TW200906769A - Diamine compound, polyamic acid, polyimide and liquid crystal aligning agent - Google Patents

Abstract

Disclosed is a novel diamine which has an effect of increasing the pretilt angle of a liquid crystal when used as a raw material for a liquid crystal aligning agent. This diamine enables to vertically align a liquid crystal even when used in a small amount.In addition, this diamine hardly precipitates even when a poor solvent is mixed in a liquid crystal aligning agent solution for improving coatability of the agent. Specifically disclosed is a diamine represented by the following formula (1). (1) (In the formula (1), R1 represents a phenylene; R2 represents a cyclohexylene or a phenylene; R3 represents a cyclohexylene; and R4 represents an alkyl group having 3-12 carbon atoms, a fluoroalkyl group having 3-12 carbon atoms, an alkoxy group having 3-12 carbon atoms or a fluoroalkoxy group having 3-12 carbon atoms.)

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel diamine compound (referred to as a diamine in the present invention) which is suitable as a raw material of a polymer used as a liquid crystal alignment film, and uses the same The obtained polyaminic acid, polyimine, and liquid crystal alignment treatment agent [Prior Art] At present, a liquid crystal alignment film used for a liquid crystal display element, in many cases, a polyimine film, a polyimine The film is a solution of a polyamic acid using a polyamidene precursor or a solution of a solvent-soluble polyimine coated on a substrate, followed by baking or the like. The polylysine or solvent-soluble polyimine is generally one of the properties sought for using a tetracarboxylic acid derivative such as tetracarboxylic dianhydride and a liquid crystal alignment film, and is a liquid crystal molecule to be coated on the substrate surface. The alignment tilt angle is maintained at any time, that is, the pretilt angle control of the so-called liquid crystal. It is known that the magnitude of the pretilt angle can be changed in such a manner that the structure of the polyimine which constitutes the liquid crystal alignment film can be selected. In the technique of controlling the pretilt angle by the structure of polyimine, and using a branched diamine as a part of the polyimine raw material, the pretilt angle can be controlled according to the ratio of use of the diamine, and It is easier to control the pretilt angle of the purpose, and is suitable as a means of increasing the pretilt angle. A branched structure of a diamine which increases the pretilt angle of a liquid crystal is known, for example, a compound having a long chain or a fluorine-based base (for example, Patent Document 1), a cyclic group or a combination of a cyclic group and an alkyl group (Example-5) - 200906769, for example, Patent Document 2), a cholesterol skeleton (for example, a patent), in addition to the stability of the inclination angle used for increasing the pretilt angle of the liquid crystal, process dependency, etc., the structure of the branched structure used for the structure is proposed. A phenyl producer (for example, Patent Documents 4 and 5). In addition, there are also three to four branched diamine compounds (for example, in recent years, liquid crystal display elements are used in conjunction with large screens (digital cameras). Or the use of a mobile phone is more practical, and when compared with the past, a phenomenon in which the unevenness of the substrate step is increased is formed. In view of the above phenomenon, a liquid crystal alignment film which is uniformly applied is formed with respect to a large substrate or a substrate step. In the process of producing an alignment film, when a solution of polyamidite-soluble polyimine is applied to a substrate, it is carried out by flexographic printing or the like. The solvent of the coating liquid, the solvent having excellent solubility (hereinafter, Also known as 焉methyl-2-pyrrolidone or 7 • Butyrolactone, etc., in order to improve the solubility of the resin with low solubility in the mixture (hereinafter, butyl cellosolve. However, the poor solvent has a very poor concentration The ability of amines, so a large amount of mixing will produce the literature 7). Especially in the solvent-soluble polyimine, the problem is particularly significant. In addition, the use of the above-mentioned branched diamines has a tendency to reduce the uniformity of solution coating. The mixing amount of the solvent 'thus, the solvent mixture described above is 3), etc. The diamine is used to improve the preliminary investigation results, or the ring structure such as cyclohexyl is proposed to be useful in the literature 6). Partially) The enlargement of the N-coating film of a wide range of floors, the basis of the display characteristics, etc., which can be formed into a solution or a solvent, which can be generally added to the tree; good solvent. It is a poor solvent) to dissolve polylysine or precipitate (for example, in the solution of the patent, the polyamine obtained from the amine requires a large amount of leanness and is also an important characteristic of the polyamine-6-200906769 amine. : 特开平2-2 Japanese Unexamined Patent Publication No. Publication No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No Patent Document 6: JP-A-2004-67589 (Patent Document 7): JP-A No. 2 - 3 7 3 2 4 SUMMARY OF THE INVENTION The present invention provides a polylysine as a liquid crystal alignment film. And/or when the raw material of polyimine (hereinafter also referred to as polymer) is used, it has the effect of increasing the pretilt angle of the liquid crystal, and at a very small use ratio, the liquid crystal can be formed into a vertical alignment, and polymerization is also performed. When the coating liquid of the substance is mixed with a poor solvent, it is intended to produce a novel diamine which is less likely to cause a precipitated polyamic acid and/or a raw material of the polyimide. Further, the present invention is directed to provide a polymer obtained by using the novel diamine described above, a liquid crystal alignment treatment agent containing the polymer, and a liquid crystal display element having a liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent. The inventors of the present invention have intensively studied the results and found that the present invention has the following main contents when the above object is achieved. A diamine represented by the following formula (〖). (1) 200906769 [Chemical 1] h2n nh2Ογλ O-Rl~R2~ (2- (In the formula (1), R1 is a phenyl group] R2 is a cyclohexyl group, R3 is a cyclohexyl group; R4 is a carbon number of 3~ An alkyl group of 12, a fluoroalkyl group, an alkoxy group having a carbon number of 3 to 12 or a carbon number of 3 to 1 group. 2. A diamine as described above, wherein R of the formula (1) Phenyl, r2 is 1,4 -cyclohexyl or I,4-phenyl and R.3. 3. A diamine of the above 1 or 2 which is of the following formula (2) Nh2 (in the formula (2-1), η is an integer of 2 to 11, and 1,4-cis-trans isomerism is a trans isomer respectively). 4. The diamine of 1 or 2 above, It is the following formula (2, [Chemical 3] ΝΗ 2

/JH (in the formula (2-2), 'n is an integer of 2 to 11, and 1,4-cis-trans isomerism is a trans isomer). The base is either benzene having a carbon number of 3 to 1 2 2 and the fluoroalkoxy group 1 is 1,4 -extended to 1,4-cyclohexylene-1), which is represented by 1-1) ring-extension hexyl-2) -8-200906769 5. A polyimine which is characterized in that a diamine component containing the diamine of any one of the above 1 to 4 is reacted with a tetracarboxylic dianhydride to prepare a polyacrylic acid. The amine acid, or the polylysine is dehydrated and closed to produce a polyimine. 6. The above-mentioned polyamine or polyimine of 5, wherein the diamine of any one of the above 1 to 4 is at least 1% by mole of the diamine component. A liquid crystal alignment treatment agent comprising the above 5 or the above 6 polyamic acid and/or polyimine. 8. The liquid crystal alignment treatment agent according to the above 7, which comprises an organic solvent containing 5 to 6 (3 mass% of a poor solvent). 9. A liquid crystal alignment film which is obtained by using the liquid crystal alignment treatment agent of the above 7 or the above 8 A liquid crystal display element having a liquid crystal display element having the above-mentioned 9-crystal alignment film. The diamine of the present invention has a marked increase when used as a polymer original half-bucket constituting a liquid crystal alignment film. The effect of the pretilt angle of the large liquid crystal. For example, as shown in Table 2, the pre-tilt angle of the liquid crystal alignment film obtained by the diamine (111_PBCH5DABZ) of the present invention represented by the formula (2-1) is about 8 6 °. The pretilt angle of the liquid crystal alignment film obtained by the diamine (m-PBCH7DABz) is about 87. The pretilt angle of the liquid crystal alignment film obtained from the conventional diamine (PCH7DAB) of Patent Document 4 having a similar structure is about 22 °, which is about 4 times larger than unexpected. Therefore, the liquid crystal alignment treatment agent obtained by the diamine of the present invention can provide a larger pretilt angle of the liquid crystal at a rare use ratio, and can form a vertical alignment of the liquid crystal. -9- 200906769 In order to obtain a liquid crystal alignment film and prepare a coating liquid to improve coating properties, and to use a good solvent and a poor solvent in a large amount, the liquid crystal alignment treatment agent obtained by the diamine of the invention is also not easy to be used when coating a large substrate. A liquid crystal alignment film having excellent properties can also be produced. Hereinafter, the present invention will be described in detail. 1 . Diamine The diamine of the present invention has a diaminobenzene ring via a bonding group, and the bonding has a stretching. a branched-chain compound of a phenyl-cyclohexyl group or a structure of a phenyl-R4 group. In the case of the following formula (], a homogeneous thin (-CH2〇-)-ring is formed by the precipitation of a native polymer. Represented by

(1) NH4 h2n〇Ka0-r1-r2-r3-r4 In the formula (1), Ri is a phenyl group, R2 is a cyclohexyl group, R3 is a cyclohexyl group; a phenyl group, and a ring extension In the hexyl group, a substituent is required; R4 is an alkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms and 3 to 12 carbon atoms, or a fluoroalkoxyfluoroalkyl group having a carbon number of 3 to 12 and an alkoxy group. And the fluoroalkoxy group may be linear or branched and linear, and may have a suitable substituent. The bond constituting the amine group on the benzene ring of the above diaminobenzene ring is particularly limited. Specifically, for example, the bonding group with respect to the branch is the position of 2, 3 on the benzene ring, the position of 2, 4, the position of 2, 5, the position of 3, 4, the position of 3, 5, and the like. Among them, it is: or the fluoride base, _ base; the base and the branch can be used, the position of the knot is not (-CH20-), 2,6 synthetic polyamide-10 - 200906769 From the viewpoint of reactivity at the acid level, it is preferable to use the positions of 2, 4, 2, 5, and 3, 5. Further, when the ease of synthesis of the diamine is added, the position of 2, 5 or 3, 5 is more preferable. Among the diamines represented by the above formula (1), when the pretilt angle of the liquid crystal is more efficiently increased, R! is preferably a 1,4-phenylene group. Further, r2 is preferably a 1,4-phenylene group or a 1,4-cyclohexylene group, more preferably a 1,4-phenylene group or a 1,4-trans-cyclohexylene group, particularly 1,4 - Anti-ring extension is preferred. Further, R3 is preferably a 1,4-cyclohexyl group, particularly preferably a 1,4-trans-cyclohexene group. Therefore, a combination of R丨, R2 and R3 is preferably ', R' is 1,4. -Extended phenyl 'R.2 is 1,4 -cyclohexyl or 1,4-phenyl, and R.sup.3 is 1,4 -cyclohexyl. More preferably, 1 is hydrazine, 4-phenylene is 1,4 -phenylene or 1,4-trans-cyclohexyl, and R3 is 1,4-trans-cyclohexyl. The preferred one of the diamine represented by the above formula (1) of the present invention is as follows. Further, n in the following formula is an integer of 2 to 11. It is preferably an integer of 2 to 8. Further, the cis-trans isomerism of the 1,4_cyclohexyl group in the formula is 'trans isomers, respectively. -11 - 200906769 [化5]

(CH2)nCH3

(CH2)nCH3 (CH2)nCH3 (CH2)nCH3 The method for producing the diamine represented by the above formula (1) of the present invention is not particularly limited, and preferred methods are, for example, the methods listed below. _N〇2 〇2nO\_Ri_R2_R3_R4 (3) The dinitro compound of the above formula (3) is synthesized and converted into an amine group by a usual method. The Ri, R2, R3, and R4 in the formula (3) are the same as those defined in the formula (1). The dinitro compound of the formula (3) is obtained by reacting a hydroxyl group-containing compound represented by the following formula (4) with dinitrobenzyl chloride or the like. Further, R!, R2, R3, and R4 in the formula (4) are the same as those defined in the formula (1). [Chem. 7] HO—r1-r2-r3-r4 (4) -12- 200906769 The method for producing a hydroxyl group-containing compound represented by the above formula (4) can be represented by the following reaction formula [1] to reaction formula [2]. The method is manufactured, but the invention is not limited thereto. In the case where R2 is a ring-extension group, the synthetic route of the reaction formula [1] is listed. The Ri, R3 and R4 in the reaction formula [1] are the same as defined in the formula (1), X is a protecting group such as a methyl group or a benzyl group, and χ2 is MgBr.

MgCl or Li. The reagent used for the dehydration reaction is, for example, an inorganic acid such as hydrochloric acid or sulfuric acid, an organic acid such as p-toluenesulfonic acid, or an acid anhydride such as acetic anhydride or trifluoroacetic anhydride. The reduction reaction is, for example, a hydrogenation reaction using palladium (Pd) or lead (Pt) or the like as a catalyst, or a contact reduction reaction using a metal such as iron, tin or zinc. The reaction of the deprotection group is carried out, for example, by using a methyl group of boron tribromide (BBr3) for decoupling reaction or by dehydrogenation of p or the like by hydrogenation using a Pd catalyst or the like. [Xiang 8] Heart X!—o—r “x2 1 (4a) HO X Factory 0—R “ (4c) • R3-R4 Dehydration Reduction X Plant O-Rr -R3-R4 Deprotection

R3 to R4 (4f) The following reaction formula [1] (4e) can be obtained by the above-mentioned reaction formula [1], ). The above formula is shown (4 -13 - 200906769 [9] r3 r4 c3h7 ~o~ C4H9 c 5 η ,, CfiH, ac 7 H 】5 -o C8H, 7 -oc 9 H ! 9 C i 〇H 2 i -o C ii H 2 3 -o- C i 2 H 2 5 When R2 is a phenylene group, the synthesis route of the reaction formula [2] is shown. The R!, R3, and R4 systems in the reaction formula [2] The same as defined in the formula (1), X! is a protecting group such as a methyl group or a benzyl group, and X3 is a dentate atom, a methanesulfonyloxy group, a benzenesulfonyloxy group, a trifluoromethanesulfonyloxy group. , B(OH) 2, MgBr, MgCl or Li; X4 is a halogen atom, methanesulfonyloxy, benzenesulfonyloxy, trifluoromethanesulfonyloxy, B(OH) 2 , MgBr, MgCl or Li And the deprotection group reaction, for example, a methylation reaction using BBr3 or a hydrodebenzylation reaction using a Pd catalyst or the like. -14- 200906769 [Chemical 10]

Xj-O-RrXa (4g) X Plant O-Rr (4i) -R3-R4 Deprotection

HO-^^-R3_R4 Reaction formula [2] (4j) W The hydroxyl group-containing compound represented by the above formula (4) can be obtained by the above reaction formula [2]. R 1 r3 r4 -0- C3H7 C4H9 ^5^11 C6H, 3 0- C7H, 5 -0 ChH, 7 -0 c 9 H 】9 -0 C 1 〇H 2 】 ~^JT -0 C] H 2 3 0- -0 C 1 2 H 2 5 The diamine of the present invention can be reacted with a tetracarboxylic acid, a tetracarboxylic acid dihalide, a tetracarboxylic dianhydride or the like, a tetracarboxylic acid or a derivative thereof. In order to obtain a poly-proline which has a specific structure and a branched structure, in addition, the poly-deuterated acid is dehydrated and closed to obtain a polyimine having a specific structure in a branched chain. -15 - 200906769 2. Polylysine The polylysine of the present invention is a polyglycolic acid obtained by reacting a diamine component of a diamine represented by the formula (1) with a tetracarboxylic dianhydride. The polyimine is a polyimine obtained by dehydration ring closure of the polyamic acid, which can be used as a polymer for producing a liquid crystal alignment film. The ratio of the diamine represented by the formula (1) to the diamine component (hereinafter also referred to as a diamine component) of the polyamic acid can be obtained by reacting with the above tetracarboxylic dianhydride. The content of the diamine represented by the formula (1) is not particularly limited. In the liquid crystal alignment film obtained by using the polyamic acid or the polyimine of the present invention, the more the content ratio of the diamine represented by the formula (1) in the above diamine component, the larger the pretilt angle of the liquid crystal. In the purpose of increasing the pretilt angle of the liquid crystal, it is preferred that the diamine represented by the formula (1) is 1 mol% or more of the diamine component. For the purpose of vertically aligning the liquid crystal, 10 mol% of the diamine component is preferably a diamine represented by the formula (1), more preferably 15 mol% or more. For the purpose of vertical alignment of the liquid crystal, the diamine component is 100 mol/0. The diamine represented by the formula (1) may be used, but the diamine represented by the formula (1) is 80% of the diamine component, from the viewpoint of uniform coating properties when the liquid crystal alignment agent is applied as described later. The ear percentage is preferably below, more preferably 40% by mole or less. In the case where the diamine represented by the formula (?) is less than 100 mol%, the diamine other than the diamine represented by the formula (1) is not particularly limited. Further, when specific examples are given, they are as follows. P-phenylenediamine-16- 200906769 m -phenylenediamine 2.4-diaminotoluene 2.5-diaminotoluene 2.6-diaminotoluene 2.4-dimethyl-oxime 3-diaminobenzene 2.5 - Dimethyl-1,4-diaminobenzene 2.3.5.6- Tetramethyl-1,4-diaminobenzene 2,4-diaminobenzene 2,5-diaminobenzene 4.6-diamine Resorcinol 2,5-diaminobenzoic acid 3.5-diaminobenzoic acid N,N-diallyl-2,4-diaminoaniline N,N-diallyl-2,5 - Diaminoaniline 4-aminobenzylamine 3-aminobenzylamine 2-(4-aminophenyl)ethylamine 2-(3-aminophenyl)ethylamine 1.5-naphthalenediamine 2.7 - Naphthalene diamine 4,4'-diaminobiphenyl 3,4 '-diaminobiphenyl 3,3 '-diaminobiphenyl 2,2'-dimethyl-4,4' -diaminobiphenyl-17- 200906769 3,3'-dimethyl-4,4'-diaminobiphenyl 3,3'-dimethoxy- 4,4'-diamine linkage Phenyl 3,3'-dihydroxy-4,4'-diaminobiphenyl 3,3'-dicarboxy-4,4'-diaminobiphenyl 3,3'-difluoro-4, 4'-Diaminobiphenyl 2,2'-trifluoromethyl-4,4'-diaminobiphenyl 3,3'-trifluoromethyl-4,4'-diaminobiphenyl 4,4'-Diaminodiphenylmethane 3.3 '-diaminodiphenylmethane 3,4'-diaminodiphenylmethane 4,4'-diaminodiphenyl ether 3,3' -diaminodiphenyl ether 3.4 '-diaminodiphenyl ether 4,4'-diaminodiphenyl fluorene 3,3'-diaminodiphenyl fluorene 4,4'-diamino Diphenylamine 3.3 '-diaminodiphenylamine 3.4 '-diaminodiphenylamine N-methyl(4,4'-diaminodiphenyl)amine N-methyl (3,3 '_Diaminodiphenyl)amine N-methyl(3,4'-monoamino-phenyl)amine 4,4'-diaminobenzophenone 3,3'-diaminodiphenyl Methyl ketone 3,4'-diaminobenzophenone-18 - 200906769 4,4'-diaminobenzidine aniline 1.2-bis(4-aminophenyl)ethane 1,2-bis(3- Aminophenyl)ethane 4,4'-diaminodiphenylacetylene 1.3-bis(4-aminophenyl)propane 1,3-bis(3-aminophenyl)propane 2,2_double (4.Aminophenyl)propane 2,2-bis(3-aminophenyl)propane 2.2-bis(3•amino-4-methylphenyl)propane 2.2-bis(4-aminophenyl) Hexafluoropropane 2.2-bis(3-aminophenyl)hexafluoropropane 2,2-bis(3-amino-4- Phenylphenyl)hexafluoropropane 1.3-bis(4-aminophenoxy)propane 1,4-bis(4-aminophenoxy)butane 1.5-bis(4-aminophenoxy)pentane 1.6-bis(4-aminophenoxy)hexane 1.7-bis(4-aminophenoxy)heptane 1.8-bis(4-aminophenoxy)octane 1,9-bis(4- Aminophenoxy)decane 1,1〇-bis(4-aminophenoxy)decane 1,11-bis(4-aminophenoxy)undecane 1,12-bis (4- Aminophenoxy)dodecane bis(4-aminophenyl)propane dicarboxylate (dioate) bis(4-aminophenyl)butanedioate-19- 200906769 bis(4-aminobenzene Pentyl dicarboxylate bis(4-aminophenyl)hexanedicarboxylate bis(4-aminophenyl)heptane diester bis(4-aminophenyl)octanedioate (4-Aminophenyl)decanedioate bis(4-aminophenyl)decanedioate 1,4-bis(4-aminophenyl)benzene 1.3-bis(4-aminobenzene Benzene 1,4- bis(4-aminophenoxy)benzene 1.3-bis(4-aminophenoxy)benzene 1.4-bis(4-aminobenzyl)benzene 1.3-bis (4-amine Benzyl)benzenebis(4-aminophenyl)terephthalate (3-Aminophenyl)terephthalate bis(4-aminophenyl)isophthalate bis(3-aminophenyl)isophthalate 1.4-phenylene [(4-Aminophenyl)methanone] 1.4-phenylphenylbis[(3-aminophenyl)methanone] 1.3-phenylphenylbis[(4-aminophenyl)methanone]- Phenyl bis[(3-aminophenyl)methanone] 1.4-phenylene bis(4-aminobenzoate) 1.4-phenylphenylbis(3-aminobenzoate) 1.3- Phenyl bis(4-aminobenzoate) 1.3-phenylene bis(3-aminobenzoate) -20- 200906769 Ν,Ν'-(1,4-phenylene) bis ( 4-aminobenzobenzoamine) N,N'-(1,3-phenylene)bis(4-aminobenzoguanamine) oxime, Ν'-(1,4-phenylene) bis ( 3-aminobenzobenzoamine) 氺 "-(1,3-phenylene) bis(3-aminobenzoguanamine) bis(4-aminophenyl)terephthalamide bis(3- Aminophenyl)terephthalamide bis(4-aminophenyl)isophthalamide bis(3-aminophenyl)isophthalamide 2.2-bis[4-(4-aminobenzene) Oxy)phenyl]propane 2.2-bis[4-(4-aminophenoxy)phenyl]hexafluoro 4,4'-bis(4-aminophenoxy)diphenylphosphonium 2.6-diaminopyridine 2,4-diaminopyridine 2.4-diamino-1,3,5-triazine 2.6 Diaminodibenzofuran 2,7-diaminodibenzofuran 3.6-diaminodibenzofuran 2.6-diaminocarbazole 2,7-diaminocarbazole 3.6-diaminocarbazole 2.4- _Amino-6-isopropyl-1,3,5-dixiao 2,5-bis(4-aminophenyl)-1,3,4-oxadiazole 1,3 -diamino Propane 1,4-diaminobutane-21 - 200906769 1,5-diaminopentane 1,6-diaminohexane 1,7-diaminoheptane 1,8-diaminooctane 1,9-diaminodecane 1,1 0-diaminodecane 1,1 1 -diaminoundecane 1, 1 2 -diaminododecane 1,4-diaminocyclohexane Alkane 1,3 -diaminocyclohexane bis(4-aminocyclohexyl)methane bis(4-amino-3-methylcyclohexyl)methane, when the polyglycolic acid of the present invention is prepared, The tetracarboxylic dianhydride which is reacted with an amine component is not particularly limited. Further, the specific examples are as follows. Pyromellitic dianhydride 2.3.6.7-naphthalenetetracarboxylic dianhydride 1.2.5.6-naphthalenetetracarboxylic dianhydride 1.4.5.8-naphthalenetetracarboxylic dianhydride 2.3. 6.7- 蒽tetracarboxylic dianhydride 1,2,5,6-nonanedicarboxylic dianhydride 3,3',4,4'-biphenyltetracarboxylic dianhydride 2,2',3,3'- Biphenyltetracarboxylic dianhydride 2,3,3',4'-biphenyltetracarboxylic dianhydride-22- 200906769 3,3',4,4'-benzophenonetetracarboxylic dianhydride 2 , 3,3',4'-benzophenone tetracarboxylic dianhydride bis(3,4-dicarboxyphenyl)methane dianhydride bis(3,4-dicarboxyphenyl)ether dianhydride double (3, 4-Dicarboxyphenyl)ruthenic anhydride 2.2-bis(3,4-dicarboxyphenyl)propane dianhydride 2.2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride 2,5-dicarboxyl Methyl terephthalic dianhydride 4,6-dicarboxymethyl isophthalic dianhydride 4- (2,5-dionetetrahydro-3-furan) phthalic anhydride 1.4-bis (2,5 -diketotetrahydro-3-furan)benzene 1.4-bis(2,6-dionetetrahydro-4-pyran)benzene 1,4-bis(2,5-dionetetrahydro-3- Methyl-3-furan)benzene 1.4-bis(2,6-dionetetrahydro-4-methyl-4-pyran)benzene 1,2,3,4-butane Tetracarboxylic dianhydride 1.2.3.4-cyclobutane tetracarboxylic dianhydride 1.2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride 1,3-dimethyl-1,2 , 3,4-cyclobutane tetracarboxylic dianhydride 1.2.3.4- tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride 1.2.3.4- cyclopentane tetracarboxylic dianhydride 2.3 .4.5- Tetrahydrofuran tetracarboxylic dianhydride 2.3.5- Tricarboxycyclopentyl acetic acid dianhydride 1,2,4,5-cyclohexane tetracarboxylic dianhydride 4- (2,5-dione tetrahydro- 3-furan)-cyclohexane-1,2-dicarboxylic anhydride-23- 200906769 5-(2,5-dionetetrahydro-3-furan)·3-methyl-3-cyclohexanedicarboxylic anhydride Bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride 3.4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride 3.4-Dicarboxy-indole, 2,3,4-tetrahydro-6-methyl-1-naphthalene succinic acid dicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic acid Anhydride 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride 2,3,5,6-norbornanetetracarboxylic dianhydride 3,5,6-tricarboxynorbornane-2-acetic acid Diacetate, tricyclo[4.2.1.02'5]nonane-3,4,7,8-tetracarboxylic dianhydride tetracyclo[4 · 4 · 1 · 02 '5 · 07 =1G] undecane · 3 , 4,8,9-tetracarboxylic acid hexacyclic ring [6.6.0.12, 7.03'6.19 14.01()'13]hexadecane-4, tetracarboxylic acid dianhydride 1,4-bis(2,5-dionetetrahydro-3-furan)hexane 1.4-bis(2,6-dione a method for reacting a diamine component with a tetracarboxylic dianhydride, for example, a method of mixing a diamine component with a tetracarboxylic dianhydride in a solvent, to simply smear the organic solvent, as long as The polyamine produced to be soluble is not particularly limited. When exemplified by the specific examples, for example, N,N-dimethylhydantoin, hydrazine, hydrazine-dimethylacetamide, N-methyl-2-pyrrolidone, N-decalamine, dimethyl arsenic, r- Butyrolactone and the like. It can be used alone or in combination. In addition, even if used alone, it will not cause the solvent of polypyramidine, and the polyamic acid produced will not produce the precipitated dianhydride dianhydride, 11,12- the organic method acid, ketomethyl group Used, or amine acid is enclosed, also -24- 200906769 can be mixed with the above solvents. Further, the water in the organic solvent hinders the polymerization reaction, which is the cause of the hydrolysis of the produced polylysine. Therefore, it is preferred that the organic solvent be dehydrated and dried as much as possible. In the organic solvent, a method of mixing a diamine component with a tetracarboxylic dianhydride, for example, a solution obtained by dispersing or dissolving a diamine in an organic solvent, dispersing or dissolving the tetracarboxylic dianhydride in an organic solvent. In addition, a method of adding a diamine to a solution obtained by dispersing or dissolving a tetracarboxylic dianhydride in an organic solvent, a method of adding a tetracarboxylic dianhydride to a diamine or simultaneously adding to an organic solvent, etc. Any of its methods can be used. The temperature at which the above polyamic acid is synthesized may be selected from any temperature of from -20 to 150 ° C, preferably from -5 to 10,000 ° C. Further, the reaction can be carried out at any concentration. However, when the concentration of the diamine component and the tetracarboxylic dianhydride of the raw material is too low, a polymer having a high molecular weight is not easily obtained. When the concentration is too high, the viscosity of the reaction solution is too high. When it is high, it is not easy to stir uniformly, so it is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and thereafter, an organic solvent may be added. In the synthesis reaction of polyamine, the molar ratio of the tetracarboxylic dianhydride to the number of moles of the diamine component is preferably 0.8 to 1.2. As with the usual polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the produced polyamine. The molecular weight of the polyproline of the present invention is not particularly limited. The weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method is 5,000 to -25 to 200906769 300,000 when considering the workability in coating the liquid crystal alignment agent to be described later, the uniformity of the coating film, and the strength of the obtained coating film. Preferably, it is preferably 10, 〇〇〇~1 5 0,000. 3. Polyimine The polyimine of the present invention is a polyimine obtained by dehydration ring closure of the above polyamic acid, which can be used as a polymer for producing a liquid crystal alignment film. In the polyimine of the present invention, the dehydration ring closure ratio of the valeric acid group (the imidization ratio) does not necessarily need to be 100%, and it can be arbitrarily adjusted in accordance with the use or purpose. A method for dehydrating a poly-proline to a closed loop, for example, a hydrazine imidization by heating a poly-proline without using a catalyst, or a ruthenium imidization using a catalyst, such as a phthalocyanine In the case of amination, the solution of polylysine is heated to 1 〇〇 to 400 ° C, preferably to 1 2 0 to 2 50 ° C, to form a hydrazine imidization reaction. The water is excluded from the reaction system to be imidized by the catalyst of the poly-proline, and the alkaline catalyst and the acid anhydride may be added to the solution of the poly-proline, and the mixture is at -20~2 50 It is preferably carried out at a temperature of 0 to 18 ° C under stirring. The amount of the basic catalyst is 醯. 5 to 30 moles, preferably 2 to 20 moles of anhydride. The amount of the anhydride is 1 to 50 moles of the amidate group, preferably For 3 to 3 0 moles. The basic catalyst, for example, pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc., wherein pyridine is further moderately alkaline in the course of the reaction, is preferred. The acid anhydride is, for example, acetic anhydride, trimesic anhydride, pyromellitic anhydride, etc., and in the case of using acetic anhydride in -26-200906769, it is preferred that the valley is purified after completion of the reaction. The imidization rate of the imidization of the catalyst oxime can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time. The molecular weight of the polyimine of the present invention is not particularly limited. When considering the workability in the application of the liquid crystal alignment treatment agent, the uniformity of the coating film, and the strength of the obtained coating film, the weight average molecular weight measured by the GPC method is preferably 5,000 to 300,000, and is 1 〇, 〇 〇〇~15〇, 〇〇〇. When the polymer component is recovered from the reaction solution of polyglycine or polyimine, the reaction solution can be poured into a poor solvent to precipitate. As the poor solvent used for the precipitation, for example, methanol 'acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water or the like can be used. The polymer which is precipitated by the lean solvent can be recovered by filtration, and then dried under normal pressure or under reduced pressure at normal temperature or under heating. 4. Liquid crystal alignment treatment agent The liquid crystal alignment treatment agent of the present invention is a coating liquid for producing a liquid crystal alignment film, and its main component is a composition containing a resin component of a resin film and an organic solvent capable of dissolving the resin component. In the liquid crystal alignment agent of the present invention, the resin component is at least any one of the above-mentioned polyamic acid and polyimine of the present invention (hereinafter also referred to as a polymer of the present invention). In the resin component, the content of the polymer of the present invention is preferably 5% by mass or more, and more preferably 10% by mass or more. The above resin component may be any polymer of the present invention or may be blended with a polymer other than the polymer of the present invention. In the other polymerization, -27-200906769, for example, a polyamine or a polyimine obtained by using a diamine other than the formula (1) can be used. The organic solvent in which the resin component is soluble is not particularly limited. Specifically, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-port pyrrolidone, N-methylcaprolactam, dimethyl飒, butyrolactone and the like. These organic solvents are good solvents in which the solubility of the resin is high. Further, in addition to the above-mentioned good solvent, in order to improve the uniformity of coating of the liquid crystal alignment agent, it is preferred to use a poor solvent having a low solubility of the polymer. In the present invention, preferred poor solvents are, for example, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, diethylene glycol diethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monobutyl ether, ethyl carbitol ant acid ester, ethylene glycol, ethylene glycol monohexyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol , 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, Propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, 2- (2) -Ethoxypropoxy)propanol, methyl lactate 'ethyl lactate, η-propyl lactate, η-butyl lactate, isoamyl lactate, and the like. The poor solvent is a poor solvent having a low solubility of the resin. The content of the solvent is preferably from 5 to 60% by mass of the organic solvent contained in the liquid crystal alignment treatment agent, more preferably from 10 to 50% by mass, based on the resin component in the liquid crystal alignment treatment agent of the present invention. The concentration can be appropriately adjusted in accordance with the film thickness of the liquid crystal alignment film to be obtained and the apparatus used for coating the liquid crystal alignment agent. The general resin concentration of the liquid crystal alignment agent -28-200906769 is, for example, 1 to 20% by mass, preferably 2 to 10% by mass. The liquid crystal alignment treatment agent of the present invention may contain components other than the above. A fluorine-based surfactant or a polyoxyalkylene-based surfactant which increases the flatness of a coating film, such as a functional decane-containing compound or an epoxy group-containing compound used for improving the adhesion between a liquid crystal alignment film and a substrate. Nonionic surfactants, etc. When the content of the functional decane-containing compound or the epoxy group-containing compound is contained, it is preferably 1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the resin component. Good for 1 to 1 part by mass. When the surfactant is contained, the content thereof is preferably 0.01 to 2 parts by mass, more preferably 1 to 1 part by mass, per 100 parts by mass of the resin component. 5. Liquid crystal alignment film and liquid crystal display element The liquid crystal alignment treatment agent of the present invention is applied to a substrate, baked, and then subjected to rubbing treatment or light irradiation, similar to a commercially available polyimine-based liquid crystal alignment treatment agent. Orientation treatment, or a part of vertical alignment use, etc., may be used as a liquid crystal alignment film without alignment treatment. The coating method of the liquid crystal alignment treatment agent of the present invention is not particularly limited, and it can be generally carried out by a method such as screen printing, letterpress printing, offset printing, or inkjet printing. Other methods of using the coating liquid include, for example, dipping, roller coating, strip coating, spin coating, and the like, which can be used in combination with the above methods. After coating on the substrate by these methods, the solvent is evaporated by a heating means such as a hot press plate to form a coating film. -29- 200906769 The calcination after coating the liquid crystal alignment agent can be carried out at any temperature of 100 to 300 ° C, preferably 150. 〇: ~250. (: The calcination can be carried out using a hot press plate, a hot air circulation furnace, an infrared furnace, etc. The rubbing treatment can use a man-made fiber cloth, an anti-loning cloth, a cotton cloth, etc. The liquid crystal alignment film for vertical alignment is not easily handled by rubbing. When the liquid crystal alignment treatment agent for vertical alignment is used, it is preferably used without using friction. The liquid crystal cell of the present invention can be produced by a usual method, and the production method thereof is not particularly limited. In general, for example, a sealant is applied to a glass substrate on which a liquid crystal alignment film is formed on at least one of the substrates, and the distance adjuster is dispersed while maintaining a constant gap, and then the two substrates are bonded together to form a sealant. Hardening to make an empty unit cell' followed by vacuum injection, liquid crystal injection into the liquid crystal injection port to re-close the injection port to make a liquid crystal cell; or, on the substrate on which the distance adjuster is dispersed, liquid crystal After that, two substrates are bonded together to form a liquid crystal cell. For the liquid crystal 'combination, a fluorine-based liquid crystal or a cyanide liquid having a positive or negative dielectric anisotropy can be used. The liquid crystal alignment film produced by the liquid crystal alignment treatment agent of the present invention can provide a larger pretilt angle of the liquid crystal, and can be used as a liquid crystal alignment film for various purposes. [Embodiment] Hereinafter, the present invention will be enumerated. The manner of the examples is specifically described, but the present invention is not limited by the examples. -30- 200906769 "Synthesis of diamine of the present invention" <Example 1 > Synthesis of diamine [9] ]

Me〇-〇-M9Br —7~► Me〇-〇^IHI)-CsH'i —^ MeO-IU Ο 1=0~0~°5~1 ^Q-OO^h” 〇2Ν^γΝ〇2 X, m

〇2N m

HzM^wNHa, ~CXIK!>csh" 4-nitrophenyl magnesium bromide [1] (0.5M - tetrahydrofuran solution, 2_4L, 1.20 mol) and tetrahydrofuran (200 mL) were added to a nitrogen-substituted four-necked flask. After cooling the reactor to 0 ° C, a solution of 4-(trans-4-n-pentylcyclohexyl)cyclohexanone [2] (300 g, 1.20 mol) in tetrahydrofuran (280 g) was added dropwise. After completion, the temperature was gradually raised to 251, and the mixture was further stirred at 25 ° C overnight. After the completion of the reaction, the reaction solution was cooled to 〇 ° C, and then a 10% aqueous acetic acid solution (1.0 L) was gradually added dropwise. Thereafter, The aqueous layer was removed by a liquid separation operation, and toluene (2.4 L) was added thereto, and washed with a saturated aqueous solution of sodium chloride (1. 〇L) > saturated aqueous sodium hydrogencarbonate (1.0 L) and saturated brine (1.0 L). After the organic layer was dried, the solvent was evaporated under reduced pressure, and the obtained compound [3] (cis-trans isomer mixture) (43 g) was used for the subsequent reaction without treatment. -NMR was carried out using TMS (Si(CH3) 4 -31 - 200906769) as a reference material in a hydrogenated chloroform using an NMR measuring apparatus (400 MHz). The measurement results of the compound [3] are as follows, and the other compounds are also the same. Compound [3] (cis-trans isomer mixture); !H-NMR (400 MHz > CDC13 ' δ ppm ) : 7.47 -7.3 0 ( 2H,m) , 6.98-6.82 ( 2H,m ) , 3 · 8 1 - 3.7 9 ( 3 H,m ), 2.34-0.8 1 ( 3 0H,m ). Compound [3] - a mixture of anti-isomer mixture) (43 0 g, 1.20 mol) and p-toluenesulfonic acid monohydrate (I3.1 g, 72.0 mmol) in a mixture of dehydrated toluene (2 · 5 L·), which was removed under reflux The reaction was carried out for 2 hours in the water. After the completion of the reaction, the temperature was set to 80 ° C, and washed with a saturated aqueous solution of sodium hydrogencarbonate (1 _ 5 L) and saturated brine (1·5 L). After the organic layer was dried, the solvent was evaporated under reduced pressure. The obtained crude product was recrystallized from ethyl acetate/ethanol (1:1 v / v) to give compound [4] (cis-trans isomer mixture) Yield 349 g, yield 89%). Compound [4] (cis-trans isomer mixture); 'H-NMR (400 MHz > CDC13, δ ppm): 7.32 (2H,d), 6.84 ( 2H'd) '6.0 2 (lH, m), 3.80 (3H, s), 2.48-1.75 (9H, m), 1.38-0.86 (19H, m). Compound [4] (cis-trans isomer mixture) (3 79 g, 1.010 m 01 ), 5% palladium carbide (aqueous, 1 9 · 0 g, 5 wt %), ethyl acetate (1.0 L A mixture of ethanol (1.0 L) was stirred at 25 ° C in the presence of hydrogen. After completion of the reaction, the reaction mixture was concentrated with diatomaceous earth, and the celite was washed with toluene (1. 〇l). The filtrate was concentrated under reduced pressure to give compound [5] ( cis-trans isomer mixture) (yield: 473 g, yield: 1:1) Compound [5] (cis-trans isomer mixture); h-NMR (400MHz, CDC13 ' δ ppm ) : 7.14 ( 2Η,m ), 6.83 ( 2H,m) . 3.78 ( 3H > s ) 5 2.64-2.3 5 ( 1 H > m ),1 .8 8 - 1.52 ( 8H,m ) > 1.49-0.74 ( 22H > m ). 〇°C, under nitrogen substitution, in a solution of compound [5] (cis-trans isomer mixture) (347 g, 1.0 mmol) in dichloromethane (2. 〇L), boron tribromide (1.0) was added dropwise. M-dichloromethane solution, 丨.01^, lOmol). After the dropwise addition, stirring was carried out for 2 hours at 〇 °C. After the reaction is completed, the reaction solution is gradually added to distilled water as little as possible. It was extracted with ethyl acetate (2 _ 0 L), and the extract was washed twice with distilled water (1.0 L). After the organic layer was dried over magnesium sulfate, the solvent was evaporated under reduced pressure. The obtained crude product was recrystallized from ethanol and washed with ethanol to give compound [6] (trans isomer) (yield: 183 g, yield: 55%). The cis-trans isomer of the 1,4-cyclohexyl group of the compound [6] is a trans isomer. Compound [6] (trans isomer); 'H-NMR (400 MHz > CDCI3 ' δ ppm ) : 7.07 ( 2H,d ), 6.75 ( 2H,d) , 4.60 ( 1H,s) , 2.37 ( 1H , m), 1.90-1.71 ( 8H, m) , 1.39-0.84 ( 22H, m). Compound [6] (trans isomer) (41.66g, 1 27mmol), 3,5-dinitrobenzyl chloride [7] (27.57g, 127mmol), THF (220g) at 25 °C A solution of sodium hydroxide (-33-200906769 5.08 g, 120 mmol) in distilled water (110 g) was added dropwise to the solution. Warm to 401: and stir for 8 hours. After completion of the reaction, the mixture was cooled to 25 ° C, and the reaction mixture was poured into distilled water (2 L). The obtained crystals were filtered and subjected to ultrasonic cleaning twice in acetonitrile. Thereafter, recrystallization was carried out twice using an acetonitrile/ethyl acetate (1:1 v/v) mixed solvent to obtain a compound [8] (trans isomer) (yield 4 3 · 4 g, yield 67%) ). The cis-trans isomerism of the 1,4-cyclohexyl group of the compound [8] is a trans isomer. Compound [8] (trans isomer); ]H-NMR (400 MHz - CDC13 > (5 ppm): 9.00 (1H, s), 8.65 (2H, s), 7.17 (2H, d), 6.92 ( 2H,d), 5.23 ( 2H > s ) , 2.41 (lH, t) , 1.92-1.60 (8H, m), 1.41-0.86 ( 22H, m). Compound [8] (trans isomer) (43.34g, 85.2mmol), a mixture of platinum (IV) oxide (4 _ 3 g, 10 wt%), dioxane (260 g), toluene (260 g), in the presence of hydrogen, under 60 After the reaction was completed, the mixture was filtered at 80 ° C. The obtained filtrate was stirred at 〇 ° C. The crystal was precipitated by cooling. The precipitated crystals were filtered and washed with toluene twice. The diamine [9] (trans isomer) was obtained (yield 24_4 g, yield 64%). The cis-trans isomer of the 1,4-cyclohexyl group of the compound [9] was a trans isomer. Amine [9] (trans isomer); lH-NMR (400MHz - CDC13 ' (5 ppm ) : 7_10 ( 2H,d )'6.88(2H,s) , 6.18(2H's) , 5.98(lH,d) , 4.86 ( 2H ' s) > 2.59 ( 4H, br 0 ad ) , 2.3 8 ( 1H,t ), -34- 200906769 1.90-1.71 ( 8H, m), 1.40-0.86 (22H, m). <Example 2 > Synthesis of diamine [15] [Chem. 13]

Br-〇-〇csHii [1〇1 0~KD~C5H11 M2]

MeO-QB(OH)2 in] 02Nr^vN〇2 112] H0O_O_j〇_C5Hi 1 [13] o^C^OKDcsh” [141 h2n^nh2 ^)O-〇-〇_C5hi 1 [151 〇2Ν^ Ν〇Ν〇2 [14] ^-Cl [71] 4-(trans-4-n-pentylcyclohexyl)bromobenzene [10] (50.0 g, 162 mmol), 4-methoxyphenyl decanoic acid [11] (36.9 g, 243 mmol), toluene (1.4 L) 'ethanol (0.1 6 L), and a mixed solution of sodium carbonate aqueous solution (sodium carbonate (44-6 g, 420 mmol) / distilled water 0.6 L) were degassed using nitrogen gas. In, under the nitrogen atmosphere

Pd(PPh3) 4 ( 〇.93 4g ' 0.80 8mmol ), at 90. . Stir for 6 hours. After completion of the reaction, the organic layer was separated and washed twice with distilled water (〇.5 L). After the organic layer was dried over magnesium sulfate, the solvent was evaporated under reduced pressure. The obtained crude product was recrystallized from a mixed solvent of ethyl acetate / hexane (1 : 1 v / v ), and washed with hexane to give the compound [1 2] (trans isomer) (yield 40.0 g, yield 73%). The 1,4-cycloexene of the compound [12] -35- 200906769 The cis-trans isomerism of the group is a trans isomer. Compound [1 2] (trans isomer); !H-NMR (400 MHz > CDC13 > δ ppm) : 7.5 1 ( 2H,d ), 7.47 ( 2H,d) , 7.26 ( 2H,d) , 6.96 ( 2H,d), 3.84 ( 3H > s ) , 2.50 (1H,t ) , 1.90 (4H,t ) , 1.53- 1.42 (2H,m) ,1.36-1.20 (9H,m) ,1.12-1.01 (2H, m ) , 0.90 ( 3H, t ). Boron tribromide (1.0M-) was added to a solution of the compound [1 2] (trans isomer) (40.0 g '119 mmol) in a solution of dichloromethyl (0.5 L) at 〇 ° C and nitrogen substitution. Methylene chloride solution, 0.120 L, 120 mmol). After the dropwise addition, the mixture was stirred at 〇 ° C for 2 hours. After the completion of the reaction, the reaction solution was slowly added to distilled water (0.5 L) a little. It was extracted with ethyl acetate (0.5 L), and the extract was washed twice with distilled water (3·L). After the organic layer was dried over magnesium sulfate, the solvent was evaporated under reduced pressure. The obtained crude product was recrystallized from a mixed solvent of ethyl acetate-hexane (1:1) and washed with hexane to give compound [13] (trans isomer) (yield: 29.5 g, yield 77%) . The cis-trans isomerism of the 1,4-cyclohexyl group of the compound [13] is a trans isomer. Compound [1 3] (trans isomer); 1H-NMR (400MHz, CDC13, δ ppm): 7.47-7.4 5 ( 4H,m) , 7_26(2H,d) ,6.88(2H,d) > 4.82 ( 1H - s ), 2.49 ( 1H, t) , 1.90 ( 4H, t) , 1.5 5 - 1.40 ( 2H > m ), 1.36-1.21 (9H, m) , 1.12-1.01 (2H, m) - 0.90 ( 3H,t ). 25 t: under compound [13] (trans isomer) (13.2 g, -36-200906769 4 0.9 mm ο 1 ) ' 3,5-mononitrosyl chloride [7] (1 0.6 g A solution of sodium hydroxide (1.97 g, 49-1 mmol) in distilled water (50 g) was added dropwise to a solution of '49.1 mmol), tetrahydrofuran oxime (60 g), and hydrazine, hydrazine-dimethylformamide (42 g). After dripping, it was stirred at room temperature for 4 hours. After the reaction was completed, it was cooled to 25 ° C' and distilled water (0.5 L) was added for ultrasonic washing. The obtained crystal was filtered to give a crude product. The crude product was recrystallized from a mixed solvent of acetonitrile / N,N-dimethylformamide (8: lv / v) to give compound [14] (trans isomer) (yield: 15.7 g, yield 76%) . The cis-trans isomerism of the 1,4-cyclohexyl group of the compound [14] is the trans isomer compound [14] (trans isomer); 'H-NMR (400 MHz - CDC13 - 5 ppm) : 9.03 ( 1H,t )'8_68(2H'd) '7.56(2H,d), 7.48(2H,d), 7.27 ( 2H - d ),7.06(2H,d),5.29(2H,s) , 2.51( 1H ' ' 191 ( 4H > t ) . 1.54- 1.40 ( 2H > m ) > 1.36- 1.20(9H'm) '113_1〇〇(2H,m),〇9〇(3H t). Mixture of compound [14] (trans isomer) (15.7g, 31.2mm〇l), oxidized (IV) (1.57g, 10wt%), and dioxane (280g) in hydrogen atmosphere After stirring at room temperature for 16 丨, then pray at 3 [C / 3 / [\ 03⁄4. 呀. After the reaction is over, filter at 8 (TC. The filtrate obtained under reduced pressure) After distilling, the crude product was obtained. The crude product was recrystallized from dioxane (yield: 68%) to amine [15] (trans isomer) (yield 9.37 g, compound [1 5] 1,4- 4 The cis-trans isomerization of hexyl is a trans isomer. -37- 200906769 Diamine [1 5] (trans isomer); 1H-NMR (400MHz, CDC13, δ ppm) 7.5 1-7.45 ( 4H,m) , 7.25 ( 2H,d) , 7.01 ( 2H,d) > 6.21 ( 2H > d ), 5.99 (lH,t) , 4.92 (2H,s) , 3.61 (4H ,brord) , 2.49 ( 1H,t ) ,1_90(4H,t ) ,1.55-1.41 (2H,m)

, 1.36-1 _21 ( 9H, m ) , 1 · 1 3 -1 _ 0 0 ( 2 H, m ) , 0.90 ( 3H , t ) ° <Example 3> Synthesis of diamine [21] 14] ΠΜ Γ:Ι

ΒΓ

Methyl 2,5-dibromobenzoate [16] (10.0 g > 34.0 mmol) in diethyl ether (1 13 mL) was cooled to -50 ° C under nitrogen atmosphere over 30 min. Diisobutylaluminum hydride (0.94 M hexane solution, 8 6.8 6 m L, 8 1 .65 mm ο 1 ) was added dropwise to the solution. After the reaction solution was stirred for 1 hour, it was further stirred at 〇 ° C for 1.5 hours. Next, water -38 - 200906769 (4.4 mL), sodium fluoride (4_4 g), and diatomaceous earth (3.8 g) were added to the reaction solution at 0 ° C to stop the reaction. After filtration through celite, the solvent was evaporated under reduced pressure to give crude compound (yield: 8.21 g). This crude product does not need to be refined, even for subsequent reactions. Compound [17]; 'H-NMR (400 MHz, CDC13, 6 ppm): 7.66 (1 Η, d), 7.39 (lH, d), 7.28 (lH, dd), 4.50 (2H, d), 2.0 1 ( 1H, t). Triethylamine (10 mL, 77.2 mmol) was added to a methylene chloride solution (0.3 L) of Compound (17). The reaction solution was cooled to 〇 ° C, and methanesulfonic acid chloride ( 4.78 mL > 61.8 mmol) was added. After stirring at 25 ° C for 16 hours, it was stirred under reflux with heating for 10 hours. After the reaction solution was cooled to 25 ° C, water was added to stop the reaction, and the mixture was extracted with dichloromethane. The organic layer was washed with water and dried over magnesium sulfate. Purification was carried out using a ruthenium gel chromatography (hexane/ethyl acetate = 20/1) to give compound [18] (yield: 8.19 g, yield (2 steps) 85%). Compound [1 8]; 'H-NMR (400 MHz > CDC13 > δ ppm): 7.63 (1H, d), 7.44 (1H, d), 7-33 (1H, dd), 4.64 (2H, s). The compound [8 8 (5.67 g, 1 7 _ 3 mmo 1 ) and the compound [6] (5 .15 g, 1 8 · 1 mm ο 1 ) synthesized in the same manner as in Example 1 were dissolved in tetrahydrofuran. Sodium iodide (0.25 9 g, 1.73 mmol) and potassium carbonate (5.01 g, 36.2 mmol) -39-200906769 were added to a mixed solvent of (50 mL) and acetonitrile (9 mL). The reaction solution was heated to 80 ° C and stirred for 48 hours. After the reaction solution was cooled to 25 ° C, the insoluble matter was removed by suction filtration. The filtrate was evaporated under reduced pressure to give a crude material. The crude product was washed with hexane and purified by EtOAc EtOAc EtOAc (EtOAc (EtOAc) Compound [1 9]; 'H-NMR (400 MHz, CDC13, 5 ppm): 7.73 (1H > d ), 7.43 (1H, d), 7.31 (1H, dd), 7.15 (2H, d), 6.91 ( 2H, d), 5.05 (2H, s) > 2.42-2.3 3 ( 1 H > m ), 1.97- 1.66 ( 8H > m ) , 1.47-0.89 ( 22H, m). Benzophenone imine (5.49 mL, 3 2.7 mmol) was added to the compound [19] (7.86 g, 13.6 mmol) and tris(dibenzylideneacetone) dimethane (〇) under a nitrogen atmosphere (62.4 mg, 0.06). 82mmol), ((soil)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP) (0.127g, 0.205mmol), t-butoxy sodium (t-BuONa) ( 3.67 g, 38.2 mmol) in toluene (55 mL) was heated to 80 ° C. The reaction solution was stirred for 24 hours, cooled to 25 ° C, and then poured into ethyl acetate ( 275 mL) to stop the reaction. After removing the insoluble matter, the filtrate was distilled off in a solvent to obtain a crude product, which was purified using a hexane gel chromatography (hexane/ethyl acetate = 10/1) to give compound [20] (trans isomer (product) 9.72 g, yield 92%). The cis-trans isomerism of the 1,4-cyclohexyl group of the compound [20] is a trans isomer. -40- 200906769 Compound [20] (trans isomer); ]H-NMR (400MHz > CDC13 > δ ppm ) : 7.73 ( 2H,d ), 7.68 ( 2H,d) , 7.46-7.3 3 ( 6H,m ) , 7.3 2-7.20 ( 4H > m ) , 7.19-7.14(2H,m) , 7.08(2H,d) ,7.04( 2H,d) ,6_99(2H,d) ,6.89(lH, d) , 6.78 (2H, d ), 6.31 (lH, dd), 6.16 (lH, d), 4_93 (2H, s), 2.42-2.3 2 ( 1 H > m) , 1 · 94 - 1_66 ( 8 H, m ) , 1.43 -0.89 ( 2 2 H,m ). To a suspension of the compound [20] (trans isomer) (13.9 g, 17.9 mmol) in methanol (180 mL), sodium acetate (7.05 g, 86.0 mmol) and base amine hydrochloride (4.48 g, 64.5 mmol). After stirring for 1 hour, the organic layer was dried over magnesium sulfate using dichloromethane and EtOAc. The solvent was evaporated under reduced pressure to give a crude material. Purified by 矽 gel chromatography (hexane/ethyl acetate = 1 / 1) and recrystallized from dichloromethane/methanol to give the diamine [2 1] (trans isomer) (yield 6.07) g, yield 76%). The cis-trans isomerism of the 1,4-cyclohexyl group of the compound [21] is a trans isomer. Diamine [2 1] (trans isomer); 】 H-NMR (400MHz, CDC13, δ ppm ) : 7.13 ( 2Η > d

), 6.92 ( 2H,d) , 6.6 5-6.5 6 ( 3 H,m ) , 4.93 ( s,2H ),3 · 70-3 _ 3 0 ( brord,4H ) ,2.4 3 - 2 _ 3 3 ( m, 1 H ), 1.93-1.61 (m, 8H), 1.44-0.81 (m, 22H). -41 - 200906769 <Example 4 > Synthesis of diamine [24]

, no2 ~ [23] 〇,

The diamine [24] (trans isomer) was obtained from the compound [22] (trans isomer) according to the same synthesis method as in the <1> Compound [2 3] (trans isomer);

iH-NMR (400MHz, CDC13, 5 ppm) : 9.0 1 ( t, 1H

), 8.65 (d, 2H), 7.17 (d, 2H), 6.94 (d, 2H), 5.23 (s, 2H), 2.46-2.35 (m, 1H), 1.93-1.70 (m, 8H) > 1.45 - 1 .20 ( m > 12H ) , 1.20-0.93 (m, 9H) - 0.88 ( t, 3H ) , 0.9 1 -0.80 ( m, 2H ). Compound [24] (trans isomer);

'H-NMR (400MHz ' CDC13 ' (5 ppm ) : 7_10 ( d,2H ), 6.88 (d, 2H) , 6.18 (d, 2H) , 5.98 (t, lH), 4.86 (s, 2H) >3.59(bs> 4H) , 2.43-2.32 (m, lH), 1.93-1.70 ( m > 8H) , 1 · 4 3 · 1 _ 1 9 ( m, 1 2 H ) , 1.19-0.92 -42- 200906769 (m, 9H), 0.88 (t, 3H), 0.91 - 0.78 (m, 2H). <Synthesis Example 1 > Synthesis of diamine [29] [Chem. 16]

Me〇_O"MgBr ϊ一^ ηο-Ο-Ο-Ο^ημ 111 [26J 127]

Br~0~0~CSH11 [25]

4-Bromo-4'-(η-pentyl)biphenyl [25] (25.0 g, 82_4 mmol) and tetrakis(triphenylphosphine) IG (0) were added to a nitrogen-substituted four-necked flask at room temperature. After (4.7 6 g '4.1 2mmo 1 ), 4-methoxyphenylmagnesium bromide [1] (0.5M-tetrahydrofuran solution, 280 mL, 140 mmol) was further added, followed by heating under reflux. After completion of the reaction, the solid was precipitated after cooling to room temperature, and then the mixture was poured into ethyl acetate (200 g) / 1M hydrochloric acid (2OOmL) and then filtered. The obtained solid was washed with water and then washed with ethyl acetate and then evaporated to afford compound (26) (yield: 268 g, yield 98%). Compound [26]; 'H-NMR (400MHz, CDC13, δ ppm) ·· 7.66-7.54 ( 8Η,m) , 7.23 ( 2H,d) , 7.0 - 6 ' 9 8 ( 2 H,m ) > 3.86 ( 3H,s ) , 2.65 ( 2H,t ) , 1 · 6 8 -1 _ 6 4 ( 2 H,m ) , 1.40-1.33 (4H,m) , 0.93-0.89 ( 3H,m). -43- 200906769 In a solution of compound [26] (25.00 g, 75.7 mmol) in dehydrated dichloromethane (300 g) at 0 ° C under nitrogen substitution, boron tribromide (1.0 M-dichloromethane solution, 75.7 mL, 75.7 mmol). After the dropwise addition, the reaction was stirred at 〇 ° C for 2 hours, and after the completion of the reaction, the reaction liquid was slowly added to distilled water. After slowly heating to 60 ° C, it was extracted with 2.5 L of ethyl acetate, and the organic layer was washed twice with 300 mL of distilled water. After the organic layer was dried over magnesium sulfate, the solvent was concentrated to about 50 mL. The precipitated solid was washed with ethyl acetate, and then dried to give compound (27) (yield: 9.1 g, yield: 80%). Compound [2 7]; 1H-NMR (400 MHz > DMS0-d6 1 δ ppm): 9.58 (1Η, s) , 7.69-7.64 ( 4 Η, m ) , 7 · 6 1 - 7 · 5 9 ( 2 Η, m ), 7.5 5 -7.5 3 ( 2H,m) , 7.27 ( 2H,d) ,6.8 8 -6.8 6 ( 2H,m ), 2.60 ( 2H,t) ,1.64- 1 .5 6 ( 2H,m ) , 1.3 5- 1.28 ( 4H,m ) , 0.87 ( 3H,t ). The compound [27] (11.00 g, 34.8 mmol) and 3.5-mononitrosyl chloride [1] (7.53 g, 34.8) were dropped from a solution of 30 g of distilled water of sodium hydroxide (1.39 g, 34.8 mmol) at room temperature. In a solution of mmol) and tetrahydrofuran (80 g), after heating to 40 ° C, stirring was carried out for 8 hours. After the end of the reaction, the mixture was cooled to room temperature, and the reaction mixture was poured into distilled water (40 mL). The obtained crystals were filtered, and then acetonitrile (150 g) was added thereto, and the mixture was washed with an ultrasonic device to carry out re-filtration. Thereafter, it was recrystallized from acetonitrile (4 〇〇g) to obtain a compound (28) as a yellow earth solid (yield -44 - 200906769 1 3 . 5 g, yield 78%). Compound [28]; iH-NMR (400MHz, DMSO-d6, δ ppm): 8.80 ( 1 Η , t ) , 8.81 ( 2H,d) , 7.71-7.69 ( 6H,m ) , 7.62-7.60 (2H,m ), 7.29-7.27 ( 2H,m ) , 7 · 2 0 - 7. 1 7 ( 2 H,m ) , 5.46(2H,s) , 2_61(2H,t) ,1.64-1.56 (2H,m) , 1.35-1 _28 ( 4H,m ) , 0.88 ( 3H,t ). A mixture of compound [28] (12.00 g, 24.2 mmol), uranium oxide (1.2 g '10 wt%), and Eryuan (180g) was stirred in the presence of hydrogen at 65 t. 7 hours. After completion of the reaction, after nitrogen substitution, tetrahydrofuran (1 L) was added, and the mixture was heated to 80 ° C to dissolve the solid, followed by filtration over celite. The filtrate was concentrated to such an extent that the amount of the solvent was about 1 〇〇g, and the mixture was washed with an ultrasonic device, filtered, and dried to obtain a white diamine [29] (yield: 7.7 g, yield: 72%). Diamine [29]; W-NMR (400MHz, DMSO-d6, δ ppm): 7.69 ( 4Η ,S ) , 7.64-7.60 ( 4H, m ), 7.29 ( 2H, d) > 7.06-7.04 (2H , m ) , 5. 8 8 ( 2H ,d ), 5.76 ( 1 Η ,t ) , 4.86 ( 2H ,s ) , 4_78 ( 4H,s ) , 2.61 (2H > t ) ,1.64- 1 .5 6 (2H , m ) , 1.3 5 - 1.2 8 ( 4H > m ), 0.88 ( 3H, t ) ° Synthesis of polyglycine or polyimine of the present invention - 45 - 200906769 Examples and comparisons below The abbreviations and structures of the compounds used in the examples are as follows. (tetracarboxylic dianhydride) BODA: bicyclo[3,3,0] xinyuan-2,4,6,8-tetradecanoic acid dianhydride CBDA : 1,2,3,4-cyclobutane tetracarboxylic acid Diacetate

p-PDA : p-phenylenediamine DBA : 3,5-diaminobenzoic acid m-PBCH5DABz : 1,3-diamino-5-{4-[trans-4-(trans-4-11 - pentylcyclohexyl)cyclohexyl]phenoxymethyl}benzene p-PBCH5DABz : 1,4 -diamino-5 - { 4 -[trans-4 -(trans-4 - η-pentylcyclohexyl) Cyclohexyl]phenoxymethyl}benzene m-BPCH5DABz : 1,3-diamino-5- { 4-[4-(trans-4-n-pentylcyclohexyl)phenyl]phenoxymethyl }Benzene m-PBCH7DABz : 1,3-diamino-5-{4-[trans-4-(trans-4-11-heptylcyclohexyl)cyclohexyl]phenoxymethyl}benzene m-PBCH5DABEs : 3,5-Diamino-{4-[trans-4-(trans-4-11-pentylcyclohexyl)cyclohexyl]phenyl}benzoate-46- 200906769 PCH7DAB : 1,3-diamine 4-[4-(trans-4-11-heptylcyclohexyl)phenoxy]benzene PBP5DABz : 1,3-diamino-4-[(4-n-pentylphenyl)phenoxy Methyl]benzene (Note) m-PBCH5DABz is the diamine [9] synthesized in the same manner as in Example 1. m-BPCH5DABz was the diamine [15] synthesized in the same manner as in Example 2. P-PBCH5DABZ was the diamine [21] synthesized in the same manner as in Example 3. m-PBCH7DABz was the diamine [24] synthesized in the same manner as in Example 4. m-PBCH5DABEs was synthesized according to the examples of the compound [6]', which is the same as the operation method of the first embodiment, according to the examples of JP-A-2004-67589. PCH7DAB is a synthesizer based on the embodiment of the Japanese Patent Publication No. Hei 9-278724. PBP5DABZ is a diamine [29] synthesized in the same manner as in Synthesis Example 1. -47- 200906769 [Chem. 18]

p-PBCH5DABz

-48- 200906769 [Chem. 20]

m-PBCH5DABEs

(Organic solvent) NMP : N -methyl-2-pyrrolidone BCS : butyl cellosolve The measurement methods used in the following examples are as follows. [Molecular weight] In the present example, the number average molecular weight (hereinafter also referred to as Μη) and the weight average molecular weight (hereinafter referred to as Mw) of the polyimine are a room temperature gel-impregnated color layer analyzer manufactured by Shodex ( The GPC) device (GPC-101) and the Shodex company column (KD-803, KD-805) were measured in the following manner. -49- 200906769

Column temperature: 50 ° C Dissolution: N,N-dimethylformamide (additive is lithium bromide-water and (LiBr. H2〇) is 30mm〇l/L, phosphoric acid. Anhydrous crystal (0-phosphoric acid) ) is 30 mm 〇 l / L, tetrahydrofuran is l 〇 mi / L) Flow rate: l.OmL / minute calibration line production standard sample: TSK standard polyethylene oxide manufactured by Tosoh Corporation (molecular weight of about 900,000, 150,000, 1 〇) 〇, 〇〇〇, 30,000), and polymer Laplacian polyethylene glycol (molecular weight of about 12,000, 4,000, 1,000) ° [醯imination rate] In this example, the ruthenium of polyimine The imidization ratio is determined in the following manner. About 20 mg of polyimine powder was placed in an NMR sample tube, and about 0.5 3 ml of a dimethyl hydride (DMSO-d6, 0.05% TMS (Si(CH3) 4 ) mixture) was added thereto, and ultrasonic waves were applied thereto. completely dissolved. This solution was used to determine the proton N M R of 5 Ο Ο Η Η z by an N M R measuring device. The sulfhydrylation rate is determined by the protons produced by the structure that has not changed before and after the imidization, and the peaks of the protons are calculated by ΝΗ, and the hydrazide of the proline which occurs near lO.Oppm The proton peaks are calculated by the following equations.

焦亚fe:Chemical rate (%) = (l-α .x/y) xlOO In the above formula, 'x is the peak of the proton peak generated by the NH group of proline, and y is the peak of the proton. In the case where α is polyamine (醯-50-200906769 imidization ratio is 0%), the ratio of the number of reference protons of one proton of the NH group of valeric acid. &lt;Example 5 &gt; BODA (5.07 g, 20.3 mmol), P-PDA (2.48 g, 22.9 mmol), and branched diamine m-PBCH5DABz (1.82 g, 4.05 mmol) in NMP (22_0 g) After mixing and reacting at 40 ° C for 5 hours, CBDA (12 g, 5.71 mmol) and NMP (20_0 g) were added and reacted at 40 ° C for 6 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (30. g) and diluting to 6 mass%, acetic anhydride (4_48 g) and pyridine (3.47 g) of a ruthenium catalyst were added and reacted at 80 ° C. 3 hours. The reaction solution was poured into methanol (42 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 1 〇 ° C to obtain a polyimine powder (A). The polyimine had a hydrazine imidation ratio of 48%, a number average molecular weight of 12,100, and a weight average molecular weight of 3,400. &lt;Example 6 &gt; BODA (4.88 g, 1 9 · 5 mm ο 1 ) ' p-PDA ( 2.39 g, 22.1 mmol ), branched-chain diamine m-BPCH 5 DABz ( 1.73 g, 3.9 1 mmol ) After mixing with NMP (22·〇g) and reacting at 40 ° C for 5 hours, CBDA (1.16 g, 5.92 mmol) and NMP (18.0 g) were added and reacted at 40 ° C for 6 hours to obtain polyamine. Acid solution. After adding NM P to the poly-proline solution (30 ° 〇g) and diluting to 6 mass -51 - 200906769 %, adding acetic anhydride (3 · 8 8 g ) and pyridine of the ruthenium catalyst. 3.01 g ) 'Reaction at 80 ° C for 3 hours. The reaction solution was poured into methanol (3 74 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol to dryness under reduced pressure at 1 ° C to obtain a polyimide pigment (B). The polyimine had a ruthenium imidation ratio of 41%, a number average molecular weight of 15,4 Å, and a weight average molecular weight of 47,000. &lt;Example 7 &gt; BODA (4.6 9 g '1 8.7 mm ο 1 ), p - PDA (2_30 g, 2 1 , 3 mmol), and branched diamine p-PBCH5DABz ( 1.63 g, 3.63 mmol) in NMP (20.0 g) was mixed, and after reacting at 40 ° C for 5 hours, 'CBDA (1 - 03 g, 5 - 25 mmol) and NMP (16.0 g) ' were reacted at 40 ° C for 6 hours to prepare a polyaminic acid solution. After the NMP was diluted to 6 mass% in the polyamic acid solution (20. g), acetic anhydride (2 · 5 9 g) and pyridine (2.01 g) were added to the ruthenium catalyst at 80 °. The reaction was carried out for 3 hours at C. The reaction solution was poured into methanol (24 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol to dryness under reduced pressure at 1 ° C to obtain a polyimide pigment (C). The polyimine had a hydrazine imidation ratio of 40%, a number average molecular weight of 12,900, and a weight average molecular weight of 35,800. &lt;Example 8 &gt; BODA (4.66 g, 17.8 mmol), p-PDA (2.18 g, 20.2 mmol), branched-chain diamine m-PBCH7DABz ( 1.70 g, -52-200906769 3.57 mmol) in NMP ( After the reaction was carried out for 5 hours at 40 ° C, CBDA (0.98 g, 5.00 mmol) and NMP (15.5 g) were added and reacted at 40 ° C for 6 hours to obtain a polyaminic acid solution. After the NMP was added to the polyamic acid solution (2〇.〇g) and diluted to 6 mass%, acetic anhydride (2.65 g) and pyridine (2.11 g) of the ruthenium catalyst were added at 80 °. The reaction was carried out for 3 hours at C. The reaction solution was poured into methanol (280 m 1 ), and the resulting precipitate was decanted. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (D). The polyamidimide had a ruthenium iodide ratio of 45%', a number average molecular weight of 14,100, and a weight average molecular weight of 399,800. &lt;Comparative Example 1 &gt; BODA (5.07 g, 20.3 mmol), p-PDA (2.48 g, 22.9 mmol), and branched diamine m-PBCH5DABEs (1.87 g, 4.04 mmol) in NMP (22.0 g) After mixing and reacting at 40 t for 5 hours, CBDA (1.0 g, 5.1 mmol) and NMP (20.0 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamidonic acid solution. After the NMP was added to the polyamic acid solution (30.〇g) and diluted to 6 mass%, acetic anhydride (4.28 g) and pyridine (3.32 g) of the ruthenium catalyst were added at 80 ° C. Reaction for 3 hours. The reaction solution was poured into methanol (4 0 8 m 1 ), and the obtained precipitate was filtered. This precipitate was washed with methanol to dryness under reduced pressure at 1 ° C to obtain a polyimide pigment (E). The polyimine had a hydrazine imidization ratio of 45%, a number average molecular weight of 14,900, and a weight average molecular weight of 380,800. -53- 200906769 &lt;Comparative Example 2 &gt; BODA ( 4.47 g, 1 7.9 mmol), p-PDA ( 2.18 g, 2 0.2 mmo 1 ), and PJ5DABz (1.56 g, 3.57 mmol) of the female in January After mixing for 5 hours at 40 t:, CBDA (1.07 g, 5.46 mmol) and NMP (17.5 g) were added at 40. (: The next reaction was carried out for 6 hours to obtain a polyaminic acid solution. After the NMP was added to the polyaminic acid solution (20.0 g) and diluted to 6 mass%, acetic anhydride (3 · 1) of the ruthenium catalyst was added. 0g), pyridine (2·3 8 g), and reacted at 80 ° C for 3 hours. The reaction solution was poured into methanol (275 ml), and the resulting precipitate was filtered off. The precipitate was washed with methanol. The polyimine powder (F) is dried under reduced pressure at 〇〇 ° C. The polyamidimide has a ruthenium imidation ratio of 45%, a number average molecular weight of 15,800, and a weight average molecular weight of 40,800. Solubility test of imine&gt; (comparison of butyl cellosolve tolerance) The polyimine powders obtained in Examples 5 to 8, Comparative Example 1, and Comparative Example 2 were used in the following order for the polyimine solution. A comparison of the allowable amount of butyl cellosolve was carried out. NMP (8.7 〇g) was added to the polyimine powder (1.3 〇g), and the mixture was stirred at 80 ° C for 40 hours to obtain a polythene having a resin concentration of 13% by mass. Imine solution. The polyimine solution (1 _ 〇〇g ) is taken as a sample tube and placed in a magnet stirrer ' stirring at room temperature In the middle, the BCS is dropped into the -54-200906769 by the pipette. The turbidity that occurs after the BCS is dropped is visually confirmed as the end point that is not extinguished after a few seconds. Also, at this time, each drop of BCS The amount is about 0.004 g, and the amount of BCS in the end point can be determined after confirming the mass of the entire sample tube before and after the BCS mixing. From the results of the above test, the end point of the polyimine of Example 5 was used. The BCS was 1.40 g, the BCS of the end point when the polyimine of Example 6 was used was 1 · 16 6 g, and the BCS of the end point when the polyimine of Example 7 was used was 1 - 07 g, and the polyfluorene of Example 8 was used. The BCS of the end point of the imine was 1.36 g, the BCS of the end point when the polyimine of Comparative Example 1 was used was 0.1 g, and the BCS of the end point of the polyimine of Comparative Example 2 was 0.64 g. The results of Examples 5 to 8, Comparative Example 1 and Comparative Example 2 are summarized as shown in Table i. From the above results, it was found that the polyimine using the diamine of the present invention was compared to the use of the comparative diamine. The quinone imine shows that the mixing tolerance of the butyl sol is very large. "The liquid crystal alignment of the present invention Preparation and evaluation of the agent" &lt;Example 9 &gt; p-PDA (1.46 g, 13.5 mmol), branched diamine ΓΓ1 - PBCH5DABz (0.67 g &gt; 1.49 mmol) in NMP (2 〇.〇g) The mixture was mixed, and CBDA (2.85 g, 14.5 mmol) and NMP (24.9 g) were added, and reacted at 25 t for 5 hours to prepare a polyaminic acid solution. NMP (24_0g) and BCS (16_0g) were added to the obtained polyamic acid solution (40.0 g), and the mixture was stirred for 1 hour at -55 to 200906769 to obtain a liquid crystal alignment treatment agent (1). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. The liquid crystal alignment treatment agent (1) obtained above was spin-coated on a glass substrate with a 1 τ Ο electrode, dried on a hot plate at 80 ° C for 5 minutes, and then dried at 23 (TC hot air circulation type). The oven was fired for 1 hour to prepare a polyimine film having a thickness of 10 nm. On the surface of the polyimide film, a friction device with a drum diameter of 120 mm was used, and the number of drum rotations was 1000 rpm, and the speed of the drum was 50 mm/ SeC and a press-in amount of 0.3 mm were rubbed with a rayon cloth to obtain a substrate with a liquid crystal alignment film. Two sheets of the substrate with the liquid crystal alignment film were prepared, and the liquid crystal alignment film was used as the inner side. With a 50 〆m pitcher clamp, the rubbing direction is combined in a reverse manner, and an empty unit cell is formed in such a manner that the sealant adheres to the surroundings. The liquid crystal cell is injected into the liquid crystal cell by a vacuum injection method. - 2 0 03 (manufactured by Melex, Japan), the injection port was sealed to obtain an antiparallel aligned nematic liquid crystal cell. The pretilt angle of the liquid crystal cell fabricated in the above manner was measured using the tilt angle Device (ELSICON) Model PAS-301) was measured at room temperature. As a result, it was found that the pretilt angle was 85.7°, and the liquid crystal cell was heat treated at 120 ° C for 1 hour, which was 8 7 · 5 °. The liquid crystal cell 'made in the same manner as above was observed by a polarizing microscope, and it was confirmed that the liquid crystal system was uniformly oriented vertically. -56-200906769 &lt;Example 1 〇&gt; P-PDA (1.34 g, 12_4 mmol), M_PBCH7DABz (0.65 g, 1.37 mmol) of branched diamine was mixed in NMP (18.5 g). Add CBDA (2.61 g, 13.3 mmol) and NMP (23. g), and react at 25 ° C for 5 hours. After the poly-proline solution was prepared, NMP (21.1 g) 'BCS (14.〇g) was added to the obtained poly-proline solution (35.0 g), and the mixture was stirred for 1 hour to obtain a liquid crystal alignment treatment agent (2). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. Using the liquid crystal alignment treatment agent (2) obtained above, a nematic type having reverse alignment was produced in the same manner as in Example 9. The liquid crystal cell was measured and its pretilt angle was measured. As a result, it was found that the pretilt angle was 86.5. The cell was treated with l2〇t and heat treated for 1 hour at 8 7.3 °. Further, except for the non-friction treatment, the liquid crystal cell prepared by the same method as above was observed by a polarizing microscope to confirm that the liquid crystal system was uniform. Vertical alignment. &lt;Comparative Example 3 &gt; P-PDA (1.56 g '14.4 mmol) and branched diamine PCH7DAB (0.6 1 g ' 1.60 mmol) were mixed in NMP (22.0 g), and CBDA was added ( 3.04 g, 1 5 .5 mm ο 1 ) A reaction with NMP (24.9 g) at 25 ° C for 5 hours to obtain a polyaminic acid solution. To the obtained polyamic acid solution (40.0 g), NMP (24.0 g) and BCS (16.0 g) -57 to 200906769 were added and stirred for 1 hour to obtain a liquid crystal alignment treatment agent (3). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. Using the liquid crystal alignment treatment agent (3) obtained above, a nematic liquid crystal cell having a reverse alignment was produced in the same manner as in Example 9, and the pretilt angle was measured. As a result, it was found that the pretilt angle was 22.2. The liquid crystal cell was subjected to 12 (TC, 1 hour heat treatment, 22.8.) In addition to the non-friction treatment, the liquid crystal cell prepared by the same method described above was observed by using a polarizing microscope to confirm the alignment of the liquid crystal. It is non-uniform and does not exhibit vertical alignment. Example 9, Example 1 The results of 〇 and Comparative Example 3 are summarized as shown in Table 2. From the above results, it is known that the polyamine of the diamine of the present invention is used. A larger pretilt angle can be obtained even when a smaller amount of the introduction of the polyamine than the comparative diamine is used. <Example 1 1 &gt; Polyimine obtained in Example 5 NMP (25_7g) was added to the powder (A) (3.50g), and it was stirred at 80 ° C for 40 hours, and then dissolved. After adding NMP (2.83g) and BCS (26.3g), it was stirred for 1 hour. The liquid crystal alignment treatment agent (4) was obtained. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. The liquid crystal alignment treatment agent (4) obtained above was spin-coated on the ITO. The glass substrate of the electrode is carried out on a hot plate at 80 °C. After the bell is dried -58-200906769, it is calcined in a hot air circulating oven at 2 1 °C for 1 hour to obtain a polyimide film having a film thickness of 10 nm. The substrate with the liquid crystal alignment film is attached. Using a friction device having a drum diameter of 120 mm, a substrate with a liquid crystal alignment film was obtained by rubbing with a rayon cloth under the conditions of a drum rotation number of 300 rpm, a drum speed of 20 mm/sec, and a press-in amount of 0.3 mm. 2 pieces of the substrate with the liquid crystal alignment film, after dispersing the 6 # m particle distance aligner on one of the liquid crystal alignment film surfaces, and then printing the sealant on the other substrate, the liquid crystal alignment film surface is used as the inner side. After the friction direction is reversed, the sealant is hardened to prepare an empty cell. The empty cell is injected into a liquid crystal MLC-6608 (manufactured by Melex Co., Ltd.) by a vacuum injection method, and the injection is performed. The inlet sealing was carried out to obtain a nematic liquid crystal cell having a reverse alignment. The pretilt angle of the liquid crystal cell prepared by the above method was measured at room temperature by a tilt angle measuring device (model PAS-301 manufactured by ELSICON Co., Ltd.). As a result, the pretilt angle is 8 5 . 7 °, the liquid crystal cell was subjected to 1 2 (TC, 86.6° after heat treatment for 1 hour. In addition, the liquid crystal cell after heat treatment at room temperature and after 1 hour was observed by using a polarizing microscope to confirm the liquid crystal system. Uniform alignment, uniform orientation after heat treatment. In addition, except for the non-friction treatment, the liquid crystal cells prepared by the same method as above were observed by a polarizing microscope to confirm that the liquid crystal system was uniformly oriented vertically. <Example 1 2 &gt; -59- 200906769 NMP (26.3 g) was added to the polyimine powder (B) (4_00 g) obtained in Example 6, and the mixture was stirred at 80 ° C for 40 hours to be dissolved. NMP (2.68 g) and BCS (29_3 g) were added to the solution, and the mixture was stirred for 1 hour to obtain a liquid crystal alignment treatment agent (5). The liquid crystal alignment agent did not cause abnormalities such as turbidity or precipitation, and it was confirmed that the resin component was uniformly dissolved. Using the liquid crystal alignment treatment agent (5) obtained above, the same treatment as in Example 11 was carried out to obtain a reverse-aligned nematic liquid crystal cell which was subjected to rubbing treatment. The pretilt angle of the liquid crystal cell was measured in the same manner as in Example 11. It was found that 45.5 ° and 1 2 at room temperature (TC, 4 5.7 ° after heat treatment for 1 hour. Further, except for the non-friction treatment The liquid crystal cell prepared in the same manner as in Example 1 was observed by a polarizing microscope, and the vertical alignment of the liquid crystal system was confirmed. <Example 1 3 &gt; Polysaccharide obtained in Example 7 NMP (23_0g) was added to the amine powder (c) (3.40g) and stirred at 80 °C for 40 hours to dissolve. Add Ν Μ P ( 4 _ 70 g ) and BCS ( 2 5 · 5) to the solution. After g), the liquid crystal alignment treatment agent (6) was obtained by stirring for 1 hour. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. The liquid crystal alignment treatment agent obtained above was used. 6), the same treatment as in Example 1 1 was carried out to obtain a reverse-aligned nematic liquid crystal cell which was subjected to rubbing treatment. The pretilt angle of the liquid crystal cell was measured by the same operation as in Example 1 -60-200906769 It is known that the heat treatment is 29.8°, 120°C, and 1 hour at room temperature. In the liquid crystal cell prepared in the same manner as in Example 1 except for the rubbing treatment, the liquid crystal cell was observed by a polarizing microscope, and it was confirmed that the liquid crystal system was uniform in vertical alignment. [Example 1 4 &gt Mixing BODA (4.3 2 g '1 7.3 mmo 1 ), p-PDA ( 1.74 g, 16.1 mmol), branched-chain diamine m-PBCH5DABz ( 3.10 g, 6.91 mmol) in NMP (22.0 g) After reacting at 40 ° C for 5 hours, CBDA (1.2 g, 5-20 mmol) and NMP (18.0 g) were reacted at 40 ° C for 6 hours to prepare a polyaminic acid solution. After the NMP was added to the solution (30.0 g) and diluted to 6 mass%, acetic anhydride (3.63 g) and pyridine (2-82 g) of a ruthenium catalyst were added, and the mixture was reacted at 80 ° C for 3 hours. The obtained precipitate was filtered off by adding methanol (3,7 ml), and the precipitate was washed with methanol and dried under reduced pressure at 1 ° C to obtain a polyimine powder (G). The amine imidization ratio was 44%, the number average molecular weight was 14,400, and the weight average molecular weight was 43,700. NMP (28.6 g) was added to the polyimine powder (G) (4.00 g). After the mixture was stirred for 40 hours at 80 t, it was dissolved in NMP (3.76 g) and BCS (29.6 g), and the mixture was stirred for 1 hour to obtain a liquid crystal alignment treatment agent (7). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. -61 - 200906769 Using the liquid crystal alignment treatment agent (7) obtained above, the same treatment as in Example 1 was carried out to obtain a reverse-aligned nematic liquid crystal cell which was subjected to rubbing treatment. The pretilt angle of the liquid crystal cell was determined by the same operation as in Example 1 and was 89.2 at room temperature. , 1201, 1 9.7 ° after 1 hour heat treatment. Further, at room temperature, and after one hour of heat treatment, the liquid crystal cells were observed by a polarizing microscope, and it was found that the liquid crystals showed a uniform orientation, which was uniform to the heat treatment. Further, the liquid crystal cell prepared in the same manner as in Example 11 except for the rubbing treatment was observed by a polarizing microscope, and the vertical alignment of the liquid crystal system was confirmed. &lt;Example 1 5 &gt; BODA (4 · 4 1 g, 1 7.6 mm ο 1 ), DBA ( 2.86 g, 1 8.8 mmol), branched-chain diamine m-PBCH5DABz ( 2.11 g, 4.70 mmol) The mixture was mixed with NMP (23.0 g), and reacted at 80 ° C for 5 hours. Then, CBDA (1.01 g, 5.15 mmol) and NMP (1 8-0 g) were added and reacted at 40 ° C for 6 hours to obtain polylysine. Solution. After the NMP was added to the polyaminic acid solution (30.0 g) and diluted to 6 mass%, acetic anhydride (3.78 g) and pyridine (2.93 g) of the ruthenium catalyst were added and reacted at 80 ° C. 3 hours. The reaction solution was poured into methanol (4 0 8 m 1 ), and the obtained precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure at 10 ° to give a polyimine powder (Η). The yield of the iranide was 40%, the number average molecular weight was 16,500, and the weight average was Molecular weight is 4 3,8 00. -62- 200906769 NMP (2 6.3 g ) was added to the polyimine powder (H) (4.00 g) and stirred at 80 ° C for 40 hours to dissolve. After adding Ν Μ P (6 _ 4 0 g ) and BCS (30 00 g) to the solution, the liquid crystal alignment treatment agent (8) was obtained by stirring for 1 hour. The liquid crystal alignment treatment agent was not found to be turbid or An abnormality such as precipitation was observed, and it was confirmed that the resin component was uniformly dissolved. Using the liquid crystal alignment treatment agent (8) obtained above, the same treatment as in Example 1 was carried out to obtain a reverse-aligned nematic liquid crystal cell which was subjected to rubbing treatment. The pretilt angle of the liquid crystal cell was determined by the same operation as in Example 11. It was 8 6 · 7 and 1 2 0 at room temperature. (: '8 7.8 ° after 1 hour heat treatment. In addition, 'room temperature' After the heat treatment of the liquid crystal cells, the liquid crystal cell is observed by using a polarizing microscope, and it is found that the liquid crystal is uniformly aligned and is hot. The treatment was also uniform, and the liquid crystal cell prepared in the same manner as in Example 1 except for the rubbing treatment was observed by a polarizing microscope to confirm that the liquid crystal system was uniformly oriented vertically. Example 1 6 &gt; BODA ( 8.07g ' 32.3mmol ), DBA ( 4.58g, 30. lmmol ), branched-chain diamine m-PBCH5DABz ( 5.79g, 12.9mmol) were mixed in NMP (43.0g) After reacting at 80 ° C for 5 hours, 'CBDA (2.05 g, 1 mmol. 5 mmol) and NMP (38.0 g) were added and reacted at 40 ° C for 6 hours to obtain a polyaminic acid solution. After the NMP was added to the solution (20. g) and diluted to 6 mass%, acetic anhydride (2 · 15 g) and pyridine (-63-200906769 1.66 g) of the ruthenium catalyst were added and reacted at 80 t. The reaction solution was poured into methanol (247 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure at 1 ° C to obtain a polyimine powder (I). The polyamidimide has a ruthenium iodide ratio of 45%, a number average molecular weight of 22,600, and a weight average molecular weight of 5,9,500. The polyimine powder (I) (3.0) Ng (14_7g) was added to 0g), and it was stirred at 80 ° C for 40 hours to dissolve it. After adding NMP (7.30g) and BCS (25.0g) to this solution, the liquid crystal alignment treatment agent was prepared by stirring for 1 hour. (9 ). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. Using the liquid crystal alignment treatment agent (9) obtained above, the same treatment as in Example 1 was carried out to obtain a reverse-aligned nematic liquid crystal cell which was subjected to rubbing treatment. The pretilt angle of the liquid crystal cell was measured under the same operation as in Example 1 1, and it was found to be 8 6 · 5 at room temperature. At 1 2 0 °C, after heat treatment for 1 hour, it is 8 7 2 °. Further, the liquid crystal cells after heat treatment at room temperature and for 1 hour were observed by a polarizing microscope, and it was found that the liquid crystals were uniformly aligned and uniformly aligned with the heat treatment. Further, the liquid crystal cell prepared in the same manner as in Example 1 except for the rubbing treatment was observed by a polarizing microscope, and it was confirmed that the liquid crystal system was uniformly aligned vertically. &lt;Example 1 7 &gt; After adding NMP to 6 mass% in the polyamidic acid solution (20.0 g) obtained in Example 16, 'addition of acetic anhydride to the ruthenium catalyst (-64 - 200906769 4.29g) Pyridine (3_33 g) was reacted at 90 ° C for 3.5 hours. The reaction solution was poured into methanol (260 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol and dried under reduced pressure at 1 ° C to obtain a polyimine powder (J). The polyimine had an oxime imidization ratio of 80%, a number average molecular weight of 1,900, and a weight average molecular weight of 5,900. NMP (1 4 · 8 g) was added to the polyimine powder (J) (3.00 g), and the mixture was stirred at 80 ° C for 40 hours to be dissolved. NMP (7.40 g) and BCS (25.1 g) were added to the solution, and the mixture was stirred for 1 hour to obtain a liquid crystal alignment treatment agent (1 〇 ). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. Using the liquid crystal alignment treatment agent (10) obtained above, the same treatment as in Example 1 was carried out to obtain a reverse-aligned nematic liquid crystal cell which was subjected to rubbing treatment. The pretilt angle of the liquid crystal cell was measured under the same operation as in Example 1 1 and was 88.9° at room temperature, 12 (TC, 89.6° after heat treatment for 1 hour. Further, at room temperature, and 1 hour). After the heat treatment, the liquid crystal cells were observed by a polarizing microscope, and it was found that the liquid crystals were uniformly aligned, and evenly aligned with the heat treatment. Further, except for the non-friction treatment, the same method as in Example 1 was used. The liquid crystal cell was observed by a polarizing microscope, and it was confirmed that the liquid crystal system was uniformly oriented vertically. <Example 1 8 &gt; In the polyamic acid solution (20.0 g) obtained in Example 16, NMP was diluted to 6 After the mass%, acetic anhydride (-65-200906769 4.2 7g) and triethylamine (1.51 g) of a ruthenium catalyst were added and reacted at 100 ° C for 4 hours. Oxalic acid (1.88) was added to the reaction solution. g) After neutralization, it is poured into methanol (253 ml), and the resulting precipitate is filtered off. The precipitate is washed with methanol and dried under reduced pressure at 10 ° C to obtain a polyimine powder (K). The polyamidimide has an imidization ratio of 98% and a number average molecular weight. 19,200, weight average molecular weight was 51,000. NMP (1 6 · 1 g ) was added to the polyimine powder (K) ( 3.30 g) and stirred at 80 ° C for 40 hours to dissolve. After adding NMP (13.6 g) and BCS (22.0 g) to the solution, the liquid crystal alignment treatment agent (1 1 ) was obtained by stirring for 1 hour. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and the resin composition was confirmed. Dissolving uniformly. Using the liquid crystal alignment treatment agent (1 1 ) obtained above, the same treatment as in Example 11 was carried out to obtain a reverse-aligned nematic liquid crystal cell which was subjected to rubbing treatment. The tilting angle was measured under the same operation as in Example 11 and found to be 88.4 at room temperature, 80.2 ° at 120 ° C, and 89.2 ° after heat treatment for 1 hour. Further, after further heat treatment at room temperature and for 1 hour, The liquid crystal cells were observed by a polarizing microscope, and it was found that the liquid crystals were uniformly aligned, and evenly aligned with the heat treatment. Further, the liquid crystal cell produced by the same method as in Example 1 except that the rubbing treatment was not performed. After observing the results using a polarizing microscope, It was confirmed that the liquid crystal system was uniformly oriented vertically. <Example 1 9 &gt; BODA (4.3 2 g '1 7.3 mm ο 1 ), p-PDA (2_llg, •66-200906769 19.5 mmol), branched-chain diamine m -PBCH7DABz (1,64g, 3 · 4 4 mm ο 1 ) was mixed in Ν Μ P ( 2 0 _ 0 g ), reacted at 80 ° C for 5 hours, then added CBDA (1.01 g, 5.15 mmol) and NMP. (16·4g), reacted at 4 ° C for 6 hours to prepare a polyaminic acid solution. After the NMP was diluted to 6 mass% in the polyamic acid solution (2〇.〇g), acetic anhydride (2.3 3 g) and pyridine (1 _ 8 1 g ) were added to the ruthenium catalyst. The reaction was carried out at 80 ° C for 3 hours. The reaction solution was poured into methanol (250 ml). The resulting precipitate was filtered. This precipitate was washed with methanol to dryness under reduced pressure at 1 〇 ° C to obtain a polyimide pigment (L). The polyimine had a hydrazine imidation ratio of 50%, a number average molecular weight of 13,900, and a weight average molecular weight of 35,800. To the polyimine powder (L) (2.06 g), NMP (13. 8 g) was added and stirred at 8 ° C for 40 hours to dissolve. NMP (3.05 g) and BCS (15.5 g) were added to the solution, and the mixture was stirred for 1 hour to obtain a liquid crystal alignment treatment agent (1 2 ). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. Using the liquid crystal alignment treatment agent (1 2 ) obtained above, the same treatment as in Example 1 was carried out to obtain a reverse-aligned nematic liquid crystal cell which was subjected to rubbing treatment. The pretilt angle of the liquid crystal cell was measured under the same operation as in Example 1 1 and was 8 8.0 at room temperature. At 1 2 0 °C, 1 hour heat is 5 8.3 ° after 5 miles. Further, the @ 'liquid crystal cell after heat treatment at room temperature and after 1 hour of heat treatment was observed by a polarizing microscope, and it was found that the liquid crystal was uniformly aligned and uniformly aligned with the heat treatment. Further, the liquid crystal cell prepared by the same method as in Example 1 1 except for the rubbing treatment was observed by a polarizing microscope, and the vertical alignment of the liquid crystal system was confirmed. &lt;Example 2 0 &gt; BODA (7.34 g, 29_4 mmol), DBA (4.17 g, 27.4 mmol), branched-chain diamine m-PBCH7DABz (5.60 g, 1 1 _ 7 mm ο 1 ) in Ν Μ P (3 9 · 5 g ) was mixed and reacted at 80 ° C for 5 hours, then CBDA (2.05 g, 10.5 mmol) and NMP (34.5 g) were added and reacted at 40 ° C for 6 hours to obtain a poly Proline solution. After adding Ν Μ P to 6% by mass of the polyamidic acid solution (2 0.0 g ), acetic anhydride (2.14 g) and pyridine (1.67 g ) were added to the ruthenium catalyst at 80 ° C. The reaction was carried out for 3 hours. The reaction solution was poured into methanol (250 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol to dryness under reduced pressure at 1 〇 ° C to obtain a polyimide pigment (Μ). The polyimine had a hydrazine imidization ratio of 45%, a number average molecular weight of 1,1,900, and a weight average molecular weight of 58,100. NMP (15_0g) was added to the polyimine powder (M) (3.00 g) and stirred at 80 ° C for 40 hours to dissolve. To the solution, Ν Μ P ( 7 · 30 g ) ' B C S ( 2 5 _ 1 g ) was added, and the liquid crystal alignment treatment agent (1 3 ) was obtained by stirring for 1 hour. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. Using the liquid crystal alignment treatment agent (13) obtained above, the same treatment as in Example 1 was carried out to obtain a reverse-aligned nematic liquid crystal cell which was subjected to rubbing treatment. The pretilt angle of the liquid crystal cell was measured by the same operation as in Example 1 -68 - 200906769, and it was found to be 8 9.6 ° at room temperature, 120 ° C at room temperature, and 8 9 · 7 ° after heat treatment for 1 hour. Further, these liquid crystal cells were further observed at room temperature and after heat treatment for 1 hour by using a polarizing microscope to observe the alignment of the liquid crystals in a uniform manner, and uniform alignment to the heat treatment. Further, the liquid crystal cell prepared in the same manner as in Example 1 except that the film was not rubbed was observed by a polarizing microscope, and it was confirmed that the liquid crystal system was uniformly oriented vertically. &lt;Example 2 1&gt; After the NMP was added to the polyamidic acid solution (15.5 g) obtained in Example 20 and diluted to 6 mass%, acetic anhydride (3.32 g) of ruthenium catalyst was added, and pyridine ( 2.5 8g), reacted at 90T: for 3.5 hours. The reaction solution was poured into methanol (200 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 10 ° to give a polyimine powder (N). The polyamidimide had an oxime imidization ratio of 80% and a number average molecular weight of 18,600. The molecular weight was 50, 100. NMP (1. 6 g) was added to the polyimine powder (N) (2.50 g), and the mixture was stirred at 80 ° C for 40 hours to dissolve. NMP (6.11 lg ) was added to the solution. BCS (21.Og) was stirred for 1 hour to obtain a liquid crystal alignment treatment agent (14). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. The liquid crystal alignment treatment agent (14) was subjected to the same treatment as in Example 11 to obtain a reverse-aligned nematic liquid crystal cell which was subjected to rubbing treatment. The pretilt angle of the liquid crystal cell was the same as in Example 11. 69- 200906769 The results of the measurement were found to be 8 9.5 ° at room temperature, 120 ° C, and 89.7 ° after heat treatment for 1 hour. In addition, the liquid crystal cell after heat treatment at room temperature and for 1 hour Using a polarizing microscope to observe the results, it is known that the liquid crystals are uniformly aligned and uniform to the heat treatment. Further, the liquid crystal cell prepared in the same manner as in Example 1 except that the film was not rubbed was observed by a polarizing microscope, and it was confirmed that the liquid crystal system was uniform in vertical alignment. <Comparative Example 4 &gt; To the polyimine powder (E) (3.15 g) obtained in Comparative Example 1, Ν Μ P ( 2 1 · 1 g ) was added, and the mixture was stirred at 80 ° C for 40 hours to dissolve. When NMP (1_95g) and BCS (26.3g) were added to the solution, the resin component precipitated when stirred for 1 hour, and the liquid crystal alignment agent could not be obtained. Therefore, the liquid crystal cell could not be produced. [Comparative Example 5 &gt; NMP (24.4 g) was added to the polyimine powder (E) (3 65 g) obtained in Comparative Example 1, and dissolved by stirring at 80 t: for 4 hours, and NMP (5.35 g) was added to the solution. , BCS (27 4g), after 1 hour of stirring, the result of the precipitation of the resin component, the stomach failed to produce the liquid crystal alignment treatment agent. Therefore, the liquid crystal cell could not be produced. <Comparative Example 6 &gt;

The polyimine powder obtained in Comparative Example (E-70-200906769) was added to NMP (20.7 g) and stirred at 80 ° C for 40 hours to dissolve. Ν Μ P ( 2 7 _ 0 g was added to the solution. And BCS (11.2 g) was stirred for 1 hour to obtain a liquid crystal alignment treatment agent (15). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. The liquid crystal alignment treatment agent (15) obtained above was spin-coated on a glass substrate with an ITO electrode, and dried on a hot plate of 8 (rc for 5 minutes, and then placed in a hot air circulating oven at 210 °C. The film was fired for 1 hour to obtain a polyimide film having a film thickness of 10 nm. When the film surface was confirmed, most of the sand holes were found. Using the substrate with the liquid crystal alignment film, the same method as in Example 11.1 was used. After treatment, the reverse-aligned nematic liquid crystal cell is subjected to rubbing treatment. The pretilt angle of the liquid crystal cell is determined by the same operation as in Example 11, and is 7 6 · 4 at room temperature, and 1 2 0 t: After 1 hour heat treatment, it is 80. Γ. Among them, the pretilt angle is found in the surface of the liquid crystal cell. In addition, the liquid crystal cells after heat treatment at room temperature and after 1 hour were observed by a polarizing microscope, and it was found that the liquid crystal alignment was inferior with the presence of sand holes. The liquid crystal cell prepared by the same method as in the above Example 1 was observed by a polarizing microscope, and it was confirmed that the liquid crystal was vertically aligned, but the presence of the sand hole was accompanied by the absence of bright light in the local portion. Comparative Example 7 &gt; BODA (1 6 · 9 g, 6 7.5 mm ο 1 ), p-PDA ( 6.80 g, 62.9 mmol), branched diamine PC Η 7 DAB (1 Ο . 3 g, 2 7 · 1 mmo 1 ) -71 - 200906769 Mix in Ν P ( 1 0 0 · 1 g ), react at 50 °C, react 5 times into CBDA (4.10g, 20.9mmol) and react with NMP (52.2g) 6 hours to obtain a polyaminic acid solution. After adding NMP to 6% by mass in the obtained poly liquid (1 3 0.3 g), acetic anhydride (1 5.6 g) and pyridine (1 2.1 g) were added. The solution was poured into methanol (1 600 m 1 ) and the precipitate was filtered off with methanol. 〇 ° C dry polyimine powder (Ο). The polyimine is 54%, the number average molecular weight is 18,300, and the weight average molecular weight is less than the polyimine powder (0) (3.2 〇 g) Add 7 2 3 . 5 g ), stir at 80 ° C for 40 hours to dissolve. After the NMP (2.63 g) and BCS (24.0 g) were added, the liquid crystal alignment treatment agent (16) was obtained over 1 hour. The liquid crystal alignment agent was turbid or precipitated abnormally, and it was confirmed that the resin component was uniformly dissolved. Using the liquid crystal alignment treatment agent (16) obtained above, the same treatment as in Example 1 was carried out to obtain a reverse-aligned crystal unit cell which was subjected to rubbing treatment. The pretilt angle of the liquid crystal cell was as follows. The same result as in Example 11 was found to be 78 _ 7 ° at room temperature, and 1201, 1 hour heat 8 1 _ 5 s. In addition, after the heat treatment at room temperature and after 1 hour of heat treatment, the cell was observed by a polarizing microscope, and it was found that the liquid crystal was uniformly mixed with the application of the liquid crystal, and the liquid crystal was not bright. After the rubbing treatment, other examples were added according to the examples, and the prolyl acid was dissolved at 40 ° C at 80 ° C, and the obtained dry reduced amination rate was 45,300, NMP. (The solution was stirred and the mixture was not found to be mixed. According to the operation of the nematic liquid, the liquid crystal crystal orientation was the same as in the case of real light. The liquid crystal cell prepared by the method was subjected to a polarizing microscope. As a result of observation, it was confirmed that the liquid crystal system was uniformly oriented vertically. <Comparative Example 8 &gt; B〇DA (1 5.0 g '60.Ommol), p-PD A (4.30 g, 39.8 mm〇l), and branched chain The diamine PCH 7 DAB (1 5 · 2 g, 4 0 _ 0 mm ο I ) was mixed in NMP ( l〇〇.3g ), and reacted at 40 ° C for 5 hours, then CBDA (3.80 g, 19.4) was added. Methyl) and NMP (53.2 g) were reacted at 40 ° C for 6 hours to obtain a polyaminic acid solution. The obtained polyaminic acid solution (1 3 0 · 3 g) After adding NMP to 6 mass%, acetic anhydride (13.9 g) and pyridine (i.8 g) of a ruthenium catalyzed catalyst were added, and the reaction was carried out for 3 hours. The obtained precipitate was filtered off (1 600 ml), and the precipitate was washed with methanol and dried under reduced pressure at 100 Torr to obtain a polyimine powder (P). The 55% 'number average molecular weight is 1,7,500 and the weight average molecular weight is 42,700 〇, and the NMP (23_lg)' is added to the polyamidimide powder (P) (3-15 g) and stirred at 80 ° C for 40 hours. After the NMP ( 2.65 g) and BCS (23_6 g) were added to the solution, the liquid crystal alignment treatment agent (17) was obtained by stirring for 1 hour. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent. The resin component is uniformly dissolved. The liquid crystal alignment agent (丨7) obtained above is spin-coated on a glass substrate with an IΤ electrode and dried on a hot plate of 8 〇〇c for 5 minutes. In a hot air circulating oven of 2 1 0 °C, the crucible is baked at -73-200906769 to obtain a film thickness of l〇〇nm. The imine film was found. When the surface of the coating film was confirmed, a sand hole was found. Using the substrate with the liquid crystal alignment film, the same treatment as in Example 1 was carried out to obtain a reverse-aligned nematic liquid crystal by rubbing treatment. Unit cell. The pretilt angle of the liquid crystal cell was determined by the same operation as in Example 11. The temperature was 87.7° at room temperature, and 12 (TC, 88.7° after heat treatment for 1 hour. Among them, the pretilt angle in the liquid crystal cell was found to be biased. In addition, the liquid crystal cells after heat treatment at room temperature and for 1 hour were observed by a polarizing microscope, and it was found that the liquid crystal alignment was inferior with the presence of the sand holes. The liquid crystal cell prepared in the same manner as in Example 1 1 was observed by a polarizing microscope, and it was confirmed that the liquid crystal was vertically aligned, but with the presence of the sand hole, the partial portion was out. There was no bright light. Comparative Example 9 &gt; NMP (23. 5 g) was added to the polyimine powder (F) (3 · 5 1 g) obtained in Comparative Example 2, and stirred at 80 ° C for 40 hours. The liquid crystal alignment treatment agent (1 8 ) was obtained by adding NMP (2.17g) and BCS (2.93g) to the solution, and the liquid crystal alignment treatment agent was not found to be abnormal, such as turbidity or precipitation. The resin component dissolves evenly. The liquid crystal alignment agent (18) was spin-coated on a glass substrate with an ITO electrode, and dried on a hot plate of TC for 5 minutes, and then subjected to a hot air circulating oven at 210 °C. The film was fired in an hour to obtain a polyimide film having a film thickness of 1 〇〇 nm. When the film surface was confirmed, most of the sand holes were found. The substrate with the liquid crystal alignment film was used, and the method was carried out -74 - 200906769 Example 1 1 The same treatment is carried out to obtain a reverse-aligned nematic liquid crystal cell which is subjected to rubbing treatment. The pretilt angle of the liquid crystal cell is determined by the same operation as in Example 11, and is 23 at room temperature. °c, 1 3.5 ° after 1 hour heat treatment, in which the pretilt angle in the surface of the liquid crystal cell was found to be extremely deviated. In addition, the liquid crystal cells after heat treatment at room temperature and after 1 hour were observed by using a polarizing microscope. It was found that the liquid crystal alignment was in a poor state with the presence of the sand hole. Further, the liquid crystal cell prepared by the same method as in Example 1 except the non-friction treatment was observed by using a polarizing microscope. The liquid crystal is vertically aligned, but With the presence of the sand hole, there was a case where there was no bright light in the partial portion. <Comparative Example 1 0 &gt; NMP (21.6) was added to the polyimine powder (F) (3.23 g) obtained in Comparative Example 2. g), dissolved at 80 t: for 40 hours to dissolve. Add Ν Μ P ( 4 _ 7 3 g ), BCS ( 2 4 · 2 g ) to the solution, and then scrambled for 1 hour. A liquid crystal alignment treatment agent (1 9 ) was obtained. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. The liquid crystal alignment treatment agent (1 9 ) obtained above was spin-coated. A glass substrate having an ITO electrode was dried on a hot plate of 8 ° C for 5 minutes, and then subjected to "1 hour baking in a hot air circulating oven of TC" to obtain a polythene having a film thickness of i 〇 0 nm. Imine film. When the coating surface was confirmed, most of the sand holes were found. Using the substrate with the liquid crystal alignment film, the same treatment as in Example 1 of -75-200906769 was carried out to obtain a rubbed-type liquid crystal cell. The pretilt angle of the liquid crystal cell was found to be 22.1 ° at room temperature, and 1 5.6 ° at 1201. Wherein the pretilt angle in the plane of the liquid crystal cell. Further, the results of observation by a polarizing microscope at room temperature and after heat treatment for 1 hour revealed that the sand hole was in a poor state. Further, in addition to the non-friction treatment, the liquid crystal cell prepared by the method was confirmed to have a vertical alignment by using polarized light microscopy, but the presence of the sand hole did not have a bright light. &lt;Printability Test&gt; Printing was carried out using Example 1 1 to 2 1 and Comparative Examples 6 to 10. The printing press used a Japanese photographic printer (S 1 5 type). It is printed as steamed chrome base 〃 8 cm, printing pressure is 0.2 mm, frame substrate is 5 pieces, printing time is 90 seconds, pre-drying temperature is 70 °C, and it is confirmed by sand hole, and it is under the sodium lamp for visual inspection. The film thickness and etching linearity were observed as shown in the results of optical microscopy Examples 1 1 to 2 1 and Comparative Examples 6 to 10. The polyimine of the diamine of the invention of Examples 1 1 to 2 1 and Comparative Examples 6 to 10 was found to be greatly deviated from the same operation for 1 hour after the same operation using the comparative reverse orientation. The liquid crystal cell was allowed to exist, and the liquid crystal alignment was observed in the same manner as in the case of Example 11. Although the printing area on the simple print of the liquid crystal alignment portion was 8 χ to the pre-drying for 5 minutes. Way to proceed. The mirror confirms. As shown in Table 3 and the results, it is known that the polyamine-76-200906769 amine using this diamine shows that a higher pretilt angle can be obtained with a smaller amount of introduction. In particular, from the comparison between Example 14 and Comparative Example 7, it is found that Comparative Example 7 is compared with Example 14 using the diamine of the present invention, and the friction treatment is accompanied by the tilt of the liquid crystal. The situation of illuminating. Namely, the polyimine which uses the diamine of the present invention exhibits a high pretilt angle even if it is subjected to rubbing treatment. With the polyimine of the diamine of the present invention, precipitation of the resin did not occur even when the yield of the ruthenium imidization was high or the mixing tolerance of the butyl cellosolve of the excess solvent was excessive. As a result, it has been found that the liquid crystal alignment treatment agent obtained by using the diamine of the present invention can form a uniform film by a usual coating means. [Table 1] Polyimine powder, branched diamine branched diamine, hydrazine imidization ratio (%) Solubility of polyimine (g) 12 Example 5 (A) m-PBCH5DABz 15 48 1.40 Example 6 (B) m-BPCH5DABz 15 41 1.16 Example 7 (C) p-PBCH5DABz 15 40 1.07 Example 8 (D) m-PBCH7DABz 15 45 1.36 Comparative Example 1 (E) m-PBCH5DABEs 15 45 0.11 Comparative Example 2 (F) PBP5DABz 15 45 0.64 -77- 1 1: Proportion of the branched diamine in the total diamine used in the synthesis of the polymer. * 2 : The quality of the B C S mixing end point. 200906769 [Table 2]

Liquid crystal alignment treatment agent branched diamine branched diamine amount (mol%) *3 pretilt angle (·) vertical alignment enthalpy friction) Example 9 (1) m-PBCH5DABz 10 B5.7 〇 Example 10 (2) m-PBCH7DABz 10 6.5 〇 Comparative Example 3 (3) PCH7DAB 10 22.2 X *3: The ratio of use of the branched diamine in the total diamine used for the synthesis of the polymer. [Table 3] Polyimidimide powder liquid crystal alignment treatment agent branched diamine branched diamine amount hydrazine imidization ratio BCS amount (mol%) * 4 (%) (mass %) *5 Example 11 (Α (4) m-PBCH5DABz 15 48 48 Example 12 (Β) (5) m-BPCH5DABz 15 41 50 Example 13 (C) (6) p-PBCH5DABz 15 40 48 Example Μ (G) (7) m-PBCH5DABz 30 44 48 Example 15 (Η) (8) m-PBCH5DABz 20 40 48 Example 16 (I) (9) m-PBCH50AB2 30 45 53 Example 17 (J) (10) m-PBCH5DABz 30 80 53 Example 18 ( (11) m-PBCH5DABz 30 98 43 Example 19 (L) (12) m-PBCH7DABz 15 50 48 Example 20 (Μ) (13) m-PBCH7DABz 30 45 53 Example 21 (Ν) (14) m-PBCH7DABz 30 80 53 Comparative Example 4 (Ε) m-PBCH5DABEs 15 45 53 Comparative Example 5 (Ε) m-PBCH5DABEs 15 45 48 Comparative Example 6 (Ε) (15) m-PBCH5DABEs 15 45 Comparative Example 7 (〇) (16) PCH7DAB 30 54 48 Comparative Example 8 (Ρ) (17) PCH7DAB 50 55 48 Comparative Example 3 (F) (18) PBP5DABz 15 45 53 Comparative Example 10 (F) (19) PBP5DABz 15 45 48 *4: Polymerization The proportion of the branched diamine in the total diamine used in the synthesis of the substance. * 5 : The ratio of the use of B C S in the entire liquid crystal alignment agent. -78- 200906769 [Table 4] Pretilt angle C) Vertical alignment (after rubbing treatment) Printed sand hole etched linearity Example 11 85.7 〇 &lt;5 〇〇 Example 12 45.5 One &lt;5 〇〇Implementation Example 13 29.3 A &lt;5 〇〇 Example 14 89.2 0 &lt;5 〇0 Example 15 86.7 〇&lt;5 〇〇Example 18 86.5 0 &lt;5 〇〇Example 17 88.9 〇&lt;5 〇〇Implementation Example 1B Β 8.4 〇 &lt; 5 〇〇 Example 19 88.0 〇 &lt; 5 〇〇 Example 20 89, 6 〇 &lt; 5 〇〇 Example 21 89.5 0 &lt; 5 〇〇 Comparative Example 4 *6 *6 *6 *6 Comparative Example 5 *6 *6 *6 *6 ♦6 Comparative Example β 76.4 *7 &gt; 50 XX Comparative Example 7 78.7 *8 &lt;5 〇〇Comparative Example β 87.7 *7 &lt;30 Δ Δ Comparison Example 9 23.1 *7 &gt; 50 XX Comparative Example 10 22.1 *7 &lt;30 Δ Λ * 6 : The resin component was precipitated and could not be evaluated. * 7 : Degradation of alignment occurring with sand holes. *8: There is no bright light. When the diamine of the present invention is used as a raw material of a polymer used for constituting a liquid crystal alignment film, it has an effect of increasing the pretilt angle of the liquid crystal, and the liquid crystal can also form a vertical alignment at a very small use ratio, and the polymer solution is used in a large amount. At the time of the solvent, it is not easy to appear. Thus, the liquid crystal alignment treatment agent of the present invention can form a uniform film by a usual coating means, and can produce a liquid crystal alignment film which gives a liquid crystal with a larger pretilt angle, and is therefore highly suitable for use in a TN element, an STN element, and a TFT liquid crystal element. And vertical alignment type liquid crystal display elements. The contents of the specification, the patent application scope, and the -79-200906769 abstract of the Japanese Patent Application No. 2007-077865, filed on March 23, 2007, the entire contents of It is the content of the invention. -80-

Claims (1)

200906769 X. Patent Application Range [Chemical Formula 1] The amine represented by the following formula (1) is H2N (1) RfR2 - R3 - R4 (in the formula (1), R! is a phenyl group, and R2 is a hexyl group or Phenyl phenyl R 3 is a cyclohexyl group, R 4 is a fenthyl group having a carbon number of 3 to 12, a fluoroalkyl group having a carbon number of 3 to 12, an alkoxy group having a carbon number of 3 to 12, or a fluoroalkane having a carbon number of 3 to 12 Any of the oxy groups). 2. The diamine of claim 1, wherein R of formula (1) is 1,4-phenylene, R2 is 1,4-cyclohexyl or 1,4-phenyl, R3 It is a 1,4-cyclohexyl group. The first round of Fan Li, the special request for the application as described in the formula for its amine II 2 or k21 H2n (2-1) (In the formula (2-1), η is an integer of 2 to 11, and the cis-trans isomerism of the 1,4-cyclohexylene group is a trans isomer, respectively). 4. The diamine of claim 1 or 2, which is represented by the following formula (2-2), [Chemical 3] ΝΗ2 H2N^=^〇-Q&gt;-〇Hf3-(CH2)nCH3 ^ ^ -81 - 200906769 (in the formula (2-2), η is an integer of 2 to 11, and the cis-trans isomer of the ι,4-cyclohexyl group is a trans isomer). A polyimine which is characterized in that a diamine component containing a diamine of any one of claims 1 to 4 is reacted with a tetracarboxylic dianhydride to produce a polyamic acid, or The polyglycolic acid is dehydrated and closed to produce a polyimine. 6. The polyamine or polyimine of claim 5, wherein 10 mol% or more of the diamine component is the diamine of any one of claims 1 to 4. A liquid crystal alignment treatment agent comprising a polyamic acid and/or a polyamidimide according to the fifth or sixth aspect of the patent application. 8. The liquid crystal alignment treatment agent of claim 7, which contains an organic solvent containing 5 to 60% by mass of a poor solvent. A liquid crystal alignment film which is characterized by using the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of claim 7 or 8. A liquid crystal display element is characterized by having a liquid crystal alignment film of claim 9 of the patent application. -82- 200906769 七明说单单单符表 is the map of the generation of the map. The map of the map is represented by the table: the representative of the table is ' ' / 代一指指Γ κιν 无无八, if there is a chemical formula in this case, please Reveal the chemical formula that best shows the characteristics of the invention: (1) NHp HgN ~^ ^0—Rj—R〇_R3~R4 (1)