TW201209078A - Liquid crystal aligning agent containing thermally cleavable group-containing compound, and liquid crystal alignment film - Google Patents

Abstract

Disclosed is a liquid crystal aligning agent which is capable of providing a liquid crystal alignment film that has high mechanical strength and thus exhibits excellent resistance to rubbing. The liquid crystal alignment film is highly reliable and has excellent liquid crystal aligning properties and excellent electrical characteristics such as voltage holding ratio at high temperatures and ion density, while giving a large pretilt angle. Specifically disclosed is a liquid crystal aligning agent which is characterized by containing: a polyimide precursor that is obtained by causing a diamine compound and a tetracarboxylic acid derivative to react with each other and/or a polyimide that is obtained by imidizing the polyimide precursor; and a compound that contains an amino group protected by a thermally cleavable group, which is substituted by hydrogen when heated at 80-300 DEG C, and has an amic acid or amic acid ester structure.

Description

201209078 VI. Description of the Invention: [Technical Field] The present invention relates to a voltage holding ratio or an ion density which is excellent in mechanical strength, excellent in honing treatment, and liquid crystal alignment, particularly at a high temperature. A liquid crystal alignment agent which is excellent in the electrical characteristics and which can provide a liquid crystal alignment film having a high pretilt angle, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element. [Prior Art] A liquid crystal display element used in a liquid crystal television, a liquid crystal display or the like is usually provided with a liquid crystal alignment film for controlling a liquid crystal alignment state in the element. In the liquid crystal alignment film, a liquid crystal alignment agent containing a solution of a polyamidene precursor such as polyamic acid or a solution of a soluble polyimine is mainly applied to a glass substrate or the like. A polyimine-based liquid crystal alignment film. With the high definition of the liquid crystal display element, and the suppression of the contrast of the liquid crystal display element or the reduction of the image sticking phenomenon, in the liquid crystal alignment film, in addition to the excellent liquid crystal alignment and the stable pretilt performance, the high voltage is maintained. The rate, the suppression of the residual image due to the AC drive, the small amount of residual charge when a DC voltage is applied, and/or the early relaxation of the residual charge accumulated by the DC voltage are also becoming more important. In the polyimine-based liquid crystal alignment agent, various proposals have been made in order to meet the above requirements. For example, in addition to a polylysine containing a polyaminic acid or a quinone imine group, a liquid crystal alignment agent having a specific structure of a tertiary amine (refer to -5-201209078 Patent Document η, containing a material used in a raw material A liquid crystal alignment agent of a soluble polyimine which is formed by a specific diamine compound such as a pyridine skeleton (refer to Patent Document 2), etc. Further, in addition to polyglycine or a ruthenium iodide polymer thereof, ruthenium A liquid crystal alignment agent containing a compound having a very small amount of a compound containing one carboxylic acid group in the molecule, a compound containing one carboxylic acid anhydride group in the molecule, and a compound containing one tertiary amino group in the molecule (refer to the patent literature) 3) A liquid crystal alignment agent comprising a polyamic acid obtained by a specific configuration of a tetracarboxylic dianhydride, a tetracarboxylic dianhydride having a cyclobutane and a specific diamine compound or a ruthenium imidized polymer thereof. (Refer to Patent Document 4). Further, together with polyglycine or polyimine, a monomer having a specific structure containing a quinone imine group or a monomer having a methionine moiety is proposed. A liquid crystal alignment agent (refer to Patent Document 5) Liquid crystal alignment of at least one polymer selected from a ruthenium imidized polymer of poly-proline and polyphthalic acid, and at least one compound selected from a proline compound and a quinone compound [Patent Document 6] [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei 9-316200 (Patent Document 2) Japanese Laid-Open Patent Publication No. Hei 9-138414 (Patent Document 5) Japanese Patent Publication No. Hei 9-138414 (Patent Document 5) Japanese Patent Publication No. Hei 9- 1 1 0 0 6 No. 201209078 [Patent Document 6] JP-A-9-269491 No. [Invention] [Problems to be Solved by the Invention] However, in recent years, with the high-definition liquid crystal television with a larger picture as the main body, and the demand for liquid crystal display elements has become more and more severe, The liquid crystal display element has a close relationship with the liquid crystal alignment film, which requires more excellent high-reliability characteristics, and requires such a higher characteristic, not only the initial characteristics are good, but also requires long-time exposure even at high temperatures. High reliability after maintaining good characteristics The present invention provides a liquid crystal alignment film obtained by which the mechanical strength is large, the resistance to honing treatment is excellent, and the liquid crystal alignment property, particularly the electric property such as the voltage holding ratio or the ion density at a high temperature, is expressed. In order to achieve the above object, the present inventors have found that a liquid crystal alignment agent for a liquid crystal alignment film having a high pretilt angle can be formed. A polyimine precursor obtained by reacting a diamine compound as a liquid crystal alignment agent component with a tetracarboxylic acid derivative, and/or a polyimide which is ruthenium imidized by the polyimide precursor, 尙By containing a compound having an amine group which can be protected by a heat dissociable group which can be substituted by heating by heating, and having a lysine or glutamate structure (hereinafter referred to as a pyrolytic group) The liquid crystal alignment agent formed by the compound) can achieve the object described in 201209078. a compound having a lysine or glutamate structure (hereinafter referred to as a thermal dissociation) added to the liquid crystal alignment agent and having an amine group protected by a heat dissociable group which can be substituted by heating with hydrogen The compound of the nature) is a novel compound not described in the literature before the application of the present application, but when the compound containing the pyrolytic group is added to the liquid crystal alignment agent, it is found that the mechanical strength of the film can be formed. It is excellent in resistance to honing treatment, and is excellent in liquid crystal alignment, particularly in electrical properties such as voltage holding ratio and ion density at high temperatures, and can provide a liquid crystal alignment film with high pretilt angle reliability. . That is, the present invention has been made in view of the gist of the following. A liquid crystal alignment agent comprising: a polyimide precursor obtained by reacting a diamine compound with a tetracarboxylic acid derivative; and/or a polyamidization of the polyimide precursor A compound composed of a ruthenium imine or a guanamine having an amine group which is substituted with a heat dissociable group which is substituted by hydrogen at a temperature of 80 to 300 ° C. 2. The liquid crystal alignment agent according to the above 1, wherein the polyimine precursor has a repeating unit represented by the following formula (7). [Chemical 1]

(wherein 乂1 is a tetravalent organic group, ¥ is a divalent organic group; R6 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 八1 and A2 are each independently a hydrogen atom or may have a substituent An alkyl group, an alkenyl group or an alkynyl group having 1 to 10 carbon atoms. -8-201209078 3. The liquid crystal alignment agent according to the above 1 or 2, wherein the content of the polyimine precursor and the polyimine is based on the total amount of the ruthenium in the liquid crystal alignment agent 5 to 15% by mass 'and a repeating unit of 1 unit of a polyimine precursor having a repeating unit represented by the above formula (7) and a ruthenium imidized polymer of the polyimide precursor In other words, the compound having a guanamine or guanamine structure which is substituted with an amine group protected by a heat dissociable group of hydrogen is contained in an amount of 0.5 to 50 mol%. 4. The liquid crystal alignment agent according to any one of the above 1 to 3, wherein the compound having the valeric acid or guanamine structure is a compound represented by the following formula (1). [Chemical 2]

(wherein X is a tetravalent organic group; 1 is a hydrogen atom or a fluorenyl group having 1 to 5 carbon atoms; and Z is a structure not represented by the following formula (2).) [Chemical 3] D "N-+- Z Guang (2)

Rs (wherein Z1 is a single bond or a divalent organic group having 1 to 30 carbon atoms. The caliper 2 and the alkyl group, the alkenyl group, and the alkyne which are each independently a hydrogen atom or may have a substituent having 1 to 3 carbon atoms The group, the aryl group or the combination of these may also form a ring structure. ^ is a hydrogen atom or an alkyl group having a carbon number of 1 to 30 which may have a substituent ^ _ u 1 玛热-9- 201209078 dissociable group). 5. The liquid crystal alignment agent according to any one of the above 1 to 4, wherein the aforementioned thermally dissociable group is tert. butoxymethyl or 9-fluorenylmethoxy anthracene 6. As described above, 1 to 5 The liquid crystal alignment agent 'where' is any one selected from the group consisting of the structures shown by the following formulas.

m XX public: ca zg: order

A liquid crystal alignment film obtained by subjecting a film obtained by baking the liquid crystal alignment agent according to any one of the above 1 to 6 to a film. The liquid crystal alignment film according to the above 7, wherein the alignment treatment is a honing treatment or an irradiation treatment of a polarized radiation. A liquid crystal display element comprising the liquid crystal alignment film according to the above 7 or 8. A compound having a compound having a guanamine or a guanamine ester represented by the following formula (1). -10- 201209078

(wherein X is a tetravalent organic group; Ri is a hydrogen atom or a C 1 alkyl group; and Z is a structure represented by the following formula (2).) [Chem. 6] D "N-ring-Zf (2) R3 (wherein, Ζ! is a single bond or a divalent organic group having 1 to 30 carbon atoms. R2 is each independently a hydrogen atom or may have a substituent having a carbon number of 1 to 30 2 , a pseudo group, an alkynyl group, and an aromatic group. The group or the combination of the above may also form an alkyl dissociable group having a ring structure far from a hydrogen atom or a substituent having 1 to 30 carbon atoms. 11. The compound according to the above 1 〇 is as follows The bischlorocarbonyl compound shown in the above formula is obtained by reacting a compound represented by the following formula (4) with 1/2 to 1/3 of a (chlorocarbonyl compound/monoamine) in the presence of a base. [Chem. 7] 5 and: alkyl! 〇R4 is hot (3 aminated A ear ratio

(wherein, X ' Z, R 2 ; R 3 ; R 4 and D are the same as those of the above formulas (1) (4) and (2); and R 5 is an alkyl group having 1 to 5 carbon atoms). -11 - 201209078. The compound according to the above 10, wherein the tetracarboxylic acid derivative represented by the following formula (5) and the monoamine compound represented by the above formula (4) are present in the presence of a condensing agent The lower one is obtained by reacting a molar ratio of (H-acid derivative/monoamine) to 1/2 to 1/3. [化8]

(wherein X and R5 are the same as defined in the above formulae (1) and (3).). 13. The compound according to the above 10, which is a tetracarboxylic dianhydride represented by the following formula (6) and a monoamine compound represented by the above formula (4) (tetracarboxylic dianhydride/single) The molar ratio of amine to 1/2~1/3 reaction

(In the formula, the X system is synonymous with the above formula (1)). 14. The compound according to the above item 1, wherein the tetracarboxylic acid dihydrate represented by the above formula (6) and the monoamine compound represented by the above formula (4) are (tetracarboxylic dianhydride) /Monamine) The molar ratio of 1/2 to 1/3 is obtained by esterification of a carboxyl group with an esterifying agent. The compound according to any one of the above-mentioned formulas, wherein the -12-201209078 is selected from the group consisting of the structures shown by the following formulas.

16. The compound according to any one of the above 10 to 15, wherein the above L is an alkyl group having 1 to 5 carbon atoms. [Effects of the Invention] According to the present invention, it is possible to provide a liquid crystal alignment film obtained with high mechanical strength, excellent resistance to honing treatment, and a liquid crystal alignment property, particularly a voltage holding ratio or an ion density at a high temperature. The liquid crystal alignment agent having excellent electrical properties and forming a liquid crystal alignment film which imparts high reliability to a high pretilt angle can be formed. The liquid crystal alignment agent of the present invention can form a liquid crystal alignment film having the above-described excellent characteristics, and is excellent in long-term storage stability when stored before use of a liquid crystal alignment agent. Further, the present invention also provides a novel compound which is a compound having an amine group protected by a thermally dissociable group and having a lysine or guaninate structure contained in the liquid crystal alignment agent of the present invention. -13-201209078 The liquid crystal alignment agent of the present invention has excellent characteristics as described above, and the mechanism thereof is still unknown, but it can be almost inferred as follows. The thermally dissociable group-containing compound contained in the liquid crystal alignment agent of the present invention is coated with a liquid crystal alignment agent on a surface of a substrate and fired to form a liquid crystal alignment film, and is thermally decomposed at a temperature during the baking process. The base will decompose and produce a highly reactive grade 1 or 2 amine. The resulting grade 1 or 2 amine system promotes the ruthenium imidization reaction of the main component of the polyimine precursor and/or the polymer of the polyimine contained in the liquid crystal alignment agent, and brings high At the same time as the imidization ratio, a crosslinking reaction occurs between the polymers, and the liquid crystal alignment film obtained by the liquid crystal alignment agent is imparted with a large mechanical strength. The increase in mechanical strength leads to an increase in honing resistance and stability of liquid crystal properties at high temperatures. Further, the thermally dissociable group-containing compound has a skeleton structure which is similar to the polymer of the polyimine precursor and/or the polyimide of the main component contained in the liquid crystal alignment agent. Or a glutamate structure, when it is added to a liquid crystal alignment agent, it will obstruct the liquid crystal alignment, but it will bring about the improvement of the liquid crystal alignment, and the voltage retention rate, ion density, and The liquid crystal characteristics such as the pretilt angle are improved. Further, the pyrolyzable group-containing compound does not decompose the thermally dissociable group of the compound before the high temperature is applied, and therefore does not adversely affect the storage stability of the liquid crystal alignment agent containing the compound. According to the present invention, it is possible to provide a liquid crystal alignment agent which is excellent in mechanical strength, excellent in resistance to honing treatment, and voltage holding ratio or ion density in liquid crystal alignment/particularly high temperature. -14- 201209078 and other electrical properties are excellent in performance, and a liquid crystal alignment film capable of imparting high pretilt angle reliability can be formed. [Embodiment] [Form of the invention] <Heat-dissociable group-containing compound> In the present invention, the pyrolyzable group-containing compound added to the liquid crystal alignment agent has a thermally dissociable group a protected amine group having a lysine or guanamine structure, the compound having a temperature of from 80 to 300 t: preferably from 1 to 25 (TC, particularly preferably from 150 to 230) C, the thermally dissociable group is decomposed and replaced by a hydrogen atom. Therefore, when the liquid crystal alignment agent is applied to the substrate of the liquid crystal display element and fired, it is at a normal temperature of 150 to 300 ° C, The thermally dissociable group is dissociated and replaced by hydrogen. In the present invention, the thermally dissociable group-containing compound to be used is preferably represented by the following general formula (1).

In the formula, X is a tetravalent organic group; Ri is a hydrogen atom or a carbon number of 1 to 5, and Z is a structure represented by the following formula (2). R2彳4 —z1-6-N-D1 (2) r3 wherein, a single bond or a divalent organic group having a carbon number of 1 to 30; r2 and -15-201209078 R3 are each independently a hydrogen atom. Or an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a combination thereof having a carbon number of 1 to 30 which may have a substituent, and may also form a ring structure: R 4 is a hydrogen atom or may have a substituent having a carbon number of 1 to 30. An alkyl group; Di is a protecting group substituted with an amine group of a hydrogen atom by heating. In the above formula (1), 1 is a hydrogen atom or a C 1 to 5 alkyl group. When R! is a large structure, when it is used as a liquid crystal alignment film, R may be preferably a hydrogen atom, a methyl group or an ethyl group, or a hydrogen atom or a methyl group because it may hinder the alignment of the liquid crystal. In the above formula (1), X is a tetravalent organic group, and the structure thereof is not particularly limited. Specific examples of X include X-1 to X-46 as shown below. Where 'more Χ·1, Χ·2, Χ·3, X-4' X-5, X-6, X-8, X-16, X-19, X-21, X-25, X- 26, X-27, X-28 or X-32 is preferred. -16- 201209078 [化13] 江考货%文文灯CHj H3C CH3 (X4) (X-1) (X-2) (X-3) (Χ·5) (X-6) (X- 7) (X-8) The original: iMX is ΧΦΧ (X-9) (X-10) (X-11) (X-12) (X-13) (X-14)

PC-15)

(X-25) (X-26) Class = 8^济Xr^xr^ (X-27) (X-28) (X-29) (X-30) (X-31) (X-32) ^ -33) ^34) (X-35) (X-36)

Oxooc

(X-46) (X-41) re In the above formula (2), R2 and R3 are each independently a hydrogen atom or an alkyl group, an alkenyl group or an alkynyl 'aryl group having 1 to 30 carbon atoms which may have a substituent. Or a combination of these may also form a ring structure. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl 'butyl group, a t-butyl group, a hexyl group, an octyl group, a decyl group, a cyclopentyl group, a cyclohexyl group, and a dicyclohexyl group. The dilute base may be a structure in which one of the above alkyl groups is substituted with a CH-CH structure on -17-201209078 to form a c=C structure, and more specifically, a vinyl group, an allyl group, 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-hexenyl, cyclopropenyl, cyclopentenyl, cyclohexenyl, and the like. The alkynyl group may be a structure in which one or more CKH 2 structures present in the alkyl group are substituted with a c ^ c structure, and more specifically, 'ethynyl group, 1-propynyl group, 2-propynyl group Wait. Examples of the aryl group include a phenyl 'fluorene: -naphthyl group, a 10,000-naphthyl group, a fluorene-biphenyl group, an m-biphenyl group, a P-biphenyl group, a 1-fluorenyl group, a 2-fluorenyl group, and 9 - anthracenyl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, and 9-phenanthryl. The alkyl group, the alkenyl group, the alkynyl group and the aryl group described above may have a substituent in the case of a carbon number of from 1 to 20, and may further form a ring structure by a substituent. Further, the formation of a ring structure by a substituent means that the substituents are bonded to each other or a part of the substituent is bonded to the parent skeleton to form a ring structure. Examples of the substituent include a halogen group, a hydroxyl group, a thiol group, a nitro 'organooxy group, an organic thio group, an organic decyl group, a decyl group, an ester group, a thioester group, a phosphate group, Amidino, aryl, alkyl, alkenyl, alkynyl. In terms of a halogen group of a substituent, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The organooxy group of the substituent may, for example, be a structure represented by a-0-R such as an alkoxy group, an alkenyloxy group or an aryloxy group. As the R aspect, an alkyl 'alkenyl group, an aryl group or the like as described above can be exemplified. In the above R, the aforementioned substituents may be further substituted. 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, and an oxime-18-201209078 oxy group. , decyloxy, lauryloxy and the like. As the organic thio group of the substituent, a structure represented by -S-R such as an alkylthio group, an alkenylthio group or an arylthio group can be represented. As the R aspect, an alkyl group, an alkenyl group, an aryl group or the like as described above can be exemplified. In the above R, the aforementioned substituent may be further substituted. 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 a heptyl group. A thio group, an octylthio group, a mercaptothio group, a mercaptothio group, a laurylthio group, and the like. The organoalkylene group of the substituent may be represented by a structure represented by _Si-(R)3. These R's may be the same or different, and the aforementioned alkyl group, aryl group and the like can be exemplified. In the above R, the aforementioned substituent may be further substituted. Specific examples of the alkyl fluorenyl group include a trimethyl decyl group, a triethyl decyl group, a tripropyl decyl group, a tributyl decyl group, a tripentyl decyl group, a trihexyl decyl group, and a pentyl group. Methyl decyl, hexyl dimethyl decyl, octyl dimethyl decyl, decyl dimethyl decyl, and the like. The thiol group of the substituent may represent a structure represented by -C(0)-R. As the R aspect, an alkyl group, an alkenyl group, an aryl group or the like as described above can be exemplified. In the above R, the aforementioned substituent may be further substituted. 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, and a benzamidine group. The ester group of the substituent may be represented by a structure represented by -C(0)0-R or -〇C(0)-R. As the R aspect, an alkyl group, an alkenyl group, an aryl group or the like as described above can be exemplified. In the above R, the aforementioned substituent may be further substituted. The thioester group of the substituent may be represented by a structure represented by -C(S)〇-R or -19-201209078 -OC(S)-R. This aspect, the suspicion, the square, and so on. In these R, the aforementioned generation. The structure of the phosphate group of the substituent can be expressed. These R's may be the same or different and may be exemplified by the base or the like. In the above R, the substituent may be represented by -C(0)NHR, -NHC(0)R, -C(0)N(R)2 in terms of a mercapto group. This R may be the same or different and may be exemplified. In the above R, the above-mentioned substituent may be an aryl group which may be a substituent, and examples thereof include an alkyl group which may be substituted with a substituent other than the above-mentioned other substituents in the front group, and may be exemplified in the front group. The alkenyl group which may be substituted with a substituent other than the above-mentioned substituent may, for example, be an alkynyl group which may be substituted with a substituent other than the above-mentioned substituent, and may be mentioned as a Further, in the above formula (2), R 4 is a hydrogen atom or an alkyl group of 1 to 3 fluorene in the above formula (2). The alkyl group and the substituent are specifically the same as the alkyl group and the substituent. In the above formula (2), 'Z' is a single bond or a carbon fluorenyl group. Ζι is a two-valent organic base of carbon number 1 to 30. The two-valent organic base shown is preferred. The substituent of the alkyl group as described above may be further substituted by the above-mentioned alkyl group and aryl, as shown by -op(o)-(or)2. -c(o)nh2 or -NRC(0)R is substituted with the above-mentioned alkyl group or aryl group. The same aryl group. This aryl is the same as the alkyl group. This alkane is the same as the alkenyl group. This alkene is the same as the alkynyl group. The acetylene 0 may have a carbon number of the substituent, and may be exemplified by the following formula (8) -20-201209078 [Chem. 14] a BrRs-B2-R9 - (8) In equation (8), _B1 and B2 are each independently a single bond or a two-valent link. However, B 1 and B 2: At least one of them is a two-valent linkage. R8 and from a single bond or a carbon number of 1 to 20 which may have a substituent, an alkylene group, an alkynyl group, an extended aryl group or a combination thereof.) The above B, and B2 are specifically for Expressed as follows, but not limited to this [Chem. 15] - 〇一 - -S - 1〇一 -〇1 _N_ \ 1N- _ -Ν-^Ν- (B-1) ( :B-2) ( B-3) (B-4) R10 (B-5) | R10 (B-6) | R10 (B-7) 1 1 R10 R11 (Β·8) —N— 〇< ch3 ο ten ch3 D 1U V NN — 〇 10 ch3 Γ \ (B-9) (B-10) (ΒΊ1) In the above B-5 B - 8, Β-1 0 ' • B-1 1 , R10 and R11 are hydrogen or may be The alkyl-alkenyl alkynyl 'aryl group having a substituent or a combination thereof may also form a ring structure. Specific examples of the alkyl group, the alkenyl group, the alkynyl group, the aryl group and the substituents are the same as those described above. When R10 and R11 are in a large structure such as an aromatic ring or an alicyclic structure, when used as a liquid crystal alignment film, 'the liquid crystal alignment property may be lowered', so a compound such as a methyl group, an ethyl group, a propyl group or a butyl group may be used. A radical or a hydrogen atom is preferred as a hydrogen atom. In the formula (8), when Rs and R9 are a C 1 to 20 alkyl group, an alkenyl group, an alkynyl group, an exoaryl group or a combination thereof, 'specifically, for example, -21 - 201209078 Show, but not limited to this. The above alkyl group may be exemplified by the removal of one hydrogen atom from the alkyl group. More specifically, a methyl group, a 1,1-extended ethyl group, a 1,2 group, a 1,2-extended propyl group, a 1,3-propanyl group, a 1,4-tert-butyl group, and 1 may be mentioned. , 2-stranded 1.2- pentyl, 1,2-extension, 1,2-extension, 1,2-extension twelve-2.3, butyl, 2,4-amyl, 1,2 - a cyclic propyl group, a 1,2·cyclobutene 1,3-cyclobutylene group, a 1,2-cyclopentyl group, a 1,2-cyclohexyl group, a 1,2-ring group, 1,2- The ring extends twelve bases and so on. The alkenyl group may be a structure in which one hydrogen atom is derived from an alkenyl group. More specifically, 1,1-extended ethylene 1,2-extended vinyl, 1,2·extended vinylmethyl, 1-methyl-I,2-extension, 1,2-extension Vinyl-1,1-extended ethyl, 1,2-extended vinyl-1,2-extension, 1,2-extended vinyl-1,2-extended propyl, 1,2-extended vinyl-1 , 3-extended propane I, 2-extended vinyl-1,4-butylene, 1,2-extended vinyl-1,2-extended 1,2-extended vinyl-1,2-exetylene The 1,2-extended vinyl-1,2-extended fluorenyl group has a structure in which one hydrogen atom is removed from an alkynyl group. In terms of the body, an exoacetylene group, a stilbene group, a methyl group, an exoethyl group, an exoethyl group, an exetylene group, a ethynyl group, a stilbene group, a stilbene group Ethylene ethynyl-1,3-extension propyl ethynyl-1,4-butylene, exo-1,2-butylene, ethynyl-indole, 2-heptyl, acetylene Base-1 thiol and the like. In the case of the aryl group, one hydrogen atom is removed from the aryl group. More specifically, it may, for example, be a 1,2-phenylene group, a 1,3-phenylene group, a phenylene group, a 1,2-anthranyl group, a 1,4-naphthyl group, a 1,5-anthracene group. Alkene, 2,3-yl, 2,6-anthranyl, 3-phenyl-1,2-phenylene, 2,2'-diphenyl, alkyl, alkenyl, alkyne The base, the aryl group, and the combination of the structure - the ethyl group, the base, the base, the exfoliation removal group, the vinyl group, the base, and the like. More decyl-propyl acetylene, 2-stretched 1,4- • naphthalene and the like. The base of these -22-201209078, as a whole, may have a substituent in the case of a carbon number of 1 to 20, and may further form a ring structure by a substituent. Further, the formation of a ring structure by means of a substituent means that the substituents are bonded to each other or the substituents of the substituent are formed in a ring structure. Examples of such a substituent include the same as described above. When R8 and R9 have a small carbon number, when used as a liquid crystal alignment film, in order to improve liquid crystal alignment, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, and a carbon number of 1 are used. An alkynyl group of ~5 is preferred. More preferably, either or both of R8 and r9 are single bonds. In the formula (2), the protective group of D and the amine group is not particularly limited as long as it is a functional group substituted with a hydrogen atom by heating. From the viewpoint of the storage stability of the liquid crystal alignment agent of the present invention, the protecting group D is preferably a non-dissociating at room temperature, preferably a protecting group which is deprotected by heat of 80 ° C or higher. Further, it is more preferably a protective group which is deprotected by heat of 100 ° C or more. Further, from the viewpoint of promoting the efficiency of the thermal hydrazylation of the polyphthalate and the crosslinking reaction with the polyimine precursor or the polyimine, it is deprotected by heat of 30 (TC or less). The protective group is preferably a protecting group which is deprotected by heat of 250 ° C or less, and more preferably a protecting group which is deprotected by heat of 200 ° C or less. It is preferred to use an ester group represented by the following formula: [Chem. 16]

(In the formula, Rn is a hydrocarbon group having 1 to 22 carbon atoms.) -23-201209078 Specific examples of the ester group represented by the above formula (9) include a methoxycarbonyl group and a trifluoromethoxycarbonyl group. Ethoxycarbonyl, η-propoxycarbonyl, isopropoxycarbonyl, η-butoxycarbonyl, tert-butoxycarbonyl, sec-butoxycarbonyl, η-pentyloxycarbonyl, η-hexyloxy A carbonyl group, a 9-fluorenylmethoxycarbonyl group or the like. Among these, a structure in which the dissociation reaction is efficiently carried out at a firing temperature of 150 ° C to 300 ° C at the time of obtaining a liquid crystal alignment film is preferable, and tert-butoxycarbonyl or 9-fluorenyl group is preferable. The oxycarbonyl group is more preferably a tert-butoxycarbonyl group. Hereinafter, in the structure represented by the formula (2), 'specifically' is preferably a structure of D-1 to D-24, but Not limited to this. -24- 201209078 [化17] h3c ch3 I , Π3 -(CH2)n-NH n = 1-10(D-l)

>:3VCc% ~〇~(CH2)n-NH 11 = I-10 (D-2) If ^n = l~10 CH3 -0-2-, (D-3.) O 〇iNH-( CH2)n-NI~K CH3 h3 n = 1 ～10 CH3 (D-5) (CH2)n-NH- n = l~10 (D-4) C n = 1~10 (D-6) 0 o Ten ch3 ch3 -(CH2)n^ ?H3 -ch3 n= 1~10 CH3 (D-7) 〇卜(.call-^.?H3 -oo tench3 n = 1-10 CH3 (D-10) • o -〇-(CH2)n—^ CH3 0 十ch3 n= 1-10 CH3 (Ο-β) -N-(CH2)n—^ CH3 0—CH3 n= 1 ～10 CH3 〇>-〇- (CH2)n—i; n = 1Ί0 (I>9) 〇,. o Bu(CH2)n—^ ?H3 NH 〇+CH3 n = *M 〇CH3 (D-12)

-{CH2)n-N fcH n = 0-10 (D-13 LJ (-^ CH3 〇ch3 13) CH, 〇^CH3 -〇-(CH2)n-N Ο PH3 ch3 'ch2_i Less ηΉ Volume h ς, ch3

-10 (D-14) CH-J 10 (D-15) CH, CH3 n = 1-10 (D-16) -10 (D-17) CH3 b+CH3 CH3 n = 1~10 (CM8> cH3 -25- 201209078 [化18]

-(CHz^-CH-^O+CHj 一〇_(CH2)n-(pHi〇十(?H3 _CLfCH ) -CH-SO-ScH H3Q H3C^fon = O-10 CH, (D-19) HN ^O CH3 HN丫〇CH3 2ηΓ Ο 3 u 1\° n = 0-10 Hs 3^? n= 0-10 ^ CH3 (D-20) H3C^CH3 (D.21) 〇9H3 O CHs -hJH 〇 CH3 (CH^n-CH-^Of-CHa 0-(CH2)n-(pH』-0+CH3 ^-(CH^n-CH-^O+CHj HN^O CH3 —^ HN^O CH3 〇 HN_〇CH, n = 0-10 H3C bH3 <°-22) n H3C CHj =0-10 (D-21) Λ -Π2;η'νη-u\ HN^OC 〇n = h3c%H3 ( Ch3 0-10 (D-23) HN-(CH2)n-CH-1]-〇-f-CH3 ~i. HN^O CH3 h3C n = 0-10 H3C^Ch3 (D-24) Again, this In the case of the compound of the invention, the following structures are mentioned, but are not limited thereto. -26- 1°201209078 [Chem. 19]

MeO

Me Q (1-a)

A

MeO Y^V°M< (1-a-l) }~Ό.

(l-a-2)

(l-a-3) -27- 201209078 [Chem. 20]

(1 7-3) -28- 201209078 [Chem. 21]

HN

(1-c)

NH

HN

HN-

Me0Ay/-〇-°N)^NHVrOMe (l-c-2)

-29- 201209078 [Chem. 22]

[Chem. 23] HN_y \=/ - H〇 06^ (1-e)

-30 - 201209078 [Chem. 24]

(l-f-l) [化25] -κ ΗΝ- (i-g) ΗΝ- Η0Υιγ( ο ο (l-g-l) 201209078 [Chem. 26]

-32- 201209078 [化27]

-33- 201209078 [化28]

(1-m)

-34 201209078 [化29] d-η) H〇~]f / ]-0Η (1-n-l)

(l-n-2)

(1-11-3) -35- £ 201209078 [Chem. 30]

HN

HO (l-o-l)

[Synthesis method of the compound of the present invention] The compound of the present invention is a tetracarboxylic acid derivative represented by the following formula (3), which is represented by the following formula (5) or by the following formula ( 6) m $ t tetracarboxylic dianhydride and a monoamination & ampere represented by the following formula (4) are used as a raw material, and are synthesized by various methods. Specifically, the methods (i) to (iii) are exemplified, but are not limited thereto. -36- 201209078 [化31]

(In the formula, the number of the bases of carbon numbers 1 to 5: X, Zi' R2, r3, ruler 4, and D! are the same as those defined by the formulas (1) and (2).) The double of the above formula (3) The chlorocarbonyl compound, for example, can be obtained by reacting the fourth residual acid dianhydride of the above formula (6) with an alcohol represented by R5〇H to form a dialkyl tetracarboxylate, and converting the carboxyl group into a chlorocarbonyl group by a chlorinating agent. Got it. The tetracarboxylic acid derivative 'of the above formula (5)' can be obtained, for example, by reacting the four residual acid dianhydride of the above formula (6) with an alcohol represented by R5?H. The monoamine compound of the above formula (4) may be a method in which a compound having a first or second amino group represented by the following formula and a di-tert-butyl dicarbonate are allowed to act in the presence of a base. In the compound having a primary or secondary amine group, a method of causing a chloroformic acid-9-thanomethyl ester to act in the presence of a base is not particularly limited as long as it is a known method. -37- 201209078 [化32]

The compound having a substituent obtained by the above method is added to a nitro compound, a monoamine compound, a diamine compound or a derivative thereof, and if necessary, a reduction of a nitro group or introduction of an amine group is carried out to obtain A monoamine compound of a thermally dissociable protecting group. The method for synthesizing the compound of the present invention includes the following methods (i) to (iii), but is not limited thereto. (i) Process for synthesizing a bischlorocarbonyl compound from a monoamine compound The compound of the present invention can be reacted with a monoamine compound represented by the above formula (4) by reacting a biscarbonyl compound represented by the above formula (3) And synthesis. Specifically, the bischlorocarbonyl compound and the monoamine compound are reacted in the presence of a base and an organic solvent at -20 ° C to 80 ° C, preferably 0 ° C to 50 ° C, for 30 minutes. ~2 4 hours, preferably 1 to 4 hours to synthesize" In the case of the above-mentioned base, pyridine, triethylamine, 4-dimethylamine-38-201209078-based pyridine, etc. may be used, but in order to stabilize the reaction It is preferred to carry out pyridine. The amount of addition of the base is preferably from 2 to 4 moles per mole of the bischlorocarbonyl compound from the viewpoint of the amount easily removed. (ii) a method of synthesizing a tetracarboxylic acid derivative from a monoamine compound, the compound of the present invention can be obtained by using the tetracarboxylic acid derivative represented by the above formula (5) and the one represented by the above formula (4) The amine compound is synthesized by dehydration condensation. Specifically, the tetracarboxylic acid derivative and the monoamine compound can be reacted in the presence of a condensing agent, a base or an organic solvent at 0 ° C to 80 ° C, preferably (TC 50 ° C in a reaction of 30 minutes ~ It is synthesized in 24 hours, preferably 3 to 15 hours. In terms of the above condensing agent, triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylmethyl) can be used. Aminopropyl)carbodiimide hydrochloride, N,N'-carbonyldiimidazole, dimethoxy-1,3,5-triazinylmethylmorpholinium, 0-(benzotriazole -1-yl)-N,N,N,,N'-tetramethylcarbamate tetrafluoroborate, 0-(benzotriazol-bu)-indole, hydrazine, Ν'Ν'-tetramethyl Carbon hexafluorophosphate, (2,3-dihydro-2-thioketo-3-benzoxazolyl)phosphonic acid diphenyl, etc. The amount of the condensing agent added is a tetracarboxylic acid derivative. In the case of the base, a tertiary amine such as pyridine or triethylamine can be used. The amount of the base added is from the viewpoint of the amount easily removed. 2 to 4 times the molar content of the diamine component is preferred. In the above reaction, the addition of Lewis acid as an additive would be The reaction is carried out more efficiently. In terms of Lewis acid, lithium halide such as lithium chloride or bromine-39-201209078 lithium is preferred. The addition amount of Lewis acid is 0~1 · 0 for monoamine (1) a method for synthesizing a tetracarboxylic dianhydride from a monoamine compound. The compound of the present invention can be obtained by using the tetracarboxylic dianhydride of the above formula (6) and the above formula (4). The monoamine compound shown is reacted. Specifically, it can be at -20 ° C to 80 ° C, preferably 0 ° C in the presence of a tetracarboxylic dianhydride and a monoamine compound machine solvent. The synthesis is carried out at a temperature of from 50 to 24 hours, preferably from 1 to 12 hours at 50 ° C. The solvent used in the above is from the viewpoint of the solubility of the tetracarboxylic dianhydride, the monoamine compound and the product. -methyl-2-pyrrolidone, 7-butyrolactone, dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, chloroform, and further N-methyl-2-pyrrolidone N,N-dimethylformamide or furan is preferred, and these may be used alone or in combination of two or more. The concentration is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass. Furthermore, the above The compound of the formula (1) wherein R1 is an alkyl group having 1 to 5 carbon atoms, which is a compound of a tetracarboxylic dianhydride and a monoamine compound, may be added with various esterifying agents, and esterified with a carboxyl group. Specifically, the synthesis can be carried out by reacting the tetracarboxylic dianhydride, the monoamine compound and the agent in the presence of an organic solvent at -20 ° C to 80 ° C, preferably ~, for 30 minutes to 24 hours. Preferably, it is 1 to 4 hours to obtain an esterification agent, and it is preferably removed by purification, and the mixture is shown to be present, and the reverse reaction is dissolved in N, N-, etc. The reaction of hydrazine is esterified with 50. . Synthesis can be -40-201209078 Ν , Ν aldehyde condensed group 乙 condensed , aldehyde propylene diamine amine 醯 二甲 安 « « 0 0 0 0 0 0 0 0 0 0 0 « « « « « « « « « « « « « « « « « « « « « « « « «

N base armor

NN dimethylamino phthalamide, di-n-pentyl butyl acetal, N,N-dimethylformamide di-t-butyl phthalate, 1-methyl-3- π-tolyl Triazine, 1-ethyl·3-ρ-tolyltriazine, 1-propyl-3-indole-tolyltriazene, 4-(4,6-dimethoxy-1,3, 5-triazin-2-yl)-4-methylmorpholine hydrochloride and the like. The amount of the esterifying agent to be added is preferably 2 to 6 mole equivalents per mole of the tetracarboxylic dianhydride. The solvent used in the reaction of the above (i) to (iii) is, in view of the solubility of the monomer and the product used in the synthesis, N-methyl-2-larobidinone 7-butene Ester, N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran 'chloroform, etc., among which N-methyl-2-pyrrolidone, N,N-dimethyl Methyl amide or tetrahydrofuran is preferred. These may be used alone or in combination of two or more. The concentration at the time of the synthesis is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass. Further, when a bischlorocarbonyl compound is used, in order to prevent hydrolysis of the bischlorocarbonyl compound, it is preferred that the solvent used in the synthesis be dehydrated as much as possible, and it is preferable to avoid the incorporation of outside air in a nitrogen atmosphere. The reaction solution obtained by the above reaction of (i) to (iii) can be used as it is for the composition of the present invention. In particular, the compound of the present invention obtained by using Ri in the formula (1) as a hydrogen atom is free from reaction by-products and must be obtained by the above method (i.e., because it is a reaction of an acid anhydride with an amine) The base or the condensing agent to be removed. Therefore, the above-mentioned compound of the present invention is particularly preferably used as the composition of the present invention by using the reaction solution. Further, the reaction obtained by the reaction of (i) to (iH) described above is carried out. The solution of the present invention can be precipitated by stirring into a poor solvent, and the compound of the present invention can be precipitated. After several times of precipitation and washing with a poor solvent, the compound powder of the present invention can be purified by normal temperature or heat drying. The poor solvent is not particularly limited, and examples thereof include water, methanol, ethanol, hexane, etc. When the purity of the obtained compound is low, when a film made of the composition is used for an electronic material, electrical characteristics may be deteriorated. Therefore, it is preferable to carry out purification by various methods. The purification method includes cerium oxide colloidal column chromatography, recrystallization, washing with an organic solvent, etc., but from the convenience of operation and purification. The rate of the rate is preferably recrystallization. The organic solvent used in the recrystallization may be an organic solvent capable of recrystallizing the compound of the present invention, and may be selected from two or more types of mixed solvents. Recrystallization. <Polyimide precursor and polyimine> The polyimine precursor contained in the liquid crystal alignment agent of the present invention has the following structure which can be produced by heating a polymer at the site of the amination reaction. [Chem. 33]

The polyimine precursor system used in the present invention has a structure represented by the following formula (7). -42- 201209078 [Chem. 34]

(LOUK6; 2 C—X^C—N—Yi~N Ο Αι A2 (7) In the above formula, r6 is a hydrogen atom or an alkyl group having a carbon number of 1 to 5, preferably 1 to 2. A and A2 are each It is independently a hydrogen atom or an alkyl group having a carbon number of 1 to 10, preferably 1 to 5, which may have a substituent. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. T-butyl, hexyl, octyl, decyl, cyclopentyl, cyclohexyl, dicyclohexyl, etc. The above alkyl group may have a substituent, and may further form a ring structure by a substituent. The substituent forms a ring structure, meaning that the substituents are bonded to each other or 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, and a nitro group. , aryl, organooxy, organothio, organodecyl, decyl, ester, thioester, phosphate, decyl, alkyl, alkenyl, alkynyl. Polyimine precursor In the body, generally, if a large structure is introduced, the reactivity of the amine group or the liquid crystal alignment property may be lowered, and the hydrogen atoms may be substituted or substituted in the aspect of Αι and A2. The alkyl group having a carbon number of 1 to 5 is more preferable, and particularly preferably a hydrogen atom, a methyl group or an ethyl group. Further, in the formula (7), the above Χι is a tetravalent organic group, and Υι is a 2-valent organic group. In the polyimine precursor, X! may be mixed in two or more types. To show a specific example thereof, X is exemplified in the structure of the preferred compound of the above-mentioned compound containing a pyrolytic group (2). In the same manner as described above, X-1 to X- 4 6 〇 may be mentioned. In the formula (7), the organic group in which 丫1 is a divalent group is not particularly limited to the y-polyimine precursor. Y i can be mixed with two or more types. Specific examples of Y include the following Υ-1, ～Y-97. Among them, in order to obtain good liquid crystal alignment, a linear diamine is introduced. Polyimine precursor or polyimide is preferred, Y, aspect » Υ-7, Υ-10 ' Υ-1 1 , Y-12 , Y -13 , Y-21 ' Y-22 &gt; Υ - 23 Υ- 25, Υ-26, Υ-27, Y-41 &gt; Y-42, Y-43, Y-44, Υ- 45 &gt; Υ- 46, Υ-48, Υ-61, Y- 63 ' Y- 64 , Y-71 , Y-72 , Υ - 73 Υ - 74 Υ-75, Υ-98 diamine is more preferable. Also, when the pretilt angle is to be changed, the side is locked with a long-chain alkyl group, an aromatic ring, an aliphatic ring steroid skeleton or a combination thereof. It is preferred that the diamine of the structure is introduced into the polyimide precursor or the polyimine. In the aspect, the system J is Y-76, Y-77, Y-78 Y-79, Υ-80, Υ- 8 1. Υ -82, Y-83, Υ-84, Υ-85, Υ-86% Y-87, Υ-.88, Υ-89, Υ-90, Y-91 'Υ-92, Υ- 93, Υ-94, Y-95, Y-9 6 or Y-97 diamine is better. By adding these diamines in an amount of from 1 to 50 mol% of the total diamine, an arbitrary pretilt angle can be expressed. [化35]

-44- 201209078 [化36]

[化37] (Υ-34) (Υ*35) (Υ-36) (Υ-37) (Υ-38)

[化38]

-oo V 6k iX (Y-4S) (Y-50) (Y-51) [39] 93⁄4 ch3 —(CH2)2-C-(CHj)2- —(CH2)4C-(CH2)3- Ch3 0Hj (V-53) (Y-54) ch3 ch3 CH2-C-(CH 2)2--C-(CH2 )2-(Y-55) CHs CHj ch3 2-C-(CH2)2-C -(CH2)3- -(CHj)2-C-(CH?)5- HH (Y-56) (Y-57) (Y-58) -(CH2)n· n = 2-5 (Y- 52)

-CH 45 201209078 [化40] HCH2)3-CH3 ch3 a (ch2)t〇-(c is called zhouzhou 3-(Y-59) (iHs 0H3 (Y^60)

(Y-61) (Υ-62) [化41]

[化42] 〇

Q, 〇'

sound. (4) (Y-74) n=2~5—double—(γ.76) n = 5~19 (Y-77) n = 5-19 [化43] 〉&quot;0~O-(CH2)n- CH3 (Y-78) n = 0~21 &gt;-^〇{C^iVC2i3 (Y-79) 0

yJQj—C^~0_(cH2)n (Y-81) -CH3 0-21 -CH3 (Y-83) n = °~21 -46- 201209078 [Chem. 44]

〇-(CH2)n-CH3 η = 0~21 [化45]

~O~&quot;QHCH2)n-CH3 (Υ-84) η = 0~21 0_O~O~°'(CH2)n-CH3 (Υ-85) η = 0~21 &quot;°~O~^0 -°-(CH2)n-CH3 (丫-87) η = 0~21

^V〇-CF3 Όζ^^-〇-〇Ρ3 (Υ-88) (Υ-89)

[Chem. 46]

(Υ-97)

〇-©— 47 201209078 [Chem. 47]

Q〇2H CO2H

(Y-98) (Υ-99) &lt;Production Method of Polyimine Precursor&gt; In the present invention, a polyphthalamide precursor or poly-proline is mentioned. Wherein the 'polyamine amide ester' can be obtained by reacting any of the tetracarboxylic acid derivatives represented by the following formulas (10) to (1 2 ) with a diamine compound represented by the formula (丨3). .

Αι A2 (wherein X丨, Y丨, 尺 6, 丨 and 八2 are each the same as defined in the above formula (?).) The polyamidoate represented by the above formula (1) can be used. The above monomers were synthesized by the methods (1) to (3) shown below. (1) Synthesis by Polyproline The polyglycolate can be synthesized by esterifying a polyfluorene-48-201209078 amino acid obtained from a tetracarboxylic dianhydride and a diamine. [Ο50] 'Ο 0 - _ a 0 0 -^ JLor Wrr MM— 乂2- X ROi κγν Specifically, poly-proline and an esterifying agent in the presence of an organic solvent at -20t: The reaction is carried out at -150 ° C, preferably 〇 ° C to 50 ° C, for 30 minutes to 24 hours, preferably 1 to 4 hours. In terms of the esterifying agent, it is preferred that it can be easily removed by purification, and N,N-dimethylformamide dimethyl acetal, hydrazine, hydrazine-dimethylformamide II can be mentioned. Acetal, hydrazine, hydrazine-dimethylformamide dipropyl acetal, hydrazine, hydrazine-dimethylformamide dinepentyl butyl acetal, hydrazine, hydrazine-dimethylformamide -t-butyl acetal, 1-methyl-3-P-tolyltriazene, 1-ethyl-3-P-tolyltriazene, 1-propyl-3-P-tolyl III Nitroene, 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholine hydrochloride, and the like. The amount of the esterifying agent to be added is preferably 2 to 6 moles per equivalent of the repeating unit of polyamic acid. The solvent used in the above reaction is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone or r-butyrolactone from the viewpoint of solubility of the polymer. One type may be used or two or more types may be used in combination. The concentration at the time of the synthesis is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass, from the viewpoint that the polymer is difficult to precipitate and the high molecular weight body is easily obtained. (2) Synthesis by reaction of tetracarboxylic acid diester dichloride with diamine Polyphthalate ester can be synthesized from tetracarboxylic acid diester dichloride and diamine -49-201209078 [Chem. 51]

Specifically, in the presence of a tetracarboxylic acid diester dichloride and a di- and an organic solvent, the reaction is carried out at -2 (TC to 15 ° C, preferably 〇. &lt;: ~ ' Pyridine, triethylamine, 4-diylpyridine, etc. may be used in the case of the above-mentioned alkalis in the range of ~24 hours, preferably 1 to 4 hours, but in order to carry out the reaction stably, pyridine is used. The amount of addition is preferably from 2 to 8 for the tetracarboxylic diester dichloride from the viewpoint of easy removal amount and easy availability of a polymer. The solvent used in the above reaction is from a single In the case of the polymer and the polymer, N-methyl-2-pyrrolidone or r-butyrolactone is preferably used alone or in combination of two or more. The polymer-concentrated polymer during synthesis is difficult to precipitate and From the viewpoint of easily obtaining a high molecular weight body, it is preferably 1 to 30% by mass, more preferably 5 to 20% by mass. Further, for the hydrolysis of the carboxylic acid diester dichloride, the polymerization in the synthesis of the polyamidite is as much as possible. It is better to use dehydration and to avoid gas incorporation in a nitrogen atmosphere. (3) Synthesis by tetracarboxylic acid diester and diamine The amine ester can be synthesized by reacting a tetracarboxylic acid diester with a diamine. The amine is in the base 50. (: in the middle. The methylamine is preferred. The alkali amount is 4 times the solubility of the base, From, to prevent the use of four-use dissolution of external condensation condensation -50-201209078 [Chem. 52]

Specifically, it can be made from 0 ° C to 150 by using a tetracarboxylic acid diester and a diamine in the presence of a condensing agent, a base, and an organic solvent. (:, preferably 0 ° C ~ loot 'reaction 30 minutes ~ 24 hours, preferably 3 ~ 15 hours to synthesize. For the above condensing agent, triphenyl phosphite, dicyclohexyl carbon di Imine, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, N,N'-carbonyldiimidazole, dimethoxy-1,3,5- Triazinylmethylmorpholinium, 0·(benzotriazol-1-yl)-N,N,N,,N,-tetramethylcarbamate tetrafluoroborate, bismuth-(benzotriazole- 1-yl)-N,N,N,,N'-tetramethylcarbon gun hexafluorophosphate, (2,3-dihydro-2-thioketo-3-benzoxazolyl)phosphonic acid The amount of the condensing agent to be added is preferably from 2 to 3 moles per mole of the tetracarboxylic acid diester. For the base, a tertiary amine such as pyridine or triethylamine can be used. The amount of addition of the base is preferably from 2 to 4 times the molar amount of the diamine component from the viewpoint of easily removing the amount and easily obtaining a high molecular weight body. Further, in the above reaction, Lewis acid is added. As an additive, the reaction proceeds more efficiently. In terms of Lewis acid, lithium chloride, lithium bromide, etc. Lithium oxide is preferred. The amount of Lewis acid added is preferably 〇~1·0 moles for the diamine component. In order to obtain a high molecular weight polymerization in the above three polyperurethane synthesis methods The glutamate is particularly preferably the above-mentioned (1) or the above-mentioned (2) synthesis method 51 - 201209078 The solution of the polyphthalate obtained as described above can be poured into a poor solvent while stirring to precipitate a polymer. After being precipitated several times and washed with a poor solvent, the powder of the purified polyphthalate can be obtained by drying at room temperature or by heating. The poor solvent is not particularly limited, and examples thereof include water, methanol, ethanol, and hexane. Butyl cellosolve, acetone, toluene, etc. The weight average molecular weight of the polyglycolate is preferably 5,000 to 30,000, more preferably 10, 〇〇〇 to 200,000. Further, the number average molecular weight is preferably 2,500 to 150,000. More preferably, it is 5,000 to 100,000 °. Further, in the case where the polyimide precursor is poly-proline, the polyamine can be obtained by the tetracarboxylic dianhydride represented by the following formula (12). The reaction of the diamine compound shown in (1 3 ) is obtained.

(wherein, X丨, Υι, A, and A2 are each the same as defined in the above formula (7).) Specifically, 'by using a tetracarboxylic dianhydride and a diamine in the presence of an organic solvent' The reaction is carried out at -20 ° C to 150 ° C, preferably 〇 ° C to 5 Torr, for 30 minutes to 24 hours, preferably 1 to 12 hours. The organic solvent used in the above reaction is N,N-dimethylformamide, N-methyl-2-pyrrolidone or r-butyrolactone in terms of solubility of the monomer and the polymer. It is better to use one of these types or a mixture of two or more types -52-201209078. The concentration of the polymer is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass, from the viewpoint that the polymer is difficult to precipitate and the high molecular weight is easily obtained. The polylysine obtained as described above can be obtained by precipitating the solution while injecting it into a poor solvent while stirring to recover the polymer. Further, it is precipitated several times, washed with a poor solvent, and dried at room temperature or by heating to obtain a purified powder of polylysine. The poor solvent is not particularly limited, and examples thereof include a water-methanol, ethanol, hexane, butyl cellosolve, acetone, toluene, and the like. The weight average molecular weight of the lysine is preferably 10,000 to 300,000, more preferably 20,000 to 200,000. . Further, the number average molecular weight is preferably from 2,500 to 15,000, more preferably from 5,000 to 10,000,000. &lt;Polyimine&gt; The ruthenium imidization reaction which dehydrates the polyimidazole precursor, which is generally enthalpy imidization or chemical hydrazylation, is carried out at a lower temperature. The chemical hydrazine imidization is preferred because it does not easily cause a decrease in the molecular weight of the polyimine. The chemical hydrazine imidization is carried out by stirring a polyimide precursor in an organic solvent in the presence of a basic catalyst and an acid anhydride. The reaction temperature at this time is -20 to 2 50 t, preferably 〇 to 180 ° C, and the reaction time is 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles of the anhydride of the polyamidene precursor, and the amount of the anhydride is 1 to 5 moles of the polyimide precursor. It is preferably 3 to 30 times Mo. If the amount of the basic catalyst or the 53-201209078 acid anhydride is small, the reaction cannot be sufficiently carried out. If the amount is too large, it is difficult to completely remove the reaction after the reaction is completed. Examples of the basic catalyst used in the ruthenium imidization include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Among them, pyridine is preferred because it has moderate alkalinity in the progress of the reaction. Further, examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and benzene tetracarboxylic anhydride. Among them, acetic anhydride is preferred because it is easily purified after completion of the reaction. As the organic solvent, the solvent used in the polymerization of the above polyamic acid can be used. The rate of imidization of the chemically imidized oxime can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time. The polyimine solution obtained in this manner is left in the solution because the added catalyst remains. In order to be used in the liquid crystal alignment agent of the present invention, the polyimine solution is put into a poor solvent which is being stirred, and precipitated. It is preferred to recycle the polyimine. The poor solvent used in the precipitation recovery of the polyimine is not particularly limited, and examples thereof include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, and ethanol. , toluene, benzene, etc. The polyimine precipitated by the introduction of a poor solvent is recovered by filtration and washing, and then dried under normal pressure or reduced pressure to form a powder. The powder is further dissolved in a good solvent, and the reprecipitation operation is repeated 2 to 10 times to purify the polyimine. It is preferable to repeat this purification step when the primary precipitation recovery operation cannot completely remove the impurities. In order to repeat the solvent in the purification step, it is preferred to mix three or more kinds of poor solvents such as alcohols, ketones, and hydrocarbons, or to use the above-mentioned solvent in order, thereby further improving the efficiency of purification. -54-201209078 The ruthenium imidization ratio of the polyimine contained in the liquid crystal alignment agent of the present invention is not particularly limited. It can be set to any 値 considering the solubility of polyimine. The molecular weight of the polyimine contained in the liquid crystal alignment agent of the present invention is not particularly limited. However, if the molecular weight of the polyimide is too small, the strength of the obtained coating film may be insufficient. When the molecular weight of the imine is too large, the viscosity of the liquid crystal alignment agent to be produced is too high, and the workability at the time of formation of a coating film and the uniformity of a coating film may worsen. Accordingly, the polyiminoimine used in the liquid crystal alignment agent of the present invention preferably has a weight average molecular weight of 2,000 to 500,000, more preferably 5,000 to 300,000. &lt;Liquid crystal alignment agent&gt; The liquid crystal alignment agent of the present invention is in the form of a solution in which the above-mentioned polyiminoimide precursor and/or polyimine is dissolved in an organic solvent. In the case of having such a form, for example, in the case of synthesizing a polyamidene precursor such as polyglycolate and/or polyglycolic acid in an organic solvent, it may be directly the obtained reaction solution or may be used. This reaction solution was diluted with a suitable solvent. Further, when the obtained polyimide precursor and/or polyimine is a powder, it is preferred to dissolve the solution in an organic solvent to form a solution. The content (concentration) of the polyimine precursor and/or polyimine (hereinafter referred to as polymer) in the liquid crystal alignment agent of the present invention can be appropriately set according to the thickness of the polyimide film to be formed. In the case of a coating film having uniform strokes and no defects, the polymer content is preferably 0.5% by mass or more based on the organic solvent, and from the viewpoint of storage stability of the solution, It is preferably 15 mass% or less, more preferably 1 to 1 mass%. Further, in the liquid crystal alignment agent of the present invention, in addition to the polymer, the above-mentioned compound containing a thermally dissociable group may be added. The compound containing a thermally dissociable group may preferably be added in an amount of from 0.5 to 50 mol% to the repeating unit of the above-mentioned polyimine precursor and the quinone imidized polymer of the polyimine precursor. The content of the compound having a thermally dissociable group is more preferably from 1 to 30 mol%, particularly preferably from 5 to 20 mol%. When the content is too small, the ruthenium imidization reaction or the crosslinking reaction of the polyimide precursor is insufficient, and when the content is too large, the liquid crystal alignment may be adversely affected. The organic solvent contained in the liquid crystal alignment agent of the present invention is not particularly limited as long as it is uniformly soluble in the polymer. Specific examples thereof include hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine-diethylformamide, hydrazine, hydrazine-dimethylacetamide, hydrazine-methyl-2-pyrrolidinone. , Ν-ethyl-2-pyrrolidone, Ν-methyl caprolactam, 2-pyrrolidone, Ν-vinyl-2-pyrrolidone, dimethyl hydrazine, dimethyl hydrazine, r - Butyrolactone, 1,3-dimethyl-tetrahydroimidazolidone, 3-methoxy-N,N-dimethylpropane decylamine, and the like. These may be used alone or in combination of two or more. Further, even if it is a solvent which cannot be uniformly dissolved by the addition of the polymer alone, it can be mixed in the above organic solvent in the range where the polymer does not precipitate. The liquid crystal alignment agent of the present invention may contain, in addition to the organic solvent for dissolving the polymer, a solvent for improving the uniformity of the coating film when the liquid crystal alignment agent is applied to the substrate. As the solvent, generally, a solvent having a lower surface tension than the above organic solvent can be used. Specific examples thereof include ethyl cellosolve, butyl cellosolve, butyl cellosolve acetate, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, and 1- Methoxy-2-propanol, 1-B-56-201209078 oxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetic acid Ester, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2·acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropane Alkyl alcohol, propanol, methyl lactate, ethyl lactate, η-propyl lactate, η-butyl lactate, isoamyl lactate, and the like. These solvents can be used in two or more types. The liquid crystal alignment agent of the present invention may further 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 are listed below, but are not limited thereto. 3-aminopropyltriethoxydecane, 3-(2-aminoethyl)aminopropyltrimethoxydecane, 3-(2-aminoethyl)aminopropylmethyldimethoxy Baseline, 3-aminopropyltrimethoxydecane, 3-phenylaminopropyltrimethoxydecane, 3-triethoxydecyl-indole-(1,3-dimethyl-butylene) An amine decane coupling agent such as propylamine or 3-aminopropyldiethoxymethyl decane; vinyl trimethoxy decane, vinyl triethoxy decane, vinyl ginseng (2-methoxy phenyl) Oxy) decane, vinyl methyl dimethoxy decane, vinyl triethoxy decane, vinyl triisopropoxy decane, allyl trimethoxy decane, fluorenyl-styryl trimethoxy decane Vinyl decane coupling agent; 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropylmethyldi Epoxy oxime, 3-glycidoxypropylmethyl-methoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, etc. ;3-Methyl propylene methoxypropyl methyl two Oxydecane, 3-methylpropenyloxy-57-201209078 propyltrimethoxydecane, 3-methylpropenyloxypropylformane, 3-methylpropenyloxypropyltriethoxy Acid-based decane coupling agent such as decane; 3-propenyloxypropyltrimethoxyenoic acid decane coupling agent; 3-ureidopropyltriethoxydecane decane coupling agent: bis(3-(triethoxy) Tert-alkyl)propyl 'bis(3-(triethoxydecyl)propyl)tetrasulfide-based decane coupling agent; 3-hydrothiopropylmethyldimethoxysilylpropyltrimethoxydecane a hydrogenthio-based decane coupling agent such as 3-octylthio-l-propyl alkane; an isocyanate mixture such as 3-isocyanate propyl alkane or 3-isocyanate propyl trimethoxy decane; triethoxy decane An aldehyde system such as butyl aldehyde or the like, and a urethane system such as (3-triethoxy)-t-butyl urethane or the like. When the amount of the decane coupling agent added to the decane is too large, the anti-crystal orientation has an adverse effect, and if it is too small, the effect is not exhibited, and the solid content of the polymer is 0. 01 to 5. Preferably, it is 0.1 to 1.0% by weight. When the above-mentioned decane coupling agent is added, in order to prevent the polymer from being fired before the addition of the solvent for improving the uniformity of the coating film, in order to In the liquid crystal alignment agent of the present invention, in addition to the above, in addition to the above, in the range of the effects of the invention, it is possible to add a liquid crystal alignment other than the polymer. An electrical property such as a dielectric constant or a conductivity of a film, a sulfonated alkane such as a disulfide or the like, a sulfonated alkane such as a dipropyl sulfide or the like矽Triethoxy oxime ester decane coupling agent: triethyl decyl propyl propionant. The effect of the liquid on the liquidity is 5%, and it is preferably added. The imidization is more the cross-linking property for the purpose of improving the hardness or density of the liquid crystal alignment film without detracting from the polymer, the -58-201209078 dielectric or conductive material for the purpose of chemical conversion. Compounds and the like The liquid crystal alignment agent of the present invention can be used as a liquid crystal alignment film after being applied and fired on a substrate, subjected to alignment treatment by honing treatment or light irradiation, or in an alignment treatment such as vertical alignment. In this case, the substrate having high transparency is not particularly limited, and a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used, and from the viewpoint of simplification of the process, It is preferable to use a substrate on which an ITO electrode for liquid crystal driving or the like is formed. Further, in the reflective liquid crystal display device, an opaque material such as a germanium wafer can be used as the substrate on one side, and an electrode such as aluminum which can reflect light can be used as the electrode. The coating method of the liquid crystal alignment agent is not particularly limited, and industrially, methods such as screen printing and lithographic printing, flexographic printing, and inkjet printing are generally employed. Other coating methods include an immersion, a roll coater, a slit coater, a rotator, etc., and these methods can be used depending on the purpose. The firing of the substrate to which the liquid crystal alignment agent has been applied can be carried out at any temperature of 100 3 50 ° C, preferably at a temperature of 150 to 300 ° C, and preferably at a temperature of 1 800 to 250 ° C. The polyimine imide contained in the liquid crystal alignment agent changes the conversion ratio of the polyimine into a polyimine according to the firing temperature, but the liquid crystal alignment agent does not necessarily have to be imidized by 100%. The firing time can be set at any time. However, if the firing time is too short, the display may be defective due to the influence of the residual solvent. Therefore, it is preferably from 60 to 40 minutes, more preferably from 10 to 40 minutes. In the calcination process, the hot film contained in the liquid crystal alignment agent of the present invention is made of a cloth on the middle of the glass, and the compound of the dissociative group is, for example, As described above, the thermally dissociable group decomposes to produce a highly reactive primary or secondary amine. The resulting amine of the first or second grade promotes the ruthenium imidization reaction of the polyimine precursor and/or the polymer of the polyimine contained in the liquid crystal alignment agent, and has a ruthenium imine. At the same time, the crosslinking reaction occurs between the polymers, and the liquid crystal alignment film obtained by the liquid crystal alignment agent can be imparted with a large mechanical strength. An increase in mechanical strength leads to an increase in honing resistance and a stability of liquid crystal properties at a high temperature. When the thickness of the coating film after firing is too thick, it is disadvantageous to the power consumption surface of the liquid crystal display element. If it is too thin, the reliability of the liquid crystal display element is lowered. Therefore, it is preferably 5 to 300 nm, more preferably 10 to 10. 100nm. When the liquid crystal is aligned or tilted horizontally, the film after firing is subjected to treatment such as honing or polarized ultraviolet irradiation. In the liquid crystal display device of the present invention, a substrate to which a liquid crystal alignment film is attached is obtained from the liquid crystal alignment agent of the present invention, and a liquid crystal cell is produced by a known method to obtain a liquid crystal display element. For example, a pair of substrates in which a liquid crystal alignment film is formed may be prepared, and a spacer may be spread on a liquid crystal alignment film of a single substrate so that the liquid crystal alignment film surface is inside. Another single-piece substrate is a method in which a liquid crystal is injected under reduced pressure and then sealed, or a method in which a liquid crystal is dropped on a liquid crystal alignment film surface on which a spacer is dispersed, and a substrate is bonded and sealed. The thickness of the spacer at this time is preferably 1 to 30/zm, more preferably 2 to 1 0 // m 实施 [Examples] -60 - 201209078 Hereinafter, the present invention will be described in more detail, but the present invention will be described in more detail. The present invention is not limited to this and the like. The methods for measuring the codes and the respective characteristics of the compounds used in the examples and the comparative examples are as follows. 1,3DMCBDE-C1 : dimethyl 1,3 -bis(chlorocarbonyl)_ 1,3 -dimethylcyclobutane-2,4-dicarboxylate CBDE-C1: dimethyl 2,4-double (Chlorocarbonyl)cyclobutane-13-dicarboxylate CBDA : 1,2,3,4-cyclobutanine tetradecanoic acid dianhydride PMDA: pyromellitic acid diterpene dry NMP: N-methyl-2- Pyrrolidone GBL : r - butyrolactone BCS : butyl cellosolve PAE : polyphthalate PAA : poly-proline ['HNMR]

Device: Fourier transform type superconducting nuclear magnetic resonance apparatus (FT-NMR) INOVA-400 (Varian) 400MHz Solvent: dihydrogen dimethyl boron (DMSO-d6), heavy hydrogen chloroform (CDC13) Reference material: four矽 矽 ( TM 黏 黏 黏 TM TM ' ' ' ' ' ' ' ' ' ' ' ' ' - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - .lmL, conical rotor TE-1 (1. 34,; R24), temperature 251 were measured. [Molecular weight] The molecular weight of the poly-glycolate is measured by a GPC (normal temperature colloidal permeation chromatography) apparatus, and the number average molecular weight (hereinafter referred to as Μη) is calculated in terms of polyethylene glycol and polyethylene oxide. With a weight average molecular weight (hereinafter referred to as M w ). GPC device: manufactured by Shodex Co., Ltd. (GPC-101) Pipe column: made by Shodex (inline of KD803, KD805)

Column temperature: 50 °C Dissolution: N,N-dimethylformamide (additives, lithium bromide-hydrate (LiBr·H20) is 30 mmol/L, o-acid·anhydrous crystal (〇-phosphoric acid) 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 (Total average molecular weight (Mw)) manufactured by TOSOH (Tosoh Corporation) About 900,000 ' 1 5 0,000 ' 1 00,000 ' 3 0,000 ), and Polymer

Polyethylene glycol manufactured by Laboratories (peak molecular weight (Mp) of about 1 2,000, 4,000, 1, 〇〇〇). In the measurement, in order to avoid overlapping of the peaks, two types of samples of 900,000, 100,000, 12,000, and 1, and a mixture of 150,000, 30,000, and 4,000 were mixed, respectively. -62- 201209078 [FT-IR measurement] Device: NICOLET5700 (manufactured by Thermo ELECTRON) Smart Orbit Accessory Measurement method: ATR method [honing resistance of liquid crystal alignment film] Rotating liquid crystal alignment agent on glass substrate with transparent electrode The film was dried on a hot plate at a temperature of 80 ° C for 5 minutes, and baked at a temperature of 23 ° C for 20 minutes to form a ruthenium imidized film having a film thickness of 1 〇〇 nm. After the coating film was subjected to honing treatment, the surface state of the film was observed, and the presence or absence of honing, the presence or absence of dicing of the film, and the presence or absence of peeling of the film were evaluated. [Liquid alignment] The liquid crystal alignment agent was spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at a temperature of 80 ° C for 5 minutes, and fired in a hot air circulating oven at 230 ° C for 20 minutes. It was formed into a coating film having a film thickness of 100 nm. A honing treatment or a photoalignment treatment is applied to the surface of the coating film to obtain a substrate with a liquid crystal alignment film. Prepare two substrates with such a liquid crystal alignment film, and spread a spacer of 6 m on the liquid crystal alignment film surface of one substrate, so that the alignment of the two substrates is reversed, leaving the liquid crystal injection port and sealing the periphery. , an empty cell with a cell gap of 6 μm was produced. In this empty cell, liquid crystal (MLC-2041, manufactured by Merck) was vacuum-injected at a normal temperature, and the injection port was sealed to form a liquid crystal cell. Using this liquid crystal cell, the liquid crystal alignment property was observed with a polarizing light of -63 - 201209078 顕 micromirror, and the liquid crystal alignment property was evaluated on the basis of the following. &lt;Evaluation criteria> 〇: No flow alignment was observed, and no light leakage was observed under crossed nibs Δ: Flow alignment was slightly observed, and light leakage was observed under crossed nibs. X: Flow alignment is observed in the whole cell. [Voltage Retention Rate] The voltage holding ratio of the liquid crystal cell is measured by applying a voltage of 4 V between 60 // s and measuring the voltage after 16.67 ms to calculate the change from the initial 値. Voltage retention rate. At the time of measurement, the temperature of the liquid crystal cell was adjusted to 23 ° C, 60 ° C, and 90 ° C, and the measurement was performed at each temperature. [Ion Density] The measurement of the ion density of the liquid crystal cell described above was carried out in the following manner. The measurement was carried out using a 6254 liquid crystal physical property evaluation apparatus manufactured by TOYOYO. A triangular wave of 10 V and 0 · 0 1 Hz was applied, and the area corresponding to the ion density of the obtained waveform was calculated by a triangle approximation as the ion density. The measurement was made such that the temperature of the liquid crystal cell was 2 3 . (:, 60: (:, and measured at each temperature) - 64 - 201209078. [Measurement of pretilt angle] The measurement of the pretilt angle of the above liquid crystal cell was measured using AxoScan manufactured by Axometrics Co., Ltd. (Synthesis Example) 1) Synthesis of diamine compound by the 4-stage process shown below (d A -1 Stage 1: Synthesis of compound (A5) [Chem. 54]

(A5) In a 500 mL eggplant flask, propargylamine (8.81 g, 160 mmol), N,N-dimethylformamide (112 mL), potassium carbonate (18.5 g, 134) were placed in sequence. Ment), the temperature was 0 ° C, and it took about 1 hour to dissolve and dissolve t-butyl bromoacetate (21.9 g, 112 mmol) in N,N-dimethylformamide (80 mL) with stirring for about 1 hour. The resulting solution. After the completion of the dropwise addition, the reaction solution was allowed to stand at room temperature and stirred for 20 hours. Thereafter, the solid matter was removed by filtration, and ethyl acetate 1 L' was added to the filtrate, washed with 300 mL of water for 4 times, and washed with 300 mL of saturated saline. Then, the organic layer was dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. Finally, the residual oil was distilled under reduced pressure at 0.6 Torr at 70 ° C to obtain -65-201209078 N-propargylaminoacetic acid t-butyl ester (compound (A5)) as a colorless liquid. The yield was 12.0 g and the yield was 63%. Stage 2: Synthesis of Compound (A6) [Chem. 55]

The above-mentioned N-propargylaminoacetate t-butyl ester (12.0 g, 70.9 mmol) and dichloromethane (600 mL) were placed in a 1 L eggplant flask as a solution, and stirred while stirring under ice cooling. A solution of di-t-butyl vine carbonate (15.5 g, 70.9 mmol) dissolved in dichloromethane (100 mL) was added dropwise over 1 hour. After the completion of the dropwise addition, the reaction solution was allowed to stand in the room gas and stirred 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. Then, the solvent was distilled off under reduced pressure to give N-propargyl-N-t-butoxycarbonylaminoacetic acid t-butyl ester (compound (A6)) as a pale yellow liquid. The yield was 18. g and the yield was 94%. Stage 3: Synthesis of Compound (A?) -66 - 201209078 [Chem. 56]

In a 300 mL four-necked flask, put 2-iodo-4-nitroaniline (225 g, 85.4 mmol), bis(triphenylphosphine), dichloride (1.2 〇g, 丨mmol), copper iodide (0.651 g, 3.42 mmol), after substituting with nitrogen, diethylamine (43.7 g, 598 mmol) &lt;RTI ID=0.0&gt;&gt; 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 the 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 ammonium chloride aqueous solution, and once with 150 mL of saturated brine, and dried over magnesium sulfate. Then, the solvent was distilled off under reduced pressure, and the precipitated solid was dissolved in 200 mL of ethyl acetate, and 1 L of hexane was added to carry out recrystallization. The solid was collected by filtration and dried <RTI ID=0.0> Nitroaniline (compound (A 7 )). The yield was 2 3.0 g and the yield was 6 6 %. Stage 4: Reduction of Compound (A7) The above 2-{3-(Nt-butoxycarbonyl-Nt-butoxycarbonylmethylamino)-1-propyne was added to a 500 mL four-necked flask. Base)}-4-nitro-67- 201209078 aniline (22.0 g, 54·2 mmol) and ethanol (200 g). After replacing the system with nitrogen, add palladium carbon (2.20 g) to hydrogen in the system. Instead, it was stirred at 50 ° C for 48 hours. After completion of the reaction, palladium carbon was removed by filtration through diatomaceous earth, activated carbon was added to the filtrate, and the mixture was stirred at 50 ° C for 30 minutes. Then, the activated carbon was filtered, and the organic solvent was distilled off under reduced pressure, and the residual oil was dried under reduced pressure to give a diamine compound (DA-1). The yield was 19.8 g and the yield was 96%. The diamine compound (DA-1) was confirmed by 1H NMR.

(DA-1) 'Η NMR ( DMSO-de ) : δ 6.5 4-6.42 ( m, 3H, Ar ) , 3.49, 3.47 ( each s, 2H, NCH2C02t-Bu ) , 3.3 8 -3.3 0 ( m, 2H , CH2CH2N), 2.5 1 -2.44 (m, 2H, ArCH2), 1.84- 1.76 (m, 2H, CH2CH2CH2), 1.48- 1.44 (m, 1 8H, NC02t-Bu and CH2C02t-Bu). (Synthesis Example 2) Synthesis of dimethyl 1,3-bis(chlorocarbonyl)-1,3-dimethylcyclobutane-2,4.dicarboxylate (1,3DMCBDE-C1 )-68- 201209078 a -1:4 Synthesis of dialkyl carboxylate [Chem. 58]

0 0 0 〇(5-1) (Μ) (2.1) In a 3 L four-necked flask, put 1,3,3-dimethylcyclobutane-1,2,3,4- in a nitrogen gas stream. Tetracarboxylic dianhydride (compound of formula (5-1), hereinafter referred to as 1,3-DM-CBDA) 220 g (0.981 mol) and methanol 2200 g (6.77 mol, 10 wt. times for 1,3-DM-CBDA) After heating and refluxing at 65 ° C, it became a homogeneous solution after 30 minutes. The reaction solution was stirred under heating and reflux for 4 hours and 30 minutes. The reaction solution was subjected to high-speed liquid chromatography (hereinafter referred to as HPLC). The analysis of the measurement results is as follows. After the solvent is distilled off from the reaction liquid in an evaporator, 130 g of ethyl acetate is added, and the mixture is heated to 80 ° C, and refluxed for 30 minutes. At a rate of 2 to 3 ° C in minutes, the internal temperature was cooled to 25 ° C, and the mixture was stirred at 25 ° C for 30 minutes. The precipitated white crystals were taken out by filtration, and the crystal was washed twice with ethyl acetate 141 g twice. After that, it was dried under reduced pressure to give a white crystals: &lt;RTI ID=0.0&gt;&gt; .5%) (yield 36.8%). 'Η NMR (DMSO-d6, 5ppm); 12.82 (s, 2H), 3.60 (s, 6H), 3.39 (s, 2H), 1.40 (s, 6H). 69 - 201209078

(5-1) (Μ) (2-1) a-2. Synthesis of 1,3-DM-CBDE-Cl [Chem. 60]

In a nitrogen gas stream, a compound (1 - 1 ) 2 3 4.1 5 g (0.81 mol) and η-heptane 1 1 70.77 g (ll.68 mol. 5wt times) were placed in a 3 L four-necked flask, and then hydrazine was added. The ratio was 0.64 g (0.01 mol), and the mixture was heated and stirred to 75 ° C under stirring with a magnetic stirrer. Then, 289.93 g (11.68 mol) of sulfite dichloride was added dropwise for an hour. The foaming started immediately after the dropping, and the reaction solution became uniform after the end of the dropping for 30 minutes, and the foaming was stopped. Subsequently, the mixture was stirred at 75 ° C for 1 hour and 30 minutes, and the solvent was distilled off in a water bath at 40 ° C to obtain a content of 924.42 g. This was heated to 6 ° C to dissolve the crystals precipitated when the solvent was distilled off, and filtered while hot at 60 t. After filtering the insoluble matter, the filtrate was cooled to 2 5 per 1 minute per minute. t so far. After directly stirring at 25 ° C for 30 minutes, the precipitated white crystals were taken out by filtration, and the crystals were washed with η-heptane 264.2 1 g. This was dried under reduced pressure to give 226.09 g of white crystal. Then, 226.09 g of the white crystal obtained and 452.1 g of η-heptane obtained in the above-mentioned three-necked flask were placed in a nitrogen gas stream, and then the mixture was heated and stirred at -70 to 201209078 to 60 ° C to dissolve the crystal. Then, the mixture was cooled to 25 ° C at a rate of i ° C per 〇 〇 minute to precipitate crystals. Directly at 25. (: After stirring for 1 hour, the precipitated white crystals were taken out by filtration, and the crystals were washed with η-hexane 113. 〇 4 g, and then dried under reduced pressure to give white crystals of 203.9 1 g. The crystals were analyzed by 1H NMR. As a result, it was confirmed that the compound (3 -1 ), that is, dimethyl-1,3-bis(chlorocarbonyl)-1,3-dimethylcyclobutane-2,4-dicarboxylate (hereinafter referred to as 1) , 3-DM-CBDE-C1) (HPLC relative area: 99.5 %) (yield 77.2%). 4 NMR (CDC13, δρριη): 3.78 (s, 6H), 3.72 (s, 2H), 1.69 (s (6) (Synthesis Example 3) A 3 L four-necked flask equipped with a stirrer was placed under a nitrogen atmosphere, and ρ-phenylenediamine 1 0.9293 g (0.101 mol) and diamine (DA-1) 10.8177 g (〇) were placed. .0285 mol ), 472 g of NMP and 23.12 g (0.292 mol) of pyridine as a base were added and stirred to dissolve. Then, the diamine solution was added with 1,3DM-CBDE-C1 39_6013 g (0.122 mol) while stirring, under water cooling. The reaction was carried out for 4 hours, and 101 g of NMP 2 was added to the obtained polyphthalate solution, followed by stirring for 30 minutes to obtain a polyglycolate solution having a solid concentration of 5 wt%. The polyglycolate solution was stirred. Into the water of 5247g The precipitated white precipitate was collected by filtration, washed once with 5247 g of water, once with 5247 g of ethanol, and washed 3 times with 1312 g of ethanol, and dried to obtain a white polyphthalate resin powder 45.9. 〇g. The yield is 87.7%. Further, the molecular weight of the polyglycolate is -71 - 201209078

Mn = 16,556, Mw = 35,901. 5.99 g of the obtained polyphthalate resin powder 3 was placed in a 300 ml three-corner flask, and 230.85 g of GBL was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (P AE-1 ). (Synthesis Example 4) A stir-filled 3 L four-necked flask was placed under a nitrogen atmosphere, and 10.532 g (53.12 mmol) of 4,4'-diaminodiphenylmethane was placed, and NMP 197.63 g was added as a base. The mixture was adjusted to 9_00 g (113.8 mmol) and dissolved. Next, 1,3DM-CBDE-C1 15.4194 g (47.42 mmol) was added while stirring the diamine solution, and the mixture was reacted for 4 hours under water cooling. The obtained solution of the polyglycolate was poured into 2196 g of water while stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 2196 g of water, once with 2196 g of ethanol, and washed with 549 g of ethanol. The powder was dried three times and dried to give a white polyphthalate resin powder of 20.37 g. The yield was 92.8%. Further, the polyglycolate has a molecular weight of Mn = U, 659 and Mw = 25,571. 3.9648 g of the obtained polyphthalate resin powder was placed in a 10 mm ml three-corner flask, and 35.7135 g of NMP was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-2). (Synthesis Example 5)

CBDA 5.8936g (30.05mmol) was placed in a l〇〇mL four-necked flask equipped with a stirring device and a nitrogen inlet tube, and then NMP-72-201209078 56.11g was placed in a stirred state, and the mixture was stirred while being fed with nitrogen. shape. While stirring this slurry, p-PDA 3.0196 g (27.92 mmol) was added thereto, and NMP was added thereto so that the solid content concentration was 1% by mass, and the mixture was stirred at room temperature for 24 hours to obtain a solution of polyamine acid (PAA-1). The polyamic acid solution has a viscosity of 136.5 mPa·s at a temperature of 25 ° C. Further, the molecular weight of the polyproline is Mn = 1 3,391, Mw = 3 2,745. (Example 1) Synthesis of Compound (Ι-a) [Chem. 61]

Phase 1 Synthesis of precursor (Ι-al) [Chem. 62]

In a 300 ml four-necked flask, 18.78 g (92.68 mm 〇l) of 2-(4 nitrophenyl)ethylamine hydrochloride was placed, followed by the addition of toluene 152 mi, triethylamine 9.847 g (97.3 1 mmol). ), (TC (冰洛) 善祥. -73- 201209078 Into the dropping funnel was placed 21.24g (97.31mmol) of di-tert-butyl dicarbonate, and it took 30 minutes to drip into the solution of the four-necked flask After the completion of the dropwise addition, the mixture was stirred at room temperature (20 ° C) for 8 hours. After the completion of the reaction, 500 ml of pure water was added to the reaction solution and extracted. The obtained organic layer was washed twice with pure water to give anhydrous magnesium sulfate. After the desiccant was removed, the solvent was evaporated to give a white solid. To a white solid, hexane (1 ml) and ethyl acetate (20 ml) were added to recrystallize. The precipitated solid was vacuum filtered and dried under reduced pressure. The white solid obtained was confirmed to be the precursor (Ι-al) by 1 H NMR. The yield was 20.92 g, and the yield was 85%. 'H NMR (400 MHz, CDC13, 6 ppm): 1.4 3 (s, 9 Η ), 2 · 9 2 (t, J = 6.8Hz, 2H ) , 3.41(q, J = 6.8Hz, 2H) , 4.56(bs, 1H), 7.35(d, J = 8.8Hz, 2H ) , 8. 16(d , J = 8.8Hz, 2H ) · Stage 2: Synthesis of precursor (l-a2) [Chem. 63]

(l-a2) In a 500 ml eggplant type flask, a precursor (i_al) of 2〇.90 g (78.49 mmol) was added to add tetrahydrofuran to 200 m 1 . After the reaction vessel was replaced with nitrogen, palladium carbon 2·0 9 g ' was added and replaced with nitrogen. The reaction vessel was replaced with hydrogen and stirred at 20 ° C for 19 hours. After completion of the reaction, palladium carbon was removed by filtration through diatomaceous earth, and the solvent was removed from the filtrate to obtain a white solid. The obtained solid was dissolved in 20 ml of acetate, and recrystallized by adding hexane 140mi, -74-201209078. The precipitated solid was collected by vacuum filtration and dried under reduced pressure. The white solid obtained was confirmed to be a precursor (b&amp;2) yield of 16.54 g and a yield of 89% by 1 H NMR. H NMR (400MHz, CDC13, δρρπι ) : 1 · 4 3 (s,9 Η ), 2 · 6 7 (t, J = 6.8Hz, 2H ) , 3.31(q, J = 6.8Hz, 2H) , 3.59 (bs, 2H), 4.52 (bs, 1H), 6.64 (d, J = 8.0 Hz, 2H), 6.97 (d, J = 8.0 Hz, 2H). Stage 3: Synthesis of compound (1-a) A 100 ml four-necked flask was placed under a nitrogen atmosphere, and 1,3DM-CBDE-C1 5.00 g (15.38 mmol) was placed therein, followed by the addition of 25 ml of tetrahydrofuran (dehydrated) and 2.68 g (33.83 mmol) of pyridine, and stirred to obtain an acid chloride. Solution. Next, 7.45 g (3 1.53 mmol) of the precursor (1 - a2 ) was placed in a 1 〇〇 ml Erlenmeyer flask, followed by the addition of 15 ml of tetrahydrofuran (dehydrogenation) as a monoamine solution. The monoamine solution was transferred to a dropping funnel, and the monoamine solution was dropped into a four-necked flask over 15 minutes. After dropping, it was stirred for 20 hours. After 20 hours, the reaction solution was poured into 200 ml of water, and 100 ml of chloroform was added for extraction. The obtained organic layer was washed twice with pure water and dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was distilled off to obtain a white solid. The obtained solid was dissolved in 30 ml of tetrahydrofuran, and 1 ml of diisopropyl ether was added thereto to carry out recrystallization. The precipitated solid was collected by vacuum filtration and dried under reduced pressure. The white solid obtained was confirmed to be a compound (Ι-a) by 1H NMR. The yield was 8.38 g and the yield was 75%. 4 NMR ( 400MHz, CDC13, δρρπι ) : 1.43(s,18H ), -75- 201209078 1.58(s, 6H ) , 2.78(t, J = 6.8Hz, 4H ) , 3.53(m, 4H ), 3.84(s , 6H ) , 4.1〇(s, 2H ) , 4.55(bs, 2H ) , 7.18(d, J = 8.0Hz, 4H) , 7.45(d, J = 8.0Hz, 4H ), 8.62(s, 2H). (Example 2) Synthesis of Compound (1-b) [Chem. 64] ^y\\Xjl〇Me

&gt;NH (1-b) Hereinafter, the compound (1 -b) is synthesized in a three-stage process. Stage 1: Synthesis of the precursor (丨-b1) [Chem. 65] In the flask, 8.95 g (44.30 mmol) of 4-bromonitrobenzene, 0.3llg (〇.44 mmol) of bis(triphenylphosphine)palladium(II) dichloride, and 0.169 g (0.89 mmol) of copper were placed. 5.38 g (53.16 mmol) of triethylamine was added to tetrahydrofuran 30 ml' and stirred at room temperature (20 ° C) for 10 minutes. Next, 8.25 g (53.16 mmol) of N-(tert-butoxycarbonyl)propargylamine was placed in a 10 ml Erlenmeyer flask, and 15 ml of tetrahydrofuran was added and dissolved. This solution was transferred to a -76-201209078 funnel and it took 5 minutes to drip the solution into the four-necked flask. After the dropwise addition, the mixture was stirred under heating at 60 ° C for 3 hours. After 3 hours, the reaction solution was poured into 250 ml of pure water to precipitate a solid. After the precipitated solid was collected by vacuum, the obtained solid was dissolved in 40 ml of toluene, and 25 ml of hexane was added to carry out recrystallization. The precipitated solid was collected by vacuum filtration and dried under reduced pressure. The obtained brown solid was confirmed to be a precursor (Ι-bl) by 1 H NMR. The yield was 7.66 g and the yield was 62.5%. *H NMR (400MHz, CDC13, 5ppm): 1 · 4 3 ( s, 9 H ), 4.2 0 (s, 2H ) , 4.82 (bs, 1H ) , 7.56 (d, J-8.0Hz, 2H) , 8.18 (d, J = 8.0Hz, 2H ). Stage 2: Synthesis of precursor (l-b2) [Chem. 66]

(l-b2) Into a 500 ml eggplant type flask, a precursor (l-bl) of 12.87 g (46.58 mmol) was added and 130 ml of methanol was added. After the reaction vessel was replaced with nitrogen, palladium carbon 1.28 g' was added and replaced with nitrogen. The reaction vessel was replaced with hydrogen and stirred with heating at 50 ° C for 24 hours. After completion of the reaction, palladium carbon was removed by filtration through diatomaceous earth, and the solvent was removed from the filtrate to obtain a brown sugary compound. The obtained saccharide compound was purified by ruthenium dioxide colloidal column chromatography (ethyl acetate: hexane = 50: 50) to give a brown sugar compound -77-201209078. The obtained brownish sugary compound was confirmed to be a precursor b2) by 1 H NMR. The yield was 4.42 g and the yield was 37.9%. 1H NMR (400MHz, CDC13, 5ppm): 1.43 (s, 1 , 75 (quin, J = 6.8Hz, 2H ) , 2.55 (t, J = 6.8Hz, 2H ), J-6.8Hz, 2H ) , 3.59(bs, 2H ) , 4.56(bs, 1 H ) J = 8.0Hz, 2H ) , 6.96(d, J = 8.0Hz, 2H ). Stage 3: Synthesis of compound (1-b) makes 100ml of four The flask was placed under a nitrogen atmosphere, and CBDE-C1 2.40 g ( 15.38 mmol) was added thereto, followed by 10 ml of tetrahydrofuran water and 1.29 g (16.24 mmol) of pyridine, and stirred to obtain a chloride solution. Next, a precursor b2) 4.07 g (16.24 mmol) was placed in a 50 ml Erlenmeyer flask, followed by the addition of tetrahydrofuran (10 ml as a monoamine solution. The monoamine solution was transferred to the dropping funnel for 5 minutes to separate the monoamine solution. The mixture was dropped into a four-necked flask. After the dropwise addition, the mixture was stirred for 3 hours. After 20 hours, the reaction solution was poured into 60 ml of water and imitation was carried out in 40 ml, and the obtained organic layer was washed with pure water and dried over anhydrous magnesium sulfate. After the desiccant, the solvent was distilled off to give the obtained product. The obtained solid was purified by silica gel column chromatography (ethyl acetate = 1 : 1) to give a white solid. b). Yield · 3.72 g, yield %. 1H NMR (400 MHz, DMSO-d6, δρρηι): 1.43 (s, 1.58 (s, 6H), 1.67 (quin, J = 6.8 Hz, 4H), 2.55 (m, body (1 - 9H), 3.16 (q, 6.67 (d, 1 , 3DM- s (dehydrated to acid (1-dehydrated), spent half a small addition of chlorine, as a white solid ester: recognized The resulting Μ 6 6.9 1 8 Η ), 4 Η ), -78- 201209078 2.97 (q, J = 6.8 Hz, 4H), 3, 59 (s, 6H), 3.62 (s, 2H), 6.86 (t, J = 6.8 Hz, 2H ) » 7.16(d, J = Synthesis of 8.0 Hz, 4H), 7.45 (d, J = 8.0 Hz, 4H), 9.43 (s, 2H).) (Example 3) Compound [Chem. 67]

(1-c) Hereinafter, the compound (1-c) was synthesized in a three-stage process. Stage 1: Synthesis of Precursor (1-cl) [Chem. 68]

(1-cl) 3-bromopropylamine hydrogen bromide 5 0.42 g (0.23 0 mol) was placed in a 2 L four-necked flask, and 672 g of dichloromethane and di-tert-butyl dicarbonate 56.28 g were added. (0.258 mol), in 〇. (: (ice bath) stirring. 60.86 g (〇-471 mol) of N,N-fluorene diisopropylethylamine was placed in the dropping funnel, and it was dropped into the slurry solution in the four-necked flask over 30 minutes. After the start, the reaction solution was vigorously foamed, and a white solid precipitated. After the completion of the dropwise addition, the mixture was stirred for 3 hours. After the completion of the reaction, -79-201209078 was added to the reaction solution to obtain pure water of 500 ml, and the mixture was extracted. The organic layer was washed twice with pure water and dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was evaporated to give a colorless, transparent oil. hexane (500 ml) was added to the oily substance at -7 8 ° C. The crystals were crystallized to give a white solid.yield, which was taken in vacuo and dried under reduced pressure. The white solid obtained was confirmed by 1H NMR as tert-butyl-3-bromopropylcarbamate, the precursor (Ι-cl). The yield was 42.99 g and the yield was 78.5%. lH NMR (400 MHz, CDC13, δρρηι) : 1.44 (s, 9 Η ), 2.05 (quin, J = 6.4 Hz, 2H ) , 3.27 (q, J = 6.4 Hz, 2H), 3, 45 (t, J = 6.4 Hz, 2H), 4.69 (bs, 1 H ). Stage 2: Synthesis of precursor (l-c2) [Chem. 69]

D-c2) A precursor (1-cl) 40.00 g (0.168 mol) and potassium carbonate 32.86 g (0-238 mol) were placed in a 1 L four-necked flask, and DMF 48 1 g was added thereto, and the mixture was stirred under heating at 60 ° C for 7 hours. After 7 hours, the obtained reaction solution was poured into 3 L of pure water with stirring, and 1 L of acetate was added thereto for extraction. The obtained organic layer was washed twice with pure water, washed with 500 ml of a 1 N aqueous solution of sodium hydroxide, and dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was distilled off to give a yellow solid. The obtained solid was dissolved in acetate -80 - 201209078 200 ml, and 1 L of hexane was added thereto with stirring to precipitate a solid. The resulting solid was vacuum filtered and dried under reduced pressure. The obtained yellow solid was confirmed to be a precursor (1-c2) by 1H NMR. The yield was 35.49 g, the yield was 71.3% 〇*H NMR (400 MHz, CDC13, 6 ppm): 1.44 (s, 9H) 2.03 (quin, J = 6.4 Hz, 2H), 3.3 4 (q, J = 6.4) H z,2 H ) , 4.12(t, J = 6.4Hz, 2H ) , 4.72(bs, 1H ) , 6.95(d, 8.0Hz, 2H ) 8.20(d, 8.0Hz, 2H ). Stage 3: Precursor Synthesis of body (1-C3) [70]

(l-c3) A precursor (1-C2) 30_04 g (0.102 m〇l) was placed in a 500 ml eggplant type flask, and 17 〇g of ethanol was added. After the reaction vessel was replaced with nitrogen, 3 · 1 1 g of palladium carbon was added and replaced with nitrogen. The reaction vessel was replaced with hydrogen and stirred at 20 ° C for 48 hours. After completion of the reaction, the palladium carbon was removed by filtration through diatomaceous earth, and the solvent was removed from the filtrate to obtain a solid. The obtained solid was dissolved in an acetate of 10 μm, and 400 ml of hexane was added thereto with stirring, and a white solid was precipitated by further cooling to -50 °C. The precipitated solid was collected by vacuum filtration and dried under reduced pressure. The yellow solid obtained was confirmed to be a precursor (1-c3) by 1 H NMR. The yield was 26.64 g and the yield was 97.7%. -81 - 201209078 1H NMR ( 400MHz, CDC13, δρρηι ) : 1.44(s, 9Η ), 1.93 (quin, J = 6.4Hz, 2H ) , 3 . 3 2 (q, J = 6.4Hz, 2H ), 3.44( Bs, 2H), 3.94 (t, J = 6.4 Hz, 2H), 4.85 (bs, 1H), 6.63 (d, 8.0 Hz, 2H), 6.73 (d, 8.0 Hz, 2H). Stage 4: Compound ( Synthesis of 1-c) A 3 L four-necked flask equipped with a stirring apparatus was placed in a nitrogen atmosphere to place a precursor (l-c3) 12.26 g (46.0 mmol)' and NMP 241 g was added as a base of 5.31 g of a pyridinium ( 67.lmmo1) 'Stirring to dissolve. Next, while stirring this monoamine solution, 1,3DM-CBDE-C1 7.43 g (22.9 mol) was added, and the mixture was reacted for 4 hours under water cooling. The obtained reaction solution was poured into 800 g of water while stirring, and the precipitated white precipitate was collected by filtration. Then, it was washed once with 1800 g of water, once with 1800 g of ethanol, and 3 times with 540 g of ethanol. A white solid was obtained. The obtained white solid was dissolved in ethyl acetate and hexane was added to carry out recrystallization. The precipitated solid was vacuum filtered and dried under reduced pressure. The yellow solid obtained was confirmed to be the precursor (hc) by 1H NMR. The yield was 15.23 g and the yield was 84.4%. 1H NMR (400MHz, CDCI3 δρρηι ) : 1.44(s, 1 8 Η ), 1. 5 8 ( s , 6 Η ) , 1.97 (quin, J = 6.4Hz, 4Η ), 3.3 1 ( q, J = 6 · 4 Η ζ, 4Η), 3.85(8, 6Η), 3 · 9 9 (t, J = 6.4 Η ζ, 4 Η), 4.80(bs, 2Η), 6.85(d, 8.0Hz, 4Η), 7.42( d, 8.0 Hz, 4 Η ) , 8.50 (s, 2H ) · (Example 4) Synthesis of compound (1 -d ) -82 - 201209078 [Chem. 71] Η 9 9

A 3 L four-necked flask equipped with a stirrer was placed under nitrogen atmosphere to place 2,5-bis(methoxycarbonyl)terephthalic acid 1.87 ru (6.631110101), pyridine ll 〇g (13.9 mmol), and dehydrated tetrahydrofuran was added. 40m 1 'heated back. To the solution was added sulfoxide dichloride i.54 g ( 12.9 mmol), and the mixture was heated under reflux for 1 hour. After 1 hour, the precursor (l-a2) 3.13 g (19.56 mmol) was placed in the reaction solution, and the mixture was heated to reflux for 2 hours. The obtained reaction solution was poured into 500 g of water while stirring, and the precipitated white precipitate was collected by filtration. Then, it was washed once with 500 g of water, once with 50 g of methanol, and washed three times with 240 g of methanol. , a white solid was obtained. The obtained white solid was placed in a 200 ml eggplant type flask, and 100 ml of ethyl acetate was added thereto, followed by heating and stirring. The residual solid was collected by vacuum and dried under reduced pressure. The white solid obtained was confirmed to be the compound (丨-d) by 1H NMR. The yield was 1.97 g and the yield was 41.4%. *H NMR (400MHz, DMSO-d6 5ppm): 1 · 3 8 (s,1 8 Η ), 2.67(t, J = 8.0Hz, 4H) , 3.13(q J = 8.0Hz, 4H) , 3.81(s , 6H ), 6.89 (t, J = 5.6Hz, 2H), 7.18(d, 8.8Hz, 4H), 7.42(d, 8.8Hz, 4H) , 8.03(s,2H) , l〇.56(s, 2H). -83- 201209078 (Example 5) Synthesis of Compound (1 -j ) [Chem. 72]

HN

OMe

NH (ij) A 30 ml four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, and the body (l-a2) was 1.04 g (4.42 mmol), and NMP 20 g was added as a base. (7.43 mmol) was stirred to dissolve. Next, 0.68 g (2.22 m) of CBDE-C1 was added while stirring the monoamine solution, and the mixture was reacted for 2 hours under water cooling. The obtained reaction solution was poured into 200 g of water with stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 200 g of water, once with 200 g of ethanol, and washed with 100 g of ethanol three times. A white solid was obtained. The obtained white solid was placed in a 50 ml eggplant type flask, and 30 ml of ethyl acetate was added thereto, and the mixture was stirred under heating at 80 ° C for 30 minutes. After 30 minutes, the residual solid was collected by vacuum and dried under reduced pressure. The obtained white solid was confirmed by NMR as a precursor (?-j). The yield was 0.42 g 'yield 27.3 %. 1H NMR (400MHz, DMSO-d6 5ppm): 1.33 (s, 18H), 1 , 58 (s, 6H ) , 2.59 (t, J = 7.2 Hz, 4H ) , 3.0 6 (q, J = 7.2 Η z, 4H), 3.47 (s, 6H), 3.56 to 3.63 (m, 2H), 3.86 to 3.91 (m, 2H), 6.83 (t, J = 5.6 Hz, 4H), 7.08 (d, 8.4 Hz, 4H), 7.43 (d, 8.4 Hz, 4H), 10.10 (s, 2H). 201209078 (Example 6) Synthesis of compound (1 - k ) [Chem. 73]

(1-k) A 30 ml four-necked flask equipped with a stirring apparatus was placed under a nitrogen atmosphere, and a precursor (l-c3) of 1.06 g (3.99 mmol) was placed, and 20 g of NMP was added as a base of pyridinium.58 g ( 7.43 mmol). Stir and dissolve to dissolve. Next, 0.658 g (1.99 mol) of CBDE-C1 was added while stirring the monoamine solution, and the mixture was reacted for 2 hours under water cooling. The obtained reaction solution was poured into 200 g of water with stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 200 g of water, once with 200 g of ethanol, and washed with 100 g of ethanol. Three times, a white solid was obtained. The obtained white solid was placed in a 50 ml eggplant type flask, and 30 ml of ethyl acetate was added thereto, and the mixture was stirred for 30 minutes at 8 (TC). After 30 minutes, the residual solid was collected by vacuum filtration and dried under reduced pressure. The white solid was the precursor (1-k). The yield was 0.58 g, and the yield was 38.4%. » H NMR (400 MHz, DMSO-d6 δρριη) : 1,44 (s, 1 8 Η ), 1.79 (quin, J = 6.4 Hz, 4H), 3, 06 (q, J = 6.4 Hz, 4H), 3.60 (s, 6H), 3.59 to 3.66 (m, 2H), 3.86 to 3.96 (m, 6H), 6.86 (d, 8.0 Hz, 4H), 6.90 (t, J = 6.4 Hz, 2H), 7.46 (d, 8.0 Hz, 4H), 10.06 (s, 2H). -85-201209078 (Example 7) Synthesis of compound (li) [化74]

C

NH A 50 ml two-necked flask equipped with a stirring apparatus was placed under a nitrogen atmosphere, and 2,5-bis(methoxycarbonyl)terephthalic acid 0.628 (2.2〇111111〇1) and pyridine 0.38 g (4.80 mmol) were placed and dehydrated. 20 ml of tetrahydrofuran was heated and refluxed. To this solution, 0.55 g (4.22 mmol) of sulfoxide dichloride was added, and the mixture was heated under reflux for 1 hour. After 1 hour, 1.23 g (4.62 mmol) of the precursor (1-c3) was placed in the reaction mixture, and the mixture was heated to reflux for 2 hours. The obtained reaction solution was poured into 200 g of water while stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 1 g of water, once with 10 g of ethanol, and washed with 50 g of ethanol. Net 3 times' to get a pale yellow solid. The obtained pale yellow solid was placed in a 50 ml eggplant type flask, and 20 ml of ethyl acetate was added thereto, followed by heating and stirring. The residual solid was vacuum filtered and dried under reduced pressure. The white solid obtained was confirmed to be the compound (1 - i ) by 1H NMR. The yield was 57.57 g and the yield was 33.1%. 1H NMR (400MHz, DMSO-d6 δρρηι ) : 1.38 (s, 18Η), 1.83 (quin, J = 6.4Hz, 4H) , 3.08 (q J = 6.4Hz, 4H ) , 3.81(s, 6H ), 3.96 ( t, J = 6.4 Hz, 4H ), 6.86 ~ 7.00 (m, 6H ), 7.58 (d, 7.2 Hz, 4H), 8.02 (s, 2H), l〇.47 (s, 2H) · -86- 201209078 (Example 8) Modulation of a solution containing the compound (1 -e ) [Chem. 75]

In a 5 〇 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube, 2.37 g (10_03 mmol) of the precursor (l-a2) was placed, followed by the addition of 9.40 g of NMP, followed by stirring with nitrogen gas to form a monoamine. Solution. While stirring the monoamine solution, 0.98 g (5.00 mmol) of CBDA was added, and further NMP was added to adjust the solid content concentration to 20% by mass, and the mixture was stirred at room temperature for 24 hours to obtain a solution containing the compound (1 - e ). To a part of the obtained solution, 1 -methyl-3 - p-tolyltriazene was added, and after methylation of the carboxylic acid, it was confirmed by 1 NMR that the same as (1) obtained in Example 5 was obtained. Compound. From this, it was confirmed that the above solution contained (1 - e ). (Example 9) Modulation of a solution containing a compound (Ι-f) [Chem. 76]

-87- 201209078 Into a 5 OmL four-necked flask equipped with a stirring device and a nitrogen inlet tube, a precursor (l-a2) of 2.37 g (10.03 mmol) was placed, followed by addition of 9.62 g of NMP, and stirred while feeding nitrogen gas. And a monoamine solution. To the monoamine solution, 1.09 g (5.00 mmol) of PMDA was added, and further NMP was added to adjust the solid content concentration to 20% by mass, and the mixture was stirred at room temperature for 24 hours to obtain a solution containing the compound (Ι-f). - a part of the obtained solution was added with methyl 3-(3-p-tolyltriazene), and methyl esterification of the carboxylic acid was carried out, and it was confirmed by 1 H NMR that it was the same as (1 -d) obtained in Example 4. compound of. From this, it was confirmed that the above solution contained (1-f). (Example 1 〇 ) Modulation of a solution containing a compound (1-g) [Chem. 77]

(]-g) In a 5 OmL four-necked flask equipped with a stirring device and a nitrogen inlet tube, 2.66 g (9.99 mmol) of the precursor (1-c3) was placed, followed by NMP 10.1 9 g, and nitrogen gas was introduced. Stir, but a monoamine solution. While stirring the monoamine solution, 1.09 g (5.00 mmol) of CBDA was added, and further NMP was added to adjust the solid content concentration to 20% by mass, and the mixture was stirred at room temperature for 24 hours to obtain a solution containing the compound (1-g). To a portion of the obtained solution, 1-methyl-3-P-tolyltri-88-201209078 nitrone was added to carry out methyl esterification of the carboxylic acid, and it was confirmed by 1 H NMR that the obtained product obtained in Example 6 was obtained. (1 - k ) the same compound. From this, it was confirmed that (1 - g ) was contained in the above solution. (Example 1 1) Modification of a solution containing the compound (1 -h ) [Chem. 78]

HN

The precursor (l-c3) 3_99g (15.0mmol) was placed in a 50 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, and then NMP 16.9 lg was added thereto, and the mixture was stirred while being fed with nitrogen gas. Amine solution. While stirring this monoamine solution, PMDAl.64 g (7.52 mmol) was added, and further NMP was added to adjust the solid content concentration to 20% by mass, and the mixture was stirred at room temperature for 24 hours to obtain a solution containing the compound (1-h). To a portion of the obtained solution, 1-methyl-3- p-tolyltriazene was added, and methylation of the carboxylic acid was carried out, and it was confirmed by 1 NMR; as obtained in Example 7 ( 1 -i ) the same compound. From this, it was confirmed that (上述-h) was contained in the above solution. (Example 1 2) In a 100 ml Erlenmeyer flask, 44.3382 g of the polyamidate solution (PAE-1) obtained in Synthesis Example 3 was placed, followed by addition of GBL 19.6930 g, -89-201209078 BCS 1 6.0 8 3 9 g, a dilute solution of polyglycolate was obtained. In the 2 〇ml sample tube in which the stirrer was placed, the above solution was 5 · 02 g, and then the compound obtained in Example 1 "τ, VJ ^ 1 - a ) 〇. 064 5 g (pairing The repeating unit of the glutamate is 1 莫1 莫 $ stomach stomach ≥ completely dissolved, obtained, and stirred at room temperature for 30 minutes to make the compound (ia) liquid crystal alignment agent (A 1 -1 ). Example 1 3) In place of the compound (i -c ) obtained in Example 3, except for the repeating unit of the polyphthalate, 1 molar, stomach sputum 1 stomach ear equivalent, instead of the compound (1 - a ) The remainder was carried out in the same manner as in Example 1 2 to obtain a liquid crystal alignment agent (A 1 - 2 ). (Example 1 4 ) Except that the repeating unit of the compound (Ι-e ) to the polyphthalate was 1 mol. A liquid crystal alignment agent (a) was obtained in the same manner as in Example 12 except that a solution containing the compound (1-e) obtained in Example 8 was added in an amount of 0.1 mol% to replace the compound (1 - a ). 1 _3) (Example 1 5) The addition of the compound obtained in Example 9 was carried out except that the repeating unit of the compound (Ι-f) to the polyphthalate was 0.1 mol. The liquid crystal alignment agent (A 1 - 4 ) was obtained in the same manner as in Example 12 except that the solution of the compound ( 1 -f ) was replaced with the compound (1 - a ). -90 - 201209078 (Example 1 6 A liquid crystal alignment was obtained by adding a solution of the formula (Ι-g) in an amount of 0.1 mol per equivalent of the compound (1 - g ) to the polyamidophenone instead of the compound (1-a). (Example 1 7) A solution of β (1-h ) was added in place of the compound (1-a) except that the compound (Ι-h) was 0.1 mol equivalent to polyammonium. 2 A liquid crystal alignment agent was obtained in the same manner. (Example 18) A polyamine solution (PAE-2) obtained by placing a 20 ml sample tube with a stir bar 4 NMP 1.4837 g, BCS 1.502 1 g &gt Addition of 7 (1-a) 0.1 02 3g (0.2 mole equivalent to polyglycolate), stirring at room temperature for 30) to completely dissolve to obtain liquid crystal alignment agent (A2-1) (Example 1 9) Except for the compound containing the repeating unit of the compound acid ester obtained in Example 4, which is obtained by repeating the unit of the ear amine equivalent of the polyphthalate, the other compound is carried out with A 1-5). In the same manner as in the case of the compound containing the compound obtained in the above-mentioned 1/6) 0, 4560 g of the synthesis example 4 was placed, and then the compound repeating unit obtained in Example 1 was added to 1 mol. In a minute, the compound (1 - a 1 molar is 0.2 mol (Ι-d) to replace the compound 91 - 201209078 (1 - a ), and the rest is carried out in the same manner as in the example i 8 to obtain a liquid crystal alignment. Agent (A 2 - 2 ). (Example 20) A solution containing the compound (1-e) obtained in Example 8 was added instead of the compound (Ι-e) to 0.2 moles of the repeating unit of the polyphthalate. The liquid crystal alignment agent (A 2 · 3 ) was obtained in the same manner as in Example 18 except for the compound (1 - a). (Example 2 1 ) The compound (1 -f) obtained in Example 9 was added except that the compound (Ι-f) was a 〇 2 molar equivalent of the repeating unit of the polyphthalate. The liquid crystal alignment agent (A2-4) was obtained in the same manner as in Example 18 except that the solution was replaced with the compound (1-a). (Example 22) Into a 20 ml sample tube in which a stir bar was placed, 4.4156 g of a polyfluorene. Amino acid solution (PAA-1) obtained in Synthesis Example 5 was placed, followed by NMp 1.3 409 g and BCS 1.4426 g. Further, the compound (1-a) obtained in Example 1 was 0.21 13 g (the molar unit of poly-proline was 1 莫2 molar equivalent), and the mixture was stirred at room temperature for 30 minutes to obtain a compound (1 _a). The liquid crystal alignment agent (A3-1) is completely dissolved. (Example 2 3 ) -92- 201209078 The compound (1 - a ) was replaced with the compound (Ι-d) obtained in Example 4 except that the repeating unit of poly-proline was 1 mol. The liquid crystal alignment agent (A3-2) was obtained in the same manner as in Example 22 except for the same. (Example 24) A solution containing the compound (Ιέ) obtained in Example 8 was added in place of the compound (Ι), except that the compound (Ι-e) was 0.2 molar equivalent to the repeat unit of polyglycine. The liquid crystal alignment agent (A3-3) was obtained in the same manner as in Example 22 except for -a). (Example 25) The addition of the compound (1-f)-containing solution obtained in Example 9 was carried out except that the compound (1-f) was added in an amount of 0.2 mol per mol of the repeating unit of polyglycine. The liquid crystal alignment agent (A 3 - 4 ) was obtained in the same manner as in Example 22. (Comparative Example 1) Into a 20 ml sample tube in which a stir bar was placed, 2.7692 g of a polyamidomate solution (PAE-1) obtained in Synthesis Example 3 was placed, followed by addition of GBL 1.23 08 g and BCS 1.012 g. The mixture was stirred at room temperature for 30 minutes to obtain a liquid crystal alignment agent (B 1 -1 ). (Comparative Example 2) -93- 201209078 Into a 20 m crucible sample tube in which a stir bar was placed, a synthetic polyamine solution (PAE-2) 4.343 1 g was placed, followed by 'NMP 1.4722 g, BCS L_4589g, stir the liquid crystal alignment agent (B2-1) for 30 minutes at room temperature. (Comparative Example 3) Into a 20 ml sample tube in which a stir bar was placed, 4.7100 g of a polyamine solution (PAE-2) obtained in the synthesis example was placed, followed by NMP 1.5935 g and BCS 1.5892 g, and then added. Example 1 obtained;; body (l-a2) 0.0985 g (repeating unit for polyphthalate is 1 ^ 0.4 molar equivalent), stirred at room temperature for 30 minutes to obtain a nominal agent (Β 2-2 ) . (Comparative Example 4) Into a 20 ml sample tube in which a stirrer was placed, a polyacrylic acid solution (PAA-1) of the synthesis example was placed in 3.97 75 g, followed by the addition of l_2069 g, BCS 1.2953 g, and stirring at room temperature. For 30 minutes, 3 interdoning agents (B 3 -1 ) were obtained. (Comparative Example 5) Into a 2 〇 ml sample tube in which a stir bar was placed, a polyacrylic acid solution (PAA-1) of 4 to 3 645 g of the synthesis example was placed, followed by addition of 1.3462 g, BCS 1.4297 g, and then Adding Example 1 before the end l-a2) 0.1 3 5 7g (for the repeating unit of poly-proline, 1 M is added, 4 is added to the front ear and the crystal is matched with 5 NMP liquid crystal 5 NMP The mixture was stirred at room temperature for 30 minutes to obtain a liquid crystal alignment agent (B3-2). (Example 26) The liquid crystal alignment agent obtained in Example 12 (A 1 -1) After filtering with a membrane filter of 1.0 m, it was spin-coated on a glass substrate, dried on a hot plate of temperature 8 (TC for 5 minutes, and then fired at 230 ° C for 1 , minutes to obtain a film. The film was imidized by a thickness of 100 nm. The film was taken, and the FT-IR spectrum was measured by the ATR method, and the yield of ruthenium was calculated. The results are shown in Table 1. (Examples 27 to 31) The liquid crystal alignment agents (A1-2) to (A1-6) obtained in Examples 13 to 17 were subjected to the same operation as in Example 26 to prepare a ruthenium imidized film, and the FT-IR spectrum was measured and calculated. The imidization ratio is shown in the table (Comparative Example 6) Using the liquid crystal alignment agent (B 1 -1) obtained in Comparative Example 1, a ruthenium imidized film was produced in the same manner as in Example 26, and FT- was measured. IR spectrum, and the yield of hydrazine imidation was calculated. The results are shown in Table 1. -95-201209078 [Table 1] Liquid crystal alignment agent additive (addition amount) Firing time 醯 imidization ratio Example 26 AM Compound (la) (0.1) 10 minutes 84% Example 27 A1-2 Compound (lc) (0.1) 10:78% Example 28 A1-3 Compound (le) (0.1) 10:72% Example 29 A1-4 Compound (1) - _) 10 minutes 70% Example 30 A1-5 Compound (lg) (〇.l) 10 minutes 66% Example 31 A1-6 Compound (lh) (0.1) 10 minutes 65% Comparative Example 6 B1-1 _ 10 minutes and 60% From the results of Examples 2 6 to 3 1 and Comparative Example 6, it was confirmed that the compound of the present invention can promote the ruthenium imidization reaction of polyphthalate. (Example 3 2 ) Example 1 8 The obtained liquid crystal alignment agent (A2-1) was filtered through a membrane filter of 1 · 0 em, and then spin-coated on a glass substrate, and dried on a hot plate at a temperature of 80 ° C for 5 minutes, and then 2 3 0 °C is baked for 丨〇 minutes to obtain a film (PEI) of the film was 1 OOnm. This coating film was taken, and the FT-IR spectrum was measured by the ATR method, and the yield of hydrazine imidation was calculated. The results are shown in Table 2. (Example 3 3 to 3 5) Using the liquid crystal alignment agents (A2-2) to (A2-4) of the present invention obtained in Examples 9 to 2, the same procedure as in Example 32 was carried out to prepare a yoke. The aminated film was subjected to measurement of FT-IR spectrum, and the yield of ruthenium was calculated. The results are shown in Table 2. (Comparative Examples 7 to 8) -96-201209078 Using the liquid crystal alignment agents (B 2 -1 ) and (B2-2 ) obtained in Comparative Examples 2 and 3, the ruthenium imidization was carried out in the same manner as in Example 32. The film was measured for FT-IR spectrum' and the yield of ruthenium was calculated. The results are shown in Table 2 [Table 2] Liquid crystal alignment agent additive (addition amount) Firing time 醯 imidization ratio Example 32 A2-1 Compound (la) (0.2) 10 minutes 100% Example 33 A2-2 Compound ( Ld) (0.2) 10 minutes 52% Example 34 A2-3 Compound (le) (0.2) 10 minutes 67% Example 35 A2-4 Compound (lf) (〇.2) 10 minutes 60% Comparative Example 7 B2- 1 _ 10 minutes 22% Comparative Example 8 B2-2 precursor (l-a2) (0.4) 10 minutes 34% From the results of Example 3 2 to 3 5 and Comparative Example 7, it was confirmed that the compound of the present invention can be promoted. The ruthenium imidization reaction of polyphthalate. Further, from the results of Examples 3 4 and 3 and Comparative Example 8, it was confirmed that the reaction product of the tetracarboxylic dianhydride and the precursor (1 - a_2 ) promoted the ruthenium imidization reaction of the polyphthalate. (Example 3 6) The liquid crystal alignment agent (A3-1) obtained in Example 22 was filtered through a membrane filter of 1.0 m, and then spin-coated on a glass substrate with a transparent electrode at a temperature of 80 ° C. After drying on a hot plate for 5 minutes, it was baked at 23 (TC for 20 minutes to obtain a yttrium imidized film having a film thickness of 1 〇〇 nm. The polyimide film was honed with rayon (roller diameter 1 2 0 mm, number of revolutions 1 0 0 0 rp m, movement -97-201209078 speed 20 mm/sec, extrusion amount 0.4 mm) After observing the surface state of the polyimide film, no honing was observed The damage, the chipping of the polyimide film, and the peeling of the polyimide film. (Example 3 7) Except that the liquid crystal alignment agent (A3-2) obtained in Example 23 was used, the other was the same as Example 3. 6 The same procedure was carried out to prepare a polyimide film, and a honing treatment was carried out. The surface state of the polyimide film was observed, and as a result, no damage due to honing, chipping and polycondensation of the polyimide film were observed. Peeling of the quinone imine film. (Example 3 8) Except that the liquid crystal alignment agent (A3-3) obtained in Example 24 was used, the same procedure as in Example 36 was carried out. The polyimide film was prepared and subjected to honing treatment. The surface state of the polyimide film was observed, and no damage caused by honing, chipping of the polyimide film and polyimide film were observed. (Example 3 9) A polyimine film was produced and subjected to honing in the same manner as in Example 36 except that the liquid crystal alignment agent (A3 -4 ) obtained in Example 25 was used. The surface state of the polyimide film was observed, and no damage due to honing, chipping of the polyimide film, and peeling of the polyimide film were observed. -98 - 201209078 (Comparative Example 9) A polyimine film was produced in the same manner as in Example 36 except that the liquid crystal alignment agent (B3-1) obtained in Comparative Example 4 was used, and a honing treatment was carried out. The surface state of the polyimide film was observed. As a result, damage due to honing or chipping of the polyimide film was observed. (Comparative Example 1 〇) Except that the liquid crystal alignment agent (B 3 - 2 ) obtained in Comparative Example 5 was used, the other systems were implemented. Example 36 was also prepared to prepare a polyimide film and subjected to honing treatment. The surface of the polyimide film was observed. As a result, damage due to honing or chipping of the polyimide film was observed as a result. From the results of Examples 36 to 39 and Comparative Example 9, it was confirmed that the compound of the present invention was added by coating. The polyaminic acid solution was fired to obtain a ruthenium imidized film which was hard to be damaged by honing and which was excellent in mechanical strength. Further, it was confirmed from the results of Examples 38, 39 and Comparative Example 10. The reaction product of the tetracarboxylic dianhydride and the precursor (A2) can increase the mechanical strength of the obtained ruthenium imidized film. (Example 40) The liquid crystal alignment agent obtained in Example 18 (A 2 _ 1) Filtered with a membrane filter of 1 · 0 A m, and then 'rotated and coated on a glass substrate with a transparent electrode, dried on a hot plate at a temperature of 80 ° C for 5 minutes' and fired at a temperature of 23 ° C. After 20 minutes, it was allowed to form a ruthenium imidized film having a film thickness of 100 nm. -99- 201209078 This coating film was honed with rayon cloth (roller diameter 120mm, number of revolutions 300rpm, moving speed 20mm/sec, extrusion amount 0.4mm), and washed in pure water after 1 minute ultrasonic irradiation. After the water droplets were removed by air flow, the substrate with the liquid crystal alignment film was dried at 8 TC for 1 minute. Two substrates with the liquid crystal alignment film were prepared, and a spacer of 6 vm was spread on the liquid crystal alignment film surface of one substrate. Thereafter, the two substrates are combined in anti-parallel direction in the honing direction, leaving a liquid crystal injection port to seal the periphery, and an empty cell having a cell gap of 6 jtz m is formed. Liquid crystals are formed on the empty cell (1^1&gt; (: -2 04 1 , manufactured by Merck) Vacuum injection at room temperature, sealing the injection port to form a liquid crystal cell, and liquid crystal cell, liquid crystal alignment observation, pretilt angle measurement, voltage retention rate measurement and ion The results of the measurement were shown in Tables 3 and 4 which will be described later. (Example 41) A liquid crystal crystal was produced in the same manner as in Example 40 except that the liquid crystal alignment agent (A2-2) obtained in Example 19 was used. Cell. In this liquid crystal cell, the concept of liquid crystal alignment The measurement, the pretilt angle measurement, the voltage retention rate measurement, and the ion density measurement were carried out. The results are shown in Tables 3 and 4 which will be described later. (Example 42) Except that the liquid crystal alignment agent (A3-1) obtained in Example 22 was used, A liquid crystal cell was produced in the same manner as in Example 40. The liquid crystal cell was observed for liquid crystal alignment, pretilt angle measurement, voltage retention ratio measurement, and ion density measurement. The results are shown in Tables 3 and 4. 201209078 (Example 43) A liquid crystal cell was produced in the same manner as in Example 40 except that the liquid crystal alignment agent (A3-2) obtained in Example 23 was used. Thus, the liquid crystal unit cell was subjected to liquid crystal alignment. Observation, pretilt angle measurement, voltage retention ratio measurement, and ion density measurement. The results are shown in Tables 3 and 4. (Comparative Example 1 1) The liquid crystal alignment agent (B2-1) obtained in Comparative Example 2 was used, and burned. The liquid crystal cell was produced in the same manner as in Example 40 except that the time was set to 1 hour. The liquid crystal cell was observed for liquid crystal alignment, pretilt angle measurement, voltage retention ratio measurement, and ion density measurement. The results are shown in Tables 3 and 4. (Comparative Example 1 2) A liquid crystal cell was produced in the same manner as in Example 40 except that the liquid crystal alignment agent (B3-1) obtained in Comparative Example 4 was used. The cell was observed for liquid crystal alignment, pretilt angle measurement, voltage retention ratio measurement, and ion density measurement. The results are shown in Table 3 and Table 4 » -101 - 201209078 [Table 3] Liquid crystal alignment agent liquid crystal alignment pretilt angle [. Example 40 A2-1 〇 1.66 Example 41 A2-2 〇 3.88 Example 42 A3-1 〇 2.97 Example 43 A3-2 〇 2.96 Comparative Example 11 B2-1 〇 1.91 Comparative Example 12 B3-1 〇 0.87 In the liquid crystal alignment film of the present invention, it was confirmed that the liquid crystal display element having good liquid crystal alignment property can be obtained by using the liquid crystal alignment film of the present invention. Further, it was confirmed that the pretilt angle was increased by using the liquid crystal alignment film of the present invention. [Table 4] Liquid crystal alignment agent 1 pressure retention ratio [%] Ion density [PC] 23 ° C 60 ° C 90 ° C 23 ° C 60 ° C Example 40 A2-1 99.6 98.4 95.9 66 283 Example 41 A2- 2 99.6 98.8 95.4 8 124 Example 42 A3-1 99.5 99.2 97.8 8 28 Example 43 A3-2 99.5 99.1 97.8 9 40 Comparative Example 11 B2-1 99.2 98.0 95.0 99 334 Comparative Example 12 B3-1 98.9 97.4 94.6 108 328 From the results of the examples 4 0 to 4 3 and the comparative examples 1 and 1 2, it was confirmed that the liquid crystal display element of the present invention can obtain a liquid crystal display element having a high voltage holding ratio and a low ion density even at a high temperature. (Example 44) -102-201209078 The liquid crystal alignment agent (A3-1) obtained in Example 22 was filtered through a membrane filter of Ι.Ομπι, and then spin-coated on a glass substrate with a transparent electrode at a temperature of 80 The plate was dried on a hot plate of °C for 5 minutes, and baked at a temperature of 230 ° C for 20 minutes to form a yttrium imidized film having a film thickness of 100 nm. The coating film surface was irradiated with ultraviolet rays of 254 nm at 1 J/cm 2 through a polarizing plate to obtain a substrate with a liquid crystal alignment film. Prepare two substrates with such a liquid crystal alignment film, and spread a spacer of 6 // m on the liquid crystal alignment film surface of a substrate, and then combine them in antiparallel with the alignment of the two substrates, leaving a liquid crystal injection port to seal the periphery. , making an empty cell with a cell gap of 6 // m. Liquid crystal (MLC-204 1, manufactured by Merck) was vacuum-injected at room temperature to seal the injection port to form a liquid crystal cell, and the liquid crystal cell was observed for liquid crystal alignment and voltage retention. And ion density determination. The results are shown in Table 5 below. (Example 45) A liquid crystal cell was produced in the same manner as in Example 44 except that the liquid crystal alignment agent (A3-2) obtained in Example 23 was used. With respect to this liquid crystal cell, observation of liquid crystal alignment, measurement of voltage holding ratio, and measurement of ion density were performed. The results are shown in Table 5. (Comparative Example 1 3) A liquid crystal cell was produced in the same manner as in Example 44 except that the liquid crystal alignment agent (B 3 -1) obtained in Comparative Example 4 was used. With respect to this liquid crystal cell, liquid crystal alignment observation, voltage retention measurement, and ion density -103 - 201209078 were measured. The results are not shown in Table 5. [Table 5] Liquid crystal alignment agent liquid crystal alignment voltage retention ratio [%} ion density [pC] 23 〇 C 60 ° C 90 ° C 23 〇 C 60 ° C Example 44 A3-1 〇 99.4 99.1 97.2 8 76 Example 45 A3-2 〇99.3 98.8 97.1 15 109 Comparative Example 13 B3-1 〇98.7 97.0 94.9 207 650 From the results of Example 4 4, 4 5 and Comparative Example 1 3, it was confirmed that by using the liquid crystal alignment film of the present invention, It is possible to obtain a liquid crystal display element which exhibits good liquid crystal alignment properties even in light alignment, and which is excellent in voltage holding ratio and low in ion density even at high temperatures. [Industrial Applicability] The liquid crystal alignment agent according to the present invention is capable of forming a mechanical strength, is excellent in resistance to honing treatment, and has a voltage holding ratio or ion density in liquid crystal alignment, particularly at a high temperature. It is excellent in the point of electrical characteristics, and it can provide a liquid crystal alignment film with high pretilt angle reliability. As a result, it can be widely applied to TN elements, STN elements, TFT liquid crystal elements, and even vertical alignment type liquid crystal display elements. In addition, the entire contents of the specification, the scope of the patent application, and the abstract of the Japanese Patent Application No. 20-10-1347, filed on May 28, 2010 are hereby incorporated by reference. -104-

Claims (1)

201209078 VII. Patent application scope: 1. A liquid crystal alignment agent, characterized in that: the polyimine precursor obtained by reacting a diamine compound with a tetracarboxylic acid derivative and/or the polyimide precursor is given The quinone imidized polyimine is a compound having a structure of a lysine or a guanamine having an amine group which is substituted by a heat dissociable group which is heated by heating at 80 to 300 ° C. 2. The liquid crystal alignment agent as described in claim 1 wherein the aforementioned polyimine precursor has a repeating unit represented by the following formula (7) - (COOR6) 2 - C - X ^C—N—Y^N- - (7) II II i Ο Ο Αί Α2 (In the formula, 1 is a tetravalent organic group, 丫! is a divalent organic group; R6 is a hydrogen atom or a carbon number of 1 to 5 The alkyl group; each of hexa 1 and A2 is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent, an alkenyl group or an alkynyl group). 3. The liquid crystal alignment agent as described in claim 1 or 2, wherein the content of the polyimine precursor and the polyimine is 0.5 to 15 in the total amount of the liquid crystal alignment agent. And % by mass of the repeating unit of the polyimine precursor having the repeating unit represented by the above formula (7) and the ruthenium imidized polymer of the polyimide precursor The compound of the lysine or glutamate structure which is substituted by the heat-dissociable group of the hydrogen, which is protected by heating, contains 〇. 5 〜50 mol%. 4. The liquid crystal alignment agent according to any one of claims 1 to 3, wherein -105-201209078' has a compound having the structure of the proline or glutamate, which is a compound represented by the following formula (1). (wherein X is a tetravalent organic group; 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; and Z is a structure represented by the following formula (2)) (wherein, Ζ is a single bond or a divalent organic group having 1 to 30 carbon atoms; and R 2 and R 3 are each independently a hydrogen atom or an alkyl group having 1 to 30 carbon atoms which may have a substituent, an alkenyl group, an alkynyl group, The aryl group or a combination thereof may also form a ring structure; R4 is an amino atom or a substituent having a carbon number of from 1 to 30; D| is a thermally dissociable group). The liquid crystal alignment agent according to any one of claims 1 to 4, wherein the thermally dissociable group is tert-butoxycarbonyl or 9-fusylmethoxycarbonyl 6. X is a liquid crystal alignment agent described in any one of θ 1 to 5, wherein any one selected from the group represented by the following formula is -106-201209078 [Chem. 4] H3c H3c ch3 h3c ch3 : rc per it: #介介CH3 HgC CH3 / \ / \_ mxx xxxa ch9 o 7. A liquid crystal alignment agent according to any one of claims 1 to 6 is applied and fired. The liquid crystal alignment film according to claim 7, wherein the alignment treatment is a honing treatment or a radiation treatment of polarized radiation. A liquid crystal display element of a liquid crystal alignment film according to 7 or 8. 10. A compound having a structure of a proline or a glutamate represented by the following formula (1), [Chem. 5] (wherein X is a tetravalent organic group; Ri is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; and Z is a structure represented by the following formula (2)) -107 - 201209078 [Chemical 6] 卩 2 D1 —N—〒—z Factory (2) r3 (wherein a single bond or a divalent organic group having 1 to 30 carbon atoms; H 0 each independently a hydrogen atom or a carbon number which may have a substituent; Or alkynyl group, aryl group or a combination thereof, may also form a ring; _ is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms which may have a substituent; t) ^ 1 transfer dissociative group). %月安和: 1 1. The compound of claim 1, wherein the bis(chlorocarbonyl) compound represented by γ (3) and the compound of the formula (4) are in the presence of a base, The reaction is carried out with a ratio of (chlorocarbonyl compound/monoamine) of 1/2 to 1/3, [Chem. 7] (wherein, X, Zi, R2, R3, R4 and D are the same as those of the above formulae (1) and (2); and R5 is an alkyl group having 1 to 5 carbon atoms). The compound described in claim 1 is a tetracarboxylic acid derivative represented by the following $$ (5) and a monoamine compound represented by the formula (4) as recited in claim 1 In the presence of a condensing agent, the molar ratio of (four residues _ derivative / monoamine) is 1/2 to 1 / 3, • 108- 201209078 [Chem. 8] (wherein X and R5 are the same as defined in the above formulas (1) and (3)). The compound of claim 10, which is a tetracarboxylic acid represented by the following formula (6) The dianhydride is obtained by reacting the monoamine compound represented by the formula (4) described in the claim 11 with a molar ratio of (tetracarboxylic dianhydride/monoamine) of 1/2 to 1/3. 9] Ο Ο (In the formula, the X system is synonymous with the above formula (1)). The compound of claim 10, which is represented by the formula (4) of the formula (6) described in the claim 13 and the formula (4) as recited in the claim η The monoamine compound is obtained by reacting a molar ratio of (tetracarboxylic dianhydride/monoamine) to 1/2 to 1/3, and esterifying the carboxyl group with an esterifying agent. The compound according to any one of the preceding claims, wherein the above-mentioned X is selected from the group consisting of the structures shown by the following formula, -109-201209078 [10] H3c h3c ch3 h3c ch3 redundancy: iq: it Gangan ch3 h3c ch3 / \ ' ^ a m xx : 〇 =: think: g: Ge The compound according to any one of claims 1 to 5, wherein the above Ri is an alkyl group having 1 to 5 carbon atoms. 17. - Any compound of the following formula (ι-a)~(1-0) '-110- 201209078 [Chemical 11] HN /0_X % H ~k P~i_ (la) NH / - lj Me 0 —if / π in —w 0 O db) N-^/ ρ-^^—Ν-ΙΙ^/ ^JL-OMe Me' ^ H (lc) HNj ◦ H 〇 O MeO 〇Me H 〇 O (1-d) -111 - 201209078 [化 12] HN NH NH (1-0 -112 - 201209078 [Chem. 13] HN. P~\ -λ ° MeO Me HN- _v°Hn 0 Me〇 (1-k) Ν_7_^Η-γν〇Η .卜》 乂 / ~~Λ H /~ΝΗ (1-m) /Vo·7&quot; (1-η) Ο Ο ΗΝ- P~i&quot;Λ 〇 ηοΥο ο (1-0) Λ-οη -113- 201209078 Four designated representatives: (1) The representative representative of the case is: No (2) The symbol of the representative figure is simple: No 201209078 If there is a chemical formula in the case, please disclose the chemical formula that best shows the characteristics of the invention: no