TW201241046A - Coating solution for forming polyimide film, liquid crystal alignment agent, polyimide film, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

Provided is a coating solution for forming a polyimide film, said coating solution comprising: a polymer of a polyimide precursor obtained by polymerizing a tetracarbonate component and a diamine component, and/or a polyimide formed by the imidization of the polyimide precursor; and a bifunctional compound represented by formula [A] and having a Meldrum's acid structure introduced into each of two amino groups of a diamine compound. Also provided are: a liquid crystal alignment agent comprising said coating solution; a polyimide film obtained by firing a substrate coated using said coating solution; a polyimide film comprising a polyimide in which the polymer is crosslinked using the bifunctional compound represented by formula [A]; a liquid crystal alignment film comprising the polyimide film; and a liquid crystal display element equipped with said liquid crystal alignment film. (In the formula, Y, R1 and R2 are groups specified in claims 1 and 4.)

Description

201241046 VI. Description of the Invention [Technical Field] The present invention relates to a novel coating liquid for forming a polyimide film, a liquid crystal alignment agent, a polyimide film formed using the same, and a liquid crystal alignment film, and Liquid crystal display element. [Prior Art] Among the liquid crystal display elements, the liquid crystal alignment film has a function of aligning the liquid crystals in a certain direction. The main liquid crystal alignment film currently used in the industry is composed of a solution of a polyamidamine precursor (polyamic acid), a polyamidomate or a polyamidene. An amine-based liquid crystal alignment agent is applied onto a substrate to form a film. Further, when the liquid crystal is aligned in parallel or obliquely with respect to the substrate surface, the surface extension treatment after rubbing is performed after the film formation. In addition, a method of using an anisotropic photochemical reaction such as polarized ultraviolet ray irradiation has been proposed in place of the friction processor, and the industrial orientation has been reviewed in recent years. In order to enhance the display characteristics of such a liquid crystal display element, a polyamine, a polyamidolate or a polyphthalamide having a different structural change or a different property of polyacrylic acid, a polyamidomate or a polyimine A mixture of amines or an additive is added to improve liquid crystal alignment or electrical properties, control of pretilt angle, and the like. In the technique of controlling the pretilt angle by the structure of polyimine, a method of using a diamine having a side chain as a part of a raw material of a polyimide, the pretilt angle can be controlled according to the ratio of use of the diamine, and the purpose is relatively easy to obtain. Inclination, -5- 201241046 can be used as a means to increase the pretilt angle. In terms of the side chain structure of the diamine which increases the pretilt angle of the liquid crystal, a long-chain alkyl group or a fluoroalkyl group (for example, refer to Patent Document 1), a cyclic group or a combination of a cyclic group and an alkyl group (for example, Patent Document 2 is a reference), a steroid skeleton (for example, Patent Document 3 for reference), and the like. Further, in such a diamine for increasing the pretilt angle of the liquid crystal, a structure for improving the stability or process dependency of the pretilt angle is also considered, and a side chain structure which can be used here is proposed to have a phenyl group or a ring. A hexyl isocyclic constructor (for example, Patent Documents 4, 5 for reference). Further, a diamine having a structure of 3 to 4 rings in the side chain is proposed (for example, refer to Patent Document 6). In recent years, liquid crystal display devices have been widely used in the field of large-screen liquid crystal televisions or high-definition mobile applications (displays for digital cameras or mobile phones), and the size of substrates used in comparison with the previous ones has become larger. Big. In such a case, from the viewpoint of display characteristics, it is desired to uniformly apply a liquid crystal alignment film to a large substrate or a step. In the production step of the liquid crystal alignment film, when a solution of a polyamic acid solution or a solvent-soluble polyimine is applied to a substrate, industrially, flexographic printing or the like is generally used. In addition to N-methyl-2-pyrrolidone or γ-butyrolactone of a solvent (hereinafter, also referred to as a good solvent) having excellent solubility in a resin, the solvent of the coating liquid is mixed in order to improve the uniformity of the coating film. A butyl cellosolve such as a solvent having low solubility (hereinafter also referred to as a poor solvent). However, the poor solvent has a poor ability to dissolve polyglycine or polyimine, and a large amount of mixing causes precipitation (for example, Patent Document 7). In particular, in a solvent-soluble polyimine solution, the problem becomes remarkable. Further, since the polyimine obtained by using the above-mentioned diamine having a side chain of from 6 to 201241046 is coated by a solution, it is necessary to increase the amount of the poor solvent, and the amount is also a polyimine. Important characteristics. Further, with the improvement of the performance of the liquid crystal display element, the power saving of a large device, and the like, the characteristics required for the alignment film in various environments are also severe. In particular, when the liquid is applied to the substrate, there is a problem that the tact time becomes long and precipitates or separates, or the problem of burning due to accumulated electric charge (RDC) is solved, and both of them are simultaneously solved. As described above, in the polyimine-based liquid crystal alignment film, the desired diamine is not easily used in the relationship of using various kinds of diamine components as a raw material, and the polyimine is particularly high in terms of its properties. In addition to the liquid crystal alignment film, the protective material and the insulating material in the field of the moon have been improved as a raw material of polyimine in the same manner as in the case of the liquid crystal alignment film. The improvement in the desired properties of the diamine component can also be easily carried out. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei. No. Hei. No. Hei. [Patent Document 4] Japanese Laid-Open Patent Publication No. Hei 9-278-724, the mixing volume of the decanting agent having a reduced uniformity, the use of the liquid crystal crystal alignment agent, and the printing failure of the liquid crystal crystal alignment agent are not expected to be improved. With other special ingredients. The mechanical strength and heat resistance are the same as the diamine component of the field of electrical and electric materials. In the case of the present invention, Japanese Patent Application Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Problems to be Solved by the Invention] An object of the present invention is to solve the problems of the above-described conventional techniques, and to provide a polyimide film which can be obtained by a polyimine film which can easily and freely improve various properties. A coating liquid, a liquid crystal alignment agent, a polyimide film formed using the above, a liquid crystal alignment film, and a liquid crystal display element. [Means for Solving the Problem] The coating liquid for forming a polyimide film of the present invention which solves the above-mentioned problems is characterized by containing at least one tetracarboxylic acid component and a diamine selected by using a tetracarboxylic acid and a derivative thereof. a polyimine precursor obtained by polymerizing a component, and at least one polymer selected from the polyimide obtained by imidating the polyimine precursor ruthenium, and each of the diamine compounds The two amine groups are introduced into the difunctional compound represented by the following formula [A] of the structure of the Michler acid. 【化1】

(wherein γ is a divalent organic group derived from the above diamine compound, and 1 and r2 201241046 are each -Η, or may contain a benzene ring, a cyclohexane ring, a heterocyclic ring, a fluorine, an acid bond, or a vinegar bond at any position. The amine-bonding bond has a monovalent organic group having 1 to 35 carbon atoms and may be bonded to a part of the oxime to form a ring. Further, 1 and R2 may be the same or different. The liquid crystal alignment agent of the present invention is characterized by The coating liquid for forming a polyimide film is formed. Further, the polyimine film of the present invention is characterized in that the coating liquid for forming a polyimide film is applied onto a substrate and baked. Next, the polyimine film of the present invention is characterized by a polyimine precursor obtained by polymerizing at least one tetracarboxylic acid component selected from a tetracarboxylic acid and a derivative thereof and a diamine component, and The at least one polymer selected from the polyimide obtained by imidization of the polyimine precursor is introduced into the following formula of the structure of the Michler acid in the amine group of each of the diamine compounds [Α] The represented difunctional compound is composed of a crosslinked polyimine. [Chemical 2]

(wherein Υ is a divalent organic group derived from the aforementioned diamine compound, and each of 1 and R 2 is -Η, or may contain a benzene ring, a cyclohexane ring, a heterocyclic ring, a fluorine, an ether bond, or an ester bond at any position. The guanamine bond has a monovalent organic group having 1 to 35 carbon atoms and may be bonded to the oxime to form a ring, and the heart and & 2 may be the same or different.) -9 - 201241046 The characteristics of the liquid crystal alignment film of the invention are constituted as described above. Further, the liquid crystal display device of the present invention is characterized in that it has a film toward the film. [Effects of the Invention] According to the present invention, the difunctionalization alignment represented by the above formula [A] in the structure of the di-minic acid of each of the diamine compounds is contained. A coating liquid for forming a polyimine film such as a solvent can obtain a polyimide film such as a liquid crystal alignment film having various properties. The difunctional compound to be described next is a structure in which a milli acid structure is introduced into each of the diamine compounds, and the diamine compound can be easily used as a diamine component for the desired properties discussed in the prior art. Improvement. Further, the polyimine precursor or the polyfluorene contained in the coating liquid for forming of the present invention is crosslinked with a difunctional compound represented by the above formula [A], and is resistant to an organic solvent. It can be hard [Best Mode of Carrying Out the Invention] Hereinafter, the present invention will be described in detail. The coating liquid for forming a polyimine film of the present invention is a difunctional compound of the following 5 in which the amine group of each of the two substances is introduced into the structure of the Michler acid. The liquid crystal of the above-mentioned liquid crystal-containing amine-based compound of the polyimide film is freely improved, and the amine groups of the above formula [A] are heated by using the obtained polyfluorene-imine film amine. Membrane. Represented by diamine compound 5 [ A ] -10- 201241046 [Chemical 3 1

(wherein Y is a divalent organic group derived from the above diamine compound, and each of 1 and r2 is -Η, or may contain a benzene ring, a cyclohexane ring, a hetero ring, a gas, an acid bond, an ester bond, or The guanamine bond has a monovalent organic group having 1 to 35 carbon atoms and may be bonded to a moiety of the oxime to form a ring, and 1 and R2 may be the same or different. In the above formula [Α], γ is as described above. The divalent organic group of the diamine compound which is a raw material of the difunctional compound represented by the above formula [Α] is not particularly limited, and specific examples thereof include the following formula (Υ_ υ 〜( 2-12 0) The divalent organic group represented by the above. When the obtained polyimine film is used as a liquid crystal alignment film, in order to obtain good liquid crystal alignment, a highly linear diamine compound is used as a raw material. The structure is preferably such that, for example, (Υ-7), (Υ-10), (Yl 1) '(Υ-12), (Υ-13), (Υ-21), (Υ -22) , (Υ-23), (Υ-25), -(Υ-26), (Υ-27) ' (Υ-41), (Υ-42), (Υ-43), (Υ- 44), (Υ-45), (Υ-46), (Υ-48), (Υ -61) , (Υ-63), (Υ-64), (Υ-65), (Υ-66), (Υ-67), (Υ-68), (Υ-69), (Υ-70) ), (Υ-71) ' (Υ-78), (Υ-?9), (Υ·80) ' (γ_81), (Υ-82) or (γ_109), etc. When the amine film is used as a liquid crystal alignment film for increasing the pretilt angle of the liquid crystal, the side chain has a long-chain courtyard group (for example, a hospital having a carbon number of 1 Å or more), an aromatic ring, an aliphatic ring, a steroid skeleton, or a combination. The structure of the diamine compound of the structure of -11 - 201241046 is preferably a raw material, and such γ may, for example, be (Υ-83), (Υ-84), (Υ-85), (Υ-86). , (Υ-87), (Υ-88), (Υ-89), (Υ-90), (Υ-91), (Υ-92), (Υ-93), (Υ-94), ( Υ-95), (Υ-96), (Υ-97), (Υ-98), (Υ-99), (Υ-100), (Υ-101), (Υ-102), (Υ- 103), (Υ-104), (Υ-丨05), (Υ-106), (Υ-107), or (Υ-108), etc. 'but not limited to this. Also, in order to make the liquid crystal display element For the case where the electric characteristics are improved, for example, (Υ-31), (Υ-40) , (Υ-64), (Υ-65), (Υ-66), (Υ-67), (Υ-109), (Υ-110), etc. Further, when it is desired to impart photoreactivity to the liquid crystal alignment film, for example, (Υ-17), (Υ-18), (Y-ll), (Υ-112), (Υ-113), (Υ- 114), (Υ-115), (Υ-116), (Υ-117), (Y-l18), (Υ-119), etc. 【化4】

-12- 201241046 【化5】

(Υ-24) (Y-25) (Y-26) (Y-27) (Y-28)

【化7】

QM7) 〇M8) (Y-49) (Y-50) (Y-51) [Chemical 8] ?h3 CH3 ch3 ch3 -(CH2)n--(CH2)2-C-(CH2)2- n = 2-5 CH3 —(CH2)4-C-(CH2)3--CH2-g-(CH2)2-g-(CH2)2-ch3 hh (Y-52) (Y-53) (Y-54 ) (Y-55) ch3 ch3 ch3 ch3 -ch2-c-(ch2)2- -C-(CH2)3-- Π (CH2)2-C-(CH2)5- Π -(CH2)4-C -(CH2)5- (Y-56) (Y-57) (Y-58) -13- 201241046 ch3 ch3 (CH2)3-Si-〇-Si-(CH2)3- CH3 ch3 (Y-60)

(Y-62) (Y-63) 【化1 0 fork (Y-64) (Y-65) (Y-66)

Xr'

0(CH2CH20)n 2-4 (Y-7〇) O η = 2·5 (Y-67) °xx /^0(CH2CH20)m_^ ^^〇(CH2CH20)n_^^ ΧΧ〇(〇Η2〇 Η2〇)ΛΛ XT n = 2_4 众(Y-69) m,n = 2-4 【化1 1 (Y-71) (Y-72) (Y-73)

^ ^°yX0J(X XiSd>^6XK "Ck0^b<0JX (Y-74) υ (Y-75) (Y-76) ^X〇J^ik〇^ ^〇η(=Η2:5〇 Χ^ -14- 201241046 【化1 2】 n = 2~5 (Y-81) η = 2~5

(Y-80) p-(CH2)n-Q η = 2~5 (CH2)n*CH3

(Y-82) [化1 3] °~0~0-(CH2)n"CH3 (Y-85) η = 0~21 Ο- (CH2)n-CH3

, 0—(CH2)n-CH3 (Υ-91) η = 0~21 ^0~〇-(CH2)n-CH3 (Υ-93) :0~21 (Y-83) -(CH2)n- CH3 η = 5-19 (γ-84) η = 5~19

丨—(3~(CH2)n-CH3 (Y-86) n = °~21 -0—Q-°-(CH2)n-CH3

(Y-88) η = 〇~21 〇-(CH2)n^CH3 p s 〇~21 (Y-90) Uncle ch3 n = 〇~21 (Y-92)

(Y-94) n = 0~21 〇-(CH2)n-CH3

[化1 4] (CH2)n-CH3

—0~(CH2)n-CH3 n = 0—21 (Y-96) o—C3C^~"o"~(CH2)n_*CH3 (Y-98) n = 0~21 15 201241046 5]

〇-cf3 (Y-99) (Υ-100)

【化1 6】

201241046 【化1 7】

The difunctional compound represented by the above formula [A] in which the respective two amino groups of the di-anthracene ampoule I are introduced into the Michler acid structure can be, for example, in orthoformic acid trimethyl vinegar or triethyl orthoformate. In the 'or, general organic synthesis can be used to -17- 201241046 organic solvents (such as ethyl acetate 'hexane, toluene, tetrahydrofuran, acetonitrile, methanol 'chloroform, hydrazine, 4-dioxane, N, N_ two In the case of methylformamide or N-methyl-2-indole-s-alkanone), trimethyl orthoformate or triethyl orthoformate is subjected to a diamine compound represented by the following formula [B] and a michroic acid. The diamine compound represented by the following formula [B] can be produced by a reaction, and a diamine component for obtaining a desired characteristic discussed in the prior art, that is, a polymerization reaction with a tetracarboxylic acid component can be used to produce a polyimine. The precursor or the diamine component of the polyimine is also the diamine component used to obtain the desired properties. Further, the reaction temperature or the reaction time is not particularly limited, and for example, it may be 60 to 12 ° C for 30 minutes to 2 hours. [化1 9]

HN—Y—NH [B] (Y ' Ri and R 2 are the same as Y, R, and R 2 in the above formula [A].) Of course, the difunctional compound represented by the above formula [A] may be one type, or It can be used in 2 or more types. Further, the coating liquid for forming a polyimide film of the present invention contains a polyimine precursor obtained by polymerizing at least one of a tetracarboxylic acid component selected from a tetracarboxylic acid and a derivative thereof and a diamine component. And at least one polymer selected from the polyimine obtained by imidating the polyimine precursor ruthenium. Of course, the polyimine precursor or the polyimine may be used in one type or in two or more types. Further, the polyimine precursor refers to polyamic acid and polyamidomate. The polyimine precursor -18-201241046 of the coating liquid for forming a polyimide film of the present invention is a tetracarboxylic acid component selected from the above tetracarboxylic acid and a derivative thereof by the above-mentioned The diamine component is obtained by polymerization. The diamine component is, for example, a diamine compound represented by the above formula [B]. Further, a diamine component used in the reaction of a conventional diamine component with a tetracarboxylic acid component to obtain a polyimide precursor can be used. Further, a part or all of the diamine component of the raw material of the polyimine precursor may be the same compound as the diamine compound of the raw material of the difunctional compound represented by the above formula [A], or a diamine component and the above formula [ The diamine compound of the raw material of the difunctional compound represented by A] is a different compound. Further, at least one of the tetracarboxylic acid components selected from the tetracarboxylic acid and the derivative thereof can be a tetracarboxylic acid component which is obtained by reacting a conventional diamine component with a tetracarboxylic acid component to obtain a polyimide precursor. As the tetracarboxylic acid derivative, for example, a tetracarboxylic acid dihalide, a tetracarboxylic dianhydride represented by the following formula [C], a tetracarboxylic acid diester dichloride, a tetracarboxylic acid diester or the like can be given. For example, polylysine can be obtained by reacting a tetracarboxylic acid dihalide, a tetracarboxylic dianhydride or the like, a tetracarboxylic acid or a derivative thereof with a diamine component. Further, a polyglycolate can be obtained by reacting a tetracarboxylic acid diester dichloride with a diamine component or by reacting a tetracarboxylic acid diester with a diamine component in the presence of a suitable condensing agent or a base. . [化2 0] 0 〇

(X is a tetravalent organic group.) -19-201241046 A specific example of X of the above formula [C] may, for example, be a tetravalent organic group represented by the following formula (x_1: to (X-46). Obtaining a difficult point of view, X is (Xl), (X-2), (X-3), (X-4), (X-5) ' (X-6), (X-8), (X-16 ), (X-17), (X-19), (X-21), (X-25), (X-26), (X-27), (X-28), (Χ·32) or (X-46) is preferred. In order to improve the transparency of the obtained polyimide film, it is preferred to use a tetracarboxylic dianhydride having an aliphatic and aliphatic ring structure, and in the X aspect, 1), (Χ-2), and (Χ-25) are more preferable, and (X-1) is more preferable from the viewpoint of reactivity with a diamine component. • 20· 201241046 [Chem. 2 1

;h3 h3c ch3 (Xl) (X-2) (X-3) (X-4) (X-5) (X-6) Zona (X-8) (X-9) (X-10) ( X-ll) (X-12) (X-13) (X-14) pC-15) (X-16)

:8: Zhiqiu (X-28) (X-29) (X-30)

(X-33) (X-34)

χΛχ d〇Ixx xfi〇C (X-35) (X-36) (X-37) (X-38)

OX (X-39) (X-40) (X-41) (X-42) (X-43) CH3

(X-45) (X-46) 201241046 Specific examples of the tetra-residic acid diester can be mentioned, for example, 1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2-dimethyl -1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2 , 3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 12,3,4-cyclopentane tetracarboxylic acid dialkyl ester, 2,3,4 , 5-dihydrofuran tetracarboxylic acid dialkyl ester, 1,2,4,5-cyclohexane tetracarboxylic acid dialkyl ester, 3,4-dicarboxy-1-cyclohexyl succinic acid dialkyl ester, 3 , 4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinate dialkyl ester, 1,2,3,4-butane tetracarboxylic acid dialkyl ester, bicyclo[3,3 , 0] octane-2,4,6,8-tetracarboxylic acid dialkyl ester, 3,3',4,4'-dicyclohexyltetracarboxylic acid dialkyl ester, 2,3,5-three Dialkyl carboxylcyclopentyl acetate, dialkyl cis-3,7-dibutylcyclooctane-1,5-diene-1,2,5,6-tetracarboxylate, tricyclo[4.2 .1.02'5] decane-3,4,7,8-tetracarboxylic acid-3,4: 7,3-dialkyl ester, hexacyclo[6.6.0.12,7.03'6.19'14.01°'13]10 Hexane-4,5,11,12-tetracarboxylic acid-4,5: 11,12-dialkyl ester, 4-(2,5-dioxytetrahydrofuran An aliphatic tetracarboxylic acid diester such as -3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarbon dialkyl ester or dialkyl pyromellitic acid, 3,3' , 4,4'-biphenyltetracarboxylic acid dialkyl ester, 2,2',3,3'-biphenyltetracarboxylic acid dialkyl ester, 2,3,3',4-biphenyl Dialkyl tetracarboxylate, dialkyl 3,3',4,4'-benzophenone tetracarboxylate, dialkyl 2,3,3',4-benzophenone tetracarboxylate , bis(3,4-dicarboxyphenyl)ether dialkyl ester, bis(3,4-dicarboxyphenyl)trialkyl ester, 1,2,5,6-naphthalenetetracarboxylic acid dialkyl An aromatic tetracarboxylic acid dialkyl ester such as an ester or a dialkyl 2,3,6,7-naphthalenetetracarboxylate. Of course, the diamine component or the tetracarboxylic acid component may be used alone or in combination of two or more. -22- 201241046 A method of synthesizing a polycarbimine precursor by polymerizing a tetracarboxylic acid component and a diamine component is not particularly limited, and a conventional synthetic method can be used. For example, a reaction between a diamine component and a tetracarboxylic dianhydride is a method of reacting a diamine component with a tetracarboxylic dianhydride in an organic solvent. The organic solvent used at this time is not particularly limited as long as it is a polyimine precursor formed by dissolution. Specific examples thereof, hydrazine, hydrazine-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethyl hydrazine , tetramethyl urea, pyridine, dimethyl milling, hexamethylarylene, γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl Mercapto ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve Acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoethyl Acid ester, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol single Acetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether 3-methyl-3-methoxybutyl B Acid ester, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyl ester, butyl Ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, η-hexane, η-pentane, η-octane, diethyl ether, cyclohexanone , ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, acetic acid η-butyl-23- 201241046 ester, propylene glycol monoethyl ether, methyl pyruvate, pyruvate Ester, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, Propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme or 4-hydroxy-4-methyl-2-pentanone. These can be used alone or in combination. Further, even if it is a solvent which does not dissolve the polyimide precursor, it can be used in combination in the above solvent without precipitating the formed polyimide precursor. Further, since the water in the organic solvent hinders the polymerization reaction and further causes hydrolysis of the produced polyimide precursor, the organic solvent is preferably dried by dehydration. When the diamine component and the tetracarboxylic dianhydride are reacted in an organic solvent, for example, a solution in which the diamine component is dispersed or dissolved in an organic solvent is stirred, and the tetracarboxylic dianhydride is directly or dispersed in an organic solvent. Or a method of adding after dissolving, a method of adding a diamine component by dispersing a tetracarboxylic dianhydride or a solution dissolved in an organic solvent, or a method of mutually adding a tetracarboxylic dianhydride and a diamine component, etc. Use any of these methods. Further, when a plurality of kinds of diamine components or tetracarboxylic dianhydrides are used for the reaction, the reaction may be carried out in a premixed state, or the respective reactions may be carried out in sequence, and the low molecular weights of the respective reactions may be further mixed to form a polymer. The polymerization temperature at this time may be any temperature of from -20 ° C to 150 ° C, but is preferably in the range of from 10,000 ° C. Further, although the reaction can be carried out at any concentration, if the concentration is too low, it is difficult to obtain a polymer having a high molecular weight, and if the concentration is too high, the viscosity of the reaction liquid becomes too high, and it is difficult to uniformly stir. Therefore, it is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and after -24 to 201241046, an organic solvent can be added. In the polymerization reaction of the polyimine precursor, the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic dianhydride is preferably 0.8 to 1.2. As with the general polycondensation reaction, the closer the molar ratio is to 1.0, the greater the molecular weight of the polyimide precursor. Further, the polyglycolate can be obtained by reacting the above tetracarboxylic acid diester dichloride with a diamine component or by reacting a tetracarboxylic acid diester with a diamine component in the presence of a suitable condensing agent or a base. Alternatively, polylysine may be preliminarily synthesized by the above method, and a carboxyl group of polylysine may be esterified by a polymer reaction. Specifically, for example, the tetracarboxylic acid diester dichloride and the diamine component are in the presence of a base and an organic solvent at -20. The polyphthalate can be synthesized at a temperature of from 150 ° C to 150 ° C, preferably from 〇 ° C to 50 ° C, for 30 minutes to 24 hours, preferably from 1 hour to 4 hours. As the base, pyridine, triethylamine or 4-dimethylaminopyrrole can be used, but pyridine is preferred for the reaction to be stable. The amount of the base to be added is preferably from 2 to 4 moles per mole of the tetracarboxylic acid diester dichloride from the viewpoint of easy removal amount and easy availability of a polymer. Further, where the tetracarboxylic acid diester and the diamine component are polycondensed in the presence of a condensing agent, the base may be triphenylphosphite, dicyclohexylcarbodiimide or 1-ethyl-3-( 3-dimethylaminopropyl)carbodiimide hydrochloride, N,N'-carbonyldiimidazole, dimethoxy-H5-triazinylmethylmorpholinium, hydrazine-(benzotriazole) Zin-1-yl)-oxime, hydrazine, Ν'Ν'-tetramethyluronium tetrafluoroborate, 〇_(benzotriazol-1-yl)-N,N,N,,N' - Tetramethyluranyl iron hexafluorophosphate ' -25- 201241046 (2,3-dihydro-2-thio-3-benzoxazolyl)phosphonic acid diphenyl ester, 4-(4,6-dimethyl Oxy-1,3,5-triazin-2-yl)4-methoxymorpholine chloride η-hydrate, and the like. Further, in the method of using the above condensing agent, the reaction can be efficiently carried out by adding Lewis acid as an additive. In terms of Lewis acid, lithium halide such as lithium chloride or lithium bromide is preferred. The amount of Lewis acid added is preferably from 0 to 1.0 times the molar amount of the diamine or tetracarboxylic acid diester. The solvent used in the above reaction can be carried out in the same solvent as the solvent used in the synthesis of the polyamic acid described above, but the solubility of the monomer and the polymer is Ν-methyl-2-pyrrolidone, γ- Butyrolactone is preferred, and these may be used alone or in combination of two or more. The concentration at the time of the synthesis is such that the polymer is less likely to be precipitated and the high molecular weight is easily obtained, and the total concentration of the tetracarboxylic acid derivative such as tetracarboxylic acid diester dichloride or tetracarboxylic acid diester and the diamine component in the reaction solution is obtained. It is preferably 1 to 30% by mass, more preferably 5 to 20% by mass. Further, in order to prevent hydrolysis of the tetracarboxylic acid diester dichloride, the solvent used for the synthesis of the polyglycolate is preferably dehydrated as much as possible to prevent the intrusion of outside air in a nitrogen atmosphere. The polyimine contained in the coating liquid for forming a polyimide film of the present invention can be obtained by dehydrating and ring-closing the above polyimide precursor. In the polyimine, the dehydration ring closure ratio (the imidization ratio) of the proline group does not necessarily need to be 100%, and can be arbitrarily adjusted depending on the intended use or purpose. The method for imidating the polyimine precursor ruthenium may, for example, be a catalyst for adding a catalyst to a solution of a hot hydrazide or a polyimide precursor directly heated by a solution of a polyimide precursor. Media imidization. -26- 201241046 Adding a polyimine precursor to a solution of a catalyst precursor having a solubility of 100 to 400 ° C, preferably a reaction, to remove the catalyst precursor of the exopolyimine precursor, adding a base Preferably, the mixture is stirred at 0 to 180 ° C for 0.5 to 30 moles, preferably 1 to 50 moles of the amine acid group, and more preferably, for example, pyridine, triethylamine, amine, etc. Pyridine has a reversed aspect, such as the use of acetic anhydride in acetic anhydride and anhydrous para-benzene, and the amination rate of the amination after completion of the reaction can be controlled by interconciliation. Further, it may be precipitated by a polyimine precursor formed of a polyimide precursor or a polyfluorene solvent. Precipitation Acetone, hexane, butyl cellosolve, ketone, ethanol, toluene, benzene, and hydrate are usually dried after filtration and recovery. Further, the operation quality of the solvent and reprecipitation recovery of the precipitation recovery machine is small. The solvent at this time is preferably a temperature of from 120 to 250 ° C in the case of heat imidization in three or more types of liquids selected in the above, and it is preferred to carry out the imidization. The imidization of ruthenium can be achieved by the use of a polyamidene catalyst and an acid anhydride at -20 to 25 (TC, line. The amount of the basic catalyst is 2 to 20 moles of the proline group, and the amount of the anhydride is 醯It is preferably 3 to 30 moles. The basic catalyst trimethylamine, tributylamine or trioctyl should be moderately alkaline. The anhydride triacid or anhydrous pyromellitic acid is refined. It is easy to change. When the catalyst is used to recover the imine in the reaction temperature, the reaction temperature, or the reaction solution of the polyimine, the solvent to be used in the reaction solution may be, for example, methanol or heptane. Methyl ethyl ketone, methyl isobutyl or the like. The polycondensate in the polymer can be re-dissolved in a polycondensation or precipitation under normal pressure or heating under reduced pressure or reduced pressure at room temperature or heating. The use of such a solvent, such as a solvent, is preferred because the efficiency of the purification is further improved. -27-201241046. The polyimine precursor or polyfluorene contained in the coating liquid for forming a polyimide film of the present invention. Imine, the strength of the obtained polyimide film, the workability of the polyimide film formation, polyimine In the case of uniformity, the weight average molecular weight measured by the GPC (Ge 1 Permeation Chromatography) method is preferably 5,000 to 1,000,000, more preferably 1 Å, 〇〇〇 1 to 150,000 °, and the polyphthalamide of the present invention. The coating liquid for forming an amine film may contain, as a polymer component, a polymer other than the above-mentioned polyimine precursor or polyimine, such as a polyimine precursor or a polymer other than polyimine. An acrylic polymer, a methacrylic polymer, polystyrene, polyoxyalkylene or polyamine, etc., by containing at least one of a tetracarboxylic acid component and a diamine component selected from a tetracarboxylic acid and a derivative thereof a polyimine precursor obtained by carrying out a polymerization reaction and at least one polymer selected from the polyimide obtained by imidating the polyimine precursor ruthenium, and each of the diamine compounds Further, the difunctional compound represented by the above formula [A] in which the amine group is introduced into the Michler acid structure, that is, the coating liquid for forming a polyimine film for forming a liquid crystal alignment film or the like, for example, further contains The above formula [A] The difunctional compound is a coating liquid for forming a polyimine film which can be used to obtain a polyimine film which can improve various properties. In detail, the difunctional compound represented by the above formula [A] is Mie. The acid structure, that is, two structures from the Mic acid at both ends, the Mic acid structure is heated (for example, 180 to 2 50 ° C or more), accompanied by the separation of carbon dioxide and C - 28 - 201241046 ketone, becoming an alkene a ketone (that is, a carbonyl compound having a divalent group > c=c = o), a dimerization of the ketene alone, a carboxyl group, a hydroxyl group, an amine group having a polyimine imine or a polyimine , thiol group, aldehyde, ketone, unsaturated bond (eg carbon-carbon double bond, carbon-carbon triple bond, imine (carbon-nitrogen double bond), carbodiimide 'sulfur ylide, phosphorus ylide) A reaction such as a guanamine bond or an ester bond, a carbonyl group of a quinone imine bond, or an active methylene group. Therefore, the state of the coating liquid for forming a polyimine film which is not heated at a high temperature (for example, 100 ° C or lower) is not bonded to the polyimide precursor or The polyimine reaction is carried out, but is heated to introduce a polyimine precursor or a polyimine through a structure of a Michaelic acid. In addition, since the difunctional compound represented by the above formula [A] has two structures of the Michler acid, it is presumed that the polyimine after heating is a structure in which the difunctional compound represented by the above formula [A] is crosslinked. Therefore, the polyimine film obtained by applying the coating liquid for forming a polyimide film of the present invention to a substrate and firing the composition is a structure of Y which the difunctional compound represented by the above formula [A] has. In other words, the structure of Y derived from the diamine compound of the raw material of the difunctional compound represented by the formula [A] is introduced into the polyimine. In view of the high mechanical strength, heat resistance, and solvent resistance of the polyimide film, it is widely used as a protective material or an insulating material in a liquid crystal alignment film or an electric and electronic field, and various kinds of materials are used in order to improve desired properties. The diamine component is a part of the raw material, but there are cases where the desired diamine component cannot be used freely. For example, in the liquid crystal alignment film, in order to improve the desired properties such as the liquid crystal alignment property or the improvement of the pretilt angle, various kinds of diamines are used as a part of the raw material, but the type of the diamine component used for obtaining the desired characteristics is used. The polymerization reactivity of the diamine component and the tetracarboxylic acid component is deteriorated in combination or in an amount, and the type or combination of the types of the diamine components for obtaining desired properties is limited. Further, it is necessary to investigate the polymerization conditions of the diamine component and the tetracarboxylic acid component for the type or combination of the diamine components to be used for obtaining desired properties. Next, in order to form a coating liquid for forming a polyimide film which can form a uniform polyimide film, it is necessary to form a solution containing a component dissolved in a solvent, but a diamine component to be used for obtaining desired properties The solubility, the polyimine precursor contained in the coating liquid for forming a polyimide film, or the polyimine is deteriorated in the type, the combination, or the amount. In the present invention, at the stage of the coating liquid for forming a polyimide film, the above formula wherein the polyimide compound precursor or the polyimide is contained in the respective compound state and the compound for which the desired properties are desired is obtained. In the case of heating (baking) the coating liquid for forming a polyimine film, the difunctional compound represented by the above formula (A) is a difunctional compound represented by the above formula [A] for obtaining a compound for desired properties. The compound is introduced into a polyimine precursor or a polyimine. Therefore, the polyimine precursor or the polyimine contained in the coating liquid for forming a polyimide film does not need to use a diamine component for obtaining a desired property as a raw material, and does not have a diamine component and a tetracarboxylic acid. The problem that the polymerization reactivity of the component is deteriorated, and there is a problem in that it is necessary to investigate the polymerization reaction conditions of the diamine component and the tetracarboxylic acid component of the kind or combination of the diamine component used to obtain the desired property, or the polyimide film. The solubility of the polyimide precursor or the polyimine contained in the coating liquid for forming is deteriorated. Therefore, the coating liquid for forming a polyimine film of the present invention may not review the polymerization reaction of the diamine component and the tetracarboxylic acid component, the polymerization reaction conditions, or the polyimine precursor or the polymerization. The solubility of the quinone imine can be obtained by using a diamine compound for obtaining a desired property, so that the properties of the obtained polyimide film can be relatively freely improved as compared with the conventional coating liquid for forming a polyimide film. . Further, the difunctional compound represented by the above formula [A] is a structure in which an amino group of each of two diamine compounds is introduced into a structure of a miscide, and the diamine compound is a diamine component to be used for obtaining desired properties. That is, a polymerization reaction is carried out with a tetracarboxylic acid component to produce a polyamine imine precursor or a diamine component of polyimine, and a diamine component for obtaining a desired property can be used. Therefore, various characteristics of the obtained polyimide film can be easily improved. Further, the polyimine precursor or the polyimine contained in the coating liquid for forming a polyimide film of the present invention is crosslinked by heating the difunctional compound represented by the above formula [A], and thus obtained The polyimide film is resistant to an organic solvent and becomes a hard film. The method for producing the coating liquid for forming a polyimide film of the present invention is not particularly limited, and a polymerization obtained by polymerizing at least one of a tetracarboxylic acid component selected from a tetracarboxylic acid and a derivative thereof and a diamine component is carried out. At least one polymer selected from the quinone imine precursor ' and the polyamidimide obtained by imidating the polyimine precursor hydrazine, and the amine group of each of the two diamine compounds are introduced into the rice The difunctional compound represented by the above formula [A] of the acid structure may be dissolved in a solvent. The solvent of the coating liquid for forming a polyimide film of the present invention is obtained by polymerizing at least one of the tetracarboxylic acid component selected from the tetracarboxylic acid and the derivative thereof and a diamine component. An amine precursor, and at least one polymer selected from the polyimine obtained by imidating the poly-31 - 201241046 yttrium imide precursor, and an amine group in each of the diamine compounds The difunctional compound represented by the above formula [A] of the Michler acid structure may be dissolved, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2. -pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinylpyrrolidone, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethyl Kia mill, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl decyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl iso An organic solvent such as propyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, and 4-hydroxy-4-methyl-2-pentanone. These can be used alone or in combination. The coating liquid for forming a polyimide film of the present invention preferably has a content of an organic solvent of 70 to 97% by mass from the viewpoint of coating a uniform polyimide film. The content can be appropriately changed depending on the film thickness of the polyimide film such as the intended liquid crystal alignment film. Further, the content of the polyimine precursor and the polyimine in the coating liquid for forming a polyimide film of the present invention is preferably 3 to 30% by mass. The content may be appropriately changed depending on the film thickness of the polyimide film such as the intended liquid crystal alignment film. The content of the difunctional compound represented by the above formula [Α] in the coating liquid for forming a polyimide film of the present invention is 100 to 1 part by mass based on 100 parts by mass of the total amount of the polyimide and the polyimide. The amount of the component is preferably from 1 to 100 parts by mass, particularly preferably from 1 to 50 parts by mass, in order to carry out the crosslinking reaction and exhibit desired film hardenability without lowering the alignment property of the liquid crystal. The coating liquid for forming a polyimide film of the present invention can be used in the form of a polyimine which is formed by coating the polyimine film of the present invention to form a cloth liquid without impairing the effect range of the present invention-32-201241046. The film thickness uniformity or surface smoothness of the film is an organic solvent (also referred to as a poor solvent) or a compound. Further, a compound which enhances the adhesion between the polyimide film and the substrate can be used. Examples of poor solvents which increase the uniformity of film thickness or surface smoothness, such as isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, cellosolve, butyl cellosolve, methyl cellosolve Acetate, ethyl cellulose ester, butyl carbitol, ethyl carbitol, ethyl carbitol acetate diol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether , glycol ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, alcohol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, glycol monoacetate, diethyl Glycol dimethyl ether, dipropylene glycol monoacetate ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropyl monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol Monoester monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl Isoether, diisobutylene, pentyl acetate, butyl butyl ester, butyl ether, diketone, methylcyclohexene, propyl ether, dihexyl ether, η-hexane, alkane, η-octane , diethyl ether 'lactate A , ethyl lactate, ethyl ester, ethyl acetate, η-butyl acetate, methyl propylene glycol monoethyl ether ketoacrylate, ethyl pyruvate, methyl 3-methoxypropionate, 3-ethoxy acid Ethyl ethyl ester, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-propionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1- Base-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1- using the coating to make the specific ethyl agent B, B-butylene dibutyl Monomethyl glycol acetate methyl butyrate isobutyl eta-pentanoic acid methyl propyl propyl methoxy methoxy oxy-33- 201241046 -2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol -1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate An organic solvent having a low surface tension, such as an ester, ethyl lactate, η-propyl lactate, η-butyl lactate or isoamyl lactate. These poor solvents can be used in combination of one type or plural types. When the above-mentioned poor solvent is used, it is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, based on the total of the organic solvent contained in the coating liquid for forming a polyimide film. Examples of the compound which improves the uniformity of the film thickness or the surface smoothness, such as a fluorine-based surfactant, an anthrone-based surfactant, a nonionic surfactant, etc., specifically, for example, EFTOPEF301, EF303, and EF3 52 (manufactured by Thochem Products), MEGAFACEF17 1, F173, R-30 (made by Dainippon Ink), Fluorad FC430, FC431 (manufactured by Sumitomo 3M), AsahiGuard AG7 10, Surflon S-3 82 'SC101, SC102, SC103 'SC104, SC105, SC106 (Asahi Glass system) and so on. The ratio of use of the surfactant is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 2 parts by mass, based on the total amount of the polymer component contained in the coating liquid for forming a polyimide film. 1 part by mass. Specific examples of the compound which improves the adhesion between the polyimide film and the substrate include, for example, 3·aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, and 2-amino group. Propyltrimethoxydecane, 2-aminopropyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl) --3-Aminopropylmethyldimethoxydecane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-34-201241046 3-aminopropyltrimethoxydecane, Ν·ethoxycarbonyl-3-aminopropyltriethoxydecane, Ν-triethoxydecylpropyltriethylenetriamine, Ν-trimethoxy Based on alkyl propyl triethylene triamine, 10-trimethoxydecyl-1,4,7-triazadecane, 10-triethoxydecyl-I. - triazanonane, 9-trimethoxydecyl-3,6-diazaindolyl acetate, 9-triethoxydecyl-3,6-diazaindolyl acetate, Ν-Benzyl-3-aminopropyltrimethoxydecane, Ν-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, hydrazine -Phenyl-3-aminopropyltriethoxydecane, anthracene-bis(oxyethylene)-3-aminopropyltrimethoxydecane, anthracene-bis(oxyethylene)-3-aminopropyl Triethoxy decane 'ethylene glycol diepoxypropyl ether, polyethylene glycol diepoxypropyl ether, propylene glycol diepoxypropyl ether, tripropylene glycol diepoxypropyl ether, polypropylene glycol epoxide Propyl ether, neopentyl glycol diepoxypropyl ether, 1,6-hexanediol diepoxypropyl ether, glycerol diepoxypropyl ether, 2,2-dibromo neopentyl glycol bicyclic Oxypropyl propyl ether, 1,3,5,6-tetraepoxypropyl-2,4-hexanediol, hydrazine, hydrazine, hydrazine, Ν', tetracyloxypropyl-m-xylene Amine, 1,3-bis(N,N-diepoxypropylaminomethyl)cyclohexane or >1, 叱>1', >1',-tetraepoxypropyl-4, Functional 矽 such as 4'-diaminodiphenylmethane Epoxy group-containing compound or compounds. When the compound to be adhered to the substrate is used, the total amount of the polymer component contained in the coating liquid for forming a polyimide film of the present invention is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 30 parts by mass. 1 to 20 parts by mass. When the amount is less than 1 part by mass, the effect of improving the adhesion is not expected, and if the amount is more than 30 parts by mass, the alignment of the liquid crystal is deteriorated. Further, in the coating liquid for forming a polyimide film of the present invention, the dielectric properties such as the dielectric constant or the conductivity of the polyimide film can be changed without impairing the effect range of the invention of the present invention. A dielectric or conductive substance of interest. Further, in the coating liquid for forming a polyimide film of the present invention, a crosslinkable compound having an epoxy group, an isocyanate group or an oxetanyl group can be incorporated without impairing the effect of the present invention, and further A crosslinkable compound having at least one substituent selected from a group consisting of a hydroxyl group or an alkoxy group or a crosslinkable compound having a polymerizable unsaturated bond. The coating liquid for forming a polyimide film of the present invention can be used as a liquid crystal alignment agent for forming a liquid crystal alignment film. Further, the liquid crystal alignment film means a film which aligns the liquid crystal in a specific direction. The polyimine film can be formed by applying the coating film for forming a polyimine film of the present invention to a substrate and baking it. In addition, when the coating liquid for forming a polyimide film of the present invention is used as a liquid crystal alignment agent, it is applied onto a substrate and fired, and then subjected to alignment treatment by rubbing treatment or light irradiation, or vertical alignment. A liquid crystal alignment film can be formed without using an alignment treatment. The substrate is not particularly limited as long as it is a coating liquid for forming a polyimide film, but it is preferable to form a liquid crystal alignment film with high transparency. Specific examples thereof include a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, and the like. Further, it is preferable to use a substrate such as an ITO electrode for driving a liquid crystal, from the viewpoint of simplification of the process. Next, in the reflective liquid crystal display device, an opaque such as a germanium wafer can be used for the substrate on only one side. In this case, a material such as aluminum or the like can be used. Further, in a TFT-type element-like high-performance device, an element formed of a transistor such as a transistor can be used between the electrode for driving a liquid crystal and the substrate -36-201241046. The coating method of applying the coating liquid for forming a polyimide film to a substrate is not particularly limited. However, industrial printing is generally carried out by screen printing, offset printing, flexographic printing, ink jet printing or the like. Other coating methods include dip coating, roll coating, slit coating, spin coating, etc., and may be used depending on the purpose. The coating liquid for forming a polyimide film is applied onto a substrate, and if necessary, one or all of the solvent is dried and then fired. This may be heated to a temperature at which the Mic acid structure of the difunctional compound represented by the above formula [A] is an ketene or the like and may react with a carboxyl group or the like of a polyimine precursor or a polyimine. For example, it is carried out at 180 to 250 ° C by means of heating means such as a hot plate, a hot air circulation furnace or an infrared furnace, and the solvent is evaporated to simultaneously react the structure of the Michler acid with the polyimine precursor or the polyimine, and in the poly The amine precursor or the polyimine is introduced into the difunctional compound represented by the above formula [A] to form the polyimide film of the present invention. The polyimine film thus obtained has a structure in which the polyimine is crosslinked by the difunctional compound represented by the above formula [A], and the hard film is excellent in cutting resistance. When the thickness of the polyimide film formed after firing is made into a liquid crystal alignment film, if it is too thick, it is disadvantageous in the power-consuming surface of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element is lowered. It is preferably 5 to 300 nm, more preferably 10 to 200 nm. ● When the liquid crystal is aligned horizontally or obliquely, the coating film after firing is treated by rubbing or polarized ultraviolet irradiation or the like. After the liquid crystal display element of the present invention is obtained by the above-described method, a liquid crystal cell is produced by a conventional method, and a liquid crystal display device is used to produce a liquid crystal display device. 37-201241046. An example of the liquid crystal alignment agent comprising a liquid crystal layer provided between the substrate and the liquid crystal layer, which is provided between the substrate and the liquid crystal layer, is provided by a liquid crystal alignment agent comprising a coating liquid for forming a polyimide film of the present invention. The liquid crystal display element of the liquid crystal cell of the above liquid crystal alignment film. In the liquid crystal display device of the present invention, for example, a twisted nematic (TN: Twisted Nematic) method, a vertical alignment (VA: Vertical Alignment) method, or an IPS (In-Plane Switching) method can be used. The substrate used for the liquid crystal display device of the present invention is not particularly limited as long as it has a high transparency. However, a substrate having a transparent electrode for driving a liquid crystal is usually formed on the substrate. Specific examples are the same as those described in the above polyimide film. Further, the liquid crystal alignment film is formed by applying the liquid crystal alignment agent of the present invention to the substrate and then firing it, as described above. The liquid crystal material constituting the liquid crystal layer of the liquid crystal display device of the present invention is not particularly limited, and a conventional liquid crystal material such as MLC-2003, MLC-6608, MLC-6609 manufactured by Merck Co., Ltd., etc., may be used. For example, a pair of substrates on which a liquid crystal alignment film is formed may be prepared, and a spacer such as a bead may be spread on a liquid crystal alignment film of one substrate, and a liquid crystal alignment film surface may be formed inside, and another substrate may be bonded to reduce liquid crystal. A method of sealing by pressure injection or a method of sealing a substrate by dropping a liquid crystal on a liquid crystal alignment film surface of a spacer, and the like. In this case, the thickness of the spacer is preferably 1 to 3 μm, more preferably 2 to 10 μηα. The liquid crystal display element produced as described above is expressed by the above formula [A] which can introduce the desired characteristic -38 to 201241046. Since the difunctional compound is produced by a liquid crystal alignment agent having at least one polyimine precursor and polyimine, it is possible to improve various characteristics. [Embodiment] [Embodiment] Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the explanation of the present invention is not limited to the examples. [Synthesis of a difunctional compound represented by the above formula [A]] <Synthesis Example 1> Compound 5,5'-(l,4-phenylenebis (azanediyl))bis (methan) represented by the following formula [4] Synthesis of -l - yl-1 - ylidene)bis(2,2-dimethyl-l,3-dioxane-4,6-dione) [Chemical 2 2]

In a 30 mL four-necked flask, Michleric acid [1] (14.7 g, 102 mmol) and trimethyl orthoformate [2] (147 g) were added, and the mixture was heated under reflux for 1 hour. Thereafter, p-phenylenediamine [3] (5. g, 46 mmol) was further added and heated under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtered, washed with hexane, and then the solid was dried to -39 - 201241046 to give 15.8 g of compound [4] (yield: 82%). 'Η-ΝΜΚ(400ΜΗζ,ΟΜ8Ο-ά6,δρριη) : 1 1 , 29(2H,d), 8.56(2H,d)>7.64(4H,s)> 1.68(12H,s). <Synthesis Example 2 > Compound 5,5'-(l,3-phenylenebis (azanediyl))bis(methan-l-yl-l-ylidene)bis(2,2- represented by the following formula [6] Synthesis of dimethyl-l,3-dioxane-4,6-dione) [Chemical 2 3]

In a 300 mL four-necked flask, Michleric acid [1] (14.7 g, 102 mmol) and trimethyl orthoformate [2] (147 g) were added, and the mixture was heated under reflux for 1 hour. Thereafter, m-phenylenediamine [5] (5.0 g, 46 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtered, washed with hexane, and then dried to give 14.1 g of compound [6] (yield: 72%). 1H-NMR (400MHz, DMSO-d6, 6ppm): 11.28 (2H, s), 8.74 (2H, s), 7.78 (1H, s), 7.44 (3H, s), 1.68 (12H, s)» < Synthesis Example 3> Compound 5,5'-(pyridine-2,6-diylbis -40 - 201241046 (azanediyl))bis(methan-l-yl-l-ylidene)bis(2) represented by the following formula [8] Synthesis of 2-dimethyl- l,3-dioxane-4,6-dione

In a 300 mL four-necked flask, Michleric acid [1] (16.0 g, lll mmol) and trimethyl orthoformate [2] (160 g) were added, and the mixture was heated under reflux for 1 hour. Thereafter, 2,6-diaminopyridine [7] (5.5 g, 50 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtered and washed with hexane. Then, the solid was dried to obtain 16.7 g (yield: 80%) of compound [8]. W-NMRHOO MHz &lt;RTI ID=0.0&gt;&gt;&gt;&gt;&gt;&gt; </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> <RTIgt; &lt;Synthesis Example 4&gt; Compound 5,5'-(4,4'-iriethylenebis(4,l-phenylene)bis(azanediyl))bis (methan-l-yl-ly 1) represented by the following formula [10] Synthesis of idene) bis (2,2 - dimethy 1 -1,3 - dioxane - 4,6 - di ο ne ) -41 - 201241046 [Chem. 2 5]

H2N nh2 [9]

[i] CH(OMe)3 [2] o

〇V ‘mx [10] oΗΛ7 In a 30 mL four-necked flask, Michleric acid [1] (14.7 g, 102 mmol) and trimethyl orthoformate [2] (l47 g) were added, and the mixture was heated under reflux for 1 hour. Thereafter, 4,4'-diaminodiphenylmethane [9] (5. g, 46 mmol) was added, and the mixture was further heated under reflux for 2 hours. After the completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtered and washed with hexane, and then the solid was dried to obtain 14.1 g (yield: 72%). 1H-NMR (400MHz, DMSO-d6, 5ppm): 1 1.23(2H,d), 8.54(2H,d) , 7.5 0-7.48 (4H,m) , 7 · 3 1 - 7 · 2 9 (4 Η , m), 3.96 (2H, m), 1.66 (12H, s). &lt;Synthesis Example 5 &gt; Compound 5,5, (4,4'-oxybis(4,l-phenylene)bis(azanediyl))bis (methan-l-yl-l) represented by the following formula [12] -ylidene) Synthesis of bis (2,2-dimethyl-l,3-dioxane-4,6-dione)

-42- 201241046 In a 200 mL four-necked flask, Mic acid [l] (7.92 g, 54.9 mm )l) and trimethyl orthoformate [2] (78 g) were added, and the mixture was heated and refluxed for 1 hour. Thereafter, 4,4'-diaminodiphenyl ether [U] (5.0 g, 2 5 · 0 m m ο 1 ) was added, and further reflux was carried out for 2 hours. After the completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtered, washed with hexane, and then the solid was dried to obtain 11.7 g (yield: 92%) of compound [12]. 1H-NMR (400MHz, DMSO-d6, 5ppm): 11.30(2H,d) ' 8.51 (2H,d), 7.62 (4H,d), 7.08 (4H,d), 1.67 (12H,s)» &lt; Synthesis Example 6&gt; Compound 5,5'-(4,4^azanediylbis(4,l-phenylene)bis(azanediyl))bis(methan-l-yl-l-ylidene)bis represented by the following formula [14] Synthesis of (2,2-dimethyl-l,3-dioxane-4,6-dione) [Chemical 2 7]

In a 200 mL four-necked flask, Michleric acid [l] (7.96 g, 55.2 mmol) and trimethyl orthoformate [2] (79 g) were added, and the mixture was heated and refluxed for 1 hour. Thereafter, 4,4'-diaminodiphenylamine [13] (5.0 g, 2 5.1 m m ο 1 ) was added, and the mixture was further subjected to a heat D reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtered, washed with hexane -43-201241046, and then solid was dried to give compound [l4]l.g (yield: 79%). 'H-NMR (400 MHz, DMSO-d6, 5 ppm): 11.29 (2H, d), 8.51 (2H, d), 7.62 (4H, d), 7.08 (4H, d) ' 4.97 (lH, s) ' 1.67 (12H, s). &lt;Synthesis Example 7&gt; The compound represented by the following formula [16], 5'-(4,4'-(methylazanediyl)bis(4,1 - phenylene)bis(azanediyl) bis(methan-l-yl) -l-ylidene) Synthesis of bis(2,2-dimethyl-1,3-dioxane-4,6-dione)

In a 500 mL four-necked flask, Michleric acid [1] (14.9 g, 103 mmol) and trimethyl orthoformate [2] (100 g) were added, and the mixture was heated under reflux for 1 hour. Thereafter, 4,4'-diaminodiphenylmethylamine [15] (10.0 g, 46.9 mmol) was added, and the mixture was further heated under reflux for 2 hours. After the completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtered and washed with hexane, and then the solid was dried to obtain 21.7 g (yield: 86%) of compound [16]. 1H-NMR (400MHz, DMSO-d6, 6ppm): 1 1 .2 1 (2H, d) &gt; 8.44 (2H, d), 7.45-7.42 (4H, m), 7.03-7.01 (4H, m), 3.24 (3H, s), 1.62 (12H, s). -44-201241046 &lt;Synthesis Example 8&gt; Compound 5,5'-(4,4'-(pentane-l,5-diylbis(oxy))bis(4,l-phenyl) represented by the following formula [18] Ene)) Synthesis of bis(azanediyl)bis(methan-l-yl-l-ylidene)bis(2,2-dimethyl-l,3-dioxane-4,6-dione)

[17]

米 In a 300 mL four-necked flask, Michleric acid [1] (16.6 g, 1 15 mmol) and trimethyl orthoformate [2] (1 1 lg) were added, and the mixture was heated under reflux for 1 hour. Thereafter, the compound [17] (15.0 g, 52.4 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtered, washed with hexane, and then dried to give 20.8 g (yield 67%) of compound [18]. 1H-NMR (400MHz, DMSO-d6, 8ppm): 1 1 . 2 3 (2H, s) * 8.45 (2H, s) , 7.5 1 - 7.47 (4H, m) , 7.0 0 - 6 · 9 4 ( 4 H, m), 4.01 (4H, t) &gt; 1.8 2- 1.72 (4H, m) &gt; 1.67 (12H, s) &gt; 1.62-1.54 (2H, m). &lt;Synthesis Example 9&gt; Compound 1 represented by the following formula [20] J-bisH-Uae-dimethyl-jJ-dioxo-lJ-dioxan-S-ylideneJmethylamincOphenethyl) -45- 201241046 Synthesis of urea

In a 200 mL four-necked flask, Mic acid [n (28.6 g, HTnimol), and dimethyl acetal [2] (2008) were added, and the mixture was heated under reflux for 1 hour. Thereafter, the compound [l9] (2 〇.〇g, 67.0 mm 〇l) was added and the mixture was heated under reflux for 2 hours. After the completion of the reaction, the reaction solution was cooled to room temperature. The precipitated solid was filtered, washed with a house, and then dried to give a compound [20] 4 〇.3 g (yield: 99%). 'H-NMR (400 MHz, DMSO-d6, 6 ppm): 1 1 . 1 7 (2H, d) ' 8.48 (2H, d), 7.40 (4H, d), 7.21 (4H, d) ' 5.89 (2H, t) ' 3.18-3.14(4H,m), 2.62(4H,t), 1.62(12H,s). &lt;Synthesis Example 1 0 &gt; Compound 5,5'-(6,7,9,10,17,18,20, 21-octahydrodibenzo[b,k][l,4 represented by the following formula [22] ,7,10,l3,l6] hexaoxacyclo〇ctadecine-2,13-diyl)bis(azanediy1) bis(methan-l-yi_i_yiidene)bis(2,2-dimethyl_l,3-di〇Xane-4,6-dione Synthesis of -46- 201241046

[Chemical 3 1 I

In a 200 mL four-necked flask, Michleric acid [1] (7.38 g, 51.2 mmol) and trimethyl orthoformate [2] (10 g) were added, and the mixture was heated under reflux for 1 hour. Thereafter, the compound [21] (10.0 g, 25.6 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed by an evaporator and dried to give Compound [2 2 ] 1 7.9 g (yield: 6%). 1H-NMR (400MHz, DMSO-d6, 5ppm): 11.16(2H,d) » 8.50(2H,d) &gt; 7.19(.2H,d) - 7.0 1 - 6.9 8 (2 Η, m) &gt; 6.93 (2H, m)·. 4.09-4.08 (4H, m) · 4.0 4 - 4.0 2 (4 H, m ) , 3.79 (8H, m), 1.6 1 (1 2H, s) ° &lt;Synthesis Example 11&gt; The compound represented by the following formula [24] is 5-((3-((2,2-dim ethyl-4,6-diox〇-l,3-dioxan-5-ylidene)methylamino)benzylamino) methylene)-2 Synthesis of 2-dimethyl-l, 3-dioxane-4,6-dione [Chemical 3 2]

In a 300 mL four-necked flask, Michleric acid [1] (23.6 g, 201241046 164 mmol) and trimethyl orthoformate [2] (10 g) were added, and the mixture was heated under reflux for 1 hour. Thereafter, 3-aminobenzylamine [23] (10.0 g, 81.9 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed by an evaporator and dried to give the compound [2 4 ] 3 6.2 g (yield 100%. 1H-NMR (400 MHz, DMSO-d6, 8 ppm) 11.21 (lH, s), 1 0.04-9.97( 1 H,m) &gt; 8.55(lH,s) &gt; 8.30(lH,d) « 7.57(lH,s) &gt; 7.48 -7.3 8(2H,m) &gt; 7.23(lH,d - 4.65 (2H, d) » 1.63 (6H, s) &gt; 1.55 (6H, s) » &lt;Synthesis Example 1 2 &gt; Compound 5,5'-( represented by the following formula [26] 4,4'-chemical 1*(^3116-1,3-diyl)bis(piperidine-4,l-diyl))bis(methan-l-yl-l-ylidene) bis(2,2-dimethyl-l , 3-dioxane-4, 6-dione) Synthesis [Chemical 3 3]

In a 200 mL four-necked flask, Michleric acid [1] (11.7 g, 81.0 mmol) and trimethyl orthoformate [2] (128 g) were added, and the mixture was heated under reflux for 1 hour. Thereafter, 1,3 -di-4-piperidylpropane [25] (8.52 g, 4 0 · 5 m m ο 1 ) was added, and further reflux was carried out for 2 hours. After completion of the reaction, the solvent was removed by an evaporator and dried to obtain a compound [2 6 ] 2 0.2 g (yield 9 9%) ° 1 Η-NMR (4 0 0 M Hz, DMS Ο - d 6, δρρ m) : 8.09(2H,s) » -48- 201241046 4.06-3.97(4H,m) * 3.5 6 - 3.4 9 (2 Η , m) &gt; 3.2 8 - 3.2 5 ( 2 Η , m )' 1.84-1.81( 4H,m)' 1.61-1.56(12H,m)&gt; 1.3 2- 1.23 (1 2H, m). &lt;Synthesis Example 13&gt; A compound 5,5'-(91:(^3116-1,3-diylbis(azanediyl))bis(methan-l-yl-l-ylidene) represented by the following formula [28] Synthesis of bis(2,2-dimethyl-l,3-dioxane-4,6-dione) [Chemical 3 4]

[27] In a 5 00 mL four-necked flask, a solution of [1] (42.8 g, 297 mmol) and trimethyl orthoformate [2] (150 g) was added, and the mixture was heated under reflux for 1 hour. Thereafter, 1,3-diaminopropane [27] (10.0 g, 135 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtered, washed with hexane, and then dried to give a compound [28] 24.8 g (yield: 48%). lH-NMR (400MHz, CDC13, 5ppm): 9.5 7 - 9 · 5 4(2H,m), 8.16(2H,d),3.59(4H,q),2.11(2H,quin),1.71(12H,s ). &lt;Synthesis Example 14&gt; The compound represented by the following formula [30] SJ'dcyclohexane-lj-diylbisimethylenenbisiazanediynbisimethan-l-yl-l--49-201241046 ylidene)bis(2,2-dimethyl-l,3-dioxane- Synthesis of 4,6-dione) [Chemical 3 5]

CH(OMe)3 [2]

In a 00 mL four-necked flask, Michleric acid [l] (44.6 g, 3 09 mmol) and trimethyl orthoformate [2] (200 g) were added, and the mixture was heated under reflux for 1 hour. Thereafter, 1,3-diaminomethylcyclohexane (cis-/trans-mixture) [29] (20.0 g, 141 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtered, washed with hexane, and then dried to give compound [30] (cis-/trans-mixture) 58.3 g (yield: 92%). . 1 H-NMR (400 MHz, DMSO-d6, 5 ppm): 9.63-9.60 (2H, m) &gt; 8.1 1-7.97 (2H, m) &gt; 3 . 5 1 - 3 .1 2 (4 Η, m) &gt; 1.87-0.54 (22H, m). &lt;Synthesis Example 1 5 &gt; Compound 3, 5-1^8 represented by the following formula [32] ((2,2-&lt;1丨111611^1-4, 6-dioxo-l, 3-dioxan -5-ylidene) Synthesis of methylamino)benzoic acid -50-201241046 [Chem. 3 6]

CH(OMe)3 [2]

[32] In a 200 mL four-necked flask, Michleric acid [l] (10 g, 72.3 mmol) and trimethyl orthoformate [2] (105 g) were added, and the mixture was heated under reflux for 1 hour. Thereafter, 3,5-diaminobenzoic acid [31] (5 Jg '32.9 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtered and washed with hexane, and then the solid was dried to give 9.0 g (yield: 59%) of compound [32]. 1 H-NMR (400 MHz, DMSO-d6, 5 ppm): 11.34 (2H,d), 8.74 (2H,d), 7.92 (2H,d), 1.69 (12H, s). &lt;Synthesis Example 16&gt; Compound 3, 5-1 &gt; 丨 3 represented by the following formula [34] ((2, 2-(1丨111611^1-4, 6-dioxo-l, 3-dioxan-5) -ylidene)methylamino)-N-(pyridin-3-ylmethyl)benzamide Synthesis [Chem. 3 7]

In a 200 mL four-necked flask, Michleric acid [l] (6-5 g, 45.4 mmol) and trimethyl orthoformate [2] (66 g) were added and heated for 1 hour to reflux -51 - 201241046. Thereafter, the compound [33] (5.0 g, 20.6 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed by an evaporator and dried to give 11.3 g (yield: 98%) of compound [34]. lH-NMR (400 MHz, DMSO-d6, 5 ppm): 1 1.35 (2H, d), 9.27 (1H, t), 8.78 (2H, d), 8.59 (lH, d), 8.49-8.47 (lH, m), 8.16-8.15 (lH, m), 7.84 (2H, d), 7.77-7.74 (lH, m), 7.40-7.36 (lH, m), 4.55 (2H, d), 1.69 (12H, s) . &lt;Synthesis Example 17&gt; The compound N-(3-(lH-imidazol-l.yl)propyl)-3,5-bis ((2,2-dimethyl-4,6-) represented by the following formula [36] Synthesis of dioxo-l,3-dioxan-5-ylidene)methylamino)benzamide [Chemical 3 8]

In a 200 mL four-necked flask, Michleric acid [l] (10. lg, 52.1 mmol) and trimethyl orthoformate [2] (50 g) were added for heating for one hour. Thereafter, the compound [35] (5. 〇g, 23.7 mm 〇l) was added and the mixture was heated under reflux for 2 hours. After completion of the reaction, the solvent was removed by an evaporator and dried to obtain 13.4 g of a compound [36] (yield: 1%). 1H-NMR (400MHz, DMSO-d6, 5ppm): 1 1.27 (2H, s) &gt; 8.71-8.65 (3H, m) &gt; 8.01(lH,t) * 7.99(lH,t) &gt; 7.75(2H , d) » -52- 201241046 7.32(lH,t),7.05(lH,t),4.07-4.03 (2H,m), 3.25-3.18(2H,m),1.97(2H,t),1.64(12H , s). &lt;Synthesis Example 1 8&gt; Compound 3,5-bis((2,2-dimethyl- 4,6-dioxo-l,3-dioxan-5-ylidene)methylamino)benzylfuran represented by the following formula [38] Synthesis of 2-carboxylate [Chemical 3 9]

In a 200 mL four-necked flask, Michleric acid [1] (13.7 g, 94.7 mmol) and trimethyl orthoformate [2] (100 g) were added and heated under reflux for 1 hour. Thereafter, the compound [37] (10.0 g, 43.1 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtered, washed with hexane, and then dried to give compound [38] 2l. lg (yield 90%). , H-NMR (400 MHz, DMSO-d6, 5 ppm): 1 1,22 (2H,d), 8.67 (2H,d) &gt; 7.94-7.93 (lH,m) &gt; 7.8 7 - 7.8 6 ( 1 Η , m) &gt; 7.46-7.45 (2H,m) &gt; 7.3 8( 1 H,dd) , 6.6 8-6 · 66( 1 H,m) ' 5.28(2H,s),1.63(12H,s) . &lt;Synthesis Example 19&gt; Compound 5,5-(4-(dodecyloxy)-l,3--53-201241046 phenylene)bis(azanediyl)bis(methan-l-yl-) represented by the following formula [40] Synthesis of l-ylidene)bis (2,2-dimethyl-l,3-dioxane-4,6-dione) [Chemical 4 Ο]

Mice acid [l] (10.8 g, 7 5.2 mmol) and trimethyl orthoformate [2] (100 g) were placed in a 300 mL four-necked flask, and heated under reflux for 1 hour. Thereafter, the compound [39] (10.0 g, 34.2 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed by an evaporator and dried to give a compound [4], 29.7 g (yield: 99%). 'H-NMR (400 MHz, DMSO-d6, 5 ppm): 11.57 (lH, d), 1 1 · 2 0 (1 Η, d) , 8 · 9 0 (1 Η, d) , 8 · 6 4 (1 Η, d), 8 . Ο 9 ( 1 Η, d), 7.31 (lH, dd), 7.13 (lH, d), 4.06 (2H, t), 1.74 - 1.68 (2H, m), 1.63 (12H, s) , 1.46- 1.40 (2H, m) &gt; 1.2 5 -1 . 1 6 (1 6 H , m) * 0.79 (3H, t). &lt;Synthesis Example 20&gt; The compound 5,5'-(4-(〇(^&lt;16〇71(^7)-l,3-phenylene)bis(azanediyl)bis) represented by the following formula [42] Methan-l-yl-l-ylidene) Synthesis of bis(2,2-dimethyl-l,3-dioxane-4,6-dione)-54- 201241046 [Chem. 4 1]

^18^37 Ο

CH(OMe)3[2] 〒18&quot;37 Ο _

Methanol acid [1] (4.2 g, 29.2 mmol) and trimethyl orthoformate [2] (42 g) were placed in a 100 mL four-necked flask, and heated to reflux for 1 hour. Thereafter, the compound [41] (5.0 g, 13-3 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtered, washed with hexane, and then dried to give compound [4 2 ] 6.4 g (yield 71%). 1H-NMR (40 0MHz, DMSO-d6, 5ppm): 1 1,63 (1H,d) &gt; 11.26(lH,d) &gt; 8.99(lH,d) » 8.72(lH,d) - 8.19(lH , d) &gt; 7.40(lH,dd) &gt; 7.20(lH,d), 4.13(2H,t),1 . 8 0 · 1.7 4 (2 H,m), 1.68( 1 2H,s) , 1.49 - 1.45 (2H, m), 1.2 5 - 1.22 (2 8 H, m), 0.85 (3H, t). &lt;Synthesis Example 2·1_&gt; The compound represented by the following formula [44], 5'-(4-(4-(trans-4-heptylcyclohexyl)phenoxy)-l,3-phenylene)bis(azanediyl) bis Synthesis of (methan-l-yl-l-ylidene)bis(2,2-dimethyl-l,3-dioxane-4,6-dione)-55-201241046 [Chem. 4 2]

Michnic acid [i] (4.2 g, 28.9 mmol) and trimethyl orthoformate [2] (41 g) were placed in a 100 mL four-necked flask, and heated to reflux for 1 hour. Thereafter, the compound [43] (5. Og, 1 3.1 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed by an evaporator and dried to give the compound [4 4 ] 9.0 g (yield 98%). 'H-NMR (400 MHz, DMSO-d6, 5 ppm): 11.64 (1H, d), ll_30 (lH, d) ' 9.03 (lH, d), 8.76 (lH, d), 8.31 (lH, d), 7.40 (lH, dd), 7.28 (2H, d), 7.03 (2H, d), 6.97 (lH, d), 1.81 (2H, d), 1.69 (10H, d), 1.44 - 1.34 (lH, m), 1.26-1.78 (1 0H, m), 1.07-1.01 (lH, m), 0.86 (3H, t). &lt;Synthesis Example 22&gt; The compound 5,5'-(4-(trans-4-(trans-4'-pentylbi(cyclohexan)-4-yl)phenoxy)-l,3 represented by the following formula [46] Synthesis of -phenylene)bis (azanediyl)bis(methan-l-yl-l-ylidene)bis(2,2-dimethyl-l,3-dioxane-4,6-dione)-56- 201241046

[Chemical 4 3 I

In a 300 mL four-necked flask, Michleric acid [l] (9.0 g, 62.1 mmol) and trimethyl orthoformate [2] (120 g) were added, and the mixture was heated under reflux for 1 hour. Thereafter, the compound [45] (12.3 g, 2 8.2 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed by an evaporator and dried to give 20.68 g (yield: 98%) of compound [46]. 1H-NMR (400MHz, DMSO-d6, 5ppm): 11.64 (1H, d), 11.30 (1H, d), 9.03 (lH, d), 8.76 (lH, d), 8.31 (lH, d), 7.39 ( lH, dd), 7.27 (lH, d) * 7.02 (2H, d) » 6.97 (2H, d), 1. 88- 1.03 (43H, m) &gt; 0.86 (3H, t). &lt;Synthesis Example 23&gt; The compound represented by the following formula [48], 5'-(5-((trans-4-(trans-4'-pentylbi(cyclohexan)-4-yl)phenoxy)methyl)-) Synthesis of l,3-phenylene)bis(azanediyl)bis(methan-l-yl-l-ylidene)bis(2,2-dimethyl-l,3-dioxane-4,6-dione)-57- 201241046 4 4]

[48]

[11 ^ CH(OMe)3 [2]

r η2ν^^νη2 [47] A milliliter flask [1] (19.0 g, 98.6 mmol) and trimethyl orthoformate [2] (200 g) were placed in a 500 mL four-necked flask, and heated under reflux for 1 hour. Thereafter, the compound [47] (20.0 g, 44.6 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed by an evaporator and dried to give 33.4 g (yield: 99%) of compound [48]. 'H-NMR (400 MHz, DMSO-d6, 8 ppm): 1 1.29 (2H, d), 8.74 (2H, d) * 7.94 (1H, s) &gt; 7.53 (2H, d), 7.12 (2H, d) , 6.92 (2H, d), 5.09 (2H, s), 1.8 1 - 1.68 (20H, m), 1.3 6-0.84 (2 3 H, m). &lt;Synthesis Example 24&gt; Compound 4^pentylbi(trans-cyclohexan)-4-yl 3,5-bis ((2,2-dimethyl-4,6-dioxo-l,3) represented by the following formula [50] Synthesis of -dioxan-5-ylidene)methylamino)benzoate 201241046 [Chem. 4 5]

In a 500 mL four-necked flask, Michleric acid [l] (i3.3 g '92.0 mmol) and trimethyl orthoformate [2] (150 g) were added, and the mixture was heated under reflux for 1 hour. Thereafter, the compound [49] (15.0 g, 41.8 mm 〇l) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed by an evaporator and dried to give a compound [5], 28.8 g (yield: 99%). 'H-NMR (400MHz, DMSO-d6, 5ppm) 1 1.28 (2H, s) &gt; 8.67 (2H, s), 8.17 (lH, t), 7.86 (2H, d), 4.79-4.73 (lH, m ), 2.02 (2H, d), 1.74-1.64 (1 8H, m) &gt; 1.4 4 -1. 3 2 (2H, m) &gt; 1.29-0.76 (20H, m) ° &lt;Synthesis Example 25&gt; The compound represented by the following formula [52] &gt; 1-(2,4-13丨8((2,2-£1丨1116〖]1乂1-4,6-dioxo-l,3-dioxan- Synthesis of 5-ylidene)methylamino)phenyl)-4-(trans-4-pentylcyclohexyl)benzamide-59- 201241046

C5H11 jQCnh h2n^^nh2

[2]

csHu [51] 〇X〇H %工七七[52] In a 300 mL four-necked flask, add Mic acid [l] (8.2 g, 56.7 mmol), and trimethyl orthoformate [2] (80 g) , heating and refluxing for 1 hour. Thereafter, the compound [51] (10 g, 25.8 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtered and washed with hexane. Then, the solid was dried to obtain 16.0 g (yield: 92%) of compound [52]. 1H-NMR (400MHz, DMSO-d6, 6ppm): 1 1.36- 1 1,27(2H,m) ' 10.38 (lH, s), 8.80-8.74 (2H, m), 8.09 (lH, s), 7.87 (2H,d), 7.44(1 H,dd) , 7.34(2H,d) , 2.51 - 2·46 (3H,m), 1.77(2H,d),l,66(6H,s),1.59( 6H, s), 1.50-1.3 7 (3H, m), l_29-1.14 (8H, m), 0.99 (2H, q), 0.82 (3H, t). &lt;Synthesis Example 2 6 &gt; Compound 1^-(2,4-1)丨8 ((2,2-(1丨111611171·4,6-dioxo-l,3) represented by the following formula [54] Synthesis of -dioxan-5-ylidene)methylamino)phenyl)-4-(trans-4-Heptylcyclohexyl)benzamide-60-201241046 [Chem. 4 7]

In a 300 mL four-necked flask, Michleric acid [1] (11.7 g, 81.0 mmol) and trimethyl orthoformate [2] (150 g) were added, and the mixture was heated under reflux for 1 hour. Thereafter, the compound [53] (15..0 g, 36.8 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtered, washed with hexane, and then solid was dried to give compound [54] 26.1 g (yield: 99%). 'Η-ΝΜΚ(400ΜΗζ,ΟΜ8Ο-(16,δρρχη) : 1 1.3 6- 1 1.27(2H,m) -10.38(lH,s) &gt; 8.78(2H,t) - 8.10(lH,s) &gt; 7.88(2H,d) &gt; 7.44(lH,dd) &gt; 7.35(3H,d) &gt; 2.52(2H,t) &gt; 1.78(2H,d) « l_65(6H,s),1.60(6H, s), 1.5 0- 1.3 7 (2H, m), 1.29-1.12 (14H, m), 0.99 (2H, q), 0.82 (3H, t) 〇 &lt;Synthesis Example 27&gt; The following formula [5 6] The compound represented 5,5'-(4-((3 3,8 3,93,1011, 13R,14S,17R)-10,13-dimethyI-17-((R)-5-methylhexan-2- Yl)-2,3,4,7,8,9,10,ll,12,13,14,15,16,17-tetradecahydro-lH-cyclopenta[a]phenanthren-3-yloxy)-l,3- Synthesis of phenylene) bis(azanediyl)bis(methan-l - yl -1 - ylidene)bis(2,2-dimethyl -l,3-dioxane-4,6-dione)-61 - 201241046

[56] [Chem. 4 8]

ο乂. 00&lt;^Λ·0 [1] CH(OMe)3 [2] In a 100 mL four-necked flask, add Mic acid [U (4.1 g, 29 mmol), and trimethyl orthoformate [2] (5 〇g) After "heating under reflux for 1 hour", 'the compound [55] (10.0 g, 13 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature. The precipitated solid was filtered and washed with hexane, and then the solid was dried to give the compound [56] 9.9 g (yield: 99%). &lt;Synthesis Example 28&gt; A compound represented by the following formula [58] (ugly)-2, 4-13丨8 ((2,2-(1丨111611^1-4,6-dioxo-l,3- Synthesis of dioxan-5-ylidene)methylamino)phenethyl 3-(4-(decyloxy)phenyl)acrylate

[58] oc10h21 In a 200 mL four-necked flask, Mic acid [i] (7.3 g, -62 - 201241046 37 mmol) and trimethyl orthoformate [2] (75 g) were added, and the mixture was heated and refluxed for 1 hour. Thereafter, the compound [57] (7.46 g '17 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed by an evaporator and dried to give Compound [58] 12.5 g (yield: 99%)» 'H-NMR (400 MHz, DMSO-d6, 6 ppm): 11.57 (lH, d), 1 1.29 ( 1 H, s), 8.82 (1 H, dd), 8.23 (lH, dd), 8.04 (lH, s) ' 7.57-7.46 (5H, m), 6.92 (2H, d), 6.35 (lH, d ), 4.34(2H,t), 3.99(2H,t) - 1.74- 1.65( 1 5H,m) , 1 · 4 3 -1 . 2 1 (1 5 H,m), 〇.85(3H,t ). &lt;Synthesis Example 29&gt; Compound (E)-3,5-bis represented by the following formula [60] ((2,2-dimethyl- 4,6&quot;diox〇'1»3-dioxan-5-ylidene) Synthesis of methylamino)benzyl 3-(4-(decy 1 oxy) phenyi) acryiate [化5 〇]

[59]

In a 2o〇mL four-necked flask, add [i] (6.3 g, 3 3 mmol) ' and trimethyl orthoformate [2] (63 g), and heat up for 1 hour, then add the compound [59] ( 6.3 g, 15 mmol), and further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed by an evaporator to give 10.7 g (yield: 99%) of compound [60]. H-NMR (400 MHz, DMSO-d6, 6 ppm): 11.25 (1H,d) &gt; -63- 201241046 8.71 (lH,d),7_93 (lH,s), 7.67-7.62 (3H,m), 7.48 (2H,d), 6.91(2H,d),6.52(lH,d), 5.19(2H,s),3.96(2H,t), 3.62-3.60(2H,m) &gt; 1 . 6 8 - 1.6 3 ( 1 5 H, m) &gt; 1 . 3 8 - 1 . 2 0 ( 1 5 H , m) - 0.8 1 (3H, t). &lt;Synthesis Example 30&gt; 5,5^(((6,7,9,10,17,18,20,21-octahydrodibenzo[b,k][l,4,7) represented by the following formula [62] ,10,13,16]hexaoxacyclooctade cine-2,14-diyl)bis(azanediyl))bis(methanylylidene)) Synthesis of bis(2,2-dimethyl-l,3-dioxane-4,6-dione) 5 1]

In a 200 mL four-necked flask, Michleric acid [l] (4.87 g, 3 3.8 mmol) and trimethyl orthoformate [2] (60 g) were added, and the mixture was heated and refluxed for 1 hour. Thereafter, the compound [61] (6.00 g, 15.4 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed by an evaporator and dried to give a compound [62] 〇. 4 g (yield: 97%). &lt;1&gt;H-NMR (400 MHz, DMSO-d6, 5 ppm): 1 1 .2 1 (2H , d), 8.54 (2H, d), 7.26 (2H, d), 7.05 (2H, dd), 6.96 (2H, d), 4.1 5-4.06 (8H, m), 3.8 8 - 3.8 0 (6 H , m) * 3. 1 7(2H,d) * 1.67(1 2H,s). -64-201241046 &lt;Synthesis Example 31&gt; 5,5'-((l,4,10,13-tetraoxa-7,16-diazacyclooctadecane-7,16-diyl)bis represented by the following formula [64] Methanylylidene)) Synthesis of bis(2,2-dimethyl-l,3-dioxane-4,6-dione) [Chemical 5 2]

[63]

In a 500 mL four-necked flask, Michleric acid [1] (24.17 g, 167.7 mmol) and trimethyl orthoformate [2] (200 g) were added, and the mixture was heated under reflux for 1 hour. Thereafter, the compound [63] (20.00 g '76_2 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed by an evaporator and dried to give 43.2 g of compound [64] (yield: 100%). &lt;Synthesis Example 32&gt; 5,5'-(((((((((((((((((((((((((((()))))) Synthesis of bis(azanediyl))bis(methanylylidene))bis(2,2-dimethyl-1,3-dioxane-4,6-dione) [Chemical 5 3]

• 65-201241046 A 500 mL four-necked flask was charged with Michleric acid [l] (22.00 g, 153 mmol) and trimethyl orthoformate [2] (200 g), and heated under reflux for 1 hour. Thereafter, the compound [65] (20.00 g, 69.4 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed by an evaporator and dried to give 40.2 g of compound [66] (yield: 97%). 1H-NMR (400MHz, DMSO-d6, 5ppm): 11.23(2H,d) &gt; 8.44(2H,d) » 7.50-7.48(2H,m) &gt; 7. Ο 1 - 6.9 9 (4 Η, m * 4.42-4.12 (4H, m), 3.89-3.78 (4H, m), 1.67 (12H, s). &lt;Synthesis Example 33&gt; 2-(methacryloyloxy)ethyl 3,5-bis ((2,2-dimethyl-4,6-diox〇-1,3-dioxan-5-) represented by the following formula [68] Synthesis of ylidene)methyl)amino)benzoate [Chemical 5 4]

In a 500 mL four-necked flask, Mic acid [l] (24.18 g, 168 mm 〇I) and trimethyl orthoformate [2] (300 g) were charged, and the mixture was heated under reflux for 1 hour. Thereafter, the compound [67] (20. 〇〇g, 76.3 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, hexane was added thereto, and the mixture was filtered and dried to give 43.7 g (yield: 100%) of compound [68]. 'H-NMR (400MHz, CDC13, 6ppm): 11.36(2H,d), -66- 201241046 8.72(2H,d), 7.80(2H,d),7.37(lH,t),6.17(lH,t) , 5.64-5.62(lH,m) &gt; 4.6 7 - 4.6 5 (2 H, m) &gt; 4.5 5 - 4.5 2 (2 H, m) « 3.79(lH,s), 3.47(lH,s), 3.34 (2H, s), 1.97- 1.96 (3H, m), 1.78 - 1.76 (1 3H, m). &lt;Synthesis Example 34&gt; (E)-2,4-bis(((2,2-dimethyl-4,6-dioxo-l,3-dioxan-5-ylidene)methyl) represented by the following formula [70] Synthesis of amino)phenethyl 3 - (4'-butoxy-[l,l'-biphenyl]-4-yl)acrylate [5 5]

In a 100 mL four-necked flask, Michleric acid [l] (4.00 g, 20.4 mm 〇l) and trimethyl orthoformate [2] (40 g) were added, and the mixture was heated and refluxed for 1 hour. Thereafter, the compound [69] (4.00 g, 9.3 mmol) was added, and further hot reflux was carried out for 2 hours. After completion of the reaction, the solvent was removed by an evaporator and dried to give 6.8 g (yield: 99%) of compound [70]. 1H-NMR (400MHz, CDC13, 5ppm): 1 1.59 (1H,d) · 11.29 (lH,d), 8.84 (lH,d), 8.78 (lH,d), 8.23 (lH,s), 8.04 (lH, s), 7.70-7.64 (7H, m), 7.62 (lH, d), 7.48 (2H, s), 7.03 (2H, d) &gt; 6.53 (lH, d) &gt; 4.41 (2H, t) &gt; 4.01(2H,t) &gt; 3.66-3.63(6H,m) &gt; 1 .6 8 - 1 . 5 7 ( 1 0 H ,m) &gt; 1.56(lH,s)» -67- 201241046 1.44-1.39(1 H,m) &gt; 0.94(3H,t). &lt;Synthesis Example 35&gt; (E)-2,4-bis(((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene)methyl) represented by the following formula [72] Synthesis of amino)phenethyl 3-(4-cycl〇hexylphenyl)acryIate [Chemical 5 6]

Mice acid [l] (4.35 g, 30 mmol) and trimethyl orthoformate [2] (50 g) were placed in a 200 mL four-necked flask, and heated to reflux for 1 hour. Thereafter, the compound [7 1 ] (5.00 g, 14 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed by an evaporator and dried to give compound [7 2 ] 9.6 3 g (yield: 9%). lH-NMR (400 MHz, CDC13, 5 ppm): 1 1 .63 (lH,d)-11.30 (lH,d)&gt; 8.64-8.6 3 (2H,m) » 7.60 (lH,d)&gt; 7.42-7.39 (3H,m) ' 7.29-7.27(2H,m) , 7.2 1 - 7 . 1 5 (3 H , m), 6 · 3 7 (1 H,d),4.4 9 - 4 · 4 6 (2 H , m),3 . 3 3 - 3 · 1 1 (2 H,m), 2.59-2.42 (lH,m),1.8 6- 1.45(2H,m),1.76- 1.70( 1 4H,m), 1.42 · 1.20 (6H, m). &lt;Synthesis Example 3 6 &gt; -68- 201241046 (E)-2,4-bis ((2,2-dimethyl-4,6-diox〇-l,3- represented by the following formula [74] Synthesis of dioxan-5-ylidene)methyl)amino)phenethyl 3-(4-([trans-l,l'-bi(cyclohexan)]-4-yl)phenyl)acrylate [Chemical 5 7]

In a 200 mL four-necked flask, Michleric acid [l] (2.84 g, 20 mmol) ' and trimethyl orthoformate [2] (40 g) were added, and the mixture was heated and refluxed for 1 hour. Thereafter, the compound [73] (4.00 g, 9.0 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed by an evaporator and dried to give 6.6 g of compound [74] (yield: 99%). 'H-NMR (400 MHz, CDC13, 5 ppm): 1 1.63 (1H, d) &gt; 1 1 .30 (lH, d) &gt; 8.67-8.60 (2H, m) - 7.60 (lH, d), 7.41 -7.39 (3H,m) , 7.26-7.14(4H,m) , 6.36(lH,d) , 4_48(2H,t), 3'12(2H,t),2.52-2.45(lH,m),1.9 1 - 1.70 (24H, m), 1. 52-1 .0 1 (8H, m). &lt;Synthesis Example 3 7 &gt; (EidJ-bisUUJ-dimethylU-dioxo-l, 3-dioxan-5-ylidene)methyl)amino)phenethyl 3-(4-(trans-4) represented by the following formula [76] Synthesis of -pentylcyclohexyl)phenyl)acrylate -69- 201241046

In a 300 mL four-necked flask, Michler's acid [13] (13.55 g, 69.8 mmol) and trimethyl orthoformate [2] (140 g)' were added and heated under reflux for 1 hour. Thereafter, the compound [75] (13.79 g, 31.7 mmol) was added, and the mixture was further heated under reflux for 2 hours. After the completion of the reaction, the solvent was removed by an evaporator and dried to obtain 22.4 g of a compound [76] (yield: 95%). 'H-NMR (400MHz, CDC13, 5ppm): 11.63(lH,d) * 11.27(lH,d)» 8.68-8.5 7(2H,m) » 7.4 1 - 7.3 9 (3 Η, m) » 7.26- 7. 1 4(4H,m) &gt; 6.3 6 (1 H, d ) » 4.4 8 (2 H, t) &gt; 3.80-3.76 (3H,m) , 3.48(2H,d) , 3.34(1 H ,s) ' 3. 12(2H,d) ' 2.47(2H,t) « 1.86(6H,d)&gt; 1.7 7 - 1.6 8 (1 0 H , m) « 1.47-1.20 (10H,m), 1.06-0.90 (5H, m). &lt;Synthesis Example 38&gt; (E)-2,4-bis(((2,2-dimethyl-4,6-dioxo-l,3-dioxan-5-ylidene)methyl) represented by the following formula [78] Synthesis of amino)phenethyl 3-(4-(trans-4-heptylcyclohexyl)phenyl)acrylate-70- 201241046

In a 100 mL four-necked flask, Michleric acid [l] (3.43 g, 23.8 mmol) and trimethyl orthoformate [2] (50 g) were added, and the mixture was heated and refluxed for 1 hour. Thereafter, the compound [77] (5. 〇〇g, 10 〇. 8 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed by an evaporator and dried to obtain 8.3 g (yield: 1%) of the compound [78]. 1H-NMR (400MHz, CDC13, 6ppm): 1 1.64( 1 H,d)-1 1 .28( 1 H,d) * 8.70-8.63 (2H,m) « 7.61(lH,d) &gt; 7.45- 7.40 (3H,m) - 7.27-7. 1 5(3H,m) &gt; 6.37(lH,d) &gt; 4.46(2H,t) · 3.60(2H,d),3.12(2H,t),2 , 34(lH,t),l_87(4H,d),1.8 5- 1 .75 ( 1 5 H,m) - 1.4 2 - 1 . 3 8 (2 H, m) &gt; 1 . 3 3 - 1.2 6 ( 1 0 H -m), 1.07- 1.02 (2H, m), 0_89 (3H, t). &lt;Synthesis Example 39&gt; (E)-3,5-bis ((2,2-dimethyl-4,6-diox〇-l,3-dioxan-5-ylidene) represented by the following formula [80] Synthesis of methyl)amino)benzyl 3-(4-(trans-4-pentylcyclohexyl)phenyl)acrylate-71 - 201241046 [Chem. 6 0]

Mice acid [l] (11.31 g, 7 8.5 mmol) and trimethyl orthoformate [2] (150 g) were added to a 300 mL four-necked flask and heated under reflux for 1 hour. Thereafter, the compound [79] (15.0 〇g, 35.7 mm〇i) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed by an evaporator and dried to obtain 25.3 g of a compound [8〇] (yield: 99%). iH-NMRHOOMHz^DCHjppm): 11.30(2H,d), 8.66(2H,d),7.74(lH,d),7.49(2H,d),7.26-7.19(4H,m) ' 7.08(lH,d) , 6.49 (lH, d), 5.27 (2H, s), 2.49 (lH, t), 1.93-1.77 (1 8H, m), 1.65-0.87 (14H, m). &lt;Synthesis Example 40&gt; (E)-3,5-bis(((2,2-dimethyl-4,6-dioxo-l,3-dioxan-5-ylidene)methyl) represented by the following formula [82] )amino)benzyl 3-(4-

Synthesis of (trans-4'-pentyl-[l,l'-bi(cyclohexan)]-4-yl)phenoxy) acrylate [Chemical 6 1 HZN

-72-201241046 In a 200 mL four-necked flask, Mic acid [i] (i.83 g '12.7 mmol) and trimethyl orthoformate [2] (45 g) were added, and the mixture was heated and refluxed for 1 hour. Thereafter, the compound [81] (3.00 g, 5.8 mmol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, the solvent was removed by an evaporator and dried to give the compound [8 2 ] 4 · 8 g (yield 1 〇 〇 %). W-NMRHOOMHz.CDCnjppm): 11.27(2H,d), 8.64(2H,d),7.85(lH,d),7.21(2H,d),7.14(2H,d), 7.10-7.09(1 H,m ) * 7.00-6·98(2H,m) , 5.57(lH,d), 5.19(2H,s),3.81(lH,s), 3.47-3.46(lH,m),3.33(4H,s), 1.91 -1.72 (20H, m), 1.41-0.84 (13H, m). [Synthesis of Polyamine or Polyimine and Preparation of Its Solution] The abbreviations used below are as follows. (tetracarboxylic dianhydride) CBDA: 1,2,3,4-cyclobutane tetraphthalic acid dianhydride BODA: bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic acid Anhydride [Chemical 6 2]

BODA

CBDA (diamine) p-PDA: p-phenylenediamine DDM: 4,4,-diaminodiphenylmethane-73- 201241046 PCH7AB : 1,3-diamino-4-[4-(trans -4-n-heptylcyclohexyl)phenoxy]benzene

H2N V ▽ nh2 DDM

[6 3] h2n-^^-nh2 p-PDA

_(CH2)6CH3 (organic solvent) NMP : N-methyl-2-pyrrolidone BCS : butyl cellosolve (measurement of molecular weight) In this example, the molecular weight of the polymer (polyproline, polyimine) is A room temperature colloidal soaking chromatography (GPC) apparatus (GPC-101) manufactured by Shodex Co., Ltd., and a pipe column (KD-8 03, KD-805) manufactured by Shodex Co., Ltd. were used in the following manner.

Column temperature: 50 ° C Dissolution: N,N-dimethylformamide (as an additive, lithium bromide-hydrate (LiBr.H20) is 30 mmol/L, phosphoric acid·anhydrous crystal (〇-phosphoric acid) is 30 mmol/ L, tetrahydrofuran (THF) is 10ml / L) Flow rate: 1.0 mL / minute calibration line standard sample: TSK standard polyethylene oxide manufactured by Tosoh Corporation (molecular weight of about 900,000, 1 50,000, 1 00,000 , -74- 201241046 30,000), and Polyethylene glycol (molecular weight of about 12,000 ' 4,000 ' 1,000) ° manufactured by Polymer Laboratories Co., Ltd. (Measurement of yttrium imidation ratio) In this example, quinone imine of polybendimimine The rate of measurement was measured as follows. About 20 mg of polyimine powder was placed in an NMR sample tube, and about 0.53 ml of dimethyl hydrazine (DMSO-d6, 0.05% TMS mixture) was added thereto, and the ultrasonic wave was applied to dissolve completely. This solution was measured for proton NMR at 500 MHz in an NMR measuring apparatus. The ruthenium imidation ratio is determined by using a proton derived from a structure which does not change before and after imidization as a reference proton, and the peak of the proton is used to accumulate 质, and the proton of the NH group derived from methionine which is present near 10 ppm. The peak accumulation is obtained by the following equation. Further, in the following formula, X is a proton peak accumulation NH from the NH group of valine acid, y is a peak accumulation 値 of the reference proton, and α is a poly-proline (the yttrium imidation ratio is 〇%). The ratio of the number of reference protons relative to a substrate of proline. Ruthenium amination rate (%) = ( 1 - α · X / y ) X 1 〇〇 &lt;Synthesis of polyaminic acid (PAA-1) and preparation of its solution&gt; 'Addition of DDM in a 100 mL four-necked flask 7.93 g (40 mmol) and NMP (20 g) were dissolved and cooled to about 1 Torr. (:, adding 7.46 g (38 mmol) of NB (67 g) slurry solution of CBDA, and returning to room temperature for 6 hours under nitrogen to obtain a concentration of poly-proline (paa-1). 15 -75 - 201241046 A solution of the amount of the polyaminic acid (PAA-1) at a concentration of 15% by mass was transferred to a 200 mL Erlenmeyer flask, and NMP 87.6 g and BCS 43.8 g were added for dilution to obtain a poly-proline (pAA·1). a polyamine acid (PAA-1) solution having 6 mass%, NMP of 74 mass%, and BCS of 20 mass%. The number average molecular weight of the polyglycine (PAA-1) is 丨2,081, weight average molecular weight For the synthesis of 30,449 « &lt;polyproline (p AA-2) and its solution&gt; P-PDA 8.65g (80mmol) and NMP (49g) were dissolved in a 200mL four-necked flask, and then cooled to A solution of CBDA 14.1 g (72 mmol) of NMP (80 g) was added to about 10 ° C., and the reaction was carried out for 6 hours under a nitrogen atmosphere at room temperature to obtain a concentration of polyamine acid (PAA-2) of 15% by mass. 125 g of a solution of the polyamine acid (PAA-2) concentration of 15% by mass was transferred to a 300 mL Erlenmeyer flask, and 118.5 g of NMP and 60.9 g of BCS were added to be diluted to obtain a polylysine. PAA-2) is a polyglycine (PAA-2) solution having 6% by mass, NMP of 74% by mass, and BCS of 20% by mass. The polyammonic acid (PAA-2) has a number average molecular weight of 7,609 and a weight. The average molecular weight is 15,837 « &lt;Synthesis of polyaminic acid (PAA-3) and preparation of its solution&gt; In a 200 mL four-necked flask, p-PDA 8.05 g (74 mmol), PCH7AB 2.13 g (5.6 mmol), NMP were added. (118g), after dissolving, cooling -76-201241046 to about 10 °C, adding CBDA 1 4.1 g (72 mmol) of NMP (100 g) slurry solution, returning to room temperature and reacting under nitrogen for 6 hours. A solution having a concentration of polyamine acid (PAA-3) of 10% by mass was obtained. 234 g of a solution of the polyglycine (PAA-3) concentration of 10% by mass was transferred to a 300 mL Erlenmeyer flask, and NMP 70.8 g was added. BCS 76.2g was diluted to obtain a polylysine (PAA-3) solution in which polyamic acid (PAA-3) was 6 mass%, NMP was 74 mass%, and BCS was 20 mass%. (PAA-3) has an average molecular weight of 6,092 and a weight average molecular weight of 12,002 ° &lt;Synthesis of soluble polyimine (SPI-1) and preparation of its solution&gt; in a 300 mL four-necked flask, BODA ( 16.9 g, 68 mmol), p-PDA (6.8 g, 6 3 mmo 1) 'PCH7AB (10.3 g, 27 mmol) was mixed in NMP (100 g), and after reacting at 40 ° C for 3 hours, CBDA (4.1 g) was added. 21 mmol) and NMP (52 g) were reacted at 40 ° C for 3 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (130 g) and diluting it to 6 mass%, acetic anhydride (16 g) and pyridine (12 g) as a ruthenium amide catalyst were added, and the reaction was carried out at 80 ° C for 3 hours. The reaction solution was poured into methanol (1.6 L), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 10 ° C to obtain a polyimine powder (SPI-1). The polyamidimide had a ruthenium iodide ratio of 54%, a number average molecular weight of 1,800, and a weight average molecular weight of 45,300. The amount of the carboxyl group in the polyimine was 0.92 with respect to the repeating unit. To the polyimine powder (SP1-1) (12.0 g) obtained above, -77-201241046 NMP (98 g) and BCS (90 g) were added, and the mixture was stirred at 80 ° C for 40 hours to dissolve to prepare a soluble polyfluorene. Imine (SP 1-1) solution. [Preparation of coating liquid for forming polyimine film (liquid crystal alignment agent)] &lt;Examples 1 to 9 &gt; In the polyacrylic acid (PAA-1) solution (10.Og) produced as described above, Each of the compounds described in the following Table 1 prepared as the above-mentioned synthesis example of the compound represented by the above formula [A] is a solid fraction of a polyacrylic acid (PAA-1) solution (that is, polylactoic acid (PAA). -1)) A coating liquid for forming a polyimine film of Examples 1 to 9 (functional polymer film) was added at a temperature of room temperature (25 ° C) until it became a homogeneous solution. A coating liquid for formation). [Table 1] Compound represented by polyglycine formula [Α] Example 1 ΡΑΑ-1 Synthesis Example 4 [10] Example 2 ΡΑΑ-1 Synthesis Example 5 [12] Example 3 ΡΑΑ-1 Synthesis Example 6 [ 14] θ Example 4 ΡΑΑ-1 Synthesis Example 8 [1 8] _ ΪΓ Example 5 ΡΑΑ-1 Synthesis Example 1 5 [3 2] Example 6 ΡΑΑ-1 Synthesis Example 1 6 [3 4] Example 7 ΡΑΑ - 1 Synthesis Example 2 0 [4 2] Example 8 ΡΑΑ-1 Synthesis Example 2 1 [4 4] Case 9 ΡΑΑ-1 Synthesis Example 2 2 [46] &lt;Examples 10 to 34&gt; The compound described in Table 2 below, which is prepared as the above-mentioned synthesis example of the compound represented by the above formula [A], in the poly-proline (PAA-1) solution (1, 〇g). Each of them is added in such a manner that the solid content of the poly-proline (paA-1) solution (i.e., polyamine acid (PAA-1)) is in the ratio described in Table 2 below, until it becomes a homogenous solution. The mixture was stirred at room temperature to prepare a polyimide film of Examples 1.0 to 34 to form a ruthenium coating liquid. [Table 2] Polyampamic acid compound represented by the formula [A] _ addition amount (wtJ!) Example 1 0 PAA-1 Synthesis Example 2 2 [46] 1 Example 1 1 PAA-1 Synthesis Example 2 2 [ 4 6] 3 Example 1 2 PAA-1 Synthesis Example 2 2 [46] 5 Example 1 3 PAA-1 Synthesis Example 2 2 [4 6] 10 Example 1 4 PAA-1 Synthesis Example 2 2 [46] 2 0 Example 1 5 PAA-1 Synthesis Example 2 0 [4 2] 1 Example 1 6 PAA-1 Synthesis Example 2 0 [4 2] 3 Example 1 7 PAA-1 Synthesis Example 2 0 [4 2] 5 Implementation Example 1 8 PAA-1 Synthesis Example 2 0 [42] 10 Example 1 9 PAA - 1 Synthesis Example 2 0 [4 2] 2 0 Example 2 0 PAA - 1 Synthesis Example 2 1 [44] 1 Example 2 1 PAA-1 Synthesis Example 2 1 [4 4] 3 Example 2 2 PAA-1 Synthesis Example 2 1 [44] 5 Example 2 3 PAA-1 Synthesis Example 2 1 [4 4] 10 Example 2 4 PAA-1 Synthesis Example 2 1 [4 4]. 2 0 Example 2 5. PAA-1. Synthesis Example 2 4. [5 0 ·} 1 Example 2 6 PAA-1 Synthesis Example 2 4 [5 0] 3 Example 2 7 PAA-1 Synthesis Example 2 4 [5 0] 5 Example 2 8 PAA-1 Synthesis Example 2 4 [5 0] 10 Example 2 9 PAA-1 Synthesis Example 2 4 [5 0] 2 0 Example 3 0 PAA - 1 Synthesis Example 2 6 [54] 1 Example 3 1 PAA-1 Synthesis Example 2 6 [5 4] 3 Example 3 2 PAA - 1 Synthesis Example 2 6 [5 4] 5 Example 3 3 PAA-1 Synthesis Example 2 6 [5 4] 10 Example 3 4 PAA-1 Synthesis Example 2 6 [ 54] 2 0 -79 - 201241046 &lt;Examples 35 to 45 &gt; The above-mentioned poly-proline (PAA-2) solution (10.0 g) was prepared as the compound represented by the above formula [A] The compounds described in the following Table 3, which were prepared in the synthesis examples, were each added in a form of a solid content (i.e., polyamic acid (PAA-2)) relative to a polyacrylic acid (PAA-2) solution to 10 mol%. The coating liquid for forming a polyimine film of Examples 35 to 45 was prepared by stirring at room temperature until it became a homogeneous solution. [Table 3] Polyamine derivative compound represented by the formula [A] Example 3 5 PAA-2 Synthesis Example 4 [10] Example 3 6 PAA-2 Synthesis Example 5 [12] Dragon Case 3 7 PAA-2 Synthesis Example 6 [14] Dragon Example 3 8 PAA-2 Synthesis Example 8 [18] Example 3 9 PAA-2 Synthesis Example 1 5 [3 2] Example 4 0 PAA-2 Synthesis Example 1 6 [34] Example 4 1 PAA-2 Synthesis Example 2 0 [42] Dragon Case 4 2 PAA-2 Synthesis Example 2 1 [4 4] Surface Example 4 3 PAA-2 Synthesis Example 2 2 [4 6] K Example 4 4 PAA-2 Synthesis Example 2 5 [5 2] Brief Example 4 5 PAA-2 Synthesis Example 2 6 [5 4] &lt;Examples 46 to 59&gt; The above-prepared polylysine (PAA-3) solution (40.0) In the g), the compounds described in the following Table 4, which are the above-mentioned synthesis examples of the compound represented by the above formula [A], each having a solid content (i.e., polyamine) relative to a polyacrylic acid (PAA_3) solution The acid (PAA-3)) was added to a homogeneous solution as shown in Table 4, and the mixture was stirred at room temperature to prepare a coating liquid for forming a polyimide film of Examples 46 to 59. 80 - 201241046 [Table 4] The amount of the compound represented by the polyglycolic acid formula [A] (W (8) Example 4 6 PAA-3 [5 8] 5 Example 4 7 PAA-3 [5 8] 10 Example 4 8 PAA- 3 [5.8] 2 0 Example 4 9 PAA- 3 [5 8] 3 0 Example 5 0 PAA- 3 [5 8] 5 0 Example 5 1 . PAA- 3 [5 8] 7 0 Implementation Example 5 2 PAA-3 [5 8] 10 0 Example 5 3 PAA-3 [60] 5 Example 5 4 PAA-3 [6 0] 10 Example 5 5 PAA-3 [6 0] 2 0 Example 5 6 PAA-3 [60] 3 0 Example 5 7 P AA- 3 [6 0] 5 0 Example 5 8 PAA- 3 [60] 7 0 Example 5 9 P AA- 3 [6 0] 10 0 &lt;Examples 60 to 62&gt; The following synthesis examples of the above-mentioned synthesis examples of the compound represented by the above formula [A] were carried out in the polyplysine (PAA-2) solution (70.0 g) produced above. The compounds described are each added in a ratio relative to the solid content of the polyamido acid (PAA-2) solution (that is, polyglycine (PAA-2)) as shown in the following Table 5, until a homogeneous solution is obtained. The mixture was stirred at room temperature to prepare a coating liquid for forming a polyimide film of Examples 60 to 62. [Table 5] Polyamine derivative [A] Compound type addition amount (wt! K) Example 6 0 PAA-2 Synthesis Example 2 1 [44] 10 Example 6 1 PAA-2 Synthesis Example 2 1 [4 4] 15 mm 6 2 PAA-2 Synthesis Example 2 1 [44] 2 0 -81 - 201241046 <Examples 63 to 76> The above-prepared soluble polyimine (SPI-1) solution (1〇.〇g) will be expressed as the above formula [A] The compounds of the following Table 6 prepared by the above-mentioned synthesis examples are each in a solid form of a solution of a relatively soluble polyimine (SPI-1) (that is, the soluble polyimine is in the ratio shown in Table 6 below). In the manner of adding a homogeneous solution, the coating liquid for forming a polyimine film of Examples 63 to 76 was prepared by stirring at room temperature. [Table 6] A compound represented by a soluble polyimine type [Α] Type addition amount (Wti!) Example 6 3 SP I - 1 Synthesis Example 4 [10] 10 Example 6 4 SP I - 1 Synthesis Example 5 [12] 10 S Example 6 5 SP I - 1 Synthesis Example 6 [14] 10 0 Example 6 6 SP I - 1 Synthesis Example 8 [18] 10 Κ Example 6 7 S Ρ I - 1 Synthesis Example 1 2 [2 6] 10 Dragon Example 6 8 SP I - 1 Synthesis Example 1 5 [3 2] 10 Dragon Case 6 9 .SPI -1 Synthesis Example 1 6 [3 4] 10 S Example 7 0 SP I - 1 Synthesis Example 2 0 [4 2] 10 S Example 7 1 S Ρ I - 1 Synthesis Example 2 1 [44] 10 Example 7 2 S Ρ I - 1 Synthesis Example 2 2 [4 6] 10 cases 7 3 SP I - 1 Synthesis Example 2 8 [5 8] 5 Dragon Example 7 4 SP I - 1 Synthesis Example 2 8 [5 8] 10 Η Example 7 5 SP I - 1 Synthesis Example 2 8 [5 8] 3 0 Dragon Example 7 6 SP I - 1 Synthesis Example 2 8 Γ [5 8] 5 0 &lt;Examples 77 to 86 and Comparative Example 1&gt; [Crosslinking Effect Confirmation Test (Stripping Test)] The coating liquid for forming a polyimine film of the above Examples 63 to 72 was spin-coated (25 00 rpm / 30 seconds) on a 82 - 201241046 矽 wafer, and baked on a hot plate at 23 ° C for 30 minutes. Form, forming a coating film [al]. The film thickness of the obtained coating film [al] was measured by SURFCORDER ET4000M manufactured by Nippon Scientific Co., Ltd. Next, the tantalum wafer on which the coating film [al] was formed was again placed in a spin coater, and the NMP was dropped until the entire wafer was covered, and after standing for 60 seconds, the NMP was spin-dried (1 500 rpm/30). In seconds, the film was fired on a hot plate at 100 ° C for 30 seconds to form a residual film as a coating film [a2]. The film thickness of the coating film [a2] was measured again, and the residual film ratio was calculated by the following calculation formula. Further, as Comparative Example 1, the same operation was carried out on the soluble polyimine (SPI-1) solution prepared as described above, that is, the soluble polyimine solution containing no compound represented by the above formula [A]. Calculate the residual film rate. The results are shown in Table 7.

Residual film rate (%) = film thickness of the coating film [a2] / film thickness of the coating film [al] xlOO This result confirmed that the coating liquid for forming a polyimide film using the compound represented by the above formula [A] was used. (Liquid crystal alignment treatment agent), the solvent resistance of the coating film (polyimine film) can be improved. Therefore, it is presumed that the soluble polyimine is a compound which is crosslinked by the compound represented by the above formula [A]. Further, it was confirmed that the solubility of the coating film can be controlled more freely by appropriately selecting the difunctional compound represented by the above formula [A]. In the same manner, a coating film was formed using the coating liquid for forming a polyimide film of Examples 1 to 62 and Examples 73 to 76, and a stripping test was performed, and each of them was compared with the case where the compound represented by the above formula [A] was not added. It is confirmed that the film rate is high, and the solvent resistance of the polyimide film can be improved by using the coating liquid for forming a polyimide film formed by adding the compound represented by the above formula [A]. [Table 7] Coating film for coating liquid [all Φ Na Na coating film [a2] 膜 film thickness (DO) residual film rate {%) Example No. 7 shown in Example No. [A] Example 6 3 Synthesis Example 4 [10] 18 0 143 7 9.4 Example 7 8 Example 6 4 Synthesis Example 5 _ [12]. 184 14 7 79. 9 Example 7 9 S Example 6 5 Synthesis Example 6 [ 14] 16 0 15 1 94. 2 Example 8 0 Example 6 6 Synthesis Example 8 [18] 16 5 152 9 2· 1 Example 8 1 Example 6 7 Synthesis Example 1 2 [26] 14 9 14 0 94 6 Example 8 2 Example 6 8 Synthesis Example 1 5 13 2] 1 24 6 9 5 5.7 Example 8 3 Example 6 9 Synthesis Example 1 6 [3 4] 16 4 10 2 6 2.2 Example 8 4 Implementation Example 7 0 Synthesis Example 2 0 [4 2] 17 7 111 6 2.7 Example 8 5 Example 7 1 Synthesis Example 2 1 [44] 17 0 10 4 6 1:2 Example 8 6 S Example 7 2 Synthesis Example 2 2 [4 6] 17 3 113 6 5.3 Comparative Example 1 None 15 1 0 No residual film [Production of liquid crystal alignment film and liquid crystal cell] Coating for forming a polyimide film prepared by the above respective examples Liquid (liquid crystal alignment agent), a liquid crystal cell was produced as follows. The coating liquid for forming a polyimide film (liquid crystal alignment agent) was spin-coated on a glass substrate or a glass substrate with an ITO transparent electrode, and dried on a hot plate at 80° C. for 70 seconds. Under conditions, a coating film having a film thickness of 100 nm was formed. Then, regarding the rubbed liquid crystal alignment treatment, the coated film surface was rubbed with a rayon cloth using a rayon cloth with a roll diameter of 1 mm to obtain a substrate with a liquid crystal alignment film. The liquid crystal alignment treatment of the light is performed by changing the linearly polarized UV light (UV wavelength 313 nm, irradiation intensity 8.0 mW/cnr2) between the exposure amount OmJ to -84-201241046 1 000 mJ on the surface of the coating film. The normal is tilted by 40°. Further, the linear polarized UV system was prepared by passing the ultraviolet light of the high pressure mercury lamp through a bandpass filter of 313 nm through a polarizing plate of 313 nm. Prepare two sheets of the substrate with the liquid crystal alignment film subjected to the liquid crystal alignment treatment, and spread a spacer of 6 μm on one of the liquid crystal alignment film surfaces, and then print the sealant thereon, and the other substrate is made of liquid crystal. The alignment film faces and the rubbing directions are parallel to each other (anti-parallel liquid crystal cells, Examples 87 to 116), or straight-line bonding (twisted nematic liquid crystal cell, Example 155) ～1 7 9、Example 2 9 6~3 1 5、Example 3 1 6~32 1 ), or, for UV irradiation, the polarized light is aligned in parallel (the vertical alignment mode is anti-parallel) The liquid crystal cell, Examples 180 to 182, and 183 to 294) hardened the sealant to prepare an empty unit cell. In the empty cell, a liquid crystal MLC-2003 (manufactured by Merck) was injected into the antiparallel liquid crystal cell, and a chiral molecule liquid crystal MLC-2003 (Merck) was injected into the twisted nematic liquid crystal cell. In the vertical alignment mode, liquid crystal MLC-6608 (manufactured by Merck) was injected into the anti-parallel liquid crystal cell in the vertical alignment mode to close the injection port to obtain each liquid crystal cell. [Evaluation of Liquid Crystal Cell] The method for measuring the physical properties of each liquid crystal cell produced and evaluating the characteristics are as follows. Further, the substrate of the liquid crystal alignment film or the liquid crystal cell prepared in each measurement and evaluation, the firing conditions, and the rubbing conditions are shown. -85-201241046 &lt;Example 8 7 to 11 6 and Comparative Examples 2 to 4&gt;&lt;Liquid alignment property evaluation&gt; The coating liquid for forming a polyimide film prepared in each of the examples shown in Table 8 was used. The formed liquid crystal cell is held by a polarizing plate. The liquid crystal cell is rotated in a state where the backlight is irradiated from the rear portion, and the light and dark changes or the presence or absence of the flow alignment and the alignment of the liquid crystal are visually observed. At this time, the evaluation was performed using the following criteria. Further, in the liquid crystal cell for liquid crystal alignment evaluation, a glass substrate was used as the substrate, and the coating film for the coating liquid for forming a polyimide film was baked on a hot plate heated to 23 ° C. The firing was carried out for 30 minutes, and the rubbing conditions were produced by a number of rolls of 300 rpm, a roll speed of 50 mm/sec, and a press-in amount of 0.15 mm. Further, the compound represented by the above formula [A] or the non-added cross-linking agent (Comparative Example 2) and the coating liquid obtained by adding the following cross-linking agent as a general commercial cross-linking agent were compared (Comparative Example 3) Or Comparative Example 4), compare the effects. The results are shown in Table 8. Evaluation criteria ◎: The alignment of the liquid crystal was confirmed and there was no flow alignment. 〇 : The liquid crystal was aligned, but some flow alignment was observed. X: Although the liquid crystal was aligned, many flow alignments were observed. [Chem. 6 4]

Crosslinking agent-1 Crosslinking agent-2 As a result, it was confirmed that, in the case of using the commercially available crosslinking agent in Comparative Example 3 and Comparative Example 4, the alignment property of the liquid crystal is generally hindered, but the addition of 1 of the present invention is used. When the polyimine film for forming a compound represented by the formula [Α] is coated with the coating liquid-86-201241046, the alignment property of the liquid crystal is not inhibited, and the alignment property is also confirmed to be improved. [Table 8]

Evaluation result of the coating liquid for forming a polyhedral film Example No. Polyamide form The compound addition amount represented by the formula [A] Example 8 7 Example 1 PAA-1 [10] 1Omo1 % 〇Example 8 8 Implementation Example 2 PAA-1 [12] 1Omo1 % 〇 Example 8 9 Example 3 PAA-1 [14] 1Omo1 % 〇 Example 9 0 Example 4 PAA-1 [18] 1Omo 1 % ◎ Example 9 1 Example 5 PAA-1 [3 2] 1Omo 1 % 〇 Example 9 2 Example 6 PAA-1 [34] 1Omo 1 % ◎ Example 9 3 Example 7 PAA-1 [4 2] 1Omo 1 % 〇 Example 9 4 Example 8 PAA-1 [44] 1Omo 1 % 〇 Example 9 5 Example 9 PAA-1 [4 6] 1Omo1 % ◎ Example 9 6 Example 1 0 PAA-1 [4 6] 1 wt % ◎ Example 9 7 Example 1 1 PAA-1 [46] 3 wt % ◎ Example 9 8 Example 1 2 PAA-1 [4 6] 5 wt % ◎ Example 9 9 Example 1 3 PAA-1 [4 6] 1 0 wt % ◎ Example 10 0 Example 1 4 PAA-1 [46] 2 Owt % ◎ Example 1〇 Example 1 5 PAA-1 [4 2] 1 wt % 〇 Example 10 2 Implementation Example 1 6 P AA - 1 [4 2] 3 wt % 〇 Example 10 3 Example 1 7 PAA — 1 [4 2] 5 wt % Example 10 4 Example 1 8 PAA-1 [4 2] 1 0 wt % 〇 Example 10 5 Example 2 0 PAA-1 [4 4] 1 wt % 〇 Example 10 6 Example 2 1 PAA-1 [ 4 4] 3 wt % 〇 Example 10 7 Example 2 2 PAA-1 [4 4] 5 wt % 〇 Example 10 8 Example 2 3 PAA-1 1 4 4] 1 0 wt % 〇 Example 10 9 Implementation Example 2 5 PAA-1 [5 0] .1 wt % 〇 Example 11 〇 Example 2 6 PAA-1 [5 0] 3 wt % 〇 Example 111 Example 2 7 PAA-1 [5 0] 5 wt % 〇Example Γ12 Example 2 8 PAA-1 [5 0] 1 0 wt % 〇 Example 113 Example 3 0 PAA-1 [5 4] 1 wt % ◎ Example 114 Example 3 1 PAA-1 [ 5 4 % 3 wt % ◎ Example 115 Example 3 2 PAA-1 [54] 5 wt % ◎ Example 116 Example 3 3 PAA-1 [541 1 0 wt % 〇 Comparative Example 2 A PAA-1 No one 〇Comparative Example 3 - PAA-1 Crosslinker-1 1Omo1 % X Comparative Example 4 - PAA-1 Crosslinker-2 1Omo1 % X -87- 201241046 &lt;Examples Π7 to 154 and Comparative Examples 5 to 6&gt;&lt; Friction resistance evaluation: Liquid crystal alignment prepared by using the coating liquid for forming an amine film prepared in each of the examples shown in Tables 9-1 to 9-2 The angle of the surface was observed with a microscope were performed by the following criteria of evaluation. Further, the glass substrate using the positive electrode was used as the substrate, and the firing condition of the polyimide film for forming a polyimide film was baked on a hot plate heated to 23 ° C, and the rubbing condition was that the number of rotation of the roller was 1000 rpm. The roll was placed at 50 mm/sec and the press-in amount was 0.5 mm. Further, when the compound represented by the above formula [A] was added, the results of Comparative Example 5 and Comparative Example were more effective. The results are shown in Table 9-1 to Table 9-2. 〇: The residue or the friction wound was not observed. △: Observed residue or frictional wound was observed. X: Film peeling was observed or a scratch was observed by visual observation. As a result, compound 5 and Comparative Example 6 represented by the above formula [A] were not added. It was confirmed that any of the polymers used in the coating liquid for forming a polyimide film formed by adding the compound represented by the invention [A] was confirmed to have improved cutting resistance. 丨聚醯亚: Point laser ITO : The liquid speed of the liquid is not added for 6 minutes. The ratio is compared with the above formula, -88- 201241046 [Table 9-1] Evaluation results of coating liquid for forming polyimide film. Example No. Polyamide Compound surface addition amount represented by acid form [A] Example 117 Example 1 PAA-1 [10] 1Omo1 % 〇 Example 118 Example 2 PAA-1 [12] 1Omo 1 % 〇 Example 119 Example 3 PAA - 1 [14] 1 0 m ο 1 % 〇 Example 12 0 Example 4 PAA-1 [18] 1Omo1 % 〇 Example 121 Example 5 PAA-1 [3 2] 1Omo1 % 〇 Example 12 2 Example 9 PAA-1 [4 6] 1Omo 1 % 〇 Example 12 3 Example 1 〇PAA-1 [46} 1 wt % 〇Implementation Example 12 4 Example 1 1 PAA-1 [4 6] 3 wt % 〇 Example 12 5 Example 1 2 PAA-1 [4 6] 5 wt % 〇 Example 12 6 Example 1 3 PAA-1 [4 6] 1 Ow t % 〇 Example 1 2 7 Example 1 4 PAA-1 [46J 2 Ow t % 〇 Example 1 2 8 Example 1 5 PAA — 1 [42] 1 wt % 〇 Example 1 2 9 Example 1 6 PAA-1 [4 2] 3 wt % 〇 Example 1 3 0 Example 1 7 PAA-1 [42] 5 wt % 〇 Example 131 Example 1 8 PAA - 1 [4 2] 1 0 Wt % 〇Example 13 2 Example 2 〇PAA-1 [44] 1 wt % 〇 Example 1 3 3 Example 2 1 PAA-1 [44] 3 wt % 〇 Example 1 3 4 Example 2 2 PAA - 1 [44] 5 wt % 〇 Example 1 3 5 Example 2 3 PAA-1 [44] 1 0 wt % 〇 Example 1 3 6 Example 2 5 PAA-1 [5 0] 1 wt % 〇Implementation Example 1 3 7 Example 2 6 PAA-1 [5 0] 3 wt % 〇 Example 1 3 8 Example 2 7 PAA-1 [5 0] 5w t % .〇Example 1 3 9 Example 2 8 PAA - 1 [5 01 1 0 wt % 〇 Example 14 0 Example 3 0 PAA-1 [54] 1 wt % 〇 Example 141 Example 3 1 ΡΑΛ-1 [5 4] 3 wt % 〇 Example 14 2 Example 3 2 PAA-1 [5.4 5 wt % 〇Example 14 3 Example 3 3 PAA-1 [5 4] 1 0 wt % 〇Comparative Example 5 A PAA-1 No - Δ -89- 201241046

[Table 9-2] Evaluation results of the coating liquid for polydecyl ether formation Example No. of the compound surface amount of the polyacrylic acid formula [A] Example 144 Example 3 5 PAA-2 110] 1 Owt% Δ Example 14 5 Example 3 6 PAA-2 [1 21 1 Owt% Δ Example 14 6 Example 3 7 PAA-2 U4] 1 Owt% Δ Example 14 7 Example 3 8 PAA-2 (1 8) 1 Owt% 〇Example 14 8 Example 3 9 PAA-2 [3 2] 1 Ow t % 〇 Example 14 9 Example 4 0 PAA-2 [34] 1 Owt% 〇 Example 150 Example 4 PAA - 2 (4 21 1 Ow t % Δ Example 151 Example 4 2 PAA-2 [44] 1 Ow t « 〇 Example 15 2 Example 4 3 PAA-2 [46] 1 Owt% 〇 Example 15 3 Example 4 4 PAA-2 [5 2] 1 Owt % 〇 Example 154 Example 4 5 PAA, 2 [54] 1 Owt% 〇Comparative Example 6 A PAA-2 No '- X &lt;Examples 155-179 And Comparative Example 7 &lt;Measurement of Pretilt Angle of Twisted Nematic Liquid Crystal Cell&gt; Liquid crystal cell prepared using the coating liquid for forming a polyimide film prepared in each of the examples shown in Table 1 The pretilt angle was measured after heating at 5 ° C for 5 minutes. The pretilt angle was Axo Metrix The "Axo Scan" of the company is measured by the Mueller matrix method. Further, the liquid crystal cell system for measuring the pretilt angle of the nematic liquid crystal cell is used as a substrate using a glass substrate with an ITO transparent electrode. The baking condition of the coating film of the coating film for imine film formation was baking on the hot plate heated to 23 ° C for 30 minutes, and the rubbing conditions were the number of rotation of a roller of 1000 rpm, the speed of a roll of 50 mm/sec, and press-in. The amount was 0.3 mm, and the compound represented by the above formula [A] was not adjusted (Comparative Example 7), and the results were compared. The results are shown in Table 1. -90 - 201241046 The result was confirmed by appropriate The type and amount of the compound represented by the above formula [A] can be selected, and the desired pretilt angle can be arbitrarily obtained. [Table 1 0] Pre-tilt angle of the coating liquid for poly-βκ» trace formation (.) Example No. Polyamide The amount of addition of the finish represented by the acid form [Α] (fftX}. Example 15 5 Example 1 0 ΡΑΑ-1 14 6] 1 3. 0 Example 15 6 Example 1 1 ΡΑΑ- 1. [46] 3 11.7 Example 15 7 Example 1 2 ΡΑΑ- 1 [4 6] 5 2 0.2 Example 15 8 Implementation 1 3 ΡΑΑ- 1 [46] 10 65. 4 Example 15 9 Example 14 ΡΑΑ-1 [4 61 20 87. 2 Example 16 0 Example 1 5 ΡΑΑ-1 [42] 1 2. 9 Example 161 Example 1 6 ΡΑΑ — 1 [4 2] 3 4. 4 Example 16 2 Example 1 7 ΡΑΑ-1 [42] 5 6. 8 Example 16 3 * Example 1 8 ΡΑΑ- 1 [4 2) 10 3 5.3 Example 16 4 Example 1 9 ΡΑΑ- 1 [4 21 2 0 54. 0 Example 16 5 Example 2 0 ΡΑΑ-1 144) 1 2· 6 Example 16 6 Example 21 ΡΑΑ-1 1441 3 3. 8 Example 16 7 Example 2 2 ΡΑΑ-1 14 4] 5 6-3 Example 16 8 Example 2 3 ΡΑΑ - 1 [4 4] 10 1 5. 2 Example 16 9 Example 2 4 ΡΑΑ-1 [4 41 20 49. 6 Example 17 0 Example 2 5 ΡΑΑ-1 [5 0] 1 2.6 Example 171 Example 2 6 ΡΑΑ-1 [5 0] 3 2,7 Example 17 2 Example 2 7 ΡΑΑ-.1 [50] 5 2. 8 Example 17 3 Example 2 8 ΡΑΑ-1 [5 0] 10 3. 4 Example 17 4 Example 2 9 ΡΑΑ — 1 15 0] 2 0 6. 6 Example 17 5 Example 3 0 ΡΑΑ-1 [5 4] 1 2. 6 Example 17 6 Example 3 1 ΡΑΑ-1 [5 4] 3 2. 7 Example 17 7 Example 3 2 ΡΑΑ -1 15 4) 5 3. 0 Example 1 7 8 Example 3 3 ΡΑΑ-1 [54] 10 3. 1 Example 17 9 Example 3 4 ΡΑΑ-1 [54] 20 4. 1 Comparative Example 7 One ΡΑΑ - 1 None. 1. &lt;Examples 180 to 1 82 and Comparative Example 8&gt;&lt;Measurement of pretilt angle of antiparallel liquid crystal cell&gt; -91 - 201241046 For the use of the polyaluminum prepared by the respective examples shown in Table 11 The liquid crystal cell produced by the coating liquid for forming an amine film was at 120. (: After preheating for 1 hour, the pretilt angle was measured. The pretilt angle was measured by the Mueller matrix method using "Αχ〇Scan" by Axo Metrix Co., Ltd. Further, the pretilt angle of the antiparallel liquid crystal cell was measured. In the liquid crystal cell system, a glass substrate with an IT〇 transparent electrode is used as a substrate, and a coating film for a coating liquid for forming a polyimide film is baked in a hot air circulating oven heated to 200° C. The liquid crystal cell was prepared by firing in a minute without the alignment treatment. Further, the compound represented by the above formula [A] was not adjusted (Comparative Example 8), and the results were compared. The results are shown in Table 11. As a result, in comparison with Comparative Example 8 in which the compound represented by the above formula [A] was not added, it was confirmed that the coating liquid for forming a polyimide film formed by adding the compound represented by the above formula [A] was remarkable. Therefore, by adding the compound represented by the above formula [A], the polyimine precursor contained in the coating liquid for forming a polyimide film is not contained in the base polymer. Polyimine imide introduction solution The side chain component can still vertically align the liquid crystal. [Table 1 1] The coating liquid for the granules mm (.) Example No. Polyglycolic acid formula [The compound surface added by A1 (Stv) Example 18 0 Example 6 0 PAA-2 [4 4] 10 90. 0 Example 181 Example 6 1 PAA-2 [4 4] 15 9 0. 0 Example 1 8 2 Example 6 2 PAA-2 [4 4] 90. 〇 Comparative Example 8 A PAA-2 No - 1. 3 &lt;Examples 183 to 294&gt;&lt;Liquid alignment property evaluation and antiparallel liquid crystal cell-92-201241046 Pretilt angle measurement&gt; The liquid crystal cell produced by using the coating liquid for forming a polyimide film prepared in each of the examples shown in Tables 12-1 to 12-4 is held by a polarizing plate, and the liquid crystal cell is allowed to be irradiated from the rear portion in a state where the backlight is irradiated. Rotation, the change of light and dark or the presence or absence of flow alignment and the alignment of the liquid crystal for visual observation, showing good alignment. After that, apply 3 V AC voltage to the liquid crystal cell, and align the liquid crystal for visual observation. The basis of the evaluation is evaluated. In addition, the liquid crystal cell for liquid crystal alignment evaluation uses a glass substrate as a substrate. The baking conditions of the coating film of the coating liquid for forming an imine film were baked in the hot-air circulation oven heated to 200 degreeC for 30 minutes, and the obtained coating film glass substrate was carried out after the said optical alignment process. The evaluation criteria were good: the alignment of the liquid crystal was confirmed, and the flow alignment was poor: although the liquid crystal was aligned, a large amount of flow alignment was observed, and the polyazide prepared by using the examples shown in Tables 12-1 to 12-4 was used. The liquid crystal cell prepared by the coating liquid for forming an amine film was heated at 120 ° C for 1 hour, and then the pretilt angle was measured. The pretilt angle is measured by the "Axo Scan" of Axo Metrix Co., Ltd. by the Mueller matrix method. The result 'by using a polyimine film to which a compound represented by the above formula [A] having a photoreactive side chain is added The coating liquid for forming (liquid crystal alignment treatment agent) confirmed that good vertical alignment property was obtained even in the case of performing photoalignment treatment. Further, the coating liquid (liquid crystal alignment treatment agent) for forming a polyimide film of the present invention is irradiated with polarized ultraviolet rays, and it is confirmed that the liquid crystal is aligned in a state of being slightly inclined from the vertical. Further, it was confirmed that the pretilt angle can be finely adjusted by controlling the amount of addition and the amount of irradiation of -93-201241046. In this way, the coating liquid for forming a polyimine film of the present invention (liquid crystal alignment treatment agent) can be used for a liquid crystal alignment film for a liquid crystal display element of a vertical alignment type, and it can be said that it can also be used as a photoalignment method. Liquid crystal alignment film. [Table 1 2 - 1] Polyimine amide is irradiated with coating liquid (m J) Liquid crystal directional pretilt angle (.) Example No. m Adding fl: _ When no voltage is applied, when voltage is applied Example 18 3 Example 4 6 [58] .5 0 Good defect 9 0.00 Example 18 4 Quality Example 4 6 [5 8] 5 2 0 Good good 9 0.00 Example 185 Example 4 6 [5 8] 5 5 0 Good and good 9 0.00 Example 18 6 Example 4 6 [5 8] 5 10 0 Good good 9 0.00 罝 Example 187 Example 4 6 [5 8] 5 2 0 0 Good good 9 0.00 Example 1 8 8 Example 4 6 [5 8] 5 4 0 0 Good Good 8 9.94 Example 1 8 9· Example 4 6 [5 8] 5 8 0 0 Good Good 8 9.92 Example 19 0 Example 4 6 [5 8] 5 10 0 0 Good good 8 9. 8 6 Example 19 1 Lean application 4 7 [58] 10 0 Good bad 9 0. 00 Example 1 9 2. Example 4 7 [5 8] 10 2 0 Good Good 9 0.00 寊Example 19 3 Example 4 7 15 8] 10 5 0 Good good 9 0. 00 Example 1 9 4 Example 4 7 [58] 10 10 0 Good good 8 9. 9 6 Example 19 5 Example 4 7 [58] 10 2 0 0 . Good good 8 9.84 Example 19 6 Example 4 7 [58] 10 4 0 0 Good 8 8.85 Example 1 9 7 Example 4 7 [5 8] 10 8 0 0 Good 8 8.77 Example 19 8 Example 47 [5 8] 10 10 0 0 Good good 89. 80 Example 199 Example 4 8 [5 8] 2 0 0 Good not humble 9 0.00 Example 2 0 0 - Example 4 8 [5 8] 2 0 2 0 Good good 8 9. 8 6 Example 2 0 1 Example 4 8 [5 8] 2 0 5 0 Good good 8 9.90 S Example 2 0 2 Example 4 8 158] 2 0 10 0. Good good 89. 97 Example 2 0 3 Example 4 8 [5 81. 2 0 200 Good good 8 9. 9 0 Quality application 2 0 4 Example 4 8 15 8} 2 0 400 Good good 89. 8 9 Example 2 0 5 Baoji Example 4 8 [5 8] 20 8 0 0 Good Good 8 9.92 Example 206 Example 4 8 [58] 20 1000 Good Good 8 9.89 Example 207 Bao Shi Example 4 9 [581 3 0 0 Good Bad 9 0. 0 0 Example 208 Example 4 9 [5 8] 3 0 2 0 Good good 8 9.89 Example 209 Si case 4 9 [581 3 0 5 0 Good good 8 9. 9 5 Quality embodiment 210 Example 4 9 [5 81 3 0 10 0 Good Good 8 9.86 0 Example 21 1 S Example 4 9 158] 30 200 Good and good 89. 89 0 Example 2 1 2 S Example 4 9 [581 30 400 Good and good 89. 86 β Example 213 Bao fine example 4 9 [5 8] 30 .800 Good and good 8 9. 9 0 0 Example 214 Example 4 9 [5 8] 30 10 0 0 Good 8 8.93 -94- 201241046 I Table 1 2 - 2] Coating liquid for forming a polyimide film (Im) J) Liquid crystal alignment pretilt angle (. Example No. mm Addition amount (ffU). Example 215 when voltage is applied without applied voltage Example 5 0 [5 81 5 0 0 . Good. Bad 9 0.00 Example 216 Example 5 0 [5 81 5 0 2 0 Good good 8 9.95 Example 217 Example 5 0 [5 8] 5 0 5 0 Good good 8 9.88 Example 218 Example 5 0 [5 81 5 0 10 0 Good good 8 9.92 Example 219 Example 5 0 [ 5 8) 5 0 2 0 0 Good good 8 9.98 Example 2 2 0 Example 5 0 [5 8] 5 0 4 0 0 Good good 8 9.93 Example 2 2 1 Example 5 0 [5 8] 5 0 8 0 0 Good good 8 9.90 Example 222 Example 5 0 [5 8] 5 0 10 0 0 Good good 8 9. 8 8 Example 2 2 3 Example 5 1 [5 8] 7 0 0 Good defect 9 0.00 Implementation Example 2 2 4 Example 5 1 [5 8] 7 0 2 0 Good Good 8 9.95 Example 225 Example 5 1 [5 8] 7 0 5 0 Good Good 8 9.97 Example 2 2 6 Example 5 1 [5 8] 7 0 10 0 Good good 8 9.93 Example 2 2 7 Example 5 1 [5 8] 7 0 2 0 0 Good good 8 9.94 Example 2 2 8 Example 5 1 [5 81 7 0 4 0 0 Good Good 8 9.95 implementation 2 2 9 Example 5 1 [5 8] 70 8 0 0 Good good 8 9.92 Example 2 3 0 Example 5 1 [5 8} 7 0 10 0 0 Good good 8 9.90 Example 2 3:1 Example 5 2 [5 81 10 0 0 good bad 9 0.00 Example 2 3 2 Example 5 2 [5 8] 10 0 2 0 Good good 8 9.93 Example 2 3 3 Example 5 2 [5 8] 10 0 5 0 Good Good 8, 9,74 Example 2 3 4 Example 5 2 [5 8] 10 0 10 0 Good Good 8 9.94 Example 2 3 5 Example 5 2 [58] 10 0 2 0 0 Good Good 8 9.91 Example 236 Example 5 2 [5 8] 1.0 0 4 0 0 Good good 8 9.85 Example 2 3 7 Example 5 2 [5 8] 10 0 8 0 0 Good good 8 9.82 Example 238 Example 5 2 [5 8] 10 0 10 0 0 Good good 8 9.81 Example 2 3 9 Example 5 3 [6 01 5 0 Good defect 9 0.00 Example 2 4 0 Example 5 3 [6 0] 5 2 0 Good good 8 9.93 Example 24 1 Example 5 3 16 0] 5 5 0 Good good 8 9.99 Example 2 4 2 Example 5 3 [6 0] 5 10 0 Good good 8 9.90 Example 2 4 3 Example 5 3 [6 0] 5 2 0 0 good good 8 9.89 embodiment 244 embodiment 5 3 16 0] 5 4 0 0 Good good 8 9〇8 8 Example 2 4 5 Example 5 3 [6 0] 5 800 Good good 8 9.92 Example 2 4 6 Example 5 3 16 0] 5 10 0 0 Good good 8 9.94 - 95- 201241046 [Table 1 2 - 3] Polyimide® Coating Fluid Irradiation Strength (m J) Liquid Crystal Alignment Pretilt Angle (. Example number of doubling amount _ when voltage is applied without applied voltage S Example 2 4 7 Example 5 4 [6 0] 10 0 Good defect 9 0. 0 0 Example 2 4 8 Example 5 4 [6 0 ] 10 2 0 Good good 8 9. 9 7 寅 Example 2 4 9 S Example 5 4 [6 01 10 5 0 Good good 8 9. 9 9 Example 2 5 0 Example 5 4 [6 0] 10 10 0 Good good 8 9. 9 3 Example 2 5 1 Example 5 4 [6 0] 10 2 0 0 Good good 8 9. 9 2 Example 2 5 2 Example 5 4 [6 0] 1 0 4 0 0 Good good 8 9. 9 4 Quality application 2 5 3 Example 5 4 [6 0] 10 8 0 0 Good good 8 9. 9 4 Example 2 5 4 Example 5 4 [6 0] 10 10 0 0 Good Good 8 9. 9 1 Example 2 5 5 Example 5 5 [6 01 2 0 0 Good bad 9 0. 0 0 Example 256 Example 5 5 [6 0] 2 0 2 0 Good good 8 9. 9 7 ΗExample 2 5 7 ΗExample 5 5 [6 0] 2 0 5 0 Good good 8 9. 9 0 Example 2 5 8 Example 5 5 [6 01 2 0 10 0 Good good 8 9. 9 9 Qualitative Example 2 5 9 Example 5 5 [6 0] 2 0 2 0 0 Good Good 8 9. 8 5 Example 2 6 0 Example 5 5 [6 0] 2 0 4 0 0 Good good 8 9. 8 7 Example 2 6 1 Example 5 5 [6 0] 2 0 8 0 0 Good good 8 9. 9 0 Example 2 6 2 Example 5 5 [6 0] 2 0 10 0 0 Good and good 8 9. 8 2 Example 2 6 3 Example 5 6 [6 0] 3 0 0 Good bad 9 0. 0 0 Example 2 6 4 Example 5 6 [6 0] 3 0 .20 Good Good 8 9. 9 2 Example 2 6 5 Θ Example 5 6 [6 0] 3 0 5 0 Good good 8 9. 7 9 Η Example 2 6 6 Example 5 6 [6 01 3 0 10 0 Good and good 8 9. 7 6 Example 2 6 7 Example 5 6 [6 0] 3 0 2 0 0 Good good 8 9. 9 0 Example 2 6 8 Example 5 6 [6 01 3 0 4 0 0 Good good 8 9. 8 7 Example 2 6 9 Example 5 6 [60]. 3 0 8 0 0 Good good 8 9. 8 7 Η Example 2 7 0 苡 Example 5 6 [6 0] 3 0 10 0 0 Good Good 8 9. 8 3 Example 2 7 1 Example 57 . [6 0] 5 0 0 Good bad 9 0. 0 0 S Example 2 7 2 Example 5 7 [6 0] 5 0 2 0 Good 8 9. 9 8 Example 2 7 3 Dragon Case 5 7 [6 01 5 0 5 0 . Good Good 8 9. 9 9 Η Example 2 7 4 苡 Example 5 7 [6 01 5 0 10 0 Good Good 8 9 9 2 Η例27 5 Capital Example 5 7 [6 0 1 5 0 2 0 0 Good Good 8 9. 7 7 Simplified 2 7 6 贲 Example 5 7 [6 0] 5 0 4 0 0 Good Good 8 9. 8 6 ΒΤ Example 2 7 7 13 Example 5 7 [6 0] 5 0 8 0 0 Good and good 8 9. 8 9 ® Application 2 7 8 Η Example 5 7 [6 0] 5 0 10 0 0 Good and good 8 9. 8 8 -96 - 201241046 I Table 1 2—4] Coating liquid for forming a polyimide film (I: J) Liquid crystal alignment pretilt angle (. Example No. lion addition amount (wtX) When a voltage is applied without an applied voltage, Example 27 9 Example 5 8 [6 0} 7 0 0 Good defect 9 0. 0 0. Example 280 Example 5 8 [60] 7 0 2 0 Good Good 8 9. 9 0 Example 2 8 1 Example 5 8 [6 0] 7 0 5 0 Good Bu Good 89. 9 9 Example 2 8 2 Example 5 8 [6 0] .70 100 Good good 8 9. 8 9 Example 2 8 3 Example 5 8 [6 0] 7 0 2 0 0 Good good 8 9. 8 6 Example 2 8 4 Example 5 8 [6 0] 7 0 4 0 0 Good good 8 9. 8 0 Example 2 8 5 Example 5 8 [6 01 70 8 0 0 Good good 8 9. 8 4 Example 2 8 6 Example 5 8 [6 0] 7 0 10 0 0 Good Good 8 9. 8 1 Example 2 8 7 Example 5 9 [6 0] 10 0 0 Good bad 9 0. 0 0 Example 2 8 8 Example 5 9 16 0] 10 0 2 0 Good good 8 9. 9 3 Example 2 8 9 Example 5 9 [6 0] 10 0 5 0 Good good 8 9. 9 6 Example 2 9 0 Example 5 9 [6 0] 10 0 10 0 Good good 8 9. 9 2 Example 2 9 1 Example 5 9 [6 0] 10 0 2 0 0 Good Good 8 9. 9 0 Example 292 * Example 59 [6 0] 10 0 4 0 0 Good good 8 9. 8 3 Example 2 9 3 Example 5 9 [6 0] 1 0 0 800 Good good 8 9. 7 5 Example 294 Example 5 9 160] 10 0 10 0 0 Good ▲ Good 8 9 7 6 &lt;Examples 295 to 315 and Comparative Example 9&gt;&lt;Measurement of voltage maintenance ratio (VHR)&gt; The coating liquid for forming a polyimide film prepared using each of the examples shown in Table 13 was used. The liquid crystal cell to be fabricated, the voltage maintenance rate in the initial state

Determination. The voltage maintenance rate is measured by applying a voltage of 4V at a temperature of 90 ° C for 60 ps, and a voltage after 16.67 ms. How long can the voltage be maintained?

Calculated as voltage maintenance rate. The voltage maintenance rate is measured using TOYO

A VHR-1 voltage maintenance rate measuring device manufactured by Corporation. In addition, the liquid crystal cell system used for the measurement of the voltage maintenance ratio (VHR) is a glass substrate using an IT0 transparent electrode as a substrate, and the coating film of the coating liquid for forming a polyimide film is heated. The firing was carried out for 30 minutes on a hot plate of 23 ° C. The friction conditions were the number of roll rotations of I OOO rpm and the speed of the rolls.

-97 - S 201241046 50mm/sec, press-in 0.3 m m for production. Further, the compound (Comparative Example 9) in which the compound represented by the above formula [A] was not added was adjusted, and the effects were compared. The results are shown in Table 13. As a result, it was confirmed that a coating liquid for forming a polyimide film having a compound represented by the above formula [A] was used, and a favorable voltage maintenance ratio characteristic was obtained even when it was not added. [Table 13] Polyssas Nacheng Coating Liquid Voltage Maintenance Rate (3⁄4) Example No. Polyethylate Formula [A] Compound lion addition amount Example 2 9 5 Example 1 PAA-1 [10] 10m〇1 % 6 5. 4 Baoji Example 2 9 6 Example 4 PAA-1 [18] 1Omo]% 6 7.. 8 Example 297 Example 5 PAA-1 13 2] 1Omo1 % 65. 6 Example 2 9 8 Example 6 PAA -1 [341 1Omo1 % 85; 2 Example 2 9 9 Shiqing 1 0 PAA-1 [4 61 lwt % 68. 0 Example 3 0 0 Example 1 1 PAA-1 [4 6] 3wt % 7 8. 2 Example 3 0 1 Example 1 2 PAA-1 (46) 5wtX 7 7. 8 Example 3 0 2 Example 15 PAA-1 14 2] lwt% 80. 9 Example 3 0 3 Example 1 6 PAA -1 [4 2] 3w t % 8 3. 0 Example 3 0 4 *Example 1 7 PAA-1 [4 2J 5w t % 7 6. 6 Example 30S Example 2 0 PAA-1 [4 4] Lwt % 1 79. 9 Example 3 0 6 Example 2 1 PAA-1 [44] 3wt涔 83. 8 Example 3 0 7 Example 2 2 PAA-1 14 4] 5wt% 8 2. 1 Example 3 0 8 Example 2 5 PAA-1 1 0 0] lwt % 6 5, 4 Example 309 Example 2 6 PAA-1 150) 3wt « 6 0. 4 Example 310 Example 2 7 PAA-1 [5 0] 5wt « 6 5.7 Example 31 1 Example 2 8 PAA-1 [5 0] 1 Owt% 6 9. 7 Example 312 Example 2 9 PAA-1 [5 0] 20wt% 6 7·' Example 313 Example 3 2 PAA-1 [54] 5v/t% 7 3. 4 Example 314 Example 3 3 PAA-1 154] '1 Owt % 7 4. 5 Example 315 Example 3 4 PAA- 1 (5 4) 2 Owt% 7 6. 2 Comparative Example 9 A PAA-1 No - 5 8.7 &lt;Examples 316 to 321 and Comparative Example 10&gt;&lt;Estimation of cumulative charge (RDC)&gt; -98- 201241046 The twisted nematic liquid crystal cell produced by using the coating liquid for forming a polyimide film prepared in each of the examples shown in Table 14 was applied at a temperature of 23 ° C at a time interval of 0 V to 0.1 V. From 1.0 V, the degree of flicker amplitude at each voltage was measured to prepare a calibration curve. After 5 minutes of grounding, an external AC voltage of 3.0 V, a DC voltage of 5.0 V, and the degree of flicker amplitude after one hour of measurement were measured. RD C (flicker control method) was estimated by comparing a previously prepared calibration curve. Further, in the liquid crystal cell system for estimating the cumulative charge (RDC), a glass substrate using a transparent electrode is used as a substrate, and a coating film for a coating liquid for forming a polyimide film is heated. The mixture was fired on a hot plate at 203 ° C for 30 minutes, and the rubbing conditions were a number of revolutions of 100 rpm, and a roll speed of 50 mm/sec. Further, the compound represented by the above formula [A] was not added (Comparative Example 10), and the effects were compared. The results are shown in Table 14. As a result, it was confirmed that a liquid crystal cell having a small RDC can be obtained by using a coating liquid for forming a polyimide film formed by adding the compound represented by the above formula [A]. [Table 1 4] Polysodium sulphate coating liquid RDC Example No. Polyamine type [A] The amount of addition of the impurity type (mo 1 %) Accumulation · (V) Loss 〃 (V) Example 316 Example 1 PAA-1 [10] 10 &gt; 1 0.3 2 Example 317 Example 2 PAA-1 [12] 10 &gt; 1 0.2 8 Example 318 Example 3 PAA-1 [14] 10 &gt ;1 0.17 Example 319. Example 4 PAA-1 Bu [1 81 10 &gt; 1 0.3 8 Example 3 2 0 Example 5 PAA-1 [3 2] 10 &gt; 1 0. 42 Example 3 2 1 Example 6 PAA-1 "[34] 10 0. 82 0.17 Comparative Example 1 0 - PAA-1 None 1 &gt; 1 0.4 6 * According to the optical scintillation reference method, the RDC 値* * stops after stopping the DC voltage (DC) Residual RDC 30-99-201241046 after direct current (DC) 30 minutes &lt;Examples 322 to 329 and Comparative Example ll&gt; Determination of ion density before and after the aging test in the above polylysine (PAA-1) solution (l 〇.〇g) The solids of each of the compounds shown in Table 15 prepared as a synthesis example of a compound for modification, which is a polyglycine (?8-8) solution (ie, polylysine (? -1)) is added in the proportions shown in Table 15 below. The coating liquid for forming a polyimide film is prepared by stirring at room temperature until it is a uniform solution. Next, a twisted nematic type produced by using a coating liquid for forming a polymer film (liquid crystal alignment agent) is used. The liquid crystal cell was subjected to ion density measurement in an initial state (23 ° C), and ion density measurement was carried out after maintaining at 60 ° C for 30 hours (aging). In the ion density measurement, measurement of a voltage applied to the liquid crystal cell was performed. The ion density at the time of the triangular wave of ±10 V and the number of cycles of 0.01 Hz. The measurement temperature was carried out at 80 ° C. The measurement device was a 6245 liquid crystal physical property evaluation device manufactured by TOYO Corporation. The results are shown in Table 15. In the lining liquid crystal cell, the firing condition of the coating film for forming a polyimide film is a firing condition of 30 minutes on a hot plate heated at 200 ° C to perform the above-described twisted nematic type. The liquid crystal cell (Examples 155 to 179) was produced in the same manner. Further, the same operation was carried out for the compound to which no modification was added, and the effect was compared. The result was obtained by appropriately selecting the compound for modification. Type and amount of addition, comparison with the case of no addition, in the liquid crystal cell to confirm significantly reduced ionic impurities. -100-201241046 polyimide film [15] Table-forming coating solution

&lt;Examples 330 to 342&gt; The compound described in the following Table 16 produced as the above-mentioned synthesis example of the compound for modification of the polyfluorene fee acid (PAA-1) solution (i〇.〇g) produced above Each of them is added in a ratio of the solid content of the poly-proline (PA A-1) solution (that is, polyamic acid (PAA-1)) as described in the following Table 16 until it becomes a homogeneous solution. The coating liquid for forming a polyimine film of Example 3 3 0 to 3 42 was prepared by stirring at room temperature. [Table 16] Addition amount (wt%) of compound for polyaminic acid modification Example 3 3 0 P AA - 1 Synthesis Example 3 7 [7 6] 10 Example 3 3 1 P AA-1 Synthesis Example 3 7 [7 6] 15 Example 3 3 2 P AA-1 Synthesis Example 3 7 [7 6] 2 0 Example 3 3 3 P AA-1 Synthesis Example 3 8 [7 8] 5 Example 3 3 4 P AA- 1 Synthesis Example 3 8 [7 8] 10 Example 3 3 5 P AA-1 Synthesis Example 3 8 [7 8] 2 0 Example 3 3 6 P AA-1 Synthesis Example 3 8 [7 8] 3 0 Example 3 3 7 P AA-1 Synthesis Example 3 8 [7 8] 4 0 Example 3 3 8 P AA-1 Synthesis Example 3 8 [7 8] 5 0 Example 3 3 9 PAA-1 Synthesis Example 3 8 [7 8] 7 0 Example 3 4 0 P AA-1 Synthesis Example 3 9 [8 0] 5 Example 3 4 1 P AA-1 Synthesis Example 3 9 [8 0] 6 Example 3 4 2 P AA- 1 Synthesis Example 3 9 [8 0] 7 • 101 - 201241046 <Examples 343 to 344> In the above-prepared polylysine (PAA-3) solution (4 μg), the above synthesis as a compound for modification was carried out. The compounds of the following Table 17 produced by the examples are each in a form of a mass fraction relative to the solid content of the polyamido acid (PAA-3) solution (that is, polyglycine (PAA-3)) as shown in Table 17. Add to, The coating liquid for forming a polyimine film of Examples 343 to 3 44 was prepared by stirring at room temperature until it became a uniform solution. [Table 1 7] Compounding amount (wt%) of compound for polyaminic acid modification Example 3 4 3 P AA- 3 [7 0] 7 0 Example 3 4 4 P AA- 3 [7 0] 10 0 &lt; [Examples 345 to 447] &lt;Liquid alignment evaluation and pre-tilt angle measurement of the antiparallel liquid crystal cell in the vertical alignment mode&gt; [Production of liquid crystal alignment film and liquid crystal cell] The modulation was carried out using the above respective examples 330 to 34. The coating liquid for forming a polyimide film (liquid crystal alignment agent) was used to produce a liquid crystal cell as follows. The coating liquid for forming a polyimide film (liquid crystal alignment agent) was spin-coated on a glass substrate, dried on a hot plate at 80 ° C for 70 seconds, and then heated to 200 ° C in a hot air circulating oven. The film was fired in 30 minutes to form a coating film having a film thickness of 100 nm. Thereafter, the coating film surface was linearly polarized with UV light (UV wavelength 3 13 nm, irradiation intensity 8.0 mW/cnT2) between exposure amounts 〇mJ to 1000 mJ, and was inclined at 40 to the normal of the plate. Irradiation. Further, the linear polarized UV system was prepared by passing the ultraviolet light of a high-pressure mercury lamp through a 313 nm band-pass filter and passing through a polarizing plate of 313 nm at -102-201241046. Prepare the substrate 2 sheet with the liquid crystal alignment film subjected to the liquid crystal alignment treatment, and spread a spacer of 6 μm on one of the liquid crystal alignment film surfaces, and then seal the sealant thereon, and the other substrate is aligned with the liquid crystal alignment film surface. The polarizing direction of the irradiation is applied in parallel so that the sealant is hardened to form an empty unit cell. This empty cell was injected into a liquid crystal MLC-6608 (manufactured by Merck) by a reduced pressure injection method, and the injection port was closed to obtain an antiparallel liquid crystal cell for each vertical alignment mode. Then, the produced liquid crystal cell is held by a polarizing plate, and the liquid crystal cell is rotated in a state where the backlight is irradiated from the rear, and the change in brightness and darkness, the presence or absence of the flow alignment, and whether or not the liquid crystal is aligned are visually observed, and the alignment is good. Thereafter, a 3 V AC voltage was applied to the liquid crystal cell to visually observe whether or not the liquid crystal was aligned. At this time, the evaluation was performed using the following criteria. The results are shown in Tables 18-1 to 18-4. Evaluation criteria Good: The alignment of the liquid crystal was confirmed, and the flow alignment was not good. Although the liquid crystal was aligned, a large number of flow alignments were observed, and the above-mentioned liquid crystal cell was produced at 120. (: The pretilt angle was measured after heating for 1 hour. The pretilt angle was measured by the "Axo Scan" of Axo Metrix Co., Ltd. by the Mueller matrix method. The results are shown in Tables 18-1 to 1 8-4. As a result, as shown in Tables 18-1 to 18-4, it was confirmed by using a coating liquid for forming a polyimide film having a photoreactive side chain (liquid crystal alignment treatment agent). In the case of performing the photo-alignment treatment, a good vertical alignment property can be obtained from -103 to 201241046. Further, by applying a polarizing ultraviolet ray to the coating liquid for forming a polyimine film of the present invention (liquid crystal alignment treatment agent), it is confirmed that it is slightly perpendicular to the vertical direction. In the slanted state, the liquid crystal alignment treatment is performed. Further, it is also confirmed that the pretilt angle can be finely adjusted by controlling the amount of addition and the amount of irradiation. Thus, the coating liquid for forming a polyimide film of the present invention (liquid crystal alignment treatment) A liquid crystal alignment film for a liquid crystal display element of a vertical alignment type can be used, and it can be said that it can also be used as a liquid crystal alignment film used for a photo-alignment method. [Table 1 8 - 1] Polyimine Brewing intensity Liquid crystal alignment example No. mm Add S (wt*) (m J) When no voltage is applied, when voltage is applied, 孭 月 (°) Example 3 4 5 S Example 3 4 3 [7 0] 7 0 0 Good Bad 9 0. 0 0 Example 3 4 6 Example 3 4 3 [7 0] 7 0 5 0 Good good 9 0, 0 0 Food application 3 4 7 S Example 3 4 3 [7 0] 7 0 10 0 Good good 8 9. 9 2 Example 3 4 8 Example 3 4 3 [7 0] 7 0 2 0 0 Good good 8 9. 9 0 _ Example 3 4 9 ET Example 3 4 3 [7 0 7 0 4 0 0 Good good 8 9. 9 0 - Example 3 5 0 Η Example 3 4 3 [7 0] 7 0 8 0 0 Good good 8 9. 8 6 ΐ Example 3 5 1 ΪΪ 3 4 3 [7 0] 7 0 10 0 0 Good good 8 9. 7 9 S: Example 3 5 2 佥 Example 3 4 4 [7 0] 10 0 0 Good bad 9 0. 0 0 Example 3 5 3 Η例例 3 4 4. [7 0] 10 0 5 0 Good Good 8 9. ί) 3 Example 3 5 4 Κ Example 3 4 4 [7 0] 10 0 10 0 "Good Good 8 9. 9 3 Example 3 5 5 Cargo Example 3 4 4 [7 0] 10 0 2 0 0 Good Good 8 9, 8 8 Example 3 5 6 Η Example 3 4 4 [7 0] 10 0 4 0 0 Good and good 8 9, 8 9 Example 3 5 7 β Example 3 4 4 [7 0] 10 0 8 0 0 Good good 8 9. 7 3 Example 3 5 8 Η Example 3 4 4 [7 0] 10 0 10 0 0 Good good 8 9. 7 0 Example 3 5 9 ΪΓ Example 3 3 0 [7 6] 10 0 Good Bad 9 0. 0 0 Example 3 6 0 β Example 3 3 0 [7 6] 10 2 0 Good good 8 9. 3 9 Example 3 6 1 S Example 3 3 0 [7 6] 10 5 0 Good Good 8 9. 0 0 Example 3 6 2 β Example 3 3 0 [7 6] 10 10 0 Good good 8 8. 7 2 Simple example 3 6 3 Example 3 3 0 [7 6] 10 2 0 0 Good 8 8, 8 8 Example 3 6 4 ST Example 3 3 0 [7 6] 10 4 0 0 Good Good 8 9. 0 6 Example 3 6 5 W Example 3 3 1 [7 6] 15 0 _ Good bad 9 0. 0 0 Example 3 6 6 β Example 3 3 1 [7 6] 1 5 2 0 . Good good 8 9. 6 5 S Example 3 6 7 ΕΤ Example 3 3 1 [7 6] 1 5 5 0 Good good 8 9. 5 7 Θ Example 3 6 8 Κ Example 3 3 1 [7 6] 15 10 0 Good good 8 9. 5 7 Dragon example 3 6 9 ΪΪ Example 3 3 1 [7 6] 15 2 0 0 - good good 8 9. 4 4 0 application example 3 7 ΕΤ embodiment 3 3 1 [7 6] 15 4 0 0 good good 8 9. 4 2 -104- 201241046 [Table 1 8 — 2] Polymerization intensity (m J) of liquid crystal alignment pre-tilt angle. Example No. Surface Addition Amount (wt%) When a voltage is applied without an applied voltage Example 3 7 1 Example 3 3 2 [7 6] 2 0 0 Good defect 9 0. 0 0 Example 3 7 2 Example 3 3 2 [7 6] 2 0 2 0 Good good 8 9〇9 0 Example 3 7 3 Example 3.3 2 [7 6] 2 0 5 0 Good good 8 9. 7 6 Example 3 7 4 Example 3 3 2 [7 6] 2 0 10 0 Good good 8 9. 7 0 Example 3 7 5 Example 3 3 2 [7 6] 2 0 2 0 0 Good good 8 9. 4 8 Example 3 7 6 Example 3 3 2 [7 6] 2 0 4 0 0 Good good 8 9. 5 4 Example 3 7 7 Example 3 3 3 [7 8] 5 0 Good defect 9 0. 0 0 Example 3 7 8 Example 3 3 3 [7 83 5 2 0 Good good 8 8. 8 0 Example 3 7 9 Example 3 3 3 [7 8] 5 5 0 Good good 8 8. 2 4 Example 3 8 0 Example 3 3 3 [7 8] 5 10 0 Good good 8 8. 2 7 Example 3 8 1 Example 3 3 3 [7 8] 5 2 0 0 Good good 8 8. 2 8 Example 3 8 2 Example 3 3 3 [7 8 ] 5 4 0 0 Good Good 8 8. 5 6 Example 3 8 3 Example 3 3 3 [7 8] 5 8 0 0 Good Good 8 8. 6 4 Example 3 8 4 Example 3 3 3 [7 8 ] 5 10 0 0 Good good 8 8. 5 8 Example 3 8 S Example 3 3 4 [7 8] 10 0 Good defect 9 0. 0 0 Example 3 8 6 Example 3 3 4 [7 8] 10 2 0 Good Good 8 9. 6 8 Example 3 8 7 Example 3 3 4 [7 8] 10 5 0 Good good 8 9. 3 8 Example 3 8 8 Example 3 3 4 [7 8] 10 10 0 Good good 8 9. 2 8 Example 3 8 9 Example 3 3 4 [7 8] 10 2 0 0 Good good 8 9. 10 Example 3 9 0 Example 3 3 4 [7 8] 10 4 0 0 Good good 8 9 2 7 Example 3 9 1 Example 3 3 4 [7 8] 10 8 0 0 Good good 8 9. 3 1 Example 3 9 2 Example 3 3 4 [7 8] 10 10 0 0 Good good 8 9 18 Example 3 9 3 Example 3 3 5 [7 8] 2 0 0 Good defect 9 0. 0 0 Example 3 9 4 Example 3 3 5 [7 8] 2 0 2 0 Good good 8 9. 8 1 Example 3 9 5 Example 3 3 5 [7 8] 2 0 5 0 Good good 8 9. 5 2 Example 3 9 6 Example 3 3 5 [7 8] 2 0 10 0 Good. Good 8 9. 5 2 Example 3 9 7 Example 3 3 5 [7 8] 2 0 2 0 0 Good good 8 9. 3 6 Example 3 9 8 Example 3 3 5 [7 8] 2 0 4 0 0 Good good 8 9. 3 2 Example 3 9 9 Real Example 3 3 5 [7 8] 2 0 8 0 0 Good Good 8 9 . 3 0 Example 4 0 0 Example 3 3 5 [7 8] 2 0 10 0 0 Good Good 8 9. 2 8 -105- 201241046 [Table 1 8 - 3] Coating for polyimine film formation 1 Liquid irradiation intensity (m J ) Liquid crystal recording pretilt angle (. Example No. Surface Addition Amount (wt%) When a voltage is applied without an applied voltage Example 4 0 1 Example 3 3 6 [7 8] 3 0 0 Good defect 9 0. 0 0 Example 4 0 2 Example 3 3 6 [7 8] 3 0 2 0 Good good 8 9. 8 8 Example 4 0 3 Example 3 3 6 [7 8] 3 0 5 0 Good good 8 9. 7 1 Example 4 0 4 Example 3 3 6 [7 8] 3 0 10 0 Good good 8 9. 5 5 Example 4 0 5 Example 3 3 6 [7 8] 3 0 2 0 0 Good good 8 9. 4 3 Example 4 0 6 Example 3 3 6 [7 8] 3 0 4 0 0 Good good 8 9. 3 1. S Example 4 0 7 Example 3 3 6 [7 8] 3 0 8 0 0 Good good 8 9. 3 0 Example 4 0 8 Example 3 3 6 [7 8] 3 0 10 0 0 Good good 8 9. 3 3 0 Example 4 0 9 Example 3 3 7 [7 8] 4 0 0 Good defect 9 0 . 0 0 Example 4 1 0 Example 3 3 7 17 8] 4 0 2 0 Good good 8 9. 8 1 Example 411 Example 3 3 7 [7 8] 4 0 5 0 Good good 8 9. 7 0 Example 4 1 2 Example 3 3 7 [7 8] 4 0 10 0 Good Good 8 9. 5 7 Example 4 1 3 Example 3 3 7 [7 8] 4 0 2 0 0 Good Good 8 9. 4 3 Example 4 1 4 βExample 3 3 7 [7 8] 4 0 4 0 0 Good good 8 9. 4 4 Example 4 1 5 Example 3 3 7 [7 8] 4 0 8 0 0 Good good 8 9. 3 2 Example 4 1 6 Dragon example 3 3 7 [7 8]. 4 0 10 0 0 Good good 8 9. 2 6 Example 4 1 7 Example 3 3 8 [7 8]. 5 0 0 Good defect 9 0. 0 0 Example 418 Example 3 3 8 [7 8] 5 0 2 0 Good good 8 9. 9 8 Example 4 1 9 Example 3 3 8 [7 8] 5 0 5 0 Good good 8 9. 8 2 Example 4 2 0 Example 3 3 8 [7 8] 5 0 10 0 Good good 8 9. 7 3 Example 4 2 1 Example 3 3 8 [7 8] 5 0 2 0 0 Good good 8 9. 7 8 S Example 4 2 2 , Example 3 3 8 [7 8] 5 0 4 0 0 Good Good 8 9. 7 5 Example 4 2 3 Decoration Example 3 3 8 [7 8] 5 0 8 0 0 Good Good 8 9. 7 3 β Example 4 2 4 贲 Example 3 3 8 [7 8] 5 0 10 0 0 Good good 8 9 . 7 4 -106- 201241046 [Table 1 8 - 4] Example 4 2 5 Polyimine oxime forming field Coating liquid irradiation intensity (m J ) 0 to A3 Example number Example 3 3 9 _ [7 8] Adding amount (wtX) 7 0 S plus good plus electric boat yc a pretilt angle (. 〉 Example 4 2 6 Example 4 2 7 Ϊ Example 4 2 R 3 3 9 Example 3 3 9 will steal gamma, 0 Λ [7 8] [7 8] 7 0 7 0 2 0 5 0 Λ Good 9 0. 〇〇8 9. 94 8 9.89 _Example 4 2 9 Example 3 3 9 L7 8] [7 8] 7 0 7 0 10 0 2 0 0 Good and good 8 9.85 Example 4 3 0 Example 3 3 9 [7 8] 7 0 4 0 0 Good good 〇 y * ( 〇. Example 4 31 Example 4 3 2 | Example 3 3 9 Example 3 3 9 [7 8] [7 8] 7 0 —71. 8 0 0 10—0 0 Good good—good good 〇y · 4 〇8 9.49 &quot;δΤΓΤΤ' 9 0 . 0 〇~ 8 9. 95 8 9. 7V 8 9 6 2 Example 4 3 3 Embodiment 3 4 0 [8 0] 5 0 Embodiment 4 3 4 Embodiment 3 4 0 [8 0] 5 2 0 Good Example 4 3 5 Example 3 4 0 "[8 0] 5 5 0 Embodiment 4 3 6 implementation for j 3 4 0 [8 0] 5 10 0 embodiment 4 3 7 embodiment 3 4 0 [8 0] 5 2 0 0 good good 8 9 6 0 embodiment 4 3 8 embodiment 3 41 [8 0] 6 0 Good-ϋ. Good 9 0. 0〇8 9 9 5—Example 4 3 9 Selling Example 341 [8 0] 6 2 0 Example 4 4 0 Example 3 41 [8 0] 6 5 0 Good good 8 9 . 7 〇~ Λ Q ο &quot; Example 4 41 Example 3 4 1 [8 0] 6 10 0 Good Example 4 4 2 Example 3 41 [8 0] 6 2 0 0 Good Good 8 9 . 6〇 - Example 4 4 3 Example 3 4 2 [8 0] 7 0 Good bad good 9 0 . 0~〇~ 8 9, 9 4, Example 444 Real_ 3 4 2 [8 0] 7 2 0 Good example 4 4 5 Example 3 4 2 [8 0] 7 5 0 Good good 8 9. 74 Example 4 4 6 Example 3 4 2 [8 0] 7 10 0 Good good 8 9. 5 7~ Example 4 4 7 Example 3 4 2 [8 0] 7 2 0 0 Good and good 8 9 . 6 3 &lt;Examples 448 to 471&gt; The polyplycine (PAA-1) solution (10.Og) produced above was produced as the above-mentioned synthesis example of the compound for modification. The compounds described in the following Tables 1 9 were each added in such a manner that the solid content of the polyacrylic acid (PAA-1) solution (that is, polyamic acid (PAA-1)) was in the proportions shown in Table 19 below. The coating liquid for forming a polyimide film of Examples 448 to 47 1 was prepared by stirring at room temperature until it became a homogeneous solution. -107- 201241046 [Table 1 9 I Compound addition amount of polyamine acid modification (wt %) S Example 4 4 8 Ρ ΑΑ - 1 Synthesis Example 3 5 [7 2] .5 0 fr Example 4 4 9 Ρ ΑΑ - 1 Synthesis Example 3 5 [7 2] 5 0 Dragon Case 4 5 0 Ρ ΑΑ - 1 Synthesis Example 3 5 [7 2] 5 0 K Example 4 5 1 Ρ ΑΑ - 1 Synthesis Example 3 5 [7 2 ] 5 0 β Example 4 5 2 Ρ ΑΑ - 1 Synthesis Example 3 5 [7 2] 5 0 贲 Example 4 5 3 Ρ ΑΑ - 1 Synthesis Example 3 5 [7 2] 5 0 13 Example 4 5 4 Ρ ΑΑ-1 Synthesis Example 3 5 [7 2] 7 0 Example 4 5 5 Ρ ΑΑ- 1 Synthesis Example 3 5 [7 2] 7 0 ΪΓ Example 4 5 6 Ρ ΑΑ - 1 Synthesis Example 3 5 [7 2] 7 0 ΒΓ 4 4 4 7 Ρ ΑΑ - 1 Synthesis Example 3 5 [7 2] 7 0 U Example 4 5 8 Ρ ΑΑ - 1 Synthesis Example 3 5 [7 2] 7 0 β Example 4 5 9 Ρ ΑΑ - 1 Synthesis Example 3 5 [7 2] 7 0 β Example 4 6 0 Ρ ΑΑ - 1 Synthesis Example 3 5 [7 2] 10 0 Simple Example 4 6 1 Ρ ΑΑ - 1 Synthesis Example 3 5 [7 2] 10 0 β: Example 4 6 2 Ρ ΑΑ- 1 Synthesis Example 3 5 [7.2] 10 0 K Example 4 6 3 Ρ ΑΑ- 1 Synthesis Example 3 5 [7 2] 10 0 S Example 4 6 4 Ρ ΑΑ- 1 Synthesis Example 3 5 [7 2] 10 0 Η Example 4 6 5 Ρ ΑΑ - 1 Synthesis Example 3 5 17 2] 10 0 β Example 4 6 6 Ρ ΑΑ - 1 Synthesis Example 3 6 [7 4] 5 0 ΪΪ Example 4 6 7 Ρ ΑΑ - 1 Synthesis Example 3 6 [7 4] 5 0 Dragon Example 4 6 8 Ρ ΑΑ - 1 Synthesis Example 3 6 [7 4] 5 0 Κ Example 4 6 9 Ρ ΑΑ - 1 Synthesis Example 3 6 [7 4] 5 0 13 Example 4 7 0 Ρ ΑΑ - 1 Synthesis Example 3 6 [7 4] 5 0 G Application 4 7 1 Ρ ΑΑ- 1 Synthesis Example 3 6 [7 4] 5 0 &lt;Examples 472 to 495&gt;&lt; Evaluation of liquid crystal alignment of anti-parallel cells by horizontal alignment mode &gt; [Production of liquid crystal alignment film and liquid crystal cell] Using the above respective examples A coating liquid (liquid crystal alignment agent) for forming a polyimine film prepared by 448 to 471, and a liquid crystal cell was produced as follows. The coating liquid for forming a polyimide film (liquid crystal alignment agent) was spin-coated on a glass substrate, dried on a hot plate at 80 ° C for 70 seconds, and then heated to 200 ° C in a hot air circulating oven. The film was fired in 30 minutes to form a coating film having a film thickness of 100 nm. Then, the coating film surface was irradiated with linearly polarized UV light (UV wavelength 313 nm, irradiation intensity 8.0 mW/cm·2) between exposure amounts of OmJ to 1000 mJ -108 to 201241046, and was irradiated directly above the substrate. Further, the linearly polarized UV was modulated by a 313 nm polarizing plate by passing ultraviolet light of a high pressure mercury lamp through a bandpass filter of 313 nm. Prepare the substrate 2 sheet with the liquid crystal alignment film subjected to such liquid crystal alignment treatment, and spread a 6 μm spacer on one of the liquid crystal alignment film faces, and then seal the sealant thereon, and the other substrate is aligned with the liquid crystal alignment film surface. The polarizing direction of the irradiation is applied in parallel so that the sealant is hardened to form an empty unit cell. This empty cell was injected into a liquid crystal MLC-204 1 (manufactured by Merck Co., Ltd.) by a vacuum injection method, and the injection port was closed to obtain an anti-parallel liquid crystal cell for horizontal alignment mode. Next, the above-described horizontal alignment mode is held by a polarizing plate by an anti-parallel liquid crystal cell, and the liquid crystal cell is rotated in a state where the backlight is irradiated from the rear, and the change of light and darkness or the presence or absence of the flow alignment and the alignment of the liquid crystal are visually observed. At this time, the evaluation was performed using the following criteria. The results are shown in Table 20. Evaluation criteria ◎: The alignment of the liquid crystal was confirmed, and the flow alignment was not observed. Although the liquid crystal was aligned, a certain flow alignment was observed. Δ: The liquid crystal was aligned, but many flow alignments k were observed: the liquid crystals were all misaligned. In the liquid crystal cell, the liquid crystal cell which is not irradiated with light has no display orientation at all, but in the liquid crystal cell which is irradiated with light, the liquid crystal alignment is confirmed in accordance with the amount of the compound to be modified and the amount of light irradiation. Further, when it was confirmed that each of the aligned liquid crystal cells was treated at 130 ° C for 30 minutes, etc. -109-201241046, the significant change in the alignment property was not confirmed. That is, it has been confirmed that the horizontally-oriented cells can be easily produced by appropriately selecting the type and amount of the additive. [Table 2 0] Irradiation strength (m J) of the coating liquid for forming a polyimide film. Alignment presence or absence of the example number mm Adding amount (wt %) Example 4 7 2 K Example 4 4 8 [7 2] 5 0 0 X Embodiment 4 7 3 Example 4 4 9 [7 2] 5 0 2 0 〇 Example 4 7 4 Example 4 5 0 [7 2] 5 0 5 0 〇 Example 4 7 5 Example 4 5 1 [7 2] 5 0 10 0 〇 Example 4 7 6 贲 Example 4 5 2 [7 2]. 5 0 2 0 0 ◎ Example 4 7 .7 Rhyme 4 5 3 [7 2] 5 0 5 0 0 ◎ Example 4 7 8 Example 4 5 4 [7 2] 7 0 0 X Example 4 7 9 Surface Example 4 5 5 [7 2] 7 0 2 0 . Example 4 8 0 Decoration Example 4 5 6 [7 2] 7 0 5 0 ◎ Example 4 8 1 Example 4 5 7 [7 2] 7 0 10 0 ◎ Example 4 8 2 Surface Example 4 5 8 [7 2] 7 0 2 0 0 ◎ Implementation Example 4 8 3 Surface Example 4 5 9 [7 2] 7 0 5 0 0 ◎ Example 4 8 4 Example 4 6 0 [7 2] 10 0 0 X Example 4 8 5 Surface Example 4 6 1 [7 2 10 0 2 0 ◎ Example 4 8 6 Cargo Example 4 6 2 [7 2] 10 0 5 0 ◎ Example 4 8 7 贲 Example 4 6 3 [7 2] 10 0 10 0 ◎ Example 4 8 8 ΗExample 4 6 4 [7 2] 10 0 2 0 0 ◎ Example 4 8 9 Κ Example 4 6 5 [7 2] 10 0 5 0 0 ◎ Example 4 9 0 贲Example 4 6 6 [7 4] 5 0 0 X Example 4 9 1 Example 4 6 7 [7 4] 5 0 2 0 〇 Example 4 9 2 ΪΓ Example 4 6 8 [7 4] 5 0 5 0 〇Example 4 9 3 Application k 4 6 9 [7 4] 5 0 10 0 ◎ Example 4 9 4 Example 4 7 0 [74]. 5 0 2 0 0 ◎ Example 4 9 5 13 Example 4 7 1 [7 4] 5 0 5 0 0 ◎ -110-

Claims (1)

201241046 VII. Patent Application No. 1 A coating liquid for forming a polyimide film, which comprises polymerizing at least one tetracarboxylic acid component selected from a tetracarboxylic acid and a derivative thereof with a diamine component. a polyimine precursor obtained by the reaction, and at least one polymer selected from the polyimine obtained by imidating the polyimine precursor ruthenium, and two of the diamine compounds a difunctional compound represented by the following formula [A] in which an amine group is introduced into a structure of a Michaelic acid, [Chemical Formula 1] (wherein 'Y is a divalent organic group derived from the above diamine compound, and each of 1 and R2 is -Η, or may contain a benzene ring, a cyclohexane ring, a heterocyclic ring, a fluorine, an ether bond, or an ester bond at any position. And a monovalent organic group having a carbon number of 1 to 35 in the guanamine bond and may be bonded to a part of the oxime to form a ring, and 1 and R2 may be the same or different). 2. A liquid crystal alignment agent comprising the coating liquid for forming a polyimine film described in claim 1. 3. A polyimine film which is obtained by applying the coating liquid for forming a polyimide film described in claim 1 to a substrate and baking it. A polyimine film characterized by a polyimine precursor obtained by polymerizing at least one of a tetracarboxylic acid component selected from a tetracarboxylic acid and a derivative thereof and a diamine component, and The polyimine precursor 醯亚-111 - 201241046 The at least one polymer selected by the amination of the polyimine is introduced into the following by the introduction of the amino acid of each of the two amine groups of the diamine compound. The polyfunctional compound represented by the formula [A] is composed of a crosslinked polyimine, [Chemical 2] (wherein Y is a divalent organic group derived from the above diamine compound, and R1 and r2 are each -Η, or may contain a benzene ring, a cyclohexane ring, a hetero ring, a town, an ether bond, an ester bond at any position' The acid-amine bond has a valence organic group having 1 to 35 carbon atoms and may be bonded to one of the oxime to form a ring, and 1 and R2 may be the same or different. A liquid crystal alignment film characterized by the polyimine film of claim 3 or 4. A liquid crystal display device comprising the liquid crystal alignment film of claim 5; -112- 201241046 IV. Designated representative map: (1) The representative representative of the case is: No (2) The symbol of the representative figure is simple: No 201241046 If there is a chemical formula in the case, please disclose the chemical formula that best shows the characteristics of the invention. :no