TW201240981A - Coating solution for forming functional polymer film, and method for forming functional polymer film - Google Patents

Abstract

Provided is a coating solution for forming a functional polymer film, said coating solution containing: at least one type of modifying compound selected from the group represented by formula A-D and having at least one Meldrum's acid structural site and a functional structural site which imparts functionality; and a polymer for modification or a monomer for the synthesis of said polymer for modification. Also provided is a functional polymer film obtained by firing a substrate coated using said coating. (In the formulae, the symbols are groups as defined in claim 1.)

Description

201240981 VI. Description of the Invention [Technical Field] The present invention relates to a novel method for forming a functional polymer film for forming a functional polymer film. [Prior Art] In a liquid crystal display device, a liquid crystal alignment film is used. The role of the liquid crystal in the direction of orientation, the main liquid crystal alignment film currently used in the industry is a polyimide system formed by a polyimide, polyglycolate or polyimine solution of a polyimide precursor. The liquid crystal alignment agent is coated on the substrate. Further, the liquid crystal is applied in a parallel alignment or oblique alignment with respect to the liquid crystal on the substrate surface, and the surface extension treatment is performed by brushing. Further, the method of the brushing treatment which has been proposed is a method in which various chemical reactions such as polarized ultraviolet rays are applied, and it has been reviewed in recent years for industrialization. In order to enhance the display characteristics of such liquid crystal display elements, polyamines, polyphthalates or polyazides which have been constructed by blending properties of polylysine, polyamidomate or polyimine. Amine, additive, etc., improve liquid crystal alignment and electrical properties, or control pretilt angle. In the technique of controlling the pretilt angle by using the structure of polyimine, the method of using the chain diamine as a partial polyimine raw material can control the pretilt angle according to the use ratio of the amine, so that the pretilt of the purpose can be easily obtained. Therefore, it is a method to increase the pretilt angle. It is known to increase the branched structure of the pre-diamine of liquid crystal, such as a long-chain alkyl group or a fluoroalkyl group (for example, reference), a cyclic group or a combination of a cyclic group and an alkyl group (for example, a reference cloth liquid must be In the case of dissolving the film, the two corners are replaced by the different sides, and the dip angle test patent-5-201240981 document 2), the nest skeleton (for example, refer to Patent Document 3), and the like. Further, in order to improve the stability of the pretilt angle and the dependency of the steps, the structure of the diamine for increasing the pretilt angle of the liquid crystal has been reviewed. The branched structure used at this time has been proposed, and a ring containing a phenyl group or a cyclohexyl group has been proposed. The structure is constructed (for example, refer to Patent Documents 4 and 5). Further, three to four branched diamines having such a ring structure have been proposed (for example, refer to Patent Document 6). In recent years, liquid crystal display devices have been widely used in large-screen liquid crystal televisions and high-definition mobile applications (displays for digital cameras or mobile phones), and the size of substrates used previously and the unevenness of substrate steps have been expanded. In this case, from the viewpoint of the characteristics, it is required to uniformly coat the liquid crystal alignment film with respect to the large substrate and the step. In the process of producing a liquid crystal alignment film, when a solution of a polyamic acid solution or a solvent-soluble polyimine is applied to a substrate, flexographic printing or the like is generally performed industrially. The solvent of the coating liquid to be added is used to improve the uniformity of the coating film when N-methyl-2-pyrrolidone or r-butyrolactone of a solvent having excellent solubility in a resin (hereinafter also referred to as a good solvent) is used. A butyl cellosolve or the like in which a solvent having a low solubility in a resin (hereinafter also referred to as a weak solvent) is mixed. However, the ability of the weak solvent to dissolve the polyamic acid and the polyimine is inferior, so a large amount of mixing is required, and as a result, precipitation occurs (for example, refer to Patent Document 7). This problem is more pronounced especially in solutions of solvent soluble polyimine. Further, the use of the polyimine obtained by the above-described branched diamine tends to lower the uniformity of coating of the solution, so that it is necessary to increase the mixing amount of the weak solvent, so that the mixing tolerance of the solvent also becomes a polyfluorene. An important property of imines. In addition, in order to improve the performance and size of the liquid crystal display device, and to save power in the -6 - 201240981 display device, the characteristics required to promote the liquid crystal alignment film are more severe in various environments. In particular, when the liquid crystal alignment agent is applied to the substrate, the contact time is elongated. Therefore, there is a problem that printing failure occurs due to precipitation or separation, and baking is caused by accumulation of electric charge (RDC). However, it is difficult to solve both of them at the same time in the prior art. In order to improve the desired properties, such a polyimide-based liquid crystal alignment film has been attempted to use various diamine components as a partial raw material, but the desired diamine component cannot be used freely in connection with other characteristics. In addition, because of its high mechanical strength, heat resistance, and solvent resistance, polyimine is widely used in protective materials and insulating materials in the field of electric electronics, in addition to liquid crystal alignment films, and when such materials are used. In the same manner, the diamine component for the raw material of the polyimine is modified, but the desired diamine component cannot be used freely. Therefore, in order to improve the desired properties of the above, the liquid crystal alignment film of the above polyamidiamine type is not limited, and a polymer film formed by coating a solution of another polymer or the like on a substrate is also known. CITATION LIST PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT Patent Document 5: International Publication No. 2004/52962, Patent Document 6: JP-A-2004-67589, No. JP-A No. Hei. In order to solve the problems of the prior art described above, an object of the present invention is to provide a coating liquid for forming a functional polymer film capable of providing a functional polymer film capable of improving various characteristics, and to use the same. A method of forming a functional polymer film. Solution to Problem The coating liquid for forming a polyimide film of the present invention which solves the above-described problems is characterized in that the characteristic system includes at least one Meldronic acid structure having a functional structural portion having a functional property. At least one compound for modification selected from the group represented by the following formulas [A] to [D], and a polymer to be modified or a monomer for synthesizing the polymer for modification. [Chemical 1]

(In the formula, Wi is an organic group having a h-valent value at a functional structural site of the function. Vi is -H, -OH, -OR, -SR or -NHR, and R may contain a benzene ring or a ring in any place. Alkane ring, heterocyclic ring, fluorine, ether bond, ester bond '醯-8- 201240981 The carbon atom of the amine bond is 1 to 35 one-valent organic group. 1^ is an integer of 1 to 8). [Chemical 2]

(In the formula, W2 is an organic group having a k2 valence of a functional structural site of a functionality. V2 is -H, -OH, -SR, -OR or -NHR, and R may contain a benzene ring or a ring in any place. The ring of the courtyard, the heterocyclic ring, the fluorine, the ether bond, the ester bond, and the guanamine bond have a carbon number of 1 to 35, and the k2 is an integer of 1 to 8. [Chemical 3]

(wherein, W3 and W4 are each an organic group in which the h-valent organic structure of the functional structural moiety is imparted to the same or different. W3 and w4 may be the same or different. k3 is an integer of 1 to 8). 201240981 [化4]

(wherein W5 is an organic base of 2 k4 valence imparting functional structural sites. k4 is an integer from 1 to 8). The method for forming a functional polymer film of the present invention is characterized in that the coating liquid for forming the functional polymer film is applied onto a substrate, and after firing, the above-mentioned function is obtained by the Meldronic acid structural portion. The structural site is bonded to the functional polymer film of the modified polymer described above. Advantageous Effects of Invention The present invention can be selected from the group represented by the above formulas [A] to [D] including at least one Meldronic acid structural portion to which the functional structural portion having the functional property is provided. The coating liquid for forming a functional polymer film of at least one of the compounds for modification shown is a functional polymer film which can be freely improved in various properties. Mode for Carrying Out the Invention The present invention will be described in detail below. The coating liquid for forming a functional polymer film of the present invention contains the following formula [A] to [including at least one meldronic acid structural portion to which the functional structural site having the functional property is attached" D] The compound of at least one modification compound selected in -10-201240981 selected from the group. [Chemical 5]

[A] The k of the structural site has a valence of -NMR, and R is an arbitrary field i, an ether bond, an ester bond, or a guanamine. Ki is from 1 to 8 (where Wi is a functional basis for imparting functionality. V! is -H, -OH, -SR, -OR or may contain a benzene ring, a cyclohexane ring, a heterocyclic ring, The number of carbon atoms in the Shou bond is 1 to 35, and the organic number is 3). [Chemical 6]

(wherein W2 is a functional organic group imparting functionality. v2 is -H, -OH, -SR, -OR. The place may contain a benzene ring, a cyclohexyl ring, a heterocyclic ring, and an amine bond having 1 to 35 carbon atoms. One of the organic numbers) The sum of the k2 valence of the structural moiety - NHR, R is any fluorine, ether bond, ester bond, or sulfhydryl group. K2 is from 1 to 8 201240981 [Chem. 7]

(wherein W3 and W4 are each an organic group having a k3 valence of a functional structural moiety imparted to the function, and w3 and W4 may be the same or different. k3 is an integer of 1 to 8). [化8]

(wherein W5 is an organic base of 2 k4 valence imparting functional structural sites. k4 is an integer from 1 to 8). Specific examples of the compound for modification represented by the above formula [A] include a compound for modification represented by the following formula [U to [iii]. In this case, when the compound for modification represented by the above formula [A] is synthesized by using an amine compound having a terminal amine group as a primary or secondary amine or a hydrazine compound as a raw material, the compound for modification represented by the following [i] is synthesized. When a compound of the above formula [A] is synthesized by using a thiol compound or carbon disulfide as a raw material, a compound for modification represented by the following formula [ii] is synthesized, and is derived from an aldehyde, a ketone compound, or a carboxylic acid. When the compound for modification described in the above formula [A] is synthesized as a raw material, a compound for modification represented by the following formula [iii] is synthesized. Further, when the carbodiimide compound is a raw material of -12-201240981, a compound represented by the following formula [i] is synthesized, and at this time, Rj is ～Η 〇 [Chemical 9]

(wherein the terminal amine group used for the raw material of the modifying compound represented by the above formula [Α] is a primary or secondary amine compound, an anthracene compound, or a k quinone imine compound k, a valence organic group , for example, a single bond, or an organic group having a linear or branched carbon atom number of 1 to 6 Å having a hetero atom and a ring structure.]^ and ... and the above formula are 1^ and 乂^ P is the same as when the amine compound or the carbodiimide compound is used as the raw material, and 2 when the ruthenium compound is used as the raw material. Rj is -H represented by Ri to R8, or the benzene ring may be contained in any place. The cyclohexane ring, the heterocyclic ring, the fluorine, the ether bond, the vinegar bond, the guanamine bond have an organic group having 1 to 35 carbon atoms, and the scales 1 to r8 may be the same or different. Further, Rj may be combined with the moiety Y. ! Link to form a ring). [化10]

(wherein Y2 is a thiol compound for use as a raw material of the compound for modification represented by the above formula [A], or an organic group of h-valent of carbon disulfide, and the example & -13-201240981 is a single bond, or may have a hetero A linear or branched carbon atom having an atomic or branched structure having a ki valence of from 1 to 60. The phantom and Vi are the same as Id and V of the above formula [VIII].

(In the formula, Y3 is an aldehyde compound, a ketone compound or a carboxylic acid derivative derived from a raw material of the modifying compound represented by the above formula [A], or k derived from an orthoformate, a valence organic group, for example, a single a bond, or an organic group having a linear or branched carbon atom number of 1 to 60, which may have a hetero atom or a ring structure. 1^ and 乂1 are the same as 1^ and V! of the above formula [8] ). In the compound for modification represented by the above formulas [i] to [iii], when h is 2, specific examples of Υι to Y4 include, for example, a divalent organic group represented by the following formulas (Y-1) to (Y-120). . When the obtained functional polymer film is used as a liquid crystal alignment film, it is preferable to use a diamine compound having a high linearity as a raw material for obtaining a good liquid crystal alignment property, such as Y-(Y- 7), (Y-10), (Υ-11), (Υ-12) ' (Υ-13) ' (Υ-21) ' (Υ-22), (Υ- 23), (Υ-25) , (Υ-26), (Υ-27), (Υ-41), (Υ-42), (γ- 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-79) ' (Υ-80) ' (Υ- -14- 201240981 8 1), (Υ-8 2) Or (Yl 09). Further, when the obtained functional polymer film is used as a liquid crystal alignment film for increasing the pretilt angle of liquid crystal, it is preferred that the branched chain has a long-chain alkyl group (for example, an alkyl group having 10 or more carbon atoms), an aromatic ring, and a fat. a family ring, a nest skeleton, or a structure in which a diamine compound of such a structure is combined as a raw material, such YW, (Y-83), (Y-84), (Y-85), (Y-86), (Y-87), (Y-88), (Y-89), (Y-90), (Y-91), (Y-92), (Y-93), (Υ-94), (Υ -95), (Υ-96), (Υ-97), (Υ-98), (Υ_99), (Υ-100), (Υ-101), (Υ-102), (Υ-103) , (Υ-104), (Υ-105), (Υ-106), (Υ-107), or (Υ·1〇8), etc., but are not limited thereto. Moreover, when it is desired to improve the electrical characteristics of the liquid crystal display element, such as '(γ·31), (Υ-40), (Υ-64), (Υ-65), (Υ-66), (Υ-67), ( Υ-109), (Υ-1 1 〇), etc. Further, when the photoreactivity is to be imparted to the liquid crystal alignment film, such as '(丫-17), (Υ-18), (Υ-111), (Υ-112), (Υ-113), (Υ·114), (Υ-115), (Υ-116)' (Υ-117), (Υ-118), (Υ-119), etc. [化 12]

S -15- 201240981 [Chem. 13] .ch5 .5 (Υ·18) ch2 (Y-19) (Y-20) (Y-21) (Y-22) CH3 (Y-23)

(Y-24) (Y-25) {Y-26) (Y-27) (Y-28) (Y-30) (Y-31) (Y-32) (Y-33) (Y-29) [Chemistry 14]

[化15]

CH3 h2) - HI C—CH 2 \I/ H2)55 (CH(Y-Η I CICH H2- c CH3 —(CH2)n- —(CH2)2-C-(CH2)2- -(CH2)4-C-(CH2)3- n = 2~5 CH3 CH3 (Y-52) (Y-53) (Y-54) ch3 ch3 ch3 ch3 -CH2-C-(CH2)2-C -(CH2)3--(CH2)2-C-(CH2)5--(CH2)4-C-(CH2)5- (Y-56) (Y-57) (Y-58) -16- 20\2409%\[化17] ch3 (一(Y-63)

〇(Υ-66) (V-65) (Υ-64) 々, v::rxx mn*2·4 (Y-68) (Y><7), o(cH2CH2〇L·[化· ( Υ-69) m, ns 2·4 (Υ-70) 9] 令.Na0Hw W0t?" (V-71) (V-72) (V-73) 〆(Y-74)V^a, (Y-77) (Y-75)〉JX (Y-78) (Y-76) n = 2-5 (V-79) -17 5 201240981 [Chem. 20]

η = 0-21 , 0- -(CH2)n-CH3

~ύ~'

,〇~C3""""^*~^~(CH2)n-CH3 (Y-85) s〇—(CH2)n-CH3 (Y-91) n = 0~21 >"~0~0~(CH2)n"CH3 n = 0~21 (Υ·86) Η〇Κ> 〇-(CH2)n-CH3 (Y-88) n = 0-21 0-(3-〇- °-(CH2)n-CH3 (Y-90) n = 0-21

(CH2)n-CH3 n = 0-21 (Y-92) O-(CH2)n-CH3 (Y-93) n = 0-21 "cc °'O-O~O_0'(CH2>n- CH3 (Y-94) n = 0-21 [Chem. 22]

n = 0~21

〇-(CH2)n-CH3 n = 0-21

(Y-96) Π = °~21 b—^〇-(CH2)n~CH3 (Y-98) n = 〇~21 Ί8- 201240981 [Chem. 23]

"CC -Q) (Y-100)

[Chem. 24]

-19- 201240981

H2n+1 [Chemistry 26]

(Y-116)

In the compound for modification represented by the above formula [Π to [iii], k is 1 hour, and specific to Y3 is, for example, a monovalent organic group represented by the following formula, or [Υ-1] to [Υ- 120] The structure in which one of the bonding hands is bonded to a hydrogen atom, but is not limited thereto. -20- 201240981 [Chem. 27] -(CH2)n-CH3 η = 0-21

-©"(CHJn-CHa -〇-(CH2)n-CH3 - CK21 〇-(boots - called η = 0-21

η = 0-21 -(CH2)n-CH3 n = CK21 ^0- η = 0-21 ^o- -(CH2)„-CH3 η = 0-21 P^: —.c -(CH2)n- CH3 η = 0-21 -〇-〇-〇(CH2)nCH3 -〇-〇-〇-(CH2)n-CH3 〖0-21 、HN-^^^^-〇-(CH2)n-CH3 n = 0~21"a ^〇-Q-(ch2)„-ch3 n * 0-21 ~®~^N~〇-(CH2)n-CH3 n = 〇~21 3-Q-〇(CH2)n -CH3 :0 ～21 -〇{CH2)a-〇-^-^-〇(CH2)nCH3 :0~21

(CH^-CHs 0-21 n = 0-21 -〇-(CH2)n-CH3 n*0~21 〇-CCH2)n-CH3 0-21 0-〇-(chz)-ch3 n = o- 2i -(CH2)-CH3 n = 0~21

Further, among the compounds for modification represented by the above formulas [i] to [iii], When it is 3 or more, Y! to Y4 is specifically a trivalent or higher organic group represented by the following formula, or a structure in which [Υ-1] to [Υ-120] is desorbed from a hydrogen atom, etc., but is not limited thereto. . Further, in the present specification, Me is a methyl group. -21 - 201240981 [化 28] Λ众1r浐浐

The method for producing the compound for modification represented by the above formula [A] is not particularly limited. For example, the compound for modification represented by the above formulas [i] and [ii] may be used in trimethyl orthoformate or orthoformate III. In ethyl ester, or an organic solvent for general organic synthesis (e.g., ethyl acetate, hexane, toluene, tetrahydrofuran, acetonitrile, methanol, chloroform, 1,4-dioxane, N,N-dimethylformamide, In the N-methyl-2-pyrrolidone), the trimethyl orthoformate or the triethyl orthoformate 'is simultaneously with the amine compound represented by the following formula [E1] or the thiol compound represented by the following formula [E2] Meldron acid reacted. The reaction temperature and reaction time of the reaction are not particularly limited, and for example, the reaction is carried out at 60 to 12 Torr for 3 0 -22 to 201240981 minutes to 2 hours. [化29]

Yi—^NHRj)^ [El] (wherein Y^Rj and 1^ are the same as YpRj and 1^ of the above formula [i]). Y2~f-SH)ki [E2] (wherein Y2 and k are the same as Υ2 and k of the above formula [ii]). Further, the modifying compound represented by the above formula [iii] may be present in pyridine or other organic alkali compound (for example, triethylamine, tributylamine, diisopropylethylamine), or coexistence. In the organic solvent for general organic synthesis of the organic base compound and the phosphine-based compound such as triphenylphosphine, the aldehyde compound represented by the following formula [E3] is reacted with Meldron acid.

Got it. The reaction temperature and reaction time of the reaction are not particularly limited, and for example, the reaction is carried out at 0 ° C to 100 ° C for 1 to 24 hours. Y3-fCH〇)ki [E3] (wherein, Y3 and 1^ are the same as the above formula [丨(1), 丫3 and k, the same)" The other modification compound represented by the above formula [A] In the production method, the amine compound such as the above [E1], the thiol compound of the above [E2], or the amine group or the thiol group of the aldehyde compound of the above [E3], or the like, is chemically modified by various organic synthesis methods generally known. After the aldehyde group, a compound having an amine group, a thiol group or an aldehyde group is introduced with a distance adjuster, and then a method of reacting with Melduronic acid S. -23-201240981 is used as a raw material. This chemical modification can be carried out multiple times. Specifically, for example, the amine group of the amine compound of the above [E1] can be chemically modified by various organic synthesis methods, and the compound represented by the following formulas [E4] to [E-4] can be obtained by the above formula [i] It is obtained by reacting the same compound as the modification compound represented by [iii] with Meldronic acid. Further, when the compound represented by the following formulas [E4] to [E6] is used as a raw material to react with Meldronic acid, the formula [A] of the following formula [i,] to [iii'] can be synthesized. A compound for modification. [化32] Q^NHRj [E4] ki

Rj ki [E5][E6] (wherein Y!, Rj and k丨 are the same as γ丨, Rj and k丨 of the above formula [i] ° Q! is a single bond ' or may have a hetero atom and a ring structure a linear or branched divalent organic group having 1 to 15 carbon atoms. The core is one of R to 'R' or any place may contain a benzene ring, a cyclohexane ring hetero ring, and an 'acid bond. The ester bond 'amine' bond has a carbon number of 1 to 35. The organic group ' Ri to Rs may be the same or different. Further, 1 may be bonded to the part Qi to form a ring). -24- 201240981 [Chem. 33]

(wherein, Yi, Rj, Ri, Qi, and ki are the same as Yi, Rj, Ri, (^ and k of the above s[E4] to [E_6], and the same '▽1 is the same as Vi of the above formula [VIII]). Specific examples of the compound for modification represented by the above formula [B] are, for example, the compounds for modification represented by the following formulas [iv] and [v].

a ketone, a ketone compound, a halogenated alkyl compound or a compound having an electron-deficient bond of 3 -25 to 201240981 (for example, a compound having a propylene fluorenyl group) may have a k2-valent organic group such as a single bond or may have a hetero A linear or branched organic group having from 1 to 60 hrs of atomic and cyclic structures. "And v2 is the same as k2 and V2 of the above formula [B].) [Chem. 35]

(wherein Y5 is a k2-valent organic group of a carboxylic acid derivative derived from a raw material of the modifying compound represented by the above formula [B], for example, a single bond, or may have a linear structure of a hetero atom and a ring structure or a branched-chain H-valent organic group having 1 to 6 Å, and h and V2 are the same as k2 and V2 of the above formula [B]. Among the compounds for modification represented by the above formulas [iv] and [v], specific examples of γ4 and γ5 are the same as those described above for 丫3 and Υ3. The method for producing the compound for modification represented by the above formula [Β] is not particularly limited. For example, the compound for modification represented by the above formula [iv] can be obtained by using pyridine in the organic solvent for general organic synthesis described above, or Other organic base compounds (such as triethylamine, tributylamine, diisopropylethylamine), or inorganic bases such as potassium carbonate, sodium hydrogencarbonate, and sodium hydroxide, together with aldehydes, ketone compounds, and halogenated alkane The base compound (halogen may be any one of -Cl, -Br, _1) or a compound having an electron-deficient unsaturated bond (for example, a compound having an acrylonitrile group) is obtained by reacting with a Meldronic acid. The reaction temperature and reaction time of the reaction are not particularly limited, and for example, from 〇 ° C to 120 ° C, the reaction time of 201240981 should be 30 minutes to 2 hours. Further, when the aldehyde, the ketone compound, the halogenated alkyl compound or the compound having an electron-deficient unsaturated bond (for example, a compound having a fluorene group) is used as a raw material, the compound for modification represented by the above formula [Β] is synthesized. The compound for modification represented by the above formula [iv] can be synthesized "directly" or via the compound 'reduced carbon-carbon double bond' represented by the above formula [iii]. Further, the compound for modification represented by the above formula [v] can be obtained by using pyridine or other organic base compounds (for example, triethylamine, tributylamine, diiso) in the above organic solvent for general organic synthesis. Propylethylamine), or an inorganic base such as potassium carbonate, sodium hydrogencarbonate or sodium hydroxide, which is obtained by reacting a carboxylic acid derivative such as a carboxylic acid or a carboxylic acid chloride with Meledronic acid. The reaction temperature and reaction time of the reaction are not particularly limited, and for example, from 2 Torr to 1 20 t for 30 minutes to 2 hours. The production method of the compound for modification represented by the above formula [B] is as follows: a method for producing a compound represented by the above formula [A], which chemically modifies an aldehyde, a ketone compound, or a halogenated hospital base by various organic synthesis methods generally known. a compound, a compound having an electron-deficient unsaturated bond, a carboxylic acid, and a carboxylic acid derivative, and having a calibrator having an aldehyde group, a ketone group, a halogenated compound, and a group having an electron-unsaturated bond (for example, an acrylonitrile group) And a compound of a carboxyl group, which is then reacted with Meldronic acid as a raw material, and the chemical modification can be carried out plural times. When such a chemical modification is carried out to produce a compound for modification represented by the above formula [B], for example, between the Y4 and Meldron acid structural sites having the compound for modification represented by the above formula [iv], the insertion is derived from The structure of the chemically modified compound (for example, the formula [B] of a divalent organic group having 1 to 15 carbon atoms which may be formed by a chain or branched structure of a hetero atom and a ring structure -27-201240981) Between the Y5 and a carbonyl group of the compound for modification or the compound for modification represented by the above formula [v], a structure derived from a chemically modified compound (for example, a chain or a branch having a hetero atom and a ring structure) A compound for modification represented by the formula [B] which has a structure in which a divalent organic group having 1 to 15 carbon atoms is formed. Specific examples of the compound for modification represented by the above formula [C] include a compound for modification represented by the following formula [vi]. [化36]

(wherein, each of 丫6 and Y7 is a halogenated alkyl compound derived from a raw material of the modifying compound represented by the above formula [C], or an k3 valent organic group of the alcohol derivative, for example, a single bond, or may have a hetero A linear or branched organic group having a k3 valence of 1 to 60 carbon atoms in the atomic and ring structure. Y6 and Y7 may be the same or different. k3 is the same as k3 of the above formula [C]). Among the compounds for modification represented by the above formula [vi], specific examples of γ6 and Y7 are the same as those of the above Yi to Υ3. The method for producing the compound for modification represented by the above formula [C] is not particularly limited. For example, the compound for modification represented by the above formula [vi] can be used in the above organic solvent for general organic synthesis while simultaneously making pyridine' or · Other organic base compounds (such as triethylamine, tributylamine, diisopropylethyl-28-201240981 amine), or inorganic bases such as potassium carbonate, sodium hydrogencarbonate, and sodium hydroxide, and the above formula [ Iv] The compound for modification and the halogenated alkyl compound or the palladium catalyst coexisting with the compound having a terminal hydroxyl group. Or may be due to the above organic solvent for general organic synthesis, simultaneously with pyridine, or other organic base compounds (such as triethylamine, tributylamine, diisopropylethylamine), or potassium carbonate, hydrogencarbonate An inorganic base such as sodium or sodium hydroxide is obtained by reacting a halogenated alkyl compound with a palladium catalyst coexisting with a compound having a hydroxyl group at the terminal. In this case, Y6 and Y7 may be the same or different, and when γ6 and Υ7 are different, in the above production method, two or more kinds of halogenated alkyl compounds and a compound having a hydroxyl group at the terminal may be present or added in stages to obtain a reaction of the reaction. The temperature and the reaction time are not particularly limited, and for example, the reaction is carried out at 60 to 12 ° C for 30 minutes to 2 hours. The production method of the compound for modification represented by the above formula [C] is as follows. For the production method of the compound represented by the above formula [A], the halogenated alkyl compound or the alcohol derivative is chemically modified by various organic synthesis methods generally known. Thereafter, a compound having a halogenated alkyl group, an alkoxy group, and a hydroxyl group is interposed with a distance adjuster, and then a method of reacting with Meldronic acid as a raw material is used. This chemical modification can be carried out plural times. When such a chemical modification is carried out to produce a compound for modification represented by the above formula [C], for example, a γ6 having a modification compound represented by the above formula [vi] and a structural site of Meldron acid or Y7 are obtained. Between the structural site of Meldronic acid, a structure derived from a chemically modified compound (for example, a divalent organic group having 1 to 15 carbon atoms formed by a chain or branched structure which may have a hetero atom and a ring structure) a compound for modification represented by the formula [C]. -29 - 201240981 The specific compound of the modification represented by the above formula [D] is, for example, a compound for modification represented by the following formula [νΠ]. [化37]

(wherein Y8 is a cyclic ketone compound, a cyclic alkoxyimine compound, or a cyclic carbodiimide compound having a carbon number of 1 derived from a raw material of the modifying compound represented by the above formula [D]; To the organic group of 2 k4, h is the same as k4 of the above formula [D]. In the compound for modification represented by the above formula [vii], specific examples of Y8 are, for example, derived from a cyclopentane ring, a cyclohexane ring or a ring. The ring structure of the octane ring or the cyclic ketone like r-pyrone. The method for producing the compound for modification represented by the above formula [D] is not particularly limited, and for example, the modification represented by the above formula [Vi i] The compound can be obtained by using pyridine or other organic base compounds (for example, triethylamine, tributylamine, diisopropylethylamine), or potassium carbonate or carbonic acid in the above organic solvent for general organic synthesis. Sodium hydride as an inorganic base like sodium oxyhydroxide, together with cyclic ketone compounds (such as cyclohexanone derivatives, T · pyrone derivatives), cyclic alkoxyimine compounds (such as 6-position alkoxy groups) Substituted tetrahydropyridine), or a quinoid carbodiimide compound (eg 3-diazepine-ls2 - The reaction temperature and reaction time of the reaction are not particularly limited, and for example, the reaction is carried out at 60 to 120 ° C for 30 minutes to 2 small -30 to 201240981. The compound for modification represented by [A] to [D] may be used alone or in combination of two or more. The coating liquid for forming a functional polymer film of the present invention contains a polymer to be modified or synthesized. The monomer for the polymer to be modified. The polymer to be modified may be one having a Meldronic acid structure and a reaction site, and for example, at least one selected from the group consisting of tetracarboxylic acid and a derivative thereof After the carboxylic acid component and the diamine component are polymerized to obtain a polyimide precursor, the polyimine imine of the polyimine precursor is imidized, the acryl-based polymer, the methacrylic polymer, and the propylene. Guanidine polymer, methacrylamide polymer, polystyrene, polyvinyl ester, polyoxyalkylene, polyamine, polyester, polyurethane, polycarbonate, polyurea, polyphenol ( Novolak resin), maleic imine polymer, or imported with three a polymer of a compound of an isocyanate skeleton and a triterpene skeleton. Further, the form of the polymer may be, for example, a branched polymer such as a resinous polymer, a highly branched polymer or a star polymer, or polyhydroxyl, a form of a non-co-bonding polymer such as a polycyclonic ring, and a monomer for synthesizing the polymer for modification, for example, when the polymer to be modified is a polyimide precursor and a polyimine At least one of a tetracarboxylic acid component and a diamine component selected from the group consisting of a tetracarboxylic acid and a derivative thereof, and an acrylic acid-based polymer, a derivative thereof, an acrylate, and a derivative thereof, are modified When the polymer is a methacrylic polymer, it is methacrylic acid and its derivatives, methacrylate and its derivatives, and when the modified polymer is a acrylamide polymer, it is acrylamide and its derivatives. When the modifying polymer is a methacrylamide polymer, it is a methacryl-31 - 201240981 decylamine and a derivative thereof, and when the modified polymer is a polystyrene, it is a styrene and a derivative thereof. When the product is a polyvinyl ester a derivative of a vinyl group, a decane compound having a methoxy group or an ethoxy group when the polymer for modification is a polyoxyalkylene oxide, and a dicarboxylic acid and a derivative thereof when the polymer for modification is a polydecylamine At least one dicarboxylic acid component and a diamine component are selected, and when the modified polymer is a polyester, at least one dicarboxylic acid component and a diol component selected from the dicarboxylic acid and a derivative thereof, the modified polymer When it is a polyurethane, it is an isocyanate compound and a compound having a hydroxyl group, and when the polymer to be modified is a polycarbonate, it is a bisphenol derivative and phosgene, or a phosgene equivalent (for example, trichlorophosgene). Or diphenyl carbonate, when the modified polymer is a polyurea, it is a diisocyanate derivative and a diamine component, and when the modified polymer is a maleic imine polymer, it is a maleimide derivative alone. Or a copolymer with styrene The polymer to be modified is a compound having a trimeric isocyanic acid skeleton or a triterpene skeleton when a polymer having a compound having a trimeric isocyanate skeleton or a tri-nral skeleton is introduced. The polymer to be modified or the monomer for synthesizing the polymer for the modification may be used alone or in combination of two or more. Further, the polyimine precursor refers to polyamic acid and polyamidomate. The polymer to be modified contained in the coating liquid for forming a functional polymer film of the present invention can be produced by a generally used method. For example, the polyimine precursor and the polyimine may be obtained by polymerizing at least one of the tetracarboxylic acid component selected from the above tetracarboxylic acid and a derivative thereof and the diamine component to obtain a β-diamine component, for example, h is 2 is a diamine compound represented by the above formula [El]. Further, a diamine component used in the production of a polyimide precursor can be used by reacting a previously diamine component with a tetracarboxylic acid component. The diamine component of the poly-imine precursor precursor-32-201240981 may be a compound partially or entirely the same as the raw material of the modifying compound represented by the above formula [A], and the diamine component may be used. It is a compound different from the raw material of the compound for modification represented by the above formula [A]. Further, at least one tetracarboxylic acid component selected from the group consisting of a tetracarboxylic acid and a derivative thereof can be used, and a tetracarboxylic acid component used in the production of a polyimide precursor is produced by reacting a previously diamine component with a tetracarboxylic acid component. The tetracarboxylic acid derivative is, for example, a tetracarboxylic acid dihalide, a tetracarboxylic dianhydride represented by the following formula [F], a tetracarboxylic acid diester dichloride, a tetracarboxylic acid diester or the like. For example, a tetracarboxylic acid such as a tetracarboxylic acid dihalide or a tetracarboxylic acid dianhydride or a derivative thereof can be reacted with a diamine component to obtain a polyamic acid. Further, the polycarboxylic acid ester can be obtained by reacting a tetracarboxylic acid diester with a diamine component by reacting a tetracarboxylic acid diester dichloride with a diamine component or by a suitable condensing agent and a base. [化38] Ο 〇

Ο 〇 (X is a 4-valent organic group).

S specifically, for example, X of the above formula [F] is a tetravalent organic group represented by the following formulas (X-1) to (X-46). From the viewpoint of the availability of the compound, X is preferably (X-1), (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) , (X-32) and (X-46). In order to enhance the functional polymerization of the polymer-33-201240981, the transparency of the film (polyimine film) is preferably an aliphatic and tetracarboxylic dianhydride having an aliphatic ring structure, and X is more preferably (X- 1), (X-2) and (x.25), and the reactivity with the diamine component is particularly preferably (X-1). [X] 39 (X-i) IH3

H3C CHa (X-2) (X-3) (X-4) (X-5) (X-6) pf-8) (X-9) (X-10) (X-ll) (X-12 ) (X-13) intern CX-14) (X-15) (X-16)

XX. (X-23) (X-24) (X-25) Attack: CCc (X-26) PC-27) =8=知如(X-28) (X-29) (X-30) - 34- 201240981 [化40]

OCC OCC >〇KI (Χ-39). pi-40) PC-41) (X-42) (X-43)

Specific examples of the tetracarboxylic acid diester are, 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 Dialkyl alkanetetracarboxylate, dialkyl 1,2,3,4-cyclopentanetetracarboxylate, dialkyl 2,3,4,5-tetrahydrofurantetracarboxylate, 1,2,4 , 5-cyclohexanetetracarboxylic acid dialkyl ester, 3,4-dicarboxy-1-cyclohexyl succinic acid dialkyl ester, 3,4-dicarboxy-1,2,3,4-tetrahydro- Dialkyl 1-naphthalene succinate, 1.2.3.4-butane tetracarboxylic acid dialkyl ester, diterpene [3,3,0]octane-2,4,6,8-tetracarboxylic acid dialkyl Ester, 3,3',4,4'-dicyclohexyltetracarboxylic acid dialkyl ester, 2,3,5-tricarboxycyclopentyl acetic acid dialkyl ester, cis-3,7-dibutyl Cyclooctane-1,5-diene-1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclo[4.2.1.02'5]indole-3,4,7,8-tetracarboxylic acid-3 , 4: 7,8-dialkyl ester, hexacyclo[6.6.0. 12'7.03'619'14.01()'13]hexadecane-4,5,1 1,12-tetracarboxylic acid-4, 5: 11,12-dialkyl ester, 4-(2,5-dicarbonyltetrahydrofuran-3-yl)-1,2,3,4- An aliphatic tetra-residual acid diacetate such as hydrogen naphthalene-1,2-carbocarbyl ester or tetraphenyl-35-201240981 dialkyl ester, 3,3',4,4'-biphenyl tetra Dialkyl carboxylate, dialkyl 2,2',3,3'-biphenyltetracarboxylate, dialkyl 2,3,3',4-biphenyltetracarboxylate, 3,3' , 4,4'-dibenzophenone tetracarboxylic acid dialkyl ester, 2,3,3',4-benzophenone tetracarboxylic acid dialkyl ester, bis(3,heart dicarboxyphenyl)ether Dialkyl esters 'bis(3,4-dicarboxyphenyl)phosphonium dialkyl ester, dialkyl 1,2,5,6-naphthalenetetracarboxylate, 2,3,6,7-naphthalenetetracarboxylic acid A dialkyl aromatic tetracarboxylic acid such as a dialkyl acid ester. Each of the diamine component and the tetracarboxylic acid component may be used alone or in combination of two or more. The method of synthesizing the tetracarboxylic acid component and the diamine component to synthesize the polyimide precursor is not particularly limited, and a known synthesis method can be used. For example, the reaction of a diamine component with 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 may be any one which is capable of dissolving the produced polyimide precursor. Specifically, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethyl hydrazine, Tetramethyl urea, pyridine, dimethyl hydrazine, hexamethylarylene, T-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl hydrazine Ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve B Acid ester, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetic 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 B Acid ester monomethyl ether, di-36- 201240981 propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate single Propyl ether, 3-methyl-3-methoxy Butyl acetate 'tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyl Acid ester, butyl ether, diisobutyl ketone, methylcyclohexane, propyl ether, dihexyl ether, dioxane, η-hexane, η-pentane, η-octane, diethyl ether ,cyclohexanone, ethyl acrylate, propyl carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, η-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate , ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxy Propionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diether or 4-hydroxy-4-methyl-2-pentanone, and the like. These may be used alone or in combination. Further, even if it is a solvent which cannot dissolve the polyimide precursor, it can be used by mixing the above solvent within the range of the polyimide precursor which is not precipitated. Further, the water in the organic solvent hinders the polymerization reaction and becomes a cause of hydrolysis of the polyimide precursor. Therefore, it is preferred to use a dehydrated and dried organic solvent. The method for reacting a diamine component with a tetracarboxylic dianhydride in an organic solvent, for example, stirring a solution in which a diamine component is dispersed or dissolved in an organic solvent, and directly or dispersing or dissolving the tetracarboxylic dianhydride in an organic solvent In addition, a method of adding a diamine component to a solution obtained by dispersing or dissolving a dicarboxylic acid dianhydride in an organic solvent, a method of mutually adding a tetracarboxylic dianhydride and a diamine component, and the like may be added, and any of the methods may be used. . Further, when a plurality of diamine components are reacted with a tetracarboxylic dianhydride, the reaction may be carried out by mixing in the state of -37 to 201240981, or separately, or the low molecular weights obtained by the respective reactions may be mixed and formed. polymer. The polymerization temperature at this time may be selected from - 20 ° C to 15 (any temperature in TC, but preferably from -5 ° C to l ° ° C. Further, the reaction may be carried out at any concentration, but when the concentration is too low It is difficult to obtain a polymer having a high molecular weight. When the concentration is too high, the viscosity of the reaction liquid is excessively increased 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 can be carried out at a high concentration. Further, an organic solvent is 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 from 0.8 to 1.2. In the condensation reaction, when the molar ratio is close to 1.0, the molecular weight of the formed polyimide precursor is increased. Further, the polyphthalate can be obtained by the above-mentioned tetracarboxylic acid diester dichloride and diamine components. The reaction may be carried out by reacting a tetracarboxylic acid diester with a diamine component in the presence of a suitable condensing agent or a base. Further, the polyamine may be synthesized by a polymer reaction by synthesizing the polyamic acid in advance as described above. The esterification of the carboxyl group of the acid gives, for example, the presence of a base and an organic solvent to - The tetracarboxylic acid diester dichloride is reacted with the diamine component at 20 ° C to 150 ° C, preferably at 〇 ° C to 50 ° C for 3 minutes to 24 hours, preferably 1 hour to 4 hours, to be synthesized. Polyamide. A base such as pyridine, triethylamine or 4-dimethylaminopyridine can be used, but in order to carry out the reaction, it is preferably pyridine. The amount of the base is easily removed, and it is easy to remove. The viewpoint of obtaining a high molecular weight substance is preferably 2 to 4 times moles relative to the tetracarboxylic acid diester dichloride. -38 - 201240981 Further, when a tetracarboxylic acid diester is condensed with a diamine component in the presence of a condensing agent a base such as triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, N,N,-carbonyldiimidazole, dimethoxy-1,3,5-tri-negylmethylmorpholine gun, 0-(benzotriazol-1-yl)-oxime, oxime, Ν', Ν '-Tetramethylurea gun tetrafluoroborate, 0-(benzotriazole-bu)-Ν, Ν,Ν',Ν'-tetramethylurea gun hexafluorophosphite, (2,3· Diphenyl-2-dihydro-3-benzoxazolyl)phosphonate, 4-(4,6-dimethoxy-1, 3,5-哄-2 -yl)4-methoxymorpholinium chloride η-hydrate, etc. Further, in the method using the above condensing agent, the Lewis acid added with the additive can be efficiently reacted. The Lewis acid is preferably chlorine. Lithium halide such as lithium or lithium bromide. The amount of the Lewis acid added is preferably 0.1 to 1.0 times the molar amount of the diamine or the tetracarboxylic acid diester for the reaction. The solvent for the above reaction may be the above-mentioned synthetic polyfluorene. The solvent used in the case of the amine acid is the same solvent, but the solubility of the monomer and the polymer is preferably Ν-methyl-2-pyrrolidone or r-butyrolactone, and one type or two or more types may be used in combination. The reaction solution in which the concentration at the time of synthesis is less likely to cause precipitation of a polymer, and a high molecular weight substance is easily obtained, and a reaction solution of a tetracarboxylic acid derivative such as a tetracarboxylic acid diester dichloride or a tetracarboxylic acid diester and a diamine component The total concentration in the mixture is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass. Further, in order to prevent hydrolysis of the tetracarboxylic acid diester dichloride, it is preferred that the solvent for the synthesis of the polyphthalate is desicient as much as possible, and it is preferable to prevent the incorporation of outside air in a nitrogen atmosphere. The polyimine contained in the coating liquid for forming the functional polymer film of the present invention is obtained by dehydrating and ring-closing the above-mentioned polyimine precursor. In the imine-39 - 201240981 imine, the dehydration ring closure ratio of the proline group (the imidization ratio) is not necessarily 100%, and can be arbitrarily adjusted depending on the purpose and purpose. The method for imidating the polyimine precursor ruthenium, for example, directly heating the solution of the polyimide precursor to the imidization, or adding the catalyst to the solution of the polyimide precursor to carry out the catalyst Amination. The temperature at which the polyamidene precursor is thermally imidized in the solution is from 100 to 400 ° C. Preferably, it is from 120 to 250 ° C. The less yttrium imidization reaction is preferably excluded from the system. . The ruthenium imidization of the polyimide precursor can be carried out by adding a basic catalyst and an acid anhydride to a solution of the polyimide precursor at -20 to 250 ° C, preferably 〇 to 180 °. Stirring is carried out under C. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, and the amount of the acid anhydride is 1 to 50 moles, preferably 3, of the amidate group. Up to 30 moles, the basic catalyst may be pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine, etc., wherein the pyridine can hold moderate alkalinity during the reaction. good. The acid anhydride may be acetic anhydride, trimellitic anhydride or pyromellitic anhydride. Among them, acetic anhydride is preferably used after the completion of the reaction. The imidization ratio of the imidization by the catalyst can be controlled by adjusting the amount of the catalyst, the reaction temperature and the reaction time. When recovering the produced polyimide precursor or polyimine from the reaction solution of the polyimine precursor or the polyimine, the reaction solution may be put into a solvent to precipitate a solvent for β precipitation, for example, Methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone 'methyl isobutyl ketone, ethanol, toluene' benzene, water, and the like. After filtering and recovering the polymer precipitated after the solvent is introduced, -40-201240981 can be dried at normal temperature or under heat at normal pressure or reduced pressure. Further, by repeating the steps of re-dissolving the precipitate-recovered polymer in an organic solvent for 2 to 10 times, and then recovering and recovering, the impurities in the polymer can be reduced. The solvent at this time is, for example, an alcohol, a ketone or a hydrocarbon, and it is preferable to use three or more solvents selected from the above to be more efficiently purified. Further, it can be used as a polyimide precursor for a polymer to be modified, and a polymer other than polyimine, such as an acrylic polymer, a methacrylic polymer, an acrylamide polymer, or a methacryl. Indoleamine polymer, polystyrene, polyvinyl ester 'polyoxane, polyamide, polyester, polyurethane, polycarbonate 'polyurea, polyphenol (novolac resin), mala Imine polymer' or a branched polymer of a polymer of a polyisocyanate skeleton and a three-till backbone, a dendrimer, a hyperbranched polymer, a star polymer, a polyether or a polycyclone a non-co-bonding polymer or the like of a ring or the like, and further having a functional group (for example, a carboxyl group, a hydroxyl group, a thiol group) capable of reacting with an enone intermediate formed by thermal decomposition of a Meldronic acid compound. When an amine group, an imine group, a carbon-carbon double bond (alkenyl group), an unsaturated bond such as a carbon-carbon triple bond (alkyne), a nitrile, a ketone 'aldehyde, an ester, a guanamine, a quinone imine, etc. These polymers are suitable for use in commercially available products and known materials. The polymer to be modified contained in the coating liquid for forming a functional polymer film of the present invention takes into consideration the strength of the obtained functional polymer film, workability in forming a functional polymer film, and functional polymer. When the film is uniform, the weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method is preferably 5,000 to 1,000,000, more preferably 1 〇, 〇〇〇 to 1 50,000 〇-41 - 201240981 as described above, A functional structural part that gives functionality! And at least one modifying compound selected from the group represented by the above formulas [A] to [D] of at least one Meldron acid structural moiety to which W5 is linked, and the polymer to be modified or synthesized The monomer for a polymer to be modified, that is, the coating liquid for forming a polymer film used for forming a polymer film or the like, for example, further comprising the group represented by the above formulas [A] to [D] The at least one compound for modification selected in the present invention can provide a coating liquid for forming a functional polymer film which can form a functional polymer film which is free from various characteristics. In detail, the compound for modification represented by the above formulas [A] to [D] has a structure of at least one Meldron acid at the end, that is, a structure derived from .meldonic acid. The bismuth acid structure is heated (for example, above 180 to 250 ° C), and can be accompanied by the detachment of carbon dioxide from acetone to form an ketene (ie, a carbonyl compound in which a divalent group is held > C = C = 0). , for example, may be present in polyimine precursors, polyimine, acrylic based polymers, methacrylic based polymers, acrylamide polymers, methacrylamide polymers, polystyrene, polyethylene Ester, polyoxyalkylene, polyamine, polyester, polyurethane, polycarbonate, polyurea, polyphenol (novolac resin), maleimide polymer' or introduction of trimeric isocyanide a non-co-bonding polymer such as a polymer of a acid skeleton and a triterpene skeleton, a dendrimer, a highly branched polymer, a branched polymer such as a star polymer, a polyether hydroxyl group, and a polycyclonic ring. Functional group that can be modified (eg, carboxyl 'hydroxyl, thiol, amine' imine, carbon-carbon double bond (chain And an unsaturated bond such as a carbon-carbon triple bond (alkyne), a nitrile group, a ketone group, an aldehyde group, an ester group, a 'mercaptoamine group, an oxime imine group, or -42-201240981, which utilizes the ketene itself. A substance that reacts by polymerization or the like. Therefore, the compound for modification represented by the above formulas [A] to [D] is not coated with a coating liquid for forming a functional polymer film which is not heated to a high temperature (for example, 1 Å or less). The modification polymer or the monomer for synthesizing the polymer for modification is reacted, but it can be introduced into the polymer for modification via heating by Mellonic acid structure. In addition, since the compound for modification represented by the above formulas [A] to [D] having k: to ku of 2 or more has two or more Meldron acid structures, it is presumed that it can be formed after heating, and the polymer to be modified is formed. The structure obtained by crosslinking the compound for modification represented by the above formulas [A] to [D]. Therefore, the functional polymer film obtained by applying the coating liquid for forming a functional polymer film of the present invention to a substrate and calcining it is a Wi to the compound for modification represented by the above formulas [A] to [D]. The structure of W5 is introduced into the polymer to be modified. Polyimine film, which is a kind of functional polymer film, has high mechanical strength, heat resistance and solvent resistance, so it is widely used as a liquid crystal alignment film and a protective material and insulating material in the field of electric electronics. In order to improve the use of various diamine components as a part of raw materials, 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 liquid crystal alignment and pretilt angle, various diamine components have been used as a part of raw materials, but the types, combinations, and amounts of diamine components used to obtain desired characteristics have been obtained. 'The polymerization reactivity of the diamine component and the tetracarboxylic acid component is deteriorated', and thus the type, combination and amount of the diamine component used to obtain the desired properties are limited. Further, regarding the types and combinations of diamine components for obtaining desired characteristics, it is necessary to review the polymerization conditions of the diamine component and the tetracarboxylic acid component -43-201240981. In addition, in order to obtain a coating liquid for forming a polyimide film (a coating liquid for forming a functional polymer film) which can form a uniform polyimide film, it is necessary to dissolve the solvent in a solvent, but The solubility, the amount and combination of the diamine component used for obtaining the desired properties, and the solubility of the polyimine precursor or polyimine contained in the coating liquid for forming the polyimide film. The problem of deterioration. Therefore, it is not limited to the polyimide film, and when the desired properties are improved in various polymer films, when various monomers are used as a part of the raw materials, there is also a problem that the polymerization reactivity is deteriorated, and it is necessary to review the desired properties. The problem of the polymerization conditions of the monomer type and the combination used, and the problem that the solubility of the polymer contained in the coating liquid for forming the functional polymer film is deteriorated. In the present invention, in the stage of forming the coating liquid for the functional polymer film, the monomer for the modified polymer or the synthetic polymer for modification is contained in the form of each compound, and the desired one is obtained. The compound for modification represented by the above formulas [A] to [D] is used in the step of heating (baking) a coating liquid for forming a functional polymer film to obtain a compound having a desired property. The compound for modification represented by the above formulas [A] to [D] is introduced into the polymer for modification. Therefore, it is not necessary to obtain a polymer for modification contained in the coating liquid for forming a functional polymer film. It is desirable that the monomer used as the raw material is used as a raw material. Therefore, there is no problem that the polymerization reactivity of the monomer is deteriorated, and it is necessary to review the problem of the polymerization reaction conditions for obtaining the monomer type and combination of the desired characteristics. The solubility of the polymer contained in the coating liquid for a functional polymer film is deteriorated. Therefore, the coating liquid for forming a functional polymer film of the present invention can be used without considering the polymerization reaction of the monomer, the necessity of reviewing the polymerization conditions, and the solubility of the polymer. Since the desired compound (functional) is modified, the various properties of the resulting functional polymer film can be relatively easily improved by comparing the coating liquid for forming a polymer film. Further, when the coating liquid for forming a functional polymer film of the present invention contains a compound for modification represented by the above formulas [A] to [D] having two or more meldene acid structures, it is modified. The polymer can be crosslinked by heating the compound for modification represented by the above formulas [A] to [D], so that the resulting functional polymer film is resistant to an organic solvent and is a hard film. Further, a polyfluorene imine 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 a polyfluorene precursor precursor are used. At least one polymer selected from the polyimide obtained by imidization is coated with a functional polymer film having a modification compound having two Meldron acid structures represented by the above formula [i] In the case of the cloth liquid, the compound for modification represented by the above formula [i] is obtained by introducing the two amine groups of the diamine compound into the structure of the Meldronic acid, and the diamine compound can be obtained by the prior review. The diamine component of the characteristic, that is, a diamine component which can be obtained by a polymerization reaction with a tetracarboxylic acid component to produce a polyimine precursor or a diamine component for polyimine. Therefore, it is easy to improve various properties of the obtained polyimide film. When it is a coating liquid for forming a functional polymer film containing a polymer for modification, the compound for modification represented by the above formulas [A] to [D] can be introduced into the modified polymerization by heating in a branched form. The compound for modification, particularly the compound represented by the above formulas [A] to [D], has two or more meldene acids.

S-45-201240981 A structure in which a polymer to be modified is crosslinked by a modifying compound represented by the above formulas [A] to [D]. Further, when it is a coating liquid for forming a functional polymer film containing a monomer for synthesizing a polymer for modification, Melalonic acid of the modifying compound represented by the above formulas [A] to [D] The structure does not react at substantially the temperature at which the polymerization of the monomer occurs. Therefore, the polymer for modification is synthesized by synthesizing the monomer for the polymer for modification at a low temperature, and then the polymer can be modified by heating. When the compound for modification represented by the above formulas [A] to [D] is introduced into the branched form, in particular, when the compound for modification represented by the above formulas [A] to [D] has two or more Meldron structures, The structure in which the polymer for modification is crosslinked by the compound for modification represented by the above formulas [A] to [D] is formed. Further, it is used for forming a functional polymer film containing a monomer for synthesizing a modified polymer and a compound for modification represented by the above formulas [A] to [D] having two or more Meldron structures. In the case of coating a liquid, the above formula [A] can also be carried out by simultaneously reacting a polymerization reaction of a monomer and a reaction of a Meldronic acid structure with a monomer polymerization and a Meldronic acid structural reaction. The modification compound represented by [D] is introduced into the main chain of the polymer for modification. The method for producing the coating liquid for forming a functional polymer film of the present invention is not particularly limited, and may be any of the above-described Meldenic Acid structural sites to which functional functional sites having functional properties are provided. At least one of the compounds for modification selected from the group represented by the formulae [A] to [D], and the monomer for modification or the monomer for synthesizing the polymer for modification are dissolved in a solvent. The solvent for forming a coating liquid for a functional polymer film of the present invention can be -46-201240981, which is a monomer capable of dissolving the above-mentioned modified polymer or synthetic modified polymer, and has a function of imparting functional properties. The compound for modification represented by the above formulas [A] to [D] of at least one Meldronic acid structural site to which the structural moiety is attached, for example, N,N-dimethylformamide, N , N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methyl caprolactam, 2-pyrrolidone 'N-ethyl-2-pyrrolidone' N-vinylpyrrolidone, dimethyl Alkali 'tetramethyl urea, pyridine, dimethyl selenium, hexamethylarylene, 7-butyrolactone, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl decyl ketone , methyl ethyl hydrazine, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethyl acrylate propyl propyl carbonate, di polyether and 4-hydroxy-4-methyl-2 - an organic solvent of pentanone. These may be used singly or in combination. - The coating liquid for forming a functional polymer film of the present invention has a content of an organic solvent of from 7 Å to 97% by mass from the viewpoint of coating a uniform functional polymer film. This content can be appropriately changed depending on the film thickness of the functional polymer film. Further, in the coating liquid for forming a functional polymer film of the present invention, the content of the monomer for the polymer to be modified or the polymer for the synthesis of the modified polymer is preferably from 3 to 30% by mass. The content may be appropriately changed depending on the film thickness of the functional polymer film. In the coating liquid for forming a functional polymer film of the present invention, the content of the modifying compound represented by the above formulas [A] to [D] may be, and the content of the compound to be dissolved is not particularly limited, but is modified relative to The total amount of the monomer used for the polymer or the polymer for modification is 1 part by mass, preferably 1 to 200 parts by mass, more preferably 1 to 1 〇〇 in order not to lower the alignment of the liquid crystal. -47- 201240981 parts, especially preferably 1 to 50 parts by mass. The coating liquid for forming a functional polymer film of the present invention can improve the functional polymer film when the coating liquid for forming the functional polymer film of the present invention can be used without impairing the effects of the present invention. An organic solvent (which may be referred to as a weak solvent) or a compound having uniform film thickness and surface smoothness. Further, a compound which enhances the adhesion between the functional polymer film and the substrate can be used. Specific examples of weak solvents which increase the uniformity of film thickness and surface smoothness, such as 'isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve Acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol Monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethyl Glycol monoacetate, diethylene glycol dimethyl ether 'dipropylene glycol monoacetate 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 acetate, tripropylene glycol methyl ether, 3-methyl-3-methyl Oxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, C base , dihexyl ether, n-hexane, η-pentane, η-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, η-butyl acetate, propylene glycol Ethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy Propionate, 3-methoxy-48- 201240981 propyl propionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-B Oxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-.1-monomethyl Ethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate An organic solvent having a low surface tension, such as an ester, η-propyl lactate, η-butyl lactate or isoamyl lactate. These weak solvents may be used singly or in combination of plural kinds. When the above-mentioned weak solvent is used, the content thereof is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass based on the total of the organic solvent contained in the coating liquid for forming the functional polymer film. A compound which enhances uniformity of film thickness and surface smoothness, for example, a fluorine-based surface active agent, a polyoxynoxy surfactant, a nonionic surfactant, etc., specifically, for example, Yvette EF301, EF303, EF352 ( Tecomm system), US card F171' F173, R-30 (Daily Ink system), Flora FC430, FC431 (Sumitomo 3M system), Isaac AG710, Saffron S-382, SC101, SC102 , SC103, SC104, SC105, SC106 (Asahi Glass System), etc. The ratio of use of the surfactants is 100 parts by mass based on the total amount of the monomers to be modified or the monomers for synthesizing the polymer to be modified contained in the coating liquid for forming the functional polymer film. It is preferably from 0.01 to 2 parts by mass, more preferably from 1 to 1 part by mass. Specific examples of the compound which enhances the adhesion of the functional polymer film to the substrate are, for example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxy Decane, 2-aminopropyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-amine-49- 201240981 ethyl) 3-aminopropylmethyldimethoxydecane, 3-aminopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyl Trimethoxy decane, N-ethoxycarbonyl-3-aminopropyltriethoxy decane, N-triethoxydecylpropyltriethylamine, N-trimethoxydecylpropyl Base triethylamine, 10-trimethoxydecyl-1,4,7-triazadecane, 10-triethoxydecyl-1,4,7-triazadecane, 9 -trimethoxydecyl-3,6-diazaindolyl acetate, 9-triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl-3-amine Propyltrimethoxydecane, N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-amine Triethoxy decane, N-bis(oxyethyl)-3,aminopropyltrimethoxydecane, N-bis(oxyethyl)-3-aminopropyltriethoxydecane, Ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6- Hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6·tetraglycidyl-2,4-hexanediol, ^>1',>^'-tetraglycidyl-111-xylenediamine, 1,3-bis(indole, fluorene-diglycidylaminomethyl)cyclohexane or hydrazine, hydrazine, Ν', Ν'-tetraglycidyl-4,4'-diaminodiphenylmethane, etc., a compound containing a functional decane and a compound containing an epoxy group" When using such a compound which is in close contact with a substrate, The total amount of 100 parts by mass of the monomer for modifying the polymer or the monomer for synthesizing the modified polymer contained in the coating liquid for forming the functional polymer film of the present invention is preferably 〇" to 3 0 The amount of parts, more preferably 1 to 20 parts by mass. When the amount is less than 1 part by mass -50-201240981 The effect of improving the adhesion is not obtained. When the functional polymer film is used as the liquid crystal alignment film, the alignment property of the liquid crystal is deteriorated when it is more than 30 parts by mass. Further, in the coating liquid for forming a functional polymer film of the present invention, a dielectric body and a conductive material for changing electrical characteristics such as permittivity and conductivity of the functional polymer film can be added without impairing the effects of the present invention. And a coating liquid for forming a functional polymer film of the present invention, which can be mixed with an epoxy group, an isocyanate group or an oxetanyl group as a cross-linking compound A crosslinkable compound having at least one substituent selected from a group consisting of a hydroxyl group or an alkoxy group, and a crosslinkable compound having a polymerizable unsaturated bond. The coating liquid for forming a functional polymer 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 refers to a film in which liquid crystals are aligned in a certain direction. By coating the coating liquid for forming a functional polymer film of the present invention on a substrate and then baking it, the functional properties of the functional structural sites having the compounds represented by the above formulas [Α] to [D] can be formed. Polymer film. In addition, when the coating liquid for forming a functional polymer film of the present invention is used as a liquid crystal alignment agent, it is applied to a substrate and then fired, and then subjected to alignment treatment such as brushing treatment or light irradiation, or vertical alignment use. The liquid crystal alignment film can be formed without the need of alignment treatment. The substrate may be any one which can be applied to form a coating liquid for forming a functional polymer film. However, it is preferable to form a liquid crystal alignment film with a high transparency. Specifically, for example, a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like. Further, in view of simplification of the steps, it is preferable to use a substrate of an ITO electrode for liquid crystal driving using the shape -51 - 201240981. In addition, when a single-sided substrate is used as a reflective liquid crystal display element, a ruthenium board can be used as an opaque material, and the electrode can be made of a material such as aluminum. Further, in a high-performance element such as a TFT-type element, a device having a transistor-like element is formed between an electrode for driving a liquid crystal and a substrate. The method of applying the coating liquid for forming the functional polymer film to the substrate is not particularly limited, and generally, screen printing, lithography, flexographic printing, inkjet, or the like is used industrially. Other coating methods such as dipping, roll coating, slit coating, spin coating, etc. may be used depending on the purpose. After the coating liquid for forming the functional polymer film is applied onto the substrate, some or all of the solvent may be dried as necessary. When the coating liquid for forming the functional polymer film contains a monomer for synthesizing the polymer for modification, it is preferred to apply the coating liquid for forming the functional polymer film on the substrate, or to dry it. At the time, the monomer is polymerized. Further, a coating liquid for forming a functional polymer film is applied onto a substrate, and if necessary, some or all of the solvent is dried and then fired. The calcination may be carried out by heating the Meldronic acid structure of the modifying compound represented by the above formulas [A] to [D] to form an ketene or the like, a carboxyl group having a modified polymer or the like, and a hydroxy group. An unsaturated bond such as an alcohol group, an amine group, an imine, a carbon-carbon double bond (alkenyl) or a carbon-carbon triple bond (alkyne), a nitrile group, a ketone group, an aldehyde group, an ester bond, a guanamine bond, The temperature at which the reactive site of the quinone bond or the like reacts. For example, it can be carried out by a heating method of a hot plate, a hot air circulating furnace, an infrared furnace or the like at 18 Torr to 250 ° C while evaporating the solvent and reacting the Meldronic acid structure with the polymer for modification, and the above formula The modified polymer represented by [A] to [D] is used to form the functional polymer film of the present invention. The thickness of the functional polymer film formed after calcination is too thick to be detrimental to the electronic consumption of the liquid crystal display element when used as a liquid crystal alignment film, and too thin will reduce the reliability of the liquid crystal display element, so it is preferable. It is 5 to 300 nm, more preferably 1 to 200 nm. When the liquid crystal is aligned horizontally or obliquely, the baked film is treated by brushing or irradiating polarized ultraviolet rays or the like. The liquid crystal display device of the present invention is a liquid crystal display device obtained by producing a liquid crystal cell by a known method by fabricating a substrate with a liquid crystal alignment film by the above method. For example, a liquid crystal layer having two substrates disposed opposite to each other and disposed between the substrates, and a liquid crystal formed by the coating liquid for forming the functional polymer film of the present invention between the substrate and the liquid crystal layer are provided. A liquid crystal display element of a liquid crystal cell of the above liquid crystal alignment film formed by an alignment agent. The liquid crystal display of the present invention is various such as a twisted nematic (TN: Twisted Nematic) method, a vertical alignment (VA: Vertical Alignment) method, and an IPS (In-Plane Switching) method. The substrate used for the liquid crystal display device of the present invention is not particularly limited as long as it has high transparency, and is generally a substrate on which a transparent electrode for driving a liquid crystal is formed. Specifically, for example, it is the same as the substrate described in the above functional polymer film. Further, the liquid crystal alignment film is obtained by applying a liquid crystal alignment agent formed by the coating liquid for forming a functional polymer film of the present invention to the substrate, followed by firing, and the details are as described above. -53- 201240981 The liquid crystal material constituting the liquid crystal layer of the liquid crystal display of the present invention is not particularly limited, and a conventional liquid crystal material such as MLC-2003 'MLC-6608, MLC-6609, etc. manufactured by Melco Co., Ltd. can be used. In the method of producing a liquid crystal cell, for example, a pair of substrates for forming a liquid crystal alignment film are prepared by dispersing a bead or the like on a liquid crystal alignment film of one substrate, and then bonding the other substrate so that the liquid crystal alignment film is inside. The method of injecting the liquid crystal into the liquid film after the pressure reduction, or the method of re-packaging the substrate after the liquid crystal is dropped on the liquid crystal alignment film surface of the spreader. The thickness of the pitch at this time is preferably from 1 to 30 μm, more preferably from 2 to ΙΟμιη. The liquid crystal display device produced as described above is used, and contains a compound for modification represented by the above formulas [Α] to [D], which can introduce desired properties, and a polymer for modification or a polymer for synthetic modification. The liquid crystal alignment agent is used to improve various properties. [Embodiment] Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the explanation of the present invention is not limited to the examples. [Synthesis of a compound for modification represented by the above formula [Α] to [D]] <Synthesis Example 1 > Compound 5,5'-(1,4-phenylene double represented by the following formula [4] was synthesized. (urea diyl)) bis(methane-1-yl-1-ylidene)bis(2,2-dimethyl-1,3-dioxin-4,6-dione) -54- 201240981 41]

s Meldronic acid [l] (14.7 g, 102 mmol) and trimethyl orthoformate [2] (147 g) were placed in a 300 mL four-necked flask and heated to reflux for 1 hour. Thereafter, p-phenylenediamine [3] (5.0 g, 46 mm 〇l) was added, followed by heating 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, washed with hexane, and then dried to yield compound [4] 15.8 g (yield 82%). 1 H-NMR (400 MHz, DMSO-d6, (5 ppm): 1 1.29 (2H, d) > 8.56 (2H, d), 7.64 (4H, s), 1.68 (12H, s). Synthesis Example 2 > The compound 5,5'-(1,3-phenylenebis(ureidodiyl))bis(methane-1-yl-1-ylidene) double represented by the following formula [6] was synthesized. (2,2-dimethyl-1,3-dioxane-4,6-dione) [化42] j〇i

CH(OMe)3 [2]

J〇i

-55- 201240981 Meldronic acid [1] (14.7 g, 102 mmol) and trimethyl orthoformate [2] (147 g) were placed in a 300 mL four-necked flask and heated to reflux for 1 hour. Thereafter, an inter-phenylenediamine [5] (5-Og, 46 mmol) was added, followed by heating 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, washed with hexane, and then dried to give compound [6] 14· lg (yield: 72%). 1 H-NMR (400 MHz, DMSO-d6, δ ppm): 11.28 (2H, s), 8.74 (2H, s), 7.78 (1H, s), 7.44 (3H, s), 1.68 (12H, s). <Synthesis Example 3 > A compound 5,5'-(pyridine-2,6-diylbis(ureidodiyl))bis(methane-1-yl-buylidene) double represented by the following formula [8] was synthesized. (2,2-dimethyl-1,3-dioxane-4,6-dione) [Chem. 43]

[7] [2] [8] Meldronic acid [l] (16.0 g, lllmmol) and trimethyl orthoformate [2] (160 g) were placed in a 300 mL four-necked flask and heated to reflux for 1 hour. Thereafter, 2,6-diaminopyridine [7] (5.5 g '50 mmol) was added, followed by heating 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, washed with hexane, and then dried to yield a compound [8], 16.7 g (yield: 80%). -56- 201240981 1 H-NMR (400MHz, DMSO-d6, δ ppm) : 11.42 (2H,d), 9_15 (2H,d), 7.96 (lH,t), 7.52 (2H,d), 1.67 (12H , s). <Synthesis Example 4> A compound 5,5',5" (benzene-1,3,5-triyltris(ureido)yl)tri(methane-1-yl-) represented by the following formula [11] was synthesized. 1-ylylene)tris(2,2-dimethyl-1,3-dioxane-4,6-dione) [44] o2n

[9] N〇2

Hz, 5wl%Pd/C 1/4-dioxane [10] NH2 H2N^^NHa

Λ 〇 乂.

[11] A mixture of 3,5-dinitroaniline [9] (32.6 g, 178 mmol), 5% palladium on carbon (3.75 g, 10 wt%) and 1,4-dioxane (37 g) The mixture was placed in a 1 L four-necked flask and stirred at room temperature under a hydrogen atmosphere. After the completion of the reaction, the palladium carbon was filtered off with celite, and the filtrate was concentrated with an evaporator to give compound [1], 21.7 g (yield: 9 9%) 〇1H-NMR (400 MHz, DMSO-d6, δ ppm): 5.1 1 (3H, s) - 4.28 (6H, s) » Add Meldronic acid [1] (83.88, 582111111〇1) and trimethyl orthoformate [2] (660g) to a 1L four-necked flask. The mixture was heated to reflux for 1 hour. Thereafter, the compound [l?] (21.7 g, 176 mmol) 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, and the precipitated solid was filtered, washed with hexane, and then dried to give compound s -57 - 201240981 [1 l] 73.0 g (yield 71%). 1H-NMR (400 MHz, DMSO-d6, <5 ppm): 11.22 (3H, s), 8 - 26 (3H, s), 7.70 (3H, s), 1.65 (18H, s). <Synthesis Example 5 > The compound 5,5'-(4,4'-extended methylbis(4,1-phenylene)bis(ureidodiyl)) double represented by the following formula [13] was synthesized. (methane-1_yl-1_ylylene) bis(2,2-dimethyl-1,3-dioxane-4,6-dione) [45]

Meldronic acid [l] (l4.7g, 102mmol) and trimethyl orthoformate [2] (147g) were added to a 300mL four-necked flask, heated for reflux for 1 hour, and then added 4,4'-two Aminodiphenylmethane [12] (5.0 g, 46 mmol) was further refluxed 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 dried to yield compound [13] 14.1 g (yield: 72%). 1H-NMR (400MHz, DMSO-d6, δ ppm): 11.23(2H,d), 8.54(2H,d), 7.50-7.48(4H,m) , 7.3 1 - 7 · 2 9 (4 H,m) , 3.96 (2H, m), 1.66 (12H, s). <Synthesis Example 6 > -58- 201240981 A compound represented by the following formula [15] 5,5,-(4,4'-oxobis(4,1-phenylene)bis(ureidodiyl) was synthesized. )) bis(methane-1-yl-1-ylidene)bis(2,2-dimethyl-1,3-dioxane-4,6-dione) [Chem. 46]

Meldron _[l] (7.92 g, 54.9 mmol) and trimethyl orthoformate [2] (7 8 g) were placed in a 200 mL four-necked flask, and heated under reflux for 1 hour. Thereafter, 4,4'-diaminodiphenyl ether [14] (5.0 g, 25.0 mmol) was added, followed by heating 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, washed with hexane, and then dried to yield compound </ </ RTI> 1.7 g (yield: 92%). 1 Η - NMR (4 0 0 Μ H z, D Μ S Ο - d 6 , δ ppm) : 11.30(2H,d) ' 8.51(2H,d), 7.62(4H,d),7.08(4H,d ), 1.67 (12H, s). &lt;Synthesis Example 7 &gt; The compound 5,5'-(4,4,-ureidodiylbis(4,1-phenylene)bis(ureidodiyl)) double represented by the following formula [17] was synthesized. (methane-1_yl-1_ylidene)bis(2,2-dimethyl-1,3-dioxane-4,6-dione)

S -59- 201240981 [化 47]

Meldronic acid [l] (7.96 g '55.2 mmol) and toluene formic acid [2] (79 £) were placed in a 20 〇 1 ^ four-necked flask, and heated under reflux for 1 hour. Thereafter, 4,4,-diaminodiphenylamine [16] (5-Og, 25.1 mmol) was added, followed by heating 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, washed with hexane and then dried to give compound [17] 10.1 g (yield: 79%). &lt;1&gt;H-NMR (400 MHz) , DMSO-d6, δ ppm) : 11.29(2H,d), 8.51(2H,d) , 7.62(4H,d) , 7.08(4H,d) ' 4.97(1H,s) ' 1.67(12H,s) ° &lt;Synthesis Example 8 &gt; Compound 5,5'-(4,4'-methylureidodiyl)bis(4,1-phenylene)bis(urea) represented by the following formula [19] was synthesized. Base)) bis(methane-1-yl-1.subunit)bis(2,2-dimethyl-1,3-dioxane-4,6-dione) [48]

-60- 201240981 Meldronic acid [1] (14.98, 103111111〇1) and trimethyl orthoformate [2] (100 g) were placed in a 500 mL four-necked flask and heated to reflux for 1 hour. Thereafter, 4,4'-diaminodiphenylmethylamine [18] (10.0 g, 46.9 mmol) was added, followed by heating 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, washed with hexane, and then dried to give the compound [19] 21.7 g (yield 86%). 1H-NMR (400MHz, DMSO-d6, δ ppm) : 1 1.2 1 (2H,d) » 8.44(2H,d) &gt; 7.45-7.42(4H,m) , 7.0 3 - 7. Ο 1 (4 H , m), 3.24 (3H, s), 1 _62 (12H, s) » &lt;Synthesis Example 9 &gt; Compound 5,5'-(4,4'-(penta) represented by the following formula [21] was synthesized. Alkan-1,5-diylbis(oxy)bis(4,1-phenylene))bis(ureidodiyl)bis(methane-1-yl-1-ylidene)bis(2,2-dimethyl Base-1,3-dioxane-4,6-dione) [Chem. 49]

[1] H2N^^ ^NH2 CH(OHe)3 [20] [2] [21] ο«Λ七将梅德伦酸 [l] (16.6g, 115mmol) and trimethyl orthoformate [2] (lllg) was placed in a 300 mL four-necked flask, and heated under reflux for 1 hour. Thereafter, the compound [20] (1 5.0 g, 52.4 mmol) was added, followed by heating under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was collected by filtration, washed with hexane, and then dried to yield compound [21] 20.8 g (yield 67%)» -61 - 201240981 j. 23(2H,s) · ^ Ppm) · 1 ^ 〇4(4H,m) ' T.00-6' 1.62- 1 Η -NMR(4^^z> DMSO-d6 8-45(2HjS) , 7.51 -7.47(4H,m) 4.〇l(4H,l) , 1.82- 1,72(4H,m) &lt;Synthesis Example 1 G &gt; A compound represented by the following formula [23] was synthesized. (4-((2,2-dimethyl-7,6-dioxo-I,3·dioxan-5-ylidene)methanyl))]

〇^ [1] -1 [22] [23] NH* CH(0Me)3 [2] Will behenic acid [Π(28·6δ, M7nim〇1) &amp; dimethyl carboxylic acid [2] (2 〇〇 g) was placed in a 200 mL four-necked flask, and heated under reflux for 1 hour. Thereafter, the compound [22] (20. 〇 g '67. 〇 mmol) 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, and the precipitated solid was collected by filtration, then washed with hexanes and then dried to yield compound [23] 40.3 g (yield: 99%) ° 1 H-NMR (400 MHz) , DMS 0-d6, δ ppm) : 11.17(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 11 &gt; Compound 5,5'--62-201240981 (6,7,9,10,17,18,20,21-octahydrodiylhydrazine) represented by the following formula [25] was synthesized. b,k][l,4,7,10,1316]hexaoxaoctadecane-2,13-diyl)bis(ureidodiyl)bis(methane-^yl-indole-subunit) bis( 2,2-dimethyl-1,3-dioxane·4,6-dione) [化51] η2ν

Ο 0 [24]

ΝΗ2

ο Meldronic acid [l] (mg, 51.2 mmol) and trimethyl orthoformate [2] (100 g) were placed in a 200 mL four-necked flask and heated to reflux for 1 hour. Thereafter, the compound [24] (10.0 g, 25.6 mmol) was added, followed by heating under reflux for 2 hours. After completion of the reaction, the solvent was removed by an evaporator and dried to give the compound [25] 17.9 g (yield: 96%). &lt;&gt;H-NMR (400 MHz, DMSO-d6, &lt;5 ppm): 1 1.16 (2H) , d) &gt; 8.50(2H,d) » 7.19(2H,d) » 7.0 1 - 6.9 8 (2 H ,m) &gt; 6.93(2H,m) » 4'09-4.08 (4H,m) , 4.04-4.02 (4H, m), 3.79 (8H, m), 1.6 1 (1 2H, s). &lt;Synthesis Example 1 2 &gt; A compound 5-((3-(2,2-dimethyl-4,6-dioxo-1,3·dioxane) represented by the following formula [2 7] was synthesized. 5-ylidene)methylamino)anilino)methyl)-2,2_~methyl-1,3-dioxane-4,6-dione-63- 201240981 [Chemical 52] „2NXXnh2 [ 26]

[2]

[27] Meldronic acid [1] (23.6 g, 164 mm 〇l) and trimethyl orthoformate [2] (100 g) were placed in a 300 mL four-necked flask, and heated to reflux for 1 hour. Thereafter, 3-aminobenzylamine [26] (10.0 g, 81.9 mmol) was added, followed by heating under reflux for 2 hours. After the completion of the reaction, the solvent was removed by an evaporator and dried to give compound [27] 36.2 g (yield 100%). 'Η-ΝΜΚ (400ΜΗζ, DMSO-d6, &lt;5 ppm) : 1 1.2 1 (1 H,s) &gt; 1 0.04-9.97(lH,m),8.55(lH,s),8.30(lH,d ), 7.57 (lH, s), 7.48-7.3 8 (2H, m), 7_23 (lH, d), 4.65 (2H, d), 1.63 (6H, s), 1.55 (6H, s). &lt;Synthesis Example 1 3 &gt; A compound represented by the following formula [29] 5,5'-(4,4'-propane-l,3-diyl)bis(piperidine-4,l-diyl) was synthesized. Bis(methane-l-yl-l-subunit) bis(2,2-dimethyl-1,3-dioxane-4,6·dione) [53]

Meldronic acid [l] (11.7 g, 81.0 mmol) and trimethyl orthoformate-64-201240981 [2] (128 g) were placed in a 200 mL four-necked flask and heated to reflux for one hour. Thereafter, 1,3-di-4-piperidylpropane [28] (8.52 g, 40.5 mmol) was added, followed by heating under reflux for 2 hours. After completion of the reaction, the solvent was removed by an evaporator and dried to give the compound [29] 20.2 g (yield: 99%). 1 H-NMR (400 MHz, DMSO-d6, δ ppm): 8.09 (2H, s) &gt; 4.06-3.97 (4H, m) » 3 . 5 6 - 3.4 9 (2 H , m) &gt; 3.2 8 - 3.2 5 (2 H , m) &gt; 1.84-1.81 (4H, m), 1.61-1.56 (12H, m), 1.32 - 1.23 (1 2H, m). &lt;Synthesis Example 1 4 &gt; A compound represented by the following formula [31] 5,5,-(propane-1,3-diylbis(ureidodiyl)bis(methane-1-yl-1-a) was synthesized. Bis(2,2-dimethyl-1,3-dioxane-4,6-dione) [Chem. 54]

Meldronic acid [l] (42.8 g, 297 mmol) and trimethyl orthoformate [2] (150 g) were placed in a 500 mL four-necked flask, and heated to reflux for 1 hour. Thereafter, 1,3-diaminopropane [30] (10.0 g, 135 mmol) was added, followed by heating 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, washed with hexane, and then dried to give the compound [3l] 24.8 g (yield 48%). 1H-NMR (400MHz, CDC13, δ ppm) : 9.5 7 - 9.5 4 (2 Η,m) s -65- 201240981 ,8.16(2H,d),3.59(4H,q),2.1 1(2H,quin) , 1.71 (12H, s) &lt;Synthesis Example 1 5 &gt; The compound 5,5'-(cyclohexane-1,3-diylbis(methyl)) double represented by the following formula [33] was synthesized. (ureadiyl)di(methane-1·•yl-1-ylidene)bis(2,2-dimethyl-1,3-dioxane-4,6-dione) [Chem. 55]

Meldronic acid [l] (44.6 g, 309 mmol) and trimethyl orthoformate [2] (200 g) were placed in a 500 mL four-necked flask, and heated to reflux for 1 hour. Thereafter, I,3-diaminomethylcyclohexane (cis-/tranS-mixture) [3 2] (20.0 g, 14 1 mmol) was added, followed by heating 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, washed with hexane, and then dried to yield compound [33] (CiS-/tranS-mixture) 58.3 g (yield 92%) ). 1 Η - NMR ( 4 Ο Ο Μ H z, DMSO-d6, δ ppm) · 9.63-9.60 (2H, m) &gt; 8. 1 1-7.97(2H,m) &gt; 3 . 5 1 - 3 . 1 2 (4 H , m) &gt; 1.87-0.54 (22H, m). &lt;Synthesis Example 1 6 &gt; -66 - 201240981 A compound represented by the following formula [35] 5,5 '- (5,8-dioxo-2,11-(^11丨3(1〇(! 6〇3116-1,12-diylylene)bis(2,2-dimethyl-1,3-dioxane-4,6-dione) [Chem. 56]

CH(OMe)3 12] [35] 〇〇7 will add Meldronic acid [1] (13.6 Lu, 94.2111〇1〇1) and trimethyl orthoformate [2] (134g) to a 200mL four-necked flask. , heating and refluxing for 1 hour. Thereafter, 3,6-dioxa-1,8-octanedithiol [34] (7.8 §, 42.8 mmol) was added, followed by heating under reflux for 2 hours. After completion of the reaction, the solvent was removed by an evaporator and dried to give the compound [35] 20.8 g (yield: 99%). 1H-NMR (400MHz, DMSO-d6, δ ppm): 9.29 (2H, s), 3.72 (4H, t), 3.57 (4H, s), 3.3 9-3.34 (4H, m), 1.66 (12H, s). &lt;Synthesis Example 1 7 &gt; A compound represented by the following formula [37] 3,5-bis((2,2-dimethyl- 4,6-dioxo-1,3-dioxane-5) was synthesized. -kiyaki)methylamino)benzoic acid [57]

Meldronic acid [1] (10.4 §, 72.3111111〇1) and trimethyl orthoformate S-67-201240981 [2] (105 g) were placed in a 200 mL four-necked flask and heated to reflux for 1 hour. Thereafter, 3,5-diaminobenzoic acid [36] (5.08, 32.9111111〇1) was added, followed by heating 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, washed with hexane, and then dried to yield compound [37] 9-0 g (yield 59%). 1 H-NMR (400 MHz, DMSO-d6, δ ppm): 11.34 (2H,d), 8 -74 (2H,d), 7.92 (2H,d), 1.69 (12H, s). &lt;Synthesis Example 1 8 &gt; A compound represented by the following formula [39] 3,5-bis((2,2-dimethyl-4,6-dioxo-I,3-dioxane-5) was synthesized. -ylylene)methylamino)-N-(pyridin-3-ylmethyl)benzamide [5]

Meldronic acid [l] (6.5 g, 45.4 mmol) and toluene formic acid [2] (66 g) were placed in a 200 mL four-necked flask, heated to reflux for 1 hour, and then compound [38] was added. 〇g, 20.6 mmol), and heated to reflux for 2 hours. After the reaction was completed, the solvent was removed by an evaporator and dried to give 11.3 g (yield 98%) of compound [39]. 1 H-NMR (400 MHz, DMSO-d6, δ ppm): 11.35 (2H,d), 9.27 (1H,t) &gt; 8.78 (2H,d) » 8.59 (lH,d) &gt; 8.4 9 - 8.4 7 (1 H, m). 8.16-8.15(lH,m) , 7.84(2H,d) , 7.77-7.74(lH,m) , 7.40- 201240981 7.36(lH,m),4.55(2H,d),l_69 (12H, s). &lt;Synthesis Example 1 9 &gt; A compound represented by the following formula [41] N-(3-(lH-imidazol-1-yl)propyl)-3,5-bis(2,2-dimethyl group) · 4,6-dioxo-1,3-dioxan-5-ylidene) methylamino)benzamide [59]

Meldronic acid [l] (l〇.lg, 52.1 mmol) and trimethyl orthoformate [2] (50 g) were placed in a 200 mL four-necked flask, and heated under reflux for 1 hour. Thereafter, the compound [40] (5.0 g, 23.7 mmol) was added, followed by heating under reflux for 2 hours. After the reaction was completed, the solvent was removed by an evaporator and dried to give 13.4 g (yield: 100%) of compound [41]. 1 Η - NMR (4 0 0 Μ H z, D Μ S Ο - d 6 , § ppm) : 11.27(2H,s), 8.71-8.65(3H,m) ' 8.01(lH,t),7.99(lH , t), 7.75 (2H, d), 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). <Synthesis Example 20 &gt; A compound represented by the following formula [43], 3,5-bis ((2,2-dimethyl- 4,6-monooxy-1,3-dioxime-5-) was synthesized. Subunit)methylamino)benzoquinone-2-yl carbonate-69- 201240981 [Chem. 60]

Meldronic acid [n (13.7 g '94.7 mmo1) and trimethyl orthoformate [2] (100 g) were placed in a 200 mL four-necked flask and heated to reflux for 1 hour. Thereafter, the compound [42] (10.0 g, 43.1 mmol) was added, followed by heating 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, washed with hexane, and then dried to give compound [43] 21.1 g (yield 90%). 1 H-NMR (400 MHz, DMS Ο - d 6 , (5 ppm): 11.22 (2H, d), 8.67 (2H, d), 7.94-7.93 (1 H, m), 7_ 87-7·86 (1) H, m), 7.46-7.45 (2H, m), 7.38 (lH, dd), 6.6 8 - 6 · 6 6 ( 1 H, m), 5.28 (2H, s), 1.63 (12H, s). Synthesis Example 2 1 &gt; The compound represented by the following formula [45] was synthesized, 5,5'-(4-(dodecyloxy)-1,3-phenylene)bis(ureidodiyl)bis ( Methane-丨-yl-yl-based subunit) bis(2,2-dimethyl-1,3-diche-4,6-dione) [Chem. 61]

-70- 201240981 Meldronic acid [l] (10.8 g, 75.2 mmol) and trimethyl orthoformate [2] (100 g) were placed in a 300 mL four-necked flask and heated to reflux for 1 hour. Thereafter, the compound [44] (10.0 g, 34.2 mmol) was added, followed by heating under reflux for 2 hours. After the completion of the reaction, the solvent was removed by an evaporator and dried to give the compound [45] 29.7 g (yield: 99%). 1H-NMR (400MHz, DMSO-d6, δ ppm): 1 1 .57 (lH,d) &gt; 11.20 (lH,d), 8.90 (lH,d), 8.64 (lH,d), 8.09 (lH, 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), 1.25 -1. 1 6 (1 6H, m), 0.79 (3H, t). <Synthesis Example 2 2 &gt; A compound represented by the following formula [47] 5,5'-(4-(decaloxy)-1,3-phenylene)bis(ureidodiyl)bis (methane) was synthesized. -1-yl-1-ylidene)bis(2,2-dimethyl-1,3-dioxane-4,6-dione) [Chem. 62]

Meldronic 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 under reflux for 1 hour. Thereafter, the compound [46] (5. g, 13.3 mmol) was added, and the mixture was further refluxed for 2 hours. After the completion of the reaction, the reaction solution was cooled to room temperature, and the solid obtained was analyzed by filtration, and the solid was eluted with hexane, and the solid was dried to give compound [47] 6-4 g (yield: 71%). 1 H-NMR (400 MHz, DMSO-d6, δ ppm): 1 1.63 (1H, d) &gt; 11.26 (lH, d), 8.99 (lH, d), 8.72 (lH, d), 8_19 (lH, d), 7.40 (lH, dd), 7.20 (lH, d), 4.13 (2H, t), 1.80- 1.74 (2H, m), 1.68 (12H, s) ' 1.49- 1.45 (2H, m), 1.25 - 1.22(28H,m) &gt; 0.85(3H,t). <Synthesis Example 23 &gt; The compound 5,5'-(4-(4-trans-4-heptylcyclohexyl)phenoxy)-1,3-phenylene group represented by the following formula [49] was synthesized. Bis(ureidodiyl)bis(methane-yl-i-subunit)bis(2,2-dimethyl-1,3-dioxane-4,6-dione) [Chem. 63]

• C7H1S

Meldronic acid [1] (4.2 g, 28.9 mmol) and trimethyl orthoformate [2] (44) were placed in a 10 〇 11 ^ four-necked flask, and heated under reflux for 1 hour. Thereafter, the compound [48] (5. g, 13.1 mmol) was added, followed by heating under reflux for 2 hours. After the reaction was completed, the solvent was removed by an evaporator and dried to give 9.0 g (yield 98%) of compound [49]. 1H-NMR (400MHz, DMSO-d6, 5 ppm): 11.64 (1H, d), -72 - 201240981 11.30 (lH, d), 9.03 (lH, d), 8.76 (lH, d), 8.31 (lH, d), 7.40 (lH, dd), 7.28 (2H, H), 7.03 (2H, d), 6.97 (lH, d), l_81 (2H, d), 1.69 (1 OH, d), 1.44-1. 34( 1 H,m) &gt; 1.26- 1.78 (10H, m), 1,07-1.01 (lH, m), 0.86 (3H, t). &lt;Synthesis Example 24&gt; A compound 5,5'-(4-(trans-4(trans-4'-pentyl)bis(cyclohexyl)-4-yl)phenoxy) represented by the following formula [51] was synthesized. ))-1,3-phenylene) bis(ureidodiyl)bis(methane-1-yl-1-ylidene)bis(2,2-dimethyl-1,3-dioxane-4, 6-diketone) [Chem. 64]

Meldronic acid [1] (9.0 g, 62.1 mmol) and trimethyl orthoformate [2] U20 g) were placed in a 300 mL four-necked flask and heated to reflux for 1 hour. Thereafter, the compound [50] (12.3 g, 28.2 mmol) was added, followed by heating under reflux for 2 hours. After the reaction was completed, the solvent was removed by an evaporator and dried to give Compound [51] 20.6 g (yield 98%). 'H-NMR (400 MHz, DMSO-d6, δ ppm): 1 1,64 (1H, d) -11.30 (1H, d), 9.03 (1H, 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), -73- 201240981 1.88- 1.03 (43H, m), 〇.86 (3H, t). <Synthesis Example 25 &gt; The compound represented by the following formula [53] was synthesized, 5, 5'-(5-((trans_4_(anti-4'-pentyl bis(cyclohexyl))-4-yl)phenoxy) Methyl phenyl) bis(ureidodiyl) bis(methane-buyl-1-ylidene) bis(2,2-dimethyl-1,3-dioxane-4,6-dione) [化65]

Meldronic acid [1] (19.0 g, 98.6 mmol) and trimethyl orthoformate [2] (200 g) were placed in a 500 mL four-necked flask, and heated to reflux for 1 hour. Thereafter, the compound [52] (20.0 g, 44.6 mmol) was added, followed by heating under reflux for 2 hours. After the reaction was completed, the solvent was removed by an evaporator and dried to give 33.4 g (yield: 99%) of Compound [53]. 1H-NMR (400MHz, DMSO-d6, δ ppm): 1 1.29(2H,d) &gt; 8_74(2H,d) , 7.94(lH,s) , 7.53(2H,d) , 7.12(2H,d) , 6.92(2H,d) , 5.09(2H,s) , 1. 8 1 -1 . 6 8 (2 Ο H,m) , 1.36- 0.84(23H,m) 〇-74- 201240981 <Synthesis Example 2 6 &gt; Synthesis of compound 4'·pentyl bis(trans-cyclohexyl)-4-yl 3,5·bis((2,2-methyl-4,6-oxy) represented by the following formula [55] -1,3-two chewing compound-5-subunit) methylamino)benzoate [Chem. 66]

Meldronic acid [1] (13.3 g, 92.0 mmol) and toluene formic acid [2] (150 g) were placed in a 500 mL four-necked flask, and heated to reflux for 1 hour. Thereafter, the compound [54] (15.0 g, 41.8 mmol) was added, followed by heating under reflux for 2 hours. After the completion of the reaction, the solvent was removed by an evaporator and dried to give the compound [55] 28.8 g (yield: 99%). 1H-NMR (400MHz, DMSO-d6, δ ppm) : 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) &gt; 1.74- 1.64(1 8H,m) - 1.4 4 - 1 . 3 2 (2 H , m) &gt; 1.29-0.76(20H,m) 〇<Synthesis example 2 7 &gt; The compound represented by the following formula [57] is synthesized as N-(2,4-bis((2,2-dimethyl)

S-75- 201240981 base-4,6-dioxo-1,3-dioxan-5-ylidenemethylamino)phenyl)-4-(trans-4-pentylcyclohexyl)benzamide Amine [67]

Meldronic acid [l] (8.2 g, 56.7 mmol) and trimethyl orthoformate [2] (80 g) were placed in a 300 mL four-necked flask and heated to reflux for 1 hour. Thereafter, the compound [56] (1 G.0 g, 25.8 mmol) was added, and the mixture was refluxed 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 dried to yield compound [57] 16 </ RTI> (yield: 92%). 1 H-NMR (400 MHz, DMSO-d6, δ ppm): 11.36- 1 1.27 (2H, m) , 1 0.38 (1 H, s) , 8.8 0 - 8.7 4 (2 H , m) &gt; 8,09 (lH, s), 7.87 (2H, d), 7.44 (lH, dd), 7.34 (2H, d), 2_5I-2.46 (3H, m), 1.77 (2H, d), I.66 (6H, s ), l_59(6H, s), 1.50- 1.37(3 H,m) &gt; 1.29-1 . 14(8H,m) , 0.99(2H,q), 0.82(3H,t). <Synthesis Example 2 8 &gt; A compound represented by the following formula [59] N-(2,4-bis((2,2-dimethyl-4,6-dioxo-1,3-dioxane)) was synthesized. -5-subunit)methylamino)phenyl)-4-(trans-4-heptylcyclohexyl)benzamide-76- 201240981 [化68] h2n

[58]

Meldronic acid [1] (11.7 g, 81.0 mmol) and trimethyl orthoformate [2] (150 g) were placed in a 300 mL four-necked flask and heated to reflux for 1 hour. Thereafter, the compound [58] (15.0 g, 3 6.8 mmol) was added, followed by heating 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, washed with hexane, and then dried to yield compound (59), 26.1 g (yield: 99%). 1 Η-NMR (4 0 0 Μ H z , DMSO-d6, 5 ppm): 11.36-11.27 (2H, m) &gt; 1 0.3 8 ( 1 H, s) &gt; 8.78 (2H, t) , 8. 10(lH,s) ' 7_88(2H,d) , 7.44(lH,dd) , 7.35(3H,d) , 2.52(2H,t), 1.78(2H,d),1.65(6H,s),1.60 (6H, s), 1.50-1.3 7(2H, m), 1.29-1.12 (14H, m), 0.99 (2H, q), 0.82 (3H, t). <Synthesis Example 2 9 &gt; A compound represented by the following formula [61] 5,5'·(4-((33,83,98,1011,1311,143,1711)-10,13-dimethyl group) was synthesized. -17-((11)-5-methylhex-2-yl)-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetrahydrogen -1Η-cyclopentyl [a]phenanthrene-3-yloxy)_ι,3-phenylene)bis(ureidodiyl)bis(methane-1-yl-1-ylidene)bis(2,2-di Methyl-1,3-dioxane-4,6-dione) 201240981 [Chem. 69]

Meldronic acid [l] (4. lg '29 mmol) and trimethyl orthoformate [2] (50 g) were placed in a 100 mL four-necked flask, and heated under reflux for 1 hour. Thereafter, the compound [60] (l〇.〇g, 13mraol) was added, followed by heating under reflux for 2 hours. After the completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was collected by filtration, washed with hexane, and then dried to yield compound [61] 9.9 g (yield: 99%). &lt;Synthesis Example 3 0 &gt; Synthesis of (Ε)·2,4·bis ((2, dimethyl-methyl-6 6-oxo-I,3-dioxaalkyl) represented by the following formula [63] Methylamino)phenethyl epoxide phenyl) acrylate [70]

Meldronic acid [l] (7.3 g, 37 mm 〇l)) 3r &amp; dimethyl formate -78-201240981 [2] (75 g) was placed in a 200 mL four-necked flask, and heated under reflux for 1 hour. Thereafter, the compound [62] (7.46 g, 17 mmol) was added, followed by heating under reflux for 2 hours. After completion of the reaction, the solvent was removed by an evaporator and dried to give compound [63] 12.5 g (yield: 99%) 1 1.57 (lH,d) ' 8.04 (1H, s), 4.34 (2H, t) -1l (15H , m), 1 H-NMR (400MHz, DMS 0-d6, δ ppm): 1 1.2 9 ( 1 Η, s ), 8.8 2 (1 Η, dd) ' 8.2 3 (1 Η, dd ) ' 7.57- 7.46 (5H, m), 6.92 (2H, d), 6_35 (lH, d), 3.99 (2H, t), 1.74- 1.65 (1 5H, m) · 1.43-1. 0.85 (3H, t). &lt;Synthesis Example 3 1 &gt; - Synthesis of (E)-3,5-bis((2,2-dimethyl- 4 6-dioxo-1,3-dioxane) represented by the following formula [65] -5-kiylidene)methylamino)phenylhydrazine 3-(4,(diepoxy)propyl) acrylate [71]

Mellonic acid, 33 mmol) and trimethyl methacrylate [2] (638) were placed in a 2 〇〇 1 ^ four-necked flask and heated to reflux at 1 pm. The compound was heated in an hour and then the compound [64] (6.3 g, 15 mmol) was added and then refluxed. After the end of the reaction, the solvent was removed by an evaporator and dried (65 g, 10.7 g, yield 99%). 201240981 】H-NMR (400MHz, DMSO-d6, δ ppm): 11.25 (lH, d), 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), 1.68 - 1. 6 3 ( 1 5 H , m) ' 1.3 8 - 1.20 ( 1 5H, m), 0.8 1 (3H, t). <Synthesis Example 3 2 &gt; Compound 5-(methoxymethyl)- 2,2-dimethyl-1,3-dioxane-4,6-dione represented by the following formula [66] was synthesized. [化72]

Meldronic acid [l] (50.0 g, 347 mmol) and trimethyl orthoformate [2] (184 g) were placed in a 500 mL four-necked flask and heated to reflux for 1 hour. After the completion of the reaction, the solvent was removed by an evaporator, and the crude material was recrystallized from hexane/tetrahydrofuran solvent to give compound [6 6 ] 4 3.7 g (yield 6 8%), H-NMR (400 MHz, CDC13, &lt;;5 ppm) : 8.16 (lH, s) - 4.29 (3H, s), 1.73 (6H, s). &lt;Synthesis Example 3 3 &gt; The compound represented by the following formula [68] was synthesized as a compound of the following formula [6] ((12-amino)methyl)-2,2-methyl-1,3-diche-4 ,6-diketone-80- 201240981 [化73]

CH(OMe)3 [2] Ο

C12H2S H2N-C12H24 [67] [68] Meldronic acid [H (21_4 g ' 148 mmol) and trimethyl orthoformate [2] (250 g) were placed in a 200 mL four-necked flask and heated to reflux for one hour. Thereafter, dodecylamine [67] (25.0 g, m mmol) was added, followed by heating under reflux for 2 hours. After the end of the reaction, the solvent was removed by an evaporator and dried to give 45.3 g (yield: 99%) of compound [68]. 1 H-NMR (400 MHz, DMSO-d6, δ ppm): 9.64 (lH, s) &gt; 8.10 (lH,d) &gt; 3 .3 5-3.3 7(2H,m) » 1 . 5 4 - 1.4 8 ( 6 H, m) &gt; 1.43- 1 .2 1 (20H, m), 0.85 (3H, t). <Synthesis Example 34> A compound represented by the following formula [7〇] was synthesized, and 2,2·dimethyl-5-((octadecylamino)methyl)-1,3-dioxane was synthesized. -4,6-dione [化74] 〇乂〇.•C18H37 [1] H2N-C18H37 — CH(OMe)3 [70] [69] [2] Will Meldronic acid [l] (14.7g , l〇2 mmol) and trimethyl orthoformate [2] (250 g) were placed in a 200 mL four-necked flask, and heated under reflux for 1 hour. Thereafter, octadecylamine [69] (25.0 g, 93 mmol) was added, followed by 2 -81 - 201240981, followed by drying under reflux for heating. After completion of the reaction, the compound [7〇] was obtained by an evaporator to obtain 38.9 g (yield: 99%). 1H-NMR (400MHz, DMSO-d6 § OOm\ , ) · 9.67(1H,s), 8.10(lH,d) , 2.89-2.47(2H,m) , l 54 , 4'°-72(38H,m ), 0.85 (3H, t). &lt;Synthesis Example 3 5 &gt; A compound 5,5,-(1,4-phenylphenylbis(methane-1-yl-1-ylidene)) bis (2, represented by the following formula [72] was synthesized. 2-dimethyl-u-dioxane_4,6-dione [化75]

To a 500 mL four-necked flask, terephthalaldehyde [71] (10.0 g, 75 mmol), Meldronic acid [1] (22.6 g, 157 mmol) and pyridine (150 g) were placed and stirred at room temperature overnight. Thereafter, the pyridine was removed by an evaporator, and the residue was dissolved in a 1,2-dichloroethane/methanol mixed solvent, and the solvent was again removed by an evaporator to carry out crystallization. The obtained solid was recrystallized from 2-propanol to give 18.8 g (yield 65%) of compound [72]. 1H-NMR (400 MHz, DMSO-d6, &lt;5 ppm): 8.56 (2H, s), 7.96 (4H, s), 1.74 (12H, s). <Synthesis Example 3 6 &gt; A compound 5,5'-(1,3-phenylene bis-82-201240981 (methane-1-yl-1-ylidene)) double represented by the following formula [74] was synthesized. (2,2-methyl-1,3-dioxane-4,6-dione) [Chem. 76]

Isophthalaldehyde [73] (10.0 g, 75 mmol), Meldronic acid [1] (22.6 g, 157 mmol) and pyridine (150 g) were placed in a 500 mL four-neck flask and stirred at room temperature overnight. Thereafter, the pyridine was removed by an evaporator, and the residue was dissolved in a 1,2-dichloroethane/methanol mixed solvent, and the solvent was again removed by an evaporator to carry out crystallization. The obtained solid was recrystallized from 2-propanol to give the compound [74] 16.2 g (yield: 56%). 1H-NMR (400MHz, DMSO-d6, (5 ppm): 8 · 5 5 (2 Η, s ), 7.80-7.76 (2H, m) ' 7.52-7.42 ( 1 H,in) , 1.74(6H,s ), 172 (61^). <Synthesis Example 3 7 &gt; The compound represented by the following formula [78] was synthesized (4_(2,2-dimethyl)

-83- 201240981 [化77]

4-hydroxybenzaldehyde [76] (35.7 g, 292 mm 〇l), triethylamine (31.5 g, 311 mmol) and tetrahydrofuran (150 g) were added to a 1 L four-necked flask, and the internal temperature was cooled to 1 〇 ° C. . At the same time as the heat generation, a solution of 1,3,5-benzenetricarbonyltrichloride [75] (25.0 g, 94 mmol) in tetrahydrofuran (225 g) was added dropwise, and after completion of the dropwise addition, the mixture was further reacted at room temperature for 2 hours. After the completion of the reaction, the reaction solution was poured into pure water (225 Og), and the precipitated solid was filtered, washed with hexane, and then dried to yield 48.0 g (yield 98%) of compound [77]. Compound [77] (48.0 g, 92 mmol), Meldronic acid [1] (56.2 g, 289 mmol) and pyridine (720 g) were placed in a 2-L four-neck flask and stirred at room temperature overnight. Thereafter, the pyridine was removed by an evaporator, and the residue was recrystallized from a mixture of tetrahydrofuran / hexanes to obtain 75.6 g of compound [78] (yield: 91%). δ ppm) : 8.57- 1 H-NMR (400MHz, DMSO-d6, -84 - 201240981 8.55(3H,m) , 8.38(3H,s) ' 7.8 3 - 7.8 1 (6 Η, m) , 7.42- 7.39 (6H, m), 1.74 (1 8H, s). <Synthesis Example 3 8 &gt; A compound represented by the following formula [80] 5-(1-hydroxyphenylphenyl)-2,2-dimethyl group was synthesized. -1,3-dioxane-4,6-dione [78]

Valeric acid [79] (25.0 g, 245 mmol)' of dichlorocarbyl (2 〇〇g) was placed in a 200 L four-necked flask, followed by the addition of N,N-dimethylaminopyridine (DMAP: 32.6 g, 267 mmol) Dicyclohexylcarbodiimide (DCC: 55.6 g, 270 mmol), Meldronic acid [l] (35.3 g, 245 mmol), stirred at room temperature overnight. After the reaction was completed, the solid component was filtered off using an algae, and the filtrate was concentrated by an evaporator. The crude product was dissolved in ethyl acetate (300 g) and washed with 1M hydrochloric acid. The organic layer was dried over magnesium sulfate, and the solvent was evaporated to ethylamine (yield: 1 H-NMR (400 MHz, CDC13, &lt; 5 ppm) : 3.09 - 3.01 (2H, m) &gt; 1.70 (6H, s) &gt; 1.70 - 1.53 (2H, m) &gt; 1.41 (2H , q) &gt; 0.92 (3H, t) a <Synthesis Example 3 9 &gt; -85- 201240981 The compound 5-(i-hydroxytetracyclohexenyl)-2 represented by the following formula [82] is synthesized, 2-dimethyl-1,3-dioxane-4,6-dione [Chem. 79]

Meldronic acid [1] (25.0 g, l73 mmol), pyridine (27.4 g, 346 mmol), dichloromethane (250 g) was placed in a 200 L four-neck flask, and the solution was cooled to 〇 ° C under nitrogen. At the same time as the heat was added, myristic acid chloride [8 1] (42.7 g, 173 mmol) was added dropwise, and after the completion of the dropping, the reaction solution was returned to room temperature and stirred for further 1 hour. After the completion of the reaction, the organic layer was washed successively with 1 mL of hydrochloric acid, purified water and brine, and dried over magnesium sulfate. After the solution was filtered to remove the solvent, the residue was purified (hexane/ethyl acetate) to afford compound (2) (yield: 66%). 1 H-NMR (400MHz, CDC13, δ ppm): 3.09- 3.04(2H,m) , 1.72(6H,s) , 1 · 7 2 - 1 _ 6 5 ( 2 H,m ) , 1.46- 1.34(2H , m), 1.26 (18H, s), 〇.88 (3H, t). <Synthesis Example 40 &gt; The compound 5-(3,5-dimethoxyphenyl)-2,2-dimethyl-1,3-dioxane-4 represented by the following formula [8 4] was synthesized. ,6-diketone-86- 201240981 [化80]

Meldronic acid [l] (5g, 28.9mmol), 3,5-dimethoxybenzaldehyde (4.70g, 28.3mmol), ethanol (50g) was added to a 200L four-necked flask, followed by the addition of pyridine gun The acid ester (〇.42 g, 2.89 mmol) was stirred for 30 minutes. Ο

V OMe [83] Thereafter, the reaction solution was cooled to 〇 ° C, and a small amount of sodium cyanoborohydride (2.7 g, 43.4 mmol) was added portionwise, and the reaction temperature was returned to room temperature. After the reaction was completed, attention was paid to the gas generated, and the mixture was quenched with 10% hydrochloric acid, and then ethanol was distilled off. The crude material was resuspended in 10% hydrochloric acid and extracted three times with dichloromethane (80 g). After the organic layer was combined, the organic layer was dried over magnesium sulfate, and then filtered, and the solvent was evaporated to give crystals of crystals to crystals to crystals to afford crystals of compound [84] 4.7 g (yield 55%) »H-NMR (400 MHz, CDC13, δ Ppm): 6.44(2H,d) &gt; 6.29(lH,t) &gt; 3.73(lH,t) &gt; 3.36(2H,d) &gt; 1.69(3H,s), 1. .5 1 (3H,s ). &lt;Synthesis Example 4 1 &gt; A compound represented by the following formula [86] 5-(3,5-dimethoxybenzene)-2,2-dimethyl-5-(pyridine-4-methyl) )-1,3-dioxane-4,6-dione

S -87- 201240981 [化 81] OMe

Compound [84] (4.70 g, 16 6 mmol), potassium carbonate (3.31 g, 24.0 mmol), dimethylformamide (DMF) (50 g) were placed in a 200 L four-necked flask, and then dropped into 4 A solution of -(bromomethyl)pyridine hydrobromide (4.45 g, 17.6 mmol) in DMF (10 g). After the reaction was completed, the reaction solution was poured into pure water (600 g), and extracted three times with ethyl acetate (150 g). Next, the organic layer was washed with saturated sodium hydrogencarbonate and saturated brine, and the organic layer was dried over magnesium sulfate. Thereafter, the solvent was evaporated to remove the solvent, and the crude material was recrystallized from methanol to give 4.4 g (yield: 72%). 1H-NMR (400MHz, CDC13, 6 ppm): 8.51 (2H, d), 7.10 (2H, d), 6.72-6.66 (3H, m), 3.82 (3H, s), 3.80 (3H, s), 3 , 39 (2H, s), 0.73 (3H, s), 0.68 (3H, s). <Synthesis Example 42> The compound phenyl 3_(2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-yl)propionate represented by the following formula [88] was synthesized. -88- 201240981 [化82] cr〇l [87]

Meldronic acid [l] (15.0 g, l 4 mmol), and B (150 g) were added to a 200 L four-necked flask. 'Addition of potassium carbonate (i4.3 g, 104 mmol), benzyl triethylammonium chloride (23.9 g, 104 mmol), stirred at room temperature for 15 minutes. Thereafter, the compound [87] (25.3 g, 156 mmol) was added, and the mixture was stirred under heating at 60 °C. After the completion of the reaction, the solvent was evaporated. The crude material was dissolved in ethyl acetate (1 50 g), and washed three times with 10% potassium hydrogen sulfate, and the organic layer was dried over magnesium sulfate. After the solvent was evaporated to remove the solvent, the obtained crude material was purified by column column (Si.sub.2: hexanes/ethyl acetate) to give the compound [88] 28.4 g (yield 89%). 1 H-NMR (400 MHz, CDC13, δ ppm) : 7.3 8 - 7.2 9 (5 Η, m) ' 5.08 (2H, s), 3.89 (lH, t), 2.67 (2H, t) &gt; 2.44-2.34 (2H,m), 1.73 (3H, s), 1.72 (3H, s). <Synthesis Example 43 &gt; Compound (s)-n-butyl 2-(n-butoxy-indenylamino)-5-(2,2-methyl-4) represented by the following formula [90] was synthesized. ,6-dioxo-1,3-dioxan-5-yl)propionate production-89- 201240981 [Chem. 83] COzt-Bu

1) DCC, DMAP, CH2CI2 2) NaBH4, AcOH, CH2CI2

s^C〇2t-BuNHBoc Will Meldronic acid [l] (15_0g, 104mmol), DMAP (18.4g, 151mmol), compound [89] (28.4g, 94mmol), dichloromethane (i〇〇g) After adding to a 200 L four-necked flask, the reaction mixture was cooled to 〇°C, and a solution of DCC (22.5 g, 109 mmol) in dichloromethane (50 g) was added and stirred overnight. After completion of the reaction, the solid was filtered off. The filtrate was washed three times with 10% potassium hydrogen sulfate, washed with saturated brine, dried over magnesium sulfate, and then acetic acid (50 mL) was added to acid. At 〇 ° C, a little sodium borohydride (9.0 g, 236 mmol) was added in portions and stirring was continued at 0 °C. After completion of the reaction, the mixture was washed with saturated brine and purified water, and the organic layer was dried over magnesium sulfate. The crude product was purified by column chromatography (SiO 2 : hexane / ethyl acetate) to afford compound (s) (3) g (yield: 79%). 1H-NMR (400MHz, CDC13, δ ppm): 5.04(lH,d), 4.20-3.08(lH,m), 3.52(lH,t), 2.20-2.00(2H,m), 1.89- 1.40 (4H, m) ' 1.77(3H,m) , 1.73(3H,s) , 1.43(9H,s), 1 '41 (9H,s). <Synthesis Example 44 &gt; A compound represented by the following formula [92] 5-(bis(methylthio)methyl-2,2-dimethyl-1,3-dioxane-4,6 was synthesized. -dione-90 - 201240981 [Chem. 84]

Et3N7 CSz, Mel, DMSO

MeS 八SMe [92] Meldronic acid [l] (40.9g, 284mmol), triethylamine (57.5g, 568mmol), DMSO (140g) into a 200L four-necked flask Carbon disulfide (21.6 g, 284 mmol) was added and stirred at room temperature for 1 hour. Thereafter, the reaction liquid was ice-cooled, and methyl iodide (80.6 g, 5 6 8 mmol) was gradually added thereto, and the reaction was continued at room temperature. After the completion of the reaction, the reaction mixture was poured into ice water (250 g), and the precipitated solid was filtered, and then washed with hexane to give 36.7 g (yield 52%) of compound [92]. 1H-NMR (400 MHz, CDC13, δ ppm): 2.57 (6H, s): 1.53 (6H, s). <Synthesis Example 45 &gt; A compound represented by the following formula [94] was synthesized, 2,2-dimethyl-5-(methylthio(neopentylamino)-methyl)-1,3-di Osterane-4,6-dione [Chem. 85]

The compound [92] (18.6 g, 75 mmol), 2,2-dimethylpropylamine (6.53 g, 75 mmol) and THF (180 g) were placed in a 200 mL four-neck flask, and stirred at -91 - 201240981 at room temperature. After completion of the reaction, the mixture was concentrated to a solvent by an evaporator to a solvent, and then diethyl ether (100 g) was added thereto, and the precipitated solid was filtered, and then recrystallized from a solvent mixture of THF/diethyl ether to give compound [94] 16.9. g (yield 7 7%) = 1H-NMR (400 MHz, CDC13, δ ppm): 3.1 1 (2H, d) &gt; 2.58 (3H, s), 1.73 (6H, s). <Synthesis Example 4 6 &gt; A compound represented by the following formula [95] was synthesized, 2,2-dimethyl-5-(methylthio(neopentylamino)-methyl)-1,3- Dioxane-4,6-dione [Chem. 86]

The compound [92] (2.428, 1〇111111〇1), 2,2-dimethylpropylamine (2.62 g, 30 mmol), and ethanol (60 g) were placed in a 200 mL four-necked flask and heated to reflux. After the reaction was completed, it was concentrated by an evaporator to about half of the solvent, and diethyl ether (5 〇g) was added thereto. After cooling to 0 ° C to precipitate a solid, the solid was collected by filtration, and then the solvent was mixed with THF / diethyl ether. Crystallization gave Compound [95] 1-62 g (yield 50%). 1H-NMR (400 MHz J CDC13, δ ppm): 9.83 (2H, s), 3.10 (2H, d), l_61 (6H, s), 0-96 (18H, s). <Synthesis Example 47 &gt; -92- 201240981 The compound 5,5'-(1,8-dihydroxyoctane-1,8-diphenyl)-bis (2,2) represented by the following formula [97] was synthesized. - dimethyl-1,3-dioxane-4,6-dione) [Chem. 87]

Mellonic acid H] (14.7 g, 1 lmmol), pyridine (19.87 g, 0.26 mmol), dichloromethane (200 g) was placed in a 200 mL four-necked flask, and the reaction solution was cooled to 〇 °c, and the interest was poured. While heating, hexane dicarboxy dichloride [96] (ll_98 g, 51 mmol) in dichloromethane (50 g) was gradually added, and the reaction was continued at 23 °C. After the completion of the reaction, the solution was made acidic using a 1% aqueous solution of hydrochloric acid, and the solvent was distilled off by an evaporator. The solid was collected by filtration, washed with purified water, and then recrystallized from methylene chloride/diethyl hydrazide to give compound [97] 16.6 g (yield 78%). 1H-NMR (400MHz, CDC13, δ ppm): 15.30 (2H, s), 3.09 (4H, t), 1.73 (12H, s), 1.66 (4H, m), 1.47 (4H, m). <Synthesis Example 4 8 &gt; A compound 5,5'-(((6,7,9,10,17,18,20,21-octahydrobiphenyl) [15, represented by the following formula [99] was synthesized. 1〇[1,4,7,10,13,16] hexaoxacyclooctadecane-2,14-diyl)bis(ureidodiyl)bis(methylphenyl)bis(2,2-di Methyl-1,3-dioxane-4,6-dione) a -93- 201240981 [化88]

[98]

CH(OMe)3 [2] Ο

J〇t o o o o [99]

O 〇W Meldronic acid [1] (4.87 g, 33.8 mmol) and trimethyl orthoformate [2] (60 g) were placed in a 200 mL four-necked flask, and heated under reflux for 1 hour. Thereafter, the compound [98] (6.00 g, 15.4 mmol) was added, followed by heating under reflux for 2 hours. After the completion of the reaction, the solvent was removed by an evaporator and dried to give compound [99] 1 0.4 g (yield: 97%). 1H-NMR (400MHz, DMS0-d6, &lt;5 ppm): 1 1 .2 1 (2H,d) &gt; 8.54(2H,d) · 7.26(2H,d) &gt; 7.05(2H,dd) &gt 6.96(2H,d) &gt; 4.15-4.06(8H,m) &gt; 3.8 8 - 3.8 0( 6 H,m ), 3.17(2H,d),1.67(1 2H,s) <Synthesis Example 49 &gt Synthesis of 5,5'-((1,4,10,13-tetraketo-7,16-diazacyclooctadecane-7,16-diyl) double represented by the following formula [101] (methyl-subunit)) bis(2,2-dimethyl-1,3-dioxane-4,6-dione) [Chem. 89]

201240981 Meldronic acid [l] (24.17 g, 167.7 mmol) and trimethyl orthoformate [2] (2 〇〇g) were placed in a 500 mL four-necked flask, and heated to reflux for 1 hour. Thereafter, the compound [10] (20.00 g, 76.2 mmol) was added, and the mixture was heated under reflux for 2 hours. After the completion of the reaction, the solvent was removed by an evaporator and dried to give 43.2 g (yield: 100%) of Compound. &lt;Synthesis Example 5 0 &gt; 5,5'-(((((((((((((((())))))) Bis(4,1-extended phenyl))bis(ureidodiyl))bis(methyl-subunit))bis(2,2-dimethyl-1,3-dioxane-4,6- Diketone) [化90] [102]

Meldronic acid [1] (22.008, 153111111〇1) and trimethyl orthoformate [2] (200 g) were placed in a 500 mL four-necked flask and heated to reflux for 1 hour. Thereafter, the compound [10〇2] (20.00 g, 69.4 mmol) was added, and the mixture was heated under reflux for 2 hours. After the completion of the reaction, the solvent was removed by an evaporator and dried to give 40.2 g (yield: 97%) of compound [3]. *Η-ΝΜΚ(400ΜΗζ, DMSO-d6, δ ppm) : 11.23 (2H,d) &gt; 8.44(2H,d) &gt; 7.5 0-7.48(2H,m) &gt; 7.0 1 - 6.9 9 (4 H , m) &gt; 4.42- 4.12 (4H, m), 3.89-3.78 (4H, m), 1.67 (12H, s)» S. &lt;Synthesis Example 5 1 &gt; -95- 201240981 The following formula [105] 2-(Methylcyclooxy)vinyl 3,5-bis(((2,2-dimethyl- 4,6-dioxo-1,3-dioxan-5-ylidene) )methyl)amino)benzoate [Chem. 91]

Meldronic acid [1] (2 4.188, 168111111〇1) and trimethyl orthoformate [2] (300 g) were placed in a 500 mL four-necked flask and heated to reflux for 1 hour. Thereafter, the compound [104] (20.0 (^, 76.3111111〇1) was added, followed by heating under reflux for 2 hours. After completion of the reaction, hexane was added, and the mixture was filtered and dried to give compound [105] 43.7 g (yield 100%). - NMR (400 MHz, CDC13, δ ppm): 11.36 (2H, d), 8,72 (2H, d), 7.80 (2H, d), 7_37 (lH, t), 6.17 (lH, t), 5.64 5.62( 1 H,m) &gt; 4.6 7 - 4.6 5 (2 H,m) , 4.5 5 - 4 · 5 2 (2 H,m ), 3.79(lH,s),3_47(lH,s),3.34 (2H, s), 1 · 9 7 - 1 . 9 6 ( 3 H, m ), 1.78-1.76 (13H, m) 0 <Synthesis Example 52 &gt; Synthesis The following formula [l〇7] is represented ( E)-2,4-bis((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene)methyl)amino)phenethyl 3- (4,-butoxybisphenyl]-4-yl)propionate-96- 201240981 [Chem. 92]

[106] [2]

Meldronic acid [l] (4.00 g, 20.4 mmol) and trimethyl orthoformate [2] (40 g) were placed in a 100 mL four-necked flask and heated to reflux for 1 hour, followed by the addition of the compound [1 06] ( 4. OOg, 9.3 mmol), followed by heating for 2 hours. After the completion of the reaction, the solvent was removed by an evaporator and dried to give a compound [107] 6.8 g (yield: 99%). 1H-NMR (400MHz, CDC13, δ ppm): 11.59(lH,d) &gt; ll_29(lH,d), 8.84(lH,d), 8.78(lH,d), 8.23(lH,s), 8.04( 1H, s), 7.70-7.64 (7H, m), 7.62 (lH, d), 7.48 (2H, s), 7.03 (2H, d), 6.53 (lH, d), 4.41 (2H, t), 4.01 (2H,t)'3.66-3.63(6H,m) , 1.68-1 .57(1 OH,m) , 1.56(1 H,s) &gt; 1.44- 1 .39(1 H,m), 0.94 (3H, t). <Synthesis Example 5 3 &gt; 0)-2,4-bis((2,2-dimethyl-1,3-dioxan-5-ylidene) represented by the following formula [1〇9] was synthesized. )methyl)amino)phenethyl 3-(4-cyclohexylphenyl)propene 201240981 [Chem. 93]

Meldronic acid [l] (4.35 g, 30 mmol) and trimethyl orthoformate [2] (50 g) were placed in a 200 mL four-necked flask, and heated under reflux for 1 hour. Thereafter, the compound [108] (5.00 g, 14 mmol) was added, followed by heating under reflux for 2 hours. After the reaction was completed, the solvent was removed by an evaporator and dried to give the compound [109], 9.63 g (yield: 99%). 1H-NMR (400MHz, CDC13, &lt;5 ppm) : 1 1.63 (lH,d) » 1 1 .30 (lH,d) , 8.64-8_63(2H,m) , 7_60(lH,d) , 7.42- 7.39(3H,m) , 7 · 2 9 - 7.2 7 (2 H,m) , 7.2 1 - 7.1 5 ( 3 H , m ), 6'37(lH,d),4.49-4.46(2H,m) , 3.33 - 3.11 (2H, m), 2.59 - 2.42 (lH, m), 1.86-l_45 (2H, m), 1.76-1.70 (14H, m), 1.42-1.20 (6H, m). &lt;Synthesis Example 54&gt; Synthesis of (E)-2,4-bis((2,2-dimethyl-4,6-dihydro-1,3-dioxane) represented by the following formula [m] -5-subunit)methyl)amino)phenethyl 3-(4-([trans-1,1 bis(cyclohexyl)]-4-yl)phenyl)propionate-98 - 201240981 94]

Meldronic acid H] (2.84 g' 20 mmol) and trimethyl orthoformate [2] (40 g) were placed in a 200 mL four-necked flask, and heated under reflux for 1 hour. Thereafter, the compound Π l〇] (4. 〇〇g '9_0 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 give a compound [1 1 1 ] 6 · 6 g (yield 99 %). 1H-NMR (400MHz, CDC13, δ ppm) : 1 1.6 3 ( 1 Η,d), 1 1 .30(lH,d) &gt; 8.67-8.60(2H, m) , 7.60(lH,d) , 7.4 1- 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 . 〇1 (8H,m). <Synthesis Example 5 5 &gt; (£)-4-(((2,2-dimethyl-4,6-dioxo-1,3-dioxane-5) represented by the following formula [113] was synthesized. -subunit)methyl)amino)phenethyl 3-(4-cyclohexylphenyl)propionate

S -99- 201240981 [化 95]

[112] [2] [113] Meldronic acid m (2.7 g '19 mmol) and trimethyl orthoformate [2] (3 Og) were placed in a 200 mL four-necked flask, and heated under reflux for 1 hour. Thereafter, the compound [1 12] (3.00 g, 8.6 mmol) was added, and the mixture was further refluxed for 2 hours. After the reaction was completed, the solvent was removed by an evaporator and dried to give the compound [1 1 3] 4.22 g (yield: 99%). 'Η-ΝΜΚ (400ΜΗζ, CDC13, δ ppm) : 1 1 .25( 1 H,d) * 8.62(lH,d), 7.64(lH,d),7.44(2H,d),7.32(2H,d ), 7,24-7.19(4H,m), 6.36(lH,d),4.42(2H,t),3.03(2H,t),1.87- 1.38(1 7H,m) » &lt;Synthesis Example 5 6 &gt; Synthesis of (E)-2,4-bis((2,2-dimethyl-4,6-dioxo-l,3-dioxane-5) represented by the following formula [115] -subunit)methyl)amino)phenethyl 3-(4-(trans-4-pentylcyclohexyl)propionate [Chem. 96]

Meldronic acid [l] (13.55 g, 69.8 mmol) and orthoformic acid trimethylacetate-100-201240981 [2] (14 g) were placed in a 300 mL four-necked flask and heated to reflux for 2 hours. Thereafter, the compound [114] (13.7% '31.7 mm〇l) was added and heated under reflux for an additional hour. After the completion of the reaction, the solvent was removed by an evaporator and dried to give the compound [115] 22.4 g (yield 95%). 1 Η - NMR ( 4 0 0 Μ H z, CD C1 3,5 PP m ) : U · 6 3 (1 H,d), 11.27(lH,d) - 8.6 8 -8.5 7(2H,m) J 7.4 1 - 7.3 9 (3 H , m) » 7.26- 7.14(4H,m) &gt; 6.36(lH,d) &gt; 4.48(2H,t) &gt; 3.8 0 - 3 . 7 6 (3 H , m &gt; 3.48(2H,d) , 3.34(lH,s) , 3.l2(2H,d) » 2.47(2H,t), 1.86(6H,d)« 1 .77- 1.68( 1 0H,m » 1.47- 1.20( 1 0H,m) · 1.06-0.90(5H,m). <Synthesis Example 5 7 &gt; 0)-2,4-bis((2,2-dimethyl- 4,6-dioxo-1,3-dioxane) represented by the following formula [117] was synthesized. -5-subunit)methyl)amino)phenethyl 3-(4-(trans-4-heptylcyclohexyl)phenyl)propionate [Chemical 97]

Meldronic acid [l] (3.43 g, 23.8 mmol) and trimethyl orthoformate [2] (508) were placed in a 10 〇! 111^ four-necked flask, and heated under reflux for 1 hour. Thereafter, the compound Π 16] (5.00 g, 10.8 mmol) was added, followed by heating under reflux for 2 hours. After the completion of the reaction, the solvent was removed by an evaporator and dried to give 8.3 g (yield: 100%). 'H-NMR (400MHz, CDC13, δ ppm): ll_64(lH,d), ll,28(lH,d), 8.70-8.63(2H,m) &gt; 7.61 (lH,d) , 7.45- 7_40( 3H, m), 7.27-7.15 (3H, m), 6_37 (lH, d), 4.46 (2H, t), 3.60 (2H, d), 3. 12 (2H, t), 2.34 (lH, t) , 1.87 (4H, d), 1.85-1.75 (15H, m), 1.4 2 -1 · 3 8 (2 H, m ), 1.33-1.26 (1 OH, m) &gt; 1.07-1 .02 (2H, m), 0.89 (3H, t). <Synthesis Example 5 8 &gt; Synthesis of (E)-3,5-bis((2,2-dimethyl-4,6-dioxo-1,3-di-chew) represented by the following formula [119] Alkan-5-ylidenemethyl)amino)phenyl 3-(4-(trans- 4-pentylcyclohexyl)phenyl)propionate [Chem. 98]

Meldronic acid [l] (H.31 g, 78.5 mmol) and trimethyl orthoformate [2] (150 g) were placed in a 300 mL four-necked flask and heated to reflux for 1 hour. Thereafter, the compound [1 18] (15.00 g, 35.7 mmol) was added, followed by heating under reflux for 2 hours. After the completion of the reaction, the solvent was removed by an evaporator and dried to give a compound [119] 25.3 g (yield: 99%). 1 H-NMR (400 MHz, CDC 13 , 5 ppm) : 1 1 · 3 0 (2 Η, d) ' 8.66 (2H, d), 7.74 (lH, d), 7.49 (2H, d) ' 7.26-7.19 ( 4H,m), -102- 201240981 7.08(lH,d),6.49(lH,d),5.27(2H,s),2.49(lH,t),1.93-1.77(18H,m),1.65-0.87( 1 4H, m). &lt;Synthesis Example 59&gt; (E)-3,5-bis((2,2·dimethyl-4,6-dioxo-1,3-dioxane) represented by the following formula [121] was synthesized. -5-subunit)methyl)amino)phenyl 3-(4-(trans-4'-pentyl[1,1,-bis(cyclohexyl)]-4-yl)phenoxy)propanoic acid Ester

Meldronic acid [l] (1.83 g, 12.7 mmol) and trimethyl orthoformate [2] (45 g) were placed in a 200 mL four-necked flask and heated to reflux for 1 hour. Thereafter, the compound [120] (3.00 g, 5.8 mmol) was added, followed by heating under reflux for 2 hours. After the completion of the reaction, the solvent was removed by an evaporator and dried to give 4.8 g (yield 100%) of compound [121]. 1 H-NMR (400 MHz, CDC 13 , δ ppm) : 11.27 (2H,d) » 8.64 (2H,d) '7.85 (lH,d) '7.21 (2H,d),7.14(2H,d),7.1〇 -7.09(lH,m) ' 7.00-6.98 (2H,m),5.57(IH,d),5.19(2H,s), 3.81(1H,s) ' 3.47-3.46(lH,m),3.33(4H , s), l_9i. 1.72 (20H, m) ' 1.41-0_84 (13H, m). <Synthesis Example 60 &gt; (E)_4_(((2,2_Dimethyl_4,6-di-103-201240981 oxy-1,3·dioxane) represented by the following formula [123] was synthesized. 5-substyl)methyl)amino)phenyl 3-(4-(trans-4.pentylcyclohexyl)phenyl)propionate [100]

Meldronic acid [l] (3.6 g, 25 mmol) and orthoformic acid monoacetate [2] (90 g) were placed in a 200 mL four-necked flask, heated to reflux for 1 hour, and then compound [122] (9.00) was added. g, 23 mmol), and heated to reflux for 2 hours. After the reaction was completed, the solvent was removed by an evaporator and dried to give 12.1 g (yield: 99%) of compound [123]. 1H-NMR (400MHz, DMSO-d6, δ ppm): 1 1.28 (lH,d) &gt; 8_61(lH,d),7_85(lH,d),7.52(2H,d),7.29-7.26 (5H, m), 6.54 (lH, d), 2.52 (lH, t), 1.89 (4H, d), 1.57-0.89 (22H, t). &lt;Synthesis Example 6 1 &gt; Synthesis of (£)-4-(((2,2-dimethyl-4,6-dioxo-1,3.dioxane) represented by the following formula [125] 5. Subunit)methyl)amino)phenethyl 3_(4-(trans-4-pentylcyclohexyl)phenyl)propionate [Chem. 101] h2n

-104- [125] 201240981 Meldronic acid [l] (2.00 g, Mmmol) and trimethyl orthoformate [2] (75 g) were placed in a 200 mL four-necked flask, and heated under reflux for 1 hour. Thereafter, the compound [124] (4.92 g, 13 mmol) was added, and the mixture was refluxed for 2 hr. After the completion of the reaction, the solvent was removed by an evaporator and dried to give the compound [125] 7.16 g (yield 100%). 1H-NMR (400MHz, CDC13, δ ppm): 1 1.24 (1 H,d), 8.62 (lH,d), 7.63 (lH,d), 7.44 (2H,d), 7.32 (2H,d), 7.24 -7.19(4H,m) , 6.36(lH,d) ,4.42(2H,t) ,3.03(2H,t), 2.48(lH,t),1.87(4H,d),1.76(6H,s), 1.49-1.21 (lH, m), 1.07-1.00 (2H, m), 0.97 (3H, t). <Synthesis Example 62 &gt; 5-(((4)-dodecylphenyl)amino)-methyl-2,2-dimethyl-1,3-di) represented by the following formula [127] Oxane-4,6-dione [Chem. 102]

Meldronic acid [l] (12.13 g, 84.2 mmol) and trimethyl orthoformate [2] (100 g) were placed in a 200 mL four-necked flask and heated to reflux for 1 hour. Thereafter, the compound [126] (20.00 g, 76.5 mmol) was added, followed by heating under reflux for 2 hours. After completion of the reaction, the solvent was removed by an evaporator and dried to give Compound [1 2 7 ] 3 1 .1 g (yield 98%). S· -105- 201240981 1H-NMR (400MHz, DMSO-d6, δ ppm) : 11.24(lH,d)' 8.50(lH,d), 7.41(2H,d), 7.20(2H,d),2.53 ( 2H,t), 2.27- 2.46(1 H,m) &gt; 1.63(6H,s) , 1 · 5 2 - 1.4 7 ( 2 H,m ) ' 1.29- 1.86(1 7H,m),0.83(3H , t). &lt;Synthesis Example 63 &gt; 5-((4-(1,1,2,2,3,3,4,4,5,5, 6,6,7) represented by the following formula [129] was synthesized. , 7,7-pentadecafluoroheptyl))amino)methyl)-2,2-dimethyl-1,3-dioxane-4,6-dione [Chem. 103] oxime. H2n j〇tC7Fis Ο [128] CH(OMe)3 Human 〇H [2] j〇rC7Fl5 [129] Will Meldronic acid [l] (3.10g, 22mmol) and trimethyl orthoformate [2] ( 20 g) was placed in a 200 mL four-necked flask and heated to reflux for 1 hour. Thereafter, the compound [128] (10.00 g, 19.6 mmol) was added, and the mixture was heated under reflux for further 2 hours. After the reaction was completed, the solvent was removed by an evaporator and then dried to give the compound [129] 12.6 g (yield 100%). 1H-NMR (400MHz, DMSO-d6, ¢5 ppm): 1 1.60( 1 H,d) » 8.70(lH,d), 7.68(2H,d),7.39(2H,d),l_77(6H,s ). [Synthesis of Polyamide or Polyimine and Preparation of Its Solution] The codes used below are as follows. -106- 201240981 (tetracarboxylic dianhydride) CBDA : 1,2,3,4-cyclobutane tetracarboxylic dianhydride BODA: ring [3,3,0] 辛院-2,4,6,8- Tetracarboxylic dianhydride [化104]

CBDA (diamine) p-PDA : p-phenylenediamine DDM: 4,4'-diaminodiphenylmethanehexyl)phenoxy] PCH7AB : 1,3-diamino-4-[4 -(trans-4-n-heptylcyclobenzene [105]

H2n^~\-nh2 j〇^〇l h2n々^ , ^nh2 p-PDA DDM

(CH2)6CH3 (organic solvent) NMP: N-methyl-2-pyrrolidone BCS: butyl cellosolve-107-201240981 (measurement molecular weight) In the present example, a polymer (polyproline, polyimine, etc.) The molecular weight was measured by the following method using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Shod Ex Co., Ltd., and a column (KD-803, KD-805) manufactured by Shodex Co., Ltd.

Column temperature: 50 ° C Dissolution: N,N-dimethylformamide (additive, lithium bromide-hydrate (LiBr · H2O) 30 mmol / L, phosphoric acid anhydride crystals (0 - phosphoric acid) 3 〇 mm 〇 l/ L, tetrahydrofuran (THF) 10ml/L) Flow rate: 1.0 mL/minometric line preparation column sample: TSK standard poly epoxy plant made by Dongsuo Company (molecular weight about 900,000, 150,000, 1〇〇, 〇〇〇, 30, 〇〇〇), and Polyethylene glycol (molecular weight of about 12, 4,000, 4,000, 1,000) ° (measured by yttrium imidation rate) in this example, The ruthenium imidization ratio of the polyimine was measured by the following method. About 2 mg of polyimine powder was placed in an NMR sample tube, and about 53 ml of deuterated dimethyl hydrazine (DMS0-d6, 0.05% TMS mixture) was added, and ultrasonic waves were applied to completely dissolve it. The 500 MHz proton NMR of the solution was measured by an NMR measuring apparatus. The imidization rate is based on the protons from the unaltered structure before and after the imidization, using the peak product of the protons to calculate the enthalpy, and the -108- from the proline in the vicinity of 1 O.Oppm. 201240981 The proton peak product of the NH group is obtained by the following formula. Further, in the following formula, x is the proton peak product of the NH group derived from proline, and y is the peak product of the reference proton. When α is a poly-proline (the imidization ratio is 〇%), The ratio of the number of reference protons to the protons of the proline.

Ruthenium amination rate (%) = (1 - α · x / y) xlOO &lt; Synthesis of polyimine (PAA-1) and preparation of the solution &gt; DDM 7.93g (40mmol), NMP (20g) was added In a 100 mL four-necked flask, after cooling, it was cooled to about 10 ° C, and then c BDA 7.4 6 g (38 mmol) of Ν ( P (67 g) slurry solution was added, and the mixture was returned to room temperature and reacted under nitrogen for 6 hours. A solution of polyamine acid (PAA-1) at a concentration of 15% by mass. 88 g of a solution of the polyamine acid (PAA-1) concentration of 15% by mass was transferred to a 200 mL Erlenmeyer flask, and 87.6 g of NMP and 43.8 g of BCS were added to prepare a polyglycine (PAA-1) to be 6 mass%. A solution of polyamido acid (PAA-1) having a NMP of 74% by mass and a BCS of 20% by mass. The polyammonium acid (PAA-1) has a number average molecular weight of 12,081 and a weight average molecular weight of 30,449 ° &lt;synthetic polyglycine (PAA-2) and preparation of the solution&gt;

S 8.65 g (80 mmol) of p-PDA and NMP (49 g) were placed in a 200 mL four-necked flask, dissolved, and cooled to about 10 ° C. Then, CBDA 14.1 g (72 mmol) of NMP (80 g) slurry solution was added, and returned to the chamber. After the reaction, the mixture was reacted under nitrogen for 6 hours to obtain a solution of poly-proline (PA A-2) at a concentration of 15% by mass of -109-201240981. 125 g of a solution of polypyridic acid (PAA-2) at a concentration of 15 mass%/〇 was transferred into a 300 mL Erlenmeyer flask, and NMP 118, 5 g, and BCS 6 (K9g diluted) were added to prepare polylysine (PAA-2). A polyammonic acid (PAA-2) solution having 6 mass%, NMP of 74 mass%, and BCS of 20 mass%. The polyamine acid (PAA-2) had a number average molecular weight of 7.609 and a weight average molecular weight of 15,837. &lt;Synthesis of polyaminic acid (PAA-3) and preparation of the solution> 8.05 g (74 mmol) of p-PDA, 2.13 g (5.6 mmol) of PCH7AB, and NMP (118 g) were dissolved in a 200 mL four-necked flask, and then cooled to about L〇 ° C, then add CBDA 14 · 1 g (72mmol) of NMP (100g) slurry solution, return to room temperature and react under nitrogen for 6 hours to obtain the concentration of poly-proline (PAA-3) 10 234 g of a solution of the polyamine acid (PAA-3) at a concentration of 10% by mass was transferred to a 300 mL Erlenmeyer flask, and 70.8 g of NMP and 76.2 g of BCS were added thereto to prepare polyglycine (PAA-3). 6 mass% of a polyamido acid (PAA-3) solution having a NMP of 74% by mass and a BCS of 20% by mass, the polyaminic acid (PAA-3) having a number average molecular weight of 6,092 and a weight average molecular weight of 12, 〇 〇2 &lt;Synthesis of soluble polydecanoic acid (SP 1-1) and preparation of the solution&gt; BODA (16.9 g, 68 mmol), p-PDA (6.8 g &gt; 63 mmol), PCH7 AB in a 300 mL four-necked flask 10.3 g, 27 mmol) was mixed into -110-201240981 NMP (100 g), and after reacting at 40 ° C for 3 hours, CBDA (4.1 g, 21 mmol) and NMP (52 g) were added, and reacted at 40 ° C for 3 hours to obtain a poly A solution of lysine. After the NMP was added to the polyamic acid solution (130 g) and diluted to 6 mass%, acetic anhydride (16 g) and pyridine (12 g) for the ruthenium catalyst were added, and the reaction was carried out at 80 °C. The reaction solution was poured into methanol (1.6 L), and the obtained precipitate was collected by filtration, and the precipitate was washed with methanol and dried under reduced pressure at 1 ° C to obtain a polyimine powder (SP1-1). The polyamidimide has a ruthenium iodide ratio of 54%, a number average molecular weight of 18,300, and a weight average molecular weight of 45,300. The amount of carboxyl groups in the polyimine is 0.92 relative to the unit of retrievation. (98 g) 'BCS (90 g) was added to the polyimine powder (SPI-1) obtained above (12.0 g), and stirred at 80 ° C for 40 hours to dissolve to prepare soluble polyimine (SPI-1). Solution. [Preparation of a coating liquid for forming a polyimide film (liquid crystal alignment agent)] &lt;Examples 1 to 1&gt; Each of the compounds described in the following Table 1 prepared by the above synthesis examples of the compound for modification, The above-prepared polyglycine (PAA-1) was added in an amount of 1 mol% relative to the solid component of the polyaminic acid (p A A-1) solution (i.e., polyamine acid (PAA-1)). In the solution (l〇.〇g), the mixture was stirred at room temperature (25 ° C) to obtain a uniform solution, and the coating liquids for forming the polyimide film of Examples 1 to 10 were prepared (for forming a functional polymer film) Coating liquid) ^ -111 - 5 201240981 [Table 1] Compound for polyaminic acid modification. Example 1 PAA-1 Synthesis Example 4 [11] Example 2 PAA-1 Synthesis Example 5 [13] Example 3 PAA - 1 Synthesis Example 6 [15] Example 4 PAA-1 Synthesis Example 7 [17] Example 5 PAA-1 Synthesis Example 9. [2 1] Example 6 PAA - 1 Synthesis Example 1 7 [3 7] Example 7 PAA-1 Synthesis Example 1 8 [3 9] Example 8 P AA-1. Synthesis Example 2 2 [4 7] Example 9 PAA-1 Synthesis Example 2 3 [49] Example 1 〇PAA-1. Synthesis Example 2 4 [5 1] <Examples 11 to 45> Each of the compounds for modification The compound described in the following Table 2 produced in the above Synthesis Example is described in Table 2 below with respect to the solid component of the polyacrylic acid (PAA-1) solution (i.e., polyamine acid (PAA-1)). The amount of the mixture is added to the polyamic acid (PAA-1) solution (10.Og) prepared above, and stirred at room temperature to obtain a homogeneous solution, and the polyimine film of the examples 1 to 45 is prepared. Coating liquid. -112- 201240981 [Table 2] Compound addition amount (wt%) of polyamine acid modification Example 1 1 PAA-1 Synthesis Example 2 4 [5 1] 1 Example 1 2 PAA-1 Synthesis Example 2 4 [5 1] 3 Example 1 3 PAA-1 Synthesis Example 2 4 [5 1] 5 Example 1 4 PAA-1 Synthesis Example 2 4 [5 1] 1 0 Example 1 5 PAA-1 Synthesis Example 2 4 [5 1] 2 0 Bao Shi Example 1 6 PAA-1 Synthesis Example 2 2 [4 7] 1 Example 1 7 PAA-1 Synthesis Example 2 2 [4 7] 3 Example 1 8 PAA-1 Synthesis Example 2 2 [4 7] 5 Example 1 9 PAA-1 Synthesis Example 2 2 [4 7] 10 Example 2 0 PAA-1 Synthesis Example 2 2 [4 7] 2 0 Example 2 1 PAA-1 Synthesis Example 2 3 [4 9] 1 Example 2 2 PAA-1 Synthesis Example 2 3 [49] 3 Example 2 3 PAA-1 Synthesis Example 2 3 [4 9] 5 Example 2 4 PAA-1 Synthesis Example 2 3 [4 9] 10 Example 2 5 PAA-1 Synthesis Example 2 3 [4 9] 2 0 Example 2 6 PAA-1 Synthesis Example 2 6 [5 5]. 1 Example 2 7 P AA-1 Synthesis Example 2 6 [5 5] 3 Example 2 8 PAA-1 Synthesis Example 2 6 [5 51 5 Example 2 9 P AA-1 Synthesis Example 2 6 [5 5] 10 Example 3.0 P AA-1 Synthesis Example 2 6 [5 5] 2 0 Example 3 1 P AA-1 Synthesis Example 2 8 [5 9] 1 Example 3 2 PAA-1 Synthesis Example 2 8 [5 9] 3 Example 3 3 PAA-1 Synthesis Example 2 8 [5 91 5 Example 3 4 PAA-1 Synthesis Example 2 8 [5 9] 10 Example 3 5 P AA-1 Synthesis Example 2 8 [5 91 2 0 Example 3 6 PAA- 1 Synthesis Example 3 3 [6 81 1 Example 3 7 P AA-1 Synthesis Example 3 3 [6 8] 3 Example 3 8 PAA-1 Synthesis Example 3 3 [6 8] 5 Example 3 9 P AA-1 Synthesis Example 3 3 [6 8] 10 Example 4 0 PAA-1 Synthesis Example 3 3 [6 8] 2 0 Example 4 1 PAA-1 Synthesis Example 3 4 [7 0] 1 Example 4 2 PAA-1 Synthesis Example 3 4 [7 0] 3 Example 4 3 P AA-1 Synthesis Example 3 4 [7 0] 5 Example 4 4 PAA-1 Synthesis Example 3 4 [7 0] 10 Example 4 5 PAA-1 Synthesis Example 3 4 [7 0] 2 0 <Examples 46 to 57 &gt; Compound 3 -113-201240981 described in the following Table of the above compound produced in Synthesis Example modification with respect to the solid content of the solution (i.e., polyamide acid (polyamide acid (PAA_2)?八八_2)), in an amount of 1〇m〇i%, added to the poly-proline (PAA-2) solution (lo.og) prepared above, and stirred at room temperature to obtain a homogeneous solution 'Modification Example 46 A coating liquid for forming a polyimide film to 57. [Table 3] Compound for polyaminic acid modification Example 4 6 PAA-2 Synthesis Example 4 [11] Example 4 7 PAA-2 Synthesis Example 5 [13] Example 4 8 PAA-2 Synthesis Example β [15] Example 4 9 --- PAA-2 Synthesis Example 7 [17] Example 5 〇PAA-2 Synthesis Example 9 [2 1] Example 5 1 PAA-2 Synthesis Example 1 7 [3 7] Example 5 2 PAA -2 Synthesis Example 1 8 [3 9] Example 5 3 PAA-2 Synthesis Example 2 2 [4 71 Example 5 4 PAA-2 Synthesis Example 2 3 [4 9] Example 5 5 PAA-2 Synthesis Example 2 4 [5 1]. Example 5 6 PAA-2 Synthesis Example 2 7 [5 7] Example 5 7 PAA-2 Synthesis Example 2 8 [5 9] &lt;Example 5 8 to 7 1 &gt; The compound described in the following Table 4 produced by the above synthesis example of the compound is described in Table 4 with respect to the solid component of the polyaminic acid (PAA-3) solution (i.e., polyamine acid (PAA-3)). The amount of the mass% was added to the polyamic acid (PAA-3) solution (40.0 g) prepared above, and stirred at room temperature to obtain a homogeneous solution to prepare the polyimine film of Examples 58 to 71. Coating solution. -114-201240981 [Table 4] Compound addition amount (wt%) for polyaminic acid modification Example 5 8 PAA-3 [6 3] 5 Example 5 9 PAA-3 [6 3] ------ -: _ 1 0 Example 6 0 PAA-3 [6 3] 2 0 Example 6 1 PAA-3 [6 3] 3 0 Example 6 2 PAA-3 [6 3] 5 0 Example 6 3 PAA- 3 [6 3] 7 0 Example 6 4 PAA-3 [6 3] 10 0 Example 6 5 P AA- 3 [6 5] 5 Example 6 6 PAA-3 [6 5] 10 Example 6 7 PAA -3 [6 5] 2 0 Example 6 8 PAA-3 [6 5] 3 0 Example 6 9 PAA-3 [6 5] To Example 7 〇PAA — 3 [6 5] 7 0 Example 7 1 P AA-3 [6 5] 10 0 <Examples 72 to 74 &gt; Each of the compounds described in the above Synthesis Examples prepared by the above-mentioned synthesis examples of the compounds for modification, with respect to poly-proline (PAA- 2) The solid content of the solution (i.e., polyamic acid (P AA-2)) is in the proportions shown in Table 5 below, and the polylysine (PAA-2) solution prepared above is added (7〇. In 〇g), the mixture was stirred at room temperature to obtain a homogeneous solution, and the coating liquids for forming polyimine films of Examples 72 to 74 were prepared. [Table 5] Amount of the compound for polyamine acid modification (wt%) Example 7 2 PAA-2 Synthesis Example 2 3 [49] 10 Example 7 3 PAA-2 Synthesis Example 2 3 [49] 15 Example 7 4 PAA-2 Synthesis Example 2 3 [4 9] 2 0 -115-201240981 <Examples 75 to 90> Each of the compounds described in the following Table 6 produced by the above-mentioned synthesis examples of the compound for modification is used in relation to The solid component of the soluble polyimine (SP 1-1) solution (ie, soluble polyimine (SPI-1)) is in the proportions shown in Table 6 below, and the soluble polyimine prepared above is added. In the (SP 1-1) solution (10. g), the mixture was stirred at room temperature to obtain a homogeneous solution, and the coating liquids for forming polyimine films of Examples 75 to 90 were prepared. [Table 6] Addition amount (wt%) of the soluble type for the soluble polyimine modification Example 7 5 SP I-1 Synthesis Example 5 [13] 10 Example 7 6 SPI - 1 Synthesis Example 6 [15] 10 Implementation Example 7 7 SP I - 1 Synthesis Example 7 [17] 10 Example 7 8 SP I - 1 Synthesis Example 9 [2 1] 10 Example 7 9 SP I -1 Synthesis Example 1 3 [2 9] 10 Example 8 0 SPI - 1 Synthesis Example 1 6 [3 5J 10 Example 8 1 SPI - 1 Synthesis Example 1 7 [3 7] 1 0 Example 8 2 SP I - 1 Synthesis Example 1 8 [3 9] 10 Example 8 3 SPI-1 Synthesis Example 2 2 [4 7] 10 Example 8 4 SP 1-1 Synthesis Example 2 3 [4 9] 10 Example 8 5 . SPI - 1 Synthesis Example 2 4 [5 1] 10 Example 8 6 SP I - 1 Synthesis Example 3 2 [6 6] 10 Example 8 7 SPI - 1 Synthesis Example 3 0 [6 3] 5 Example 8 8 SP I - 1 Synthesis Example 3 0 [6 3] 10 Example 8 9 SP I - 1 Synthesis Example 3 0 [6 3] 3 0 Example 9 0 SPI - 1 Synthesis Example 3 0 [6 3] 5 0 &lt;Examples 91 to 1 02 and Comparative Example 1 &gt; [Crosslinking effect Confirmation test (release test)] The coating liquids for forming the polyimide film of the above Examples 75 to 86 were spin-coated (2500 rpm / 30 seconds) on a ruthenium circuit board, and placed. 2 3 0 art hot plate is baked for 30 minutes to form a coating film [al]. The film thickness of the obtained coating film [al] was measured using a Suffolk ET4000M company. Next, the circuit board of -116-201240981 film [al] will be installed again on the spin coater, and the NMP will be completely covered with the circuit board and left to stand for 60 seconds. Then spin dry NMP (1500 rpm / 30 seconds). The film was fired on a hot plate at 100 ° C for 30 seconds, and the residual film was used as a coating film [0.2]. The film thickness of the coating film [a2] was measured again, and the residual film ratio was calculated by the following calculation formula. In Comparative Example 1, the same operation was carried out on the above-prepared soluble polyimine (SPI-1) solution, that is, the soluble polyimine solution containing no modification compound represented by the above formulas [A] to [D]. , calculate the residual film rate. The results are shown in Table 7. Residual film rate (%) = film thickness of coating film [a2] / film thickness of coating film [al] X100 From the results, it was confirmed that a coating liquid for forming a polyimide film using a compound for adding a modification (liquid crystal alignment) The treatment agent) can improve the solvent resistance of the coating film (polyimine film). Therefore, the compound for modification is introduced into the soluble polyimine. Further, in Examples 75 to 85 in which the compound for modification represented by the above formula [A] having two or more Meldronic acids was used, in particular, the residual film ratio was high. Therefore, it is estimated that the soluble polyimine can be crosslinked by the modifying compound represented by the above formula [A]. Further, by appropriately selecting the compound for modification represented by the above formula [A], it was confirmed that the solubility of the coating film can be controlled relatively freely. Similarly, after the release film test was carried out using the coating film formed by using the coating liquid for forming a polyimide film of Examples 1 to 74 and Examples 87 to 90, when the compound for the modification was not added, the residue was improved. Since the film ratio was confirmed, it was confirmed that the solvent resistance of the polyimide film was improved by using the coating liquid for forming a polyimide film with the compound for modification. S-. -117- 201240981 [Table 7] . Coating solution for forming a polyimide film. Film 丨a 1] MM (nm) Coating film ia2] (nm) Rate (%) Implementation Example No. Modified 潍 Example 9 1 » Example 75 Synthesis Example 5 [1 3] 18 0 14 3 7 9.4 Example 9 2 Example 7 6 Synthesis Example 6 [15] 1 84 147 7 9.9 Example 9 3 Example 7 Synthesis Example 7 [1 7] 16 0 15 1 94. 2 Example 9 4 Example 7 8. Synthesis Example 9 [2 1] 16 5. 15 2 9 2.1 Example 9 5 Example 7 9 Synthesis Example 1 3 [2 91 14 9 14 0 94. 6 Example 9 6 Example 8 0 Synthesis Example 1 6 [3 5] 1.4 7 10 7 7 2. 8 Example 9 7 Example 8 1 Synthesis Example 1 7 [ 3 7] 1 24 6 9 5 5.7 Example 9 8 Example 8 2 Synthesis Example 1 8 [3 9] 16 4 10 2 62. 2 Example 9 9 Example 8 3 Synthesis Example 2 2 [4 7] 17 7 111 6 2. 7 Example 1Q 0 Example 8 4 Synthesis Example 2 3 [4 91 17 0 10 4 6 1. 2 Example 10 1 Example 8 5 Synthesis Example 2 4 [5 1] 17 3 113 6 5.3 Implementation Example 1 0 2 Example 8 6 Synthesis Example 3 2 16 6] 146 7 3 50. 〇Comparative Example 1 - None 15 1 0 No residual film [Production of liquid crystal alignment film and liquid crystal cell] The coating liquid (liquid crystal alignment agent) for forming a polyimide film prepared in each of the Examples was prepared, and a liquid crystal cell was produced by the following method. The coating liquid (liquid crystal alignment agent) for forming a polyimide film is 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, and then baked at a certain degree. The film was formed to have a film thickness of 10 nm. Thereafter, using a brushing device having a roll diameter of 1 to 20 nm, the surface of the coating film is brushed with artificial silk using a certain brushing condition, and the liquid crystal alignment by brushing is performed.

The substrate of the liquid crystal alignment film V is attached. In addition, the amount of exposure is changed from linear polarized UV light (UV wavelength 313 nm, irradiation intensity 8.0 mW/cnT2) between OmJ and 1000 mJ, and is irradiated onto the surface of the coating film by a direction inclined by 40° with respect to the normal line of the sheet. It is processed by the liquid crystal alignment. The method of modulating the linear polarized UV is to pass the ultraviolet light of the high pressure mercury lamp through a 313 nm band pass filter and then through a 313 nm polarizing plate. -118- 201240981 Prepare two substrates of this type of liquid crystal alignment film with liquid crystal alignment processing. Spread a 6μηι modulator on one of the liquid crystal alignment films and print the encapsulant on top of it. The substrates are bonded in such a manner that the brushing directions are parallel to each other in a liquid crystal alignment film (anti-parallel liquid crystal cells 'Examples 103 to 133), and are bonded in a straight manner (twisted nematic liquid crystal cell, Examples 1 74 to 206, Example 3 22 to 3 43 and Examples 344 to 3 50), in addition, the UV-irradiated material is attached in such a manner that the direction of polarization of the irradiation is parallel (vertical alignment type anti-parallel liquid crystal cell, Example 2〇7 to 209, Examples 210 to 321), wherein the hardening encapsulant is used to make an empty cell. The liquid crystal MLC-20〇3 (manufactured by Mercury Co., Ltd.) was injected into the antiparallel liquid crystal cell or the liquid crystal MLC-2003 (manufactured by Murku Co., Ltd.) to which the chiral agent was added, with respect to the empty cell. The twisted nematic liquid crystal cell is injected, or liquid crystal MLC-6608 (manufactured by Murku) is injected into the vertical alignment type anti-parallel liquid crystal cell, and then the injection port is packaged to obtain respective liquid crystal cells. [Evaluation of Liquid Crystal Cell] The physical properties of each of the obtained liquid crystal cells and the method of evaluating the characteristics are as follows. Further, the total of the substrate, the baking conditions, and the brushing conditions of the liquid crystal alignment film and the liquid crystal cell produced in each measurement and evaluation are as follows. <Example 1 〇3 to 133 and Comparative Examples 2 to 4 &gt; <Liquid alignment evaluation> With a polarizing plate, the coating for forming a polyimide film prepared by using the respective examples shown in Table 8 was used. After the liquid crystal cell produced by the cloth liquid, the liquid crystal cell is rotated by the backlight-119-201240981 backlight to visually observe the change of light and dark and whether or not the liquid crystal is aligned with the liquid crystal. This is evaluated on the basis of the following criteria. In addition, in the liquid crystal cell produced by the liquid crystal alignment evaluation, the baking condition of the coating film using the glass substrate and the coating liquid for forming a polyimide film is placed on a hot plate heated to 23 ° C. The baking was carried out for 30 minutes, and the brushing conditions were as follows: a roll rotation number of 300 rpm, a roll speed of 50 mm/sec, and an extrusion amount of 0.15 mm. Further, a coating liquid (Comparative Example 2) in which a compound for modifying and a crosslinking agent were not added (Comparative Example 2) and a crosslinking agent to which a commercially available crosslinking agent was added (Comparative Example 3 or Comparative Example 4) was prepared and compared. effect. The results are shown in Table 8. Evaluation criteria ◎: The liquid crystal alignment can be confirmed, and there is no flow alignment. 〇: Although the liquid crystal has an alignment, a number of flow alignments are observed. X: Although the liquid crystal has an alignment, a large amount of flow alignment is observed. [Chem. 06]

Crosslinking agent-1 Crosslinking agent-2 From the results, it was confirmed that, in Comparative Example 3 and Comparative Example 4, when a commercially available crosslinking agent is used, it tends to hinder the alignment of the liquid crystal, but the compound for addition modification of the present invention is used. When a coating liquid for a polyimide film is formed, even if a compound for modifying having two or more Meldron structure sites is used, the alignment property of the liquid crystal is not inhibited, so that the alignment property can be improved depending on the case. . -120- 201240981 [Table 8]

Evaluation result of coating liquid for forming a blister surface Example No. of compounding amount of compound for polyaminic acid modification (wt%) Example 1 0 3 Food application example 1 PAA-1 [11] 1Omo 1 % 〇 Example 10 4 Example 2 PAA-1 [13] 1Omo1 % 〇 Example 1 〇 5 Example 3 PAA-1 [15] 1Omo1 % 〇 Example 1 〇 6 Example 4 PAA-1 [1 7] 1Omo1 % 〇 Example 1 0 7 «Example 5 PAA-1 [2 1] 10 mo 1 % ◎ Example 1 〇 8 Example 6 PAA-1 [3 7] 1Omo 1 % 〇 * Example 1 0 9 Example 7 PAA- 1. 13 9] 1Omo1 % ◎ Example 11 〇 Example 8 PAA-1 [4 7] 1Omo1 % ο Example 1 1 1 Example 9 PAA-1 [4 91 1Omo1 % 〇 Example 1 1 2 Example 1 〇PAA-1 [5 1) 1Omo1 % ◎ Selling Example 1 1 3 Example 1 1 PAA-1 [5 1] 1 wt % ◎ Example 1 1 4 Example 1 2 PAA-1 [5 1] 3wt % ◎ Example 1 1 5 Example 1 3 PAA-1 [5 11 5 wt % ◎ Example 1 1 6 * Example 1 4 PAA-1 [5 11 1 Owt% ◎ Example 1 1 7 Example 1 5 PAA- 1 [5 11 2 0 wt % ◎ Greedy Example 1 1 8 *Example 1 6 PAA-1 [4 7] lwt % 〇9mm 19 Example 1 7 PAA-1 [4 7J 3w t % 〇黉Example 12 0 Example 1 8 PAA-1 [4 7] 5 wt% 〇 Example 12 1 Example 1 9 PAA-1 [471 1 Ow t % ο Example 12 2 Example 2 1 PAA-1 [4 91 lwt % 〇Example 12 3 Example 2 2 PAA-1 [4 9] 3 wt % 〇 Example 12 4 Example 2 3 PAA-1 [4 9] 5 wt % 〇 Example 12 5 Example 2 4 PAA- 1 [4 9] 1 Owt % 〇 Example 12 6 Example 2 6 PAA. — 1 [5 5] lwt% 〇 Example 12 7 Example 2 7 PAA-1 [5 5] 3w t % ο Example 12 8 Example 2 8 PAA-1 [5 5] 5 wt % 〇 Example 12 9 Example 2 9 ΡΛΑ - 1 [5 51 1 Ow t % 〇 Example 13 0 Example 3 1 PAA-1 [5 9] Lwt% ◎ Example 13 1 Example 3 2 P AA-1 [5 9] 3 wt % ◎ Example 13 2 Example 3 3 PAA-1 [5 9] 5 wt % ◎ Example 13 3 Example 3 4 P AA - 1 [5 9] 1 Ow t % 〇Comparative Example 2 A PAA-1 Μ ^\w — 〇Comparative Example 3 A PAA-1 . Crosslinking agent - 1 1 OmoI % X Comparative Example 4 - PAA-1 Crosslinking agent-2 1Omo1 % X &lt;Example 1 3 4 to 1 7 3 and Comparative Examples 5 to 6 &gt; <Brushing resistance evaluation> Using a confocal laser microscope to observe Table 9-1 to Table The surface of the liquid crystal alignment film produced by the coating liquid for forming a polyimide film prepared in each of the examples shown in 9-2 was evaluated on the basis of the following criteria. Further, the substrate is used to heat the glass substrate of the ITO transparent electrode and the coating film for forming the coating liquid for the polyimide film of 201240981 by baking on a hot plate heated to 230 ° C for 30 minutes, and The brushing conditions were produced by a method of a light swing number of 1000 rpm, a roll speed of 50 mm/sec, and a crushing amount of 55 mm. Further, the compound to which the compound for modification was not added (Comparative Example 5 and Comparative Example 6) was prepared to compare the effects. The results are shown in Table 9-1 to Table 9-2. 〇: No slag and brushing were observed. Δ: slag and brushing were observed. X: Film peeling or visual observation of the brushing was confirmed by the results, and Comparative Example 5 and Comparative Example 6 in which no modifying compound was added were compared. When a coating liquid for forming a polyimide film is added by using a compound for modification having two or more Meldronic acid structural sites, the peeling resistance can be improved even if any polymer is used. -122-201240981 [Table 9-1] Coating liquid for forming a polyimide film Example Example No. Polysaccharide-modified compound surface addition amount (Wt%) Example 1 3 4 Example 1 PAA-1 [11] 1Omo 1 % 〇 Example 1 3 5 Example 2 ΡΑΛ-1 [i 31 10 mo 1 % 〇 Example 1 3 6 Example 3 PAA-1 [1 5] 1Omo 1 % 〇 Example 1 3 7 Example 4 PAA-1 [17] 1Omo1 % 〇 Example 1 3 8 Example 5 PAA-1 [2 1] 1Omo 1 % 〇 Example 1 3 9 Example 6 PAA-1 [3 7] 1Omo 1 % 〇 Example 14 0 Example 1 0 PAA-1 [5 1] 1Omo 1 % 〇 Example 141 Example 1 1 PAA — 1 [5 1] 1 wt % 〇 Example 14 2 Example 1 2 PAA-1 [5 1.] 3 wt % 〇 Example 14 3 Example 1 3 PAA-1 [5 1] 5 wt % 〇 Example 14 4 Example 1 4 PAA-1 [5 1] 1 0 wt % 〇 Example 14 5 Example 1 5 PAA-1 [5 1] 2 0 wt % 〇 Example 14 6 Example 1 6 PAA-1 [4 7] 1 wt % 〇 Example 14 7 Example 1 7 PAA-1 [4 7] 3 wt % 〇 Example 14 8 Example 1 8 PAA-1 [4 7] 5 wt % 〇 Example 14 9 Example 1 9 PAA-1 [4 7] 1 0 wt % 〇 Example 1 5 0 Example 2 1 PAA-1 [4 9] 1 wt % 〇 Example 151 Example 2 2 PAA-1 [49] 3 wt % 〇 Example 1 5 2 . Example 2 3 PAA- 1 [4 9] 5 wt % 〇 Example 1 5 3 Example 2 4 PAA-1 [4 9]. 1 0 wt % 〇 Example 1 5 4 Example 2 6 ΡΛΑ-1 [5 5] 1 wt % 〇Example 1 5 5 Example 2 7 PAA-1 [5 5] 3 wt % 〇 Example 1 5 6 Example 2 8 PAA-1 [5 5] 5 wt % 〇 Example 1 5 7 Example 2 9 PAA-1 [5 5] 1 0 wt % 〇 Example 1 5 8 Example 3 1 PAA-1 [5 9] 1 wt % 〇 Example 1 5 9 Example 3 2 PAA-1 [5 9] 3 w ΐ % 〇 Example 1 6 0 Example 3 3 PAA-1 [5 9] 5 wt % 〇 Example 161 Example 3 4 PAA-1 [5 9] 1 0 wt % 〇Comparative Example 5 - PAA- l None — △

S -123- 201240981 [Table 9-2]

The coating liquid for forming a polyimide film was used. Example No. Polyamphenic acid modification compound 雠 addition amount (wt%) Example 16 2 Example 4 6 FAA-2 [11] 1 0w t % Δ Example 16 3 Example 4 7 PAA-2 [1 31 1 Owt% Δ Example 16 4 Example 4 8 PAA-2 (1 5) 1 0 wt % △ Example 16 5 Example 4 9 PAA-2 [17] 1 0w t % △ Example 1 6 6 Example 5 0 PAA-2 12 1] 1 0 wt % 〇 Example 16 7 Example 5 1 PAA-2 [3 7] 1 Ow t % 〇 Example 16 8 Implementation Example 5 2 PAA-2 13 9] 1 Owt % 〇 Example 16 9 Example 5 3 PAA-2. [4 71 1 Owt % Δ Example 17 0 Example 5 4 PAA-2 [4 9] 1 Owt % Example 171 Example 5 5 PAA-2 "[5 1] 1 Owt% 〇 Example 17 2 Example 5 6 PAA-2 15 7] 1 Owt % 〇 Example 17 3 Example 5 7 PAA-2 [ 5 9] 1 0 wt % 〇Comparative Example 6 - PAA-2 None - X <Example 1 74 to 2 06 and Comparative Example 7 &gt; <Measurement of pretilt angle of twisted nematic liquid crystal cell> Charge at 105 ° C The liquid crystal cell prepared by forming the coating liquid for the polyimide film prepared by the respective examples shown in Table 10 for 5 minutes Thereafter, the pretilt angle was measured, and the pretilt angle was measured by the Axo Metrix "Axo Scan" by the Miller matrix method. Further, the liquid crystal cell produced by measuring the pretilt angle of the twisted nematic liquid crystal cell is placed on the substrate using a glass substrate with an ITO transparent electrode and a coating film for forming a coating liquid for a polyimide film. It was baked on a hot plate heated to 23 ot for 30 minutes, and the brushing conditions were as follows: the number of revolutions of the roller was 1000 rpm, the speed was 50 mm/sec, and the amount of extrusion was 0.3 mm. Further, the compound to which the compound for modification was not added (Comparative Example 7) was prepared to compare the effects. The results are shown in Table 10. From the results, it was confirmed that the desired type of pretilt angle can be obtained by appropriately selecting the type and amount of the compound for modification. -124-201240981 [Table 10] Pre-tilt angle of coating liquid for forming polyimide film Example No. Compound for polyamido acid modification (.) Surface addition amount hm) Example 1 7 4 Example 1 1 PAA- 1 [5 1] 1 3. 0 Example 1 7 5 Example 1 2 PAA-1 [5 1] 3 11 7 Example 17 6 Example 1 3 PAA-1 [5 1] 5 2 0 2 Example 1 7 7 Example 14 .PAA-1 [5 1] 10 6 5 4 Example 1 7 8 Example 1 5 PAA-1 1 1 1 2 0 8 7 2 Example 17 9 Example 1 6 PAA-1 [4 7] 1 2. 9 Example 18 0 Example 1 7 PAA-1 1 7 7] 3 4. 4 Example 18 1 Example 1 8 PAA-1 [4 7] 5 6. 8 Example 18 ? 19 PAA-1 [47] 10 3 5· 3 Example 18 3 Example 2 0 PAA-1 [4 7] 2 0 5 4. 0 Example 184 Example 2 1 PAA- 1. (4 9] 1 2 6 Example 18 5 Example 2 2 PAA-1 [4 9] 3 3. 8 Example 18 6 Example 2 3 PAA-1 1 9 9] 5 6. 3 Example 18 7 Example 2 4 PAA-1 [4 9] 10 1 5. 2 Example 18 8 Example 2 5 PAA - 1 [4 9] 2 0 4 9· 6 Example 18 9 Example 2 6 PAA — 1 15 5] 1 2. 6 Example 19 0. Example 27 PAA- 1 15 5 3 2. 7 Example 1 9 1 Example 2 8 PAA - 1 [5 51 5 2. 8 Example 1 9 2 Example 2 9 PAA-1 [5 51 10 3. 4 Example 1 9 3 Example 3 0 PAA-1 [5 5] 2 0 6. 6 Example 194 Example 3 1 PAA-1 [5 9] 1 2. 6 Example 1 9 5 Example 3 2 PAA-1 [5 9] 3 2 7 Example 1 9 6 Example 3 3 PAA-1 [5 9] 5 3. 0 Example 1 9 7 Example 3 4 PAA-1 [5 9] 10 3. 1 Example 1 9 8 Example 3 5 ΡΑΛ— 1 [5 9] 2 0 4. 1 Example 19 9 Example 3 6 PAA-1 [6 8] 1 1. 5 Example 2 0 0 Example 3 8 PAA-1 [6 8] 5 1.6 Example 2 0 ]. Example 3 9 PAA-1 [6 8] 10 1. 6 Example 2 0 2 Example 4 0 PAA-1 [6 8] 2 0 1. 7 Example 2 0 3 Example 4 1 PAA-1 [7 0] 1 2. 1 Example 2 0 4 Example 4 3 PAA-1 [7 0] 5 2. 3 Example 2 0 5 Example 4 4 PAA-1 [7 0] 10 2 5 Example 6 0 6 Example 4 5 PAA-1 1 0 0] 2 0 4, 3 Comparative Example 7 - PAA-1 None - 1. 4 <Examples 207 to 2 09 and Comparative Example 8 &gt; Pretilt angle of parallel liquid crystal cell &gt; Heating at 1200 ° C using the various examples shown in Table 11 After forming the liquid crystal cell was made of polyimide coating film of 1 hour, the pretilt angle was measured. The pretilt angle was measured using the Axo Metrix "Axo Scan" in meters -125 - 201240981. Further, the liquid crystal cell produced by measuring the pretilt angle of the antiparallel liquid crystal cell is heated to the baking condition of the glass substrate with the ITO transparent electrode and the coating film for forming the polyimide film. The liquid crystal cell was produced by a method of baking in a hot air circulating oven of 200 ° C for 30 minutes without performing an alignment treatment. Further, a compound (Comparative Example 8) to which no compound for conditioning was added was prepared, and the effects were compared. The results are shown in Table 11. From the results, it was confirmed that when Comparative Example 8 in which the compound for modification was not added, the pretilt angle was remarkably increased by using the coating liquid for forming the polyimide film with the compound for modification. Therefore, when a compound for modification is added, even if the polyimine precursor or the polyimine containing the coating liquid for forming the polyimide film is not introduced into the branched component of the dispersed liquid crystal, the liquid crystal can be vertically aligned. Table 11] Pre-tilt angle of the coating liquid for forming a polyfluorene film (.) Example No. Polyamide-modified compound 喔 Addition amount (3) Example 2 0 7 Example 7 2 PAA- 2 [4 9 10 9 0.0 Example 2 0 8 Example 7 3 PAA-2 [4 91 1 5 9 0.0 Example 2 0 9 Example 7 4' PAA- 2 14 9] 2 0 9 0. 0 Comparative Example 8 - PAA - 2 Jrrr m - 1. 3 &lt;Example 2 1 0 to 32 1 &gt;&lt;Evaluation of liquid crystal alignment and measurement of pretilt angle of antiparallel liquid crystal cell&gt; Use of polarizing plates to hold Tables 12-1 to 12-4 After the liquid crystal cell produced by the coating liquid for forming a polyimide film prepared in each of the examples shown in the above, the liquid crystal cell was rotated from the back surface to illuminate the liquid crystal cell, and the light and dark change and the presence or absence of the liquid crystal were observed by visual observation. Orientation, the result has a good alignment. Thereafter, an alternating voltage of 3 V was applied to the liquid crystal cell to visually observe whether the liquid crystal was aligned -126-201240981. At this time, the evaluation is based on the following criteria In addition, the liquid crystal cell system for liquid crystal alignment is evaluated, and the baking condition of the coating film using the glass substrate and the coating liquid for forming a polyimide film is placed in a hot air circulating oven heated to 20 (TC). After calcination for 30 minutes, the obtained glass substrate with a coating film was subjected to the above-described photoalignment treatment. The evaluation criteria were good: liquid crystal alignment was confirmed, and no flow alignment was poor: although the liquid crystal was aligned, a large amount of flow alignment was observed. Further, the liquid crystal cell prepared by using the coating liquid for forming a polyimide film prepared in each of the examples shown in Tables 12-1 to 12-4 was heated at 120 ° C for 1 hour, and then the pretilt angle was measured. The tilt angle was measured by the Miller matrix method using "Αχ〇Scan" of Axo Metrix Co., Ltd. From the results, it was confirmed that a coating liquid for forming a polyimide film using a compound having a photoreactive branching modification was confirmed ( When the liquid crystal alignment agent is subjected to photo-alignment treatment, good vertical alignment property can be obtained. It is also confirmed that the polarized ultraviolet light is irradiated to the coating liquid for forming a polyimide film of the present invention (liquid crystal distribution) The treatment agent can obtain the ability of liquid crystal alignment with only a slight tilt to the vertical state. It is also confirmed that the pretilt angle can be finely adjusted by controlling the amount of addition and the amount of irradiation. Thus, it is known that the polyimide film of the present invention is formed. The coating liquid (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 is also suitable for a liquid crystal alignment film using a photo alignment method. -127- 201240981 [Table 12-1] For yttrium imide film 1 Liquid irradiation intensity (ni J) Liquid crystal alignment pretilt angle (°) Example No. Surface addition amount _ When voltage is applied when no voltage is applied Example 2 1 0 Example 5 8 [6 3] 5 0 Good defect 9 0. 0 0 Example 2 1 1 Example 5 8 [6 3] 5 2 0 Good good 9 0. 0 0 Example 2 1 2 Example 5 8 [6 31 5 5 0 Good good 9 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Example 2 1 5 Example 5 8 [6 3] 5 4 0 0 Good Good 8 9. 9 4 Example 21 6 Example 5 8 16 3] 5 8 0 0 Good Good 8 9. 9 2 Example 2 1 7 Example 5 8 [6 3] 5 1 0 0 0. Good good 8 9. 8 6 Example 2 I 8 Example 5 9 [6 3] 10 0 Good defect 9 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Example 2 2 1 Example 5 9 [6 3] 1 0 10 0 Good good 8 9. 9 6 Example 2 2 2 Example 5 9 16 3] 10 2 0 0 Good good 8 9. 8 4 Example 2 2 3 Example 5 9 [6 3] 10 4 0 0 Good good 8 9. 8 5 Example 2 2 4 Example 5 9 [6 3] 10 8 0 0 Good good 8 9. 7 7 Example 22 5 Example 5 9 [6 31 1 0 10 0 0 Good Good 8 9. 8 0 Example 2 2 6 Example 6 0 [6 3] 2 0 0 Good defect 9 0. 0 0 Example 2 2 7 Example 6 0 [6 3] 2 0 2 0 Good good 8 9, 8 6 Example 2 2 8 Example 6 0 [6 3] 2 0 5 0 Good good 8 9. 9 0 Example 2 2 9 Example 6 0 [ 6 3] 2 0 10 0 Good good 8 9. 9 7 Example 2 3 0 Example 6 0 [6 31 2 0 2 0 0 Good good 8 9. 9 0 Example 2 3 1 Example 6 〇 [6.3] 2 0 4 0 0 Good good 8 9. 8 9 Example 2 3 2 Example 6 0 16 31 2 0 8 0 0 Good good 8 9. 9 2 Example 2 3 3 Example 6 0 [6 3] 2 0 10 0 0 Good Good 8 9. 8 9 Example 2 3 4 Example 6 1 [6 3] 3 0 0 Good defect 9 0, 0 0 Example 23 5 Example 6 1 [6 3] 3 0 2 0 Good good 8 9. 8 9 Example 2 3 6 Example 6 1 [6 3] 3 0 5 0 Good good 8 9. 9 5 Example 237 Example 6 1 [6 3] 3 0 10 0 Good good 8 9. 8 6 Example 2 3 8 Example 6 1 [6 3] 3 0 2 0 0 Good good 8 9. 8 9 Example 2 3 9 Example 6 1 [6 3] 3 0 4 0 0 Good good 8 9. 8 6 Example 2 4 0 Example 6 1 [6 3] 3 0 8 0 0 Good good 8 9. 9 0 Example 2 4 1 Example 6 1 [6 3] 3 0 10 0 0 Good good 8 9. 9 3 -128 - 201240981 [Table 12-2] Coating liquid for forming a polyimide film. Irradiation intensity (m J) Liquid crystal alignment pretilt angle (. Example No. Surface Addition Amount (wt«) When a voltage is applied when no voltage is applied Example 242 Example 6 2 [6 31 5 0 0 Good Good 9 0. 0 0 Example 243 Example 6 2 [6 3] 5 0 2 0 Good good 8 9. 9 5 Example 2 4 4 Example 6 2 [6 3] 5 0 5 0 Good good 8 9- 8 8 Example 245 Example 6 2 [6 3] 5 0 10 0 Good Good 8 9. 9 2 Example 2 4 6 Example 6 2 [6 3] 5 0 2 0 0 Good good 8 9. 9 8 Example 247 Example 6 2 [6 3] 5 0 4 0 0 Good good 8 9. 9 3 Example 248 Example 6 2 [6 3] 5 0 8 0 0 Good good 8 9. 9 0 Example 2 4 9 *Example 6 2 [6 3] 5 0 10 0 0 Good good 8 9 8 8 Example 2 5 0 Example 6 3 [6 3] 7 0 0 Good defect 9 0. 0 0 Example 2 5 1 Example 6 3 [6 3] 7 0 2 0 Good 圩 good 8 9. 9 5 Implementation tree 2 5 2 Example 6 3 [6 3] 7 0 5 0 Good good 8 9. 9 7 Example 2 5 3 Example 6 3 [6 3] 7 0 10 0 Good good 8 9·. 9 3 Example 2 5 4 Example 6 3 [6 3] 7 0 2 0 0 Good good 8 9. 9 4 Example 2 5 5 Example 6 3 [6 3] 7 0 4 0 0 Good good Good 8 9. 9 5 Example 2 5 6 Example 6 3 [6 3] 7 0 8 0 0 Good good 8 9. 9 2 Example 2 5 7 Example 6 3 [6 3] 7 0 10 0 0 Good Good 8 9. 9 0 Example 2 5 8 Example 6 4 [6 31 1 0 0 0 Good bad 9 0. 0 0 Example 2 5 9 Example 6 4 [6 31 10 0 2 0 Good good 8 9. 9 3 Example 2 6 0 Example 6 4 [6 3] 10 0 5 0 Good good 8 9. 7 4 Example 2 6 1 Example 6 4 [6 3] 10 0 10 0 Good good 8 9. 9 4 Example 2 6 2 Example 6 4 [6 3] 10 0 2 0 0 Good Good 8 9. 9 1 Example 2 6 3 Selling Example 6 4 [6 3] 1 0 0 4 0 0 Good Good 8 9. 8 5 Example 264 Example 6 4 [6 31 10 0 8 0 0 Good good 8 9. 8 2 Example 2 6 5 Example 6 4 [6 3] 10 0 10 0 0 Good good 8 9. 8 1 Implementation Example 2 6 6 Example 6 5 [6 5] 5 0 Good defect 9 0. 0 0 Example 2 6 7 Example 6 5 [6 5] 5 2 0 Good good 8 9. 9 3 Example 268 Example 6 5 [6 5] 5 5 0 Good good 8 9. 9 9 Example 2 6 9 Example 6 5 [6 5]. 5 10 0 Good good 8 9. 9 0 Example 2 7 0 Example 6 5 [6 51. δ 2 0 0 Good good 8 9. 8 9 Example 2 7 1 Example 6 5 [6 5] 5 4 0 0 Good good 8 9〇8 8 Example 2 7 2 Example 6 5 [6 5] 5 8 0 0 Good and good 8 9. 9 2 Example 2 7 3 Example 6 5 [6 5] 5 10 0 0 Good good 8 9. 9 4 -129- 201240981 [Table 12-3] Coating for forming a polyimide film Liquid irradiation intensity (m J) Liquid crystal alignment pretilt angle (. Example No. Addition Amount _ When a voltage is applied when no voltage is applied Example 2 7 4 Example 6 6 [6 5] 10 0 Good defect 9 0. 0 0 Example 275 Example 6 6 [6 5] 1 0 2 0 Good good 8 9. 9 7 Example 2 7 6 Example 6 6 [6 5] 1 0 5 0 Good good 8 9. 9 9 Example 2 7 7 Example 6 6 [6 51 10 10 0 Good and good 8 9. 9 3 Example 2 7 8 Example 6 6 [6 5] 10 2 0 0 Good Good 8 9. 9 2 Example 279 Example 6 6 [6 51 10 4 0 0 Good Good 8 9. 9 4 Example 2 8 0 Example 6 6 [6 51 10 8 0 0 Good Good 8 9. 9 4 Example 2 8 1 Example 6 6 [6 51 1 0 10 0 0 Good Good 8 9. 9 1 Example 2 8 2 Example δ 7 [6 5] 2 0 0 Good. Poor 9 0. 0 0 Example 2 8 3 Example 6 7 [6 5] 2 0 2 0 Good good 8 9. 9 7 Example 2 8 4 Example 6 7 [6 5] 2 0 5 0 Good Good 8 9. 9 0 Example 285 Example 6 7 [6 5] 2 0 10 0 Good Good 8 9. 9 9 Example 2 8 6 Example 6 7 [6 5] 2 0 2 0 0 Good good 8 9. 8 5 Example 28 7 Example 6 7 [6 5] 2 0 4 0 0 Good good 8 9. 8 7 Example 2 8 8 Example 6 7 16 5] 2 0 8 0 0 Good good 8 9* 9 0 Example 2 8 9 Example 6 7 [6 51 2 0 . 10 0 0 Good good 8 9. 8 2 Example 2 9 0 Example 6 8 [6 51 3 0 0 Good bad 9 0. 0 0 Example 29 1 Example 6 8 [6 5] 3 0 2 0 Good good 8 9. 9 2 Jia Shi Example 2 9 2 Example 6 8 [6 51 3 0 5 0 Good good 8 9. 7 9 Example 2 9 3 Example 6 8 [6 5] 3 0 10 0 Good good 8 9. 7 6 Example 2 9 4 Implementation Example 6 8 [6 51 3 0 2 0 0 Good Good 8 9. 9 0 Example 2 9 5 Example 6 8 [6 5] 3 0 4 0 0 Good Good 8 9. 8 7 Example 2 9 6 Example 6 8 [6 5] 3 0 8 0 0 Good good 8 9. 8 7 Example 2 9 7 Example 6 8 [6 5] 3 0 10 0 0 Good good 8 9. 8 3 Example 2 9 8 Example 6 9 [6 5] 5 0 0 Good bad 9 0. 0 0 Example 2 9 9 Example 6 9 [6 5) 5 0 2 0 Good good 8 9. 9 8 Example 3 0 0 Example 6 9 ( 6 5] 5 0 5 0 Good good 8 9. 9 9 Example 3 0 1 Example 6 9 [6 5] 5 0 10 0 Good good 8 9. 9 2 Example 3 0 2 Example 6 9 [6 5 ] 5 0 2 0 0 Good good Good 8 9. 7 7 Example 3 0 3 Example 6 9 [6 51 5 0 4 0 0 Good Good 8 9. 8 6 Example 304 Example 6 9 [6 51 5 0 8 0 0 Good Good 8 9. 8 9 Example 3 〇 5 Example 6 9 16 5) 5 0 10 0 0 Good and good 8 9. 8 8 -130- 201240981 [Table 12-4] Irradiation strength of coating liquid for forming a polyimide film ( m J) ------ LCD alignment _______ foresight (. Example No. Surface Addition Amount _ When a voltage is applied without applying a voltage Example 306 Embodiment 7 0 [6 5] 7 0 0 Good defect 9 0. 0 0 Embodiment 3 0 7 Example 7 0 [6 5] 7 0 2 0 Good Μ & 8 9. 9 0 Example 3 0 8 Example 7 0 [6 5] 7 0 5 0 Good good 8 9. 9 9 Example 309 Example 7 0 [65] 7 0 10 0 Good Good 8 9. 8 9 Example 3 1 0 Example 7 0 [6 5] 7 0 2 0 0 Good "Good 8 9. 8 6 Example 3 1 1 Example 7 0 [6 5] 7 0 4〇〇 Good good 8 9, 8 0 Example 3 12 Example 7 0 [6 5] 7 0 8 〇〇 Good good 8 9. 8 4 Example 3 1 3 Example 7 0 [6 5] 7 0 10 0 0 Good Good 8 9. 8 1 Example 314 Example 7 1 [6 5] 10 0 0 Good bad 9 0. 0 0 Example 3 +1 5 Example 7 1 16 5] 10 0 2 0 Good good 8 9. 9 3 Example 3 1 6 Example 7 1 [6 5] 10 0 5 0 Good 8 9. 9 6 Example 317 Example 7 1 16 5] 10 0 10 0 Good Good 8 9. 9 2 Example 318 Example 7 1 [65] 10 0 2 〇〇 good good 8 9. 9 0 Example 319 Example 7 1 [65] 10 0 4 0 0 Good good 8 9. 8 3 Example 3 2 0 Example 7 1 [6 5] 10 0 8 0 0 Good good 8 9. 7 5 Example 3 2 1 Example 7 1 [65] 10 0 10 0 0 Good 8 9. 7 6 <Example 3 22 to 3 43 and Comparative Example 9> &lt;Measurement voltage holding ratio (VHR) &gt; Measurement The coating for forming a polyimide film prepared by using the respective examples shown in Table 13 was measured. The voltage holding ratio of the initial state of the liquid crystal cell produced by the cloth liquid. The voltage holding ratio is measured by applying a voltage of 4 V to 60 at a temperature of 90 ° C, and measuring the voltage after 16.67 ms to calculate how much voltage can be maintained. In the measurement of the voltage holding ratio, the VHR-1 voltage holding ratio measuring device manufactured by Toyo Denki Co., Ltd. was used. The liquid crystal cell produced by measuring the voltage holding ratio (VHR) was used, and the glass substrate with the ITO transparent electrode was used for the substrate. The baking condition of the coating film for forming the coating film for the polyimide film is to be calcined on a hot plate heated to 203 ° C for 30 minutes, and the brushing condition is a light rotation number of 1000 rpm, and the light speed is 50 mm. /sec, the amount of extrusion is 0.3mm. Further, the compound (Comparative Example 9) in which the compound for modification s -131 - 201240981 was not added was prepared, and the effect was compared. The results are shown in Table 13. From the results, it was confirmed that a coating liquid for forming a polyimide film using the compound for modifying can obtain a voltage holding ratio characteristic which is better than that at the time of no addition. [Table 13] The coating liquid voltage retention ratio (3⁄4) for forming a polyimide film was carried out. Example No. Polyamide modification 4 Hydrate species addition amount Example 322 Example 1 PAA-1 111] 1Omo1 % 6 5. 6 Example 32 3 Example 2 PAA-1 [13] 1 Omo 1 % 6 5. 4 Example 3 2 4 Example 5 PAA-1 [2 11. 1Omo1 % 6 7. 8 Example 3 2 5 Example 6 PAA-1 [37] 1 OmoI % 6 5. 6 Example 3 2 6 Example 7 ΡΛΑ-1 13 9] 1Omo1 % 8 5. 2 Example 3 2 7 _ Example 1 1 PAA — 1 15 1] 1 wt % 6 8. 0 Example 3 2 8 Example 12 PAA-1 [5 1] 3 wt % 7 8. 2 Example 3 2 9 Example 1 3 PAA-1 [5 1] 5w t % 7 7. 8 Example 3 3 0 Example 1 6 P AA-1 147] 1 wt % 8 0. 9 Example 3.3 1 Example 1 7 ΡΑΛ - 1 [4 7] 3 wt % δ 3. 0 Implementation Example 3 3 2 Example 1 8 PAA-1 [4 7] 5 wt % 7 6. 6 Example 3 3 3 Example 2 1 PAA-1 1 149] 1 wt % 7 9. 9 Example 3 3 4 Example 2 2 PAA-1 [49] 3w t % 8 3. δ Example 3 3 5 Example 2 3 P AA-1 [49] 5 wt % 8 2. 1 Example 3 3 6 Example 2 6 PAA-1 [5 51 1 wt % 6 5. 4 real Example 3 3 7 Example 2 7 PAA-1 [5 51 3 wt % 6 0. 4 Example 3 3 8 Example 2 8 PAA-1 [5 5] 5 wt % 6 5. 7 Example 3 3 9 Implementation Example 2 9 PAA-1 [551 1 Ow t % 6 9. 7 Example 3 4 0 Example 3 0 PAA-1 [5 5] 2 0 wt % 6 7 · 4 Example 3 4 1 Example 3 3 PAA - 1 [5 9] .5 wt % 7 3. 4 Example 3 4 2 Example 3 4 P AA-1 [5 9] 1 Owt % 7 4. 5 Example 3 4 3 Example 3 5 PAA - 1 [5 9] 2 0 wt % 7 6. 2 Comparative Example 9 - PAA-1 1 &lt;ftrr m - 5 8. 7 &lt;Example 3 44 to 3 50 and Comparative Example 1 0 &gt; <Estimulated accumulated charge ( RDC) &gt; The twisted nematic liquid crystal cell system prepared by using the coating liquid for forming a polyimide film prepared in each of the examples shown in Table 14 was used at a temperature of 23 ° C to 0 V to 〇. A DC voltage was applied to the V-interval to 1.0 V, and the flicker amplitude level at each voltage of -132 - 201240981 was measured to prepare a calibration curve. After 5 minutes of grounding, an AC voltage of 3.0 V and a DC voltage of 5.0 V were applied, and the flicker amplitude level after one hour was measured, and RDC (Flicker Reference Method) was estimated by comparison with a previously prepared calibration curve. Further, it is estimated that the liquid crystal cell to be used for the measurement of the accumulated charge (RDC) is such that the substrate is formed by using a glass substrate with an ITO transparent electrode and a coating film for forming a coating liquid for a polyimide film. The hot plate was baked on a hot plate at 230 ° C for 30 minutes, and the brushing condition was a roll rotation number of 1000 rpm, a roll speed of 50 mm/sec, and an extrusion amount of 0.3 mm. Further, the compound to which the compound for modification was not added (Comparative Example 1) was prepared, and the effects were compared. The results are shown in Table 14. From this 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 of the compound for modification. [Table 14] Formation of polyimine! Coating liquid RDC for use Example No. Polyhalic acid modification compound apparent addition amount (τηο \ %) Accumulation · (V) Missing 〃 (V) Example 3 4 4 Example 1 PAA-1 [11] 10 &gt; 1 0.6 4 Example 3 4 5 Example 2 PAA-1 [1 3] 10 &gt; 1 0, 3 2 Example 3 4 6 Example 3 PAA-1 [ 1 5] 10 &gt; 1 0.2 8 Example 3 4 7 Example 4 PAA-1 [17] 10 &gt; 1 0.17 Example 3 4 8 Example 5 PAA-1 [2 1 J 10 &gt; 1 0.3 8 Example 34 9 Example 6 PAA-1 [3 7] 10 &gt; 1 0. 42 Example 3 5 0 Example 7 PAA-1 [3 91 10 0.8 2 0. 17 Comparative Example 1.1 〇 - .PAA-1 None - &gt;1 0.4 6 * RDC値* from the DC voltage (DC) after the optical flicker reference method is stopped *Residual RDC after 3 minutes of stopping the DC voltage (DC) <Example 3 5 1 to 3 5 8 and Comparative Example 1 1 &gt; Determination of ion density before and after the aging test Each of the compounds shown in Table 15 prepared by using the compound for modification as a compound with respect to the poly-proline (PAA-1) solution The solid content is s -133- 201240981 The amount shown in Table 15 below, plus Above polyamide acid (PAA-1) solution (10.〇g), the homogeneous solution was stirred at room temperature to prepare a coating solution for forming the film Juxi alkylene amines. Next, the ion density in the initial state (23 ° C) of each of the twisted nematic liquid crystal cells produced by using the coating liquid for forming a polymer film (liquid crystal alignment agent) was measured, and the measurement was carried out for 30 hours at 60 ° C ( Ion density after aging). The ion density measured was an ion density when a triangular wave having a voltage of ±10 V and a number of cycles of 0.01 Hz was applied to the liquid crystal cell. The measurement temperature was 80 °C. The measuring device used the 6245 liquid crystal property evaluation device manufactured by Dongyang Technology Co., Ltd. The results are shown in Table 15. Further, the twisted nematic liquid crystal cell is fired under the conditions of a coating film for forming a coating liquid for a polyimide film by firing on a hot plate heated to 2 ° C for 30 minutes. The twisted nematic liquid crystal cell (Examples 174 to 206) was fabricated in the same manner. Further, the same operation was carried out on the compound to which the compound for modification was not added, and the effect was compared. From the results, it was confirmed that the type and amount of the compound for modification can be appropriately selected, and when it is not added, the ionic impurities in the liquid crystal cell can be greatly reduced. -134- 201240981 [Table 15] Coating liquid ions for forming a polyimide film 3 PC) Polyamide for modification of polyamine 2 3*C 6 or mm. Adding amount (wt %) Example 3 5 1 P AA-1 Synthesis Example 4 8 [9 9] 5 7 1. 2 7 5 17. 7 Example 3 5 2 PAA-1 Synthesis Example 4 8 [9 9] 1 ο 4 6.70 3 4 5. 3 Example 3 5 3 P AA-1 Synthesis Example 4 8 [9 9] 2 0 2 5. 9 2 2 2 1.4 Example 3 5 4 P AA-1 Synthesis Example 4 8 [9 9] 5 0 1 2. 5 5 10 3 8 Example 5 5 5 P AA-1 Synthesis Example 5 0 [10 3] 5 6 1. 17 5 6 1.9 Example 3 5 6 P AA-1 Synthesis Example 5 0 [10 3] 10 6 2. 5 8 4 7 0. 8 Example 3 5 7 PAA-1 Synthesis Example 5 0 [10 3] 2 0 6 2 . 7 6 4 3 0. 3 Example 3 5 8 PAA-1 Synthesis Example 5 0 [10 3] . 5 0 3 5.38 3 3 2. 2 Comparative Example 1 1 P AA-1 - 1 - 10 3.4 9 6 7.2 [Synthesis of Polymer and Preparation of Solution] The symbols used below are as follows. (Monomer) HEMA : 2-hydroxyethyl methacrylate MAA · Methyl propylene flammable acid MMA : Methyl methacrylate CHMI : Cyclohexyl maleimide TEOS : Tetraethoxy decane (polymerization initiator) AIBN : &lt;2,α'-azobisisobutyronitrile (solvent) PGMEA: propylene glycol monoethyl ether CHN: cyclohexane HG: hexanediol BCS : butyl cellosolve 1,3-BDD: 1,3- Butanediol The acrylic acid-based polymer obtained from the following synthesis example and the polyoxyalkylene number-135- 3: 201240981 The average molecular weight Μη and the weight average molecular weight Mw are obtained by using a GPC device manufactured by JASCO Corporation (Shodex ( Registered trademark) KF803L and KF804L, measured in the column (column temperature 40 ° C) at a flow rate of 1 ml / min to dissolve the solvent tetrahydrofuran through the dissolution, and the number average molecular weight Μη and the weight average molecular weight Mw In terms of polystyrene, 値 represents β (commercially available polymer). The following commercially available polymer is prepared by mixing a NMP/BCS (weight ratio of 80:20) solution into a polymer solution having a solid concentration of 6 mass%. Form use. In addition, PSM-4326 is owned by Qunrong Chemical Industry Co., Ltd. Meridian company purchased. In addition, MEK is methyl ethyl ketone.

Polymer — 1 : Poly[(〇-cresy I glycidyl ether)-c〇-formaldehyde] Po I yme r —2 :Poly[N,N'-bis(2,2,6, 6-hexanediamine-co-2, 4-dichloro-6-morpholino-l, 3,5-triazine]

Po I yme r —3 : Poly(Bisphenol A-co-epichlorohydrin)

Po I yme r—4 : Poly(melamine-co-formaldehyde) acrylated, 80 wt% MEK Solution. P ο I yme r- 5 : Novolac resin made by Qunrong Chemical Industry Co., Ltd., PSM-4 3 2 6 &lt;Synthesis Polymer-6 and its solution> MMA with a molar ratio: MAA: HEMA: CHMI=13: 26: 25: 36, MMA, MAA, HEMA and CHMI with PGMEA at a solid concentration of 40% by weight To prepare a solution for the solvent, a polymerization catalyst AIBN was added to the solution, and the mixture was reacted at 80 ° C for 20 hours to obtain a solution of a copolymer (acrylic based polymer). The obtained copolymer had a number average molecular weight Μη of 4,000, a weight average molecular weight Mw of 7,500, and secondly, the obtained solution was diluted with NMP to a solid concentration of -136 to 201240981 5 wt% to obtain an acrylic-based polymer (p〇iymer-6). ) solution. &lt;Synthesis of Polymer-7 and preparation of the solution&gt; The mixed solvent (weight ratio HG: BCS: l, 3-BDO = 65: 30: 5) and TEOS were added to a thermometer equipped with a 'return tube' A solution of the alkoxydecane monomer was prepared in a vial. The solution obtained by premixing the above mixed solvent, water and oxalic acid for the catalyst was dropped into the solution at room temperature for 30 minutes. The solution was stirred for 30 minutes, heated to reflux for 1 hour, and allowed to cool to obtain a concentration of SiO 2 in an amount of 12% by weight. Polyoxane solution. Next, the obtained polyoxysiloxane solution having a concentration of SiO 2 of 12 wt% was diluted with the above mixed solvent to obtain a 5 wt% solution of Pölymer-7. [Production of Liquid Crystal Alignment Film and Liquid Crystal Cell] Each of the compounds shown in Table 16 prepared by using the compound for modification is a solid component (ie, Polymer-Ι to Polymer-7) of the polymer solution. The amount of the ratio described in Table 16 is added to each of the above polymers (Polymer-Pluronium to Polymer-5) solution, Propyl-based polymer (Polymer-6) solution or Polyoxane (Polymer-7) solution. The mixture was stirred at room temperature to form a uniform solution, and a coating liquid for forming a polymer film was prepared. Next, the antiparallel liquid crystal cells each having the coating liquid for forming a polymer film (liquid crystal alignment agent) were heated at 1 °C for 1 hour. The liquid crystal unit was placed on the backlight, and the vertical alignment was visually observed through a polarizing plate. Also, when the vertical alignment is marked as "vertical", when it is not vertically aligned, it is recorded as

S -137- 201240981 "Non-vertical", the results are shown in Table 16. The anti-parallel liquid crystal cell is prepared by using a glass substrate with an ITO transparent electrode in addition to the substrate, and baking conditions of various coating films for forming a polymer film are baked in a hot air circulating oven heated to 200 ° C. The same operation as that of the vertical alignment type anti-parallel liquid crystal cell (Examples 210 to 321) was carried out for 30 minutes without performing the alignment treatment. Further, the same operation was carried out on the compound to which no modification compound was added, and the effect was compared. [Table 16] Coating liquid for forming a polymer film '~* with or without vertical alignment polymer species) Addition amount of electrochemical decoration type (wt*) Example 3 5 9 Po 1 yme r — 1 [5 1] 5 Vertical implementation Example 3 6 0 Polymer-1 [5 1] 10 Vertical Example 3 6 1 P ο 1yme r-1 [5 1] .2 0 Straight Comparative Example 1 2 Polymer-1 None - Non-Vertical Example 3 6 2 P o 1yme r — 2 [5 1] 3 0 Vertical implementation furnace ί 3 6 3 Polymer — 2 [5 1] 4 0 Vertical comparison example 1 3 P ο 1 yme r — 2 None — Non-vertical embodiment 3 6 4 Polymer — 3 [4 9] 2 0 Vertical Embodiment 3 6 5 P ο 1yme r — 3 [5 1] 2 0 Vertical Comparative Example 1 4 P o 1yme r- 3 No __ Non-Vertical Example 3 6 6 Polymer — 4 [ 4 9] 2 0 Vertical Embodiment 3 6 7 P ό 1yme r — 4 [5 1] 5 Vertical Embodiment 3 6 8 P ο 1yme r — 4 [5 1] 10 Vertical Embodiment 3 6 9 P o 1yme r — 4 [5 1] 2 0 Vertical Comparative Example 1 5 P ο 1 y τη er — 4 None — Non-Vertical Example 3 7 0 Polymer-5 [4 9] 5 Vertical Example 3 7 1 Polymer — 5 [49] 1 0 Vertical Embodiment 3 7 2 P ο 1 yme r — 5 [4 9] 2 0 Vertical implementation 3 7 3 Polymer-5 [5 1] 5 Vertical Example 3 7 4 Polymer — 5 [5 1] 10 Vertical Example 3 7 5 Polymer — 5 [5 1] 2 0 Vertical Comparative Example 1 6 Polymer-5 None— Non-Vertical Example 3 7 6 Po lyme r — 6 [4 9] 5 Non-Vertical Example 3 7 7 P o 1 yme r — 6 [4 9] 2 0 Vertical Embodiment 3 7 8 P ό 1 yme, r — 6 [5 1] 10 Vertical. Example 3 7 9 Polymer-6 [5 1] 2 0 Vertical Comparative Example 1 7 Polymer-6 No - Non-Vertical Example 3 8 0 P o 1yme r — 7 [4 9] 5 Vertical Example 3 8 1 Polymer-7 [49] 10 Vertical Example 3 8 2 P o 1yme r- 7 [49] 2 0 Vertical comparison gamma 1 8 Polymer a 7 sister - vertical * * Liquid crystal injection port There is light leakage (ie, non-sag®-138-201240981. It is confirmed from this result that even in any polymer of Polymer-1 to Polymer-6, Comparative Example 1 2 to 1 8 without addition of a modifying compound has no vertical alignment property. However, when a coating liquid for forming a polymer film is added to a compound for modification, vertical alignment property can be obtained by adding an appropriate amount to each polymer. That is, the type and amount of the additive are appropriately selected, and it is confirmed that the vertical alignment unit is easily produced regardless of the type of the basic polymer. Further, since Polymer-7 has vertical alignment without adding an additive, it is not necessary to prepare an additive for the vertical alignment unit, but it is confirmed that the vertical alignment property is improved when the additive is added. &lt;Example 3 8 3 to 401 &gt; Each of the compounds described in the above Synthesis Table prepared by using the compound for modification described above was used as a solid component with respect to polyacrylic acid (Pa plant solution) Polyammonic acid (PAA-1)) is added to the above-prepared polylysine (PAA-1) solution (l〇.〇g) in the proportions shown in Table 17 below, and is disturbed at room temperature. The coating liquid for forming a polyaniline film was prepared by using the homogenous solution's to prepare Examples 383 to 401. -139- 201240981 [Table 17] Polyampinic acid's compounding amount (% by weight) of the compound for modification Example 3 8 3 PAA-1 Synthesis Example 5 6 [115] 10 Example 3 8 4 PAA-1 Synthesis Example 5 6 [115] 15 Example 3 8 5 P AA-1 Synthesis Example 5 6 [115] 2 0 Example 3 8 6 PAA-1 Synthesis Example 5 7 [117] 5 mm 3 8 7 PAA- 1 Synthesis Example 5 7 [117] 10 Example 3 8 8 PAA-1 Synthesis Example 5 7 [117] 2 0 Example 3 8 9 PAA-1 Synthesis Example 5 7 [117] 3 0 Example 3 9 0 P AA-1 Synthesis Example 5 7 [117] 4 0 Example 3 9 1 P AA- 1. Synthesis Example 5 7 [117] 5 0 Implementation Example 3 9 2 PAA-1 Synthesis Example 5 7 [117] 7 0 Example 3 9 3 P AA-1 Synthesis Example 5 8 [119] 5 Example 3 9 4 PAA-1 Synthesis Example 5 8 [119] 6 Example 3 9 5 PAA-1 Synthesis Example 5 8 "119] 7 Example 3 9 6 Γ PAA-1 Synthesis Example 6 0 [12 3] 5 Example 3 9 7 PAA-1 Synthesis Example 6 1 [12 5] 5 Example 3 9 8 P AA-1 Synthesis Example 6 1 [12 5] 7 Example 3 9 9 PAA-1 Synthesis Example 6 1 [12 5 10 Example 4 0 0 PAA-1 Synthesis Example 6 1 [12 5] 15 Example 4 0 1 PAA-1 Synthesis Example 6 1 [12 5] 2 0 &lt;Examples 402 to 403 &gt; The compound described in the following Table 18 produced by the above-mentioned synthesis example is described as a solid component of the polyacrylic acid (paA-3) solution (i.e., polyamine acid (PAA-3) is shown in Table 18). The amount of the mass% was added to the polyamic acid (PAA-3) solution (40.0 g) prepared above, and stirred at room temperature to obtain a homogeneous solution, and the coatings of the polyimine films of Examples 402 to 403 were prepared. Cloth liquid. [Table 18] Amount of addition of compound for polyamic acid modification (wt%) Example 4 0 2 P AA-3 [10 7] 7 0 Example 4 0 3 P AA- 3 [10 7] 10 0 Example 4〇4 to 53 6 &gt; <Evaluation of liquid crystal alignment and measurement of pretilt angle of anti-parallel liquid crystal cell for vertical alignment type] -140 - 201240981 [Production of liquid crystal alignment film and liquid crystal cell] Using the above embodiments 383 to 403 A liquid crystal cell was produced by the following method by preparing a coating liquid (liquid crystal alignment agent) for forming a polyimide film. The coating liquid (liquid crystal alignment agent) for forming a polyimide film is spin-coated on a glass substrate, dried on a hot plate at 80 ° C for 70 seconds, and then placed in a hot air circulation heated to 2 ° C. The oven was baked for 30 minutes to form a coating film having a film thickness of 10 nm. Thereafter, the exposure amount was changed from linear polarized UV light (UV wavelength 313 nm, irradiation intensity 8.0 mW/cnT2) between OmJ and 100 OmJ, and the film surface was irradiated in a direction inclined by 40 ° C with respect to the normal line of the plate. . The method of modulating the linear polarized UV is to pass the ultraviolet light of the high pressure mercury lamp through a bandpass filter of 3 13 nm and then pass through a polarizing plate of 313 nm. Prepare two substrates of the liquid crystal alignment film which are processed by liquid crystal alignment, spread a 6μπι distance adjuster on one of the liquid crystal alignment films, and then print the encapsulant on the liquid crystal alignment film in a face-to-face manner. The direction in which the polarized light is irradiated is applied to the other substrate in parallel with each other, and then the hardening encapsulant is used to form an empty cell. Liquid crystal MLC-6608 (manufactured by Murku Co., Ltd.) was injected into the empty unit ’ 'package injection port' by a vacuum injection method to obtain each of the vertical alignment type anti-parallel liquid crystal cells. Next, the obtained liquid crystal cell was held by a polarizing plate, and the liquid crystal cell was rotated while being irradiated with a backlight from the rear side to visually observe the change in brightness and darkness and whether or not the liquid crystal was aligned in the downward direction, resulting in good alignment. Thereafter, an alternating voltage of 3 V was applied to the liquid crystal cell', and then it was visually observed whether or not the liquid crystal was aligned. At this time, the evaluation is based on the following criteria The results are shown in Tables 19_i to 19_5 -141 - 201240981. Evaluation criteria Good: Liquid crystal alignment was confirmed, and no flow alignment was observed. The liquid crystal was aligned, but a large amount of flow alignment was observed. The liquid crystal cell was heated at 1200 ° C for 1 hour, and the pretilt angle was measured. The pretilt angle was measured by the Miller matrix method using Axo Metrix's "Αχ〇 S c an". The result is like a watch! 9 -1 to 1 9 - 5 are shown. From the results, it was confirmed that, as shown in Tables 19-1 to 19-5, a coating liquid (liquid crystal alignment treatment agent) for forming a polyimide film with a compound for modification having a photoreactive branch was used, even A good vertical alignment can also be obtained by performing photoalignment processing. Further, it has been confirmed that the polarized ultraviolet light is applied to the coating liquid (liquid crystal alignment treatment agent) for forming a polyimide film of the present invention, and the ability to obtain liquid crystal alignment can be obtained with little inclination to the vertical state. Further, it is confirmed that the pretilt angle can be finely adjusted by controlling the amount of addition and the amount of irradiation. Thus, the coating liquid (liquid crystal alignment treatment agent) for forming a polyimide film of the present invention can be used for a liquid crystal alignment film for a liquid crystal display element of a vertical alignment type, and is also suitable for liquid crystal alignment using a photo alignment method. membrane. -142- 201240981 [Table 19-1] Coating liquid for forming a polyimide film, irradiation intensity (m J ) Liquid crystal alignment pretilt angle (.) Example No. mm Adding amount (wt%) Applied when no voltage is applied Example 4 0 4 Example 4 0 2 [10 7] 70 0 Good defect 9 0. 0 0 Example 4 0 5 Example 4 0 2 [10 7] 7 0 5 0 Good good 9 0. 0 0 Example 4 0 6 Example 4 0 2 [10 7] 7 0 1 0 Q Good good 8 9. 9 2 Example 4 0 7 Example 4 0 2 [10 7] 7 0 2 0 0 Good good 8 9 · 9 0 Example 4 0 8 Example 4 0 2 [10 7] 7 0 4 0 0 Good good 8 9. 9 0 Example 4 0 9 Example 4 0 2 [10 7] 7 0 8 0 0 Good 8 9. 8 6 Example 4 1 0 Example 4 0 2 [10 7] 7 0 10 0 0 Good good 8 9. 7 9 Example 4 1 1 Example 4 0 3 [10 7] 10 0 0 Good defect 9 0. 0 0 Example 412 Example 4 0 3 [10 7] 10 0 5 0 Good good 8 9. 9 3 Example 413 Example 4 0 3 [10 7] 10 0 10 0 Good good 8 9. 9 3 Example 414 Example 4 0 3 [10 7] 10 0 2 0 0 Good Good 8 9. 8 8 Example 415 Example 4 0 3 [10 7] 10 0 4 0 0 Good good 8 9. 8 9 Example 416 Example 4 0 3 [10 7] 10 0 8 0 0 Good good 8 9. 7 3 Example 417 Example 4 0 3 [10 7] 10 0 10 0 0 Good Good 8 9. 7 0 Example 4 1 8 Example 3 8 3 [115] 1 0 0 Good defect 9 0. 0 0 Example 4 1 9 Example 3 8 3 [115] 10 2 0 Good good 8 9. 3 9 Example 4 2 0 Example 3 8 3 [115] 10 5 0 Good good 8 9. 0 0 Example 4 2 1 Example 3 8 3 [1 1 5] 10 10 0 Good good 8 8. 7 2 Example 4 2 2 Example 3 8 3 [1 1 5] 1 0 2 0 0 Good Good 8 8. 8 8 Example 4 2 3 Example 3 8 3 [115] 10 4 0 0 Good Good 8 9. 0 6 Example 4 2 4 Example 3 8 4 [115] 15 0 Good defect 9 0. 0 0 Example 4 2 5 Example 3 8 4 [115] 15 2 0 Good good 8 9. 6 5 Example 4 2 6 Example 3 8 4 [1. 1.5] 15 5 0 Good good 8 9. 5 7 Example 4 2 7 Example 3 8 4 [115] 1 S 10 0 Good good 8 9. 5 7 Example 4 2 8 Example 3 8 4 [115] 15 2 0 0 Good Good 8 9. 4 4 Example 4 2 9 Example 3 8 4 [1 \ 5] 15 4 0 0 Good Good 8 9. 4 2 -143- 20124 0981 [Table 19-2] Coating liquid for forming a polyimide film, irradiation intensity, liquid crystal alignment, example No. surface addition amount (wt*) (m J ) When a voltage is applied, voltage is applied (°) Example 4 3 0 Example 3 8 5 [115] 2 0 0 Good defect 9 0 . 0 0 Example 4 3 1 Example 3 8 5 [115] 2 0 2 0 Good good 8 9〇9 0 Example 4 3 2 Example 3 8 5 [115] 2 0 5 0 Good good 8 9. 7 6 Example 4 3 3 Example 3 8 5 [115] 2 0 10 0 Good good 8 9. 7 0 Example 4 3 4 Example 3 8 5 [115] 2 0 2 0 0 Good Good 8 9. 4 8 Example 4 3 5 Example 3 8 5 [115] 2 0 4 0 0 Good Good 8 9. 5 4 Example 4 3 6 Example 3 8 6 [117] 5 0 Good defect 9 0. 0 0 Example 4 3 7 Example 3 8 6 [117] 5 2 0 Good good 8 8. 8 0 Example 4 3 8 Example 3 8 6 [117] 5 5 0 Good Good 8 8 . 2 4 Example 4 3 9 Example 3 8 6 [117] 5 10 0 Good Good 8 8. 2 7 Example 4 4 0 Example 3 8 6 [117] 5 2 0 0 Good good 8 8. 2 8 Example 4 4 1 Example 3 8 6 [117] 5 4 0 0 Good good 8 8, 5 6 Real Example 4 4 2 Example 3 8 6 [117] 5 8 0 0 Good Good 8 8. 6 4 Example 4 4 3 啻 Example 3 8 6 [117] 5 10 0 0 Good Good 8 8. 5 8 Implementation Example 4 4 4 Example 3 8 7 [117] 10 0 Good defect 9 0. 0 0 Example 44 5 Example 3 8 7 [117] 10 2 0 Good good 8 9. 6 8 Example 4 4 6 Example 3 8 7 [117] 1 0 5 0 Good good 8 9. 3 8 Example 4 4 7 Example 3 8 7 [117] 1 0 10 0 Good good 8 9. 2 8 Example 4 4 8 Example 3 8 7 [1. 1 7 ] 1 0 2 0 0 Good good 8 9 . 10 Example 4 4 9 Example 3 8 7 [117] 10 4 0 0 Good good 8 9. 2 7 Example 4 5 0 Example 3 8 7 [117] 10 8 0 0 Good good 8 9. 3 1 Example 4 5 1 Example 3 8 7 [1 1.7] 10 10 0 0 Good good 8 9 . 18 Example 4 5 2 Example 3 8 8 [117] 2 0 0 Good bad 9 0. 0 0 Example 4 5 3 Example 3 8 8 [117] 2 0 2 0 Good good 8 9. 8 1 Example 4 5 4 Example 3 8 8 [117] 2 0 5 0 Good good 8 9 . 5 2 Example 4 5 5 Example 3 8 8 [117] 2 0 10 0 Good good 8 9. 5 2 Example 4 5 6 Example 3 8 8 [117] 2 02 0 0 Good good 8 9. 3 6 Example 4 5 7 Example 3 8 8 [117] 2 0 4 0 0 Good good 8 9. 3 2 Example 4 5 8 Example 3 8 8 [1 1. 7 ] 2 0 8 0 0 Good good 8 9. 3 0 Example 4 5 9 Example 3 8 8 [117] 2 0 10 0 0 Good good 8 9. 2 8 -144- 201240981 [Table 19-3] Formation of poly Coating liquid for yttrium imide film Irradiation intensity (m J ) Liquid crystal alignment pretilt angle (. Example Number Addition Quantity (wt%) When a voltage is applied when no voltage is applied Example 4 6 0 Example 3 8 9 [117] 3 0 0 Good defect 9 0. 0 0 Example 4 6 1 Example 3 8 9 [117] 3 0 2 0 Good good 8 9. 8 8 Example 4 6 2 Example 3 8 9 [117] 3 0 5 0 Good good 8 9. 7 1 Example 4 6 3 Example 3 8 9 [117] 3 0 1 0 0 Good good 8 9 * 5 5 Example 4 6 4 Example 3 8 9 [117] 3 0 2 0 0 Good good 8 9. 4 3 Example 4 6 5 Example 3 8 9 [117] 3 0 4 0 0 Good good 8 9. 3 1 Example 4 6 6 Example 3 8 9 [117] 3 0 8 0 0 Good good 8 9. 3 0 Example 4 6 7 Example 3 8 9 [117] .30 10 0 0 Good good 8 9 . 3 3 Example 4 6 8 Example 3.9 0 [117] 4 0 0 Good bad 9 0 . 0 0 Example 4 6 9 Example 3 9 0 [117] 4 0 2 0 good good 8 9. 8 1 embodiment 4 7 0 embodiment 3 9 0 [117] 4 0 5 0 good good 8 9. 7 0 embodiment 4 7 1 embodiment 3 9 0 [117] 4 0 10 0 Good good 8 9. 5 7 Example 4 7 2 Example 3 9 0 [1 17] 4 0 2 0 0 Good good 8 9. 4 3 Example 4 7 3 Real Example 3 9 0 [117] 4 0 4 0 0 Good Good 8 9. 4 4 Example 47 4 Example 3 9 0 [117] 4 0 8 0 0 Good Good 8 9. 3 2 Example 4 7 5 Example 3 9 0 [117] 4 0 10 0 0 Good good 8 9 _ .2 6 Example 4 7 6 Example 3 9 1 [117] 5 0 0 Good defect 9 0 . 0 0 Example 4 7 7 Example 3 9 1 [117] 5 0 2 0 Good good 8 9. 9 8 Example 4 7 8 Example 3 9 1 [117] 5 0 5 0 Good good 8 9. 8 2 Example 4 7 9 Example 3 9 1 [117] 5 0 10 0 Good Good 8 9 . 7 3 Example 4 8 0 Example 3 9 1 [1 1 .7 ] 5 0 2 0 0 . Good Good 8 9· 7 8 Example 4 8 1 Example 3 9 1 [117] 5 0 4 0 0 Good good 8 9 . 7 5 Example 4 8 2 Example 3 9 1 [117] 5 0 8 0 0 Good good 8 9. 7 3 Example 4 8 3 Example 3 9 1 [117] 5 0 10 0 0 Good and good 8 9. 7 4 S, -145- 201240981 [Table 19-4] Coating liquid for forming polyimide film. Irradiation intensity (m J) Liquid crystal alignment Pretilt angle (°) Example No. Addition amount (wt%) When voltage is applied when no voltage is applied Example 4 8 4 Example 3 9 2 [117] 7 0 0 Good defect 9 0. 0 0 Example 4 8 5 Example 3 9 2 [117] 7 0 2 0 Good good 8 9 . 9 4 Example 4 8 6 Example 3 9 2 [117] 7 0 5 0 Good good 8 9 8 9 Example 4 8 7 Example 3 9 2 [117] 7 0 10 0 Good good 8 9 . 8 5 Example 4 8 8 Example 3. 9 2 [117] 7 0 2 0 0 Good good 8 9 7 5 Example 4 8 9 Example 3 9 2 [117] 7 0 4 0 0 Good good 8 9. 4 8 Example 4 9 0 Example 3 9 2 [117] 7 0 8 0 0 Good good 8 9 4 9 Example 4 9 1 Example 3 9 2 [117] 7 0 10 0 0 Good good 8 9. 6 1 Example 4 9 2 Example 3 9 3 [119] 5 0 Good bad 9 0. 0 0 Example 4 9 3 Example 3 9 3 [119] 5 2 0 Good Good S 9 . 9 5 Example 4 9 4 Example 3 9 3 [119] 5 5 0 Good Good 8 9 . 7 0 Example 4 9 5 Example 3 9 3 [119] 5 10 0 Good good 8 9. 6 2 Example 4 9 6 Example 3 9 3 [119] 5 2 0 0 Good good 8 9. 6 0 Example 4 9 7 Example 3 9 &lt;1 [1 19] 6 0 Good bad 9 0. 0 0 Example 4 9 8 Example 3 9 4 [119] 6 2 0 Good good 8 9. 9 5 Example 4 9 9 Example 3 9 4 [ 119] 6 5 0 good good 8 9 . 7 0 embodiment 5 0 0 embodiment 3 9 4 [119] 6 10 0 good good 8 9 . 6 2 embodiment 5 0 1 embodiment 3 9 4 [119] 6 2 0 0 Good good 8 9 . 6 0 Example 5 0 2 Example 3 9 5 [119] 7 0 Good defect 9 0. 0 0 Example 5 0 3 Example 3 9 5 [119] 7 2 0 Good good 8 9. 9 4 Example 5 0 4 Example 3 9 5 [1 19] 7 5 0 Good good 8 9. 7 4 Example 5 0 5 Example 3 9 5 U 1 9] 7 10 0 Good good 8 9. 5 7 Example 5 0 6 Example 3 9 5 [119] 7 2 0 0 Good good 8 9. 6 3 Example 5 0 7 Example 3 9 6 [12 3] 5 0 Good defect 9 0. 0 0 Implementation Example 5 0 8 Example 3 9 6 [12 3] 5 2 0 Good Good 8 9. 1 4 Example 5 0 9 Example 3 9 6 [1 2 3] 5 5 0 Good Good 8 9. 5 4 Example 5 1 0 Example 3 9 6 [12 3] 5 1 0 0 Good good 8 8. 2 0 Example 5 1 ] Example 3 9 6 [12 3] 5 2 0 0 Good good 8 8· 2 4 -146 - 201240981 [Table 19-5] Irradiation strength (m J ) of coating liquid for forming a polyimide film - Hi Example No. 雠 Adding amount (wt%) Pretilt angle (Example 5 1 2 Example 3 9 7 [12 5] 5 0 Good Tube Example 513 Example 3 9 7 [12 5] 5 2 0 Good 3g: s: 9 0.00 Example 5 14 Example 3 9 7 [1 2 5] 5 5 0 7. 5 5 眚Example 515 Example 3 9 7 [12 5] 5 10 0 8 9 Window Example 5 16 Example 3 9 7 [12 5] 5 2 0 0 — 8 8. 〇〇 Example 5 1 7 Example 3 9 8 [12 5] 7 0 Good-8 8. 4 8 Window Example 5 1 8 Example 3 9 8 [12 5] 7 2 0 Good Bu?—〇 · 0 0 Example 5 1 9 Example 3 9 8 [12 5] 7 5 0 Good good 8 8. 7 6 ~§_β· 0 5 -A»· 1 8 —8 8. 4 2 —9 〇0 0 Example 5 2 0 Example 3 9 8 [12 5] 7 10 0 Good Poor Example 5 2 1 Example 3 9 8 [12 5] 7 2 0 0 Example 5.2 2 Implementation and J 3 9 9 [12 5] 10 0 窨 Example 5 2 3 Example 3 9 9 [12 5] 10 2 0 Good ~ Example 5 2 4 Example 3 9 9 [12 5] 10 5 0 Good Good»»? ^ . 4 2 -§ 9. 12 ΙΙΙΓτΤ' —8 8 . 3 fi 9 0.00 μ§ θ. 5 9 Blind Example 5 2 5 Example 3 9 9 [12 5] 10 10 0 Hz 眚 Example 5 2 6 Example 3 9 9 [12 5] 10 2 0 0 Good Tube Practice 5 2 7 Example 4 0 0 [12 5] 15 0. Good example S 2 8 Example 4 0 0 [12 5] 1 5 2 0 Good good example 5 2 9 Example 4 0 0 [12 5] I 5 5 0 Good example 5 3 0 Example 4 0 0 [12 5] 15 10 0 Good good one V port 丄 8 ft η ο 窨 Example 5 3 1 Example 4 0 0 [12 5] 15 2 0 0 Good good -^ ° » » 4, 8 8.86 Example 5 3 2 Example 4 0 1 [12 5] 2 0 0 _ Good bad example 5 3 3 Example 4 0 1 [12 5] 2 0 2 0 Good good ~ Example 5 3 4 Example 4 0 1 [12 5] 2 0 5 0 Good good Λ±,~Τ3~ -111 2 5 8 8. 9 #? Example 5 3 5 Example 4 0 1 [12 5] 2 0 100 good good example 5 3 6 Example 4 0 1 [12 5] 2 0 2 0 0 Good <Examples 537 to 578> Each of the following synthesis examples of the compound for modification was prepared as follows _ 20-1 to The compound described in 20-2 is added in an amount relative to polyamic acid (the solid component of the pAA_q solution (ie, polyaminic acid (PAA-1)) is in the ratios shown in the following Tables to 20-2. The polylysine (PAA-1) solution (10.Og) prepared above is stirred at room temperature to form a homogeneous solution. Example 5 3 7 to 5 7 8 Coating solution for forming a polyimide film] -147- 201240981 [Table 20-1] Compound addition amount (wt %) of polyamine acid modification Example 5 3 7 P AA-1 Synthesis Example 5 3 [10 9] 5 0 Example 5 3 8 P AA-1 Synthesis Example 5 3 [10 9] 5 0 Example 5 3 9 P AA-1 Synthesis Example 5 3 [10 9] 5 0 mm 5 4 0 P AA-1 Synthesis Example 5 3 [10 9] 5 0 Example 5 4 1 P AA-1 Synthesis Example 5 3 [10 9] 5 0 Example 5 4 2 P AA-1 Synthesis Example 5 3 [10 9] 5 0 Example 5 4 3 P AA-1 Synthesis Example 5 3 [10 9] 7 0 Example 5 4 4 P AA-1 Synthesis Example 5 3 [10 9] 7 0 Example 5 4 5 P AA-1 Synthesis Example 5 3 [10 9] 7 0 Example 5 4 6 P AA-1 Synthesis Example 5 3 [10 9] 7 0 Example 5 4 7 P AA-1 Synthesis Example 5 3 [10 9 7 0 Example 5 4 8 P AA-1 Synthesis Example 5 3 [10 9] 7 0 Example 5 4 9 P AA-1 Synthesis Example 5 3 [10 9] 10 0 Example 5 5 0 P AA-1 Synthesis Example 5 3 [10 9] 10 0 Example 5 5 1 P AA-1 Synthesis Example 5 3 [10 9] 10 0 Example 5 5 2 P AA-1 Synthesis Example 5 3 [10 9] 10 0 Example 5 5 3 P AA-1 Synthesis Example 5 3 [10 9] 10 0 Example 5 5 4 P AA - 1 Synthesis Example 5 3 [10 9] 10 0 Example 5 5 5 P AA-1 Synthesis Example 5 4 [111] 5 0 Example 5 5 6 P AA-1 Synthesis Example 5 4 [111] 5 0 Example 5 5 7 P AA- 1 Synthesis Example 5 4 [111] 5 0 Example 5 5 8 P AA - 1 Synthesis Example 5 4 [111] 5 0 Example 5 5 9 P AA - 1 Synthesis Example 5 4 [111] 5 0 Example 5 6 0 P AA-1 Synthesis Example 5 4 [111] 5 0 -148- 201240981 [Table 20-2] Addition amount of polyamine derivative for modification (wt %) Example 5 6 1 P AA-1 Synthesis Example 5 5 [0105] Example 5 6 2 P AA-1 Synthesis Example 5 5 [113] 5 0 Example 5 6 3 P AA-1 Synthesis Example 5 5 [113] 5 0 Example 5 6 4 PAA-1 Synthesis Example 5 5 [113] 5 0 Example 5 6 5 P AA-1 Synthesis Example 5 5 [113] 5 0 Example 5 6 6 PAA-1 Synthesis Example 5 5 [113] 5 0 Example 5 6 7 P AA - 1 Synthesis Example 5 5 [113] 7 0 Example 5 6 8 P AA-1 Synthesis Example 5 5 [113] 7 0 Example 5 6 9 P AA-1 Synthesis Example 5 5 [113] 7 0 Example 5 7 0 PAA-1 Synthesis Example 5 5 [113] 7 0 Example 5 7 1 P AA-1 Synthesis Example 5 5 [113]. 7 0 Example 5 7 2 P AA-1 Synthesis Example 5 5 [113] 7 0 Example 5 7 3 PAA — 1 Synthesis Example 5 5 [113] 10 0 Example 5 7 4 P AA-1 Synthesis Example 5 5 [113] 10 0 Example 5 7 5 PAA-1 Synthesis Example 5 5 [113] 10 0 Example 5 7 6 P AA-1 Synthesis Example 5 5 [113] 10 0 Example 5 7 7 PAA-1 Synthesis Example 5 5 [113] 1 0.0 Example 5 7 8 PAA-1 Synthesis Example 5 5 [113] 10 0 <Example 5 79 to 620 &gt;&lt;Horizontal alignment type anti-parallel unit Evaluation of Liquid Crystal Alignment &gt; [Production of Liquid Crystal Alignment Film and Liquid Crystal Cell] Using the coating liquid (liquid crystal alignment agent) for forming a polyimide film prepared in each of the above Examples 5 3 to 5 7 8 Method of making a liquid crystal cell. The coating liquid (liquid crystal alignment agent) for forming a polyimide film is spin-coated on a glass substrate, dried on a hot plate at 80 ° C for 70 seconds, and then placed in a hot air circulation type heated to 200 ° C. It was baked in an oven for 30 minutes to form a coating film having a film thickness of 100 nm. Thereafter, the amount of exposure was changed to linearly polarized UV light (UV wavelength 3 1 3 nm, irradiation intensity 8.0 mW/cm·2) between OmJ and 100 mJ, and the coating film surface was irradiated from directly above the substrate. Also, a method of modulating linearly polarized UV

In order to pass the ultraviolet light of the high pressure mercury lamp through the 313 nm band pass filter S-149 - 201240981, it passes through a 313 nm polarizing plate. Prepare two substrates of this type of liquid crystal alignment film with liquid crystal alignment treatment, spread a 6μπι distance adjuster on one of the liquid crystal alignment film faces, and then print the encapsulant on top of it, and then face the film with the liquid crystal alignment film. The method is such that the polarizing direction of the irradiation is parallel to each other and the other substrate is bonded to each other, and the hardening encapsulant is made into the empty cell β. The liquid crystal MLC-2041 (manufactured by Mercury Co., Ltd.) is injected into the empty cell by a reduced pressure injection method, and the injection port is sealed. A horizontal alignment type anti-parallel liquid crystal cell is used. Next, the horizontal alignment type anti-parallel liquid crystal cell obtained by the polarizing plate is held, and the liquid crystal cell is rotated by the backlight while being irradiated, and then the light and dark changes are observed visually and whether the liquid crystal is aligned with the liquid crystal. The baseline assessment is described below. The results are shown in Table 2, 1 to 2 1 - 2. Evaluation criteria ◎: Liquid crystal alignment was confirmed, and no flow alignment was observed. Although the liquid crystal was aligned, a certain flow alignment was observed. Δ: Although the liquid crystal was aligned, a large amount of flow alignment was observed. X: The liquid crystal was completely unaligned. When the liquid crystal cell is not irradiated with light, the liquid crystal cell is completely unaligned, but the liquid crystal cell which is irradiated with light can align the liquid crystal in accordance with the amount of the compound to be modified and the amount of light irradiation. Further, even if the respective liquid crystal cells which were confirmed to be aligned at 130 °C were subjected to isotropic treatment for 30 minutes, the alignment property could not be remarkably changed. That is, it is confirmed that the type and amount of the additive are appropriately selected, and it is confirmed that the horizontal alignment unit is easily produced. -150-201240981 [Table 21-1] Irradiation strength (m J) of coating liquid for forming polythene sub-film; presence or absence of alignment example number surface addition amount (wt %) Example 5 7 9 Example 5 3 7 [10 9] 5 0 0 X Example 5 8 0 Example 5 3 8 [10 93 5 0 2 0 〇 Example 5. 8 1 Example 5 3 9 [10 9] 5 0. 5 0 〇 Example 5 8 2 Example 5 4 0 [10 9] 5 0 10 0 〇 Example 5 8 3 Example 5 4 1 [10 9] 5 0 2.0 0 ◎ Example 5 8 4 Example 5 4 2. [10 9] 5 0 5 0 0 ◎ Example 5 8 5 Example 5 4 3 [10 9] 7 0 0 X Example 5 8 6 Example 5 4 4 [10 9] 7 0 2 0 〇 Example 5 8 7 Example 5. 4 5 [10 9] 7 0 5 0 ◎ Example 5 8 8 Example 5 4 6 [10 9] 7 0 10 0 ◎ Example 5 8 9 Example 5 4 7 [10 9] 7 0 2 0 0 ◎ Example 5 9 0 Example 5 4 8 [10 9] 7 0 5 0 0 ◎ Example 5 9 1 Example 5 4 9 [10 9] 10 0 0 X Example 5 9 2 Example 5 5 0 [10 9] 10 0 2 0 ◎ Example 5 9 3 Example 5 5 1 [10 9] 10 0 5 0 ◎ Example 5 9 4 Example 5 5 2 [10 9] 10 0 10 0 ◎ Example 5 9 5 Example 5 5 3 [10 9] 10 0 2 0 0 ◎ Example 5 9 6 Example 5 5 4 [10 9] 10 0 5 0 0 ◎ Example 5 9 7 Example 5 5 5 [111] 5 0 0 X Example 5 9 8 Example 5 5 6 [111] 5 0 2 0 〇 Example 5 9 9 Example 5 5 7 [111] 5 0 5 0 〇 Example 6 0 0 Example 5 5 8 [111] 5 0 10 0 ◎ Example 6 0 1 Example 5 5 9 [111] 5 0 2 0 0 ◎ Example 6 0 2 Example 5 6 0 [111] 5 0 5 0 0 ◎ [Table 21-2] Forming the coating irradiation intensity of the polyimide film ( m J ) presence or absence of alignment example number type addition amount (wt %) Example 6 0 3 Example 5 6 1 [113] 5 0 0 X Example 6 0 4 Example 5 6 2 [113] 5 0 2 0 △ Example 6 0 5 Example 5 6 3 [113] 5 0 5 0 Δ Example 6 0 6 Example 5 6 4 [113] 5 0 10 0 〇 Example 6 0 7 Example 5 6 5 [113] 5 0 2 0 0 〇Example 6 0 8 Example 5 6 6 [113] 5 0 5 0 0 ◎ Example 6 0 . 9 Example 5 6 7 [113] 7 0 0 X Example 6 1 0 Example 5 6 8 [113] 7 0 2 0 〇 Embodiment 6 1 1 Embodiment 5 6 9 [113] 7 0 5 0 〇 Embodiment 6 1 2 Example 5 7 0 [113] 7 0 10 0 〇 Example 6 1 3 Example 5 7 1 [113 7.0 2 0 0 ◎ Example 6 1 4 Example 5 7 2 [113] 7 0 5 0 0 ◎ Example 6 1 5 Example 5 7 3 [113] 10 0 . 0 X Example 6 1 6 Example 5 7 4 [113] 10 0 2 0 ◎ Real - Example 6 1 7 Example 5 7 5 [113] 10 0 5 0 © Example 6 1 8 Example 5 7 6 [113] 10 0 10 0 ◎ Implementation Example 6 1 9 Example 5 7 7 [113] 10 0 2 0 0 ◎ Example 6 2 0 Example 5 7 8 [1131 10 0 5 0 0 ◎ 151

Claims (1)

201240981 VII. Patent Application Area 1. A coating liquid for forming a functional polymer film, which comprises: a functional structural portion having functional properties, and at least one Meldron acid (Meld) At least one compound for modification selected from the group represented by the following formulas [A] to [D] at the structural site of the rum's acid; and the monomer for modification or the monomer for synthesizing the polymer for modification described above 1] (wherein, W is a kl-valent organic group imparting a functional structural site, Vi is -H, -OH, -OR, -SR or -NHR, and R is an arbitrary site containing a benzene ring, cyclohexane a ring, a heterocyclic ring, a fluorine, an ether bond, an ester bond, or a guanamine bond having 1 to 35 carbon atoms, and 1 ^ is an integer of 1 to 8) (wherein W2 is a k2 valent organic group imparting functional structural sites, V2 is -H, -OH, -SR, -OR or -NHR, and R is a benzene ring or a cyclohexane ring contained in any place. , heterocyclic ring, fluorine, ether bond, ester bond, guanamine bond -152- 201240981 carbon number 1 to 35 one-valent organic group, 1^ is an integer from 1 to 8) [Chemical 3] (wherein W3 and w4 are each a h-valent organic group imparting functional structural sites, W3 and W4 may be the same or different, and k3 is an integer from 1 to 8) [Chem. 4] (wherein W5 is a machine base of 2 k4 valence that gives functional structural parts, h is an integer from 1 to 8). 2. A method for forming a functional polymer film, which comprises applying a coating liquid for forming a functional polymer film according to claim 1 of the patent application to a substrate, and baking the obtained plum The raldenic acid structural portion and the functional structural portion are bonded to the functional polymer film of the polymer for modification. -153- 201240981 IV. Designated representative map: (1) The representative representative of the case is: No (2) The symbol of the representative figure is a simple description: No. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention. :式[A]~[D] [化1] [Chemical 3] [Chemical 2] -4-