TW200906768A - 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 or a cyclohexylene; and R2 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 (abbreviated as a diamine in the present invention) which is a raw material of a polymer used as a liquid crystal alignment film, and a polycondensation obtained by using the same Proline, polyimine, and liquid crystal alignment treatment agents. [Prior Art] At present, in the liquid crystal alignment film used for the liquid crystal display element, a polyimide film is mostly used, and the polyimide film is coated with a polyamidene precursor coated with a polyimide precursor on the substrate. A method of firing a solution or a solvent-soluble polyimine solution. In general, the polylysine or the solvent-soluble polyimine is synthesized by reacting a tetracarboxylic acid derivative such as tetracarboxylic dianhydride with a diamine. One of the characteristics desired for the liquid crystal alignment film is to maintain the alignment tilt angle of the liquid crystal molecules on the substrate surface at an arbitrary level, i.e., to control the pretilt angle of the liquid crystal. The size of the pretilt angle can be changed by selecting the structure of the polyimine which constitutes the liquid crystal alignment film. In the technique of controlling the pretilt angle by the structure of polyimine, a method of using a side chain diamine as a partial polyimine raw material, the pretilt angle can be controlled depending on the ratio of use of the diamine, Therefore, it is easy to successfully complete the pretilt angle of the purpose, and it is extremely useful as a method for increasing the pretilt angle. The side chain structure of the diamine which increases the pretilt angle of the liquid crystal is a long-chain alkyl group or a fluorinated alkyl group (for example, refer to Patent Document 1), a cyclic group or a combination of a cyclic group and an alkyl group (for example, refer to a patent) The literature 2), the steroid structure (for example, refer to Patent Document 5 - 200906768, 3), etc., are known. In addition, in order to improve the stability of the pretilt angle or the structure of the step in order to increase the pretilt angle of the liquid crystal, the side chain structure used herein is preferably a phenyl group or a cyclohexyl group. The ring constructor (for example, refer to Patent Documents 4 and 5). Further, it is proposed to have three or four diamines having such a ring structure in the side chain (for example, refer to Patent Document 6). In recent years, 'liquid crystal display elements are used with large-screen LCD TVs or high-definition mobile phones (m 〇bi 1 e) (digital cameras or mobile phone display parts) have been widely used, compared with conventional ones. The substrate is enlarged, and the unevenness of the substrate step is increased. In this case, in terms of display characteristics, a liquid crystal alignment film which can be uniformly coated for a large substrate or a step is required. In the production step of the liquid crystal alignment film, when a solution of a polyamic acid solution or a solvent-soluble polyimine is coated on a substrate, it is generally industrially carried out by flexible printing or the like. In the solvent of the coating liquid, in addition to N-methyl-2-pyrrolidone or γ-butyrolactone, which is a solvent having excellent solubility in a resin (hereinafter referred to as a good solvent), in order to improve the uniformity of the film, the resin can be dissolved. A low-solvent solvent (hereinafter referred to as a poor solvent) of butyl cellosolve or the like. However, since the poor solvent has a poor ability to dissolve polyamic acid or polyimine, precipitation occurs when a large amount of the mixture is mixed (for example, refer to Patent Document 7). Especially in the solution of the solvent-soluble polyimine, this problem is particularly remarkable. Further, 'the polyimine obtained by using the above-described diamine having a side chain tends to lower the uniformity of coating coverage, so it is necessary to increase the mixing amount of the poor solvent. The mixing tolerance of the solvent also becomes polyfluorene. An important property of imines. Patent Document 1: Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. 2-3-7324. SUMMARY OF THE INVENTION The present invention provides a polyamine which constitutes a liquid crystal alignment film. When an acid and/or a polyimide (hereinafter referred to as a polymer) is used as a raw material, it has an effect of increasing the pretilt angle of the liquid crystal, and the liquid crystal alignment treatment can be made even if the liquid crystal is vertically aligned with a small use ratio. When a poor solvent is mixed in the coating liquid, precipitation is unlikely to occur, and a novel diamine which is a raw material of polyglycolic acid and/or polydecylamine is used. Further, the present invention has an object of providing a liquid crystal display element comprising the above-mentioned polymer obtained from a novel diamine, a liquid crystal alignment treatment agent containing the polymer, and a liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent. The present inventors have further intensively reviewed the results of the review, and have achieved the above objectives. The present invention has the following gist. 1 . A diamine represented by the following formula (1), [Chemical 1]

(1) 200906768 (In the formula (1), Ri represents a phenyl or cyclohexyl group. R2 represents a fluorenyl group having a carbon number of 3 to 12, a fluorinated group having a carbon number of 3 to 12, and a carbon number of 3 to I2. a oxy group or a fluorinated oxy group having a carbon number of 3 to 12). 2. A diamine as described in the above 1, wherein Ri in the formula (1) is 1,4·phenyl or 1,4 ring Stretch out the base. 3. The diamine as described in the above 1 or 2, which is represented by the following formula (2 - 1), [Chemical 2] nh2 (2 - 1)

h2NQ (in the formula (2-1), η represents an integer of 2 to 11', and in the cis-trans anisotropic 1,4-cyclohexyl group, each is a trans isomer) ° 4. As described above 1 or The diamine described in the following formula (2-2), [Chemical 3] νη2/=|=\H2N%_f M〇^〇K<3-"(CH2)nCH3 (2-2) (In the formula (2-2), η represents an integer of 2 to 11, and in the cis-transverse anisotropy of a 1,4-cyclohexyl group, each is a trans isomer). -8-200906768 5. A polyimine which is obtained by reacting a diamine component containing the diamine according to any one of the above 1 to 4 with a tetracarboxylic dianhydride, Or the polypyridic acid is dehydrated and closed. 6. The polyamine or the polyimine according to the above 5, wherein the diamine of the diamine component is the diamine of any one of the above 1 to 4. A liquid crystal alignment treatment agent comprising a compound containing at least one of polyamine and polyamidiamine according to the above 5 or 6. 8. The liquid crystal alignment treatment agent according to the above 7, which contains an organic solvent containing 5 to 60% by mass of a poor solvent. A liquid crystal alignment film characterized by using a liquid crystal alignment treatment agent as described in the above 7 or 8. A liquid crystal display device comprising the liquid crystal alignment film according to the above 9. [Effects of the Invention] When the diamine of the present invention is used as a raw material of a polymer constituting the liquid crystal alignment film, it has an effect of remarkably increasing the pretilt angle of the liquid crystal. For example, as shown in Table 2 below, the pretilt angle of the liquid crystal alignment film obtained from the diamine (PBC Η 5 DAB) of the present invention represented by the formula (2-1) is about 8 2 ° 'by two The pre-tilt angle of the liquid crystal alignment film produced by the amine (PBCH7DAB) was about 83. However, the liquid crystal alignment film obtained by the conventional diamine (PCH7DAB) described in Patent Document 4 having a similar structure has a pretilt angle of about 22°, which is about 4 times, which is a great surprise. -9 - 200906768 Therefore, the liquid crystal alignment treatment agent prepared by the diamine of the present invention can have a large pretilt angle even in a small use ratio, and the liquid crystal can be vertically aligned. In addition, when a coating liquid in the case of obtaining a liquid crystal alignment film is used, when a good solvent and a poor solvent are often used for improving the coating property, the liquid crystal alignment treatment agent obtained from the diamine of the present invention is less likely to be precipitated and coated on the polymer. When a large substrate is formed, a uniform film can be formed, and a liquid crystal alignment film having excellent characteristics can be produced. [Best Mode for Carrying Out the Invention] Hereinafter, the present invention will be described in detail. 1 Diamine The diamine of the present invention is a bond group (-〇-) on a diaminobenzene ring, and has a -phenyl-phenylene ring or a cyclohexyl-cyclohexyl-R2 bond. A compound of a side chain constructed. In other words, 'is a novel diamine benzene derivative as seen from the following formula (1).

In the formula (1), Ri is a phenyl group or a cyclohexyl group. The substituent may also have a substituent on the ring of the phenyl or cyclohexyl group. Preferred is 1,4-phenylene or 1,4-cyclohexyl. It may also have a substituent on the -10-200906768 ring of 1,4-phenylene or M-cyclohexylene. Κ·2 is a hospital base having a carbon number of 3 to 12, a fluorinated base having a carbon number of 3 to 12, a decyloxy group having a carbon number of 3 to 12, or a fluorinated alkoxy group having a carbon number of 3 to 12. The alkyl group, the fluorinated alkyl group, the alkoxy group, and the fluorinated alkoxy group may be linear or branched, preferably linear, and have a suitable substituent. Wherein R 2 is preferably an alkyl group having 3 to 12 carbon atoms or a fluorinated alkyl group having 3 to 12 carbon atoms, more preferably an alkyl group having 3 to 12 carbon atoms, and more preferably an alkyl group having 3 to 9 carbon atoms. The most preferred alkyl group having a carbon number of 3 to 7. There is no particular limitation on the position of the amine group bonded to the benzene ring constituting the above diaminobenzene ring. Specifically, for example, for the bonding group of the side chain (-Ο-), the position of 2, 3 on the benzene ring, the position of 2, 4, the position of 2, 5, the position of 2, 6, the position of 3, 4 , 3, 5 position. Among them, the position at the time of the synthesis of polyamine is preferably 2, 4, 2, 5 or 3, 5. The position at the position of 2, 4 or 2, 5 is more preferable in terms of the ease of synthesis of the diamine. In the diamine of the above formula (1), R! is a 1,4-transcyclohexylene group, and a diamine represented by the following formula (2-1) and formula (2-2) can be used in a small amount. The effect of increasing the pretilt angle of the liquid crystal is large, which is preferable. In particular, the diamine represented by the formula (2-1) is more preferable since it is excellent in the effect. nh2η2Λ O~OO^(CH2)nCH3 (2-1) -11 - 200906768 In the formula (2-1), the η system represents the rectification-reverse anisotropy of 2 to 11, each of which is a reverse Isomers. ^^ΟΌ-(_η〇Η3 In the formula (2-2), the η system represents a total of 2 to 11 and the cis-trans anisotropy is each a trans isomer. Further, in the following formula, η is an integer of 2 to 11 and more preferably an integer of 2 to 6. The cis-trans group of each of the hexyl groups In the anisotropy, each is f [7], 14-ring is extended to

Preferred examples of (2-2) &,^4-cyclohexyl are the following f-numbers, preferably 2 to 1, in the formula 1, 4-ring I trans isomer.

-12- 200906768

(CH2)nCH3 The method for producing the above-described diamine represented by the formula (1) of the present invention is not particularly limited, and a preferred method is, for example, the following method. [化8] o2n

(3) A dinitro compound of the above formula (3) is synthesized, and a nitro group is converted into an amine group by a usual method. The R! and R2 systems in the formula (3) are the same as those defined in the formula (1). The dinitro compound of the formula (3) can be obtained by reacting a hydroxyl group-containing compound represented by the following formula (4) with dinitrochlorobenzene or the like. Further, R! and R2 in the formula (4) are the same as those defined in the formula (1). H0^0^R1<3~R2 (4) The compound having a radical group which is not represented by the above formula (4) can be represented by the following reaction formula [1] to reaction formula [2]. Manufacture, except that the invention is not limited by these -13-200906768.

When Ri is a cyclohexylene group, for example, a synthetic route of the reaction formula]. In the reaction formula [1], Ri and R2 are the same as those defined by the formula (1), and the oxime is a protecting group such as a methyl group or a benzyl group, and the oxime 2 is represented by MgBr, MgCl or Li. The reagent used in 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 platinum (Pt) 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 a decarboxylation reaction using a methyl group of boron tribromide or a hydrogenation of a palladium catalyst or the like. [化10]

According to the above reaction formula [1], the hydroxyl group-containing compound represented by the above formula (4) can be produced. -14- 200906768

C12H25

HO

CuH23H0

When Ri is an arylene group, for example, the synthetic route of the reaction formula [2]. R! and R2 in the reaction formula [1] are the same as those defined by the formula (1), Xi represents a protecting group such as a methyl group or a benzyl group, and χ3 represents a halogen atom, a methanesulfonyloxy group or a benzenesulfonate.醯oxy, trifluoromethanesulfonyloxy, B(OH)2, MgBr, MSC1 or Li, etc., X4 represents a halogen atom, methanesulfonyloxy, benzenesulfonyloxy, trifluoromethanesulfonyloxy , B(OH)2, MgBr, MgCl or U, and the like. The deprotection reaction is carried out, for example, by using a detachment of a methyl group of BBr3 or by a hydrogenation using a palladium catalyst or the like to carry out a debenzylation reaction or the like. [化11]

(4j) The hydroxyl group-containing compound represented by the above formula (4) can be produced by the above reaction formula [2]'. -15- 200906768 [Chemistry 12]

HO

C4h9 C3H7

The diamine of the present invention can be obtained by reacting with a tetracarboxylic acid, a tetracarboxylic acid difluoride, a tetracarboxylic dianhydride or the like, a tetracarboxylic acid or a derivative thereof to obtain a polyfluorene having a specific structure in a side chain. Amino acid, in addition, by subjecting the polyamic acid to a dehydration ring-closure reaction, a polyimine having a specific structure in a side chain can be obtained. 2. Polyproline The polylysine of the present invention is a polylysine obtained by reacting a diamine component of a diamine represented by the formula (1) with a tetracarboxylic dianhydride. The polyimide of the present invention is a polyimine obtained by subjecting the polyamic acid to dehydration ring closure. Any of the polyamic acid and the polyimine is extremely useful as a polymer for producing a liquid crystal alignment film. In the case of a diamine component (hereinafter referred to as a diamine component) obtained by reacting the above tetracarboxylic dianhydride to obtain a polyamic acid, the content ratio of the diamine represented by the formula (1) is not limited. The pre-tilt angle of the liquid crystal when the ratio of the diamine represented by the formula (1) is more than the liquid of the above-mentioned diamine component using the poly-proline or the polypeptone of the present invention. The bigger it is. In order to increase the pretilt angle of the liquid crystal, it is preferable that the diamine represented by the formula (1) is 1 mol% or more of the diamine component. For the purpose of vertical alignment of the liquid crystal, the diamine of the formula (1) is preferably 1 or more mol% of the diamine component, and more preferably 15 mol% or more. For the purpose of the vertical alignment of the liquid crystal, the diamine of the diamine component may be a diamine represented by the formula (1), and the uniform coating property when the liquid crystal alignment agent is coated as described below may be used. The diamine represented by the formula (1) is preferably 80% by mole or less of the diamine component, and more preferably 4% by mole or less. In the above-mentioned one amine component, the diamine other than the diamine component represented by the formula (1) which is used when the diamine represented by the formula (1) is less than 1 mol% is not particularly limited. Specifically, for example, as described below. p-Benzyldiamine m-phenylenediamine 2,4-diaminotoluene 2,5-diaminotoluene 2,6-diaminotoluene 2.4-dimethyl-1,3-diaminobenzene 2.5- Dimethyl-1,4-diaminobenzene 2.3.5.6-tetramethyl-1,4-diaminobenzene 2.4-diaminophenol 2.5-diaminophenol 4.6-diaminoresorcinol- 17- 200906768 2,5-Diaminobenzoic acid 3,5-diaminobenzoic acid hydrazine, hydrazine-diallyl-2,4-diaminoanilinium oxime, Ν- _ propyl propyl-2,5 - _Aminoaniline 4-aminobenzylamine 3-aminobenzylamine 2-(4-aminophenyl)ethylamine 2-(3-aminophenyl)ethylamine 1,5-naphthalenediamine 2,7-naphthalenediamine 4,4'-diaminobiphenyl 3,4'-diaminobiphenyl 3.3 '-diaminobiphenyl 2,2'-dimethyl-4,4'-di Aminobiphenyl 3,3'-dimethyl-4,4'-diaminobiphenyl 3,3, dimethoxy-4,4'-diaminobiphenyl 3.3 '-dihydroxy-4, 4'-diaminobiphenyl 3,3'-dicarboxy-4,4'-diaminobiphenyl 3,3'-difluoro-4,4'-diaminobiphenyl 2,2'-three Fluoromethyl-4,4'-diaminobiphenyl 3,3'-trifluoromethyl-4,4'-diaminobiphenyl 4,4'-diaminodiphenylmethane 3,3' -diaminodiphenyl Methane 3,4'-diaminodiphenylmethane-18- 200906768 4,4'-diaminodiphenyl ether 3,3 '-diaminodiphenyl ether 3,4'-diaminodiphenyl ether 4,4'-Diaminodiphenylphosphonium 3,3 '-diaminodiphenylphosphonium 4,4'-diaminodiphenylamine 3,3 '-diaminodiphenylamine 3,4'-di Aminodiphenylamine N-methyl(4,4'-diaminodiphenyl)amine N-methyl(3,3'-diaminodiphenyl)amine N-methyl (3,4'- Diaminodiphenyl)amine 4,4'-diaminobenzophenone 3,3'-diaminobenzophenone 3,4'-diaminobenzophenone 4,4'-di Aminobenzoaniline 1.2-bis(4-aminophenyl)ethane 1.2-bis(3-aminophenyl)ethane 4,4'-diaminodiphenylacetylene 1.3-bis(4-amino group Phenyl)propane 1.3-bis(3-aminophenyl)propane 2.2-bis(4-aminophenyl)propane 2.2-bis(3-aminophenyl)propane 2,2-bis(3-amino group -4-methylphenyl)propylamine 2,2-bis(4-aminophenyl)hexafluoropropane-19- 200906768 2.2-bis(3-aminophenyl)hexafluoropropane 2.2-bis(3- Amino-4-methylphenyl)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-amino group Phenoxy)heptane 1,8-bis(4-aminophenoxy)octane 1,9-bis(4-aminophenoxy)decane 1,10-bis(4-aminophenoxyl)癸 癸 Ι, Π-bis(4-aminophenoxy)undecane 1,12-bis(4-aminophenoxy)dodecane bis(4-aminophenyl)propane Bis(4-aminophenyl)butane dioleate bis(4-aminophenyl)pentane dioleate bis(4-aminophenyl)hexane dioleate bis (4) -aminophenyl)heptane dioleate bis(4-aminophenyl)octane dioleate bis(4-aminophenyl)decane dioleate bis(4-aminophenyl) Octane dioleate 1.4-bis(4-aminophenyl)benzene 1,3-bis(4-aminophenyl)benzene 1,4 -bis(4-aminophenoxy)benzene 1, 3-bis(4-aminophenoxy)benzene-20- 200906768 1,4-bis(4-aminobenzyl)benzene 1,3-bis(4-aminobenzyl)benzene bis (4 -aminophenyl)terephthalate bis(3-aminophenyl)terephthalate bis (4- Phenyl)isophthalate bis(3-aminophenyl)isophthalate 1,4-phenylenebis[(4-aminophenyl)methanone] 1,4-亚Phenyl bis[(3-aminophenyl)methanone] 1.3-phenylenebis[(4-aminophenyl)methanone] 1.3-phenylenebis[(3-aminophenyl)methanone ] 1,4-phenylene bis(4-aminobenzoate) 1,4-phenylene bis(3-aminobenzoate) 1.3-phenylene bis(4-aminobenzoic acid) Acidate) 1.3-phenylene bis(3-aminobenzoate) deuterated-(1,4-phenylene) bis(4-aminobenzophthalamide) Ν,Ν'-(1, 3-phenylene) bis(4-aminobenzophthalamide) 虬 "-(1,4-phenylene) bis(3-aminobenzophthalamide) Ν, Ν'-(1,3- Phenylene) bis(3-aminobenzoguanamine) bis(4-aminophenyl)terephthalamide bis(3-aminophenyl)terephthalamide bis(4-amine Phenyl)isophthalamide bis(3-aminophenyl)isophthalamide 2.2-bis[4-(4-aminophenoxy)phenyl]propane 2.2-bis[4- (4-Aminophenoxy)phenyl]hexafluoropropane-21 - 200906768 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-diaminobenzo Furan 2.6-diaminocarbazole 2.7-diaminocarbazole 3,6-diaminocarbazole 2.4-diamino-6-isopropyl-1,3,5-triazine 2,5-double ( 4-aminophenyl)-1,3,4-oxadiazole 1,3 -diaminopropane 1.4- _ Aminodin, 1,5-diaminopentane 1,6-diaminohexane 1 , 7 -diaminoheptane 1,8 -diaminooctane 1,9 -diaminodecane 1,10-diaminodecane 1,1 1 -diaminoundecane 1, 1 2-diaminododecane 1,4-diaminocyclohexane 1,3-diaminocyclohexane-22- 200906768 bis(4-aminocyclohexyl)methane bis(4-amino-3 -Methylcyclohexyl)methane is a tetracarboxylic dianhydride which reacts with a diamine component when the poly phthalic acid of the present invention is produced, and is not particularly limited. Moreover, it is specifically described below. 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-indole tetracarboxylic dianhydride 3,3',4,4'-biphenyltetracarboxylic dianhydride 2,2',3,3'-biphenyltetracarboxylic dianhydride 2,3,3' , 4'-biphenyltetracarboxylic dianhydride 3,3'4,4'-benzophenone tetracarboxylic dianhydride 2,3,3',4'-benzophenonetetracarboxylic dianhydride double ( 3,4-dicarboxyphenyl)methane dianhydride bis(3,4-dicarboxyphenyl)ether dianhydride bis(3,4-dicarboxyphenyl)ruthenium hydride dianhydride 2.2-bis(3,4-dicarboxyl Phenyl)propane dianhydride 2.2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride 2.5-dicarboxymethylterephthalic dianhydride 4.6 -dicarboxymethylisophthalic acid dianhydride 4- (2,5-Dicarbonyltetrahydro-3-furanylphthalic anhydride)-23- 200906768 1.4-bis(2,5-dicarbonyltetrahydro-3-furanyl)benzene 1,4-bis (2, 6-dicarbonyltetrahydro-4-furanyl)benzene 1.4-bis(2,5-dicarbonyltetrahydro-3-methyl-3-furanyl)benzene 1,4 -bis(2,6-dicarbonyltetra Hydrogen-4-methyl-4-pyranyl)benzene 1.2.3.4-butane tetracarboxylic dianhydride 1,2,3,4-cyclobutane tetracarboxylic acid Dihydride 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride 1.3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride 1.2. 3.4- Tetramethyl-1,2,3,4-cyclobutanetetracarboxylic 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-dicarbonyltetrahydro-3-furanyl)-cycloethane-1,2-dicarboxylic anhydride 5 - (2,5-Dicarbonyl-3-furanyl)-3-methyl·3_cyclohexene-1,2-dicarboxylic 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-1,2,3,4-tetrahydro- 6-methyl-1-naphthalene succinic dianhydride bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride 3 , 3 ',4,4 '-dicyclohexyltetracarboxylic acid Acid dianhydride 2.3.5.6- Propentane tetracarboxylic dianhydride 3.5.6- Tricarboxy-propentane-2-acetic acid dianhydride tricyclo[4.2.1 ·02,5]decane-3,4,7, 8-tetracarboxylic dianhydride-24- 200906768 tetracyclic [4.4_1·〇2'5·〇7, ι〇] decane-3,4,8,9-tetracarboxylic dianhydride hexacyclic [6.6· 0.12'7·〇3,6·ι9=ΐ4·〇1〇'13]hexadecane 112_tetracarboxylic dianhydride 1,4 - (2,5-dicarbonyltetrahydro-3-furanyl)hexane 1,4-bis(2,6-dicarbonyltetrahydro-4-pyranyl)hexane to make the above diamine component and tetracarboxylic acid The method of reacting a dianhydride is a simple method of mixing a diamine component and a tetracarboxylic dianhydride in an organic solvent. The organic solvent is not particularly limited as long as it is a polylysine which can be formed by dissolving. Specifically, for example, hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine-dimethylacetamide, hydrazine-methyl-2-pyrrolidone, hydrazine-methylcaprolactone, dimethyl hydrazine, γ- Butyrolactone and the like. These can be used alone or in combination. Further, when it is used alone, it may be a poor solvent in which polylysine cannot be dissolved, and it may be used in the above solvent in a range in which the produced polyamine acid is not precipitated. Further, since the water in the organic solvent hinders the polymerization reaction and causes the produced polyamic acid to be hydrolyzed, it is preferred that the organic solvent be dehydrated and dried as much as possible. A method of mixing a diamine component and a tetracarboxylic dianhydride in an organic solvent, for example, stirring a solution in which a diamine is dispersed or dissolved in an organic solvent, and dispersing the tetracarboxylic dianhydride directly or in an organic solvent Or a method of adding the solution, or a method of adding a diamine in a solution in which a tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent, and a method of adding a tetracarboxylic dianhydride or a diamine to each other or in an organic solvent. Etc., can be any of these methods. -25- 200906768 The reaction temperature at the time of synthesis of the above polylysine, any temperature of π 150 ° C, preferably in the range of _5~loot, and the 'reaction can be carried out at any concentration, but the raw material and tetracarboxylic acid When the concentration of the acid dianhydride is too low, a high fraction cannot be obtained. When the concentration is too high, the viscosity of the reaction liquid becomes too high, and no mixing is preferred, so that it is preferably 1 to 50% by mass, more preferably 5 ~ The initial stage of the reaction can also be carried out at a high concentration, and then added to the synthesis reaction of poly-proline, and the ratio of the molar ratio of the tetracarboxylic dianhydride to the diamine component is preferably 0.8 to 1.2. Similarly, when the molar ratio is close to 1. The molecular weight of the acid is increased. When the molecular weight of the polyamic acid of the present invention is not particularly coated with the liquid crystal alignment treatment agent described below, and the strength of the film obtained by the film, the weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method is 300,000. Good, with 10,000 to 150, 〇〇〇 better. 3-Polyimine The polyimine of the present invention is a polyimine obtained by preparing the above polyamic acid, and is useful as a liquid crystal alignment film. In the polyimine of the present invention, the amidation rate of the amidino group is not necessarily required to be 1% by weight, and is adjusted depending on the purpose or purpose. ίSelect a polymerization method of -20~ > diamine component amount to uniformly stir 30% by mass. Machine solvent. In terms of the number of moles. With the general formation of polyamines. Considering the uniformity, the 5,0 0 0~ row dehydration ring-closing polymer is extremely closed-loop rate (depending on the method of -26-200906768, the poly-proline acid is dehydrated and closed, and the polymerization is carried out without using a catalyst. The hydrazine imidization of the proline acid is heated, and the polyamidic acid solution is heated at 100 to 400 ° C when the polyimide is subjected to thermal imidization using a catalyst quinone imine. Heating at 120~250 °c), the water formed by the ruthenium imidization reaction is removed to the outside of the system and is preferably carried out. The catalyst of the polyaminic acid is imidized by polyamidolic acid. The alkaline catalyst and the acid anhydride are added to the solution, and the mixture is stirred at -20 to 250 ° C (preferably, 〇 1 to 180 ° C). The amount of the basic catalyst is decylamine. The acid group is 0.5 to 30 moles, preferably 2 to 20 moles, and the amount of the anhydride is 1 to 50 moles of the valeric acid group, preferably 3 to 30 moles. The catalyst is, for example, pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine. Among them, in order to carry out the reaction, pyridine is preferred because it has an appropriate basicity. Triacetic acid anhydride, pyromellitic anhydride, etc., in which acetic anhydride is used, it is easy to carry out the purification treatment after the completion of the reaction, and therefore, the imidization rate of the imidization by the catalyst oxime can be adjusted by The amount of the polymer, the reaction temperature, and the reaction time are controlled. The molecular weight of the polyimine of the present invention is not particularly limited, and the workability, the uniformity of the film, and the strength of the obtained film when the liquid crystal alignment agent described below is coated are considered. The weight average molecular weight measured by the GpC method is preferably 5,000 to 300,000, preferably 10,000 to 150,000. When the polymer component is recovered from the reaction solution of polyphosphoric acid or polyimine, the reaction solution is put into a poor solvent. It is precipitated. The -27-200906768 lean solvent used in the precipitation is, for example, methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, and the like. It is preferred to carry out the drying of the polymer which has been precipitated in the poor solvent after drying, under normal pressure or reduced pressure, at normal temperature or under heating. 4- Liquid crystal alignment treatment agent The treatment agent' is a coating liquid in the case of producing a liquid crystal alignment film, and the main component thereof is a composition containing an organic component in which a polymer component is formed and a polymer component is dissolved. The liquid crystal alignment treatment agent of the present invention, Any one of the above-mentioned polyamic acid and polyimine of the present invention containing at least the above-mentioned resin component (hereinafter referred to as a polymer of the present invention). The content of the polymer of the present invention in the resin component is 5% by mass or more. Preferably, it is more preferably 10% by mass or more. The above resin component may be all of the polymer of the present invention, and other polymers may be mixed in the polymer of the present invention. In addition to polyamine or polyimine obtained from a diamine other than the diamine represented by the formula (1) as a diamine component which is reacted with a tetracarboxylic dianhydride. The organic solvent that dissolves the resin component is not particularly limited. Specifically, for example, hydrazine, dimethyl-dimethylformamide, hydrazine, hydrazine-dimethylacetamide, N-methyl-2-pyrrolidone, hydrazine-methylhexylamine, dimethyl hydrazine, γ-butyl Lactones, etc. These organic solvents are good solvents with high solubility of the resin. 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. -28-200906768 In the present invention, preferred poor solvents such as ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, diethylene glycol diethyl ether, diethylene glycol monoethyl ether , diethylene glycol monobutyl ether, ethyl carbitol acetate, ethylene glycol, ethylene glycol monohexyl ether, b-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 group ) propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate. The poor solvent is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, based on the organic solvent contained in the liquid crystal alignment agent. The concentration of the resin component in the liquid crystal alignment agent of the present invention can be appropriately adjusted by combining the film thickness of the obtained liquid crystal alignment film and the apparatus used for coating the liquid crystal alignment agent. The general resin concentration of the liquid crystal alignment agent is from 1 to 20% by mass, preferably from 2 to 1% by mass. The liquid crystal alignment agent of the present invention may contain components other than the above. For example, the functional decane-containing compound or the epoxy group-containing compound when the adhesion between the liquid crystal alignment film and the substrate is improved, the fluorine-based surfactant, the polyoxyalkylene-based surfactant, and the like, in order to improve the planarization property of the film, Nonionic surfactants, etc. When the functional decane-containing compound or the epoxy group-containing compound is contained, the amount is preferably from 01 to 30 parts by mass, more preferably from 1 to 20 parts by mass, per 1 to 1 part by mass, per 100 parts by mass of the resin component. optimal. When the surfactant is contained, the amount is preferably from 0.01 to 2 parts by mass, more preferably from 0.01 to 1 part by mass, per part by mass of the resin component of -29 to 200906768. 5 _ Liquid crystal alignment film and liquid crystal display device The liquid crystal alignment treatment agent of the present invention is coated on a substrate, fired, and then subjected to rubbing treatment or light irradiation, similarly to a commercially available polyimine-based liquid crystal alignment treatment agent. The alignment treatment is performed, or the alignment treatment is not performed as a liquid crystal alignment film in some of the vertical alignment applications. The coating method of the liquid crystal alignment agent of the present invention is not particularly limited, and generally it can be carried out by screen printing, flexographic printing, off-line printing, ink jetting or the like. Further, the method of using the coating liquid may be immersion, roll coating, slit coating, a rotator, or the like, and may be used depending on the purpose. After being coated on the substrate by such a method, the solvent can be evaporated by a heating method such as a hot plate to form a film. The baking treatment after coating the liquid crystal alignment treatment agent can be carried out at any temperature of from 100 to 300 ° C, preferably from 150 to 250 ° C. This firing can be carried out by a hot plate, a hot air circulating furnace, an infrared furnace or the like. For the rubbing treatment, a thunder cloth, a nylon cloth, a cotton cloth, or the like can be used. Vertical alignment With the liquid crystal alignment film, since it is not easy to obtain a uniform alignment state by rubbing treatment, when it is used as a liquid crystal alignment treatment agent for vertical alignment, it is preferably used without rubbing treatment. The liquid crystal cell of the present invention can be produced by a general method, and the production method thereof is not particularly limited. In general, a binder can be coated on a glass substrate having a liquid crystal alignment film formed on at least one of the substrates, and the spacer can be dispersed while maintaining a constant pitch, and then two substrates can be bonded to each other to bond -30-200906768. After the agent is hardened, the liquid crystal cell is injected, the liquid crystal is injected from the liquid crystal injection port under vacuum, the injection port is sealed, the liquid crystal cell is prepared, or the liquid crystal is dropped on the substrate on which the spacer is dispersed, and then the two substrates are pasted. In combination, a method of producing a liquid crystal cell, and the like. For the liquid crystal, a fluorine-based liquid crystal or a cyano liquid crystal having positive or negative dielectric anisotropy can be used depending on the application. As described above, the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention can impart a large pretilt angle to the liquid crystal, and can be used as a liquid crystal alignment film for various purposes. [Embodiment] The present invention will be specifically described by way of examples, but the present invention is of course not limited by the embodiments. [Examples] [Synthesis of diamine of the present invention] <Example 1 > Synthesis of diamine [9] Μθ〇-〇-Μ9Β<·_7~~Μβ°·〇Τ〇^ 〇*°5Η” ——mb0-〇-〇-^〇-csHii m { 0H ... I 13] [4] θΟ^Ο-CsH,, (2] [4] -► -► H〇-〇-〇 -〇-CSH,i [5] [6] -31 - 200906768 〇2Νγ^Ν〇2 Η2Νγ^ΝΗ2 [61 -T^ ^0〇O〇5Ht1-^ XXo^y^yc^ I [*] [9 0zN〇::;2 m 4-methoxyphenylmagnesium bromide [1] (0.5 Μ-tetrahydrofuran solution, 2.4 liters (L), 1.20 m〇l) was added to a nitrogen-substituted 4-neck flask. Tetrahydrofuran (200 mL). After cooling the reactor at 〇 ° C, 4-(trans-4-n-pentylcyclohexyl)cyclohexanone [2] (300 g, 1.20 mol) of tetrahydrofuran (28 0 g) was added dropwise. After the completion of the dropwise addition, the temperature was gradually raised to 25 ° C, and then stirred at 25 ° C for 15 hours. After the completion of the reaction, the reaction solution was cooled at 0 ° C, and then slowly dropped. 1 0% aqueous acetic acid solution (1.0 L). Then, the aqueous layer was removed by a liquid separation operation, and toluene (2.4 L) was added thereto, followed by saturated brine (1.0 L), saturated aqueous sodium hydrogencarbonate (1.0 L), and saturated. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to give the compound [3] (the cis-trans isomer mixture) (43 0 g). It is used directly in the subsequent reaction. Further, 1 Η - NMR of the obtained compound is based on TMS (S i (C Η 3) 4), and NMR measuring apparatus (400 MHz) is used in the hydrogenated chloroform. The measurement results of the compound [3] are as follows, and the other compounds are also the same. Compound [3] (cis-trans isomer mixture) 1H-NMR (400 MHz, CDCl3, 6 ppm): 7.47-7.30 ( 2H,m), 6.98 -6.8 2(2H,m), 3.81-3.79(3H,m), 2.3 4-0.8 1 (3 0H,m). Compound [3 ] (cis-trans isomer) a mixture of (4 3 〇g, i · 2 〇mol) and p-toluenesulfonic acid monohydrate (13 lg, 72 〇 mm〇i) of dehydrated A-32-200906768 benzene (2.5 L), under reflux The reaction was carried out for 2 hours. After the completion of the reaction, the mixture was washed with a saturated aqueous solution of sodium hydrogencarbonate (1·5 L) and brine (1. 5 L) at a temperature of 80 °C. After the organic layer was dried over anhydrous magnesium sulfate, the solvent was evaporated under reduced pressure. The obtained crude product was recrystallized in a mixed solvent of ethyl acetate/ethanol (1:1 v/v) to obtain a compound [4] (a mixture of cis-trans isomers) (amount of 3 79 g, obtained) The rate is 89%). Compound [4] (cis-trans isomer mixture) 1H-NMR (400 MHz, CDCl3, 5 ppm): 7.32 (2H, d), 6.84 (2H, d), 6.02 (1H, m), 3.80 (3H) , s), 2.48- 1.75 (9H, m), 1. 3 8 -0.86 (1 9H, m). A mixture of the compound [4] (3 79 g, 1-1 mol), 5% palladium carbide (aqueous, 19.0 g, 5 wt%), ethyl acetate il, ethanol (1 L) in the presence of hydrogen at room temperature (25 ° Stir in C). After completion of the reaction, the reaction mixture was filtered in a zeolite to wash the zeolite with toluene (1 L). When the filtrate was concentrated under reduced pressure, compound [5] (yield of cis-trans isomer) was obtained (yield of 3 47 g, yield: 91%). Compound [5] (cis-trans isomer mixture) 1H-NMR (400 MHz, CDCl3, 5 ppm): 7.14 (2H, m), 6.83 (2H, m), 3.78 (3H, S), 2.6 4 - 2.3 5 ( 1 Η , m), 1.88-1.52 (8H, m), 1.49-0.74 (22H, m). In a dichloromethane solution of 2.0 L of compound [5] (cis-trans isomer mixture) (347 g, l_00 mol) in a solution of 〇 ° C and nitrogen substitution, boron tribromide (1 . - dichloromethane solution, 10 l, 1. 〇〇m 〇 1). After the completion of the dropwise addition, stirring was carried out for 2 hours at 〇 °C. After the reaction is completed, add a small amount of the reaction solution to -33-200906768 in distilled water. After extracting with ethyl acetate (2. 〇 L), 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 obtain a compound [6] (trans isomer) (yield: 183 g, yield: 55%). In the anisotropy of the cis-trans isomer of 1,4-cyclohexene of the compound [6], each is a trans isomer. Compound [6] (trans isomer) 1H-NMR (400 MHz, CDCl3, 5 ppm): 7.07 (2H, d), 6.75 (2H, d), 4.60 (1H, s), 2.37 (lH, m), 1.9 0 - 1 . 7 1 (8 H, m ), 1.39-0.84 (22H, m in compound [6] (trans isomer) (20.0g' 61.0mmol), potassium carbonate (25.3g, A mixture of 183 mmol) and toluene (149 g) was added dropwise to a solution of 1-chloro-2,4-dinitrobenzene [7] (12.4 §, 61. 〇111111 〇1) in toluene (49.0 §) under reflux. After completion, the mixture was stirred under reflux for one night. After the completion of the reaction, the reaction mixture was washed three times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. Recrystallization from 2-propanol and washing with ethanol gave compound [8] (trans isomer) (yield 27.4 g, yield 90%). 1,4-5 of compound [8] In the cis-trans transatropy, each is a trans isomer. Compound [8] (trans isomer) 1H-NMR (400 MHz, CDCl3, 6 ppm): 8.84 (1 H, d), 8.30 (lH, dd), 7.30 (2H, d), 7.04 (3H, m), 2.5 〇 (lH, t), 1.96-l_76 (8H, m), 1.49-0.86 (22H, m). Compound [8] (trans isomer) (27.4 g, 55.0 mmol) a mixture of 5% carbon-34 - 200906768 palladium (2.74 g, 10 wt%) and 1,4-dioxane (3 29 g) was stirred in the presence of hydrogen at 26 ° C for 4 hours. Filtration with zeolite, and the crude product was obtained by distilling off the solvent under reduced pressure. The crude product was recrystallized from ethanol/ethyl acetate (1:1 v/v) solvent to obtain two. Amine [9] (trans isomer) (amount of 22. Og, yield 91%). Among the cis-trans anisotropy of 1,4-cyclohexene of compound [9], each is The trans isomer. Diamine [9] (trans isomer) 1H-NMR (400MHz, CDCl3, 5ppm): 7.09 (2H, d), 6.84 (2H, d), 6.73 (lH, d), 6.17(lH,d), 6.08(lH,dd), 3.57(4H,broad), 2.39(lH,t), 1. 9 0 -1 . 7 1 (8 H , m), 1 .3 9 -0.8 6(22H,m) 〇<Example 2> Synthesis of diamine [1 5 ][Chemistry 14] ^OO-CsH, M〇l

Me0O~〇^〇*csHi 1 112]

MeO-Q-B(OH)2 [11] 12 Η0Ό~Ο^〇·ε5Ηιι [131 02Nv^vN02 〇2NcC [71

HaN^NHa O-O^-OO-CsHu

[15J-35- [14] [14] 200906768 4-(trans-4-n-pentylcyclohexyl)bromide benzene [10] (50.0 g, 162 mmol), 4-methoxyphenyl succinic acid [ Ll] (36.9 g, 243 mmol), toluene (1.4 L), ethanol (0.16 L) and a mixed solution of sodium carbonate aqueous solution (sodium carbonate (44.6 g, 0.42 mol) / distilled water 0.6 L), degassed by nitrogen gas . Pd(PPh3)4 (0.934 g, 0.808 mm) was added to this solution under a nitrogen atmosphere, and the mixture was stirred at 90 ° C for 6 hours. After completion of the reaction, the organic layer was separated and washed twice with distilled water (0.5 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 obtain a compound [1 2] (trans isomer). The amount is 40.0 g, and the yield is 73%). In the cis-trans anisotropy of the 1,4-cyclohexene of the compound [12], each is a trans isomer. Compound [12] (trans isomer) 1H-NMR (400 MHz, CDCl3, 5 ppm): 7.5 1 (2H, d), 7.47 (2H, d), 7.26 (2H, d), 6.96 (2H, d) , 3.84(3H,s), 2.50(lH,t), 1.90(4H,t), 1. 5 3 - 1.4 2 ( 2 H, m), 1.36- 1,20(9H, m), 1 1 2 -1 . 0 1 (2 H,m),0 · 9 0 (3 H, t). Boron tribromide (1_0M-dichloromethane solution) was added dropwise to a solution of 'Compound Π2' (trans isomer) (40.0 g, 120 mmol) in dichloromethane (500 mL) at 〇 ° C under a nitrogen atmosphere. (120 mL, 120 mmol)). After the completion of the dropwise addition, stirring was carried out at 0 ° C for 2 hours. After the reaction was completed, a little reaction solution was added to distilled water (50 mL). The extract was extracted with ethyl acetate (500 mL), and the extract was washed twice with distilled water (300 mL). After the organic layer was dried over sulfur-36-200906768 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 obtain a compound [13] (trans isomer). 29.5g, yield 77%). In the cis-trans anisotropy of 1,4-cyclohexene of the compound [13], each is a trans isomer. Compound [13] (trans isomer) 1H-NMR (400 MHz, CDCl3, 5 ppm): 7.47-7.45 (4H, m), 7.26 (2H, d), 6.88 (2H, d), 4.82 (lH, s ), 2.49(lH,t), 1.90(4H,t), 1.5 5 - 1.40(2H,m), 1. 3 6 - 1.2 1 (9 H , m), 1 . 1 2- 1 _ 0 1 ( 2H, m), 0.90 (3H, t) 〇 in a mixture of compound [13] (trans isomer) (15.3 g, 47.5 mmol), potassium carbonate (19.7 g, 140 mmol), and toluene (69.0 g) A solution of toluene (3 5. 〇g) of chloro-2,4-dinitrobenzene [7] (9.62 g, 48.0 mmol) was added dropwise under reflux. After the completion of the dropwise addition, the mixture was stirred under reflux for 5 hours. After the completion of the reaction, the reaction solution was washed twice with distilled water. After the organic layer was dried over anhydrous magnesium sulfate, the solvent was evaporated under reduced pressure. When the obtained crude product was washed with 2-propanol, the compound [14] (trans isomer) was obtained (yield 2 1.0 g, yield: 90%). The cis-trans of the 1,4-cyclohexene of the compound [1 4 ], each of the isomers, is a trans isomer. Compound [14] (trans isomer) 1H-NMR (400 MHz, CDCl3, 6 ppm): 8.87 (1H, d), 8.34 (1H, dd), 7.67 (2H, d), 7.5 1 (2H, d), 7.3 1 (2 H, d), 7.19(2H,d), 7.12(lH,d), 2.53(lH,t), 1.92(4H,t), 1.55-1 _42(2H,m ), 1.36-1.20 (9H, m), -37- 200906768 1.14-1.01 (2H, m), 0.90 (3H, t). Compound [1 4 ] (trans isomer) (2 1 .0 g, 4 3 0 m ο 1), 5% palladium carbide (2.1 g, 10 wt%), 1,4-dioxane (240 g) The mixture was stirred under a hydrogen atmosphere at reflux for 32 hours, and then stirred at 25 ° C for 72 hours. After the reaction was completed, it was filtered with zeolite. When the filtrate was distilled off under reduced pressure, a crude material was obtained. The crude product was recrystallized twice with toluene to obtain a diamine [15] (trans isomer) (yield: 9.42 g, yield 51%). Among the cis-trans anisotropy of the 1,4-cyclohexene of the compound Π5], each is a trans isomer. Diamine [15] (trans isomer)] H-NMR (400MHz, CDCl3, 3ppm): 7.47(2H,d), 7.45(2H,d), 7.25(2H,d), 6.9 7 (2 Η , d), 6.7 8 ( 1 Η, d), 6.1 9 ( 1 Η , d), 6.10 (lH, dd), 3.62 (4H, broad), 2.49 (lH, t), 1.90 (4H, t), 1.54-1.40 (2H, m), 1.36-1.20 (9H, m), 1.13-1 .00 (2H, m), 0.90 (3H, t). <Example 3 > Synthesis of diamine [1 8 ] [Chem. 15]

-38- 200906768 The diamine [丨8] was obtained by the same synthesis method as in the example <1>, using the compound [i 6 ], via the compound [1 7 ] (trans isomer). Isomer). In the cis-trans anisotropy of the compound [17] and the 1,4-cyclohexene of the diamine [18], each is a trans isomer. Compound [17] (trans isomer) 1H-NMR (400 MHz, CDCl3, 6 ppm): 8.84 (d,lH), 8.29 (dd,lH), 7.30 (d, 2H), 7.04 (d, 2H), 7.0 3(d,lH), 2.5 6-2.42(m, 1 Η), 1. 9 6 - 1 . 8 2 (m , 4 Η), 1. 8 1 -1.7 0 (m, 4 Η), 1.50 -1.36 (m, 2H), 1.35-1.20 (m, 10H), 1.20-0.95 (m, 9H), 0-88 (t, 3H), 0.95 - 0.8 (m, H). Diamine [18] (trans isomer) 1H-NMR (400MHz, CDCl3, 6ppm): 7.09 (d, 2H), 6.84 (d, 2H), 6.73 (d, lH), 6.17 (d, lH) , 6.08(dd,lH), 3.66(bs,2H), 3.49(bs,2H),2.44-2.34(m,lH), 1.93 - 1.70(m,8H), 1.4 5 - 1. 2 0 (m, 1 2 H), 1.2 0 - 0.9 2 (m, 9 H), 0.88 (t, 3H), 0.90-0.7 8 (m, 2H). <Synthesis Example 1 > Synthesis of diamine [23] -39- 200906768 [Chem. 16] ϊ-^-MgBr

MeO- )_〇-〇*〇-c*Hn —h〇-〇-〇-〇-c5h<i r_0~〇-csHii C19] [2β] 121] 0O~0~〇-cshi« [22] 4-bromo-4'-(n-pentyl)biphenyl [19] (25. g, 82.4 mmol) and hydrazine (triphenylphosphine) palladium (0) were added to a nitrogen-substituted 4-neck flask at room temperature. After (4.76 g, 4.12 mm 〇l), 4-methoxyphenylmagnesium bromide [1] (0.5 M - tetrahydrogen (furan solution, 280 mL, 140 mmol) was added, and then heated to reflux. After cooling to room temperature, the solid was precipitated, and the reaction liquid was added to ethyl acetate (20 g) / 1 M hydrochloric acid (280 mL), and filtered. The obtained solid was washed with water and washed with ethyl acetate. The compound [20] was obtained as a yellow solid (yield: 2 6 · 8 g, yield: 98%). Compound [20] 1H-NMR (400 MHz, CDCl3, 5 ppm): 7.66-7.54 (8H, m), 7.23(2H,d), 7.0-6.98(2H,m), 3. 8 6 (3 Η, s), 2.6 5 (2H , t), 1.68- 1.64(2H,m), 1.40- 1.3 3 (4H, m), 0.93 - 0.8 9 (3 H, m). Dehydration of compound [20] (25.〇g, 75.7 mm ο 1) at 0 ° C under nitrogen substitution ( 3 〇〇g) solution, drip boron tribromide (1_0M- Methyl chloride solution, 75.7 mL, 75.7 mm 〇l). After the completion of the dropwise addition, stir the reaction for 2 hours under TC. After the reaction is completed, add a little reaction solution in the steaming water -40 - 200906768. After extracting the warm ethyl acetate (2.5 L), the organic layer was washed twice with distilled water (300 mL). The organic layer was dried over magnesium sulfate, and the solvent was concentrated to 5 OOmL. The solid was filtered, washed with ethyl acetate, and dried to give a compound [21] (yield: 19.1 g, yield: 80%) of the orange-colored solid. Compound [2 1] 1H-NMR (400 MHz, CDCl3) , 5ppm): 9.58(1 H,s), 7.69-7.64(4H,m), 7.6 1 - 7.5 9 (2 Η , m), 7.5 5 - 7.5 3 (2 Η , m), 7.27(2H,d ), 6.8 8-6.86(2H,m), 2.60(2H,t), 1. 6 4 -1 · 5 6 ( 2 H,m),1 · 3 5 - 1.2 8 (4 H,m),0.8 7 ( 3 H,t). In a mixture of the compound [21] (10.0 g, 31.6 mmol), potassium carbonate (13.10 g, 3 1.6 mmol), toluene (46 g), l-chloro-2,4-dinitrobenzene was added dropwise under reflux [ 7] (6.40 §, 31.6111: 11 〇 1) toluene (31 §) solution. After the completion of the dropwise addition, the reaction was carried out by stirring at reflux for 17 hours. After completion of the reaction, ethyl acetate (2.5 L) and distilled water (200 g) were added to the reaction mixture, and then the aqueous layer was partitioned. Then, the organic layer was washed 3 times with distilled water (200 mL). After the organic layer was dried over anhydrous magnesium sulfate, the solvent was evaporated under reduced pressure. Ethyl acetate (50 g) was added to the obtained crude product, and the mixture was washed with an ultrasonic device, and then filtered and dried to obtain a white solid compound [22] (yield 12.1 g, yield 79%) ).

Compound [2 2 J 1H-NMR (400 MHz, CDCl 3 , 6 ppm): 8.92 (1H, d), 8.48 (1H, dd), 7.89-7.87 (2H, m), 7.8 1- 7.75 (4H, m) , 7.65-7.63(2H,m), 7.3 9 - 7.3 7 (2 H, m), 7.3 1 - 7.2 7 (3 H , m), -41 - 200906768 2.62(2H,t), 1.63 - 1.5 9( 2H, m), 1.34- 1.29 (4H, m), 0_88 (3H, t). A mixture of the compound [2 2 ] (1 1 . 〇g, 2 2 · 8 mmo 1), 5% palladium carbide (i.g, 10 wt%), 1,4-dioxane (165 g) Stirring was carried out in the presence of hydrogen at 65 t:. After the reaction was completed, it was filtered with zeolite. When the filtrate was distilled off under reduced pressure, a crude material was obtained. Dioxane (50 g) was added to the crude product, and the mixture was washed with an ultrasonic device, and then filtered and dried to obtain a pale white solid diamine [23] (amount of 7.8 g, yield 8) 1%). Diamine [23] W-NMRHOOMHz^DCUppm): 7.72-7.66(4H,m), 7.66-7.60(4H,m), 7.28(2H,d), 6.9 4 - 6.9 0 (2 Η, m), 6.58 (lH,d), 6.06(lH,d), 5.86(lH,dd), 4.75(2H,s), 4.60(2H,s), 2.61(2H,t),1.64-1.56(2H, m), 1 . 3 5 - 1.2 8 (4 H , m), 0_82 (3H, t). [Synthesis of Polyproline or Polyimine of the Present Invention] Abbreviations and structures of the compounds used in the following Examples and Comparative Examples (tetracarboxylic dianhydride) BODA: bicyclo[3.3.0] octane Alkane-2,4,6,8-tetracarboxylic dianhydride CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride-42- 200906768 [Chem. 17]

(diamine) p-PDA: p-phenylenediamine DBA: 3,5-diaminobenzoic acid DAA: Ν, Ν-diallyl-2,4-diaminoaniline PBCH5DAB: i, 3_two Amino group 4·[4_[trans _4_(trans _4_n-pentylcyclohexyl)cyclohexyl]phenoxy]benzene BPCH5DAB: 1'3-diamine _4{4-[4-( Trans_4_n-pentylcyclohexyl)phenyl]phenoxy}benzene PBCH7DAB : 1,3-diamino-4{4-[trans- 4-(trans-4-n-pentylcyclohexyl) Cyclohexyl]phenoxy}benzene m-PBCH5DABEs: 3,5-diamino-{4-[trans-4-(trans-4-n-pentylcyclohexyl)cyclohexyl]phenyl}benzene Acid ester PCH7DAB: 1,3-diamino-4-[4-(trans-4-n-pentylcyclohexyl)phenoxy]benzene PBP5DAB: 1,3-diamino- 4- [(4 - n-Pentylphenyl)phenoxy]benzene (Remarks) PBC Η 5 DAB is a monoamine [9] synthesized in the same manner as in Example 1. B P C Η 5 D A B is a -43-200906768 amine [1 5 ] which was prepared in the same manner as in Example 2. PBCH7DAB is a diamine synthesized in the same manner as in Example 3 [18]. m-PBCH5DABEs is a compound [6] synthesized in the same manner as in Example ,, and is synthesized based on the examples of JP-A-2004-67589. PCH7DAB is synthesized based on the examples of JP-A-9-27 8724. PBP5DAB is a diamine synthesized in the same operation as in Synthesis Example [23] ° [Chemical 18]

P-PDA

[Chem. 19]

PBCH5DAB

(CH2)4CH3

BPCH5DAB

(CH2)6CH3 -44- 200906768 [Chem. 20]

m-PBCH5DABEs

(CH2)6CH3 PCH7DAB

PBP5DAB (organic solvent) NMP: N-methyl-2-pyrrolidone BCS: butyl cellosolve The measurement method used in the following examples is % T m ^ [molecular weight] In this example, polyimine The molecular weight was measured by a room temperature gel permeation chromatography (GPC) apparatus (GPC_i〇1) manufactured by Shodex Co., Ltd., and a column (KD-803, KD-805) manufactured by Shodex Co., Ltd., as follows.

Column temperature: 50 °C Dissolved solution · N,N-dimethylformamide (additive lithium bromide-hydrate (LiBr·H20 is 30.0 mmol/L, phosphoric acid. Anhydrous crystal (o-phosphoric acid 30.0 mmol/L) , tetrahydrofuran is 10.0ml / L)) Flow rate: lOOmL / min -45- 200906768 Standard sample for test line preparation: TSK standard polyoxyethylene produced by Dongsuo (transliteration) company (molecular weight of about 900,000, 150,000, 100,000, 3 0,000), and polyethylene glycol (molecular weight of about 12,000, 4,000, 1,000) manufactured by Labrador Co., Ltd. [醯imination rate] In this example, the polyimide of polyimine The amination rate was determined as follows: 20. 〇mg of polyimine powder was added to the NMR sample tube, and about 0.53 ml of dimethyl sulfoxide (DMSO-d6, 0.05% TMS (Si(CH3)4) was added. The mixture was subjected to ultrasonic treatment and completely dissolved. The solution was measured for proton NMR at 500 MHz by an NMR measuring apparatus. The sulfhydrylation rate was determined based on protons from the unaltered structure before and after the imidization. The protons of the protons accumulate 値, with protons from the NH group of proline under the lO.Oppm The peak is accumulated, and the imidization ratio (%) = (1 - a· x / y) is determined by the following formula: X 1 is in the above formula, and x is a proton derived from the NH group of proline. The peaks are cumulative, y is the peak cumulative 値 of the reference proton, and α is the number of protons based on the ruthenium matrix of one lysine when the poly-proline is 〇%. Proportion. <Example 4> -46-200906768 BODA (5_07 g, 20.3 mmol), p-PDA (2.48 g, 22.9 mmol), and PBCH5DAB (l_76 g, 4.05 mmol) as a side chain diamine were mixed in NMP (22.0 g). After the reaction was carried out at 40 ° C for 5 hours, CBDA (1.22 g, 6.22 mmol) and NMP (20.0 g) were added, and the reaction was carried out at 40 ° C for 6 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (30.0 g) and diluting it to 6 mass%, acetic anhydride (4.63 g) and pyridine (3 _ 5 9 g ) as a ruthenium amide catalyst were added at 80 ° The reaction was carried out for 3 hours at C. The reaction solution was poured into methanol (442 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (A). The polyimine has a ruthenium imidation ratio of 45%, a number average molecular weight of 1,5,300, and a weight average molecular weight of 3,600 00. <Example 5> BODA (4-88 g, 19.5 mmol), p-PDA (2.39 g, 22.1 mm), and BPCH5DAB (1.67 g, 3.90 mmol) as a side chain diamine were mixed in NMP (22.0 g). After the reaction was carried out at 40 ° C for 5 hours, CBDA (1.16 g, 5.92 mmol) and NMP (18.0 g) were added, and the reaction was carried out at 40 ° C for 6 hours to obtain a polyaminic acid solution. After the NMP was added to the polyamic acid solution (35.0 g) and diluted to 6 mass%, acetic anhydride (4.67 g) and pyridine (3.62 g) as a ruthenium catalyst were added to carry out the reaction at 80 ° C. 3 hours. The reaction solution was poured into methanol (4 4 3 m 1) to filter the respective obtained quenchers. The precipitate was washed with methanol to dry under reduced pressure at 100 ° C to obtain a polyimide pigment (B). -47- 200906768 The polyamidimide has an imidization ratio of 40%, a number average molecular weight of 1,300, and a weight average molecular weight of 380,400. <Example 6 > BODAMJSg'SS.OmmoU'p-pDAO.SSg, 30.8ramol), PBCH5DAB as a side chain diamine (5.7 4 g, 1 3 _ 2 mm ο 1) was mixed in NMP (38_0g) After the reaction was carried out at 40 ° C for 5 hours, CBDA (2.10 g > 10.7 mmol) and NMP (40.0 g) were added, and the reaction was carried out at 40 ° C for 6 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (20.0 g) and diluting it to 6 mass%, acetic anhydride (2.32 g) and pyridine (1.80 g) as a ruthenium amide catalyst were added at 90 ° The reaction was carried out for 3.5 hours under C. The reaction solution was poured into methanol (279 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 10 ° C to obtain a polyimine powder (C). The polyimine had a hydrazine imidation ratio of 60%, a number average molecular weight of 15,800, and a weight average molecular weight of 50,900. <Example 7> 8008 (4_138, 16.5〇1111〇1) was mixed in NMP (20.0 g). - PDA (2.01 g, 18.6 mmol), PBCH7DAB (1.53 g, 3 · 3 1 mm ο 1 ) as a side chain diamine, and reacted at 40 ° C for 5 hours, 'added CBDA (0.97 g) 4.95 mmol) and NMP (14.6 g)' were reacted at 40T: for 6 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (20.0 g) and diluting it to 6 mass -48 - 200906768 %, acetic anhydride (2.59 g) and pyridine (2·0 1 g) as a ruthenium amide catalyst were added. The reaction was carried out at 80 ° C for 3 hours. The reaction solution was poured into methanol (250 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (D). The polyimine had a ruthenium iodide ratio of 52%, a number average molecular weight of 14,600, and a weight average molecular weight of 36,300. <Example 8> BODA (6.44 g, 25.7 mmol), p-PDA (2.60 g, 24.0 mmol), and PBCH7DAB (4.77 g, 10.3 mmol) as a side chain diamine were mixed in NMP (30.0 g). After the reaction was carried out at 40 t for 5 hours, CBDA (1.64 g, 8.35 mmol) and NMP (31.2 g) were added, and the reaction was carried out at 40 ° C for 6 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (20.0 g) and diluting it to 6 mass%, acetic anhydride (2_ 3 1 g) and pyridine (1.80 g) as a ruthenium amide catalyst were added at 90 ° C. The reaction was carried out for 3.5 hours. The reaction solution was poured into methanol (290 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 1 ° C to obtain a polyimine powder (E). The polyimine had a hydrazine imidation ratio of 59%, a number average molecular weight of 1,600,400, and a weight average molecular weight of 478,600. <Comparative Example 1> In a NMP (22.0 g), BODA (5.07 g, 20.3 mmol), ρ-ρϋΑρ^δβ, 22_9 mm〇l), and a side chain diamine m. -49-200906768 PBCH5DABEs (l_87 g, After reacting at 40 ° C for 5 hours, CBDA (1.00 g, 5-1 mmol) and NMP (20.0 g) were added, and the reaction was carried out at 40 ° C for 6 hours to obtain a polyaminic acid solution. . After adding NMP to the polyamic acid solution (30.0 g) and diluting it to 6 mass%, acetic anhydride (4.28 g) and pyridine (3.32 g) as a ruthenium amide catalyst were added to carry out the reaction at 80 ° C. 3 hours. The reaction solution was poured into methanol (409 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (F). The polyimine has a hydrazine imidation ratio of 45%, a number average molecular weight of 1,400, and a weight average molecular weight of 380,800. <Comparative Example 2> BODA (5.03 g, 20.1 mmol), p-PDA (2.03 g, 18.8 mmol), and m-PBCH5DABEs (3.73 g, 8.06 mmol) as a side chain diamine were mixed in NMP (23.0 g). After the reaction was carried out at 40 ° C for 5 hours, CBDA (1.28 g, 6.53 mmol) and NMP (24.5 g) were vigorously introduced, and the reaction was carried out at 40 ° C for 6 hours to obtain a polyaminic acid solution. After the NMP was added to the polyamic acid solution (20.0 g) and diluted to 6 mass%, acetic anhydride (2-28 g) and pyridine (1.82 g) as a ruthenium catalyst were added to carry out the reaction at 90 ° C. 3.5 hours. The reaction solution was poured into methanol (280 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 10 ° C to obtain a polyimine powder (G). The polyimine had a hydrazine imidation ratio of 60% and a number average molecular weight of 15,600' and a weight average molecular weight of 42,800. -50- 200906768 <Comparative Example 3 > BODA (4.13 g, 16.5 mmol), p-PDA (2.02 g, 18-7 mmol), and PBP5DAB (1.39 g, 3.29 mmol) as a side chain diamine were mixed in NMP (19.0 g). After the reaction was carried out at 40 ° C for 5 hours, CBDA (0.86 g, 4.39 mmol) and NMP (14.6 g) were added, and the reaction was carried out at 40 ° C for 6 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (20.0 g) and diluting it to 6 mass%, acetic anhydride (2.60 g) and pyridine (2 · 0 2 g) as a ruthenium-imiding catalyst were added at 80 ° The reaction was carried out for 2.5 hours under C. The reaction solution was poured into methanol (250 ml) to filter the resulting precipitate. The precipitate was washed with methanol, and dried under reduced pressure at 1 ° C to obtain a polyimine powder (Η). The polyimine has a ruthenium imidation ratio of 45%, a number average molecular weight of 1,400, and 00, and a weight average molecular weight of 3,3,300. <Solubility Test of Polyimine]> (Comparison of Allowable Amount of Butyl Cellulose) The polyimine powders obtained in Examples 4 to 8 and Comparative Examples 1 to 3 were used in the following order. A comparison of the allowable amounts of butyl cellosolve in the case of the amine solution. NMp (87 〇g) was added to the polyimine powder (1.30 g), and stirred at 8 (TC for 40 hours) as a polyimine solution having a resin concentration of 13% by mass. (〗 〖g) In the sample tube, add the magnet stirrer ' stirring at 2 5 °c and drip into the B c S with a pipette. After -51 - 200906768 BCS after the drop, 'have turbidity In the case, after a few seconds without disappearing, visually confirm that 5 is the end point. And 'one drop of BCS is about 0 _ 0 0 4 g at this time. The bc S mixture at the end point is confirmed by the sample before and after b CS mixing. The quality of the whole tube was obtained. As a result of the above test, the BCS at the end point when the polyimine of Example 4 was used was 1.33 g, and the BCS at the end point when the polyimine of Example 5 was used was 1.08 g' The BCS at the end point when the polyimine of Example 6 was used was 丨.43^' The BCS at the end point when the polyimine of Example 7 was used was 1 · 2 6 g 'The polyimine of Example 8 was used. At the end of the time, b CS is 1 - 3 8 g 'BCS at the end point when the polyimine of Comparative Example 1 is used. CS·1 1 g 'Use the polypyrene of Comparative Example 2 At the end of the time, B c S is 〇.〇8g 'The BCS at the end point when the polyimine of Comparative Example 3 was used was 0.7 6 g °. The results of Examples 4 to 8 and Comparative Examples 1 to 3 were as shown in Table 1. According to the above results, it was confirmed that the polyimine using the diamine of the present invention has a very large mixing tolerance compared with the butyl cellosolve of the polyimine using the comparative diamine. [Liquid alignment treatment agent of the present invention] Modulation and evaluation] <Example 9> P-PDA (1.46 g, 13.5 mmol), PBCH5DAB (0.65 g, :I · 50 mm ο 1 ) as a side chain diamine was mixed with NMP (20_0g), and CBDA (2.85 g) was added. 14.5 mmol) and NMP (24.7 g) were reacted at 25 ° C for 5 hours to obtain a polyaminic acid solution. NMP (24.0 g) and BCS (16.0 g) were added to the obtained polyamic acid solution -52 - 200906768 (40.0 g), and the mixture was stirred for 1 hour to obtain a liquid crystal alignment treatment agent (1). In the liquid crystal alignment treatment agent, there was no abnormality such as turbidity or precipitation, 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 an ITO electrode, and dried in a hot air circulating oven at 203 °C after drying on a hot plate of 8 (rc for 5 minutes). The film was fired for 1 hour to prepare a polyimide film having a thickness of 100 nm. The polyimide film surface was rubbed with a roll diameter of 120 mm, and the number of roll rotations was 1000 rpm, the roll speed was 50 mm/Sec, and the amount of pushing was 0.3 mm. The substrate is rubbed with a thunder cloth to obtain a substrate with a liquid crystal alignment film. Two substrates having the liquid crystal alignment film are used, and the liquid crystal alignment film surface is inside, and the 50 μιη spacer is sandwiched to The friction direction is reversed and combined, and the adhesive is adhered to the periphery to form an empty unit cell. Liquid crystal MLC-2003 (manufactured by Merugu. Japan Co., Ltd.) is injected into the empty cell by a vacuum injection method to seal the injection port. The nematic liquid crystal cell having a parallel alignment was obtained. The pretilt angle of the liquid crystal cell prepared above was measured at room temperature using a tilt angle measuring device (model PAS-301 manufactured by ELSICON Co., Ltd.). As a result, the pretilt angle was 81.8. °, make the liquid crystal cell at 120 °C After the heat treatment was carried out for 1 hour, it was 84.2°. In addition, the liquid crystal cell produced in the same manner as above was observed under a polarizing microscope, and the liquid crystal was uniformly distributed in the vertical direction. -53- 200906768 <Example 〇> p-PDA (1.39 g, 12-8 mmol), PBCH7DAB (0.66 g, 1.43 mmol) as a side chain diamine, and CBDA (2.71 g, 13.8 mmol) were added to NMP (19.2 g). The reaction was carried out for 5 hours at 25 ° C with NMP (23.5 g) to prepare a polyaminic acid solution. NMP (23.8 g) and BCS (16.0 g) were added to the obtained polyamic acid solution (40.0 g), and the mixture was stirred for 1 hour to obtain a liquid crystal alignment treatment agent (2). In the liquid crystal alignment treatment agent, there was no abnormality such as turbidity or precipitation, and it was confirmed that the resin component was uniformly dissolved. In the same manner as in Example 9, the liquid crystal alignment treatment agent (2) obtained above was prepared in the same manner as in Example 9, and a pretilt angle was measured. As a result, the pretilt angle was 83.4°, and the liquid crystal cell was subjected to heat treatment at 120 ° C for 1 hour and then 8 5 . Further, in the case where the liquid crystal cell produced in the same manner as above was observed under a polarizing microscope, the liquid crystal was confirmed to have a uniform alignment. <Comparative Example 4 > p-PDA (1.56 g, 14.4 mmol) and PCH7DAB (0.61 g, 1.60 mm 〇l) as side chain diamine were mixed in NMP (22_0g), and CBDA (3.04 g ' was injected into the mouth. 15.5 mmol) and NMP (24.9 g) were reacted at 25 ° C for 5 hours to obtain a polyaminic acid solution. NMP (24.0 g) and BCS (16.0 g) were added to the obtained polylysine solution (40.0 g), and the mixture was stirred for 1 hour to obtain a liquid crystal alignment treatment agent (3). When the liquid crystal alignment agent was not turbid or precipitated in the absence of -54 to 200906768, it was confirmed that the resin component was uniformly dissolved. In the same manner as in Example 9, the liquid crystal alignment treatment agent (3) obtained above was prepared in the same manner as in Example 9, and a pretilt angle was measured. The result 'pretilt angle is 22.2. So that the liquid crystal cell is at 12 〇. (2: 2.8 ° after the heat treatment for 1 hour. In addition, when the liquid crystal cell produced in the same manner as above was observed under a polarizing microscope, the alignment of the liquid crystal was uneven, and there was no vertical alignment. The results of Example 9, Example 1 and Comparative Example 4, as shown in Table 2, TJn 0, by the above results, it was confirmed that the polyamine of the diamine of the present invention was used as the polyamine which used the comparative diamine. Less introduction of acid with a greater pretilt angle. <Example 11> The polyimine powder (A) (4·0 0 g) obtained in Example 4 was added to NMP (28.8 g), 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 stirred! The liquid crystal alignment treatment agent (4) was produced in a small hour. In the liquid crystal alignment treatment agent, there was no abnormality such as turbidity or precipitation, and it was confirmed that the resin component was uniformly dissolved. The liquid crystal alignment treatment agent (4) obtained above was spin-coated on a glass substrate with an IT crucible electrode and dried on a hot plate at 80 ° C for 5 minutes - 55 - 2009 06768 'at 2 1 0 ° C The hot air circulating oven was fired for 1 hour to prepare a polyimide film having a thickness of 100 nm. The polyimide film surface was rubbed with a roller having a roll diameter of 1 to 20 mm, and subjected to rubbing treatment with a Thunder cloth under the conditions of a roll rotation number of 300 rpm, a roll speed of 20 mm/sec, and a pushing amount of 3.3 mm. The substrate of the liquid crystal alignment film. Using two substrates with the liquid crystal alignment film, after spreading a 6 μm spacer on a liquid crystal alignment film surface, the sealant is printed thereon, and the other substrate is aligned on the inner side of the liquid crystal alignment film to The rubbing direction is pressed against the downward direction to bond the surrounding area with an adhesive to make an empty unit cell. Liquid crystal ML C - 6 6 0 8 (manufactured by Merugu Japan Co., Ltd.) was injected into the empty cell by a vacuum injection method, and the injection port was sealed to obtain a nematic liquid crystal cell resistant to parallel alignment. The pretilt angle of the liquid crystal cell prepared as described above was measured at room temperature using a tilt angle measuring device (model PAS-301 manufactured by EL SIC ON Co., Ltd.). As a result, the pretilt angle was 47.1 °, and the liquid crystal cell was heat-treated at 120 ° C for 1 hour and was 5 4.8 °. Further, in the case where the liquid crystal cell produced in the same manner as above was observed under a polarizing microscope, the liquid crystal was confirmed to have a uniform vertical alignment. <Example 1 2> The polyimine powder (B) (4.0 g) obtained in Example 5 was added to NMP (26.3 g), and the mixture was stirred at 80 ° C for 40 hours to dissolve. NMP (6.40 g) and BCS (30,0 g) were added to the solution, and the mixture was stirred for 1 hour -56 to 200906768 to prepare a liquid crystal alignment treatment agent (5). In the case where the liquid crystal was subjected to an abnormality such as turbidity or precipitation, the resin solution was confirmed. Using the same treatment as the liquid crystal alignment treating agents (5), 11 obtained above, a rubbed anti-parallel liquid crystal cell was obtained. When the pretilt angle was measured in the same manner as in Example 11, '5 4.6 at room temperature. The heat treatment of the liquid crystal cell was 1 5.3 after 1 hour of heat treatment. . Further, in addition to the rubbing treatment, when the liquid crystal cell fabricated in the field was observed by a polarizing microscope, it was uniformly aligned vertically. <Example 1 3 > In the NMP (22.0 g), the final (B) (3.00 g) obtained in Example 6 was added, and the mixture was stirred at 80 ° C for 40 hours, and NMP (2.50 g) and BCS were added to the solution. (22.5g), in the case of 'liquid crystal alignment treatment agent (6). In the case where the liquid crystal was subjected to an abnormality such as turbidity or precipitation, the resin solution was confirmed. The rubbed anti-parallel liquid crystal cell was obtained by the same treatment using the liquid crystal alignment treatment agent (6) obtained above. When the pretilt angle was measured in the same manner as in Example 11, it was 8 4.3 ° at room temperature, and the liquid crystal cell was heat treated at 86.2 °C for 1 hour. Further, the polarized light was uniformly dissolved in the treating agent, and the liquid crystal cell having the nematic type in the alignment with the Example was uniformly dried at 1 2 0 ° C in the same manner as in Example 1 to confirm that the liquid crystal was uniform. To dissolve. In this case, the mixture was stirred for 1 time, and the components were uniformly dissolved in the nematic liquid crystal cell of the embodiment, and the liquid crystal cell was subjected to a microscope observation chamber at -120 to 200906768, and after heat treatment for 1 hour. The timing of such liquid crystal cells is also uniform for heat treatment. Further, in addition to the rubbing treatment, the liquid crystal cells prepared in the same manner were uniformly aligned perpendicularly when observed by a polarizing microscope. <Example 14> BODA (4.32 g PDA (1.74 g, 16.1 mm)) and side chain diamine (3.0 g, 6.90 mmol) were mixed in NMP (22.0 g), and the reaction was carried out at 4 (TC). CBDA (1.01g, 5.15mmol) and NMP (18.0g) should be prepared for 6 hours to obtain a polyaminic acid solution. After adding the mass% in the obtained polyaminic acid solution (30.0g), it was added as a quinone. Acetic acid (2.90 g) of a catalytic catalyst was reacted at 80 ° C for 3 hours, and methanol (400 ml) was filtered, and the resulting precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to prepare hydrazine ( I). The polyamidimide has a ruthenium imidation ratio of 45%, 1 5,900, and a weight average molecular weight of 40,800. Add 8 (TC) to the polyimine powder (1) (4.00 g). The mixture was stirred for 40 hours and dissolved. In this solution (2.69 g) and BCS (29.0 g), the mixture was stirred for 1 hour, and the agent (7) was added. The liquid crystal alignment treatment agent was not mixed, and the resin component was confirmed to be uniform. Dissolved in the ground. The liquid crystal is in the same manner as in the example. The liquid crystal is uniform, 17.3 mm ο 1), p-PBCH5DAB is added for 5 hours, and the anti-NMP is diluted to 6 anhydride (3 · 7) at TC. 5 g ), the reaction solution is put into the pyrimidine. The precipitate is obtained; the number average molecular weight of the polyimine powder is NMP (28_8g), and the NMP is added to the liquid crystal to obtain turbidity or precipitation of the liquid crystal alignment -58-200906768 Using the liquid crystal alignment treatment agent (7) obtained above, the same treatment as in Example 11 was carried out to prepare a rubbed anti-parallel alignment nematic liquid crystal cell. The same operation as in Example 11 was carried out. When the pretilt angle of the liquid crystal cell is 85.6° at room temperature, the liquid crystal cell is heat-treated at 120 ° C for 1 hour and then 8 7 · 3 °. Further, the room temperature is observed by a polarizing microscope, and the heat treatment is performed for 1 hour. In the case of the liquid crystal cell, the liquid crystal is uniformly aligned, and is uniformly aligned in the heat treatment. Further, the liquid crystal cell produced in the same manner as in Example 1 was observed under a polarizing microscope except that the rubbing treatment was not performed. It can be confirmed that the liquid crystal is a uniform vertical alignment. <Example 15> In a NMP (23.0 g), BODA (4.41 g, 17.6 mmol), DBA (2.86 g, 18.8 mmol), and a side chain diamine PBCH5DAB (2.04 g, 4.69 mm) were mixed. After the reaction was carried out at 80 ° C for 5 hours, CBDA (1.0 1 g '5 - 15 mmol) and NMP (18.0 g) were added, and the reaction was carried out at 40 ° C for 6 hours to obtain a polyaminic acid solution. After the NMP was added to the obtained polyaminic acid solution (30.0 g) and diluted to 6 mass%, acetic anhydride (3.79 g) and pyridine (2.94 g) as a ruthenium amide catalyst were added, and the mixture was carried out at 80 ° C. Reaction for 3 hours. The reaction solution was poured into methanol (40 8 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimine powder (J). The polyimine had a hydrazine imidation ratio of 40%, a number average molecular weight of 17,300, and a weight average molecular weight of 46,800. -59-200906768 NMP (26_3 g) was added to the polyimine powder (J) (4.00 g), and the mixture was stirred at 8 ° C for 40 hours to dissolve. NMP (6.40 g) and BCS (30.0 g) were added to the solution and stirred for 1 hour to obtain a liquid crystal alignment agent (8). In the liquid crystal alignment treatment agent, there was no abnormality such as turbidity or precipitation, 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 rubbed anti-parallel alignment nematic liquid crystal cell. When the pretilt angle of the liquid crystal cell was measured in the same manner as in Example 11, it was 87_2 at room temperature, and the liquid crystal cell was heat treated at 120 ° C for 1 hour and then 88.6 °. Further, when the room temperature and the liquid crystal cell after the heat treatment for 1 hour were observed by a polarizing microscope, the liquid crystal was uniformly aligned, and the heat treatment was uniform alignment. Further, the liquid crystal cell produced in the same manner as in Example 1 1 was observed by a polarizing microscope, except that the rubbing treatment was not carried out, and it was confirmed that the liquid crystal had a uniform vertical alignment. <Example 16> BODA (8.26 g, 33.0 mmol), DBA (4.69 g, 30.8 mmol), and PBCH5DAB (5.74 g, 13.2 mol) as a side chain diamine were mixed in NMP (45.0 g) at 80°. After the reaction was carried out for 5 hours at C, CBDA (2.10 g '1 〇. 7 mmol) and NMP (38.0 g) were added, and the reaction was carried out at 40 ° C for 6 hours to obtain a polyaminic acid solution. After the NMP was added to the obtained polyamic acid solution (20.0 g) and diluted to 6 mass%, acetic anhydride (2.16 g) as a ruthenium amide catalyst and pyridine-60-200906768 (1.67 g) were added. The reaction was carried out at 80 ° C for 3 hours. The reaction solution was poured into methanol (274 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 (K). The polyimine had a hydrazine imidization ratio of 45%, a number average molecular weight of 19,100, and a weight average molecular weight of 50,800. NMP (16. g) was added to the polyimine powder (K) (3.30 g), and the mixture was stirred at 80 Torr for 40 hours to be dissolved. NMP (8.20 g) and BCS (27.5 g) were added to the solution, and the mixture was stirred for 1 hour to obtain a liquid crystal alignment treatment agent (9). In the liquid crystal alignment treatment agent, there was no abnormality such as turbidity or precipitation, 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 rubbed anti-parallel alignment nematic liquid crystal cell. When the pretilt angle of the liquid crystal cell was measured in the same manner as in Example 11, it was 88 °C at room temperature, and the liquid crystal cell was heat-treated at 120 ° C for 1 hour and then 89.0 °. Further, when the room temperature and the liquid crystal cell after the heat treatment for 1 hour were observed by a polarizing microscope, the liquid crystal was uniformly aligned, and the heat treatment was uniform alignment. Further, when the liquid crystal cell produced in the same manner as in Example 11 was observed under a polarizing microscope, the liquid crystal was confirmed to have a uniform vertical alignment. <Example 1 7> After the NMP was added to the polyamidic acid solution (20.0 g) obtained in Example 16 and diluted to 6 mass%, acetic anhydride as a ruthenium catalyst was added -61 - 200906768 (4.31 g) Pyridine (3.34g) was reacted for 9 hours at 9 (TC). The reaction solution was poured into methanol (260 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol and at 1 〇〇. The polyimine powder (L) was obtained by drying under reduced pressure at ° C. The polyamidimide had an oxime imidization ratio of 80%, a number average molecular weight of 15,200, and a weight average molecular weight of 45,500. To the amine powder (L) (3.30 g), NMP (16.1 g) was added, and the mixture was stirred at 8 (TC) for 40 hours to dissolve. NMP (8.24 g) and BCS (27.6 g) were added to the solution, and the mixture was stirred for 1 hour. In the liquid crystal alignment treatment agent, there is no abnormality such as turbidity or precipitation, and it is confirmed that the resin component is uniformly dissolved. The liquid crystal alignment treatment agent (10) obtained above is used to carry out the reaction. The same treatment as in Example 11 was carried out to obtain a rubbed anti-parallel alignment nematic liquid crystal cell. When the pretilt angle of the liquid crystal cell was measured in the same manner as in Example 11, it was 8 7 · 7 ° at room temperature, and the liquid crystal cell was heat-treated at 120 ° C for 1 hour and then 8 8.3 °. When the liquid crystal cell was observed under a polarizing microscope at room temperature and after heat treatment for 1 hour, the liquid crystal was uniformly aligned and uniformly aligned for the heat treatment. Further, in addition to the rubbing treatment, Example 1 was used. When the liquid crystal cell produced in the same manner was observed with a polarizing microscope, it was confirmed that the liquid crystal had a uniform vertical alignment. <Example 1 8 > After adding NMP to a polyamine acid solution (20.0 g) obtained in Example 16 and diluting it to 6 mass%, acetic anhydride was added as a ruthenium-catalyzed catalyst-62-200906768 (4.3 1 g), pyridine (1 - 52 g), and the reaction was carried out at 100 ° C for 4 hours. After adding oxalic acid (1.90 g) to the reaction mixture for neutralization, the mixture was poured into methanol (253 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (M). The polyimine had a hydrazine imidation ratio of 98%, a number average molecular weight of 1,900, and an average weight molecular weight of 6,500. NMP (15.6 g) was added to the polyimine powder (M) (3-2 g), and the mixture was stirred at 80 ° C for 40 hours to be dissolved. NMP (12.6 g) and BCS (21.2 g) were added to the solution, and the mixture was stirred for 1 hour to obtain a liquid crystal alignment treatment agent (1 1 ). In the liquid crystal alignment treatment agent, there was no abnormality such as turbidity or precipitation, and it was confirmed that the resin component was uniformly dissolved. Using the liquid crystal alignment treatment agent (1 1 ) obtained above, the same treatment as in Example 11 was carried out to obtain a rubbed anti-parallel alignment nematic liquid crystal cell. When the pretilt angle of the liquid crystal cell was measured in the same manner as in Example 11, 'the temperature was 87_5° at room temperature, and the liquid crystal cell was 88.2° after heat treatment for 12 hours at TC. In addition, a polarizing microscope was used. When the liquid crystal cell was treated at room temperature and after heat treatment for 1 hour, the liquid crystal was uniformly aligned, and it was uniformly aligned for the heat treatment. Further, the same treatment as in Example 1 was carried out except that the rubbing treatment was not carried out. When the liquid crystal cell was observed by a polarizing microscope, it was confirmed that the liquid crystal was a vertical alignment of the uniform sentence. <Example 1 9> DBA (1.05 g, 6.90 mmol), -63-200906768 DAA (1.87 g, 9.20 mmol), and PBCH5DAB as a side chain diamine (3.0 g) were mixed in Ν ( P (2 0.0 g). 6.90 mmol), CBDA (4.47 g, 22.8 mmol) and NMP (21.5 g) were reacted at 25 ° C for 1 hour to obtain a polyaminic acid solution. After the NMP was added to the obtained polyaminic acid solution (20. g) to be diluted to 6 mass%, acetic anhydride (4.5 1 g) and pyridine (3. 50 g) as a ruthenium imidization catalyst were added. The reaction was carried out at 50 ° C for 3 hours. The reaction solution was poured into methanol (2 6 1 ml), and the resulting precipitate was passed through. The precipitate was washed with methanol and dried under reduced pressure at 1 ° C to obtain a polyimine powder (N). The polyimine had a hydrazine imidation ratio of 98%, a number average molecular weight of 1,600, and a weight average molecular weight of 47,900. NMP (20.5 g) was added to the polyimine powder (N) (3.10 g), and the mixture was stirred at 5 ° C for 20 hours to dissolve. NMP (13.2 g) and BCS (24.5 g) were added to the solution, and the mixture was stirred for 1 hour to obtain a liquid crystal alignment treatment agent (1 2). In the liquid crystal alignment treatment agent, there was no abnormality such as turbidity or precipitation, and it was confirmed that the resin component was uniformly dissolved. Using the liquid crystal alignment treatment agent (12) obtained above, the same treatment as in Example 1 was carried out to obtain a rubbed anti-parallel alignment nematic liquid crystal cell. When the pretilt angle of the liquid crystal cell was measured in the same manner as in Example 11, it was 86.7 ° at room temperature, and the liquid crystal cell was subjected to heat treatment at 120 ° C for 1 hour and then 8 7.5 °. Further, when the room temperature and the liquid crystal cell after the heat treatment for 1 hour were observed by a polarizing microscope, the liquid crystal was uniformly aligned, and the heat treatment was uniform alignment. Further, in the case where the liquid crystal cell produced in the same manner as in Example 1 -64-200906768 was observed by a polarizing microscope, it was confirmed that the liquid crystal had a uniform vertical alignment, except that the rubbing treatment was not carried out. <Example 20> NMP (1 4 · 3 g) was added to the polyimine powder (E») (2.14 g) obtained in Example 7, and the mixture was stirred at 80 ° C for 40 hours to be dissolved. NMP (3.16 g) and BCS (16.1 g) were added to the solution, and the mixture was stirred for 1 hour to obtain a liquid crystal alignment treatment agent (13). In the liquid crystal alignment treatment agent, there was no abnormality such as turbidity or precipitation, 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 rubbed anti-parallel alignment nematic liquid crystal cell. When the pretilt angle of the liquid crystal cell was measured in the same manner as in Example 11, it was 76.5 ° at room temperature, and the liquid crystal cell was heat-treated at 120 ° C for 1 hour and then 7 7 · 7 °. Further, the liquid crystal cell produced in the same manner as in Example 11 was observed by a polarizing microscope, except that the rubbing treatment was not carried out, and it was confirmed that the liquid crystal had a uniform vertical alignment. <Example 21> NMP (2 1.8 g) was added to the polyimine powder (E) (3.00 g) obtained in Example 8, and the mixture was stirred at 80 ° C for 40 hours to be dissolved. NMP (2.51 g) and BCS (22.5 g) were added to the solution, and the mixture was stirred for 1 hour to obtain a liquid crystal alignment treatment agent (14). In the liquid crystal alignment treatment agent, there was no abnormality such as turbidity or precipitation, and it was confirmed that the resin component was uniformly dissolved. -65-200906768 The same treatment as in Example 11 was carried out using the liquid crystal alignment treatment agent (?4) obtained above to prepare a rubbed anti-parallel alignment nematic liquid crystal cell. When the pretilt angle of the liquid crystal cell was measured in the same manner as in Example 11, ' at room temperature was 8 6.5 °, and the liquid crystal cell was at 12 Torr. (: 87.8° after heat treatment for 1 hour. In addition, when the liquid crystal cell was observed at room temperature and after heat treatment for 1 hour, the liquid crystal was uniformly aligned and uniformly aligned for heat treatment. The liquid crystal cell produced in the same manner as in Example 1 was observed by a polarizing microscope, except that the rubbing treatment was not carried out, and it was confirmed that the liquid crystal had a uniform vertical alignment. <Example 2 2 > BODA (8.34 g, 33.3 mmol), DBA (4.74 g, 31.2 mmol), and PBCH7DAB (6.15 g, 13.3 mol) as a side chain diamine were mixed in NMP (45.5 g). After the reaction was carried out at 80 ° C for 5 hours, CBDA (2.12 g > 10.8 mm Ol) and NMP (38·0 g) were added, and the reaction was carried out at 40 ° C for 6 hours to obtain a polyaminic acid solution. After the NMP was added to the obtained polyamic acid solution (20. g) to be diluted to 6 mass%, acetic anhydride (4.30 g) and pyridine (3.30 g) as a ruthenium amide catalyst were added at 90 °. The reaction was carried out for 3.5 hours under C. The reaction solution was poured into methanol (30 〇 m 1), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure at 10 ° C to obtain a polyimide pigment (0). The polyamidimide had an oxime imidization ratio of 80%' number average molecular weight of 16,100 and a weight average molecular weight of 48,900. -66- 200906768 NMP (16.5 g) was added to the polyimine powder (〇) (3.29 g), and dissolved by stirring at 80 t for 4 hours. NMP (8.25 g) and BCS (27.5 g) were added to the solution, and the mixture was stirred for 1 hour to obtain a liquid crystal alignment treatment agent (15). In the liquid crystal alignment treatment agent, there was no abnormality such as turbidity or precipitation, and it was confirmed that the resin component was uniformly dissolved. Using the liquid crystal alignment treatment agent (15) obtained above, the same treatment as in Example 11 was carried out to obtain a rubbed anti-parallel alignment nematic liquid crystal cell. When the pretilt angle of the liquid crystal cell was measured in the same manner as in Example 11, it was 8 8.3 ° at room temperature, and the liquid crystal cell was heat-treated at 120 ° C for 1 hour and then 89.1 °. Further, when the room temperature and the liquid crystal cell after the heat treatment for 1 hour were observed by a polarizing microscope, the liquid crystal was uniformly aligned, and the heat treatment was uniform alignment. Further, the liquid crystal cell produced in the same manner as in Example 1 1 was observed by a polarizing microscope, except that the rubbing treatment was not carried out, and it was confirmed that the liquid crystal had a uniform vertical alignment. <Comparative Example 5 > In the polyimine powder (F) (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. . NMP (1.95 g) and BCS (26.3 g) were added to the solution, and the mixture was stirred for 1 hour to cause precipitation of a resin component, whereby a liquid crystal alignment treatment agent could not be obtained. Therefore, a liquid crystal cell cannot be produced. <Comparative Example 6> -67- 200906768 Into the polyimine powder (F) (3.6 5 g) obtained in Comparative Example 1, Ν Μ P (2.44 g) was added, and stirred at 80 Torr for 40 hours. Dissolve. NMP (5.35 g) and BCS (27.4 g) were added to the solution and stirred for 1 hour to cause precipitation of the resin component, and the liquid crystal alignment treatment agent could not be obtained. Therefore, a liquid crystal cell cannot be produced. <Comparative Example 7 > NMP (2 0.7 g) was added to the polyimine powder (F) (3.10 g) obtained in Comparative Example 1, and the mixture was stirred at 80 ° C for 40 hours to be dissolved. NMP (27.0 g) and BCS (11.2 g) were added to the solution, and the mixture was stirred for 1 hour to obtain a liquid crystal alignment treatment agent (16). In the liquid crystal alignment treatment agent, there was no abnormality such as turbidity or precipitation, and it was confirmed that the resin component was uniformly dissolved. Using the liquid crystal alignment treatment agent (16) obtained above, it was spin-coated on a glass substrate with an ITO electrode, and dried on a hot plate at 80 ° C for 5 minutes, and then in a hot air circulating oven at 210 ° C. After firing for 1 hour, a polyimide film having a thickness of 10 Å was produced. When the film surface is confirmed, many pinholes are visible. Using the substrate with the liquid crystal alignment film, the same treatment as in Example 1 was carried out to prepare a rubbed anti-parallel alignment nematic liquid crystal cell. When the pretilt angle of the liquid crystal cell was measured in the same manner as in Example 11, it was 76.4 at room temperature. After the heat treatment of the liquid crystal cell at 120 X: for 1 hour, it was 80.1. . However, there is a case where the pretilt angle is large in the liquid crystal cell surface. Further, when the liquid crystal cell after the room temperature treatment and the heat treatment for 1 hour was observed by a polarizing microscope, the alignment of the liquid crystal may be poor depending on the pinhole. -68- 200906768 In addition, when the liquid crystal cell produced in the same manner as in Example 11 was observed by a polarizing microscope, it was confirmed that the liquid crystal was uniform in the vertical alignment, except for the pinhole. section. <Comparative Example 8 > BODA (16.9 g, 67.5 mmol), p. PDA (6.80 g, 62.9 mmol), and PCH7DAB as a side chain diamine (10.3 g, 27.1) were mixed in NMP (1 〇〇, lg). After reacting for 5 hours at 40 ° C, CBDA (4.10 g '20.9 mmol) and NMP (52_2 g) were added, and the reaction was carried out at 40 ° C for 6 hours to obtain a polyaminic acid solution. After the NMP was added to the obtained polyaminic acid solution (130.3 g) and diluted to 6 mass%, acetic anhydride (1 5 -6 g) as a ruthenium amide catalyst was added, and 卩 ratio was steep (1 2 · 1 g). ), at 80. (: The reaction was carried out for 3 hours. The reaction solution was poured into methanol (1600 m 1), and the precipitate obtained by the furnace was separately passed. The precipitate was washed with methanol and decompressed at 100 〇c. The polyimine powder (P) was obtained by drying, and the polyamidimide had a ruthenium imidation ratio of 54%, a number average molecular weight of 18,300, and a weight average molecular weight of 45,300. In the polyimine powder (P) NMP (23.5g) was added to (3.20g), and it was dissolved by stirring at 80 ° C for 40 hours. NMP (2 _ 6 3 g) and BCS (2 4 · 0 g) were added to the solution to stir. In the case of the liquid crystal alignment treatment agent, there is no abnormality such as turbidity or precipitation, and it is confirmed that the resin component is uniformly dissolved. The liquid crystal alignment treatment agent (17) obtained above is used. The same treatment as in Example 11 was carried out to obtain a rubbed anti-parallel alignment nematic type -69-200906768 liquid crystal cell. When the pretilt angle of the liquid crystal cell was measured in the same manner as in Example 11, 7 8 · 7 ° at room temperature, the liquid crystal cell is heat treated at 120 ° C for 1 hour and then 8 1. 5 ° Further, when the liquid crystal cell was observed under a polarizing microscope at room temperature and after heat treatment for 1 hour, the liquid crystal was uniformly aligned. However, when compared with Example 14 or Example 21, there was a case where the liquid crystal was tilted. Further, in the liquid crystal cell produced in the same manner as in Example 1 except that the rubbing treatment was not carried out, it was confirmed that the liquid crystal was uniform in the vertical alignment when observed by a polarizing microscope. <Comparative Example 9> BODA (15.0 g, 60.〇mm〇l), p. PDA (4.30 g, 39.8 mmol), and PCH7DAB as a side chain diamine (15.2 g, 39.9) were mixed in NMP (100.3 g). After reacting for 5 hours at 40 ° C, CBDA (3.80 g, 19.4 mmol) and NMP (53.2 g) were added, and the reaction was carried out at 40 ° C for 6 hours to obtain a polyamidonic acid solution. After adding N MP to the obtained poly-proline solution (1 3 0 · 3 g) and diluting it to 6 mass%, acetic anhydride (13.9 g) and pyridine (1 0.8 g) as a ruthenium catalyst were added. The reaction was carried out at 80 ° C for 3 hours. The reaction solution was poured into methanol (1 600 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under a pressure of 100 t to obtain a polyimide pigment (Q). The polyamidimide has a ruthenium iodide ratio of 55%, a number average molecular weight of I7,500, and a weight average molecular weight of 42,700 °. In the polyimine powder (Q) (3.15 g), NMP (23_lg) is added. It was dissolved by stirring at -70 to 200906768 at 80 ° C for 40 hours. NMP (2 · 6 5 g) and B C S (2 3.6 g) were added to the solution, and the mixture was stirred for 1 hour to obtain a liquid crystal alignment agent (18). In the liquid crystal alignment treatment agent, there was no abnormality such as turbidity or precipitation, and it was confirmed that the resin component was uniformly dissolved. Using the liquid crystal alignment treatment agent (18) obtained above, it was rotated and coated on a glass substrate with an ITO electrode, and dried on a hot plate of 8 Torr for 5 minutes, and then placed in a hot air circulating oven at 210 °C. The firing was carried out for 1 hour to prepare a polyimide film having a thickness of 100 nm. When the film surface is confirmed, many pinholes are visible. Using the substrate with the liquid crystal alignment film, the same treatment as in Example 1 was carried out to obtain a rubbed anti-parallel alignment nematic liquid crystal cell. When the pretilt angle of the liquid crystal cell was measured in the same manner as in Example 11, it was 8 7.7 ° at room temperature, and the liquid crystal cell was heat-treated at 120 ° C for 1 hour and then 8 8.7 °. However, there is a case where the pretilt angle is uneven in the plane of the liquid crystal cell. Further, when the liquid crystal cell was observed at room temperature and after heat treatment for 1 hour by a polarizing microscope, the alignment of the liquid crystal may be poor depending on the pinhole. Further, the liquid crystal cell produced in the same manner as in Example 11 was observed by a polarizing microscope except that the rubbing treatment was not carried out. It was confirmed that the liquid crystal had a uniform vertical alignment, but partial pinning occurred depending on the pinhole. <Comparative Example 10> In the polyimine powder (H) (3_05 g) obtained in Comparative Example 3, Ν Μ P (2 0 · 4 g) was added, and the mixture was stirred at 80 ° C for 40 hours to be dissolved. NMP (1.89 g) and BCS (25.5 g) were added to the solution, and the mixture was stirred for 1 hour to prepare a liquid crystal alignment treatment agent (19). In the liquid crystal alignment treatment agent, there was no abnormality such as turbidity or precipitation, and it was confirmed that the resin component was uniformly dissolved. Using the liquid crystal alignment treatment agent (1 9 ) obtained above, it was spin-coated on a glass substrate with an ITO electrode, and dried on a hot plate at 80 ° C for 5 minutes, and then placed in a hot air circulating oven at 210 ° C. The firing was carried out for 1 hour to prepare a polyimide film having a thickness of 100 nm. When the film surface is confirmed, many pinholes are visible. Using the substrate with the liquid crystal alignment film, the same treatment as in Example 11 was carried out to obtain a rubbed anti-parallel alignment nematic liquid crystal cell. When the pretilt angle of the liquid crystal cell was measured in the same manner as in Example 11, it was 11.2 ° at room temperature, and the liquid crystal cell was heat-treated at 120 ° C for 1 hour and then 8.60 °. However, there is a case where the pretilt angle is largely uneven in the plane of the liquid crystal cell. Further, when the liquid crystal cell after the room temperature treatment and the heat treatment for 1 hour was observed by a polarizing microscope, the alignment of the liquid crystal may be poor depending on the pinhole. Further, in the liquid crystal cell produced in the same manner as in Example 11 except that the rubbing treatment was not carried out, it was confirmed that the liquid crystal had a uniform vertical alignment, but the pinhole was partially removed. <Comparative Example 1 1> NMP (10.4 g) was added to the polyimine powder (H) (1.56 g) obtained in Comparative Example 3, and the mixture was stirred at 80 ° C for 40 hours to be dissolved. NMP (2.30 g) and BCS (11.7 g) were added to the solution and stirred for 1 hour to prepare a liquid crystal alignment treatment agent (20). In the liquid crystal alignment treatment agent, there was no abnormality such as turbidity or precipitation, and it was confirmed that the resin component was uniformly dissolved. -72- 200906768 The liquid crystal alignment agent (20) obtained above was spin-coated on a glass substrate with an ITO electrode, and dried on a hot plate at 80 ° C for 5 minutes, and then hot air was circulated at 210 ° C. The firing was carried out for 1 hour in an oven to prepare a polyimide film having a thickness of 1 〇〇 nm. When the film surface is confirmed, many pinholes are visible. Using the substrate with the liquid crystal alignment film, the same treatment as in Example 11 was carried out to obtain a rubbed anti-parallel alignment nematic liquid crystal cell. When the pretilt angle of the liquid crystal cell was measured in the same manner as in Example 为, it was 10.9 ° at room temperature, and the liquid crystal cell was heat-treated at 120 ° C for 1 hour and then 8.50 °. However, there is a case where the pretilt angle is largely uneven in the plane of the liquid crystal cell. Further, when the liquid crystal cell after the room temperature treatment and the heat treatment for 1 hour was observed by a polarizing microscope, the alignment of the liquid crystal may be poor depending on the pinhole. Further, in the liquid crystal cell produced in the same manner as in Example 11 except that the rubbing treatment was not carried out, it was confirmed that the liquid crystal had a uniform vertical alignment, but the pinhole was partially removed. Further, in the case where the liquid crystal cell produced in the same manner as in Example 11 was observed by a polarizing microscope, the liquid crystal cell was not subjected to 'vertical alignment, and partial de-lighting was observed, except that the rubbing treatment was not performed. <Printability Test> The liquid crystal alignment treatment agents obtained in Examples 1 to 22 and Comparative Examples 7 to 1 were used for the printing treatment. The printing machine uses a Japanese photo printing public stomach simple printing machine (s 1 5 type). The printing is performed on the washed chrome-steamed substrate with a printing area of 8×8 cm, a printing pressure of 0 _ 2 mm, a discarding substrate of 5 sheets, and a period of -73-200906768 from the time of printing to the false drying, 90 seconds. Leave the drying temperature for 5 minutes. The confirmation of the pinhole was visually observed under a sodium lamp. The film thickness and the etching linearity were as shown in the results of Examples 1 1 to 22 and Comparative Examples 7 to 1 1 using an optical microscope. From the results of Examples Π 2 and 2, Comparative Examples 7 to 1 1 The polyimine of the present invention and the polyfluorene using the comparative diamine have a large pretilt angle with a small amount of introduction. In particular, when compared with Example 8, Comparative Example 8 was shaped in comparison with the use of the diamine of the present invention when the rubbing treatment was carried out. In other words, the polyimine using the diamine of the present invention, i.e., treated, still has a large pretilt angle. The use of the diamine of the present invention has a high oxime imidization ratio, and even if the butyl solubility of the poor solvent is large, no resin precipitation is observed. As a result, the liquid crystal alignment treatment agent obtained by the diamine can be invented by forming a uniform film in general. 70 ° C, to confirm. In Tables 3 and 4, it can be seen that, in comparison with the imine, in Example 14, and in the case of Example 14, there is a stripping effect to carry out the rubbing of the polyimide, and the mixing of the fiber is confirmed by using the coating method -74-200906768 [ Table i] Amount of side chain diamine side chain diamine (mol%) of polyimine powder" 醯imination rate (%) Solubility of polyimine (g)*2 Example 4 (A) PBCH5DAB 15 45 1.33 Example 5 (B) BPCH5DAB 15 40 1.08 Example 6 (C) PBCH5DAB 30 60 1.43 Example 7 (D) PBCH7DAB 15 52 1.26 Example 8 (E) PBCH7DAB 30 59 1.38 Comparative Example 1 (F) m- PBCH5DABEs 15 45 0.11 Comparative Example 2 (G) m-PBCH5DABEs 30 60 0.08 Comparative Example 3 (H) PBP5DAB 15 45 0.76 1: Ratio of use of side chain diamine in all diamines used in polymer synthesis. · The quality of the BCS mixing endpoint. [Table 2]

Liquid crystal alignment agent Side chain diamine side chain diamine amount (mol%)*3 Pretilt angle η Vertical alignment (no rubbing treatment) Example 9 (1) PBCH5DAB 10 81.8 〇 Example 10 (2) PBCH7DAB 10 83.4 〇Comparative Example 4 (3) PCH7DAB 10 22.2 X 3 : ratio of use of side chain diamine in all diamines used in polymer synthesis. -75- 200906768 [Table 3] Polyimine powder liquid crystal alignment agent side chain diamine side chain diamine amount (mol%) *4 醯 imidization ratio (%) BCS amount (% by mass) * 5 Example 11 (A) (4) PBCH5DAB 15 45 48 Example 12 (B) (5) PBCH5DAB 15 40 48 Example 13 (C) (6) PBCH5DAB 30 60 48 Example 14 (I) (7) PBCH5DAB 30 45 48 Example 15 (J) (8) PBCH5DAB 20 40 48 Example 16 (K) (9) PBCH5DAB 30 45 53 Example 17 (L) (10) PBCH5DAB 30 80 53 Example 18 (M) (11) PBCH5DAB 30 98 43 Example 19 (N) (12) PBCH5DAB 30 98 42 Example 20 (〇) (13) PBCH7DAB 15 52 48 Example 21 (E) (14) PBCH7DAB 30 59 48 Example 22 (〇) 05) PBCH7DAB 30 80 53 Comparative Example 5 (F) m-PBCH5DABEs 15 45 53 Comparative Example 6 (F) m-PBCH5DABEs 15 45 48 Comparative Example 7 (F) (16) m-PBCH5DABEs 15 45 19 Comparative Example 8 (P) (17 ) PCH7DAB 30 54 48 Comparative Example 9 (Q) (18) PCH7DAB 50 55 48 Comparative Example 10 (H) (19) PBP5DAB 15 45 53 Comparative Example 11 (H) (20) PBP5DAB 15 45 48 4: Synthesis of polymer The proportion of the side chain diamine used in all the diamines used. 5: The ratio of the use of BCS in the entire liquid crystal alignment agent. -76- 200906768 L"" Pretilt angle (°) Vertical alignment (after rubbing treatment) Printability_One pinhole film thickness spot etching Linearity Example 11 47.1 <5 〇〇Example 12 54.6 - <5 〇〇Example 13 84.3 〇<5 〇〇Example 14 85.6 〇<5 〇〇Example 15 87.2 〇<5 〇〇Example 16 88.5 〇<5 〇〇Example Π87.7 〇<5 〇〇Example 18 86.7 〇<5 〇〇Example 19 87.5 〇<5 〇〇Example 20 76.5 - <5 〇〇Example 21 86.5 〇<5 〇〇Example 22 88.3 〇<5 Comparative Example 5 *6 *6 *6 *6 *6 Comparative Example 6 *6 *6 *6 *6 *6 Comparative Example 7 76.4 >50 XX Comparative Example 8 78.7 *8 <5 〇〇Comparative Example 9 87.7 *7 <30 Δ Δ Comparative Example 10 11.2 *1 > 50 XX Comparative Example 11 10.9 *7 <30 Δ Δ 1 * 6 : Unrecognizable due to precipitation of resin component * 7 : With pinhole condition There may be a poor alignment* 8 : There is a case of light stripping. [Industrial use price 値] The diamine of the present invention is used as a polymer constituting a liquid crystal alignment film. When the raw material is used, it has an effect of making the pretilt angle of the liquid crystal large, and even if the liquid crystal is vertically aligned in a small amount of use ratio, it is difficult to cause precipitation when the solvent is used in a large amount in a polymer solution. The -77-200906768 liquid crystal alignment treatment agent of the present invention is extremely useful because it can produce a liquid crystal having a large frequency TN element, an STN element, a TFT liquid liquid crystal display element, etc. by using a thin film. In the description of the present invention, the contents of the specification of the present invention are disclosed in the description of the present invention. The general coating method forms a liquid crystal alignment film of the i-angle of the uniform sentence, so the patent application for the crystal element and the vertical alignment type is applied on the 23rd of the month. It is used in the scope of application for patents and the full text of the manual. -78-

Claims (1)

200906768 X. Patent application scope 1 · A diamine represented by the following formula (1) [Chemical 1] nh2 h2n (1) In the formula (1), Ri represents a phenyl or cyclohexyl group. R2 represents an alkyl group having 3 to 12 carbon atoms, a fluorinated alkyl group having 3 to 12 carbon atoms, and a carbon number of 3 to 12 Alkoxy, or a fluorinated alkoxy group having a carbon number of 3 to 12). 2. A diamine as in the first aspect of the patent application, wherein Ri in the formula (1) is 1,4-phenylene or 1,4 - Ring-extension. 3. For the diamine of claim 1 or 2, which is represented by the following formula (2-1), [Chemical 2] νη2 (In the formula (2-1), the η system represents an integer of 2 to 11'. In the cis-trans anisotropy of the 1,4-cyclohexyl group, each is a trans isomer). 4. The diamine of claim 1 or 2 is represented by the following formula (2-2), -79-200906768 (In the formula (2-2), η represents an integer of 2 to 11, and in the cis-trans anisotropy of a 1,4-cyclohexyl group, each is a trans isomer). 5-Polyimine, which is characterized in that the polyamine derivative obtained by reacting a diamine component of the diamine according to any one of claims 1 to 4 with a tetracarboxylic dianhydride, or Polylysine is obtained by dehydration ring closure. 6. The polyamine or polyimine of claim 5, wherein 1% by mole of the diamine component is a diamine according to any one of claims 1 to 4. A liquid crystal alignment treatment agent comprising a compound containing at least one of a polyamic acid and a polyamidene 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 obtained by using a liquid crystal alignment treatment agent according to claim 7 or 8. A liquid crystal display element characterized by having a liquid crystal alignment film according to claim 9 of the patent application. -80- 200906768 VII. Designated representative map: (1) The representative representative of the case is: No (2), the representative symbol of the representative figure is a simple description: No. 8. If there is a chemical formula in this case, please reveal the best display invention. Characteristic chemical formula: (1) (1)