one of claims 1 to 8, wherein, in the formula (2), Y1 2 is at least one selected from the structures represented by the following formulas. [Chemical 6]

-12-110, a liquid crystal alignment film, which is obtained by coating the liquid crystal alignment agent according to any one of claims 9 to 9 and firing it. 2 1 1 . A liquid crystal alignment film which is characterized in that it is irradiated with polarized radiation on a film obtained by firing a liquid crystal alignment agent according to any one of the claims ～9, and is obtained. An element characterized by a liquid crystal alignment film of claim 1 or loaded. The liquid crystal alignment film according to claim 1, wherein the liquid crystal alignment layer is provided between the pair of substrates, and the polymerization is performed by at least one of an active energy ray and heat between the pair of substrates. The liquid crystal composition of the polymerized composition is a liquid crystal display element produced by a step of polymerizing a polymerizable compound while applying a voltage between the electrodes. 14. A liquid crystal display element characterized by having a request item 13 for a liquid crystal alignment film. The liquid crystal display device according to claim 1, wherein the liquid crystal display element is provided between the pair of substrates provided in the liquid crystal alignment film, and the active energy line and the heat are disposed between the pair of substrates. A liquid crystal composition of at least one polymerizable polymerizable compound is produced by a step of polymerizing the polymerizable compound while applying a voltage between the electrodes. [Effects of the Invention] In the liquid crystal alignment agent provided by the present invention, the pretilt angle is expressed by a polyphthalate which does not produce a guanamine exchange reaction, so that a high stability pretilt angle is expressed by a predetermined content, and at the same time The accumulation of charge is suppressed by the poly-proline which is excellent in the function of the charge, so that the generation of electric charge and the generation of the residual image are small. In addition, since the liquid crystal alignment agent of the present invention is polyimidized by the imidization of the liquid crystal alignment agent, the solubility of the component contained in the liquid crystal alignment agent is high, and the coating and the printing property are excellent when the liquid crystal alignment film is formed on the substrate. A configuration of the first step enables the front-loaded electrode to be applied beforehand, which is not required, and is not required to be subjected to the guanamine exchange in a step -13 to 35,535,386. Since the liquid crystal alignment agent should be used as described above, the properties are not changed during storage, and it can be stably maintained in the case of storage and storage. [The best mode for carrying out the invention] <Polyurethane> Precursor, and polymer for the reaction site. The polyglycolate used in the present invention is a polyfluorene which has been heated to have the following quinone imine.

Ο Ο

构造 The structure represented by the poly(1) contained in the liquid crystal alignment agent of the present invention. The glutamate has the following formula [Chem. 8] (COOR-,) 2. C-X1-CN-Y1-N-〇〇A1 A2 In the above formula (1), 'R is a carbon number of l~5, Μ- 14- (1) An alkyl group of preferably 1 to 2. 201235386 Polyglycolate, with an increase in the carbon number in the alkyl group, increases the temperature at which the imidization is carried out. Therefore, it is particularly preferable to use a methyl group from the viewpoint of the ease of imidization by heat. In the formula (1), each of A2 is independently a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkenyl group which may have a substituent. Specific examples of the above alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a cyclopentyl group, a cyclohexyl group, a dicyclohexyl group and the like. The alkenyl group may, for example, be a structure in which one or more CH-CH structures present in the above alkyl group are substituted with a c=c structure, and more specifically, for example, a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, or the like. 2. Butanyl, 1,3-butadienyl, 2-pentenyl, 2-hexenyl, cyclopropenyl, cyclopentenyl, cyclohexenyl and the like. The alkynyl group may, for example, be substituted with one or more CH2-CH2 structures present in the above alkyl group to form a C=C structure, and more specifically, for example, an ethynyl group, a 1-propynyl group, or a 2-propyne group. Base. The alkyl group, the alkenyl group or the alkynyl group may have a substituent and may form a ring structure, and the total number of carbon atoms may be 1 to 1 Å. Further, in the present invention, the formation of a ring structure by a substituent means that the substituents or the substituents are bonded to a part of the parent skeleton to form a ring structure. Examples of the substituent include a halogen group, a hydroxyl group, a thiol group, a nitro 'aryl group, an organic oxy group, an organic thio group, an organic decyl group, a decyl group, a acetoxy group, a thioester group, and a phosphate ester. Examples of the halogen group of the substituent of the hydrazino group, the alkyl group, the alkyl group, the alkenyl group or the alkynyl group include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The aryl group of the substituent may, for example, be a phenyl group. The aryl group may be substituted for the other substituents of the former -15-201235386. The organooxy group of the substituent may, for example, be a structure represented by 0-R. The R may be the same or different and may, for example, be an alkyl group, an alkenyl group, an alkynyl group or an aryl group. The above substituents may be further substituted in these R. Specific examples of the organooxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group and the like. The organic thio group of the substituent may, for example, be a structure represented by -S - R . The R' may, for example, be an alkyl group, an alkenyl group, an alkynyl group or an aryl group. The above substituents may be further substituted in these R. Specific examples of the organic thio group such as methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, heptylthio group, octyl group Thio group and the like. The organoalkylene group of the substituent may, for example, be a structure represented by -Si-(R)3. The R may be the same or different, and examples thereof include the above-mentioned alkyl group, alkenyl group, alkynyl group, aryl group and the like. The above substituents may be further substituted in these R. Specific examples of the organic decyl group are, for example, trimethyldecyl, triethyldecyl, tripropyldecyl, tributyldecyl, tripentyldecyl, trihexyldecyl, pentyldimethyldecyl, hexyl Dimethyl decyl group and the like. The thiol group of the substituent may be, for example, a structure represented by _C(0)-R. The R' may, for example, be an alkyl group, an alkenyl group or an aryl group. The above substituents may be further substituted in these R. Specific examples of the mercapto group include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentamidine group, an isovaleryl group, a benzamidine group and the like. The ester group of the substituent may, for example, be a structure represented by -C(0)0-R or -0C(0)-R. The R may, for example, be an alkyl group, an alkenyl group, an alkynyl group or an aryl group. The above substituents may be further substituted in these R. -16- 201235386 The thioacetic acid group of the substituent may, for example, be _C(S)〇_R or a structure represented. The R may, for example, be the above alkyl group, alkenyl aryl group or the like. The above substituents may be further substituted in these R. The phosphate group of the substituent may, for example, be a 〇p(〇)_(〇r) 2 structure. The R may be the same or different, and examples thereof include the aforementioned alkyl group, group, aryl group and the like. The above substituents may be further substituted in these R. The amine group ' of the substituent' may, for example, be represented by -C(〇)NH2, or ., -NHC(0)R, -C(0)N(R)2, ·(ΝΙΙ(:0)ΙΙ The above-mentioned alkyl group, alkenyl group, alkyne, etc. may be mentioned, for example, the above-mentioned substituent may be further substituted in these R. Α and Α2 are generally introduced into a bulky structure, and the alignment of the amine-based liquid crystal is lowered. The possibility is such that a hydrogen atom or an alkyl group having a carbon number of 1 to 5 is preferred, and a hydrogen atom, a methyl group or an acetamidine group has a pretilt performance performance structure ( Hereinafter, the side chain structure having a pretilt angle means a structure having the ability to align liquid crystal molecules to the substrate at a certain angle, and the ability is not limited thereto. Or a long-chain fluoroalkyl group, a cyclic group having an alkyl group at the terminal, a steroid group, etc., are also suitable for use in the present invention. The main chain of the side-polyglycolate may be directly bonded or bonded through a bond group. The side chain structure of the dip performance ability is, for example, the structure represented by the following (5) - 〇C(S)-R, alkynyl group, the represented singular group, 诀C(0)NHR structure The group, a reactive group or a substituted aryl group tilting state force particularly preferred side chain groups are now configured ability embodiments inch or fluoroalkyl chain junction structure of formula (3) to -17-201235386 [Formula 9]

Zi-z2—z3_z4 ten z5 ten ζβ b (3)

(4) In the formula (3), each of B, and Z3 is independently a single bond or at least one divalent organic group selected from the group consisting of A F (B-1) to (B-16). Among them, 2] and Z3 are difficult to synthesize, and are preferably a single bond, B-l, B-3, B_4, B_5, B_6, B-7, B-ll, B-13, or B-16. In the following formula b-ι to the formula B_16, each of R2 is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof. Specific examples of the above alkyl group, alkenyl group, alkynyl group and aryl group can be exemplified in the same manner as described above. The alkyl group, the alkenyl group, the alkynyl group, and the aryl group may have a substituent when the total carbon number is from 1 to 10, and may further form a ring structure with a substituent. Specific examples of the respective substituents are the same as those described above. -18- 201235386 [化10]—〇一一S一一〇一—一ν—ϋ—ν— I | 〇Ni I (Β-1) (Β-2) (Β-3) (Β*4 R2 r2 (Β-5) (Β-6) r2 (B-7) -Ν—〇=K 9Hs 〇10ch3 ch3 r2 Ν Ν- R2 I(CH2)n-η=1~10 one CH2— 0—(Β·9) (Β-10) (Β-11) (Β-12) (Β-13) A Q-, ll.,. Q— Ο II —S— II Ο—"'CH2 - One (Β-14) II ο (Β·15) (Β-16)

-N 戌2戌2 (Β·8) In the formula (3), Ζ2 is a single bond, or an alkylene group having a carbon number of 1 to 10 which may have a substituent, an alkenyl group having a carbon number of 2 to 1 Å or At least one selected from the group consisting of an alkynyl group having 2 to 10 carbon atoms and a group of exoaryl groups. The alkylene group may have a structure in which one argon atom is removed from the alkyl group. More specifically, for example, a methylene group, a 1,1-vinyl group, a 1,2-vinyl group, a 1,2-propenyl group, a 1,3-propenyl group, a 1,4-butenyl group, and 1,2 -butenyl, 1,2-pentenyl, 1,2-hexenyl, 1,2-decenyl 1,2-dodecenyl 2,3-butenyl, 2,4- Pentenyl, 1,2-cyclopropenyl, 1,2-cyclobutenyl, 1,3-cyclobutenyl, 1,2-cyclopentenyl, 1,2-cyclohexenyl, 1, 2-cyclodecenyl, 1,2-cyclododedecyl and the like. The alkenyl group may have a structure in which one hydrogen atom is removed from the above alkenyl group. More specifically, '1, 1-vinylidene, 1,2-vinyl, 1,2-ethylidene, 1-methyl-1,2-ethylene, ι , 2-extension B--1,1-ethyl stilbene, 1,2-ethylidene-1,2-acetoxy, ι,2-exetyl- 1,2-propenyl, 1 2 -Extended vinyl-1,3-propenyl, anthracene, 2-vinylene-1,4-butenyl' U2-strandyl-1,2-butenyl and the like. The alkynyl group may, for example, be a structure in which one hydrogen atom is removed from the above alkenyl group, for example, -19 to 201235386. More specifically, for example, an ethynyl group, an extended acetylene 'methylene group, an ethynyl group-1,1-vinyl' ethynyl-1,2-vinyl group, an exetylene group-i, a 2-propene group And ethynyl-1,3-propenyl, ethynyl-1,4-butenyl, ethynyl-1,2-butenyl and the like. The aryl group may, for example, have a structure in which one hydrogen atom is removed from the above aryl group. More specifically, it may, for example, be a 1,2-phenylene group, a 1,3-phenylene group or a 1,4-phenylene group. The alkyl group, the alkenyl group, the alkynylene group, the aryl group, and the combination may have a substituent, and the substituent may form a ring structure. Specific examples of the respective substituents are the same as those described above. Z2 is preferably a single bond or an alkyl group having 2 to 6 carbon atoms. In the formula (3), Z4 is a divalent group selected from the group consisting of an aliphatic ring having 3 to 20 carbon atoms, an aromatic ring having 6 to 30 carbon atoms, and a heterocyclic ring having 1 to 20 carbon atoms which may have a substituent. At least one divalent organic group selected from a cyclic group or an organic group having 12 to 25 carbon atoms having a steroid skeleton. Among them, a cyclic group having a carbon number of 12 to 25 having a benzene ring, a cyclohexyl ring or a steroid skeleton is more preferable. When the total number of carbon atoms of the divalent organic group is from 4 to 30, the substituent may be substituted, and the substituent may form a ring structure. Specific examples of the respective substituents are the same as those described above, and are preferably a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, a oxy group having 1 to 3 carbon atoms, and a carbon number! The fluorinated alkyl group of ～3, -NHCOOR (R is a group of carbons 1-4), the fluorinated alkoxy group represented by the carbon number of 〜3, and the fluorine atom are selected from the group. #(3)中中' Z5 is an aliphatic ring having 3 to 20 carbon atoms which may have a substituent, an aromatic ring having 6 to 30 carbon atoms, and a heterocyclic ring having a carbon number of 1 to 20-20-201235386 At least one selected divalent cyclic group. Among them, a benzene ring or a cyclohexane ring is more preferable. When the total number of carbon atoms of the divalent cyclic group is from 1 to 30, the substituent may be substituted, and the substituent may form a ring structure. Specific examples of the respective substituents are the same as those described above, and are preferably a mercapto group, a mercapto group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a fluorine-containing alkyl group having 1 to 3 carbon atoms. The group selected from the group consisting of a hydrazine group represented by -NHCOOR (R is an alkyl group having 1 to 4 carbon atoms), a fluorine-containing alkoxy group having 1 to 3 carbon atoms, and a fluorine atom is selected. In the formula (3), a is an integer of 0 to 4, preferably an integer of 0 to 2. In the formula (3), Z6 is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and a fluorine-containing alkoxy group having 1 to 18 carbon atoms. At least one selected from the group. Among them, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 10 carbon atoms is preferred. Preferred are an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. More preferably, it is an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms. b is an integer of 1 to 4, preferably an integer of 1 to 2. In the formula (4), W is at least one selected from the group consisting of an aliphatic ring having 3 to 20 carbon atoms, an aromatic ring having 6 to 30 carbon atoms, and a heterocyclic ring having 1 to 20 carbon atoms which may have a substituent. A trivalent organic group selected from a trivalent cyclic group or an organic group having a carbon number of 12 to 25 having a steroid skeleton. Among them, a benzene ring, a cyclohexane ring or an organic group having a carbon number of 12 to 25 having a steroid skeleton is preferred. The trivalent organic group may have a substituent or a substituent to form a ring structure, and the number of carbon atoms may be 4 to 30. Specific examples of the respective substituents are the same as those described above, and are preferably a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or - 21 - 201235386 NHCOOR (R is an alkyl group having 1 to 4 carbon atoms) selected from the group consisting of a mercapto group, a carbon number of a fluorine alkoxy group, and a fluorine atom. In the formula (4), W2 is defined in the same manner as Z5 in the above formula (3). Among them, a benzene ring or a cyclohexane ring is preferred. When the total number of carbon atoms of the divalent organic group is 1, it may have a substituent, and further, a substituent may form a ring structure. Specific examples of the respective examples are the same as those described above, and preferred are a hydroxyl group, a carbon number of 1 to an alkyl group, an alkoxy group having a carbon number of 1 to 3, and a fluorine-containing alkane having a carbon number of 1 to 3 | NHCOOR (R is carbon 1) The group of the guanamine group, the fluoroalkoxy group having a carbon number, and the fluorine atom represented by the alkyl group of ～4 is selected. c is 0 to 4, preferably an integer of 〇~2. In the formula (4), W3 is defined in the same manner as Z2 in the above formula (3). Among them, a single bond or an alkylene group having 2 to 6 carbon atoms is preferred. The alkyl group, the stretching group, the stretching group, the aryl group, and the group in combination may have a substituent, and the substituent may form a ring structure. Further, the substituent-forming ring structure means that the substituents are bonded to each other or the substituents of the substituent and the parent skeleton are in a ring structure. Specific examples of the respective substituents are the same as described above. <1 is an integer of 0 to 4, preferably an integer of 0 to 2. In the formula (4), W4 is defined by the same as Z6 in the above formula (3). Among them, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 carbon atom or a fluorine-containing alkoxy group having 1 to 10 carbon atoms is preferred. Preferred are an alkyl group of 12 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. More preferably, it is a C 1 - alkyl group or a C 1 - 9 alkoxy group. e is an integer of 1 to 4, preferably an integer of 1 to 2. In the formula (5), E! also includes a preferred example, and Z of the formula (3), and Z3, with an integer of 〜30 代基3, with an alkenyl group of ~1 0 to take a part, to ~1 8 Number 1 9 is the same as -22- 201235386. E2 is an alkyl group having 4 to 30 carbon atoms or a fluorine-containing alkyl group having 4 to 30 carbon atoms. Among them, a fluorine-containing alkyl group having an alkyl group having 10 to 30 carbon atoms and a carbon number of 1 to 30 is preferred. f is an integer of 1 to 4, preferably an integer of 1 to 2. The pretilt performance performance differs depending on the side chain structure described above. However, when the amount of side chain structure contained in the general polymer is increased, the pretilt angle is higher and the pretilt angle is decreased. Further, the side chain structure represented by the formula (3) or the formula (4) having a cyclic structure is compared with the side chain structure of only the long-chain alkyl group represented by the formula (5), and has a small amount and also exhibits a high pretilt angle. tendency. The polyglycolate having the above side chain structure in the present invention can use a diamine of a side chain structure or a tetracarboxylic acid derivative having a side chain structure as a raw material, and reacts with a diamine and a tetracarboxylic acid derivative. And got it. Among them, a method of using a diamine compound having a side chain structure is preferred from the viewpoint of easiness of synthesis of raw materials and the like. That is, in the above formula (1), the polyglycolate of the present invention has a part or all of the divalent organic group, or all of the above-mentioned divalent organic groups having a side chain structure (hereinafter, also referred to as ruthenium). The structure of the glutamic acid ester is preferably a structure represented by the following formula [1-1] to Π-3], but is not limited thereto. -23- 201235386 [Chem. 11]

[1-1] A3-

A4—

A7-W_As Ding

A4— [1-3] In the formula [1-1] to [1-3], 八3 and a4 are each independently a single bond or an alkyl group having a carbon number of 1 to 10, and A5 is a single bond or a carbon number of 1. a valence organic group of -20, a6 is a nitrogen atom, or a trivalent organic group having a carbon number of 1 to 30, and VIII and A8 are each independently a divalent organic group having a carbon number of 1 to 30, and Z is the above formula (3). Or the side chain structure represented by the above formula (5), and W is a structure of a side chain structure represented by the above formula (4), and a structure of Y〆, and a more specific example, for example, the following formula [2-1] The configuration shown in the formula [2-51] is not limited thereto. -24- 201235386 [Chem. 12]

In the above formula [2-1] to [2-3], Z7 is -0-, -0 (: 112-, -COOCH2-, -CH20C0, -CONH-, or -NHCO-, having a carbon number of 1~ The alkyl group, the alkoxy group, the fluorine-containing alkyl group or the fluorine-containing '-CH2〇-Z 8 is a pen-oxy group. -25- 201235386 [Chemical 13]

In the above formula [2-4]~form [2-6], 'Z9 is -(:00-,-0(:0-, -(:00(:1^2-, -CH2OCO-, -CH20-, -OCH2-, -CH2-, -CONH- or -NHCO., z10 is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group.

-26- 201235386 In the above formula [2-7] and formula [2-8], 21| is -(:00-,-0(:0-, -(:00<:112, -CH2OCO- ' .CH2 〇-, -〇CH2_, -CH2-, -NHCO-, -CONH- or 〇·, Z!2 is a fluorine group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a methyl group, an ethyl group Base, ethoxylated or hydroxy.

[2-10] In the above formula [2-9] and formula [2_10], Z|s is an alkyl group having 3 or more and 12 or less carbon atoms. The cis-trans isomers of L 4 ·cyclohexene are each trans-isomerized -27- 201235386 [Chem. 16]

[2-11] [2-13] In the above formula [2-11] to formula [2-13], Z14 is an alkyl group having 3 to 12 carbon atoms, and 1,4-cyclohexene The cis-trans isomers are each a trans isomer. [Chem. 17]

In the above formula [2-15], 八9 and A1() are each independently -0-*, -(:00-*, -OCO-*, -cooch2-*, -ch2oco-*, -ch2o-*, -och2-*, -CH2-*, -CONH-* or -NHCO-* (however, the bond key labeled "*" is (CH^az^A^ is 1,4-cyclohexenyl or 1, 4-phenylene, A12 is an alkyl group having 3 to 20 carbon atoms which may be substituted by a fluorine atom, and the heart is an integer of 0 or 1, -28-201235386 a2 is an integer of 2 to 10, and a3 is an integer of 0 or 1. [化18] 0

-29- 201235386 [Chem. 19]

-30- 201235386 [Chem. 20]

201235386 [化 21]

-32- 201235386 [Chem. 22]

33- 201235386 [Chem. 23]

In the above formula [2-36] to the formula [2.40], E3 is an alkyl group having 4 to 22 carbon atoms or a fluorine-containing alkyl group. [Chem. 24]

[2-41] [2-42] [2-43] -34- 201235386 [Chem. 25]

Η

Η [2-44] [2-45] [2-46] In the above formula [2-41]~[2-46], W9 is -COO-'-OCO-'-CONH-'-NHCO-, -CH2-, -0-, -CO- or NH-, W1Q is an alkyl group having a carbon number of 1 to 22 or a fluorine-containing alkyl group. -35- 201235386 [Chem. 26]

-36- 201235386 [化27]

In the above formula [2-47] to [2-51], Wn is a single bond or an alkylene group having a carbon number of 1 to 10, and W12 is an alkyl group having 1 to 22 carbon atoms, an alkoxy group or a fluorine-containing alkane. The base, w13 is -0-, -CH2-'-NH-, -CO-, -S02-, or -S-. The divalent organic group having a side chain structure represented by the above-mentioned Y!' may have one or two or more types depending on characteristics such as liquid crystal alignment property, pretilt angle, voltage maintaining property, and charge accumulation when used as a liquid crystal alignment film. Further, in order to achieve the object of the present invention, Yl, the repeating unit of the structure relative to the polyglycolic acid vinegar is preferably 1 to 50 mol%, preferably 5 to 3 mol%, preferably For 5 to 2 0 mol%. In the above-mentioned formula (1), the divalent organic group (hereinafter, also referred to as Y) having no such side chain structure is not particularly limited, and two or more types may be mixed. Specific examples of γ include the following (Y-1) to (γ_77). Among them, in order to obtain a good liquid crystal alignment property, it is preferred to introduce a diamine having a high linearity into a polyphthalate, and 丫·7, Y-10, γ-ll, γ-!2, Υ-13 , Υ-21, Υ-22, Υ-23, Υ-25, Υ-26, Υ-27, Υ-41, Υ-42 > Υ-43 > Υ-44, Υ-45, Υ-46 , Υ-48, Υ-61, Υ-63, Υ-64, Υ-71, Υ-72, Υ-73, Υ-74, Υ-75 are better. Further, in order to improve the solubility of the polymer, it is preferred to use a diamine having a curved structure, Υ-2, Υ-3, Υ-4, Υ-5, Υ-8, Υ-9, Y-ll, Υ. -14, Υ-16, Υ-17, Υ-20, Υ-21, Υ-22, Υ-28, Υ-29, Υ-30, Υ-31, Υ-35, Υ-37, Υ-38 Υ-40, Υ-65, Υ·66, Υ-68 are better. -38- 201235386 [化 28]

"8- (Υ-18) Cl^ (Υ-19) (V-20) (Υ-21) (Υ-22) (Υ-23) (Υ-24) (Υ-25) (Υ-26 ) (Υ-27) Ο (Υ-28)

-39- 201235386 [化 29]

-(CH2)n-η = 2-5 (Υ-52) CH3 ch3 -(CH2)2-C-(CH2)2-CH3 (Y-53) CH3 ch3-(〇H2)4-C· ch3 ( Y-54) CH3 ch3 ch3 :H2-C-(CH2)2-C-(CH2)2- (Y-55) CH3 -CH2-C-(CH2)2-0-(CH2)3--(CH2 )2-C-(CH2)5--(CH2)4-0-(CH2)5- (Y-56) (Y-57) (Y-68) CH3 ch3 —(CH2)r〇-(CH2) R〇-(CH2)3- -(CH2)3-Sr〇-Si-(CH2)3- CH, CH, (Y-59) (Y-60)

(Y-61) (Y-62) (V-63) -40- .201235386 [Chem. 30]

(Υ-64) (Υ-6^ (Υ-66) (Υ-67) ^ (Υ-68) (Υ-69)

p〇2H 9°2Η )γ (Υ-76) (Υ-77) In the above formula (1), X is a tetravalent organic group, and two or more kinds thereof may be mixed, and the structure thereof is not particularly limited. Specific examples of X1 in the polyphthalate include, for example, the following (Χ-1) to (Χ_46). Among them, it is difficult to obtain the monomer, X] is Χ-1, Χ-2, Χ-3, χ_4, Χ-5, χ·6, χ_8, Χ.16, X -1 9 'X - 2 1 good. Χ-25, Χ-26, Χ-27, Χ-28, Χ-32, or Χ-46 -41 - 201235386 [化31] Redundancy: J| H3£况文允介xx ch3 h3c ch3 (X-1) ( X-2) (X-3) (X-4) (X-5) (X-6) (Χ·7) (X-8) Come: C〇来: ΜΧ 攻 Attack: ΧΦΧ (X-9) ( X-10) (X-11) (X-12) (X-13) (X-14) CH3

Ch3 (X-21) (X-15) (X-16) (X-17)^

(X-25) (X-26) [Chem. 32]

(X-30) 〇X^Xr^ (X-27) (X-23) (X-29) (X-31) o (X-32) : OXC χτ〇ΧΧ (X-33) (X-34 ) (X-35) (X-36) 〇

(X-37)

(X-42) (X-38)

(X-43)

(X-44) (X-39) (X-40) (X-41) ^ CH3

(X, (X-46) [Polyuric Acid] The polyaminic acid used in the present invention is obtained by using the polyimine-42-201235386 precursor of the polyimine which has been heated to carry out the following The polymer of the site of the oxime imidization reaction shown preferably has a structure represented by the following formula (2).

In the formula (2), eight! And A2 are the same as defined in the above formula (1). In the formula (2), X2 is a tetravalent organic group, and the structure thereof is not particularly limited. Specific examples include the structures of the above formulae (X-1) to (X-46). In the formula (2), Y2 is a divalent organic group, and the structure thereof is not particularly limited. Specific examples are, for example, the structures of the above formula (Υ -1) to (γ - 7 7). The polylysine of the present invention has a purpose of making the pretilt angle higher, and in the above formula (2), a part of Υ2 It may be a divalent organic group having a side chain structure having the above-described pretilt performance ability (Υ!,). In this case, for example, the structure shown by the above formulas [2-1] to [2-51] is specifically described. Since the residual resistivity caused by the accumulation of the DC voltage is reduced due to the decrease in the volume resistivity of the poly-proline, the structure having a hetero atom, a polycyclic aromatic structure, or a diamine having a biphenyl skeleton is introduced into the polyfluorene. Amino acid is preferred. For this purpose, γ2 is Υ-19, Υ-23, Υ-25, Υ-26, Υ-27, Υ-30, Υ-31, Υ- -43- 201235386 32, Y-33, Υ-34, Υ -35, Υ-36, Υ-40, Υ-41, Υ-42, Υ-44, Υ-45, Υ-49, Υ-50, Υ-51, Υ-61, Υ-76, or Υ- 77 Preferably, Υ-31, Υ-40, Υ-76 or Υ-77 are particularly good. Further, since the surface free energy of the polylysine is high, the phase separation of the polyphthalate and the poly-proline is further promoted, and the surface of the liquid crystal alignment film obtained by coating and firing becomes more uniform. Smoothing is preferably carried out by introducing a 2-stage amine group, a hydroxyl group, a guanamine group, a urea group, or a diamine having a carboxyl group into the polyglycolic acid. For this reason, 2 is preferably Υ-19, Υ-31, Υ-40, Υ-45, Υ-76, or Υ-77, and carboxy--76 or Υ-77 is particularly good. <Polyamine The method of producing the acid ester of the above formula (1) can be any one of the tetracarboxylic acid derivatives represented by the following formulas (6) to (8) and the formula (9). The reaction of the represented diamine compound is obtained. [化 34] 〇 Ο

(where Χι, Υι 'R with). Α, Α, and Α2 are each defined in the above formula (丨)-44 - 201235386 The polyphthalate represented by the above formula (i) can be used as the above-mentioned monomers (1) to (3) shown below. Method synthesis. (1) In the case of synthesis from poly-proline, the polyglycolate can be synthesized by esterification of a polyamic acid obtained from a tetracarboxylic dianhydride and a diamine. [,35] ·, Μ 0 0 ”^〇Η -卜_ 0 0 —(jL〇RX ΗΟτί -0 0 Ai A 2« RY—- specifically by polyglycine and an esterifying agent in an organic solvent In the presence of -2 0 ° C to 150 ° C, preferably 0 ° C to 50 ° C, 30 minutes to 24 hours, preferably 1 to 4 hours, the reaction is carried out to synthesize. The agent is preferably removed by purification, and may, for example, be N,N-dimethylformamide dimethyl acetal or N,N-dimethylformamide diethyl acetal 'N,N-di Methylformamide dipropyl acetal, N,N-dimethylformamide dineopentyl butyl acetal, hydrazine, hydrazine-dimethylformamide di-t-butyl acetal, 1 -methyl-3-p-tolyltriazene, 1-ethyl-3_P-tolyltriazene, 1-propyl-3-p-tolyltriazine, 4-(4,6-one Methoxy-1,3,5-tris-2-yl)-4-methylmorpholine chloride, etc. The amount of esterification agent added is 'relative to the repeat unit of poly-proline, 1 mol, to 2 ～6 molar equivalent is preferred. The solvent used in the above reaction is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone or γ-butyrolactone from the solubility of the polymer. These -45- 20123 5386 may be used singly or in combination of two or more kinds. The concentration of the polymer during synthesis is preferably from 1 to 30% by mass, and from 5 to 20% by mass, from the viewpoint that the polymer is not easily precipitated and that a high molecular weight is easily obtained. % is more preferable. (2) When the tetracarboxylic acid diester dichloride is reacted with a diamine, the polyglycolate can be synthesized from a tetracarboxylic acid diester dichloride and a diamine. Ο '〇-^ y~c\citxn + HN-Y-NH II Ai A2

O

^OR

R〇~ff 'jpfjl—Y-lsl-- L 0 0 A! A can be specifically obtained by using a tetracarboxylic acid diester dichloride and a diamine in the presence of a base and an organic solvent, -20 ° C to 150 ° The reaction is carried out at ° C, preferably 0 ° C to 50 ° C, for 30 minutes to 24 hours, preferably 1 to 4 hours. As the base, pyridine, triethylamine, 4-dimethylaminopyridine or the like can be used, but in order to stabilize the reaction, pyridine is preferred. The amount of the base to be added is preferably 2 to 4 moles per mole of the tetracarboxylic acid diester dichloride from the viewpoint of easy removal of the high molecular weight. The solvent to be used in the above reaction is preferably N-methyl-2-pyrrolidone or γ-butyrolactone, and may be used alone or in combination of two or more. The polymer concentration at the time of the synthesis is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass, from the viewpoint that the polymer is less likely to be precipitated and the high molecular weight is easily obtained. Further, in order to prevent hydrolysis of the tetracarboxylic acid diester dichloride, it is preferred that the solvent used for the synthesis of the polyphthalate is dehydrated as much as possible, and it is preferable to prevent the incorporation of outside air in the environment of nitrogen -46 - 201235386. (3) When a polyamic acid is synthesized from a tetracarboxylic acid diester and a diamine, the polyglycolate can be synthesized by polycondensation of a tetracarboxylic acid diester with a diamine. [Chem. 37] XΟΛ YO .ο ο R Η

Specifically, the tetracarboxylic acid diester and the diamine can be used in the presence of a condensing agent, a base or an organic solvent, 〇 ° C to 150 ° C, preferably 〇 ° C to 100 ° C, 30 minutes to 24 minutes. The reaction is carried out in an hour, preferably from 3 to 15 hours. The above condensing agent may be a triphenylphosphite, a dicyclohexylcarbodiimide or a 1-ethyl-3-(3-dimethylamino group). Propyl) carbodiimide hydrochloride, N,N'-carbonyldiimidazole, dimethoxy-1,3,5-triazinylmethylmorpholine, 〇_(benzotriazin-1 -基)-N,N,N',N'-tetramethylurea-tetrafluoroborate, 0-(benzotriazol-1-yl)-1^,;^,;^',:^- Tetramethylurea hexafluorophosphate, diphenyl (2,3-dihydro-2-thio-3-benzoxazolyl)phosphonate, and the like. The amount of the condensing agent added is preferably 2 to 3 moles per mole of the tetracarboxylic acid diester. As the base, a tertiary amine such as pyridine or triethylamine can be used. The amount of the base to be added is preferably 2 to 4 moles per mole of the diamine component from the viewpoint of easy removal amount and easy availability of a high molecular weight body. -47- 201235386 In the above reaction, the reaction is efficiently carried out by adding Lewis acid as an additive. Lewis acid is preferably lithium halide such as lithium chloride or lithium bromide. The amount of Lewis acid added is preferably from 1 to 0 moles per mole of the diamine component. In the method for synthesizing the above three polyglycolates, the synthesis method of the above (1) or (2) is particularly preferable in order to obtain a high molecular weight polyglycolate. The solution of the polyphthalate obtained as described above is poured into a poor solvent while being sufficiently stirred to precipitate a polymer. The precipitated powder is precipitated several times, washed with a poor solvent, and dried at room temperature or by heating to obtain a purified polyphthalate powder. The poor solvent is not particularly limited, and examples thereof include water, methanol, ethanol, hexane, butylcellulose, acetone, toluene, and the like. <Production Method of Polylysine> The polyamic acid represented by the above formula (2) can be represented by the tetracarboxylic dianhydride represented by the following formula (10) and the formula (1 1 ) The reaction of an amine compound gives 〇 [化38]

Specifically, the tetracarboxylic dianhydride and the diamine can be used in the presence of an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C, 30 minutes to 24 hours -48 - The reaction is carried out at a time of 201235386, preferably 1 to 12 hours. The organic solvent used in the above reaction is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone or γ-butyrolactone from the solubility of the monomer and the polymer. It is used in combination of two or more kinds. The concentration of the polymer is determined by the fact that the polymer is not easily precipitated and the high molecular weight is easily obtained. ～300% by mass is preferred, and 5 to 25% by mass is more preferable. The polyamic acid obtained as described above can be recovered by precipitating the polymer solution by injecting the reaction solution into a poor solvent while sufficiently stirring. Further, by performing a plurality of precipitations, the mixture is washed with a poor solvent, and then subjected to normal temperature or heat drying to obtain a purified polyamic acid powder. The poor solvent is not particularly limited, and examples thereof include water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene, and the like. <Liquid crystal alignment agent> The liquid crystal alignment agent of the present invention contains the polyglycolic acid ester represented by the above formula (1) and the polyamic acid represented by the formula (2). The weight average molecular weight of the polyphthalate and the weight average molecular weight of the polyglycolic acid are preferably from 5,000 to 30,000, more preferably from 10,000 to 200,000. Further, the number average molecular weight is preferably 2,500 to 1 50,000, more preferably 5,000 to 1 0,0 0 0 〇 the content of the aforementioned polyphthalate in the liquid crystal alignment agent of the present invention and the content of the aforementioned polyamid acid The mass ratio of (polyperurethane/polyglycolic acid) is preferably 1/9 to 9/1, preferably 2/8 to 8/2, and more preferably 3/7 to 7/3. By setting the ratio within this range, a liquid crystal alignment agent having good liquid crystal alignment properties and electrical characteristics can be provided. C: -49- 201235386 The liquid crystal alignment agent of the present invention is in the form of a solution in which the above polylysine and polylysine are dissolved in an organic solvent. As long as it has such a form, for example, when the polyamic acid ester and/or the polyamic acid are synthesized in an organic solvent, the obtained reaction solution or the reaction solution may be diluted with a suitable solvent. Further, when the polyglycolate and/or polyglycolic acid are obtained as a powder, they may be dissolved in an organic solvent to form a solution. The polyamic acid and polyphthalate (also referred to as polymers in the present invention) in the liquid crystal alignment agent of the present invention. The content (concentration) may be appropriately changed depending on the thickness of the polyimide film to be formed. However, from the viewpoint of forming a uniform and defect-free coating film, the content of the polymer component relative to the organic solvent is 〇. 5 mass% or more is preferable, and from the viewpoint of solution storage stability, it is preferably 15% by mass or less, preferably 1 to 10% by mass. Further, in this case, a concentrated solution of the polymer can be prepared in advance, and it can be diluted in the case where the liquid crystal alignment agent is formed from the concentrated solution. The concentrated solution concentration of the polymer component is preferably 10 to 30% by mass, more preferably 10 to 15% by mass. Further, when the powder of the polymer component is dissolved in an organic solvent to prepare a solution, it can be heated. The heating temperature is 20%. 〇 ~ 15 0 ° C is better, 2 〇 t: ~ 80 ° C is particularly good. The organic solvent contained in the liquid crystal alignment agent of the present invention is not particularly limited as long as the polymer component is uniformly dissolved. Specific examples thereof include N,N-dimethylformamide, hydrazine, hydrazine-diethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and N. -ethyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, fluorene-vinyl-2-pyrrolidone, dimethyl hydrazine, dimethyl hydrazine, γ-butyrolactone, 1 , 3· dimethyl-imidazolidinone, 3-methoxy-indole, hydrazine-dimethylpropane decylamine, and the like. These may be used in combination of one or more types -50- 201235386. Further, even if the polymer component alone cannot be dissolved uniformly, the liquid crystal alignment agent of the present invention may be mixed with the organic solvent, and the liquid crystal alignment agent may be coated on the substrate in addition to the dissolved polymer composition. Solvent for one sex. As the solvent, a solvent having a tension higher than the above can be generally used. Specific examples thereof include ethyl cellosolve, butyl cellosolve acetate, ethyl carbitol, butyl carbitol acetate, ethylene glycol, and methoxy-2-propanol propanol. , 1-butoxy-2-propanol, 1-phenoxy-2-propanol ester, propylene glycol diacetate, propylene glycol-1-monomethyl i propylene glycol-1-monoethyl ether·2- Acetate, dipropylene glycol, oxy) propanol, methyl lactate, ethyl lactate, milk! Η-butyl lactate, isoamyl lactate, and the like. For these solvents. The liquid crystal alignment agent of the present invention may contain a decane coupling agent additive. The decane coupling agent is a specific example of the decane coupling agent for the purpose of adhering the liquid crystal alignment film formed thereon to the liquid crystal alignment film, and is not limited thereto. Specific examples of the decane coupling agent used in the present invention are, for example, bis-ethoxy decane, 3-phenylaminopropyltrimethoxypropyltriethoxy decane, (aminoethylaminomethyl) benzocane, and the like. Amine; ethylene such as ethylene trimethoxy decane; propyltrimethoxydecane, 3-glycidoxypropyltriethyleneoxypropyloxypropylmethyldiethoxydecane, 3-epoxy Solvent, if it is used in the organic solvent-removing coating film, the solvent is low surface agent, butyl-solvent carbitol, ethyl, 1-ethoxy-2-, propylene glycol, mono-acetic acid-2-acetate, 2. (2-ethoxypropyl η-propyl ester, can be added to the substrate of each of the two kinds of agents such as a top coat or a cross-linking agent. The following 3-aminopropyl formane, 3-amino B Tris-methoxy 3-glycidoxyoxydecane, 3-propoxypropyl-methyl-51 - 201235386-dimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyl, etc. Epoxy; 3-(methyl)propenyloxypropylmethyldimethyl; methyl)propenyl; 3-ureidopropyltriethoxydecane, etc. (3-(triethoxydecyl) Sulfide such as propyl) disulfide An anthracene group such as propylmethyldimethoxydecane; an isocyanate such as 3-isocyanate decane; or a carbamic acid such as triethoxy decyl butyl aldehyde ethoxy hydroxyalkyl methyl carbamoate; When the amount of the coupling agent added is too large, the unreacted property is adversely affected, and if it is too small, the effect of adhesion is not obtained. Therefore, the solid content is preferably 0.01 to 5.0% by weight, more preferably 0.1 to: When the above decane coupling agent is added, in order to prevent the addition of the decane coupling agent before the addition of the solvent for improving the uniformity of the coating film, the polyamine can be added before the polyamine amide solution is mixed. An acid ester solution, a polyamidamine polyamine solution and a polyamic acid solution. Further, a phthalate-polyaminic acid mixed solution. When the coating film is fired, a ruthenium imidization accelerator may be added in order to carry out the polymerization of the polyamidite. In the case of adding a yttrium, it is preferred to carry out the sulfonium imidization by heating and/or to reduce the amount of the poor solvent. <Liquid Crystal Alignment Film> The liquid crystal alignment film of the present invention is a liquid crystal alignment agent such as methoxy decane R-based decane or the like (urea-based; bis-line; 3- benzyl propyl triethoxy aldehyde system: three gifts It is preferable to precipitate the liquid crystal alignment relative to the polymer, 〇% by weight, and further, the solution and the polyphthalic acid solution or the polyimidation effective amination accelerator may be applied to the solution. The substrate to be dried and fired is used as the substrate to which the liquid crystal alignment agent of the present invention is applied, and the substrate having high transparency is not particularly limited, and a glass substrate or a tantalum nitride substrate can be used. A plastic substrate such as an acrylic substrate or a polycarbonate substrate is used, and a substrate on which an ITO electrode or the like is formed by liquid crystal driving is preferable from the viewpoint of simplification of the process. Further, the substrate of the reflective liquid crystal display element is only one side. Further, an opaque material such as a ruthenium wafer may be used. In this case, a material that reflects light such as aluminum may be used as the electrode. The method for applying the liquid crystal alignment agent of the present invention may, for example, be a spin coating method, a printing method, or an inkjet printing method. Law The drying and baking step after applying the liquid crystal alignment agent of the present invention may be carried out at any temperature and time. Usually, in order to sufficiently remove the organic solvent contained, it is dried at 50 ° C to 120 ° C for 1 minute to 1 minute. Then, it is baked at 150 ° C to 300 ° C for 5 minutes to 120 minutes. The thickness of the coating film after firing is not particularly limited, and if the thickness is too thin, the reliability of the liquid crystal display device is lowered, so that it is 5 to 300 nm. The liquid crystal alignment film obtained by the alignment treatment is preferably 10 to 200 nm. For example, a rubbing method or a photo-alignment treatment method can be used, and the liquid crystal alignment agent of the present invention is particularly useful in the case of use in a photo-alignment treatment method. Specifically, the alignment treatment method is a method in which the surface of the coating film is irradiated with a radiation in a certain direction, and the surface is heated at a temperature of 150 to 250 ° C to provide a liquid crystal alignment ability. Ultraviolet light and/or visible light having a wavelength of from 100 nm to 800 nm. Among them, ultraviolet rays having a wavelength of from 10 nm to 400 nm are preferred, and those having a wavelength of from 200 nm to 40 nm are particularly preferable. Good liquid crystal alignment, or -53- 201235386 The radiation of the coated substrate is heated at 50 to 250 ° C. The irradiation amount of the radiation is preferably 1 to l, 〇〇〇mJ/cm 2 , 100 to 5,000. mJ/cm2 is particularly preferable. The liquid crystal alignment film produced as described above can stably align liquid crystal molecules in a certain direction. [Liquid Crystal Display Element] The liquid crystal display element of the present invention is obtained by the above-described method from the liquid crystal alignment agent of the present invention. The substrate is formed by a conventional method, and a liquid crystal cell is produced by a conventional method as a liquid crystal display element. The method for producing the liquid crystal cell is not particularly limited, and for example, a pair of substrates on which a liquid crystal alignment film is formed may be used. It is common to provide a method in which the liquid crystal alignment film surface is provided on the inner side and the spacer is preferably 1 to 30 μm, more preferably 2 to 10 μm, and the periphery is sealed with a sealant, and the liquid crystal is injected and sealed. The method of encapsulating the liquid crystal is not particularly limited, and examples thereof include a vacuum method in which a liquid crystal cell to be produced is decompressed and then injected into a liquid crystal, a dropping method in which a liquid crystal is dropped, and a sealing method. The liquid crystal alignment film of the present invention comprises a liquid crystal layer between a pair of substrates having electrodes, and a liquid crystal composition containing a polymerizable compound polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates. A liquid crystal display element produced by a step of polymerizing a polymerizable compound by at least one of irradiation and heating of an active energy ray is preferably used. Here, the active energy ray is preferably ultraviolet ray. The above liquid crystal display element is a PSA (P〇lymer Sustained Alignment) method for controlling the liquid crystal molecule pretilt angle. In the PSA method, a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer, is mixed in advance in the liquid crystal material -54 to 201235386, and after the liquid crystal cell is combined, a photopolymerizable compound is irradiated with ultraviolet rays or the like by applying a specific voltage state to the liquid crystal layer. The pretilt angle of the liquid crystal molecules is controlled by the generated polymer. The alignment state of the liquid crystal molecules at the time of polymer formation is also memorized after the voltage is removed, so that the pretilt angle of the liquid crystal molecules can be adjusted by controlling the electric field formed in the liquid crystal layer or the like. Further, in the PS A method, since the rubbing treatment is not required, it is suitable for the formation of a vertical alignment type liquid crystal layer which is difficult to control the pretilt angle by the rubbing treatment. In the liquid crystal display device of the present embodiment, the liquid crystal alignment cell is obtained by the liquid crystal alignment treatment agent of the present embodiment, and the liquid crystal cell is produced, and at least one of ultraviolet light irradiation and heating is used for polymerization. The compound is polymerized to control the alignment of the liquid crystal molecules. An example of the production of the PSA liquid crystal cell is, for example, a pair of substrates on which a liquid crystal alignment film is formed, and a spacer is spread on the liquid crystal alignment film of the single-sided substrate so that the liquid crystal alignment film surface is inside and the other surface is bonded to the other surface. The substrate is a method in which a liquid crystal is injected under reduced pressure and sealed, or a method in which a liquid crystal is dropped on a liquid crystal alignment film surface of a spacer, and a substrate is bonded and sealed. A polymerizable compound which is polymerized by irradiation with heat or ultraviolet rays is mixed in the liquid crystal. The polymerizable compound may, for example, be a compound having one or more polymerizable unsaturated groups such as an acrylate group or a methacrylate group in the molecule. In this case, the polymerizable compound is preferably 0·0 1 to 10 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the liquid crystal component. When the amount of the polymerizable compound is less than 0.01 part by mass, the polymerizable compound does not polymerize and the liquid crystal alignment is not controlled. When more than 10 parts by mass, the unreacted polymerizable compound -55-201235386 is increased, and the image retention characteristics of the liquid crystal display element are increased. reduce. After the liquid crystal cell is produced, an alternating current or a direct current voltage is applied to the liquid crystal cell, and the polymerizable compound is polymerized while irradiating heat or ultraviolet rays. Therefore, the alignment of the liquid crystal molecules can be controlled. Further, the liquid crystal alignment treatment agent of the present invention has a liquid crystal layer between a pair of substrates including an electrode, and it is preferable to use a liquid crystal alignment treatment between at least one of the pair of substrates to be polymerized by at least one of an active energy ray and heat. A liquid crystal display element produced by a step of applying a voltage between electrodes of a polymerizable group liquid crystal alignment film. Here, the active energy ray is preferably ultraviolet ray. In order to obtain a liquid crystal alignment film containing a polymerizable group polymerized by at least one of an active energy ray and heat, for example, a method of adding a compound containing the polymerizable group to a liquid crystal alignment treatment agent or a polymerization-containing method can be used. A method of polymerizing a polymer component. The implementation of the formula is implemented. The example is given by the actual implementation of the present invention. However, the abbreviations and structures of the compounds used in the examples and comparative examples are as follows, and the determination methods of the respective characteristics are as follows. the following. • 1,3DM-CBDE-C1: dimethyl L3·bis(chloroindenyl)_1>3·dimethylcyclobutane-2,4-dicarboxylate. CBDE: 2,4-bis(methoxy Carbonyl)cyclobutane-i,3-dicarboxylic acid • BODE : 3,6-bis(methoxycarbonyl) octahydrocyclopentane (pentalene)-l,4-dihydroxy acid-56- 201235386 •DMT-MM : 4-(4,6-Dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholine-minide chloride•NMP : N-methyl-2- Pyrrolidone • BCS : butyl cellosolve • γ-BL : γ-butyrolactone • BCA : butyl cellosolve acetate [39]

[Viscosity] -57- 201235386 In the synthesis example, the viscosity of the polyglycolate and the poly-proline solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), sample size 1.1 mL, Cornroter TE-1 ( L°34', R24), measured at a temperature of 25 °C. [Molecular weight] The molecular weight of the polyglycolate is measured by a GPC (normal temperature colloidal osmosis chromatography) apparatus, and the number average molecular weight (hereinafter also referred to as Μη) is calculated in terms of polyethylene glycol and polyethylene oxide. With weight average molecular weight (hereinafter, also known as Mw) 〇 . • GPC device: manufactured by Shodex Co., Ltd. (GPC-101). Pipe column: made by Shodex (inline of KD803, KD805)

• Column temperature: 50 °C • Dissolved solution: N,N-dimethylformamide (as additive, lithium bromide hydrate (LiBr'HzO) is 30 mmol/L, phosphoric acid·anhydrous crystal (〇-phosphoric acid) ) 30 mmol / L, tetrahydrofuran (THF) 10 ml / L). Flow rate: 1.0 ml / min • Calibration line for standard samples: TSK standard polyethylene oxide manufactured by Tosoh Corporation (weight average molecular weight (Mw) approx. 900,000, 150,000, 1 〇〇, 〇〇〇, 30, 0 〇〇), and polyethylene glycol (polymer peak molecular weight (Mp) of about 1 2,000, 4,000, 1,000) manufactured by Polymer Laboratory. In order to avoid peaks, two samples of 900,000, 100,000, 12,000, and 1,000 samples were mixed, and two samples of three samples of 150,000, 30,000, and 4,000 were mixed. -58- 201235386 [Determination of the pretilt angle] The pretilt angle is obtained by heating the liquid crystal cell at 110 ° C for 30 minutes, and then using M ue 11 er M atri X Ρ ο 1 arimeter (AX 〇metrics, manufactured by the company) Name: AxoScan) To determine [Evaluation of residual DC] The charge accumulation characteristics were evaluated in a liquid crystal cell, and a rectangular wave of ±5.8 V/30 Hz was applied at a temperature of 23 t, and DC IV was superposed for 90 hours of driving. Immediately after cutting off 1 V DC, the residual voltage remaining in the liquid crystal cell was measured by an optical Flicker minimizing method. When the residual voltage is 0.4 V or less, it is evaluated as good, and when it is 0.4 V or more, it is bad. (Synthesis Example 1) Synthesis of dimethyl-1,3-bis(chlorocarbonyl)-1,3-dimethylcyclobutane-2,4-dicarboxylate (1,3DMCBDE-C1) (a- Ι) Synthesis of dialkyl tetracarboxylate [40]

In a 3-L four-necked flask under nitrogen flow, '丨, 3-dimethylcyclobutane-1,2,3,4-tetracarboxylic dianhydride (compound of formula (5-1), hereinafter referred to as 1, 3_-59- 201235386 DM-CBDA) 220g (0.981mol), 2200g (6.87mol, relative 1,3-DM-CBDA is 10wt times), heated under reflux at 65 °C, uniformed at 30 minutes Solution. The reaction solution was heated under reflux for 4 hours and 30 minutes and stirred. This reaction liquid was measured by high-speed liquid chromatography (hereinafter, abbreviated as HPLC). The analysis of the measurement results will be described later. After the solvent was distilled off from the reaction mixture by an evaporator, 1301 g of ethyl acetate was added, and the mixture was heated to 80 ° C, and refluxed for 30 minutes. Thereafter, the internal temperature was cooled to 25 ° C at a rate of 10 minutes 2 to 3 t, and stirring was continued for 30 minutes at 25 ° C. The precipitated white crystals were taken out by filtration, and the crystals were washed twice with ethyl acetate (141 g), and dried under reduced pressure to give white crystals of 3.97 g. The crystal was analyzed by 1 H NMR analysis and X-ray crystal structure, and it was confirmed that the compound (1-1) (HPLC relative area: 97-5%) (yield 36·8%) 〇1Η NMR (DMSO-d6, δρριη) ; 12_82(s ' 2Η) ' 3.60(s,6Η) , 3.39(s,2H), 1.40(s ' 6H). (a-2) Synthesis of l,3-DM-CBDE-Cl [Chem. 41]

-60- •201235386 After adding a compound (1 - 1 ) 234.1 5 g (0.81 mol) and η-Gengyuan 1170.77 g (11.68 mol. 5wt times) in a 3 L four-necked flask under nitrogen flow, pyridine 0.64 g was added. (0.01 mol), heating and stirring were carried out until stirring at 75 ° C with a magnetic stirrer. Next, 289.93 g (11.68 m〇l) of sulfinium chloride was dropped for 1 hour. The foaming started immediately after the dropping, and after the dropping was completed for 30 minutes, the reaction solution became uniform and the foaming was stopped. Subsequently, the mixture was stirred at 75 ° C for 1 hour and 30 minutes, and then the solvent was distilled off by an evaporator at a temperature of 40 ° C in a water bath at 924.42 g. The mixture was heated to 60 t: the crystals precipitated when the solvent was distilled off were dissolved, and the insolubles were filtered by 6 (TC), and the filtrate was cooled to 25 ° C at a rate of 10 ° C for 10 minutes. Directly at 25 ° After C was stirred for 30 minutes, the precipitated white crystals were taken out by filtration, and the crystals were washed with η-heptane 264.2 1 g, and dried under reduced pressure to give 226.09 g of white crystals. After adding 226.09 g of the white crystal obtained above and 452.1 g of η-heptane obtained in the four-necked flask, the crystal was dissolved by heating and stirring at 60 ° C. Thereafter, the mixture was cooled and stirred to 25 ° at a rate of 10 ° C for 10 minutes. C. The crystals were precipitated, and the mixture was stirred at 25 ° C for 1 hour, and the precipitated white crystals were taken out by filtration, and the crystals were washed with n. hexane (113.04 g), and then dried under reduced pressure to give white crystals. 203.9 1 g. The crystal was analyzed by 1H NMR to confirm the compound (3-1), that is, dimethyl-1,3-bis(chlorocarbonyl)-1,3-dimethylcyclobutane-2. 4-Dicarboxylate (hereinafter, referred to as 1,3-DM-CBDE-C1)» (HPLC relative area: 99.5%) (yield 77. 2%). 1Η NMR (CDC13 ' 5ppm) : 3.7 8 (s,6 Η),3 · 7 2 (s,2 Η), -61 - 201235386 1.69(s,6H)_ (Synthesis Example 2) In a 〇ml four-necked flask, 'CBDE 2.4707 g (9.50 mmol) was added, and NMP 64.22 g was added, and the mixture was stirred to dissolve. Then, triethylamine 0·5 1 26 g (5.00 mmol) and 4,4'-diamine were added. 1.6042 g (8.01 mmol) of bisphenyl ether and 0.7579 g (2.01 mmol) of Octadecanoxy-2,4-diaminobenzene were stirred and dissolved. The solution was stirred while stirring. Add DMT-MM (1 5 ± 2 wt% hydrate) 8.45 g (30.5 mmol), and then add 11.79 g of NMP, and stir at room temperature for 18 hours to obtain a solution of polyphthalamide. The viscosity of the acid ester solution was 17.75 mPai at 25 ° C. The melamine solution was charged with 490 g of methanol while stirring, and the precipitate was collected by filtration, followed by washing 5 times with 178 g of methanol. And dried to obtain 3.70 g of a polyphthalate resin powder. The molecular weight of the polyphthalate was Mn = 1 3, 5 73, Mw = 30, 201. The obtained polyfluorene was obtained in a 50 ml sample tube to which a stir bar was added. Amine tree Powder 1.3 040g, was added NMP 11.7663g, stirred for 24 hours at room temperature to dissolve, to obtain a solution of polyamide acid ester (PAE-1). (Synthesis Example 3) CBDE 2.4790 g (9.5 3 mmol) was placed in a l〇〇ml four-necked flask equipped with a stir bar, and NMP 64.08 g was added thereto, followed by stirring to dissolve. Next, triethylamine 〇.5 05 g (4.99 mmol), 4,4'-diaminodiphenylmethyl-62-201235386 alkane 1.5883 g (8.01 mmol), and DA-l 0.7691 g (2.02 mmol) were added. ), stirring to dissolve. To the solution, 8.17 g (30.2 mmol) of DMT-MM (15 ± 2% by weight hydrate) was added while stirring, and 11.47 g of NMP was further added thereto, and the mixture was stirred at room temperature for 18 hours to obtain a solution of polyphthalate. The polyglycolate solution had a viscosity of 9.77 mPai at 25 °C. The melamine solution was charged with 490 g of methanol, and the deposited precipitate was collected by filtration, and then washed and dried five times with 1 78 g of methanol to obtain a polyglycolate resin powder of 3.71 g. . The molecular weight of the polyglycolate was Mn=1 2,046, Mw=25,4 0 8 〇 in a 5 Oml sample tube to which a stir bar was added, and the obtained polyamidate resin powder was 1.263 9 g, and NMP 1 was added. 1.3 76 1 g, dissolved at room temperature for 24 hours to obtain a polyphthalate solution (PAE-2). (Synthesis Example 4) CBDE 2.4715 g (9.50 mmol) was placed in a 100 ml four-necked flask equipped with a stir bar, and NMP 64.7 8 g was added thereto, followed by stirring to dissolve. Next, triethylamine oxime. 511 g (5.05 mmol), 4,4'-diaminodiphenylmethane 1_5 83 2 g (8.01 mmol), and DA-20.8 1 69 g (2.00 mmol) were added, followed by stirring to dissolve . To the solution, 8.13 g (30.1 mmol) of DMT-MM (15 ± 2 wt% hydrate) was added while stirring, and 11.07 g of NMP was further added thereto, and the mixture was stirred at room temperature for 18 hours to obtain a solution of polyglycolate. The polyglycolate solution had a viscosity of 1 1.92 mPa «s at 25 ° C. The lysine solution was charged with 495 g of methanol while stirring, and the deposited precipitate was collected by filtration, and then washed with 100 g of methanol for 5 times and dried to obtain poly-proline-63-201235386 ester resin. Powder 3.64 g. The molecular weight of the polyamidomate was Mn = 10,926 and Mw = 23,652. In a 50 ml sample tube to which a stir bar was added, the obtained polyphthalate resin powder was 9689682 g, and NMP 8.723 g was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE- 3). (Synthesis Example 5) A 300 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, and m-phenylenediamine 1.5123 g (14.0 mmol) and DA-3: 1.0387 g (2.45 mmol) were added, and NMP was added to 121.76. g. 2.91 g (36.8 mmol) of pyridine as a base was stirred and dissolved. Next, 1,3DM-CBDE-C1 4.9904 g (15.3 mmol) was added while stirring the diamine solution, and the reaction was carried out for 4 hours under water cooling. The obtained solution of the polyglycolate was poured into 641 g of water while stirring, and the precipitated white precipitate was collected by filtration, followed by once with 64 1 g of water, once with 641 g of ethanol, and once with 130 g of ethanol for 3 times. It was washed and dried to obtain 4.39 g of a polyphthalate resin powder. The polyglycolate has a molecular weight of Mn = 6,757 and Mw = 13,415. In a 50 ml sample tube to which a stir bar was added, 2.073 g of the obtained polyamidate resin powder was added, and 28.696 g of NMP was added thereto, and stirred at room temperature for 24 hours to dissolve, thereby obtaining a polyamidate solution (PAE- 4). (Synthesis Example 6) A 300 mL four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, and DA-8 3.498 8 g (l 3.5 mmol) and DA-4 0.857 1 g (2.39 mmol) were added, and the addition was -64-201235386. 154.59 g of NMP and 2.84 g (15.0 mmol) of pyridine as a base were stirred and dissolved. Next, this diamine solution was added to CBDE-C1 4.8709 g (36.0 mmol) while stirring, and the reaction was carried out for 4 hours under water cooling. The obtained solution of the polyglycolate was poured into 8.1 g of water while stirring, and the precipitated white precipitate was collected by filtration, followed by 814 g of water once, 814 g of ethanol once, and 207 g of ethanol for 3 times. Washed and dried to obtain a polyphthalate resin powder of 7.46 g. The molecular weight of the polyglycolate was Mn = 17,559 and Mw = 45,602. In a 50 ml sample tube to which a stir bar was added, 1.2935 g of the obtained polyamidate resin powder was added, and NMP 11.6417 g was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-5). ). (Synthesis Example 7) CBDE 2.4717 g (9.50 mmol) was placed in a 〇〇ml four-necked flask equipped with a stir bar, and 61.43 g of NMP was added thereto, followed by stirring to dissolve. Next, 0.5077 g (5.02 mmol) of triethylamine, 1.5866 g (8.00 mmol) of 4,4'-diaminodiphenylmethane, and 0.8627 g (1.99 mmol) of DA-5 were added, followed by stirring to dissolve. To the solution, DMT-MM (15±2 wt% hydrate) 8.30 g (30.0 mmol) was added while stirring, and then Ν 1 P 1 1 · 7 1 g was added, and the mixture was stirred at room temperature for 18 hours to obtain polyfluorene. A solution of an amine ester. The polyglycolate solution had a viscosity of 12.64 mPa*s at a temperature of 25 °C. 500 g of methanol was added to the polyglycolate solution while stirring, and the deposited precipitate was collected by filtration, and then washed with 100 g of methanol for 10 times and dried to obtain a polyglycolate resin powder of 3.95 g. The molecular weight of the polyglycolate is Mn = 1 0, 73 7 , Mw = -65 - 201235386 23, 149 ° The obtained polyamidate resin powder is 1.62 g in a 50 m crucible sample tube to which a stir bar is added. Approximately 1.5582 g of NMP was added to the solution, and the mixture was stirred at room temperature for 24 hours to dissolve, thereby obtaining a polyamidate solution (PAE-6). (Synthesis Example 8) BODE 2.3591 g (7.51 mmol) and CBDE 0.6525 g (2.51 mmol) were placed in a 〇〇ml four-necked flask equipped with a stir bar, and 32 g of NMP was added thereto, followed by stirring to dissolve. Then, 53 g (5.24 mmol) of triethylamine oxime, 0.9194 g (8.50 mmol) of p-phenylenediamine, and 0.695 g (1.50 mmol) of DA-6 were added, and the mixture was stirred and dissolved. The solution was added with dmt-mm (1 5±2 weight 0/〇 hydrate) 8.3176 g (30.1 mmol) while stirring, and then NMP 1 〇. 1 g was added thereto, and the mixture was stirred at room temperature for 18 hours to obtain polyfluorene. A solution of an amine ester. The polyglycolate solution had a viscosity of 15.0 mPa*s at 25 °C. The polyglycolate solution was added to 1300 g of methanol while stirring, and the deposited precipitate was collected by filtration, and then washed with ll g of methanol for 5 times and dried to obtain a polyglycolate resin powder 3.60. g. The polyglycolate has a molecular weight of Mn = 6,75 7 and Mw = 13,415. In a 50 ml sample tube to which a stir bar was added, 1.7 5 85 g of the obtained polyamidate resin powder was added, and 6.225 3 g of NMP 1 was added thereto, and stirred at room temperature for 24 hours to dissolve, thereby obtaining a polyamidate solution. (PAE-7). (Synthesis Example 9) In a 10 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, -66 - 201235386 p-phenylenediamine l_825 8 g (16.9 mmol) and D-7: 1.5253 g (3.00 mmol) were taken. Add 35.6 g of NMP and stir while stirring with nitrogen. While the diamine solution was stirred, 4.4822 g (20.0 nmim) of 2.3.5-tricarboxycyclopentyl acetic acid dianhydride was added, and NMP was added in such a manner that the solid content concentration was 15% by weight, and it was carried out at room temperature. A solution of polyamine acid (PA A-1) was obtained by stirring for 24 hours. The polyglycine solution had a viscosity of 167 mPa-s at a temperature of 25 °C. Further, the molecular weight of the poly-proline was Mn = 16 223 and Mw = 47,846. (Synthesis Example 10) 20.23 g of a solution of polylysine (PAA-1) obtained in Synthesis Example 9 was placed in a 50 ml eggplant type flask to which a stirrer was added, and 13.55 g of NMP was added and stirred. To the solution, 1-methyl-3-P-tolyltriazene (3.87 g (2 5.9 mmol) was added, and the mixture was stirred at room temperature for 4 hours. After 4 hours, 340 g of methanol was added to the reaction mixture while stirring, and the deposited precipitate was collected by filtration. Then, the mixture was washed five times with methanol of ll g, and dried to obtain 2.44 g of a poly phthalate resin powder. The molecular weight of the polyglycolate is Mn = 9,206 ' Mw = 2 8,8 8 3 . In a 50 ml sample tube to which a stir bar was added, 1.5485 g of the obtained polyamidate resin powder was added, and 13.03 g of NMP was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE- 8). (Synthesis Example 11) A 300 mL four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, and 4,4'-diaminodiphenylmethane 2.407 1 g (12.1 mmol) and DA-7: 1.087 1 -67 were added. - 201235386 g (2.15 mmol), 130.3 g of NMP and 2.54 g (32.1 mmol) of pyridine as a base were added and stirred to dissolve. Next, 1,3DM-CBDE-C1 4.3526g (13.4mmol) was added to the diamine solution while stirring, and the reaction was carried out for 4 hours under water cooling. The obtained polyglycolate solution was poured into 686 g of water while stirring, and the precipitated white precipitate was collected by filtration, followed by 686 g of water once, 686 g of ethanol once, and 170 g of ethanol for 3 times. The mixture was dried to obtain 4.58 g of a polyphthalate resin powder. The molecular weight of the polyglycolate was Mn = 9,23 3 and Mw = 20,108. In a 50 ml sample tube to which a stir bar was added, the obtained polyacetate resin powder 1.5485 g' was added to NMP 13.9603 g, and stirred at room temperature for 24 hours to dissolve, thereby obtaining a polyamidate solution (PAE-9). ). (Synthesis Example 12) In a l〇〇mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 1.48 g (9.23 mm 〇l) and 3,5-two of 4,4'-diaminodiphenyl ether were taken. Amino benzoic acid 2.1 02 5g (13.82 mmol), and force [] was added to N9.7 (39.7 g), and then stirred and dissolved by stirring with nitrogen. While the diamine solution was stirred, 4.8162 g (22.08 mm 〇l) of pyromellitic dianhydride was added, and NMP was added so that the solid content concentration became 15% by weight, and the mixture was stirred at room temperature for 24 hours to obtain a polyfluorene. A solution of aminic acid (PAA-2). The polyglycine solution had a viscosity of 25 7 mPa*s at a temperature of 25t. Further, the molecular weight of the poly-proline is Mn = 1 3,620 and Mw = 28,299. (Synthesis Example 13) -68-201235386 In a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 7.9693 g (40 mmol) of 4,4'-diaminodiphenylamine was added, and NMP 31.7 g was added thereto. Stir in nitrogen to dissolve. After the diamine solution was stirred, 1,2,3,4-butanetetracarboxylic dianhydride 7_1 3 3 9 g (36.01 mmol) was added, and NMP was added so that the solid content concentration became 25% by weight. The mixture was stirred at room temperature for 24 hours to obtain a solution of polyamine acid (PAA-3). The polyglycine solution had a viscosity of 26 80 mPa·s at a temperature of 25 ° C. Further, the molecular weight of the polyamic acid was Mn = 8,176 and Mw = 1, 6,83 4 . (Synthesis Example 14) In a 10 OmL four-necked flask equipped with a stirring apparatus and a nitrogen introduction tube, 4,4'-diaminodiphenylamine 1.5987 g (8.02 mm 〇l) and 3,5-two were taken. Amino benzoic acid 1.83 04 g (12.03 mmol) was added to 56.7 g of NMP, and the mixture was stirred while stirring to dissolve nitrogen. While the diamine solution was stirred, 3.7675 g (19.21 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was added, and NMP was added so that the solid content concentration became 15% by mass, at room temperature. Stirring was carried out for 24 hours to obtain a solution of polyamic acid (PA A-4). The temperature of the polyaminic acid solution was 3 6 8 mPa _s at 25 ° C. Further, the molecular weight of the poly-proline was Mn = 15,117, Mw = 3 4, 63 8 〇 (Synthesis Example 15) In a 10 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 2 was taken. 2.13 g (10,04 mmol) of 2'-dimethyl-4,4'-diaminobiphenyl, and 9.6 g of NMP 2 was added thereto, followed by stirring with nitrogen to dissolve. Adding 1,2,3,4-cyclobutanetetracarboxylic dianhydride 902.902g (4.60 mmol) and pyromellitic dianhydride 1.0905g (5.00mmol) while stirring the diamine solution into -69-201235386 Further, NMP was further added so that the solid content concentration became 10% by weight. The mixture was stirred at room temperature for 24 hours to obtain a solution of polyamine acid (P AA_5). The polyamic acid solution has a viscosity of 585.7 mPa_s in a temperature of 25 ° C and the molecular weight of the poly-proline is Mn = 13 3, 93 6 and Mw = 37,376. (Synthesis Example 16) 4,4'-diaminodiphenyl ether 1.92 1 7 g (9.60 mmol) and octadecyloxy group were taken in a l〇〇mL four-necked flask equipped with a stirring device and a nitrogen introduction tube. (Octadecanoxy)-2,4-diaminobenzene 0.9028g (2.40mmol), added 36.62g of NMP, and stirred while adding nitrogen to dissolve the diamine solution and add 1,2,3,4 - 2.3088 g (1 1.8 mmol) of cyclobutane tetracarboxylic dianhydride, further adding NMP so that the solid content concentration is 10% by weight, and stirring at room temperature for 24 hours to obtain a solution of polyamine acid (PAA-6) . The polyglycine solution had a viscosity of 15.6 mPa, s at a temperature of 25 t. Further, the molecular weight of the polyamic acid was Mn = 1,8,794 and Mw = 53,139. (Synthesis Example 17) 4,4'-diaminodiphenylmethane 1.9086 g (9.63 mmol) and DA-1 0.9125 g ( 2.40) were placed in a 10 mL flask equipped with a stirring apparatus and a nitrogen introduction tube. Mm), force into the NMP 36.59g, while stirring and dissolving while feeding nitrogen. While the diamine solution was stirred, 1,2,3,4-cyclobutanetetracarboxylic dianhydride (2.39 9 g (l 1.8 mm 〇l) was added, and the solid content concentration was 10% by weight -70-201235386 NMP was added in this manner, and the mixture was stirred at room temperature for 24 hours to obtain a solution of polyamine acid (PAA-7). The polyamine solution had a temperature of 25T: a medium viscosity of 49.2 mPa, si. Further, the molecular weight of the poly-proline was Mn = 14,544, Mw = 37, 86 2 〇 (Synthesis Example 18) 4,4'-diamine lotus was taken in a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube. 1.102 g (9.59 mmol) of diphenylmethyl ketone and 0.9833 g (2.41 mmol) of DA-2 were added, and 36.59 g of NMP was added thereto, and the mixture was stirred while stirring to dissolve nitrogen. While the diamine solution was stirred, 2.3,137 g (1.8 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was added, and NMP was added in such a manner that the solid content concentration became 10% by weight. The mixture was stirred at room temperature for 24 hours to obtain a solution of polyaminic acid (PAA-8). The polyglycine solution had a viscosity of 61.1 mPa.s at a temperature of 25 °C. Further, the molecular weight of the poly-araminic acid was Mn = 15, ll 〇, Mw = 40,878. (Synthesis Example 19) In a 50 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, m-phenylenediamine 1.6494 g (l 5.3 ramol) and D A-3 :1 .1 5 0 8 g (2 7 ) were taken. 1 mm ο 1), 30.8 g of NMP was added, and the mixture was stirred while being fed with nitrogen to dissolve. 1,3-Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride 3.99 5 g (17.8 mmol) was added while stirring the diamine solution, so that the solid content concentration became 15 NMP was added in a weight % manner, and stirred at room temperature for 24 hours to obtain a solution of polyamine acid (PAA-9). The polyglycine solution has a viscosity of -71 - 201235386 80 mPa.s at a temperature of 25 °C. Further, the molecular weight of the poly-proline was Mn = 9,546 and Mw = 20,553 〇 (Synthesis Example 20) DA-8 3.2943 g (12.8 mmol) was taken in a 5 〇 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube. And 0.84 g (2.26 mmol) of DA-4, and 33.7 g of NMP was added, and it stirred by stirring with nitrogen. 1,3-Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride 3.3297 § (14.9 mmol) was added while stirring the diamine solution, so that the solid content concentration became 15 weights. The NMP was added in a manner of %, and stirred at room temperature for 24 hours to obtain a solution of polyamine acid (PAA-10). The polyamic acid solution has a viscosity of 3 32.5 mPa-s at a temperature of 25 ° C. Further, the molecular weight of the polyproline is Mn = 1,7,05 8 and Mw = 39,0 1 62. (Synthesis Example 21) 4,4'-diaminodiphenylmethane 1.9044 g (9.61 mmol) and DA-5: 1.0487 g (2.41 mmol) were placed in a 100 mL four-necked flask equipped with a stirring apparatus and a nitrogen introduction tube. Then, 7.49 g of NMP 3 was added, and the mixture was stirred while being fed with nitrogen to dissolve. After the diamine solution was stirred, 2.3123 g (11.8 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was added, and NMP was added in such a manner that the solid content concentration became 1% by weight. The mixture was stirred for 24 hours to obtain a solution of polyaminic acid (PAA-11). The polyglycine solution had a viscosity of 47 mPa.s at a temperature of 25 °C. Further, the molecular weight of the poly-proline is Mn = 7,520, M w = 15 5, 4 0 3 . -72-201235386 (Synthesis Example 22) In a 5 OmL four-necked flask equipped with a stirring device and a nitrogen introduction tube, pentalene-l,3,4,6-tetracarboxylic dianhydride was taken. 5.03g (20. lmmol), p-phenylenediamine 2.03g (l 8.8mmol), and DA-6 3.73g ( 8.05mmol), added NMP 23.0g, reacted at 40 ° C for 5 hours, then added l, 2,3,4-cyclobutanetetracarboxylic acid 12.28 g (6·53 nlmol) and NMP 24.5 g were reacted at 40 ° C for 6 hours to obtain a solution of poly-proline (PAA-12). The molecular weight of the poly-proline is Μη: 12,900, Mw: 3 1,500. (Synthesis Example 23) 4,4'-diaminodiphenylmethane 2.5 26 g (12.7 mmol) and DA-7: 1.1413 g (2.2 5 mmol) in a 50 mL four-necked flask equipped with a stirring apparatus and a nitrogen introduction tube. ), 31.8 g of NMP was added, and it was stirred and dissolved by sending nitrogen. While stirring the diamine solution, 3.3266 g (14.8 mm 〇l) of 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride was added to further increase the solid content concentration. NMP was added in a manner of 15% by weight, and stirred at room temperature for 24 hours to obtain a solution of polyaminic acid (PAA-13). The polyamic acid solution has a viscosity of 1 1 1.6 mPa 1 at a temperature of 2 5 °C. Further, the molecular weight of the poly-proline is Mn = 10, 050, Mw = 22, 23, 53. (Example 1)

A 20 ml sample tube to which a stir bar was added was taken, and 1.444 1 g of the polyamidomate solution (PAE-1) obtained in Synthesis Example 2 and the polyamidic acid solution (PAA-2) obtained in Synthesis Example 2.2 (2.2827 g) were added. NMP 2.7117 g, BCS-73-201235386 1.63 6 g were added, and the mixture was stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal alignment agent (Α-1). (Example 2) A polyamine solvent solution obtained by synthesizing Example 13 was obtained by using a polyacetate solution (PAE-2) 1.4471 g obtained in Synthesis Example 3 in a 20 m 丨 sample tube to which a stir bar was added. (PAA-3) l_1812g, NMP 3.8092g, BCS 1.6005g, and stirred by a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (A-2) 〇 (Example 3) 20 m 1 with a stir bar added The sample tube was obtained by using the polyphthalate solution (PAE-3) 1.4544 g obtained in Synthesis Example 4 and the polyaminic acid solution (ΡΑΑ-4) 2· 141 9 g obtained in Synthesis Example 14 and adding NMP 2_8338 g. BCS 1.6377 g, which was stirred by a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (A-3) (Example 4) A polyacetate obtained in Synthesis Example 5 was obtained by adding a 20 ml sample tube having a stir bar. 1.4469 g of a solution (PAE-4), 3.3168 g of a polyaminic acid solution (PAA-5) obtained in Synthesis Example 15, 1.6505 g of NMP, and 1.5985 g of BCS were added, and stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal alignment agent. (A-4). -74-201235386 (Example 5) A polyamine solution (PAE-5) obtained in Synthesis Example 6 was taken from a 20 ml sample tube to which a stirrer was added. 1.449 1 g of the polyamine obtained in Synthesis Example 13. Acid solution (PAA-3) 1.1 5 63 g, NMP 3.8169 g, BCS 1.6 1 0 7 g were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (A-5). (Example 6) 1.4613 g of a polyamidomate solution (PAE-6) obtained in Synthesis Example 7 and a polyaminic acid solution (PAA) obtained in Synthesis Example 13 were placed in a 20 ml sample tube to which a stir bar was added. -3) 1.1 505 g, NMP 3.8275 g, BCS 1.6049 g were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (A-6). (Example 7) A polyamine solution (PAE-7) obtained in Synthesis Example 8. 1.75 75 g of the polyamine solvent solution (PAA) obtained in Synthesis Example 12 was added to a 20 ml sample tube to which a stir bar was added. -2) 2.28 5 g ' Add NMP 2.67 83 g, BCS 1.6070 g, and stir with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (A-7). (Example 8) A polyglycolate solution (PAE-8) obtained in Synthesis Example 1 (1.48 g) and a poly-75-201235386 indoleamine obtained in Synthesis Example 15 were placed in a 20 ml sample tube to which a stir bar was added. 3.3261 g of an acid solution (PAA-5) was added to NMP 1.6521 g and BCS 1.6 0 16 g, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (A-8). (Example 9) A polyhydrazide solution obtained by synthesizing Example 1 was obtained by using a 2 〇 ml sample tube to which a stir bar was added, and a polyamidomate solution (PAE-9) obtained in Synthesis Example 1 1.455 3 g. The solution (PAA-4) was 2.1 457 g, and NMP 2.8221 g and BCS 1.6070 g were added, and the mixture was stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal alignment agent (A-9). (Comparative Example 1) A polylysine solution (PAA-6) obtained in Synthesis Example 16 was taken in a 20 ml sample tube to which a stirrer was added. 1.48 8 8 g of the polyaminic acid solution (PAA) obtained in Synthesis Example 12. -2) 2.2959 g, NMP 2.7135 g, BCS 1.6 0 5 9 g were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (B-1). (Comparative Example 2) 1.5 064 g of the polyaminic acid solution (PAA-7) obtained in Synthesis Example 17 was taken in a 20 ml sample tube to which a stirrer was added, and the polymerization obtained in Synthesis Example 13 was obtained.

Proline solution (PAA-3) 1.1 675 g ' Add NMP 3.7665g, BCS 1 ·6 1 64g, stir with a magnetic stirrer for 30 minutes to obtain liquid crystal alignment agent (B-2) 〇-76- 201235386 (Comparative Example 3) A polyamine solvent solution (PAA-4) obtained by synthesizing Example 18 was obtained from a 20 ml sample tube to which a stir bar was added, and a polylysine solution (PAA-8) obtained in Synthesis Example 18. 2.1 3 29g, NMP 2.8 003 g, BCS 1.6 1 9 1 g were added, and stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal alignment agent (B-3). (Comparative Example 4) A polyglycine solution obtained in Synthesis Example 15 was obtained by adding a polyamine solution (PAA-9) of 0.96 5 8 g obtained in Synthesis Example 19 to a 20 ml sample tube to which a stirrer was added ( PAA-5) 3.3 279 g, NMP 2.1 364 g, BCS 1.6 U7 g were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (B-4). (Comparative Example 5) A polyamine solution (PAA-1) 1.045 9 g obtained in Synthesis Example 20 and a polyaminic acid solution obtained in Synthesis Example 13 (PAA-) were placed in a 20 ml sample tube to which a stir bar was added. 3) 1.1 662g ' Add NMP 4.253 7g, BCS 1.6159g, and stir with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (B-5). (Comparative Example 6) A polyamine solution (PAA-ll) of -77-201235386 obtained in Synthesis Example 2 was added to a 20 ml sample tube to which a stirrer was added. 1.439 g of Synthesis Example 1 Proline solution (PAA- 3) 1.1 662g, adding NMP 1.623 7g, stirring with a magnetic stirrer for 30 minutes to obtain (B-6). (Comparative Example 7) A 20 ml sample tube to which a stir bar was added was taken as a polylysine solution (PAA-1 2) of 0.73 8 8 g, and a synthesis example 1 proline solution (PAA-2) 2.3 08 7 g 'Addition of NMP 2 1.6510 g, and stirring with a magnetic stirrer for 30 minutes to obtain (B-7). (Comparative Example 8) Into a 20 ml sample tube to which a stir bar was added, 0.9645 g of a polyamic acid solution (PAA-1) of a combined month and 3.3282 g of a synthetic acid solution (PAA-5) of Synthesis Example 15 were added, and NMP 2.2074 g was added. The mixture was stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal (Comparative Example 9). A 20 ml sample tube to which a stir bar was added was used to obtain a total polyamine acid solution (PAA-1) 0.9954 g, Synthesis Example 1 Amino acid solution (PAA-4) 2.1 5 7 8 g 'NMP: 1.6107 g was added, and stirred with a magnetic stirrer for 30 minutes to obtain (B-9). 3 obtained 3,824 g, BCS to liquid crystal alignment agent: 2, obtained from 2, 391 5 g obtained from Example 22, BCS to liquid crystal alignment agent K, 9 obtained from polypyrene, BCS 1.6223 g (B) -8). : Example 23 obtained 4 of the obtained poly 275 50 g, BCS to liquid crystal alignment agent -78-201235386 (Example 10) The liquid crystal alignment agent (A-1) obtained in Example 1 was a film of Ι.Ομηη After filtering through ί®, it was spin-coated on a glass substrate with a transparent electrode. It was dried on a hot plate of a temperature of 80 deg. for 5 minutes, and fired in a hot air circulating oven at 230 ° C for 20 minutes. A ruthenium film having a film thickness of 100 nm. The coating film was rubbed with a rayon cloth (roll diameter: 20 mm, rotation number: 300 rpm, moving speed: 20 mm/sec, press-in amount: 0.2 mm), and subjected to ultrasonic treatment for 1 minute in pure water, followed by washing. The blower removes the water droplets at 80. (: drying was performed for 10 minutes to obtain a substrate with a liquid crystal alignment film. Two sheets of the substrate having the liquid crystal alignment film were prepared, and 6 μm of the spacer was spread on the liquid crystal alignment film surface of one of the substrates, and then the rubbing directions of the two substrates were made. In the anti-parallel combination, the liquid crystal injection port is left to seal the periphery, and an empty cell having a cell gap of 6 μm is formed. In the empty cell, liquid crystal (MLC-6608, manufactured by Merck Co., Ltd.) is injected at room temperature vacuum to seal the injection port. The liquid crystal cell was subjected to measurement of the pretilt angle and the measurement of residual DC. The results are shown in Table 1 (Example 11) to (Example 18) and (Comparative Example 10) to (Comparative Example 18). A liquid crystal cell was produced in the same manner as in Example 10 except that each of the liquid crystal alignment agents shown in Table 1 below was used. Measurement of the pretilt angle and measurement of residual DC were performed for each liquid crystal cell. -1 - 201235386 [Table i] Liquid crystal alignment agent pretilt residual DC Example 10 Al (Example 1) 89.6 ° Good Example 11 A-2 (Example 2) 88.6. Good Example 12 A- 3 (Example 3) 61.3. Good Example 13 A- 4 (Example 4) 47.2. Good Example Η A-5 (Example 5) 22.1. Good Example 15 A-6 (Example 6) 89.2° Good Example 16 A-7 (Example 7) 85.0. Good Example 17 A-8 (Example 8) 80.7° Good Example 18 A-9 (Example 9) 80.8° Good Comparative Example 10 Bl (Comparative Example 1) 65.1. Good Comparative Example 11 B-2 (Comparative Example) 2) 57.5° Good Comparative Example 12 B-3 (Comparative Example 3) 31.2. Good Comparative Example 13 B-4 (Comparative Example 4) 27.6. Good Comparative Example 14 B-5 (Comparative Example 5) 17.5. Good Comparative Example 15 B-6 (Comparative Example 6) 85.1. Good Comparative Example 16 B-7 (Comparative Example 7) 84.5. Good Comparative Example Π B-8 (Comparative Example 8) 32.7. Good Comparative Example 18 B-9 (Comparative Example 9) 49.7°. Good (Example 19) The liquid crystal alignment agent (A-1) obtained in Example 1 was filtered through a membrane of LOpm, and then spin-coated on a glass substrate with a transparent electrode at a temperature of 80. (: The hot plate was dried for 5 minutes on the hot plate. The film was fired in a hot air circulating oven at 230 ° C for 20 minutes to form a ruthenium film having a thickness of 100 nm. The film was rubbed with rayon cloth (roller diameter). 1 2 0 mm, rotation number 300 rpm, moving speed 20 mm/sec, press-in amount 〇.2 mm), after 1 minute of ultrasonic treatment in pure water, wash it. After removing the water droplets of -80-201235386 by a blower, The substrate was dried at 80 ° C for 1 minute to obtain a substrate with a liquid crystal alignment film. Two sheets of the substrate having the liquid crystal alignment film were prepared, and a spacer of 6 μm was spread on the liquid crystal alignment film surface of one of the substrates, and then the alignment directions of the two substrates were combined by 85 degrees in parallel, leaving the liquid crystal injection port to seal the periphery. An empty unit cell having a cell gap of 6 μm was produced. In the empty cell, a twisted nematic liquid crystal (MLC-2003 (C080), manufactured by Merck Co., Ltd.) was injected at a normal temperature in a vacuum, and the injection port was sealed to form a liquid crystal cell. The liquid crystal cell was subjected to measurement of pretilt angle and measurement of residual DC. The results are shown in Table 2. (Example 20) - (Example 25) and (Comparative Example 19) - (Comparative Example 25) The same procedure as in Example 19 was carried out except that the "liquid crystal alignment agent" shown in Table 2 below was used. Liquid crystal cell. The measurement of the pretilt angle and the measurement of residual DC were performed for each liquid crystal cell. The results are shown in Table 2. 201235386 ‘J Liquid Crystal Alignment Agent Pretilt Residual DC Example 19 VIII-1 (Example 1) 47.9. Good Example 20 A-2 (Example 2) 41.1° Good Example 21 A-3 (Example 3) 22.9. Good Example 22 A-4 (Example 4) 8.2. Good Example 23 A-6 (Example 6) 89.2. Good Example 24 A-8 (Example 8) 55.0. Good Example 25 A-9 (Example 9) 40.2. Good Comparative Example 19 Β·1 (Comparative Example 1) 8_7. Good Comparative Example 20 Β-2 (Comparative Example 2) 9.8. Good Comparative Example 21 Β-3 (Comparative Example 3) 14.8. Good Comparative Example 22 Β-4 (Comparative Example 4) 7.3 ° Good Comparative Example 23 Β-6 (Comparative Example 6) 61.9. Good Comparative Example 24 Β·8 (Comparative Example 8) 24.6. Good Comparative Example 25 Β-9 (Comparative Example 9) 25.4° Good [Industrial Applicability] The liquid crystal alignment agent of the present invention can be used for a TN device, an STN device, a τ FT liquid crystal device, and a vertical alignment type liquid crystal display. The formation of a medium liquid crystal alignment film. The disclosure of the specification of the patent application and the disclosure of the entire disclosure of the entire disclosure of the disclosure of the entire disclosure of the entire disclosure of the entire disclosure of -82-

Claims (1)

201235386 VII. Patent application: 1. A liquid crystal alignment agent characterized in that it contains a polyphthalate having a structural unit of the following formula (1), and a polyamine having a structural unit of the following formula (2) Acid, and organic solvent, and the polyglycolate has a side chain structure with pretilt performance ability, [C1Ri)2 I (1) -N-C-Y| Αι Ο Ο Α2 {COOH 2 I-C—X2~C—Ν—Υ2- Ο Α2 (2) (wherein X, Χ2 are tetravalent organic groups, γ丨 and γ2 are divalent organic groups, and Ri is a carbon number of 1 to 5 The alkyl group, A, and A2 are independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms or an alkynyl group. The liquid crystal alignment agent according to claim 1, wherein the aforesaid polymerization The content of the glutamate and the content of the polyamic acid are 1/9 to 9/1 by mass ratio of the content of the polyglycolate/the content of the polyglycolic acid. The liquid crystal alignment agent according to the above, wherein the total content of the polyphthalate and the polyamic acid is 0.5 to 15% by mass based on the organic solvent. 4. The method according to any one of claims 1 to 3 Liquid crystal alignment agent Wherein 'having a pretilt angle generating capability by the following formula a side chain structure (3), (4) and (5) 201 235 386 -83- groups selected from at least one, [Formula 2] (E factory E2) f (5) (In the formula (3), Z, and Z3 are bonding groups, and each is independently a single bond, or a group of the following formulas (B-1) to (B-16) At least one selected from the group consisting of Z2 being a single bond, or a C 1 to 10 alkyl group having a substituent, an alkenyl group having a carbon number of 2 to 10, an alkynyl group having a carbon number of 2 to 10, and an extended aromatic group At least one selected from the group consisting of 24 is an aliphatic ring having 3 to 20 carbon atoms which may have a substituent, an aromatic ring having 6 to 30 carbon atoms, and a heterocyclic ring having 1 to 20 carbon atoms. At least one divalent cyclic group selected, or a divalent organic group having a carbon number of 12 to 25 having a steroid skeleton, and Z5 is an aliphatic ring having 3 to 20 carbon atoms which may have a substituent, and carbon number 6 to 30 At least one divalent cyclic group selected from the group consisting of an aromatic ring and a heterocyclic group having 1 to 20 carbon atoms, a is an integer of 0 to 4 'Z6 is a carbon number 1 to 18 which may have a substituent At least one selected from the group consisting of an alkyl group, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and a fluorine-containing alkoxy group having 1 to 18 carbon atoms, and b is 1 to 1 An integer of 4, in the formula (4), Wi is an aliphatic-84-201235386 ring having a carbon number of 3 to 20 which may have a substituent. At least one trivalent cyclic group selected from the group consisting of an aromatic ring of 6 to 30 and a heterocyclic ring having 1 to 20 carbon atoms, or a trivalent organic group having a carbon number of 12 to 25 having a steroid skeleton, Wz It has the same definition as 25 of the formula (3), c is an integer of 0 to 4, W3 has the same definition as Zz of the formula (3), w4 has the same definition as Z6 of the formula (3), and e is an integer of 1 to 4. In the formula (5), E! has the same definition as in the formula (3) and Z3, and £2 is an alkyl group having a carbon number of 4 to 30 or a fluorine-containing alkyl group 'f is an integer of 1 to 4). ] —〇一一一一一〇一-0-2-~~N_ -_ I | 一—I -N-^N- ir (B-1) (B-2) -N- 0=3⁄4 9H3 . Ten ch3 ch3 (B-3) (B-4) R2 (B-5) (B-6) r2 (B-7) 1 1 戌 2 slices 2 (Β·8) r2 ^—one N −/ a r2 -(CH2)n- n=1-10 A CH2—〇—(B-9) (B-10) (B-11) (B-12) (B-13) Ο Π 0, 〇 _ _S— —〇一CH2一〇(B-14) (B-15) (B-16) (in the formula (B-1) to (B-16), each of which is an ammonia atom or a carbon number which may have a substituent 1 to 0 alkyl, alkenyl, alkynyl, aryl, or a combination thereof. The liquid crystal alignment agent according to any one of the above-mentioned formulas (1), wherein one or all of Υι has at least one type selected from the above formulas (3) to (5). The structure of the divalent organic group (Y,,). The liquid crystal alignment agent according to claim 5, wherein the ratio of the above γ, ' is 1 to 50 mol% with respect to the entire Y 1 . The liquid crystal alignment agent according to claim 6, wherein the structure of the above Y! ' is selected from at least one type of structure of the following formulas [1-1] to [1-3]. 4] _ — [1-2] Z (In the formula [1-1] to [1-3], A3 and A4 are each independently a single bond, or an alkyl group having a carbon number of 1 to 10, and A5 is a single bond or a carbon number. a valence organic group of 1 to 20, A6 is a nitrogen atom, or a trivalent organic group having a carbon number of 1 to 30, and each of human 7 and A8 is independently a divalent organic group having a carbon number of 1 to 30, and Z is the above formula (3). Or the side chain structure represented by the above formula (5), and W is a side chain structure represented by the above formula (4). The liquid crystal alignment agent according to any one of the above-mentioned formulas (1) and (2), wherein X2 is independently selected from at least one type of the structure represented by the following formula, - 86- 201235386 [化5] H3c ch3 CH3 h3c ch3 mxx xx oax The liquid crystal alignment agent of any one of the above-mentioned formula (2), wherein Y 2 is selected from at least one type of the structure represented by the following formula, Η Η [Chem. 6] A liquid crystal alignment film which is obtained by coating the liquid crystal alignment agent according to any one of claims 1 to 9 and firing it. And a liquid crystal alignment film which is obtained by applying the liquid crystal alignment agent according to any one of claims 1 to 9 and irradiating the film obtained by firing the polarized radiation. -87-201235386 12. A liquid crystal display element characterized by having a liquid crystal alignment film according to claim ι or n. 13. The liquid crystal alignment film according to claim 10, wherein the electrode is provided with a liquid crystal layer between the substrates, and the use of at least one of the active energy ray and the heat is disposed between the pair of substrates. A liquid crystal display device produced by the step of polymerizing the polymerizable compound while applying a voltage between the electrodes, the liquid crystal composition of the polymerizable polymerizable compound. A liquid crystal display element comprising the liquid crystal alignment film of claim 13 . The liquid crystal display device according to claim 14, wherein the liquid crystal display layer is provided between the pair of substrates including the electrode and the liquid crystal alignment film, and the active energy ray and the heat are disposed between the pair of substrates. A liquid crystal composition of a polymerizable compound which is polymerized is produced by a step of polymerizing the polymerizable compound while applying a voltage between the electrodes. -88- 201235386 Four designated representatives: (1) The representative representative of the case is: None (2) The symbol of the representative figure is a simple description: No. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: no