TW201200561A - Polyamic acid ester liquid crystal alignment agent, and liquid crystal alignment film using same - Google Patents

Abstract

Disclosed is a liquid crystal alignment agent which can reduce microscopic irregularities on the surface of liquid crystal alignment films, improves liquid crystal alignment properties, and has improved electrical characteristics of every kind. The liquid crystal alignment agent contains component (A), component (B) and component (C). Component (A): a polyamic acid ester obtained from a tetracarboxylic acid dialkyl ester derivative containing a tetracarboxylic acid dialkyl ester derivative represented by general formula (1) as at least 60 mol% of the total tetracarboxylic acid dialkyl ester derivative, and a diamine containing at least one diamine selected from the diamines represented by general formulae (2-5). Component (B): a polyamic acid obtained from a tetracarboxylic acid dianhydride, and a diamine. Component (C): a mixed solvent containing at least one type of organic solvent (C1) selected from a group comprising -butyrolactone and derivatives thereof, and at least one type of organic solvent (C2) selected from a group comprising N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and derivatives thereof, and in which the content of the organic solvent (C2) is 2%-30% by mass relative to the total amount of both organic solvents (C1, C2). (In general formula (1), R1 is a C1-5 alkyl group, and R2 is a hydroxyl group or a chlorine atom.) (In general formulae (2-5), A1 is a single bond, an ester bond, an amide bond, thioester bond, or a C2-10 divalent organic group, A2 is a halogen atom, a hydroxyl group, an amino group, a thiol group, a nitro group, a phospate group, or a C1-20 monovalent organic group, a is an integer from 1-4, and when a is 2 or higher, the structure of A2 can be the same or different.)

Description

201200561 VI. Description of the Invention: [Technical Field] The present invention relates to a liquid crystal alignment film obtained by producing a liquid crystal alignment agent containing a polyphthalate for a liquid crystal alignment film and the liquid crystal alignment agent. [Prior Art] In a liquid crystal display device used for a liquid crystal television or a liquid crystal display, a liquid crystal alignment film for controlling a liquid crystal alignment state is usually provided inside the device. In the liquid crystal alignment film, a liquid crystal alignment agent containing a solution of a polyamido acid precursor such as polyamido acid or a soluble polyimine is mainly applied to a glass substrate or the like. The polyimine-based liquid crystal alignment film obtained by the polymerization. With the high definition of the liquid crystal display element, the liquid crystal alignment film has high pre-tilt angle (Pretiltangle) in addition to excellent liquid crystal alignment or stable pre-tilt angle for suppressing the decrease in contrast of the liquid crystal display element or reducing the image sticking phenomenon. Retention rate, suppression of residual images due to AC drive, generation of less residual charge when DC voltage is applied, and/or early mitigation of the characteristics of residual charge accumulated by DC voltage, etc. The imide-based liquid crystal alignment film has been proposed in response to the above requirements. For example, a liquid crystal alignment film capable of shortening the time until the disappearance of a DC voltage to disappear is proposed, and a specific structure may be used in addition to a polyaminic acid or a polyamido acid containing a quinone imine group. A liquid crystal alignment agent (for example, Patent Document 1) of the amine group, or a liquid crystal alignment agent containing a soluble polyimine having a specific diamine compound having a pyridine skeleton of 201200561 as a raw material (for example, Patent Document 2) . Further, the liquid crystal alignment film having a high voltage holding ratio and shortening the time from the occurrence of the residual voltage due to the DC voltage, for example, a polyamine or a ruthenium imidized polymer thereof can be used. A liquid crystal alignment agent other than a compound containing one carboxylic acid group in the molecule, a compound containing one carboxylic acid anhydride group in the molecule, and a compound selected from a compound having one tertiary amino group in the molecule (for example, Patent Document 3) And other proposals. Further, a liquid crystal alignment film having excellent liquid crystal alignment, high voltage holding ratio, less residual image, excellent reliability, and exhibiting a high pretilt angle is known, for example, using a tetracarboxylic dianhydride having a specific structure. A liquid crystal alignment agent of polyammonic acid or a quinone imidized polymer obtained from tetracarboxylic dianhydride and a specific diamine compound with cyclobutane (for example, Patent Document 4). Further, in a liquid crystal display device of a lateral electric field driving method, a method of suppressing image sticking due to AC driving is known, and it has been known to use a liquid crystal alignment property and have a large interaction with liquid crystal molecules. A method of a specific liquid crystal alignment film (for example, Patent Document 5) 〇 However, in recent years, a large-screen and high-definition liquid crystal television is mainly used, so the requirements for image sticking are more severe and demanding It is also resistant to long-term use in the environment of use. At the same time, the liquid crystal alignment film used must have a higher reliability than the conventional one. Therefore, in addition to having good initial characteristics, various characteristics of the liquid crystal alignment film are required, for example, a long time even at a high temperature. After exposure, it can also maintain good characteristics of good -6 - 201200561. Further, in the polymer component constituting the polyimine-based liquid crystal alignment agent, when the polyglycolate is heat-treated during the imidization of the oxime, the molecular weight is not lowered, so that stability can be obtained. A report on the liquid crystal alignment, the excellent information, and the like (for example, Patent Document 6). However, polyglycolate generally has a problem of generating a large amount of residual charge due to high volume resistance and application of a direct current voltage. However, there has been no method for improving the properties of a polyimine-based liquid crystal alignment agent containing the polyphthalate. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei 8- No. Hei 8-76 No. [Patent Document 4] Japanese Laid-Open Patent Publication No. JP-A No. Hei No. Hei. No. 2003-2 6918. The problem to be solved by the present invention] The inventors of the present invention have begun to carry out research on polyglycolate and polyamine having excellent electrical properties in a method for improving the characteristics of a liquid crystal alignment agent containing the above polyphthalate. Liquid crystal alignment agent obtained by acid blending. However, the liquid crystal alignment film obtained by the liquid crystal alignment agent obtained by mixing the polyphthalate and polyphthalic acid is not available in the liquid crystal alignment and electrical properties 201200561. To the extent of satisfaction. That is, the liquid crystal alignment film obtained by the liquid crystal alignment agent containing the polyphthalate and the poly-proline does not cause white turbidity, and in the case where the liquid crystal display element is used at a high temperature, the voltage retention rate is lowered. When the DC voltage is accumulated, image sticking occurs, and an image or the like is caused by an AC drive. The present invention provides a liquid crystal alignment agent containing a polyphthalate and a polyaminic acid, which can have excellent liquid crystal alignment and electrical properties, and can also have transparency without white turbidity. A liquid crystal alignment agent for a liquid crystal alignment film is intended. [Means for Solving the Problem] As a result of analysis by a liquid crystal alignment film formed of a liquid crystal alignment agent containing a polyphthalate and a polyphthalic acid, it was confirmed that fine irregularities were formed on the surface of the film. Further, in the case of using a polyphthalate having a specific structure, it was confirmed that the fine unevenness on the surface of the film was further enlarged. However, the fine concavities and convexities generated on the surface of the film may be an organic solvent used in the liquid crystal alignment agent, and may contain two or more organic solvents having a high affinity with a polyglycolate having a specific structure. When a mixed solvent of a solvent such as an organic solvent having a high affinity with polyglycine is used, when the ratio of the two or more organic solvents is controlled, it is found that the phase of the polyglycolate and the poly-proline Separating, the fine concavities and convexities can be suppressed to a low degree, and when the fine concavities and convexities generated on the surface of the film are lowered, the liquid-containing alignment of the liquid -8 - 201200561 containing the polyphthalate and the polyaminic acid can be obtained. The above various difficulties of the agent are eliminated, and thus the present invention has been completed. That is, the present invention has been completed based on the above findings, and has the following main contents. 1. A liquid crystal alignment agent containing the following components (A), (B) and (C). (A) component: a tetracarboxylic acid dialkyl ester derivative containing 60 mol% or more of a dicarboxylic acid dialkyl ester derivative represented by the following formula (1) in the tetracarboxylic acid dialkyl ester derivative, and a polyglycolate obtained from a diamine containing at least one diamine selected from the group consisting of diamines represented by the following formulas (2) to (5), [Chemical Formula 1]

0) (In the formula (1), R is an alkyl group having 1 to 5 carbon atoms, and R2 is a hydroxyl group or a chlorine atom). -9- 201200561 [Chem. 2]

[Chemical 3]

(In the formulas (2) to (5), 'Αι is a single bond, an ester bond, a guanamine bond, a thioester bond, or a divalent organic group having a carbon number of 2 to 10'. A2 is a halogen atom or a hydroxyl group. An amine group, a thiol group, a nitro group, a phosphoric acid group or an organic group having a carbon number of 1 to 2 Å, a is an integer of 1 to 4 'a is 2 or more cases' The structure of A2 may be the same or phase (B) Component: polyamic acid obtained from tetracarboxylic dianhydride and diamine; (C) Component: at least one organic solvent selected from the group consisting of butyrolactone or a derivative thereof (C1) And with N-methyl-2-pyrrolidone, 1,3 - dimethyl imipenone (1,3-D i me thy limi d azo 1 i dinone ), or derivatives thereof a mixed solvent of at least one organic solvent (C2) selected in the group, which is an organic solvent (C2) content, and is 2% by mass based on the total amount of the organic solvent (C1) and the organic solvent (C2). ~ 3 〇 mass% of the mixed solvent. 2. The liquid crystal alignment agent according to the above 1, wherein the ratio of the component (A) to the component (B) is 1/9 to -10-201200561 9/1' in the mass ratio (A/B) ( The content of the component (c) is 70% by mass or more based on the total amount of the component (a), the component (B), and the component (C). The liquid crystal alignment agent according to the above 1 or 2, wherein the component (a) is represented by the above formulas (2) to (5) containing 40% to 1% by mole based on the total diamine. A polyglycolate obtained from a diamine of at least one diamine selected from the group consisting of diamines. 4. The liquid crystal alignment agent according to any one of the above-mentioned items 1 to 3, wherein the component (A) is a group comprising a diamine represented by the formula (2) and a diamine represented by the formula (3) a diamine of at least one selected from the group consisting of at least one selected from the group consisting of a diamine represented by the formula (4) and a diamine represented by the formula (5); The resulting polyphthalate. The liquid crystal alignment agent of any one of the above-mentioned 1 to 4, wherein the component (A) is a diamine represented by the formula (2) and a diamine represented by the formula (4). A polyphthalate obtained from a diamine of at least one diamine selected from the group. The liquid crystal alignment agent of any one of the above-mentioned formula (4), wherein the person 2 of the above formula (4) is a structure represented by the following formula (6). -A3-R3 (6) (A3 in the formula (6) is a single bond, -0-, -S-, -ΝΙΓ3-, ester bond, guanamine bond, thioester bond, urea bond , carbonate linkage, or urethane linkage, R3 is selected from a group having a carbon number of 1 to 10 which may have a substituent, an alkenyl group, an alkynyl group, an aryl group, and a combination thereof And the bases may have a substituent. The ir3 is selected from a hydrogen atom, or an alkyl group, an alkenyl group, an alkynyl group, and a combination of the groups, and the groups may have a substitution of 0. In the liquid crystal alignment agent according to any one of the above aspects, the component (A) is a diamine containing at least one selected from the group consisting of the following formulas (A-i) to (A-5). a polyamine obtained from a diamine, a aryl ester

The liquid crystal alignment agent according to any one of the above 1 to 7, wherein the component (A) is a diamine containing the above formula (1) and is formed by the above A-1) to (A-5). A polyglycolate of the second selected from the group consisting of at least one diamine. 9. The liquid crystal alignment agent according to any one of the above-mentioned items 1 to 8, wherein the component (B) is contained in the following formula (B-1) to (B-9); Tetracarboxyl-12-201200561 A polyphthalic acid obtained by grouping at least one tetracarboxylic dianhydride selected from a group of acid dianhydrides.

The liquid crystal alignment agent according to any one of the above-mentioned items 1 to 9, wherein the component (B) is a compound (B-1) having a molar ratio of 20 mol% or more to the total tetracarboxylic dianhydride. (B-9) Polyphthalic acid obtained by grouping at least one tetracarboxylic dianhydride of a tetracarboxylic dianhydride and a diamine. 1. The liquid crystal alignment agent according to any one of the above-mentioned items 1 to 10, wherein the component (B) is selected from the group consisting of the following formulas (B-10) to (B-13). Polylysine obtained from at least one diamine. -13- 201200561 [化7]

The liquid crystal alignment agent according to any one of the above-mentioned items 1 to 11, wherein the (Β) component is used in an amount of 20 mol% or more based on the total diamine. -13) Polylysine obtained by grouping at least one of the diamine diamines selected. The liquid crystal alignment agent according to any one of the above-mentioned, wherein the organic solvent (01) of the component (C) is 7-butyrolactone, and the organic solvent (C2) is Ν-methyl- 2-pyrrolidone. 14. The liquid crystal alignment agent according to any one of the above 1 to 13, wherein the component (C) is a mixed solvent of r-butyrolactone and fluorene-methyl-2-pyrrolidone, and the component (C) The total amount of the components (A), (B), and (C) is 80% by mass or more. A liquid crystal alignment film obtained by coating and baking a liquid crystal alignment agent according to any one of the above items 1 to 14. A liquid crystal alignment film obtained by applying and baking a liquid crystal alignment agent according to any one of the above 1 to 14, and irradiating the radiation of polarized light. -14-201200561 [Effect of the Invention] The present invention provides an effect of having low fine concavities and convexities on the surface of a liquid crystal alignment film regardless of a coating method such as relief printing or inkjet coating. In addition, the obtained liquid crystal alignment film can reduce the residual image caused by the AC driving, thereby improving the interface characteristics between the liquid crystal and the liquid crystal alignment film, and can also improve the electrical characteristics such as voltage holding ratio, ion density, and DC voltage residual. A liquid crystal alignment agent that enhances reliability. In the present invention, the organic solvent used in the liquid crystal alignment agent contains two or more organic solvents having a high affinity with a polyglycolate having a specific structure, and has a high affinity with polyglycine. When a mixed solvent of an organic solvent such as an organic solvent is used to control the ratio of the two or more organic solvents, the fine unevenness generated on the surface of the film is lowered, and the polyglycolate is contained. In the case of a liquid crystal alignment agent of polylysine, the above problems can be eliminated, and the reason for this is not clear, but the effect obtained by the following reason is almost the same. The polyglycolate having the specific structure described in the present invention has a high affinity for the r-butyrolactone and its derivative (organic solvent (ci)) 'N-methyl-2-pyrrolidone or 1 3 - dimethyltetrahydroimidazolone and its derivative (organic solvent (C2 )) have a tendency to have low affinity. Further, polyamic acid 'generally' has a high affinity for the above organic solvent (C2). The inventors of the present invention have found that a polyglycolate obtained by dissolving in an organic solvent (C 1 ) is mixed with a polylysine dissolved in an organic solvent (C2) to form a poly The effect of the organic solvent (C2) of the poor solvent of glutamate 'changes the above polyglycolate to poly-proline to -15-201200561. This phenomenon is presumed to be related to the solubility of the above polyglycolate and polylysine. Conventionally, after coating a liquid crystal alignment agent by letterpress printing or inkjet coating, the coating film is dried at 50 ° C to 120 ° C, and has an organic solvent having a high vapor pressure (C1) as compared with the above organic solvent (C2 ). ) is more volatile than the organic solvent (C2). Thus, the organic solvent (C2) which forms the poor solvent of the polyphthalate in the film exhibits an excessive state, which promotes aggregation or precipitation of the polyphthalate, so that before the polyglycolate moves to the surface layer of the film, Since agglomerates of polyphthalate are formed in the polyamine acid phase, a film having a large number of fine irregularities formed on the surface of the film is formed. Further, when the organic solvent (C2) is too small, aggregation or precipitation of polyglycolic acid is promoted, and agglomerates of polyglycine are formed in the polyphthalate phase, so that a film having a large number of fine irregularities on the surface of the film is formed. On the other hand, the liquid crystal alignment agent of the present invention, in the case of using a polyphthalate having a specific structure, is controlled by the ratio of the organic solvent (C 1 ) to the organic solvent (C2 ). Or poly-proline does not produce agglomeration or precipitation, resulting in phase separation, and the formation of polyglycolate is not mixed with the poly-proline in the vicinity of the surface of the membrane, and poly-proline in the membrane and substrate interface A state in which it is not mixed with a polyphthalate. Namely, since the surface of the obtained liquid crystal alignment film is separated from the polyphosphonate by the phase of the polyphthalate, it is possible to form a smooth surface without forming irregularities, and it is possible to reduce the cloudiness of the film due to occurrence of unevenness. Subsequently, a liquid crystal alignment film having a smooth surface having no unevenness is coated on the surface of the film having a polyamic acid ester having an orientation stability and excellent reliability, and is present in the interior of the film and at the electrode interface of the -16-201200561 It has excellent properties due to reasons such as polyacrylic acid with excellent electrical properties. [Embodiment of the Invention] <(A) Component> The polyglycolate used in the present invention is a polyimine precursor used in the production of polyimine, which has the following properties by heating. A polymer showing the site of the imidization reaction.

-R!〇H

In the (A) component of the present invention, the tetracarboxylic acid dialkyl ester derivative of the tetradecanoic acid diester represented by the following formula (1) is contained in the tetracarboxylic acid dialkyl ester derivative. A polyglycolate obtained by polycondensation of a diamine containing at least one diamine selected from the group consisting of diamines represented by the following formulas (2) to (5).

-17- 201200561 [化 ίο]

(2) (3) [Chem. 11]

In the formula (1), R! is an alkyl group having 1 to 4 carbon atoms, and R2 is a hydroxyl atom. M e is a methyl group. Specific examples of R! are, for example, methyl, ethyl, propyl, butyl, . The polyglycolate is accompanied by an increase in the number of carbon atoms in the alkyl group, and the temperature of the amination is increased. Therefore, it is preferable to use a methyl group or an ethyl group as a methyl group or an ethyl group. . It is more preferable that R2 is a chlorine atom to form a compound having a high bis(chlorocarbonyl) compound with a diamine. The diamine which may be combined with the dicarboxylic acid dialkyl ester derivative represented by the formula (1) is at least one selected from the group consisting of the formula (2) to the formula (5), wherein a 3 diamine selected from the group consisting of a diamine of the formula (2) and a diamine represented by the formula (3), and a diamine represented by the formula (4) and at least a group selected by the group represented by the formula (5) In the case of one type of diamine, it is more preferable to improve the solubility of r. In particular, the reactivity of the group of formula (2) or the reaction of chloroi-butyl group for quinone imidization is carried out. The condensed amine group is a group of at least one of the diamines represented by the formula (4) and the diamines represented by the formula (4). In the case of a diamine of an amine, a liquid crystal alignment film having a high liquid crystal alignment property can be obtained, which is more preferable. In the formula (3) and the formula (5), it is a single bond, an ester bond, a guanamine bond, a thioester bond, or a divalent organic group having a carbon number of 2 to 10. Αβ, the ester linkage is represented by -C(O) 0-, or - 〇C(0)-, the indoleamine is bonded to -C ( Ο ) NH-, or, -C ( 0 ) NR-, -NHC (0) -, -NRC (Ο) - The structure represented. R is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a thioester bond having a carbon number of 1 to 1 Å, or a combination thereof. Specific examples of the above alkyl group include methyl 'ethyl 'propyl, butyl, t-butyl, hexyl, octyl, cyclopentyl, cyclohexyl, dicyclohexyl and the like. Alkenyl group For example, one or more CH2-CH2 structures present in the above alkyl group are substituted by a CH=CH structure, more specifically, for example, a vinyl group, an allyl group, a 1-propenyl group, an isopropylene group. A group, a 2-butenyl group, a 1,3-butadienyl group, a 2-pentenyl group, a 2-hexenyl group, a cyclopropenyl group, a cyclopentenyl group, a cyclohexenyl group or the like. The alkynyl group is, for example, one or more of the CH2-CH2 structures present in the above-mentioned substituents, and are substituted by a cec structure, and more specifically, for example, an 'ethynyl group, a 1-propynyl group, a 2-propynyl group or the like. An aryl group such as a phenyl group or the like. The thioester linkage is such as that represented by _ c(0) S-, or -sc(o)-. The case where A! is an organic group having 2 to 10 carbon atoms can be represented by the structure of the following formula (6). -A4 - R4 - A5 - R5 - A6 - (6) -19 - 201200561 In the formula (6), A4, A5, A6 are each independently a single bond, or, -0-, -S-, -NR8- , ester linkage, guanamine linkage, thioester linkage, urea linkage, carbonate linkage, urethane linkage. 118 is a hydrogen atom, or an alkyl group, an alkenyl group, an alkynyl group, an aryl group having 1 to 10 carbon atoms, or a combination thereof, and is, for example, the same as the above-mentioned alkyl group, alkenyl group, alkynyl group or aryl group. Illustrative. In A4, A5 and VIII, the ester bond, the guanamine bond, and the thioester bond have the same structure as the ester bond, the guanamine bond, and the thioester bond described above. A urea bond, such as a structure represented by -NH-C ( Ο ) NH- ' or -NR-C ( Ο ) NR-. R is an alkyl group having 1 to 10 carbon atoms, an alkenyl 'alkynyl group, an aryl group, or a combination thereof, and examples thereof are the same as those of the above-mentioned alkyl group, alkenyl 'alkynyl group, and aryl group. Carbonate linkage, such as the structure represented by -0-C ( 〇 ) -〇-. A urethane linkage, such as ->^-(:(〇)-〇-, -〇-(:(〇)-NH-, -NR-C(0)-〇-, or - OC( O) -NR- represents the structure. R is an alkyl group, an alkenyl group, an alkynyl group, an aryl group having a carbon number of 1 to 1 Å, or a combination thereof, and examples thereof include the above-mentioned group, a rare base, and an alkyne. The aryl group and the aryl group are the same exemplified. In the formula (6) and Rs, each independently represents a single bond, or a C 1 to 10 alkyl group, an alkenyl group, an alkynyl group, an exoaryl group and The groups obtained by the combination are selected, and the groups may have a substituent to be a single bond with any one of them, or 5 may be a stretching base, a stretching base, and a stretching of 2 to 10 carbon atoms. The alkynyl group, the aryl group, and the group obtained by the combination are selected, and the groups may have a substituent of -20 to 201200561. The above alkyl group, for example, a structure obtained by removing one hydrogen atom from the above alkyl group, etc. Specifically, for example, a methyl group, a 1,1-ethyl group, a 1,2 _ethyl group, a 1,2-propyl group, a 1,3 propyl group, a fluorene group, a 4-butyl group , hydrazine, 2_butylene, 1,2-extended pentyl, 1,2-extended hexyl, 2,3-butylene, 2,4-exylpentyl, 1,2-ring a propyl group, a 1,2-cyclobutylene group, a 1,3-cyclobutylene group, a 1,2-cyclopentyl group, a 1,2-cyclohexyl group, etc. The above alkenyl group, for example, the aforementioned alkenyl group 1 The structure obtained by hydrogen atoms, etc. More specifically, for example, 1,1-vinyl group, 1,2·vinyl group, 1,2-extended ethylene methyl group, 1-methyl-i,2- Vinyl, i, 2-extended ethylene-1,1·extended ethyl, 1,2-extended ethylene-1,2-extended ethyl, 1,2-extended ethylene-i,2-extended propyl, 1 , 2-extended ethylene-1,3-propanyl, 1,2-extended ethylene·1,4-butylene, 1,2-extended ethylene-1,2-extended butyl, etc. The structure obtained by removing the above alkynyl group by one hydrogen atom, etc. More specifically, for example, an ethynyl group, an exoacetylene methyl group, an exoacetylene-1,1-ethyl group, an exoacetylene-1,2-an Base, acetylene-1,2 _ propyl, acetylene-1,3-propenyl, acetylene- l,4-butylene, acetylene-hydrazine, 2-butylene, etc. For example, a structure obtained by removing one hydrogen atom from the aryl group, etc., more specifically, for example, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, etc. Alkyl, stretch The alkenyl group, the alkynylene group, the extended aryl group, and the group obtained by combining these may have a substituent at a carbon number of 1 to 20, and may further form a ring structure via a substituent. Further, via a substituent The formation of the ring-21 - 201200561 structure means that the substituents are bonded to each other or a part of the parent skeleton to form a ring structure. The substituents are, for example, 'halogen group, hydroxyl group, thiol group, nitrate Base, organooxy, organothio, organodecyl, sulfhydryl, ester, thioester, phosphate, decyl, aryl, decyl, dilute, alkynyl, and the like. The yl group in the substituent, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like. The organooxy group in the substituent is a structure represented by -0-R such as an alkoxy 'alkenyloxy group, an aryloxy group or the like. This R is, for example, the aforementioned alkyl group, alkenyl group, aryl group or the like. These R may be further substituted by the aforementioned substituents. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group and the like. The organothio group in the substituent, such as an alkylthio group, an alkenethio group, an arylthio group or the like, is represented by -S_R. This R is, for example, the aforementioned alkyl group, alkenyl group, aryl group or the like. These R may be further substituted by the aforementioned substituents. Specific examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group and the like. The organic decyl group in the substituent, for example, the structure represented by -Si_(R) 3 . The R may be the same or different, and may be, for example, the aforementioned alkyl group, aryl group or the like. These R may be further substituted by the aforementioned substituents. Specific examples of the alkyl fluorenyl group are, for example, trimethyldecylalkyl, triethyldecylalkyl, tripropyldecylalkyl, tributyldecylalkyl and the like. The thiol group in the substituent, for example, the structure represented by -C ( Ο ) -R. This R is, for example, the aforementioned alkyl group, alkenyl group, aryl group or the like. These Rs can be replaced by the aforementioned -22-201200561. Specific examples of the fluorenyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentamidine group, an isovaleryl group, a hexyl group, and the like. The ester group in the substituent, such as the structure represented by -C(0) 〇-R, or _0C(0)-R. This R is, for example, the aforementioned alkyl group, alkenyl group, aryl group or the like. These R may be further substituted by the aforementioned substituents. The thioester group in the substituent, such as the structure represented by -C(S)0-R, or -〇C(S)-R. This R is, for example, the aforementioned alkyl group, alkenyl group, aryl group or the like. These R may be further substituted by the aforementioned substituents. The phosphate group in the substituent, for example, the structure represented by -OP ( 〇 ) 〜(0R ) 2 . The R may be the same or different, and may be, for example, the aforementioned alkyl group, aryl group or the like. These R may be further substituted by the aforementioned substituents. a sulfhydryl group in the substituent, for example, -C(Ο)NH2, or, -C(Ο)NHR, -NHC(O)R, -C(O)N(R) 2'-NRC( Ο ) R Indicates the construction. These R may be the same or different and may, for example, be the aforementioned alkyl group, aryl group or the like. These R may be further substituted by the aforementioned substituents. The aryl group in the substituent is, for example, the same as the aforementioned aryl group. The aryl group may be further substituted with the other substituents described above. The alkyl group in the substituent is, for example, the same as the alkyl group described above. The alkyl group may be further substituted with the other substituents described above. The alkenyl group in the substituent is, for example, the same as the above-mentioned alkenyl group. The alkenyl group may be further substituted with the other substituents described above. The alkynyl group in the substituent is, for example, the same as the alkynyl group described above. This alkynyl group can be further substituted with the other substituents described above. When a diamine having a high linear structure or a rigid structure is used, a liquid crystal alignment film having a good liquid crystal alignment property can be obtained from -23 to 201200561, so that the structure of A i is a single bond, or the following formula (A1-1) The structure of ~(A1-23) is better. [Chemical 13] \ )- -(CH2)n -O -NH -S n=2-6 (Al-1) (Al-2) (Al-3) (Al-4) Η Η —o— - (CHA 〇——S——(CHjJn-S——1 1 -N-(CH^n-N- 11=2-6 n=2~6 n=2~6 (Al-5) (Al-6 (Al-7) Me 0 0 -O- 0-(CH2)n-0- n=2^6 (Al-9) -N-(CH2)nN- n=2^-6 ( Al-8) ooo

O -(CH2)n- n=2^~6 -O-(CH2)n-o- if=2t~6 (A 1-10) [Chem. 15]

O

O

Q

O -(CHaJn- n=2~6 (Al-12) -o- -N- -(CH2)n-H- n=2~6 (Al-13) -〇-

O -N—(CH2)n—N— n=2~6 (Al-14) OH II Η H •N~~u—N—(CH2)„—N- n=2 ～6 (AM5) -N - -24- 201200561 [Chem. 17]

O *(CH2)n-〇- -0——(CH2)n ο •(CH2)nN—^—N—(CH2)n- n=l~4 (Al-16) n=l ～4 (AM7 )

In the above formula (4) and formula (5), 'A2 is a halogen atom, a hydroxyl group, an amine group, a thiol group, a nitro group, a phosphoric acid group' or a monovalent organic group having a carbon number of 1 to 2 Å, & An integer of ~4, where a is 2 or more, the configuration of A2 may be the same or different. The halogen atom is, for example, the same as the above-mentioned halogen atom. The amine group may be represented by a structure represented by -NH2, -NHR, or -NR(R)-. R is an alkyl group, an alkenyl group, an alkynyl group or an aryl group having 1 to 10 carbon atoms, or a combination thereof, and examples thereof are the same as those of the above-mentioned alkyl group, alkenyl group, alkynyl group and aryl group. a monovalent organic group having 1 to 20 carbon atoms, for example, an organic oxy group, an organic thio group, an organic decyl group, a decyl group, an ester group, a thioester group, a phosphate group, a decyl group, a hospital base, a stilbene group, Fast base, aryl, etc. The organooxy group' has a structure represented by _〇_R such as an anthraceneoxy group, a dilute oxy group or an aryloxy group. This R is, for example, the aforementioned alkyl group, alkenyl group, aryl group or the like. Specific examples of the compound oxygen--25-201200561, such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, etc., an organic thio group, for example, an alkylthio group, an arylthio group, The structure represented by -SR such as an arylthio group. This R is, for example, the aforementioned alkyl group, alkenyl group, aryl group or the like. Specific examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group and the like. The organic decyl group is, for example, a structure represented by -Si-(R) 3. These R may be the same or different, and may be, for example, the aforementioned alkyl group, aryl group or the like. Specific examples of the alkyl decyl group include a trimethyl decyl group, a triethyl decyl group, a tripropyl decyl group, a tributyl decyl group and the like. A thiol group, such as the structure represented by -C(0)-R. This R is, for example, the aforementioned alkyl group, alkenyl group, aryl group or the like. 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 hexyl group, and the like. The ester group is, for example, a structure represented by -C(Ο)Ο-R, or -OC(Ο)-R. This R is, for example, the aforementioned alkyl group, alkenyl group, aryl group or the like. A thioester group, such as a structure represented by -C(S)Ο-R, or -OC(S)-R. This R is, for example, the aforementioned alkyl group, alkenyl group, aryl group or the like. These R may be further substituted by the aforementioned substituents. Phosphate group, for example, the structure represented by -OP(0)~(OR)2. The R may be the same or different, and may be, for example, the aforementioned alkyl group, aryl group or the like. Amidino group, for example, -C(Ο)NH2, or -C(Ο)NHR, -NHC(〇)R, -C(O)N(R) 2, -NRC(O)R. The R may be the same or different, and may be, for example, the aforementioned alkyl group, aryl group or the like. -26- 201200561 Alkyl, alkenyl, alkynyl, and aryl are the same as the alkyl, alkenyl, alkynyl, and aryl groups described above. The above alkyl group, alkenyl group, alkynyl group, and aryl group may have a substituent when the total number of carbon atoms is from 1 to 20, and may further form a ring structure via a substituent. Further, the formation of a ring structure via a substituent means that the substituents are bonded to each other or a part of the substituent is 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 group, an organic oxy group, an organic thio group, an organic decyl group, a decyl group, an ester group, a thioester group, a phosphate group, a decyl group, and an amine group. Formate group, aryl group, alkyl group, alkenyl group, alkynyl group and the like. The halogen group in the substituent is, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like. The organooxy group in the substituent, such as an alkoxy group, an alkenyloxy group, an aryloxy group or the like, is represented by -0-R. This R is, for example, the aforementioned alkyl group, alkenyl group, aryl group or the like. These R may be further substituted by the aforementioned substituents. Specific examples of the alkoxy 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, a decyloxy group, a decyloxy group, and a lauryloxy group. Base. The organothio group in the substituent is a structure represented by -S-R such as an alkylthio group, an alkenethio group, an arylthio group or the like. This R is, for example, the aforementioned alkyl group, alkenyl group, aryl group or the like. These R may be further substituted by the aforementioned substituents. Specific examples of alkylthio groups such as 'methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio, heptylthio, octylthio, decylthio , mercaptothio group, laurylthio group and the like. The organic decyl group in the substituent, e.g., the structure represented by -Si_(R) 3 , may be the same or different, and may be, for example, the aforementioned alkyl group, aryl group or the like. These R may be further substituted by the aforementioned substituents. Specific examples of the alkyl fluorenyl group are, for example, 'trimethyldecylalkyl, triethyldecylalkyl, tripropyldecylalkyl, tributyldecylalkyl, tripentyldecylalkyl, trihexyldecylalkyl, pentyldimethylalkylalkyl And hexyl dimethyl decyl, octyl dimethyl decyl, decyl dimethyl decyl and the like. The thiol group in the substituent, for example, the structure represented by -C(0)-R. This R is, for example, the aforementioned alkyl group, alkenyl group, aryl group or the like. These R may be further substituted by the aforementioned substituents. Specific examples of the fluorenyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentamidine group, an isovaleryl group, a hexyl group, and the like. The ester group in the substituent, for example, the structure represented by -C(0)0-R, or -OC(0)-R. This R is, for example, the aforementioned alkyl group, alkenyl group, aryl group or the like. These R may be further substituted by the aforementioned substituents. A thioester group in the substituent, such as -C(S)0-R, or -OC(s)-R. This R is, for example, the aforementioned alkyl group, alkenyl group, aryl group or the like. These R may be further substituted by the aforementioned substituents. The structure represented by the phosphate group '' in the substituent, for example, -ΟΡ(0) ·(〇R) 2 . These R may be the same or different and may, for example, be the aforementioned alkyl group, aryl group or the like. These R may be further substituted by the aforementioned substituents. The amidino group in the substituent, for example, -C(0)nh2, or -C(〇)NHR, -NHC(〇)r, -c(0)N(R) 2, _NRC(0)R Construction. The R may be the same or different and may be, for example, the aforementioned hospital base, aryl group or the like. These may be further substituted by the aforementioned substituents. A urethane group as a substituent, for example, _〇_C ( 0 ) NH 2 , -28- 201200561 or, -OC ( O ) NHR, -NHC ( O) -OR, -NR-C ( O) OR The structure represented. These R may be the same or different and may, for example, be the aforementioned alkyl group, aryl group or the like. These R may be further substituted by the aforementioned substituents. The aryl group in the substituent is, for example, the same as the above-mentioned aryl group. The aryl group may be further substituted with the other substituents described above. The alkyl group in the substituent is, for example, the same as the alkyl group described above. The alkyl group may be further substituted with the other substituents described above. The alkenyl group in the substituent is, for example, the same as the above-mentioned alkenyl group. The alkenyl group may be further substituted with the other substituents described above. The alkynyl group in the substituent is, for example, the same as the alkynyl group described above. This alkynyl group can be further substituted with the other substituents described above. In the formulae (4) and (5), A2 is a group having an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof, and the carbon number is preferably from 1 to 14. When A2 is an alkyl group, an alkenyl group, an alkynyl group, an aryl group having a carbon number of 15 or more, or a combination of these, it may cause a decrease in the alignment property of the liquid crystal accompanying the introduction amount, or may cause difficulty in controlling the pretilt angle. Sex. A2 in the above formula (4) and formula (5) is preferably a structure represented by the following formula (6). A3—r3 (6) A3 in the formula (6) is a single bond '-s-, -NR/3-, an ester bond, a guanamine bond, a thioester bond, a urea bond, a carbonate Bonding, or urethane linkage, R3 is a court group, a stilbene group, an alkynyl group, an aryl group having a carbon number of 1 to 10, preferably 1 to 5 -29 to 201200561, which may have a substituent, and The group obtained by the combination is selected, and the chelating group may have a substituent. R 3 is selected from the group consisting of an amino group, or a group, a stilbene group, an alkynyl group, an aryl group, and combinations thereof, and the groups may have a substituent. Further, the configuration of the eighth embodiment is a configuration having a dissociation group which is dissociated by heating, and the solubility of the polymer can be improved without affecting the liquid crystal alignment property, the pretilt angle, and the like. The structure of Az having a dissociation group which is dissociated by heating is preferably a structure represented by the following formulas (A2-1) to (A2*24). [化 19] 〇Η3〇^3

Vd -<0Η2)η-ΝΗ η= 1—4 (Α2-1) -<CH2)„-NH- n= 1~4 (A2-3) H3QCH3 V/-CH3

-0-(CH2)n-NH a= 1~4 (A2-2)

O -(〇H2)„-nh-< CH3 n= 1~4 CH3 (A2-4) -NH-(CH2)n-NH- -HN-^-(CH2)n-NH-<〇CH3 n= 1~4 CM3 n = l~4 , CH3' (A2-5) (A2-6) [Chem. 20] -(CH2)i, -^ CH3 〇10 CH3 n=1~4 CH3 (A2-7 ) 〇-_η-ξ_^Η3 η = 1^4 ch3 (A2-8) >〇-(four)-{and 丨ns1~4 CH3 (A2-9) 〇^(〇Η2>η-^0 -0 Ten ch3 ° „=1-4 CH3 (11) >-(ch2)„-C ch3 —NH ...〇10 CH3 n = 1^4 ch3 n = 1~4 CH3 (A2-10) (A2-1D (A2-12) h3 o -30- 201200561 [Chem. 21] -(CH2)nN Ο ch2—^ ?Ha n = 0-4 2 bf-CH3 1-4 (A2-13) ch3 -o PH3 hCH3 bH^ 〇^3

Ch3 ch3 <A2,14) CH3 CH3 ne^y Η〇Η2)η·Ν, Bu 4 C (A2-17) un Cl· CH3 -p?; ><%>otHr ►_Brick 7, CH3 1-4 (A2-16) [Chem. 22]

'2/ny* * HN^O Η3〇νϊ H3^CH3 n = 0-3 (A2-20) O CH3 -(CHA·^-11·.10 CH3 HN^.0 CH3 H3C Γ n = W H3C fcH3 (A2-21) [Chemical 23] H3C^CH3 (A2-21) o ch3 H/KCHaVCH-U-O+CHa Ή HN>^〇CH3 ° H3C X n = 0-3 HsC-Kh, (A2-24 ) -〇. 〇9h3 o ch3 _nh o ch3 ^-(CH2)n{H. Ten CH3 ten CHa ^(ΟΗ^-ΟΗ-^Ο+ΟΗ: ° HN^O ch3 -i〇Hisyo CH3 & hn ^o ch3 h3Q A n = 0-3 H3Q 〇n = 0*3 H3C ζ η = 0·3 ^*3° CH3 (A2'22) H3C^H3 (A2'23> The above formula (2)~(5 The ratio of the diamine represented by the amine is preferably from 5 mol% to 100 mol% in the amine. When the ratio of the diamine represented by the above formula (2) to (the higher the ratio of the diamine) is obtained, it is good. The viewpoint of a liquid crystal alignment film or the like is preferably from 40 mol% to 100 mol%, preferably from 60 mol% to 100 mol%, wherein a diamine which is a raw material of the component (A) is used. The diamine having at least one of the diamine represented by the formula (2) and the diamine represented by the formula (3), and the diamine represented by the formula (4) and the formula -31 - all two :5 ) The crystal is selected by the formula: 5) 201200561 The diamine selected from the group consisting of diamines is preferred. The diamine as the raw material of the component (A) is particularly composed of the diamine represented by the formula (2) and the formula (4). It is preferable that at least the diamine of the diamine selected in the group is selected. Thus, in particular, the solubility in the butyrolactone as a solvent can be improved. In this case, the diamine represented by the formula (2) The amount used, or the total amount of the diamine represented by the formula (2) and the diamine represented by the formula (3), and the amount of the diamine represented by the formula (4), or the formula (4) The total amount of the diamine and the diamine represented by the formula (5) is preferably 95/5 to 60/40, more preferably 90/10 to 80/20, in terms of the molar ratio. In view of the structure in which the structure is a rigid structure, in order to obtain a liquid crystal alignment film having excellent liquid crystal alignment, the diamine of the polyphthalate of the present invention is obtained to contain the following formula (A-1). Preferably, the diamine of at least one of the diamines selected in the group of the formula (A-5) is preferably a diamine obtained by containing the diamine and the diamine represented by the above formula (2). situation In the above formula (2), the amount of the diamine used is not more than the amount of the diamine selected from the group consisting of the formula (A-1) to the formula (A-5) of the diamine. The ratio of the ears is preferably 95/5 to 60/40, more preferably 90/10 to 80/20 » -32- 201200561 [Chem. 24]

(A-l)

In the present invention, the tetracarboxylic acid dialkyl ester preferably contains 60 mol% or more of the dicarboxylic acid dialkyl ester represented by the above formula (1), more preferably 8 mol% or more. In this case, the dicarboxylic acid dialkyl ester derivative represented by the above formula (1) and the tetracarboxylic acid dialkyl ester derivative represented by the following formulas (10) to (11) can be used simultaneously as the tetracarboxylic acid. derivative. [Chem. 25]

In the above formulae (10) to (11), X is a tetravalent organic group, and R! contains a preferred example, and is also the same as in the case of the formula (1). X is not particularly limited, and specific examples thereof include, for example, the structures shown in the following X-1 to X-46. Further, these tetracarboxylic acid derivatives may be used in combination of two or more kinds - 33 - 201200561. [化26] h3c h3c ch3 h3c ch3 友此#文介ch3 h36 ch3 / \ (Xl) (X-2) (X-3) (X-4) (X-5) (X-6) ^yxxcy^ Xcyw: (X-7) (X-8) (X-9) (X-10) (X-ll) (X-12) Take: nltc WXKΙΧΣ (Xl 3) (X-14) (Xl 5) ( Xl 6) [Chem. 27]

(X-22) (X-23) (X-24) (X-25)

-34 201200561 [Chem. 28]

Further, in the present invention, the total diamine represented by the above formulas (2) to (5) preferably contains 5 to 100 mol%, more preferably 5 Å, and ear%. The diamine represented by the following formula (12) can be used in the same manner as the diamine represented by the above formulas (2) to (5). [:化 29] HN—Y—NH (12)

Re R7 In the formula (12), R6 and R? each independently represent a hydrogen atom, and an alkyl group, an alkenyl group or an alkynyl group having 1 to 1 carbon atoms of the substituent. Specific examples of the above-mentioned base group and alkynyl group are the same as those described above. The above-mentioned alkyl group, alkenyl group, and alkynyl group have the same carbon number as diamine, and may have a base or alkene at 100 moles. 9 to 10:00 -35 - 201200561 ' may have a substituent which may form a ring structure via a substituent. Further, the formation of a ring structure via a substituent means that the substituents are bonded to each other or a part of the substituent is 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 group, an aryl group, an organic oxy group, an organic thio group, an organic decyl group, a decyl group, an ester group, a thioester group, a phosphate group, and a decyl group. , alkyl, alkenyl, alkynyl and the like. Specific examples of the respective substituents are the same as those described above. In general, when a large volume structure is introduced, there is a possibility that the reactivity of the amine group or the liquid crystal alignment property is lowered, so that r6 and r7 are a hydrogen atom, or an alkyl group having a carbon number of 1 to 5 which may have a substituent. More preferably, it is particularly preferably a hydrogen atom, a methyl group or an ethyl group. In the above formula (12), Y is a divalent organic group. Y is not particularly limited, and examples thereof include a structure represented by the following formulas Y-1 to Y1 13 and the like. Further, two or more kinds of diamine compounds may also be used. In view of the fact that a good liquid crystal alignment property can be obtained, it is preferred to introduce a diamine having a high linearity into the polyphthalate, and Y! is Y-7, Y-1 0 , Y- 11 , Y- 1 2, Y-13, Y-21, Y-22, Y-23, Y-25 Y- 26, Y- 27 Y-41, Y-42, Y-43, Y-44, Y-45, Y -46 > Y- 48 Y- •6 1 Y- •63, Y-64 'Y-71, Y-72, Y-73, Y-74, Y-75 Y-98 diamine is more preferred. Further, it is preferred to: increase the pretilt angle to introduce a diamine fluorene having a long chain of a home chain, an aromatic ring, an aliphatic ring, a steroid skeleton or a combination thereof into a polyglycolate. , Υι is Y-76% Y-77, Y-78, Y-79, Y-80, Y-8 1 , Y-82 > Y-83, Y- •84, Y-85, Y •86, Y-87, Y-88, Y-89, Y-90 > Y-91, Y-92-36-201200561, Υ-93, Υ-94, Υ-95, Y-96, or Y-97 The diamine is more preferred. These diamines may have an arbitrary pretilt angle by adding 1 to 50 mol% to the total diamine, more preferably 5 to 20 mol%. [化30] •Ο众χηαΗ3Χη〇Γ3 (Y-l) (Υ-2) (Υ-3) (Υ-4)

[化如

-37- 201200561 [Chem. 33] § H3QPH3 f3ccf3

(Y-37) H

(Y-38) 03⁄4 X (Y-40) X (Y-41)

(Y-43)

CH3 ch3 —(CH2)n—(CH2)2-0-(CH2)2--(CH^-C-iCH^s (Y-53) (Y-54) (Y-52) iY-53, 死H3 <fH3 CH3 -ch2-c-<ch2>2-c-(ch2)2— -ch (Y-55)H (Y-ch3 —(CH2)2~^~(CH2 ) 5— ^(CH2)4-i (Y-57) ; H2-i-(CH2)24 -56)HH ch3 H ch3 Cl )3-Qi—〇—$i- H3 —(CH2)3- ( Y-58) ch3 —(C H2)3-〇-<C H2)2-〇-iCH2)3--(C H2)3-^i-〇-Si-〇-(CH2)3- (Y -59) (Y-60) 0H3 CH3 -38- 201200561 [化36]

[化37] -ζ^~(0^2)η-^}- J〇T〇S(CH2)^〇X^ (Υ-71) η=3~5 (Υ-72) η=2~5 Cartridge:; [Chem. 38] (Υ-74) (Υ-75)

PiCH2)n 2-5'

HCH2)n-CH3 (Υ-76) n=5~19 <CH2)n-CH3 (Υ-77) η=5~19 -39- 201200561 [fls39] (4) >-〇-〇-<CH2 )n-CH3 ^(Y-82) ff=0~21 * (Υ-83)[化40]

CH2)n-CH3 η=0~21

(Υ-89)

-40- 201200561 [化42]

C02H i (Y-98) [化 44] C02H A (Υ-99)

(Y-103) (Υ-104) -41 - 201200561 [Chem. 45]

[化州

~0~n3i'0~ (Υ-110)

(Y-113) -42- 201200561

[Component (B)] The polylysine used in the present invention is a polymer obtained by producing a polyimine polyimide precursor having a reaction site which can be subjected to the reaction shown below by heating.化 〆 〆 J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J

The component (B) of the present invention is a polyamic acid obtained by reacting a tetracarboxylic dianhydride with a diamine. The tetracarboxylic dianhydride may be represented by the following formula: wherein 乂1 is a tetravalent organic group, and the structure thereof is not specifically exemplified, for example, the above formula (X-η~(X-made, etc.) via polycondensation (1 3) is not limited. 46) The structure [化48] Ο

The diamine compound may be represented by the following formula (14), and the organic group of the formula 2 is not particularly limited. For example, the above formula (Υ-1)~(Υ-99) and (Υ) -110 -43- Medium, 丫! For its specific example) ~(Υ- (14) 201200561 113) structure. [化49]

HN-Yi-NH R6 R7 (wherein, r6 and R7 are defined as each of the above formula (12)). When the component (B) is deposited on the surface of the film, the alignment property of the liquid crystal is hindered. Further, when the component (A) can be deposited on the surface of the film, a liquid film having excellent reliability or image retention characteristics can be obtained. Therefore, the polyamic acid of the component (B) is preferably a poly-proline which has a polarity which can improve the surface transition property of the component (A) and which has a high solubility. In this regard, the polyamine obtained from the tetracarboxylic dianhydride and the diamine containing at least one of the tetracarboxylic acids selected from the above (B-1) to (B-9) is used. Acid is better. (B _ ί ) Β-9) The use ratio of at least one tetracarboxylic dianhydride selected in the group is preferably 5 mol% to 1 mol% based on the total tetracarboxylic dianhydride. When the ratio is higher, the viewpoint of the polarity and solubility of the polymer can be improved. 2 〇%% to 100% by mole is more preferable, and 40% by mole is the best. The viewpoint of using a substituent having a high polarity also allows the polyamine of the (Β) component to be deviated from the diamine having a highly polar substituent inside the film and the substrate, for example, also having a secondary or tertiary level. A diamine of a hydroxy group, a decylamino group, a ureido group or a carboxyl group is preferred. Specifically, the dianhydride of the formula can be crystallized. (Example, the amine is used as the amine, and the amine is, for example, -44 - 201200561. The above formula (14) is Υ Υ-19' γ_3ΐ Γ-40, Υ-45, Y-49~Υ-51, Υ-61, Υ-98, Υ-99, etc., γ_98 and γ-99 having a carboxyl group are more preferable. The amount of the amine compound used is preferably from 5 mol% to loomo% relative to the total amine. The higher the amount of use, the higher the polarity of the polymer, in terms of the rods t, A, + gauge δ ε ( a) The ratio of the film surface ratio of the component is preferably 10 mol% to 10 〇m ^ _ _ 0 〇 mol %, and 30 mol % 〜 1 〇〇 mol % is the best. (B) Composition a tetracarboxylic dianhydride of at least one type selected from the group consisting of the following formula (Β-1)~((-9), μZ tetracarboxylic dianhydride The dianhydride is hydrazine. [Chem. 50]

-45- 201200561 At least one type of tetracarboxylic dianhydride selected from the group consisting of the formulas (B1) to (B-9) for use in the tetracarboxylic dianhydride used as a raw material of the component (B) Preferably, it is contained in an amount of 20 mol% or more, more preferably 40 mol% or more. Further, the diamine which is a raw material of the component (B) is preferably at least one type of diamine selected from the group consisting of the following formulas (B-10) to (B-13). [化 51]

At least one type of diamine selected in the above group (B-10) to (B-13) is preferably used in a total amount of 20% of the total diamine used as a raw material of the component (B). More than %, more preferably 40% by mole or more. [Component (C)] The component (C) of the present invention contains at least one organic solvent (C1) selected from the group consisting of butyrolactone and a derivative thereof, and N-methyl-2-pyrrole The at least one organic solvent (C2) selected from the group consisting of pyridine ketone, 1,3-dimethyltetrahydroimidazolidone and the derivatives thereof, and the content of the organic solvent (C1), A mixed solvent of 2 to 30% by mass based on the total amount of the organic solvent (C1) and the organic solvent (C2). The example of the 7-butyrolactone and the derivative thereof in the organic solvent (C1) is not particularly limited as long as it is an organic solvent having a lactone structure, but is suitable as a polycondensate for dissolving the component (A) of the present invention. When the solvent of the amine ester is used, r-butyrolactone and r-valerolactone are particularly preferable organic solvents (C2), such as N-methyl-2-pyrrolidone and 1,3-dimethylimidazoline. a ketone, or a derivative thereof, for example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N-methylhexene Indoleamine, 2-pyrrolidone, 1,3 -dimethylimidazolidinone and the like. When the boiling point is too high, the solvent will remain in the film, and there is a possibility that the characteristics of the liquid crystal alignment film are deteriorated, so N-methyl-2-pyrrolidone and 1,3-dimethyl-2- Tetrahydroimidazolidone is preferred, and N-methyl-2-pyrrolidone is more preferred. The polyphthalate ester of the component (A) of the present invention has a high affinity for the organic solvent (C1) and is easily dissolved in the organic solvent. However, the polyamine amide of the component (A) of the present invention has a low affinity for the organic solvent (C2). When the content is too large, the polyamine amide of the component (A) precipitates or may affect the polymerization. The possibility of phase separation of the phthalate and polylysine. Therefore, in the component (C) of the present invention, the content of the organic solvent (C2) is preferably 2% by mass to 30% by mass based on the total amount of the organic solvent (C1) and the organic solvent (C2), more preferably It is 2% by mass to 20% by mass, particularly preferably 5% by mass to 15% by mass. The content of the organic solvent (C2) varies depending on the coating method of the liquid crystal alignment agent -47-201200561, and the solvent composition is not easily changed when the letterpress printing method is applied, generally t 30 The mass % is more preferably 5% by mass to 15% by mass. In the case of the inkjet coating method, at the time of coating, the agent forms minute droplets, so the solvent composition before coating The composition of the solvent after the alignment agent is attached to the substrate may be different. Specifically, the butyrolactone having a high vapor pressure is applied and volatilization occurs, and the content of r-butyrolactone at the time of adhesion to the substrate is lowered. Therefore, the composition using the organic solvent (C1) is preferred, and the content of the organic solvent (C2) is more preferably 2% by mass, and most preferably 2% by mass to 10% by mass. [Method for Producing Polyurethane Amine] The component (A) of the liquid crystal alignment agent of the present invention is produced by a known production method, specifically, for example, the method (a), but is not limited thereto. (a) Production of a polyfluorene polyphthalate from an acid chloride and a diamine compound, which can be obtained from a bis(chlorocarbonyl) compound. Specifically, in the presence of a bis(chlorocarbonyl) compound and a diamine and an organic solvent, it is carried out at -20 ° C to 140 ° C, but in ° C, for 3 Torr to 24 hours, preferably 1 〜 In the case of 4 hours, 5% by mass of Γ 〇 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶The amine diamine compound compound is obtained from a base; it is a reaction of 0 ° C to 50 ° and can be obtained from -48 to 201200561. As the base, pyridine, triethylamine or 4-dimethylaminopyridinium can be used, but from the viewpoint that the reaction proceeds stably, it is preferred to use pyridine. When the amount of alkali added is too small, it is not easy to remove. When the amount is too small, the molecular weight is too small. Therefore, for the bis(chlorocarbonyl) compound, it is preferable to use 2 to 4 times moles of the above formula (i). The solvent used for the amine ester is preferably N-methyl-2-pyrrolidone or r-butyrolactone in terms of the solubility of the monomer and the polymer, and one or two of them may be used. More than one kind of mixture is used. When the concentration at the time of production is too high, the precipitation of the polymer is likely to occur, and when the molecular weight is too low, the molecular weight cannot be increased. Therefore, it is preferably 1 to 30% by mass based on the total amount of the bis(chlorocarbonyl) compound and the diamine compound in the reaction liquid. It is preferably 5 to 20% by mass. Further, in order to prevent hydrolysis of the bis(chlorocarbonyl) compound, it is preferred to use a solvent which is used in the production of the polyglycolate as far as possible, and it is preferred to prevent the incorporation of other gases in a nitrogen atmosphere. (b) A polyphthalate ester produced from a dicarboxylic acid dialkyl ester and a diamine compound. The polyglycolate ester can be obtained by condensing a dicarboxylic acid tetraalkyl ester with a diamine compound via a condensing agent. Specifically, the dialkyl dicarboxylate and the diamine compound are carried out in the presence of a condensing agent, a base, and an organic solvent at 〇 ° C to 140 ° C, preferably 0 ° c to 100 ° C. It can be obtained by reacting for 30 minutes to 24 hours, preferably 3 to 15 hours. Among the above condensing agents, triphenyl phosphite, dicyclohexyl carbon-49-201200561 diimine, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide can be used. Hydrochloride, hydrazine, Ν'-carbonyldiimidazole, dimethoxy-1,3,5-triazaphenylmethylmorpholine, 0-(benzotriazol-1-yl)-indole, Ν,Ν',Ν'-tetramethylurea cation tetrafluoroborate, 〇-(benzotriazol-1-yl)-oxime, Ν,Ν',Ν'-tetramethylurea cation hexafluorophosphate And (2,3-dihydro-2-thio(keto)yl-3-benzoxazolyl)phosphonic acid diphenyl ester. The amount of the condensing agent to be added is preferably 2 to 3 moles per mole of the dialkyl dicarboxylate. As the base ', a tertiary amine such as pyridine or triethylamine can be used. If the amount of the base is too large, it will not be easily removed. When the amount is too small, the molecular weight will be too small, and it is generally 2 to 4 times the molar amount of the diamine component. Further, in the above reaction, when Lewis acid is used as an additive, the reaction can be efficiently carried out. The Lewis acid is preferably lithium halide such as lithium chloride or lithium bromide. The amount of Lewis acid added is preferably 0 to 1.0 times the molar amount of the diamine component. In the method for producing the above three polyglycolates, a high molecular weight polyglycolate can be obtained, and the production method of (a) is particularly preferable. The solution of the polyglycolate obtained by the above method can precipitate a polymer when it is injected into a poor solvent with sufficient stirring. After several times of precipitation and washing with a poor solvent, the purified polyacetate powder can be obtained at room temperature or after heating and drying. The poor solvent is not particularly limited, and is generally, for example, water, methanol, ethanol or hexane. , butyl cellosolve, acetone, toluene, and the like. [Production of Polylysine] -50- 201200561 The component (B) of the liquid crystal alignment agent of the present invention, and, for example, a polyglycine which is a raw material of the polyamine amide of the component (A), a tetracarboxylic acid The acid dianhydride and the diamine compound can be obtained by condensation polymerization. In the case of producing polyamic acid, the tetracarboxylic dianhydride and the diamine compound are preferably in the presence of an organic solvent at -20 ° C to 140 ° C, preferably 0 ° C to 50 ° C. It can be obtained by reacting for 30 minutes to 24 hours, preferably 1 to 12 hours. The solvent used in the production of polylysine of the above formula (iii), in terms of the solubility of the monomer and the polymer, N,N-dimethylformamide, N-methyl-2-pyrrolidine The ketone and the butyrolactone are preferred, and one type may be used alone or two or more types may be used in combination. When the concentration at the time of production is too high, the precipitation of the polymer is likely to occur, and when the molecular weight is too low, the molecular weight cannot be increased. Therefore, it is preferably 1 to 30% by mass based on the total amount of the tetracarboxylic dianhydride and the diamine compound in the reaction liquid. It is preferably 5 to 20% by mass. The polyamine acid obtained by the above method can be used as the component (B). However, in the case where the liquid crystal alignment agent does not contain the solvent used for the polymerization, the polymer is recovered as a solid, and then The component (B) of the present invention is preferably used. The polymer can be injected into a poor solvent while the reaction solution is sufficiently stirred, and the polymer is precipitated and recovered. The precipitated powder is washed several times, washed with a poor solvent, and dried at room temperature or by heating to obtain a powder of purified polyaminic acid. The poor solvent is not particularly limited, and is generally, for example, water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene or the like. The ratio of the diamine component used in the polymerization reaction to the tetracarboxylic acid derivative (tetracarboxylic dianhydride, tetracarboxylic acid dialkyl derivative), in terms of molecular weight control -51 - 201200561 points, with molar ratio 1: 0.7~1: 1.2 is better. The closer the molar ratio is to 1: i, the molecular weight of the resulting polyimine precursor can be increased. The molecular weight of polyglycolate and polyaminic acid will affect the viscosity of the varnish or the physical strength of the polyimide film. Therefore, when the molecular weight of the polyglycolate and polyamide is too large, varnish will be caused. When the coating workability or the uniformity of the coating film is deteriorated, if the molecular weight is too small, the strength of the obtained polyimide film may be insufficient. Therefore, the molecular weight of the polyglycolate and polyglycolic acid of the present invention is preferably 2,000 to 500,000 by weight average molecular weight, more preferably 5,000 to 30,000,000 > particularly preferably 10,000 to 100,000. [Liquid Crystal Aligning Agent] The liquid crystal alignment agent of the present invention contains a polyperurethane ((A) component) having a specific structure and polylysine ((B) component), and contains an organic solvent as described above. (C1) a mixed solvent with an organic solvent (C2) (component (C)). In the liquid crystal alignment agent of the present invention, the ratio of the component (A) to the component (B) is preferably 1/9 to 9 /1 by mass ratio (A/B), and more preferably 3/7 to 7/3. good. When the ratio is in this range, a liquid crystal alignment agent which is excellent in liquid crystal alignment or electrical properties can be provided. In the liquid crystal alignment agent of the present invention, the content of the component (C) is preferably 7 〇 mass% or more, and 80% by mass based on the total amount of the component (A), the component (B), and the component (C). The above is more preferable, and 90% by mass or more is the best. When the content of the component (C) is too small, there is a possibility that the polymer may be precipitated. In addition, if the concentration of the polymer is too large, the concentration of the polymer may be lowered, and -52-201200561 may have a coating film in which a sufficient film thickness cannot be obtained. Not good. Further, the total content (concentration) of the component (A) and the component (B) in the liquid crystal alignment agent of the present invention can be appropriately changed in accordance with the thickness setting of the liquid crystal alignment film to be formed, but uniform and non-formed. In view of the coating film of the defect, the component (C) is preferably contained in an amount of 0.5% by mass or more based on the organic solvent, and is preferably 15% by mass or less, particularly preferably 1% to 10% by mass, from the viewpoint of storage stability of the solution. The liquid crystal alignment agent of the present invention is characterized by having a component (C) having an organic solvent, but may contain other solvents. The solvent used for the liquid crystal alignment agent of the present invention can be used, for example, to dissolve a solvent of polyphthalate and polylysine (hereinafter also referred to as a good solvent) and to apply a liquid crystal alignment agent to a substrate to improve the coating film. Two types of solvents (hereinafter, also referred to as poor solvents) of uniformity. The good solvent is not particularly limited as long as it can dissolve the polyphthalate of the component (A) and the solvent of the polyamine of the component (B). That is, when specific examples are given, for example, N,N-dimethylformamide, N,N-diethylformamide, hydrazine, hydrazine-dimethylacetamide, N-ethyl-2-pyrrole Iridone, N-methyl caprolactam, 2-pyrrolidone' Ν-ethylpyrrolidone, Ν-vinylpyrrolidone, monomethyl hydrazine, methyl maple, hexamethyl argon , 7-butyrolactone, 3-methoxy-oxime, hydrazine-dimethylpropionamide, and the like. These may be used alone or in combination of two or more. Further, even if the solvent of the polymer cannot be dissolved alone, a mixed solvent may be used in the range in which the polymer is not precipitated, or two or more kinds may be used as the mixed solvent. The poor solvent 'is not particularly limited as long as it is a solvent having a low surface tension and improving the uniformity of the coating film. That is, when a specific example is given, the example -53-201200561 such as ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1 -Methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol Diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2·acetate, butyl cellosolve acetate, dipropylene glycol, 2-(2- Ethoxypropoxy)propanol, methyl lactate, ethyl lactate, η·propyl lactate, η-butyl lactate, isoamyl lactate, and the like. These solvents can be used in combination with two types of tops. The liquid crystal alignment agent of the present invention may contain various additives such as a decane coupling agent or a crosslinking agent. The decane coupling agent is added for the purpose of improving the adhesion of the substrate coated with the liquid crystal alignment agent to the liquid crystal alignment film formed thereon. Specific examples of the decane coupling agent will be listed below, but are not limited thereto. 3-aminopropyltriethoxydecane, 3-(2-aminoethyl)aminopropyltrimethoxydecane, 3-(2-aminoethyl)aminopropylmethyldimethoxy Baseline, 3·aminopropyltrimethoxydecane, 3-phenylaminopropyltrimethoxydecane, 3-triethoxydecyl-N-(l,3-dimethyl-butylene) An amine decane coupling agent such as propylamine or 3-aminopropyldiethoxymethyl decane; vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris (2-methoxy phenyl) Oxy) decane, vinyl methyl dimethoxy decane, vinyl triethoxy decane, vinyl triisopropoxy decane, allyl trimethoxy decane, P styrene trimethoxy decane, etc. Vinyl decane coupling agent; 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropylmethyldiethoxydecane An epoxy-based decane coupling agent such as 3-cyclo-54-201200561 oxypropoxypropylmethyldimethoxydecane or 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane; 3-methyl propylene methoxypropyl methyl dimethyl Oxydecane, 3-methacryloxypropyltrimethoxydecane, 3-methylpropenyloxypropylmethyldiethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, etc. a methacrylic decane coupling agent; an acrylic decane coupling agent such as 3-propenyl methoxypropyltrimethoxy decane; a ureido decane coupling agent such as 3-ureidopropyltriethoxy decane: double ( a thioether decane coupling agent such as 3-(triethoxydecyl)propyl)disulfide or bis(3-(triethoxydecyl)propyl)tetrasulfide; 3-hydrothiopropylpropane Hydrogenthio-based decane coupling agent such as methyl dimethoxy decane, 3-hydrothiopropyltrimethoxy decane, 3-octyl thiol-1-propyltriethoxy decane; 3-isocyanate Isocyanate-based decane coupling agent such as propyl triethoxy decane or 3-isocyanate propyl trimethoxy decane; aldehyde decane coupling agent such as triethoxy decyl butyl aldehyde; triethoxy decyl propyl group A urethane-based decane coupling agent such as a urethane or a (3-triethoxydecylpropyl)-t-butylcarbamate. When the amount of the above-mentioned decane coupling agent is too large, the unreacted substance will adversely affect the liquid crystal alignment property, and when it is too small, the effect of adhesion will not be exhibited, so the solid content of the polymer is 0.01 to 5 The % by weight is preferably from 0.1 to 1.0% by weight. In the case where the above decane coupling agent is added, it is preferred to prevent the precipitation of the polymer and to add the solvent for improving the uniformity of the coating film. Further, the case where the decane coupling agent is added can be 'added to the polyamidate solution, the polyaminic acid solution-55-201200561, or added to the polyfluorene before mixing the polyphthalate solution with the polyaminic acid solution. Both the amine ester solution and the polyaminic acid solution are acceptable. Further, it may be added to a polyphthalate-polyaminic acid mixed solution. The decane coupling agent is added for the purpose of improving the adhesion between the polymer and the substrate, and the method of adding the decane coupling agent is, for example, added to a polyamic acid solution which can be interposed between the inside of the film and the substrate, and the polymer and After the decane coupling agent is sufficiently reacted, it is preferably mixed with the polyamidate solution. When the baked film is baked, a quinone imidization accelerator may be added in order to effectively carry out the ruthenium imidization of the polyamidite. Specific examples of the ruthenium imidization accelerator of polyperurethane are listed below, but are not limited thereto.

HS

D-I D (D-1) (•>2) \ H2I OH D-MH OH (I>6) (C>6)

H2N

[化53] Ο

(D-7)

8 D-NH OH (D-9)

-56- 201200561 D in the above formulae (D-1) to (D-17) independently represents tert-butoxycarbonyl group or 9-fluorenylmethoxycarbonyl group. Further, when there are a plurality of Ds in one of (D-14) to (D-17), they may be the same or different from each other. The content of the sulfonium imidization accelerator which promotes the effect of the thermal hydrazylation of the polyamidite is not particularly limited, and is contained in the polyphthalamide corresponding to the liquid crystal alignment agent. The valinate moiety 1 mol of the following formula (12) preferably contains hydrazine, 〇 1 mol or more, more preferably 0.05 mol or more, and most preferably 0.1 mol or more. Further, the main body of the hydrazine imidization promoter remaining in the film after baking is reduced to a minimum amount which adversely affects various characteristics of the liquid crystal alignment film, and is relative to the liquid crystal alignment agent. The valinate moiety of the following formula (12) contained in the polyamidolate preferably has a molar amount of 2 moles or less, more preferably 1 mole or less, most preferably Below 0.5 m. [化54] Ο

Ο In the case where a ruthenium imidization accelerator is added, since it can be imidized by heating, it is diluted with a good solvent and a poor solvent, and then added as a liquid crystal alignment agent of the present invention, of course, it can be further added. Various additives such as a crosslinking agent such as -57-201200561 are used. Further, the polyamic acid of the component (A) of the present invention and the polyamic acid of the component (B) may be used alone or in combination of two or more. The concentration (content) of the polymer containing the polyphthalate ((A) component) and the poly-proline (component (B)) in the liquid crystal alignment agent of the present invention can be blended with the desired polyimine The thickness of the film is appropriately changed, and it is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, based on the organic solvent. When it is less than 1% by mass, it is not easy to form a uniform and defect-free coating film, and when it exceeds 10% by mass, the solution storage stability may deteriorate. [Method for Producing Liquid Crystal Aligning Agent] The liquid crystal alignment agent of the present invention, Polyurethane ((A) component) and polyglycine ((B) component) having a specific structure are characteristic. The ratio of the component (A) is preferably 5% by mass to 95% by mass based on the total amount of the component (A) and the component (B). When the ratio of the component (A) is too small, sufficient liquid crystal alignment property may not be obtained, and when the ratio of the component (B) is too small, the effect described in the present invention may not be obtained. Therefore, the ratio of the component (A) is preferably 20% by mass to 80% by mass, and more preferably 30% by mass to 70% by mass. A method of mixing the component (A) and the component (B), for example, a method in which a polyammonium ester of the component (a) and a polyamic acid powder of the component (B) are mixed and dissolved in an organic solvent, and (A) a method of mixing a powder of a polyglycolate of a component with a polyamic acid solution of the component (B), mixing a polyamidate solution of the component (a) with a powder of a polyamic acid of the component (B) The method of mixing the poly-phthalate solution of the component (A) with the poly-proline solution of the component (B), etc., in the method of -58-201200561. In the case where the polyglycolate which dissolves the component (A) is different from the good solvent of the polyamic acid of the component (B), a uniform polyamine derivative of the component (A) can also be obtained (B) The method of mixing the polyamic acid mixed solution of the component is more preferably a method of mixing the polyamidate solution of the component (A) with the polyamic acid solution of the component (B). A method for producing a polyamine phthalate solution of the component (A), preferably a method of dissolving a powder of the polyamidate of the component (A) in r-butyrolactone or a derivative thereof or other good solvent A method of dissolving using r-butyrolactone or a derivative thereof is more preferable. At this time, the polymer concentration is preferably 10 to 30%, particularly preferably 10 to 15%. Further, when the poly (A) component of the (A) component is dissolved, heating may be carried out. The heating temperature is preferably from 20 ° C to 150 ° C, particularly preferably from 20 t to 80 ° C. A method for producing a polyaminic acid solution of the component (B), for example, dissolving a powder of polyproline in N-methyl-2-pyrrolidone, 1,3-dimethylpyrrolidone, or the above-mentioned good solvent The method of using the polyaminic acid solution, and the method of using the polymerization reaction solution without treatment, and the method of using the polymerization reaction solution without treatment are more preferable. A solvent for polymerizing polylysine to use butyrolactone or a derivative thereof with N-methyl-2-pyrrolidone, 1,3-dimethylpyrrolidone or a derivative thereof as a mixed solvent' The method of preparing a polyamidonic acid solution is more preferable. In the case where the poly-proline powder is redissolved, the concentration of the polymer is preferably from 1 Torr to 30%, and particularly preferably from 1 Torr to 15%. Further, heat treatment can be performed while dissolving the powder of the polymer. The heating temperature is preferably 20 ° C to 15 ° C, and particularly preferably 20 ° C to 80 ° C. -59- 201200561 In the case of adding a decane coupling agent, it can be added to the poly (A) component of the (A) component before mixing the polyamine phthalate solution of the component (A) with the polyaminic acid solution of the component (B). The solution, the polyaminic acid solution of the component (B), or both the polyamidate solution of the component (A) and the polyamine solution of the component (B). Further, it may be added to a mixed solution of the polyamidomate of the component (A) and the polyamic acid of the component (B). The decane coupling agent is added for the purpose of improving the adhesion between the polymer and the substrate, and the method of adding the decane coupling agent is, for example, added to a polyamic acid solution which can be interposed between the inside of the film and the interface of the substrate (B). After the polymer is sufficiently reacted with the decane coupling agent, it is preferably mixed with the polyamine amide solution of the component (A). When the amount of the decane coupling agent is too large, the unreacted substance will have an adverse effect on the alignment of the liquid crystal, and when it is too small, the effect of the adhesion will not be exhibited. Therefore, the solid content of the polymer is 0.01 to 5.0. The mass % is preferably from 0.1 to 1.0% by mass. When the polyammonium ester solution of the (Α) component is mixed with the poly (protonic acid) solution of the (Β) component, the polymer concentration is preferably 10 to 30%, particularly preferably 1 to 15%. Further, heating may be carried out at the time of mixing, and the heating temperature is preferably 2 〇 ° C to 1 0 0 ° C, and is preferably 20 ° C to 6 (TC is particularly preferred. In the case of adding a decane coupling agent or a crosslinking agent, In order to prevent the precipitation of the polymer, it is preferable to add it before adding the lean solvent. Further, when the film is baked, the ruthenium imidization accelerator can be added to effectively carry out the ruthenium imidization of the polyamidite. In the case where a ruthenium imidization accelerator is added, since the ruthenium imidization treatment can be carried out by heating, it is preferably added after dilution with a good solvent and a poor solvent. -60- 201200561 The poly(醯) of the obtained (A) component The present invention can be obtained by adding the above-mentioned good solvent and the above-mentioned concentration to a specific polymer in a mixed solution of a B acid; g·[Liquid Crystal Alignment Film] The liquid crystal alignment film of the present invention is The liquid is applied to the substrate after filtration, and the substrate of the liquid crystal alignment agent of the present invention is applied to the substrate by drying and baking. The substrate is not particularly limited as long as it is a substrate, and a glass plate, an acrylic substrate or a polycarbonate can be used. Plastics such as ester substrates are used to form ITO electrodes by liquid crystal driving It is preferable from the viewpoint of the substrate, and the substrate of the reflective liquid crystal display side, so that an opaque electrode such as a ruthenium wafer or a material that can reflect light such as aluminum can be used. The coating method of the alignment agent, an example, a printing method, an inkjet method, etc. The liquid crystal of the present invention is applied to be dried and baked. In order to sufficiently remove the liquid crystal alignment solvent, it is preferably 50 to 12 (TC, preferably For drying, it is preferably 150 to 300 ° C, more preferably 150 to baking time, depending on the baking temperature, preferably a clock, more preferably 5 to 60 minutes. The liquid crystal alignment film of the present invention. The thickness is not limited. When it is too thin, there may be a liquid crystal alignment agent which is usually reduced in a liquid crystal display element of 5 to 300 nm, preferably 10 to 200 nm. The alignment agent preferably forms a coating film, and can have a substrate having high transparency, a tantalum nitride-based substrate, or the like, and is used in a simple process to show that the element is only a single substance, and in this case, for example, a spin coating method. After the alignment agent, the organic substance contained in the preferred agent is ¥1 10 minutes. Baking at / 25 ° C. For the special limitation of 5 to 120 minutes, the general reliability is doubtful. The film surface can be used as a liquid crystal alignment film after being subjected to the alignment treatment of -61 - 201200561. A method of performing the alignment treatment on the coating film, for example, a rubbing method, a photo-alignment treatment method, etc. The liquid crystal alignment film of the present invention can form a liquid crystal alignment film having a liquid crystal alignment energy by radiation of the polarized light. When the liquid crystal alignment film of the present invention is compared with a conventional light alignment liquid crystal alignment film, it has a light irradiation range in which a wider liquid crystal alignment property can be obtained, and even when the irradiation intensity is uneven in the substrate surface, it is obtained. A liquid crystal alignment film having uniform and good liquid crystal alignment. Specifically, for example, a method of irradiating the surface of the coating film with a polarized light in a specific direction and, if necessary, heat-treating at a temperature of 150 to 250 ° C to impart a liquid crystal alignment energy thereto. The radiation can use ultraviolet rays and visible rays having a wavelength of 100 to 800 nm. At this time, it is preferable to use ultraviolet rays having a wavelength of 100 to 400 nm, and ultraviolet rays having a wavelength of 200 to 40 nm are particularly preferable. Further, from the viewpoint of improving the liquid crystal alignment property and the like, the coated substrate may be heated to 50 to 250 ° C and irradiated with radiation. The irradiation amount of the radiation is preferably in the range of 1 to 10,0 0 m J / c m2 , and particularly preferably in the range of 100 to 5,000 mJ/cm 2 . [Embodiment] [Examples] Hereinafter, examples will be given and the invention will be specifically described. However, the present invention is not limited or construed by the examples. 1,3DMCBDE-C1: dimethyl1,3-bis(chloroindenyl)-1,3-dimethyl-62-201200561-cyclobutane- 2,4·dicarboxylic acid vinegar BDA : 1,2,3,4-butane tetracarboxylic acid dianhydride ΝΜΡ: Ν-methyl-2-pyrrolidone BCS : butyl cellosolve GBL : r - butyrolactone BCA : butyl cellosolve acetate DA-7: the following formula (DA-7) [Chem. 55]

[Viscosity] The viscosity of the polyglycolate and the polyaminic acid solution in the synthesis example, using the E-type viscosity meter TVE-22H (manufactured by Toki Sangyo Co., Ltd.), the sample amount, the cone mixer TE-1 (Γ34, R24), temperature 25. (The next measurement [molecular weight] The molecular weight of poly-branched vinegar is measured by GPC (normal temperature gel permeation S analyzer) device, and the average molecular weight is calculated by polyethylene glycol and polyethylene oxide (below) , also known as Mn) and weight average eve (hereinafter, also known as Mw). GPC device. Sodode X company (〇pc _ 1 〇1) to make 1.1 mL. I color layer I count 値h sub-quantity -63- 201200561 Column: made by Shodex (KD803, KD805 inline)

Column temperature: 50 ° C Dissolution: N,N-dimethylformamide (additive is lithium bromide-water and (LiBr·H2O) is 30 mmol/L, phosphoric acid. Anhydrous crystal (〇-phosphoric acid) is 30 mmol/ L, tetrahydrofuran (THF) 10 ml / L) Flow rate: 1.0 ml / min Standard sample for the production of the calibration line: TSK standard polyethylene oxide manufactured by Tosoh Corporation (weight average molecular weight (Mw) about 900,000, 1 50,000, 1 00,000, 3 0,000), and polyethylene glycol (a peak top molecular weight (Mp) of about 12,000, 4,000, 1,000) manufactured by Polymer Laboratories. In the measurement, in order to avoid overlapping of the peaks, four kinds of mixed samples of 900,000, 1 〇〇, 〇〇〇, 12,000, and 1,000, and 2 samples of 3 kinds of mixed samples of 150,000, 30,000, and 4,000 were respectively measured. [Relief Printing] Angstromer (S-15 type) with a chrome-plated anilox roller (Anilox Roller) with a wire count of 25 lines/inch and a line of 400 lines/inch APR resin (Japanese photo printing) Co., Ltd.), which is coated with a liquid crystal alignment agent having a solid concentration adjusted to 6 mass%. [Inkjet Coating] An ink jet coating device (manufactured by Hitachi, Ltd.) was used to apply a liquid crystal alignment agent having a solid concentration adjusted to 3.6% by mass. -64 - 201200561 [Determination of the average thickness of the center line] The coating film of the liquid crystal alignment agent obtained by letterpress printing or inkjet coating was dried on a hot plate at a temperature of 80 ° C for 5 minutes at a temperature of 230 ° C. The hot air circulating oven was baked for 30 minutes to 1 hour to form a coating film having a film thickness of 13 Onm. The surface of the film of the coating film was observed by an atomic force microscope (AFM), and the average thickness (Ra) of the center line of the film surface was measured to evaluate the flatness of the film surface. Measuring apparatus: L-trace probe microscope (manufactured by SII·Technology Co., Ltd.) [AC-driven burn-in treatment of FFS-driven liquid crystal cell] On the glass substrate, a film having a thickness of 50 nm as an electrode was formed on the glass substrate. The IT◦ electrode, the second layer is tantalum nitride having a film thickness of 50 μm as an insulating film, and the third layer is a comb-shaped ITO electrode having electrodes (electrode width: 3 μm, electrode spacing: 6 μm, electrode height) : 50 nm ) Fringe Field Switching (hereinafter, also referred to as FFS) The glass substrate of the driving electrode was coated with a liquid crystal alignment agent by inkjet coating. After drying on a hot plate at 80 °C for 5 minutes, it was baked in a hot air circulating oven at 23 (60 times for 60 minutes to form a film having a film thickness of 100 nm. The ultraviolet light at 254 nm was 400 mJ/by a polarizing plate. The coating film surface is irradiated with cm2 to obtain a substrate to which a liquid crystal alignment film is attached. Further, a glass substrate having a columnar distance controller having a height of 4 μm which is not formed on the opposite substrate is formed into a coating film by the same method, and the alignment is performed. The two substrates are used as a group, and the sealant is printed on the substrate, and the other substrate is bonded to the liquid crystal alignment film surface at a direction of 0°-65-201200561. It is hardened to produce an empty unit cell. In this empty cell, liquid crystal MLC-2041 (manufactured by Merck Co., Ltd.) was injected by a vacuum injection method, and the injection port was closed to obtain an FFS-driven liquid crystal cell. The FFS-driven liquid crystal cell was measured. After a VT characteristic (voltage-transmittance characteristic) at a temperature of 58 ° C, a rectangular wave of ±4 V / 120 Hz was applied for 4 hours. After 4 hours, the electric calendar was cut off and placed at a temperature of 58 ° C for 60 minutes. After 're-measuring its VT characteristics, calculate the application The difference between the voltages before and after the wave shape is %. [Evaluation of charge accumulation characteristics] The FFS-driven liquid crystal cell is placed on a light source, and the VT characteristic (voltage-transmittance characteristic) is measured, and then ±1.5 V is applied. Transmittance (Ta) in the state of a rectangular wave of /60 Hz. Then, after applying a rectangular wave of ±1.5 V/60 Hz for 10 minutes, the DC IV is overlapped and driven for 30 minutes. The DC voltage is cut off and the AC drive is measured. The transmittance (Tb) after 〇 minutes is calculated by the difference between Tb and Ta, and the difference in transmittance due to the voltage remaining in the liquid crystal display element is calculated. • Dimethyl 1,3-bis(chlorocarbonyl)-1,3 Synthesis of dimethylcyclobutane-2,4-dicarboxylate (1,3DMCBDE-C1) a-oxime: synthesis of dialkyl tetracarboxylate-66 - 201200561 [Chem.

Adding 1,3-dimethylcyclobutane-1,2,3,4-tetracarboxylic dianhydride (a compound of formula (5-1), below, in a three-liter four-necked flask under a nitrogen stream 1,3-DM-CBDA ) 220g ( 0.981 mol ), with methanol 2200g ( 6.87mol, 10wt times relative to 1,3-DM-CBDA), heated under reflux at 65 ° C, uniformed in 30 minutes Solution. The reaction solution was stirred under heating and refluxing for 4 hours and 30 minutes in this state. This reaction liquid was measured using a high-speed liquid chromatography analyzer (hereinafter, abbreviated as HPLC). The analysis contents of the measurement results are as described later. The reaction liquid was evaporated to a solvent using an evaporator, and then ethyl acetate (1,30 g) was added, and the mixture was heated to 80 ° C, and refluxed for 30 minutes. Subsequently, the internal temperature was cooled to 25 ° C at a rate of 2 to 3 ° C per 10 minutes, and stirred at 25 ° C for 30 minutes in this state. The precipitated white crystals were taken out by filtration, and the crystals were washed twice with ethyl acetate (1,1 g), and then dried under reduced pressure to yield white crystals of 3.97 g. This crystal was analyzed by i NMR, and the crystal structure was analyzed by X-ray analysis, and it was confirmed that the compound (1-1) (relative area of HPLC was 97.5%) (yield 36.8%). 1H NMR (DMSO-d6, 5 ppm); 12.82 (s, 2H), 3.60 (

-67- 201200561 a-2. Synthesis of 1,3-DM-CBDE-Cl [Chem. 57]

Under a nitrogen flow, a compound (1-1) 234.15 g (0.81 mol) and η-heptane 1170.77 g (ll.68 mol. 5wt times) were added to a three-liter four-necked flask, followed by the addition of pyridinium. 64 g (0.01 mol). The mixture was heated and stirred to 75 t with stirring using a magnetic stirrer. Subsequently, 289.93 g (11.68 mol) of sulfinium chloride was added dropwise over 1 hour. The foaming started immediately after the dropping, and after the completion of the dropping for 30 minutes, the reaction solution formed a uniform solution, and the foaming was stopped. Then, in this state, after stirring at 75 ° C for 1 hour and 30 minutes, the solvent was distilled off to an amount of 924.42 g in an evaporator and a 40 ° C water bath. Further, the mixture was heated at 60 ° C to dissolve the crystals precipitated when the solvent was distilled off, and the insoluble matter was distilled off by hot filtration at 60 ° C, and then the filtrate was cooled to 25 ° at a rate of 1 ° C per 10 minutes. C. After stirring at 25 ° C for 30 minutes in this state, the precipitated white crystals were taken out by filtration, and the crystals were washed with η-heptane 264.2 lg. After drying under reduced pressure, white crystals 2 2 6.0 9 g were obtained. Subsequently, 226.09 g of the white crystals obtained above and 452.18 g of η-heptane were added to a three-liter four-necked flask under a nitrogen stream, and then at 60. (: The crystals were dissolved by heating and stirring. Then, 'the crystal was cooled and stirred to 25 ° C every 10 minutes.' The crystals were precipitated. After stirring in this state at 25 ° C for 1 hour, the precipitated white crystals were The crystals were taken out by the filtration method, and the crystals were washed with n-hexane-68-201200561 113.04 g, and dried under reduced pressure to give white crystals of 203.9 1 g. The crystals were confirmed by h NMR analysis to confirm that the compound (3_1) was dimethyl. -1,3-bis(chlorocarbonyl)-i,3-dimethylcyclobutane-2,4-dicarboxylate (1,3-DM-CBDE-C1) (relative area of HPLC 99.5%) (yield 77.2%) » 1HNMR (CDC13, <5 ppm): 3.78 (s, 6H), 3.72 (s, 2H), 1.69 (s, 6H). (Synthesis Example 1) The 4-step process is shown to synthesize the diamine compound (A-5). Step 1: Synthesis of the compound (A5) [Chem. 58]

Add propargylamine (8.81 g, 160 mmol), N,N-dimethylformamide (112 mL), potassium carbonate (18. 5 g, 134 mmol) to a 500 mL flask. The solution obtained by dissolving t-butyl bromoacetate (21.9 g, 112 mmol) in N,N-dimethylformamide (80 mL) was added dropwise with stirring over a period of about 1 hour. After the completion of the dropwise addition, the reaction solution was returned to room temperature and stirred for 2 hours. Subsequently, the solid matter was removed by filtration. 1 L of ethyl acetate was added to the filtrate. The mixture was washed 4 times with 300 mL of water and once with 300 mL of saturated brine. Subsequently, the organic layer was dried using magnesium sulfate. The solvent was distilled off under reduced pressure. Finally, the residual oil was distilled under reduced pressure at 〇.6 Torr' at 70 ° C. [N-propargyl-69-201200561-aminoacetic acid t-butyl vinegar (compound (A5)) 12. 〇g' production _ is 6 3 %. Step 2: Synthesis of Compound (A6) [Chem. 59]

〇h3 Ο ^p~CH

Into a 1 L eggplant type flask, the above N-propargyl aminoacetic acid t_T ester (12_0g, 70.9 mmol) and dichloromethane (600 mL) were added as a solution, and the dicarbonate was dissolved in ice-cooled stirring. A solution of butyl ester (15.5 g, 7 0.9 mmol) in dichloromethane (100 mL) was added dropwise over 1 hour. After the completion of the dropwise addition, the reaction solution was returned to room temperature and mixed for 20 hours. After the completion of the reaction, the reaction solution was washed with 300 mL of saturated brine and dried over magnesium sulfate. Subsequently, the solvent was distilled off under reduced pressure to give N-propargyl-N-t-butoxycarbonylaminoacetic acid t-butyl ester (compound (A 6 )) as a pale yellow liquid. The yield was 18.0 g and the yield was 94%. Step 3: Synthesis of Compound (A7) [Chem. 60] ch3

〇 2NV /) ~ m2. Ten ch3 v ch3 -70- 201200561 In a 300 ml four-necked flask, 2-iodo-4-nitroaniline (22.5 g, 85.4 mmol), bis(triphenylphosphine)palladium dichloride (1 · 2) was added. 0 g, 1.7 1 mmo 1 ), copper iodide (0.651 g, 3_42 mmol), after substitution with nitrogen, diethylamine (43.7 g, 5 98 mmol), N,N-dimethylformamide (128 mL) The above-mentioned N-propargylamino-Nt-butoxycarbonylacetic acid t-butyl ester (27.6 g, 102 mmol) was added and stirred at room temperature for 20 hr. After completion of the reaction, 1 L of ethyl acetate was added, and the mixture was washed three times with 150 mL of a 1 mol/L aqueous ammonium chloride solution, and once with 150 mL of saturated brine, and dried over magnesium sulfate. Subsequently, the solid which was obtained by distilling off the solvent under reduced pressure was dissolved in ethyl acetate (200 mL), and 1 L of hexane was added, followed by recrystallization. The solid was collected by filtration and dried <RTI ID=0.0> Aniline (compound (A7)). The yield was 23.0 g and the yield was 66%. Step 4: Reduction of Compound (A7) in a 500 mL four-necked flask, and adding the aforementioned 2-{3-(Nt-butoxycarbonyl-Nt-butoxycarbonylmethylamino)-1-propynyl) 4-Nitroaniline (22.0g' 54.2mmol) and 'Ethanol (200g), after the reaction was replaced with nitrogen, palladium carbide (2.20g), the reaction system was replaced by hydrogen, and stirred at 50 °C for 48 hours. . After completion of the reaction, palladium carbide was removed by filtration through cerite, activated carbon was added to the filtrate, and the mixture was stirred at 50 ° C for 30 minutes. Subsequently, the activated carbon was filtered under reduced pressure to remove the organic solvent, and the residual oil was dried under reduced pressure to give the diamine compound (A-5). The yield was 19.8 g and the yield was 96%. -71 - 201200561 The diamine compound (A-5) was confirmed by 1H NMR. *HNMR ( DMSO-d6 ) : &lt;5 6.54-6.42 ( m,3H,Ar ), 3.49, 3.47 ( eachs,2H,NCH2C02t-Bu ) ,3.3 8 - 3.3 0 ( m,2 Η, CH2CH2N ) , 2.51 -2.44 (m,2H,ArCH2),1.84- 1.76 (m,2H,CH2CH2CH2), 1.48-1.44 (m, 18H,NC02t-Bu and CH2C〇2t-Bu) 〇(Synthesis Example 2) Synthesis of A-2 The diamine compound (A-2) was synthesized by the two-step process shown below. Step 1: Synthesis of Compound (A8) [Chem. 61]

To a four-necked flask after nitrogen substitution, 2·iodo-4-nitroaniline (5.11 g, 19.4 mm) and bis(triphenylphosphine)palladium(II) dichloride (2861) were added. 7 mg » 0.401 mmol ), copper moth (160.7 mg, 0.844 mmol), 30 ml of diethylamine, stirred at room temperature (2 (TC) for 10 minutes. Then, N-propargylamino acetic acid t- Butyl ester (compound (A5)) ( 3.72 g, 24.0 mmol) was stirred at room temperature (20 ° C) for 4 hours. After confirming the disappearance of the starting material by HPLC, 200 ml of ethyl acetate and 200 ml of 1 M aqueous ammonium chloride solution were added. The organic layer was washed twice with 1 M aqueous ammonium chloride solution and dried over anhydrous magnesium sulfate. After removing the desiccant, the filtrate was concentrated -72-201200561, cerium oxide gel column chromatography (ethyl acetate) : hexane = 3: 7) Refining. Yield: 4.97 g, yield: 88.0% ^ Step 2: Synthesis of compound (A-2) in a four-necked flask, and the above-mentioned dinitrogen (A8) (12.45 g) , 42.7mmol ), suspended in 200ml of ethanol * After degassing, nitrogen substitution, adding palladium carbide (1.2:3g), replacing with hydrogen, stirring at room temperature (2 ° ° C) for 2 days After filtering with vermiculite, the palladium carbide was removed, and the solvent was distilled off. The obtained solid was dissolved in toluene (1 ml), and then 50 ml of hexane was added to carry out recrystallization. The obtained solid was dried under reduced pressure to give a pale brown solid. : 9.13 g, yield: 80.6%) 1H-NMR of the obtained solid was confirmed to be a diamine (A-2) 〇^-NMR (DMSO-d6 » δ ppm): 1.38 (s, 9H) ' 1.57 (q, J = 7.2 Hz, 2H), 2.30 (t &gt; J- 7.2 Hz &gt; 2H ) &gt; 2.94 (quin * J = 6.0 Hz · 2H ), 3.88~4.22 (m, 4H), 6.22 (dd , J = 2.1Hz, 8.1Hz, 1H) ' 6.25 (d· J = 2.1Ηζ» 1H) ' 6.37 ( d &gt; J = 8. 1Hz &gt; 1H ) ' 6.84 ( t &gt; J = 6.0Hz &gt; 1H) &lt;Synthesis Example 3 &gt; In a 3 L four-necked flask equipped with a stirring device, P-phenylenediamine 44.04 g (0.407 mol) and diamine (A-5) 43.59 g (0.115 mol) were added under a nitrogen atmosphere. Further, 1891 g of NMP and 92.19 g of a base pyridine (-73-201200561 1.1 7 mol) were further added, followed by stirring to dissolve. Next, this diamine solution was stirred, and 1,3DM-CBDE-C1 157.90 g (0.486 mol)' was added and reacted under water cooling for 4 hours. To the solution of the obtained polyphthalate, 101 g of NMP 2 was added, and the mixture was stirred for 30 minutes to obtain a polyglycolate solution having a solid concentration of 5 wt%. The polyglycolate solution was poured into 2101 2 g of water under stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 21 〇 12 g of water, washed with 21012 g of ethanol once, and washed with 5253 g of ethanol. 3 times 'white urethane resin powder 175.94 g after drying. The yield was 83.7%. Further, the molecular weight of the polyglycolate was Mn = 13,350 and Mw = 28,323. The obtained polyamidite resin powder 丨1.1148g was placed in a 200 ml Erlenmeyer flask, and GBL74.3905g was added thereto, and stirred at room temperature for 24 hours to be dissolved to obtain a polyglycolate having a solid concentration of 13% by weight. Solution (PAE-1 &lt; Synthesis Example 4 &gt; In a 3 L four-necked flask equipped with a stirring apparatus, p-phenylenediamine 34.01 g (0.315 mol) and diamine (A-2) 15.65 were added under a nitrogen atmosphere. g (0.059 mol), diamine (A-5) 7.46 g (0.0197 mol), and further added 1344 g of NMP and 69.41 g (0.878 mol) of pyridine as a base, followed by stirring to dissolve. Next, the diamine solution was stirred. Add 1,30\1-€80 ugly-C1 1 18.9g (0_3 66mol), and react for 4 hours under water cooling. Add 1493g of NMP to the solution of the obtained polyphthalate and stir for 30 minutes to obtain a solid form. A polyglycolate solution having a concentration of 5 wt%. The polyphthalate solution was poured into 1 4934 g of water under stirring, and the precipitated white precipitate was eluted -74-201200561, followed by washing with 14934 g of water. Next, 14934g of ethanol was washed once, and 373 3g of ethanol was washed 3 times, and 127.23g of white polyphthalate resin powder was obtained after drying. The yield was 85.2%. Further, the molecular weight of the polyglycolate was Mn = 13,442 and Mw = 29,570. The obtained polyphthalate resin powder 1 5.3 794 g was placed in a 200 ml Erlenmeyer flask and added to GBL 1 3 8.4228. g, stirred at room temperature for 24 hours to dissolve, to obtain a solid concentration of polyamine solution (PAE-2 &lt; Synthesis Example 5 &gt; with a stirring device and a nitrogen introduction tube l〇〇mL four In the flask, 4.86 g (20.0 mmol) of 4,4'-diaminodiphenylamine and 4.5681 g (30.0 mmol) of 3,5-diaminobenzoic acid were weighed, and 11.05 g of NMP and 27.6 g of GBL were added. The mixture was stirred and dissolved in nitrogen gas. The diamine solution was added with BDA9.9036g (49.99mm〇l) while stirring, and then added with GBL to make the solid content concentration up to 25% by mass, and stirred at room temperature for 24 hours. A polyamine acid solution (PAA-1) is obtained, and the ratio of NMP/GBL is 2/8. The viscosity of the polyaminic acid solution at a temperature of 25 ° C is 8830 mPa · s. Further, the poly-proline The molecular weight was Mn = 12509 and Mw = 27832. &lt;Synthesis Example 6 &gt; 4, 4, and diamino 2 were weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube. Phenyl ether 4.0048g (20.0mmol), 3,5-diamine

4.5676 g (30.0 mmol) of benzoic acid was added, and 11.02 g of NMP was added, and 27.72 g of GBL-75-201200561 was added, and it was stirred and continuously dissolved in nitrogen gas to dissolve. This diamine solution was added with BDA 9.9046 g (49.99 mmol), and further added with GBL to have a solid content concentration of 25% by mass, and stirred at room temperature for 24 hours to obtain a polyaminic acid solution (PAA-2). Make the ratio of NMP/GBL 2/8. The polyamic acid solution had a viscosity of 3,607 mPa·s at a temperature of 25 °C. Further, the molecular weight of the polyamine was Μη = 10788 and Mw = 22,416. &lt;Example 1 &gt; In a 100 ml Erlenmeyer flask equipped with a stirrer, the polyphthalate solution (PAE-1) obtained in Synthesis Example 3 was 5.5 3 34 g and the polyamidonic acid solution obtained in Synthesis Example 5 was weighed. (PAA-1) 3.4645g After stirring into NMP 1.6968g, GBL3 4.3 647g, and BCA 5.0620g, the mixture was stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal alignment agent (Ia). (NMP/GBL ratio: 5/95) &lt;Example 2> The polyphthalate solution (PAE-1) obtained in Synthesis Example 3 was weighed in a l〇〇ml conical flask equipped with a stirrer. 5.549 1 g and 3.4078 g of the polyaminic acid solution (PAA-1) obtained in Synthesis Example 5 were added to N897 (2.7897 g, GBL3, 3.2928 g, and BCA 5.0429 g, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (Ib). (solid content concentration: 3.6 wt%, NMP / GBL ratio: 7.5/92.5) &lt;Example 3 &gt; In a l〇〇ml conical flask equipped with a stirrer, 'weighed from Synthesis Example 3 -76-201200561 Polyammonium ester solution (PAE-1) 5.5 3 5 4g and the polyaminic acid solution (PAA-1) obtained in Synthesis Example 3.4191g ' After adding NMP 6.0227g, GBL30.1 129g, BCA5.0263g, The magnetic stirrer was stirred for 30 minutes to obtain a liquid crystal alignment agent (Ic). (solid content concentration: 3.6 wt%, NMP / GBL ratio: 15/85) &lt;Comparative Example 1> The polyphthalate solution (PAE) obtained in Synthesis Example 3 was weighed in a 100 ml Erlenmeyer flask equipped with a stir bar. - 1 ) 5.5499g of polyamic acid solution (PAA-1 ) obtained in Synthesis Example 5 3.4118g, adding NMP8.203 3g, GBL27.8722g, BCA5.0610g, stirring with a magnetic stirrer for 30 minutes to obtain liquid crystal alignment agent (Id). (solid content concentration: 3.6 wt%, NMP / GBL ratio: 20/80) &lt;Comparative Example 2 &gt; The polyphthalate solution obtained in Synthesis Example 3 was weighed in a 100 ml Erlenmeyer flask equipped with a stir bar ( PAE-1) 5.5 545 g of the polyamic acid solution (PAA-1) obtained in Synthesis Example 5 3.4429 g, adding NMP12.5101g, GBL23.5576g, BCA5.0314g, and stirring with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent. (Ie). (solid content concentration: 3.6 wt%, NMP / GBL ratio: 30/70) &lt;Example 4> In a 100 ml Erlenmeyer flask equipped with a stirrer, the polyamine acid of -77-201200561 obtained in Synthesis Example 4 was weighed. The ester solution (PAE-2) 7.2090g and the polyaminic acid solution (PAA-2) obtained in Synthesis Example 4 3_4230g were added to NMP 0.6286g, GBL3 3.7993 g, BCA5.0192g, and then stirred for 30 minutes with a magnetic stirrer. Liquid crystal alignment agent (Π-a ). (solid content concentration: 3.6 wt%, NMP / GBL ratio: 2.5/97.5) &lt;Example 5 &gt; In a 1 〇〇 ml three-corner flask equipped with a stirrer, the polypethane obtained in Synthesis Example 4 was weighed. Amino acid ester solution (PAE-2) 7.2068 g and polyamic acid solution (PAA-1) obtained in Synthesis Example 5 3.4458 g, and after adding NMP 1.6911 g, GBL 32.6904 g, BCA 5.0167 g, stirring with a magnetic stirrer 3 0 Minutes, get the liquid crystal alignment agent (Π-b). (NMP/GBL ratio: 5/95) &lt;Example 6 &gt; In a 100 ml Erlenmeyer flask equipped with a stirrer, the polyamine ester solution (PAE-2) obtained in Synthesis Example 4 was weighed and synthesized. 3.4142 g of the polyaminic acid solution (PAA-1) obtained in Example 5 was added to N728 (2.7728 g), GBL 31.6135 g, and BCA 5.549 g, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (Π-c). (solid content concentration: 3.6 wt%, NMP / GBL ratio: 7.5/92.5) &lt;Comparative Example 3 &gt; The polylysine obtained in Synthesis Example 4 was weighed in a l〇〇ml conical flask equipped with a stir bar. Ester solution (PAE-2) 7.2009g and Synthesis Example 5 Poly-78- 201200561 Proline solution (PAA-l) 3.4260g ' After adding NMP6.0261g, GBL2 8.3 75 8g, BCA5.0213g, magnetic stirrer After stirring for 30 minutes, a liquid crystal alignment agent (Π-d) was obtained. (solid content concentration: 3.6 wt%, NMP / GBL ratio: 15 / 85) &lt;Comparative Example 4 &gt; The polydecylamine obtained in Synthesis Example 4 was weighed in a l〇〇ml conical flask equipped with a stir bar. Acid ester solution (PAE-2) 7.2006g and polyamic acid solution (PAA-1) obtained in Synthesis Example 3. 3.37 27g, after adding NMP8.1 874g, GBL26.2 1 67g, BCA 5.0 0 8 9 g, The magnetic stirrer was stirred for 30 minutes to obtain a liquid crystal alignment agent (Π-e). (solid content concentration: 3.6 wt%, NMP / GBL ratio: 20 / 80) &lt;Comparative Example 5 &gt; The polyphthalate solution obtained in Synthesis Example 4 was weighed in a 100 ml Erlenmeyer flask equipped with a stirrer ( PAE-2) 7.2175g and 3.4183g of polyamic acid solution (PAA-1) obtained in Synthesis Example 5, adding NMP 12.4940g, GBL21.9220g, BCA5.0327g, and stirring with a magnetic stirrer for 30 minutes to obtain liquid crystal alignment agent (Π-f). (solid content concentration: 3.6 wt%, NMP / GBL ratio: 30 / 70) &lt;Example 7 &gt; The polyphthalate solution obtained in Synthesis Example 3 was weighed in a 20 ml sample tube provided with a stir bar ( PAE-1) 1.87 11 g and polypyrene-79-201200561 Amino acid solution (PAA-1) obtained in Synthesis Example 1.1 1.1123 g, and added NMP 0.2143 g, GBL4.8191 g, BCS 2.0020 g, and further into the 醯N-α-(9-fluorenylmethoxycarbonyl)-Nt-butoxycarbonyl-L-histidine acid (hereinafter abbreviated as Fmoc-His) of the imidization promoter is stirred at a magnetic stirrer 30 In minutes, a liquid crystal alignment agent (III-a) was obtained. (solid content concentration: 6.0 wt%, NMP/GBL ratio: 5/95) &lt;Example 8 &gt; The polyamidomate solution obtained in Synthesis Example 3 was weighed in a 20 ml sample tube provided with a stir bar ( PAE-1) 1.8648g of polylysine solution (PAA-1) obtained in Synthesis Example 5, 1.1533g, adding NMP0_59g, GBL4.4782g, BCS2.0022g, and further injecting Fmoc- as a ruthenium promoter. After His 0.0606 g, the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (ΠΙ-b). (solid content concentration: 6.0 wt%, NMP/GBL ratio: 10/90) &lt;Example 9 &gt; The polyamidate solution obtained in Synthesis Example 3 was weighed in a 20 ml sample tube provided with a stir bar ( PAE-1) 1.8 79 1 g and the polyaminic acid solution (PAA-1) obtained in Synthesis Example 1.1 1.1 632 g, force into NMP 1.3 3 95 g, GBL3.6976g, BCS2.0394g' and then added as quinone The Fmoc-His of the accelerator was 0.0575 g, and then stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (III-c). (solid content concentration: 6.0 wt%, NMP/GBL ratio: 2 0 / 8 0 ) -80 - 201200561 &lt;Example 1 〇&gt; The sample obtained in Synthesis Example 3 was weighed in a 20 ml sample tube provided with a stir bar. Polyurethane solution (PAE_ 1 ) 1.863 5 g and 1.1301 g of polyaminic acid solution (PAA-1 ) obtained in Synthesis Example 5, adding NMP 2.0570 g, GBL 2.9560 g, BCS 2.0165 g, and further injecting as After the imidization promoted Fmoc-His 0.05 80, the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (ΙΙΙ-d). (solid content concentration: 6.0 wt%, NMP/GBL ratio: 30/70) &lt;Comparative Example 6 &gt; The polyphthalate solution obtained in Synthesis Example 3 was weighed in a 20 ml sample tube provided with a stir bar ( PAE-1) 1.863 8g and the polyaminic acid solution (PAA-1) obtained in Synthesis Example 1 1.1 340g, adding NMP2.8074g, GBL2.23 1 lg, BCS2.03 13g, and then adding as a ruthenium amide promoter After Fmoc-His was 0.0549 g, it was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (ΙΙΙ-e). (solid content concentration: 6.0 wt%, NMP/GBL ratio: 40/60) &lt;Comparative Example 7 &gt; The polyphthalate solution obtained in Synthesis Example 3 was weighed in a 20 ml sample tube provided with a stir bar ( PAE-1) 1.865 3 g of the polyaminic acid solution (PAA-1) obtained in Synthesis Example 1.1 766g ' Addition of NMP 3.5495g, GBL1.4903g, BCS2.0125g, and then added as a ruthenium iodide promoter - 81 - 201200561

After Fmoc-His was 0.0589 g, it was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (ΙΙΙ-f). (solid content concentration: 6.0 wt%, NMP/GBL ratio: 50/50) &lt;Example 11 &gt; The polyphthalate solution obtained in Synthesis Example 3 was weighed in a 20 ml sample tube provided with a stir bar ( PAE-1) 1.8748g and polyamic acid solution (PAA-2) 1.2008g obtained in Synthesis Example 6, adding NMP0.229 1 g, GBL4.8059g, BCS2.0692g, and stirring with a magnetic stirrer for 30 minutes to obtain liquid crystal Orienting agent (-a). (solid content concentration: 6.0 wt%, NMP/GBL ratio: 5 / 95) &lt;Comparative Example 8 &gt; The polyphthalate solution obtained in Synthesis Example 3 was weighed in a 20 ml sample tube provided with a stir bar ( PAE-1) 1.8504g and 1.1918g of the polyaminic acid solution (PAA-2) obtained in Synthesis Example 6. After injecting NMP2.8065 g, GBL2.1 5 76g, BCS2.0034g, stir with a magnetic stirrer for 30 minutes. , a liquid crystal alignment agent (-b). (solid content concentration: 6.0 wt%, NMP/GBL ratio: 40/60) &lt;Example 1 2 &gt; The liquid crystal alignment agent (Ι-a) obtained in Example 1 was filtered with a filter of Ι.Οηηι, The liquid crystal alignment agent is applied by inkjet coating to a glass substrate with a transparent electrode. The obtained coating film was dried on a heat-82-201200561 pressure plate at a temperature of 80 ° C for 5 minutes, and baked for 1 hour in a hot air circulating oven at a temperature of 230 ° C to form a coating film having a film thickness of 130 nm. The film surface of the coating film was observed using an atomic force microscope (AFM), and the average thickness (Ra) of the center line of the film surface was measured to evaluate the flatness of the film surface. The results are shown in Table 1 below. &lt;Examples 13 to 17 and Comparative Examples 9 to 13&gt; Each of the liquid crystal alignment agents (Ia) to (II-c) and liquid crystal alignment agent (Id) obtained in the above Examples 2 to 4 and Comparative Examples 1 to 4, respectively Each of the coating films was prepared in the same manner as in Example 12 except for the case of ~(II-f). The film surface of each coating film was observed using an atomic force microscope (AFM). Further, the average thickness (Ra) of the center line of each of the coating films was measured to evaluate the flatness of the film surface. The measurement results are shown in Table 1 below. [Table 1] Average thickness of liquid crystal alignment agent polymer NMP/GBL than center line [nm] Example 12 I - a PAE-l (40) / PAA-1 (60) 5. 0/95.0 0. 98 Implementation Example 13 I-b PAE-1(40)/PAA-1(60) 7·5/92. 5 0.45 Example 14 I-c PAE-1(40)/PAA-1(60) 15/85 0.87 Implementation Example 15 Il-a PAE-2(40)/PAA-1 (60) 2. 5/97. 5 1.62 Example 16 II-b PAE-2(40)/PAA-l(60) 5. 0/9 5 0.41 Example 17 II a c PAE-2 (40) / PAA-1 (60) 7. 5/92, 5 1.01 Comparative Example 9 I a d PAE-1 (40) / PAA-1 (60) 20 /80 1.54 Comparative Example 10 I - e PAE-1 (40) / PAA-1 (60) 30 / 70 2.42 Comparative Example 11 Il-d PAE-2 (40) / PAA-l (60) 15 / 85 5.52 Comparison Example 12 II-e PAE-2 (40) / PAA-1 (60) 20/80 7.63 Comparative Example 13 II-f PAE-2 &lt; 40) / PAA-1 (60) 30 / 70 8.82 As shown in Table 1 As a result, it was found from the results of Examples 1 2 to 17 and Comparative Examples 9 to 13 that depending on the composition of the polyglycolate and the polyamic acid, the optimum solvent ratio was different, and the amount of NMP was ' Compared with the total amount of NMP and GBL -83-201200561, in the case of inkjet coating, when it is 2.5% by mass to 15% by mass, the polyperurethane and polylysine can be reduced. It was confirmed that a flat film was obtained by the minute projections which occurred in the phase separation. &lt;Example 1 8&gt; The liquid crystal alignment agent (ΙΠ-a) obtained in Example 7 was filtered through a filter of Ι.Οιη, and the liquid crystal alignment agent was applied by letterpress printing on a glass substrate with a transparent electrode. on. The obtained coating film was dried on a hot plate at a temperature of 80 ° C for 5 minutes, and baked at a temperature of 23 (TC hot air circulating oven for 30 minutes to form a coating film having a film thickness of 130 nm. The atomic force microscope (AFM) was used to observe the film. The film surface of the coating film and the average thickness (Ra) of the center line of the film surface were measured to evaluate the flatness of the film surface. The results are shown in Table 2 below. <Examples 19 to 22 and Comparative Examples 14 to 16 &gt In addition to the respective liquid crystal alignment agents (ΠΙ-b) to (-〇 and liquid crystal alignment agents (III_e) to (·b) obtained in the above Examples 8 to 4 and Comparative Examples 1 to 5, respectively, A coating film was produced in the same manner as in Example 18. The film surface of each coating film was observed by an atomic force microscope (AF Μ ), and the average thickness (Ra ) of the center line of the film surface was measured to evaluate the flatness of the film surface. 2 shows -84- 201200561 [Table 2] Liquid crystal alignment agent polymer NMP/GBL average roughness fnml of Φ core line Example 18 III- a PAE-1(40)/PAA-1(60) 5.0/95.0 0,84 Example 19 III-b PAE-1(40)/PAA-1(60) 10/90 0. 88 Example 20 III-c PAE-1(40)/PAA-1(60) 20/80 0.88 Example 21 III-d PAE-1(40)/PAA-1(60) 30/70 0.92 Sinus Case 22 — a PAE-l(40)/PAA-2(60) 5.0/9.5 0.84 1Ϊ Comparative Example 14 ee e PAE-1(40)/PAA-1(60) 40/60 1.21 Comparative Example 15 III- f PAE-l(40)/PAA-l(60) 50/50 1.30 Comparative Example 16 —b PAE -l&lt;40)/PM-2(60) 40/60 4.64 As shown in Table 2, it was found from the results of Examples 18 to 22 and Comparative Examples 14 to 16, that the polyphthalate and the poly-proline were The difference in composition will result in the difference of the optimal solvent ratio. The amount of NMP is relative to the total amount of NMP and GBL. In the case of letterpress printing, when it is set within 5 mass% to 30 mass%, the polyamine can be reduced. The fine unevenness which was formed by the phase separation of the acid ester and the poly-proline was confirmed to be a flat film. <Example 23 &gt; The liquid crystal alignment agent (Ib) obtained in Example 2 was filtered using a Ι.Οιη filter. An IT ruthenium electrode having a first layer of 50 nm and a thickness of 50 nm was formed by inkjet coating on a glass substrate, and the second layer was a tantalum nitride having a film thickness of 50 nm as an insulating film, and the third layer was a comb-like layer. ITO electrode (electrode width: 3μιη, electrode spacing: 6μιη, electrode height: 50 nm) glass substrate for FFS drive electrodes. After drying on a hot plate at 80 ° C for 5 minutes, it was baked in a hot air circulating oven at 23 ° C for 60 minutes to form a coating film having a film thickness of 130 nm. The coating film surface was irradiated with ultraviolet rays of 254 nm at 400 mJ/cm 2 through a polarizing plate to obtain a substrate to which a liquid crystal alignment film was attached. Further, a glass substrate having a columnar distance controller having a height of 4 μm which is not formed on the substrate, is formed into a coating film by the same method as -85-201200561, and subjected to an alignment treatment. The two substrates were used as a group, and a sealant was printed on the substrate, and the other substrate was bonded in such a manner that the alignment direction of the liquid crystal alignment film surface was 〇°, and then the sealant was cured to prepare an empty cell. In this empty cell, liquid crystal MLC-204 1 (manufactured by Merck Japan Co., Ltd.) was injected by a vacuum injection method, and the injection port was closed to obtain an FFS-driven liquid crystal cell. The FFS was used to drive the liquid crystal cell, and the AC drive burn-in and charge accumulation characteristics were evaluated. The results are shown in Table 3 below. <Example 24 &gt; An FFS-driven liquid crystal cell was produced in the same manner as in Example 23 except that the liquid crystal alignment agent (ΙΙ-b) obtained in Example 5 was used. The FFS was used to drive the liquid crystal cell to evaluate the AC drive burn-in and charge accumulation characteristics. The results are shown in Table 3 below. <Comparative Example 1 7 &gt; An FFS-driven liquid crystal cell was produced in the same manner as in Example 23 except that the liquid crystal alignment agent (I - d ) obtained in Comparative Example 1 was used. The F F S was used to drive the liquid crystal cell, and the AC drive burn-in and charge accumulation characteristics were evaluated. The results are shown in Table 3 below. &lt;Comparative Example 1 8 &gt; An FFS-driven liquid crystal cell was produced in the same manner as in Example 23 except that the liquid crystal alignment agent (11 - e ) obtained in Comparative Example 4 was used. The -86-201200561 FFS was used to drive the liquid crystal cell to evaluate the AC drive burn-in and charge accumulation characteristics. The results are shown in Table 3 below. [Table 3] AC drive burn-in _ imVl charge accumulation characteristic r%i Example 23 0.0 0.1 Example 24 0.2 0.1 Comparative Example 17 0.2 0.1 Comparative Example 18 0.9 0.5 From Example 2 3 to 2 4 and Comparative Example 1 7~ As a result of 18, it was confirmed that the liquid crystal alignment film having more excellent AC drive, burn-in, and charge storage characteristics was obtained by reducing the result of fine unevenness generated by phase separation of the polyphthalate and the poly-proline. • Synthesis of diamine compound (A-1) (precursor synthesis 1) [Chem. 62]

1) BHs-THF

2) aq. HCI

3) aq. NaOH on a 1 L four-necked flask, equipped with a Dimroth tube, a 100 mL dropping funnel, and a 2-cyano-4-nitroaniline (15 g, 92 mm 〇 1 ) reaction system. After nitrogen substitution, 400 mL of THF was added and the mixture was cooled to 0 °C. -87-201200561 Next, a boron-THF complex (IMinTHF, 100 mL, 100 mmol) was added dropwise via a dropping funnel over a period of 30 minutes. It was confirmed that a gas was generated from the reaction system, and a yellow solid was precipitated. After the completion of the dropwise addition, the mixture was stirred at room temperature for 2 days. After completion of the reaction, hydrochloric acid (2N, 200 mL) was added, and the mixture was stirred at room temperature for 2 hours, and then aqueous sodium hydroxide (2N, 250 mL) was added at 10 ° C to make it basic and extracted with dichloromethane. The organic layer was washed with brine (500 mL) and dried over magnesium sulfate. The yield was 11.9 g and the yield was 77%. (Precursor Synthesis 2) [Chem. 63]

To the 1 L eggplant type flask, the above cyano group (4.60 g' 2 7.5 mmol) and dichloromethane (900 mL) were added as a solution, and diter-butyrate dicarbonate (6.00 g, 27.5 mmol) was added thereto. Stir at temperature (20 °C) for 3 days. After the completion of the reaction, the reaction solution was washed with saturated brine and dried over magnesium sulfate. The organic layer was concentrated under reduced pressure to give a solid solid, which was crystallised from ethyl acetate-hexane. The yield was 5.25 g and the yield was 71%. (Synthesis of DA-2) -88- 201200561 [Chem. 64]

To the 100 mL eggplant type flask, the Boc adduct (5.0 g, 18.7 mmol) and ethanol (40 ml) were added. The reaction system was replaced with nitrogen, and then platinum oxide (500 mg) was added thereto, and the reaction was replaced with hydrogen. The yellow suspension-forming reaction mixture was stirred at room temperature for 15 hours. After completion of the reaction, ethanol was added to dissolve the precipitated white solid, and the catalyst was removed by filtration through vermiculite. The filtrate was concentrated and the obtained brown solid was crystallised from ethyl acetate-hexane to yield pale pale solid. The yield was 3.40 g and the yield was 77%. The 1H-NMR of the obtained solid was measured, but the term was A-1. 'H-NMR (DMSO-d6 · δ ppm): 1.44 ( s, 9H), 3.87 (d, J = 6.3 Hz, 2H), 4.10 to 4.30 (m, 4H), 6.27 (dd, J = 2.4 Hz, 8.1 Hz, 1H), 6.31 (d, J = 2.4 Hz, 1H), 6.38 (d, J = 8.1 Hz), 7.14 (t, J = 6.3 Hz, lH). (Synthesis Example 7) A 300 mL four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, and p-PDA (2.52 g (23.30 mmol), (A-1) 1, 3725 g (5.78 mmol)) was added, and NMP 97.20 was added. g. 5.21 g (65.8 9 mmol) of pyridine as a base, and stirred to dissolve. Next, this diamine solution was stirred in a stirred mixture of -89 - 201200561, and 1.930 g (27.47 mmol) of 1,3DM-CBDE-C1 was added, and the mixture was reacted for 4 hours under water cooling. After 4 hours, NMP 1 07.94g was added to the reaction solution, and stirred at room temperature (2 (TC) for 15 minutes. The resulting solution of polyglycolate was added to 108 0 g of water with stirring, and the precipitate was separated by filtration. The precipitate was white, and then washed once with 100 g of water, washed once with 1 080 g of ethanol, and washed with 27 g of ethanol for 3 times, and dried to obtain a white polyphthalate resin powder. The molecular weight of the amine ester was Μη = 12119, Mw = 25695». In a 100 ml Erlenmeyer flask, 7.7151 g of the obtained polyphthalate resin powder was taken, and after adding GB. 69.4528 g, it was stirred at room temperature for 24 hours to dissolve. A polyacetate solution (PAE-3) was obtained. (Synthesis Example 8) A 300 mL four-necked flask equipped with a stirring device was set in a nitrogen atmosphere to put in - phenylenediamine 2_8118 Lu (26. 〇111111〇) 1), (8-5) 1.0964§ ( 2.89mmol), then add NM P 5 1.9 9 g, GB L 1 5 5.9 7 g, as base pyridine 5.1 6g (6 5.18m mol ), stir and dissolve Next, the diamine solution was stirred, and 1,3DM-CBDE-C1 8.830 1 g (27.16 mmol) was added, and the reaction was carried out for 4 hours under water cooling. 0.7532 g ( 8.32 mmol) of olefinic chloride was reacted for 30 minutes under water cooling. The obtained polyphthalate solution was poured into 9 〇 5 g of 2-propanol under stirring to filter out the precipitate which was precipitated, and then used. 448 g of 2-propanol was washed 5 times to obtain a polyphthalate resin powder after drying. The molecular weight of the polyglycolate was Mn = 15 62 3 and Mw = 30510. In a 100 ml Erlenmeyer flask, weighed The obtained polyphthalate resin powder-90-201200561 was 10.10 g at the end, and GBL 91.06 g was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-4). A 300 mL four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, and 2.7958 g (13.17 mmol) of 4,4'-ethylenediphenylamine, (2.35 g) (3.41 mmol), and NMP 35.40 were added. g, GBL 35.39g, and 2.87g (3 6.3 4mmol) as the base pyridine, and then stirred to dissolve. Secondly, the diamine solution was stirred, and 1,3DM-CBDE-C1 4.9228g (15.14mmol) was added. The mixture was reacted for 4 hours under water cooling. After 4 hours, 35.40 g of NMP and 35-40 g of GBL were added to the reaction solution, and the mixture was stirred at room temperature (20 ° C) for 15 minutes. The obtained solution of the polyglycolate was put into 78 6 g of water with stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 786 g of water, once with 786 g of ethanol, and washed with 197 g of ethanol. After 3 times, it was dried to obtain a white polyphthalate resin powder. The molecular weight of the polyglycolate was Mn = 16710 and Mw = 32,198. In a 100 ml Erlenmeyer flask, 4.7855 g of the obtained polyphthalate resin powder was weighed, and GBL 32.0428 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 1 〇) A 500 mL four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere. After placing p-phenylenediamine 5.5027 g (50.88 mmol) and (Al) 1.052 1 g (4.43 mmol), NMP was added. 95.07 g, GBL 285.2 1 g, 9.87 g (124.7 mmol) of pyridine as a base 201200561, and stirred to dissolve. Next, this diamine solution was stirred, and 1,3DM-CBDE-CL 1 6.895 6g (5 1 · 9 7 m m ο 1 ) was added, and the reaction was carried out for 4 hours under water cooling. After 4 hours, 1.4410 g (1.92 mmol) of propylene chloride was added, and the mixture was reacted for 30 minutes under water cooling. The obtained polyglycolate solution was poured into 165 g of 2-propanol under stirring, and the precipitate was precipitated by filtration, and then washed with 829 g of 2-propanol for 5 times, and dried to obtain a poly A phthalate resin powder. The polyglycolate has a molecular weight of Mn = 1 5623 and Mw = 305 1 0. Into a 200 ml Erlenmeyer flask, 12.8291 g of the obtained polyphthalate resin powder was weighed, and GBL 115.4259 g was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-6). (Synthesis Example 1 1) A 300 mL four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, and p-PDA 2.03 g (18.77 mmol) and (A-2) 1.2280 g (4.63 mmol) were placed, and then NMP was added. 1 67.80 g of 4.31 g (5 3.26 mmol) of pyridine as a base, and stirred to dissolve. Next, this diamine solution was stirred, and 1,3DM-CBDE-C1 7.21 82 g (22.20 mmol) was added for 4 hours under water cooling. The obtained polyglycolate solution was poured into 885 g of water with stirring, and the precipitated white precipitate was collected by filtration, followed by 'washing with 885 g of water once, 885 g of ethanol for 1 wash, and 220 g of ethanol for washing 3 Then, after drying, a white polyphthalate resin powder was obtained. The polyglycolate had a molecular weight of Mn = 14116 and Mw = 27044. In a 100 ml Erlenmeyer flask, the obtained polyphthalate resin powder was weighed to 7.2601 g at the end of 92-201200561, and added to GBL 65.3489 g, and stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution ( PAE-7). (Synthesis Example 1 2) A 500 mL four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere to place (Al) 4.0093 g (1.689 mmol), and then NMP 156.7 g, and a base pyridine 3.20 g (40.42 mmol) were added. After that, it is stirred to dissolve. Next, this diamine solution was stirred, and U3DM-CBDE-C1 5.4798 g (16.85 mmol) was added, and the reaction was carried out for 4 hours under water cooling. The obtained polyamidate solution was poured into 825 g of water with stirring, and the deposited precipitate was collected by filtration, and then washed once with 825 g of water, washed once with 825 g of ethanol, and washed with 20 Og of ethanol. Three times, after drying, a white polyphthalate resin powder was obtained. The molecular weight of the polyglycolate was Μη=17330, Mw=39781. In a 100 ml Erlenmeyer flask, 7.1 430 g of the obtained polyphthalate resin powder was weighed, added to GBL 64.2906 g, and stirred at room temperature for 24 hours. This was dissolved to obtain a polyamine solution (PAE-8). (Synthesis Example 1 3) A 300 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, and p-phenylenediamine 2.0044 g (18.54 mmol) and 4,4'-diaminodiphenylmethane 1.6278 g were placed. ( 8.21 mmol), 48.15 g of NMP, 44.44 g of GBL 1 and 4.77 g (60.27 mmol) of pyridine as a base were further added, followed by stirring to dissolve. Next, the diamine solution was stirred, and 1,3DM-CBDE-C1 -93-201200561 8.1678 g (25.12 mmol) was added, and the mixture was reacted for 4 hours under water cooling. The obtained polyglycolate solution was poured into 835 g of 2-propanol with stirring. 'The precipitate was precipitated by filtration, and then washed 5 times with 413 g of 2-propanol. After drying, polylysine was obtained. Ester resin powder. The molecular weight of the polyglycolate was Μη = 13 107 and Mw = 29407. In a 1000 ml Erlenmeyer flask, 9.7076 g of the obtained polyphthalate resin powder was weighed and added to GBL 87.3683 g, and then stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE). -9 ). (Synthesis Example 1 4) A 300 mL four-necked flask equipped with a stirring device was set in a nitrogen atmosphere, and 4,4,-diaminodiphenylacetylene 2.003 (^(9.62111111〇1), 4,4'-two was placed. Aminodiphenylmethane 1.9063 g (9.62 mmol) was added to NMP 40.90 g of 'GBL 122.69 g, 3.43 g (43.79 mmol) as a base pyridine, and then stirred to dissolve. Next, the diamine solution was added while stirring. 1,3DM-CBDE-C1 5.93 60g (1 8.26mmol), reacted under water cooling for 4 hours. The obtained polyglycolate solution was added to 7〇6g of 2-propanol under stirring, and the precipitate was precipitated by filtration. Then, it was washed 5 times with 3 49 g of 2-propanol, and dried to obtain a polyphthalate resin powder having a molecular weight of Mn = 93 80 and Mw = 325 67. In 100 ml. In the Erlenmeyer flask, 8.23 8 5 g of the obtained polyphthalate resin powder was weighed, and after adding GBL 74.1 5 3 7 g, it was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-10). -94-201200561 (Synthesis Example 1 5) A 300 mL four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, and p-phenylenediamine 3.1 482 g (29.11 mmol) and (A-5) were placed. After adding 1.2270 g (3.23 mmol), NMP 59-66 g, GBL 178.98 g, and 5.77 g (72.94 mmol) of the base pyridine were added, and the mixture was stirred to dissolve. Next, the diamine solution was stirred, and 1,3DM-CBDE- was added. CL 9.8861 g (30.41 mmol), reacted for 4 hours under water cooling. After 4 hours, 1.5885 g (9.31 mmol) of 4-methoxybenzimid chloride was added, and the reaction was carried out for 30 minutes under water cooling. The ester solution was poured into 1,040 g of 2-propanol under stirring, and the precipitate was separated by filtration, and then washed with 515 g of 2-propanol for 5 times, and dried to obtain a polyphthalate resin powder. The molecular weight of the glutamate was Μη = 16781, Mw = 32537. In a 200 ml Erlenmeyer flask, 10 to 20 g of the obtained polyphthalate resin powder was weighed, and 91.80 g of GBL was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved. A polyamidate solution (PAE-11) was obtained. (Synthesis Example 16) In a 50 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 3,5-diaminobenzoic acid 6.087 § was taken. 40.01111111〇1), force into NMP 71.04g, and continue to send nitrogen to stir and dissolve. Next, 4,4'-diaminodiphenylamine 31.88§(16〇111111〇1), 〇8[124.3(^, which was continuously stirred and dissolved in nitrogen gas was added to dissolve it. This diamine solution was stirred. Add BDA 3 1.7 0g (160mmol), stir for 2 hours under water cooling. Next, add GBL 8 8.7 8g, stir for 10 minutes, then let the reaction solution continue to stir at -95-201200561, add pyromellitic acid The anhydride was 8.51 g (39.0 mmol), and further added with GBL to have a solid content concentration of 18% by mass, and stirred under water cooling for 24 hours. The obtained polyaminic acid solution had a viscosity of 2864 mPa·s at a temperature of 25 ° C. The molecular weight of the poly-proline is Mn=14435, Mw=30525. Further, a 3-glycidoxypropylmethyl group diluted to 0.3% by mass in a mixed solvent of N/GBL ratio of 2/8 is added to the solution. 77.81 g of a solution of diethoxy decane to obtain a polyamic acid solution (PAA-3). (Synthesis Example 7 7) In a 500 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 3,5-two were weighed. 3.0402 g (19.98 mmol) of aminobenzoic acid, 17.3 g of NMP was added, and it was stirred and continuously dissolved in nitrogen gas. Secondly, 4,4'-diaminodiphenyl was added. -N-methylamine 17.0801g (86_60mmol), GBL 86.87g, which was stirred and continuously dissolved in nitrogen gas. The diamine solution was added with BDA 17.1588g (80.10mmol) and stirred under water cooling for 2 hours. Next, after adding GBL 34.75g and stirring for 10 minutes, 'the reaction solution was further stirred, and 2.1 847 g (10.02 mmol) of pyromellitic dianhydride was added, and then the GBL was added to make the solid content concentration of 18% by mass. The mixture was stirred under water cooling for 24 hours. The obtained polyamic acid solution had a viscosity of 534 mPa·s at a temperature of 25 ° C. Further, the molecular weight of the polylysine was Mn = 9287 ' Mw = 1 8073. Into, a solution of 38% by mass of 3-glycidoxypropylmethyldiethoxydecane diluted to a mass ratio of 1/9 of NMP/GBL was added to obtain 4 g of a solution of polyglycine (PAA-4). -96- 201200561 (Synthesis Example 18) In a 500 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 3,5-diaminobenzoic acid 4.5648 § (30_〇111111〇1) was taken. Add NMP 15.8g' to continue to feed nitrogen to stir to dissolve. Secondly, add m-phenylenediamine 2.1625g (20_0mmol), GBL 11.90g, Continuously feeding nitrogen, stirring to dissolve. This diamine solution was stirred, and bda 2.9736 g (15.01 mmol) was added, and the mixture was stirred under water cooling for 2 hours. Next, after adding GBL 23.68g 'stirring for 10 minutes', the reaction solution was added with 7.6308 g (34.99 mmol) of pyromellitic dianhydride under continuous stirring, and then adding GBL to make the solid content concentration up to 18% by mass, under water cooling. Stir for 24 hours. The viscosity of the obtained polyaminic acid solution at a temperature of 25 ° C is 2084 mPa. s», the molecular weight of the poly-proline is Mn = 19201, Mw = 52329 ^ In this solution, NMP / GBL ratio is added 17.3 g of a 3-glycidoxypropylmethyldiethoxydecane solution diluted to a mass ratio of 2/8 to 0.3% by mass to obtain a polyamic acid solution (pAA_5) ^ (Synthetic Example 19)

To a 200 mL four-necked flask equipped with a stirring device and a nitrogen gas introduction tube, 8.2 l 76 g (54.01 mmol) of a female base formic acid of 3,5 -1 month, and 28.31 g of NMP were added, and the mixture was continuously stirred with nitrogen to be dissolved. Next, DA-7 8.7267 g (36.02 mmol) and NMP 56.62 g were added, and the mixture was continuously stirred and supplied with nitrogen to dissolve. This diamine solution was stirred while stirring, and bda 12.4025 g (62.60 mmol) was added and stirred under water cooling for 2 hours. Next, add -97-201200561 into GBL 28.30g, stir for 10 minutes, then let the reaction solution continue to stir, add 6.0594g (25.01mmol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride, Further, NMP was added to have a solid content concentration of 20% by mass, and the mixture was stirred under water cooling for 24 hours. The resulting polyamic acid solution had a viscosity of 372 mPa·s at a temperature of 25 °C. Further, the molecular weight of the poly-proline is Mn = 7517, Mw = 15376. Further, 0.1 062 g of 3-glycidoxypropylmethyldiethoxy decane is added to the solution, and the mixture is stirred at room temperature for 24 hours. , obtained a polyamine solution (PAA-6). (Synthesis Example 20) In a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 3,5-diaminobenzoic acid 3.6536 (24.011^111〇1) was weighed, and NMP 12.5 2 g was added thereto, and the mixture was continuously supplied. Stir in nitrogen to dissolve. Next, DA-7 3.8765 g (16.41 mmol) and GBL 25.02 g were added, and the mixture was continuously stirred and supplied with nitrogen to dissolve. This diamine solution was stirred, and BDA 5.5501 g ( 28.01 mmol) was added, and the mixture was stirred under water cooling for 2 hours. Next, after adding GBL 12.52g, stirring for 10 minutes, the reaction solution was further stirred, adding 2.5736 g (11. 8 mmol) of pyromellitic dianhydride, and adding GBL to make the solid content concentration up to 20% by mass, under water cooling. Stir for 24 hours. The obtained polyaminic acid solution had a viscosity of 1313 mPa·s at a temperature of 25 °C. Further, the molecular weight of the polyamic acid was Mn = 7841 and Mw = 15582. Further, in this solution, a solution of 15.65 g of 3-glycidoxypropylmethyldiethoxydecane-98-201200561 diluted to 0.3% by mass with a mixed solvent of NMP/GBL ratio of 2/8 was obtained. Polylysine solution (PAA-7). (Synthesis Example 2 1 ) In a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 3,5-diaminobenzoic acid 2.44358 (16.06111111〇1) was weighed, and 1,3-dimethyl-2 was added thereto. - tetrahydroimidazolone 25.2 Og, which was stirred and continuously dissolved in nitrogen. Next, 4,4'-diaminodiphenylamine 4_7794 g (23.99 mmol) and GB L 4 2.0 g were added, and the mixture was continuously stirred and supplied with nitrogen to be dissolved. The diamine solution was stirred, and 1,2,3,4-cyclobutanetetracarboxylic dianhydride 7_6070 g (38-79 mm, ol) was added, and then GBL was added to make the solid content concentration 15% by mass, and the mixture was stirred under water cooling. hour. The resulting polyamic acid solution had a viscosity of 1 3 80 mPa·s at a temperature of 25 ° C. Further, the molecular weight of the polyamic acid was Μη = 13275 and Mw = 28956. Further, 445 g of 3-glycidoxypropylmethyldiethoxydecane ruthenium was added to obtain a polyamidonic acid solution (PAA-8). (Example 25) A stirrer was placed in a 100 ml Erlenmeyer flask, and 7.2022 g of the polyamidate solution (PAE-3) obtained in Synthesis Example 7 and a polyamidic acid solution (PAA-6) obtained in Synthesis Example 19 were weighed. 5.520 1 g, force into NMP 2.9310g, GBL 29.3 534g, and BCA 5.0297g, add Fmoc-His 0"859g of ruthenium promoter, stir using a magnetic stirrer for 30 minutes to obtain liquid crystal alignment agent (V) -1 ) ^ (solid content concentration: 3.6 wt%, NMP / GBL ratio: 1 5 / 8 5 ) -99 - 201200561 (Comparative Example 19) A stirrer was placed in a 100 ml Erlenmeyer flask, and the synthesis example 7 was weighed. The obtained polyamidate solution (PAE-3) 7.2075 g, the polyaminic acid solution (PAA-6) obtained in Synthesis Example 95, 5.5385 g, and NMP 13.7383 g, GBL 1 8.5640 g, and BCA 4.9927 g were added. Fmoc-His 0.1 85 8 g of a ruthenium iodide promoter was added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (Va). (solid content concentration: 3.6 wt%, NMP / GBL ratio: 40/60) (Example 26) A stirrer was placed in a 100 ml Erlenmeyer flask, and the polyamine solution obtained in Synthesis Example 9 was weighed (PAE-5). 5.5452g, polyamine acid solution (PAA.5) obtained in Synthesis Example 18, 6.7566g, added NMP 1.0141g, GBL 3 1.65 99g, and BCA 4.9937g, and added Fmoc-His 0.1460 of ruthenium promoter g, stirring using a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (V-2). (solid content concentration: 3.6 wt%, NMP/GBL ratio: 5/95) Example of application ✓ fv A stirrer was placed in a 100 ml Erlenmeyer flask, and the polyamine solution obtained in Synthesis Example 8 was weighed (PAE-4). 7.2138g, polypyridic acid solution (PAA-4) obtained in Synthesis Example 17. 6.632 1 g, adding NMP 1.0482g, GBL 30.1 339g, and BCA 5.0290g, and adding hydrazine imidization accelerator -100- 201200561

Fmoc-His 0.1811 g was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (V-3). (solid content concentration: 3.6 wt%, NMP/GBL ratio: 5/95) (Example 2 8) A stirrer was placed in a 10 ml Erlenmeyer flask, and the polyphthalate solution (PAE) obtained in Synthesis Example 12 was weighed. -8) 7.2162g, polyamic acid solution (PAA-7) obtained in Synthesis Example 20. 6.087 1 g, NMP 5.463 1 g, GBL 26.2444 g, and BCA 5.0040 g, and Fmoc added with ruthenium promoter -His 0.151 0g, stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (V-4) » (solid content concentration: 3.6 wt%, NMP/GBL ratio: 15/95) (Example 29) in a 100 ml Erlenmeyer flask The stirrer was placed, and the polyphthalate solution (PAE-1) obtained in Synthesis Example 3 was weighed 4.43 08 g, and the polyaminic acid solution (PAA-7) obtained in Synthesis Example 20 was 4.8 860 g, and NMP 7.8416 g, GBL was added. 18_8822g, and BCA 4.0082g, Fmoc-His 0.1 3 47g of a ruthenium iodide promoter was further added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (V-5). (solid content concentration: 3.6 wt%, NMP/GBL ratio: 2 0 / 8 0 ) (Example 30) A stirrer was placed in a 100 ml Erlenmeyer flask, and the mixture of -101 - 201200561 obtained in Synthesis Example 1 {) was weighed. Amino acid ester solution (PAE-6) 7.2170 g, Polyamide acid solution (PAA-4) obtained in Synthesis Example 17 6.6319 g, NMP 1.0542 g, GBL 30.1 1 56 g, and BCA 5.0141 g were added, and ruthenium was added. Fmoc-His 0.1 896 g of a chemical accelerator was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (V-6). (solid content concentration: 3.6 wt%, NMP / GBL ratio: 5/95) (Example 3 1 ) A stirrer was placed in a 100 ml Erlenmeyer flask, and the polyamine solution obtained in Synthesis Example 13 was weighed (PAE- 9) 7.2141g, polyamine acid solution (PAA-5) obtained in Synthesis Example 18, 6.7968g, adding NMP 1.0209g, GBL 3 0.1 03 0g, and BCA 5.0183g, and adding Fmoc- of the ruthenium promoter His 0.1 63 6 g was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (V-7). (solid content concentration: 3.6 wt%, NMP/GBI^t: Μ 5/95) A stirrer was placed in a 100 ml Erlenmeyer flask, and the polyamine solution obtained in Synthesis Example 8 was weighed (PAE-4). 13.30g, 12.26g of polylysine solution (PAA-3) obtained in Synthesis Example 16 was added to NMP 2.52g, GBL 62.49g, and BCA 10.05g, and then added with ruthenium promoter. Fmoc- His 0.3 4 6 g was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (V-8). (solid content concentration: 3.3 wt%, NMP/GBL ratio: 5/95) -102-201200561 (Example 3 3) A stirrer was placed in a 100 ml Erlenmeyer flask, and the polyamidate obtained in Synthesis Example 14 was weighed. Solution (PAE-1 0 ) 7.2022 g, polylysine solution (PAA-5) obtained in Synthesis Example 18. 6.78 99 g, NMP l_0185 g, GBL 30.1015 g, and BCA 5.0143 g were added, followed by addition of a ruthenium promoter. Fmoc-His 0.1622g was stirred using a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (V-9). (solid content concentration: 3.6 wt% 'NMP/GBL ratio: 5/95) (Example 3 4) A stirrer was placed in a 100 ml Erlenmeyer flask, and the polyamidate solution obtained in Synthesis Example 7 was weighed (PAE- 3) 1.9916g, polyglycine solution (PAA-7) obtained in Synthesis Example 16: 1.6669g, adding NMP 1.2121g, GBL 2_0042g ' and BCS 1.6075g, and adding Fmoc-His 0.0698g of ruthenium promoter The mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (VI-1). (solid content concentration: 6_0 wt%, NMP/GBL ratio: 2 5 / 7 5 ) (Example 3 5 ) A stirrer was placed in a 100 ml Erlenmeyer flask, and the polyamidate solution obtained in Synthesis Example η was weighed (ΡΑΕ -7 ) 1.93 93 g, the polylysine solution (PAA-3 ) obtained in Synthesis Example 1 was 1.7745 g, and NMP 0_2977g, GBL 2.4057g, and BCS 1.6293g were added, and Fmoc- of the ruthenium promoter was added. His 0.0819 g was stirred using a magnetic stirrer for 30 minutes to obtain a liquid crystal-103-201200561 alignment agent (VI-2). (solid content concentration: 6.0 wt%, NMP/GBL ratio: 10/90) (Example 3 6) A stirrer was placed in a 100 ml Erlenmeyer flask, and the polyamine solution obtained in Synthesis Example 8 was weighed (PAE- 4) 1.9957g, lysine solution (PAA-3) obtained in Synthesis Example 16 1.7908g, adding NMP 0.3158g, GBL 2.4442g, and BCS 1.6242g, and adding Fmoc-His 0.0653 of ruthenium promoter g, stirring using a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (VI-3). (solid content concentration: 6-% by weight, NMP/GBL ratio: 5/95) (Example 3 7) A stirrer was placed in a 100 ml Erlenmeyer flask, and the polyphthalate solution (PAE-8) obtained in Synthesis Example 12 was weighed. 1.95 20g, polyacetamide solution (PAA-6) 1.4775g obtained in Synthesis Example 19, adding NMP 0.5335g, GBL 2.4708g, and BCS 1.6135g, and adding Fmoc-His 0.05 70g of ruthenium promoter The mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (VI-4). (solid content concentration: 6_0 wt%, NMP/GBL &amp; Example: 2 5 / 7 5 ) (Example 3 8 ) A stirrer was placed in a 100 ml Erlenmeyer flask, and the polyamidate solution obtained in Synthesis Example 13 was weighed ( PAE-9) 1.9500 g, poly-104-201200561 proline acid solution (PAA-8) obtained in Synthesis Example 21, 1.9556 g, and 1,3-dimethyl-2-tetrahydroimidazolidone (hereinafter referred to as DMI) was added. 0.0996 g, GBL 2.4600 g, and BCS 1.6048 g, followed by addition of Fmoc-His 0.0617 g of a ruthenium iodide promoter, and stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (VI-5). (solid content concentration: 6.0 wt%, DMI/GBL ratio: 10/90) (Example 3 9) A stirrer was placed in a 100 ml Erlenmeyer flask, and the polyamidate solution obtained in Synthesis Example 15 was weighed (PAE- 11) 3.6113g, 2.7746g of polyaminic acid solution (PAA-6) obtained in Synthesis Example 19, adding NMP 0.5025g, GBL 5.96 8 g, and BCS 2.9958g, and adding Fmoc-His of ruthenium promoter 0.1 223 g, stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (VI-6). (solid content concentration: 6.0 wt%, NMP/GBI^t Example: 20/80) (Comparative Example 20)

A stirrer was placed in a 10 ml Erlenmeyer flask, and 1.9418 g of the polyamidomate solution (PAE-3) obtained in Synthesis Example 7 and a polyamidic acid solution (PAA-7) 1.6452 g obtained in Synthesis Example 20 were weighed. NMP 2.1092g, GBL 0.7577g, and BCS 1.6097g were added to the mixture, and then 0.0725 g of Fmoc-His of hydrazine imidization accelerator was added, and stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (VI-a). (solid content concentration: 6.0 wt%, NMP/GBL ratio: 4 0 / 60) -105 - 201200561 (Comparative Example 2 1 ) A stirrer was placed in a 100 ml Erlenmeyer flask, and the polycondensate obtained in Synthesis Example 13 was weighed. Amino acid ester solution (PAE-9) 1.9606 g, polylysine solution (PAA-8) obtained in Synthesis Example 21 1.9393 g' Add DMI 1.8650 g, GBL 0.6754 g, and BCS 1.6059 g, and add ruthenium iodide The promoter Fmoc-His 0.06 18g was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (VI-b). (solid content concentration: 6.0 wt%, DMI / GBL ratio: 40/60) (Example 40) After filtering the liquid crystal alignment agent (V-1) obtained in Example 25 as a filter of Ι.Ομηη, The liquid crystal alignment agent was applied by inkjet coating onto a glass substrate with a transparent electrode. The obtained coating film was dried on a hot plate at a temperature of 80 ° C for 5 minutes, and baked in a hot air circulating oven at a temperature of 230 ° C for 20 minutes to form a coating film having a film thickness of 130 nm. The surface of the film of the coating film was observed using an atomic force microscope (AFM), and the average thickness (Ra) of the center line of the film surface was measured to evaluate the flatness of the film surface. The results are shown in Table 4 below (Examples 41 to 45 and Comparative Example 22) except that each of the liquid crystal alignment agents obtained in the above Examples 27 to 31 and Comparative Example 19 was used, and the same was carried out in the same manner as in Example 40. The method forms individual coating films. The film surface of each coating film was observed using AFM. Further, the average thickness (Ra ) of the center line of each coating film was measured. The measurement results are shown in Table -106 - 201200561 4 which will be described later. [Table 4] Liquid crystal alignment agent aggregation (mass ratio) NMP/GBL compensation ratio) Center line average roughness [nm] Example 40 V-1 PAE-3(40)/PAA-6(60) 5/95 1.27 Example 41 V-3 PAE-4(40)/PAA-4(60) 5/95 1.30 Example 42 V-4 PAE-8(40)/PAA-7(60) 15/85 0. 23 Implementation Example 43 V-5 PAE-1 (40) / PAA-7 (60) 20/80 0. 53 Example 44 V-6 PAE-6 (40) / PAA-4 (6 〇) 5 / 95 0, 39 Example 45 V-7 PAE-9(40)/PM-5(60) 5/95 0·57 Comparative Example 22 V-a PAE-3(40)/PAA-6(60) 40/60 7.62 (implementation Example 46) After the liquid crystal alignment agent (VI-1) obtained in Example 34 was filtered through a filter of Ι. Ομηη, the liquid crystal alignment agent was applied by letterpress printing onto a glass substrate with a ΙΤΟ transparent electrode. The obtained coating film was dried on a hot plate at a temperature of 80 ° C for 5 minutes, and baked in a hot air circulating oven at a temperature of 230 ° C for 20 minutes to form a coating film having a film thickness of 13 〇 nm. The surface of the film of the coating film was observed using an atomic force microscope (AFM), and the average thickness (Ra) of the center line of the film surface was measured to evaluate the flatness of the film surface. The results are shown in Table 5 below. (Examples 46 to 49 and Comparative Example 23) Each of the coating films was formed in the same manner as in Example 46 except that each of the liquid crystal alignment agents obtained in the above Examples 35 to 37 and Comparative Example 20 was used. The film surface of each coating film was observed using AFM. Further, the average thickness (Ra ) of the center line of each coating film was measured. The measurement results are shown in Table 5 below. -107- 201200561 [Table 5] Liquid crystal alignment agent polymer (mass ratio) NMP/GBL ratio fi ratio) Center line average roughness [nm] Example 46 VI-1 PAE-3(40)/PAA-7 (60 25/75 0.75 Example 47 VI -2 PAE-7 (40) / PAA-3 (60) 10 / 90 0.91 Example 48 VI -3 PAE-4 (40) / PAA-3 (60) 5 / 95 0. 57 Example 49 VI -4 PAE-8(40)/PAA-6(60) 25/75 0. 72 Comparative Example 23 VI -a PAE-3(40)/PAA-7(60) 40/60 3. 10 (Example 50 and Comparative Example 24) Each of the coating films was formed in the same manner as in Example 46 except that each of the liquid crystal alignment agents obtained in the above Example 38 and Comparative Example 2 was used. The film surface of each coating film was observed using AFM. Further, the average thickness (Ra ) of the center line of each coating film was measured. The measurement results of these are as shown in Table 6 below. [Table 6] Liquid crystal alignment agent polymer (mass ratio) NMP/GBL ratio (mass ratio) Center line average roughness [nm] Example 50 VI -5 PAE-9(40)/PAA-8(60) 10/ 90 1· 16 Comparative Example 24 VI—b PAE-9(40)/PAA-8(60) 40/60 3.10 [Industrial Applicability] The liquid crystal alignment agent of the present invention can reduce the obtained liquid crystal alignment film. The fine concavities and convexities on the surface are reduced, and the interfacial properties caused by the AC drive are reduced to improve the interface characteristics between the liquid crystal and the liquid crystal alignment film, and the electrical characteristics such as the voltage holding ratio, the ion density, and the residual voltage of the DC voltage can be improved. As a result, the present invention can be widely applied to TN elements, STN elements, TFT liquid crystal elements, and even vertical alignment type liquid crystal display elements. -108-

Claims (1)

201200561 VII. Patent application scope: 1. A liquid crystal alignment agent characterized by 'liquid crystal alignment agent containing the following (A) component, (B) component, and (C) component' (A) component: due to all four The dicarboxylic acid dialkyl ester derivative contains 6 mol% or more of a tetracarboxylic acid dialkyl ester derivative of a tetracarboxylic acid dialkyl ester derivative represented by the following formula (1), and contains a formula (2) a polyglycolate obtained from a diamine of at least one diamine selected from the group consisting of the diamines represented by the group (5); [Chemical Formula 1] 〇〇^r/-〇Rl r2 (1) RtO (In the formula (1), R1 is an alkyl group having 1 to 5 carbon atoms, and R2 is a hydroxyl group or a chlorine atom) [Chemical 2] [Chemical 3] 201200561 (In the formulas (2) to (5), A is a single bond, an ester bond, a guanamine bond, a thioester bond, or a two-valent organic group having a carbon number of 2 to 1 '. Atom, a hydroxyl group, an amine group, a thiol group, a nitro group, a phosphoric acid group or an organic group having a carbon number of 1 to 20, a is an integer of 1 to 4 'a is 2 or more'. The structure of A2 can be (B) component: polyamic acid obtained from tetracarboxylic dianhydride and diamine; (c) component: containing at least selected from the group consisting of r-butyrolactone and its derivatives One type of organic solvent (C1)' and at least selected from the group consisting of N-methyl-2-pyrrolidone, 1,3-dimethyl-2-tetrahydroimidazolidone, and derivatives thereof The organic solvent (C2) and the organic solvent (C2) are a mixed solvent of 2% by mass to 30% by mass based on the total amount of the organic solvent (C1) and the organic solvent (C2). 2. The liquid crystal alignment agent of claim 1, wherein the ratio of the component (A) to the component (B) is 1/9 to 9/1 by mass ratio (A/B), (C) The content of the component is 70% by mass or more based on the total amount of the component (A), the component (B), and the component (C). 3. The liquid crystal alignment agent according to claim 1 or 2, wherein the component (A) is represented by the above formula (2) to formula (5) containing 40 to 100 mol% relative to the total diamine. A polyphthalate obtained from a diamine of at least one diamine selected from the group consisting of diamines. 4. The liquid crystal alignment agent according to any one of claims 1 to 3, wherein '(A) component is a diamine represented by the formula (2) and a diamine represented by the formula (3) At least one of the diamines selected in the group and at least one selected from the group consisting of the diamine represented by the formula (4) and the diamine represented by the formula (5) -110-201200561 The amine diamine, the polyamine obtained from the obtained diamine. The liquid crystal alignment agent of any one of Claims 1 to 4, wherein the '(A) component is a diamine represented by the formula (2), and the second is represented by the formula (4) A polyglycolate obtained from a diamine of at least one diamine selected from a group of amines. 6. The liquid crystal alignment agent according to any one of claims 1 to 5, wherein the person 2 of the above formula (4) is a structure represented by the following formula (6), [Chem. 4] - A3-R3 (6) (A3 in the formula (6) is a single bond, -〇-, -s-, -NR-3-, an ester bond, a guanamine bond, a thioester bond, a urea bond, a carbonate bond, Or a urethane linkage; R3 is selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkenyl 'alkynyl group, an aryl group, and a combination thereof, which may have a substituent, and the groups may have a substituent; Τ 3 is selected from a hydrogen atom, or an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and a combination thereof, and the groups may have a substituent) 〇7. The liquid crystal alignment agent according to any one of the items 6, wherein the (Α) component is at least one selected from the group consisting of diamines of the following formula (Α-1) to (Α-5); Polyamine obtained from diamine, -111 - 201200561 [Chemical 5] 8. The liquid crystal alignment agent of claim 7, wherein the component (A) is a diamine containing the above formula (2) and is contained by the above formula (A-1) to (A-5) The polyamine obtained from the diamine selected from the group, and the polyamine obtained from the obtained diamine. 9. The liquid crystal alignment agent according to any one of claims 1 to 8, wherein the component (B) is a tetrahydro acid dianhydride containing the following formula (B-1) to (B-9); Polylysine obtained by grouping at least one selected tetracarboxylic dianhydride, -112- 201200561 [Chem. 6] (B-2) Ο Ο The liquid crystal alignment agent of any one of Claims 1 to 9, wherein the (Β) component is 20 mol% or more of the above formula with respect to the total tetracarboxylic dianhydride (Β- 1) a tetracarboxylic dianhydride of at least one selected tetracarboxylic dianhydride of the formula (Β-9), and a polyamic acid obtained from the diamine. The liquid crystal alignment agent of any one of Claims 1 to 10, wherein the (Β) component is selected and contains a formula selected from the following formula (Β-10)~式(Β-13) Polylysine obtained from at least one diamine, -113- 201200561 [Chemical 7] H2N (B-10) co2h Η2νύ, nh2 (B-12) 1 2 . The liquid crystal alignment agent of claim 11, wherein the component (B) is used in an amount of 20 mol% or more relative to the total diamine, and the above formula (B-10) to (B-13) The poly-proline acid obtained by the diamine of at least one of the selected diamines. The liquid crystal alignment agent of any one of the above-mentioned claims 1 to 12, wherein the organic solvent of the component (C) C1) is r-butyrolactone, and the organic solvent (C2) is N-methyl-2-pyrrolidone. 14. The liquid crystal alignment agent of any one of claims 1 to 13 wherein the component (C) is a mixed solvent of r-butyrolactone and N-methyl-2-pyrrolidone, (C) The content of the component is 8% by mass or more based on the total amount of the component (A) and the component (B) and the component (C). A liquid crystal alignment film obtained by coating and baking a liquid crystal alignment agent according to any one of claims 1 to 4, wherein the liquid crystal alignment film is characterized by a liquid crystal alignment film. The liquid crystal alignment agent according to any one of the first to fourth aspects of the invention is applied, baked, and irradiated with polarized ultraviolet rays. -114- 201200561 IV. Designated representative map: (1) The representative representative of the case is: None (2) The symbol of the symbol of the representative figure is simple: 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