TW201226390A - Diamine, polyimide precursor, polyimide, liquid-crystal alignment material, liquid-crystal alignment film, and liquid-crystal display element - Google Patents

Abstract

A diamine represented by formula [1] is disclosed. (In formula [1], two of R1 to R9 are primary amino groups, and the remainder each is a hydrogen atom or a monovalent organic group other than amino and may be the same or different. Symbol n is 1 or 2. The hydrogen atoms of the saturated hydrocarbon moiety which constitutes a ring each may have been replaced with a halogen atom or a monovalent organic group other than amino.)

Description

201226390 VI. TECHNOLOGICAL FIELD The present invention relates to a novel diamine, a polyimide precursor and a polyimide, a liquid crystal alignment agent for a liquid crystal display element, a liquid crystal alignment film, and a liquid crystal representation. element. [Prior Art] In the liquid crystal display element, the liquid crystal alignment film functions as a so-called alignment of the liquid crystal in a certain direction. Now, the main liquid crystal alignment film which is industrially utilized is a polyelectron imide precursor. A polyimine-based liquid crystal alignment agent prepared from a solution of proline (also known as polyglycolic acid), polyphthalate or polyimine is applied to a substrate and formed by film formation. . Further, when the liquid crystal is aligned in the parallel direction or obliquely to the substrate surface, the surface extension treatment is performed by rubbing after the film formation. In addition, as a method of replacing the rubbing, a method of using an anisotropic photochemical reaction such as polarized ultraviolet ray irradiation has been proposed, and in recent years, industrialization has been reviewed. In order to enhance the representational characteristics of such liquid crystal display elements, by changing the structure of polylysine, polyphthalate or polyimine; polyamine or polylysine having different blending characteristics or Polyimine or an additive or the like is being improved in liquid crystal alignment, electrical properties, etc., or pretilt angle control. For example, to obtain a high voltage holding ratio, by using a polyimine resin having a specific repeating structure (refer to Patent Document 1), or using a soluble polyimine having a nitrogen atom in addition to the quinone imine group, The time until the afterimage is removed (refer to Patent Document 2), and the high voltage retention rate is maintained by the introduction of the 1-phenylfluorene structure into the diamine of the poly-plycine raw material by -5 to 201226390. Various techniques have been proposed while reducing the residual DC (refer to Patent Document 3). However, as the liquid crystal display element is improved in performance, large in area, and power saving of the device, etc., it has been used in a wide variety of environments, and is required for a liquid crystal alignment film. The characteristics are also severe. In particular, the station time when the liquid crystal alignment agent is applied to the substrate is prolonged, printing failure due to precipitation or separation, or burning due to stored charge (RDC). The problem has become a problem, and it is difficult to solve both problems at the same time using the prior art. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. Disclosure of the Invention [Problems to be Solved by the Invention] The problem of the present invention is to solve the above problems of the prior art, and to provide a liquid crystal alignment agent which is excellent in printability, and which has a low storage charge and a mitigation of stored charge. A fast liquid crystal alignment film of a diamine, a polyimide precursor and a polyimide, a liquid crystal alignment agent using the liquid crystal alignment film, and a liquid crystal display element. 201226390 [Means for Solving the Problem] As a result of intensive research, the present inventors have found that a diamine component containing a polydiimide precursor or a polyimine which is a specific diamine represented by the following formula [1] is used as the diamine component. The liquid crystal alignment agent 'is extremely effective for achieving the above object, and the present invention has been completed. The diamine compound represented by the following formula [1] is a novel compound not described in the literature. A novel diamine of the present invention which solves the aforementioned problems, a diamine represented by the following formula [1], [Chemical Formula 1]

Re

(In the formula [1], two of Ri to R9 are a 1-stage amine group', and the residue is a hydrogen atom or a monovalent organic group other than the amine group, which may be the same or different, and n is 1 or 2, forming a ring. The hydrogen atom of the saturated hydrocarbon moiety may be substituted by a halogen atom or a monovalent organic group other than the amine group). Further, the diamine is preferably not represented by the following formula [2]. [Chemical Formula 2] 201226390 (In the formula [2], p is an integer of 0 to 3, and R1Q is a monovalent organic group other than the amine group. -(R1())P is shown as having P substituents R1(), and may be the same or different, respectively. q is shown as an integer of 〇~4, and Ru is a one-valent organic group other than an amine group, -( R^h is shown as having q substituents Rh and may be the same or different. η is 1 or 2, and a hydrogen atom forming a saturated hydrocarbon moiety of the ring may be substituted by an organic group other than a halogen atom or an amine group) Further, the above diamine is preferably represented by the following formula [3], [Chemical 3] / Yan 2 (R12)

NH2 -0 [3] (In the formula [3], 'η is 1 or 2, m is an integer of 〇~2(n+l), and R12 is a fluorine atom or an amine group other than the amine group, _(R12 m is shown to have m substituents R1 2 and may be the same or different, respectively. Further, the above R12 is preferably a hydrocarbon group having 1 to 6 carbon atoms, and more preferably R1 is a methyl group. Among them, n = 1 is preferred. Further, it may be a diamine represented by the following formula [4_a] to [4-d],

-8- 201226390 [化4]

Nh2 The polyimine precursor of the present invention is obtained by reacting at least one selected from a tetracarboxylic acid and the derivative with a diamine component containing the above diamine. In the above polyimine precursor, when the total molar amount of the tetracarboxylic acid and the derivative is 100 mol%, the diamine is preferably 5 to 95 mol%. Further, the polyimine of the present invention is obtained by imidating the above-mentioned polyimine precursor ruthenium. Next, the liquid crystal alignment agent of the present invention contains the above-mentioned polyimine precursor and the above-mentioned polyfluorene At least one of the imines is selected. The liquid crystal alignment film of the present invention is obtained by applying and forging the above liquid crystal alignment agent onto a substrate. The liquid crystal display element of the present invention is provided with the above liquid crystal alignment film. [Effects of the Invention] According to the present invention, it is possible to provide a novel diamine which is capable of obtaining a liquid crystal alignment agent having good printing properties, and which can provide a liquid crystal alignment film which has a small storage charge and a fast relaxation of a stored charge. Then, by using this diamine, it is possible to form a liquid crystal alignment agent having good printability from -9 to 201226390. Further, by using the liquid crystal alignment agent, since a liquid crystal alignment film having a small storage charge and a fast relaxation of the stored charge can be obtained, the liquid crystal display element having the liquid crystal alignment film is less likely to cause contrast reduction or burning. Excellent performance. [Best Mode of Carrying Out the Invention] Hereinafter, the present invention will be described in detail. The diamine of the present invention is represented by the following formula [1]. [Chemical 5]

Re

(In the formula [1], two of the '1 to 119' are i-group amine groups, and the residue is a hydrogen atom or a monovalent organic group other than the amine group, which may be the same or different, respectively. η is 1 or 2' to form a ring. The hydrogen atom of the saturated hydrocarbon moiety may be substituted by a halogen atom or a monovalent organic group other than the amine group). In the formula [1], examples of the halogen atom include a fluorine atom and the like. Further, in the formula [1], as the valent organic group other than the amine group, for example, a hydrocarbon group, a terminal group 'carboxy group, a hydroxyl group, a thiol group, or a hydrocarbon group having a carboxyl group; by an ether linkage 'ester linkage' a hydrocarbon group to which a bonding group such as a guanamine bond is bonded; a hydrocarbon group containing a sand atom, a halogenated hydrocarbon group, or the like. Further, as the monovalent organic group other than the amine group, for example, the amine group may be an amine group such as t-butoxycarbonyl group.

-10- 201226390 An inert base protected by a protecting group of an acid ester. In the formula [1], the position of the amine group is not particularly limited, and the diamine is not particularly limited. From the viewpoint of liquid crystal alignment or ease of synthesis, it is preferably the following formula [2]. Show location. [Chemical 6]

(In the formula [2], p is an integer of 0 to 3, R1G is a one-valent organic group other than the amine group, and _(R1())P is represented as having p substituents R1Q, and may be the same or Different, q is shown as an integer from 0 to 4, and Rh is a monovalent organic group other than an amine group, having q substituents Rm, and may be the same or different, respectively, and η is 1 or 2, forming a ring. The hydrogen atom of the saturated hydrocarbon moiety may be substituted by a halogen atom or an organic group other than the amine group). In addition, as shown in the above formula (2), the hydrogen atom of the benzene ring having an amine group may be substituted by R1 () or Rh of a monovalent organic group other than the amine group, and various kinds of reagents may be used depending on the availability of the reagent. Choice. In the formula [2], as the monovalent organic group R1G, R!, other than the amine group, for example, a hydrocarbon group, a carboxyl group, a hydroxyl group, a thiol group, or a hydrocarbon group having the same; by an ether bond, an ester a hydrocarbon group to which a bonding group such as a bond or a hydrazine bond is bonded; a hydrocarbon group containing a halogen atom; a halogenated hydrocarbon group; Further, as R, G or R! i, for example, the amine group is an inert group which is protected by a urethane-based protecting group such as t-butoxycarbonyl group. However, in view of the availability of the reagent or the ease of synthesis, the hydrogen atom of the benzene ring having an amine group is preferably unsubstituted. More specifically, the configuration is as shown in the following formula [3]. [n7] nh2 (R12

Nh2 [31 (in the formula [3], η is 1 or 2, m is an integer of 0 to 2 (n+1), and R12 is a fluorine atom or a monovalent organic group other than the amine group, -(R12)m is shown It has m substituents R12 and may be the same or different, respectively. In the formulas [1] to [3], when n = 1, it is a diamine having a porphyrin structure, and when n = 2, it is a diamine having a tetrahydroquinoline structure. Although they are all saturated hydrocarbon sites forming a ring, the hydrogen hydrogen atom of the saturated hydrocarbon moiety may be substituted by a halogen atom such as a fluorine atom or a monovalent organic group other than the amine group. In the formula [3], the substituent of the hydrogen atom replacing the saturated hydrocarbon moiety is R, 2» is a monovalent organic group other than the amine group of the hydrogen atom substituted for the saturated hydrocarbon moiety, and examples thereof include a hydrocarbon group, a hydroxyl group, a carboxyl group, and the like. . The hydrocarbon group herein may be any of a linear or branched 'ring, and may be a saturated hydrocarbon or an unsaturated hydrocarbon, wherein a part of a hydrogen atom of the hydrocarbon group may be a carboxyl group, a hydroxyl group, a thiol group, Alternatively, it may be substituted by a halogen atom, a halogen atom or the like, or may be bonded by a bonding group such as an ether bond, an ester bond or a guanamine bond. On the other hand, R|2 is preferably a hydrocarbon group composed only of a carbon atom and a hydrogen atom in terms of the ease of synthesis or the availability of a reagent.

-12- 201226390 The substituent of the hydrogen atom replacing the carbon of the saturated hydrocarbon moiety is preferably a hydrocarbon group having a carbon number of from 1 to 6. The polyimine precursor or the polyimine which uses the polyamine of the diamine of the present invention has high solubility in a solvent, so that the printability is good, but if the hydrogen atom of the saturated hydrocarbon moiety is When a diamine substituted with a hydrocarbon group having 1 to 6 carbon atoms is substituted, the solubility of the polyamidene precursor such as polyglycine or the polyimine is more improved in the organic solvent, so that the printability is further improved. good. Further, the polyamidene precursor such as polylysine or the polyimine has high solubility in a solvent, and is excellent in compatibility with other polymers, and the polyamine imide of the present invention is used. The precursor or polyimine is not easily separated or precipitated when used in combination with other polymers, and is excellent in printability. Specific examples of the hydrocarbon group having 1 to 6 carbon atoms include, for example, a methyl group, an ethyl group, a propyl 'butyl group, a t-butyl group, a hexyl group, a cyclopentyl group, a cyclohexyl group, a vinyl group, an allyl group, and a 1-propene group. The group is a 2-propenyl group, an isopropenyl group, a 1-methyl-2-propenyl group, a 1 or 2 or a 3-butenyl group, a hexenyl group, a phenyl group or the like, but is not limited thereto. When the hydrogen atom of the saturated hydrocarbon moiety is substituted by this or the like, the position or amount of substitution is not particularly limited, and various options can be selected depending on the ease of synthesis or the availability of the reagent. A particularly preferred structure is that the hydrogen atom of the saturated hydrocarbon moiety is replaced by a methyl group. Further, from the viewpoint of easiness of synthesis, it is preferred that the hydrogen atom in the saturated hydrocarbon portion is unsubstituted. The following is a preferred specific example of the diamine of the present invention, but it is not. 201226390

-14 201226390 [化9]

ΝΗ2 h2n

[4-24]

H2N

[4-26] [4-27] [4-28] [Chem. 10]

The particularly preferred diamine of the present invention is as follows -15- 201226390 [Chemical 11]

t-WJ is a polyimine imine precursor or polyimine which is a polyamine or a polyamidamide of the present invention having the diamine of the present invention represented by the above formula [1] as a raw material, since The solubility of the solvent is good, and the formation of pinholes or the uneven thickness of the edge portion or the like is not formed when the liquid crystal alignment film is formed, so that a liquid crystal alignment agent having good printability can be obtained. Moreover, when the liquid crystal alignment agent is used, since a liquid crystal alignment film which is less likely to generate charge storage and which has a fast elimination of stored charges can be obtained, the liquid crystal display element having the liquid crystal alignment film is less likely to be reduced in contrast or burned. Indicates the effect of excellent characteristics. Further, it is also possible to suppress an increase in ion density used for a long period of time. Furthermore, the liquid crystal alignment is also good. The effect of the present invention is that the diamine of the present invention contains a diphenylamine structure and a saturated hydrocarbon moiety having a site which acts as a steric hindrance, and can enhance the solubility or enhance the phase of the polymer by maintaining the electrical properties of the diphenylamine. Solubility, it is speculated that it can exhibit the characteristics as described above. On the other hand, the diamine of Patent Document 3 is constructed such that the saturated hydrocarbon site at the position of the diamine of the present invention has a double bond but does not have a saturated hydrocarbon moiety; when using a diamine such as Patent Document 3, it is compared as described later. As shown in the example, it is not possible to get the same as using this hair.

-16- 201226390 The reason of the phenyl hydrazine skeleton. In the case of the diamine, the storage charge is small, the alignment film, and the liquid crystal alignment property is also soluble or compatible. The diamine of the literature 3 is rich in the dimorphic electronic state of the diphenylamine. In the case of the present invention, the method described below is a diamine of the present invention, and after the reduction of the following, the nitro group is converted into a benzene ring and a halogen atom or an amine group other than the amine group. One is to be recorded. [Chem. 12] The liquid crystal which has a moderate relaxation of the stored charge is deteriorated, and then, the organic solvent property is also poorly obtained. This is specific and is presumed to have been described as the main synthesis method with diamine. The example is not limited to this. As shown in the reaction formula, a dinitro group is obtained as an amine group.尙, as a case where the hydrogen atom of the hydrocarbon moiety is a diamine which is not substituted with a fluorine atomic valent organic group

Nh2 Reduction of dinitro compound Palladium-carbon, uranium oxide, and Raney nickel are used as a catalyst, and a hydrogen method is used in a solvent such as an acetic acid acetate. Depending on the necessity, the monthly method is not particularly limited, and examples thereof include autoclaving such as ruthenium, ruthenium-aluminum oxide, ruthenium sulfide carbon, toluene, tetrahydrofuran, dioxane, hydrazine, hydrogen chloride, and the like. It is carried out under pressure from a pot or the like. On the other hand, when the structure of the substituent of the hydrogen atom replacing the benzene ring or the saturated fluorene moiety is such that palladium carbon or platinum carbon is used when the unsaturated bond site is contained, the unsaturated bond site is reduced because 彳ί Since it becomes a saturated bond, it is preferable to use -17-201226390 as a reducing condition for using a transition metal such as reduced iron or tin or tin oxide as a catalyst. In the synthesis of the dinitro compound, as shown in the following reaction formula, the commercially available nitroporphyrin derivative or the nitrotetrahydroporphyrin derivative is substituted with a leaving group X such as a halogen. The nitrobenzene is reacted to obtain the dinitro compound. Preferred examples of the leaving group X include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a tosylate (-OTs), and a meSylate (-OMs). [Chem. 13]

The above reaction can be carried out in the presence of a base. The base to be used is not particularly limited as long as it can be synthesized, and examples thereof include an inorganic base 'pyridine" such as potassium carbonate, sodium carbonate, cesium carbonate, sodium alkoxide, potassium alkoxide, sodium hydroxide, potassium hydroxide or sodium hydride. An organic base such as dimethylaminopyridine, trimethylamine, triethylamine or tributylamine. Further, depending on the case, when a palladium catalyst such as dibenzylideneacetone palladium or diphenylaluminum ferrocene palladium or a copper catalyst is used, the yield can be improved. From the viewpoint of easiness of synthesis, it is preferred to use the sodium hydride or the like, and the -NH- which is present in the nitroguanidine porphyrin derivative or the nitrotetrahydroquinoline derivative, as in the following reaction formula. The method in which the hydrogen is taken out and reacted with 4-nitrofluorobenzene can be synthesized in addition to the method, and the synthesis method is not particularly limited. -18- 201226390 [Chem. 14]

The diamine of the present invention can be obtained by reacting at least one selected from the group consisting of a tetracarboxylic acid and a tetracarboxylic acid derivative to obtain a polyimine precursor precursor of the polyglycolic acid or polyphthalate of the present invention. . The ratio of the diamine of the present invention to the tetracarboxylic acid and the derivative is not particularly limited, and the total molar amount of the tetracarboxylic acid and the derivative is determined as In the case of 1% by mole, the second Φ of the present invention is preferably 5 to 9 5 mol%. As the tetracarboxylic acid derivative, a dianhydride or a tetracarboxylic acid diester dichloride is used to make the tetracarboxylic acid dihalide or the tetracarboxylic acid contain the diamine of the present invention. Further, by reacting the diamine component of the tetracarboxylic acid di-i or the diamine component of E, for example, a tetracarboxylic acid dihalide or a tetracarboxylic acid tetracarboxylic acid diester is appropriately condensed. For example, by reacting a tetracarboxylic acid such as a dianhydride or the derivative with a hydrazine moiety, a polyamine amine dichloride and a diamine carboxylic acid diester containing the present invention and a diamine agent of the present invention or A reaction occurs in the presence of a base to obtain a polyphthalate.尙, in the present specification, the so-called diamine component is used to obtain a polyimine precursor or a polyimine, and a diamine which reacts with at least one selected from a tetracarboxylic acid and a tetracarboxylic acid derivative. The diamine of the present invention may also be used alone or in combination with other diamines. Next, the polyamidiamine precursor is subjected to hydrazine imidization, specifically, the polyglycine is dehydrated and closed, or the polyglycolate is heated by the lettuce, and the ring closure is obtained by promoting the dealcoholization. The polyimine of the present invention. -19-201226390 The polyimine precursors and polyimines of polyglycines and polyphthalates of the present invention are described in more detail below. It is used in a diamine component which is obtained by reacting at least one selected from a tetracarboxylic acid and a tetracarboxylic acid derivative such as the above tetracarboxylic dianhydride to obtain a polyamidene precursor such as polylysine. The content ratio of the diamine of the present invention is not limited. When the polyimine precursor of the present invention or the liquid crystal alignment film obtained by the imidization of the ruthenium iodide is used, the more the content ratio of the diamine of the present invention shown above, the more the storage charge can be obtained. A liquid crystal alignment film that has a low relaxation and a fast charge. In order to accelerate the relaxation of the stored charge, it is preferred that the diamine component is 1 mol% or more of the diamine of the present invention. On the other hand, when other characteristics such as liquid crystal alignment property and pretilt angle characteristics are considered, the content of the diamine component of the present invention in the diamine component used in the polymerization is preferably from 20 to 90 mol%, which is particularly preferable. For 30 to 80 moles. In the above diamine component, when the use of the diamine represented by the formula [1] is less than 100% by mole, the other diamines other than the diamine represented by the formula [1] are not particularly limited. To exemplify the specific example, it is as follows. Examples of the alicyclic diamines include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, and 4,4'-diaminodicyclohexylmethane 4,4. , -Diamino-3,3'-dimethyldicyclohexylamine, isophorone diamine, and the like. Examples of the aromatic diamines include quinone-phenylenediamine, m-phenylenediamine, P-phenylenediamine, 2,4-diaminotoluene' 2,5-diaminotoluene, and 3,5. -diaminotoluene, 1,4-diamino-2-methoxybenzene, 2,5-diamino-P-xylene, 1,3-diamino-4-chlorobenzene, 3,5 -diamine benzoic acid, iota, 4-diamine-20- 201226390, base-2,5-dichlorobenzene, 4,4'-diamino-1,2-diphenylethane, 4,4' -diamino-2,2'-dimethylbibenzyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diamino Diphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 2,2'-diaminopurine, 4,4'-diaminopurine, 4,4 '-Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylanthracene, 3,3'-diaminodiphenyl milling, 4,4'-diaminodiphenyl ketone, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4- Aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 3,5-bis(4-aminophenoxy)benzoic acid, 4,4'-bis (4- Aminophenoxy)bibenzyl, 2,2 - bis[(4-aminophenoxy)methyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-( 4-aminophenoxy)phenyl]propane, bis[4-(3-aminophenoxy)phenyl]anthracene, bis[4-(4-aminophenoxy)phenyl]anthracene, 1 , 1-bis(4-aminophenyl)cyclohexane, α,α'-bis(4-aminophenyl)-1,4-diisopropylbenzene, 9,9-bis(4-amine Phenyl, fluorene, 2,2-bis(3-aminophenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-diaminodiphenylamine , 2,4-diaminodiphenylamine, 1,8-diaminonaphthalene, 1,5-diaminonaphthalene, 1,5-diamino onion peptide, 1,3-diaminopurine, 1, 6-Diaminoguanidine, 1,8-diaminoguanidine 2,7-diaminoguanidine, 1,3-bis(4-aminophenyl)tetramethyldioxane, benzidine, 2 , 2'-dimethylbenzidine, 1,2-bis(4-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,4-bis(4-amine Phenyl)butane, 1,5-bis(4-aminophenyl)pentane, 1,6-bis(4-aminophenyl)hexane, 1,7-bis(4-aminobenzene) Heptane, 1,8-bis(4-aminophenyl)octane 1,9-bis(4-aminophenyl)decane, 1,10-bis(4-aminophenyl)decane, 1,3-bis(4-aminophenoxy)propane, 1 ,4-bis(4-aminophenoxy)butan-21 - 201226390 alkane, 1,5-bis(4-aminophenoxy)pentane, iota, 6-bis(4-aminophenoxy) Hexane, 1,7-bis(4-aminophenoxy)heptane, iota, 8-bis(4-aminophenoxy)octane, 1,9-bis(4-aminophenoxy) Base) decane, ι, 1 〇 _ bis ("aminophenoxy" decane, bis(4-aminophenyl)propane-1,3-dicarboxylate (dioate), di(4-amino) Phenyl)butane-1,4-diester, bis(4-aminophenyl)pentane-is diester, bis(4-aminophenyl)hexane-l,6-dicarboxylate , bis(4-aminophenyl)glycine-1,7-diacid vinegar, bis(4-aminophenyl) xinyuan-1,8-diacid vinegar, bis(4-aminophenyl) Decane-1,9-diester, bis(4-aminophenyl)decane_ι,ι〇-diester, 1,3-bis[4-(4-aminophenoxy)benzene Oxy]propane, 14-bisindole-aminophenoxy)phenoxy]butane, 1,5-bis[4-(4-aminophenoxy)phenoxy]pentane, 1,6 - bis[4-(4-amine Phenoxy)phenoxy]hexane, 1>7_bis[4-(4-aminophenoxy)phenoxy]heptane, 1>8-bis[4_(4-aminophenoxy) Phenoxy]octane, 1,9-bis[4-(4-aminophenoxy)phenoxy]decane, 1,10-bis[4-(4-aminophenoxy)benzene Oxy] decane and the like. As an example of the aromatic-aliphatic diamine, for example, 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, 4-amino-N-methyl Benzylamine, 3-aminophenethylamine, 4-aminophenethylamine, 3-amino-N-methylphenethylamine, 4-amino-N-methylphenethylamine , 3-(3-Aminopropyl) aniline, 4-(3-aminopropyl)aniline, 3-(3-methylaminopropyl)aniline, 4-(3-methylaminopropyl) Aniline, 3-(4-aminobutyl)aniline, 4-(4-aminobutyl)aniline, 3-(4-methylaminobutyl)aniline, 4-(4-methylamino group Butyl) aniline, 3-(5-aminopentyl)aniline, 4-(5-aminopentyl)aniline, 3-(5-methylaminopentyl)aniline, 4-(5-methyl Aminopentyl)aniline, 2-(6-aminonaphthyl)methylamine, 3-(6-aminonaphthyl)methylamine, 2-(6-aminonaphthyl)ethyl 22-201226390 Amine, 3-(6-aminonaphthyl)ethylamine, and the like. As examples of the heterocyclic diamines, for example, 2,6-diamino 2,4-diaminopyridine, 2,4-diamino-1,3,5-triterpene, 2,7- Dibenzofuran, 3,6-diaminocarbazole, 2,4-diamino-6-isopropyltriazine, 2,5-bis(4-aminophenyl)-1,3, 4-oxadiazole and the like. Examples of the aliphatic diamines include 1,2-diamino1,3-diaminopropane, 1,4-diaminobutane, and 1,5-diaminopentanediamine. Alkane, 1,7-diaminoheptane, 1,8-diaminooctane, aminodecane, 1,1 -diaminodecane, 1,3-diamino-2,2- Dioxane, 1,6-diamino-2,5-dimethylhexane, 1,7-diamino-2,5-heptane, 1,7-diamino-4,4-dimethyl Heptane, 1,7-diamino-3-alkane, 1,9-diamino-5-methylheptane, 1,12-diaminododecanediamine octadecane, 1, 2-bis(3-aminopropoxy)ethane, etc. Further, examples of the other diamine include an alkylalkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, and the like in the side chain. A diamine compound of a substituted substituent. Specifically, a diamine represented by the following formula [DA·[DA-30] can be exemplified. Pyridine, aminodi-1,3,5-ethane, '1,6-1,9-dimethylpropanemethylglycolide 1,18-, fluorine-containing macrocycle.1]~ -23- 201226390 [Chem. 15]

(wherein Rl3 is represented by an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group, and S5 is represented by -COO-, -OCO-, -CONH-, -NHCO-, -CH2-, -0-, -CO -, or -NH-). [Chemistry 16]

(wherein s6 is represented by -0-, -OCH2-, -CH20-, -COOCH2-, or -CH2OCO-, and R14 is represented by an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a Fluoroalkoxy). [Chem. 17]

-24- 201226390 (wherein s7 is shown as -COO-, -OCO-, -CONH-, -NHCO-, -COOCH2-, -CH2OCO-, -CH20-, -OCH2-, or -CH2-, R15 It is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group). [Chem. 18]

(where 's8 is shown as -COO-, -OCO-, -CONH-, -NHCO-, -COOCH2- '-CH2OCO- ' -CH2O- ' -OCH2- ' -CH2- ' -ο- ' or - NH -, R16 is represented by a fluoro group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a decyl group, an ethyl group, an ethoxy group, or a hydroxy group). [Chem. 19]

(wherein R17 is represented by an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans group, respectively). -25- 201226390 [化 20]

When the alignment treatment with light is carried out, a more stable pretilt can be obtained by using the above-mentioned diamine of the formula [?] with the above-mentioned [DA-1] to [DA-30] diamine. As the diamine to be used, a compound of the formula [DA-10] to [DA-30] is preferred, and a diamine of [DA-l〇]~[DA-l6] is more preferred. The preferred content of such diamines is not limited to -26-201226390, and is preferably 5 to 50 mol% based on the total amount of the diamine component, and is preferably 5 to 30 m from the viewpoint of printability. %. Further, examples of the other diamine include the following diamines. [Chem. 21]

-〇< [DA-31] ' η2Ν Γη2Ν

Ηη2 [DA-35]

NH2

[DA-38] (where i is an integer of 0 to 3, and j is an integer of i to 5). By introducing [DA-31] or [DA-32], the voltage holding ratio (VHR) can be increased by 'and' [DA-33]~[DA-38] to lower the stored charge. Further, for example, a diamine oxane or the like as shown by the following formula [DA_39] may be mentioned. -27- 201226390 [化22] / 9H3\ ?«3 H2N-<CH2hb--0------------------ It is an integer of 1 to 10). In this way, one or two or more kinds of other diamine compounds may be mixed in accordance with characteristics such as liquid crystal alignment property, voltage holding property, and storage charge when the liquid crystal alignment film is formed. A tetracarboxylic acid such as a tetracarboxylic dianhydride which is obtained by reacting a polyimine precursor such as polyglycine of the present invention with a diamine component, and the derivative are not particularly limited. Specific examples of the tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure include, for example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1, 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3 -dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetra 1,2-,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1 -cyclohexyl succinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetra Hydrogen-1-naphthalene succinic dianhydride 1,2,3,4-butane tetracarboxylic dianhydride, bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride, 3,3',4,4' -dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, cis,3,7-dibutylcyclooctane-1,5-diene-1,2,5, 6-tetracarboxylic dianhydride, tricyclo[4.2.1.02'5]nonane-3,4,7,8-tetracarboxylic acid-3,4: 7,8-dianhydride, hexacyclo[6.6.0.12' 7·03, 6.19, 14.01()'13]hexadecane·4,5,11,12-tetracarboxylic acid-4,5: 11,12-dianhydride, 4-(2,5-dioxotetrahydrofuran -3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride and the like.

-28- 201226390 Further, in addition to the tetracarboxylic dianhydride having the above alicyclic structure or aliphatic structure, when an aromatic tetracarboxylic dianhydride is used, liquid crystal alignment property can be improved, and liquid crystal cell storage can be performed. The charge is reduced, so it is appropriate. Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, and 2,2',3,3'-biphenyl. Tetracarboxylic dianhydride, 2,3,3',4-biphenyltetracarboxylic dianhydride '3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride, 2,3,3' , 4-diphenyl ketone tetracarboxylic dianhydride 'bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)ruthenic anhydride, 1,2,5,6 - naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, and the like. The polycarboxylic acid ester of the present invention is also used, and the dialkyl tetracarboxylic acid which reacts with the diamine component is also not particularly limited. The specific example is exemplified below. Specific examples of the aliphatic tetracarboxylic acid diester include, for example, 1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4-ring. Dialkyl butane tetracarboxylate, dialkyl 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylate, 1,2,3,4-tetramethyl-1 , 2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2,3,4-cyclopentane tetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofuran tetracarboxylic acid Alkyl ester, dialkyl 1,2,4,5-cyclohexanetetracarboxylate, dialkyl 3,4-dicarboxy-1-cyclohexyl succinate, 3,4-dicarboxy-1, Dialkyl 2,3,4-tetrahydro-1-naphthalene succinate, dialkyl 1,2,3,4-butanetetracarboxylate, bicyclo[3,3,0]octane-2, Dialkyl 4,6,8-tetracarboxylate, dialkyl 3,3',4,4'-dicyclohexyltetracarboxylate, dialkyl 2,3,5-tricarboxycyclopentylacetate Ester, cis-3,7-dibutylcyclooctane-1,5-diene-1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclo[4.2.1.02'5]nonane-3 ,4,7,8-tetracarboxylic acid-3,4:7,8-dialkyl ester,hexacyclic-29- 201226390 [6.6·0.12,7·03'6·19'14·〇1ΰ'13] Hexadecane-4,5,11,12-tetracarboxylic acid-4,5:11,12-dialkyl ester, 4-(2,5-dioxotetrahydrofuran -3-3·yl)-丨^^, 4_tetrahydronaphthalene-1,2-di-residual acid, di-linyl ester, and the like. As the aromatic dicarboxylic acid dialkyl ester, for example, dialkyl pyrethinate, 3,3,4,4'-biphenyltetracarboxylic acid dialkyl ester, 2, 2, 3, Dialkyl 3'-biphenyltetracarboxylate, dialkyl 2,3,3',4-biphenyltetracarboxylate, 3,3',4,4'-diphenyl ketone tetracarboxylate Dialkyl acid ester, dialkyl 2,3,3,4-diphenyl ketone tetracarboxylate, bis(3,4-dicarboxyphenyl)ether dialkyl ester, bis(3,4- Dicarboxyphenyl) decyl dialkyl ester, 1,2,5,6-naphthalene tetracarboxylic acid dialkyl ester, 2,3,6,7-naphthalene tetracarboxylic acid dialkyl ester, and the like. Further, polyamine can be synthesized by reacting a diamine component such as a diamine of the present invention with a dicarboxylic acid. The dicarboxylic acid used to obtain the polyamine to react with the diamine component is not particularly limited. This specific example is exemplified below. Specific examples of the dicarboxylic acid or the aliphatic dicarboxylic acid of the derivative include malonic acid, oxalic acid, dimethylmalonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, and bismuth. Acid, 2-methyl adipic acid, trimethyl adipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethyl succinic acid, azelaic acid, sebacic acid and Dicarboxylic acid such as suberic acid. Examples of the alicyclic dicarboxylic acid include 1,1-cyclopropanedicarboxylic acid, 1,2-cyclopropanedicarboxylic acid, hydrazine, 1-cyclobutanedicarboxylic acid, and ι,2-cyclobutylene. Alkanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 3,4-diphenyl-1,2-cyclobutanedicarboxylic acid, 2,4-diphenyl·ι, 3-cyclobutane Dicarboxylic acid, 1-cyclobutene-12-dicarboxylic acid, 1-cyclobutene·3,4-dicarboxylic acid, 1,1-cyclopentanedicarboxylic acid, anthracene, 2-cyclopentanedicarboxylate Acid, 1,3-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, hydrazine, 2_ -30- 201226390 cyclohexyl dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1 'Cyclohexanedicarboxylic acid, 1,4-(2-norbornene) dicarboxylic acid, norbornene 2,3-dicarboxylic acid, bicyclo[2.2.2]octane-1,4-dicarboxyl Acid 'bicyclo[2 2 2]octane-2,3-dicarboxylic acid, 2,5-dioxo-I,4-bicyclo[2.2.2]octanedicarboxylic acid, anthracene, 3·adamantane Carboxylic acid, 4,8-dioxo-1,3-adamantane dicarboxylic acid, 2,6-spiro[3.3]heptane dicarboxylic acid, 1,3-adamantane diacetic acid, camphoric acid, and the like. Examples of the aromatic dicarboxylic acid include hydrazine phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, and 5-tert-butyl isophthalic acid. 5-aminoisophthalic acid, 5-hydroxyisophthalic acid, 2,5-dimethylterephthalic acid, tetramethylterephthalic acid, iota, naphthalene dicarboxylic acid, 2, 5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,4- onion dicarboxylic acid, 1,4- onion peptide dicarboxylic acid, 2,5-biphenyl Dicarboxylic acid, 4,4'-biphenyldicarboxylic acid, i,5-extended biphenyl dicarboxylic acid, 4,4"-biphenyldicarboxylic acid, 4,4'-diphenylmethane Dicarboxylic acid, 4,4,-diphenylethane dicarboxylic acid, 4,4'-diphenylpropane dicarboxylic acid, 4,4'-diphenylhexafluoropropane dicarboxylic acid, 4,4' Diphenyl ether dicarboxylic acid, 4,4,-bibenzyldicarboxylic acid, 4,4,-indole dicarboxylic acid, 4,4'-diphenylacetylene dicarboxylic acid, 4,4,-carbonyl dibenzoin Acid, 4,4 '-millyl dibenzoic acid '4,4 '-dithiodibenzoic acid, p _phenylenediacetic acid, 3,3'-p-phenylenedipropionic acid, 4-carboxyl Cinnamic acid, p_phenylene dipropylene acid, 3,3,-[4,4 -(methylenedi-fluorene-phenylene)]dipropionic acid, 4,4,_[4,4'-(oxydi-p_phenylene)dipropionic acid, 4,4,_[4 , 4, _(·:·ρ^φ* base)]dibutyric acid, (isopropene di-fluorene-phenylene dioxy)dibutyric acid, bis(ρ-carboxyphenyl)dimethyl decane, etc. Dicarboxylic acid. The dicarboxylic acid containing a heterocyclic ring may, for example, be 1,5-(9-fluorenone)dicarboxyl 31 - 201226390 acid, 3,4-furan dicarboxylic acid, 4,5-thiazole dicarboxylic acid, 2 - Phenyl-4,5-thiazole dicarboxylic acid, 1,2,5-thiadiazole-3,4-dicarboxylic acid, 1,2,5-oxadiazole-3,4-dicarboxylic acid, 2, 3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid Acid, etc. The various dicarboxylic acids described above may be the construct of an acid dihalide or anhydride. In order to maintain the alignment property of the liquid crystal molecules, these dicarboxylic acids are preferably dicarboxylic acids of a polyamine which can impart a linear structure. Among these, terephthalic acid, isoterephthalic acid, 1,4-cyclohexanedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenyl are preferred. Methane dicarboxylic acid, 4,4'-diphenylethane dicarboxylic acid, 4,4'-diphenylpropane dicarboxylic acid, 4,4'-diphenylhexafluoropropane dicarboxylic acid, 2, 2-bis(phenyl)propane dicarboxylic acid, 4,4"-biphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,5-pyridinedicarboxylic acid or such acid dihalides . There are also isomers present in such compounds, and mixtures containing such may also be present. Further, two or more kinds of compounds can be used. The dicarboxylic acid used in the present invention is not limited to the above-exemplified compounds. The tetracarboxylic acid or the like of the above-mentioned tetracarboxylic dianhydride or the like may be one or more selected from the group consisting of liquid crystal alignment properties, voltage retention characteristics, and storage charges when the liquid crystal alignment film is formed. . A conventional synthesis means can be used as a method of reacting a diamine component with at least one selected from a tetracarboxylic acid and a tetracarboxylic acid derivative to obtain a polyimine precursor such as polyglycine. For example, as a method for obtaining the polyproline of the present invention by a reaction of a tetracarboxylic dianhydride with a diamine component, for example, a tetracarboxylic dianhydride and a diamine-32-201226390 component are produced in an organic solvent. The method of reaction. The reaction of tetracarboxylic dianhydride with a diamine is relatively easy to carry out in an organic solvent, and it is advantageous in that no by-products are produced. The organic solvent used for the reaction of the tetracarboxylic dianhydride and the diamine is not particularly limited as long as the produced polyamic acid is dissolved. Specific examples include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone. N-methyl caprolactam, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethine, γ-butyrolactone 'isopropanol, methoxymethylpentanol, dipentane Alkene, ethyl amyl ketone, methyl decyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cytosine 'ethyl acesulfame, methyl ace Subacetate, ethyl cyproterone acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol Monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert. butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethyl Glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, Dipropylene glycol monoacetate monopropyl ether, 3-methyl 3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentane acetate Ester, butyl butyrate, butyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, dioxane 'η-hexane, η-pentane, η-octane' Diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate 'ethyl acetate, B-33-201226390 n-butyl acid acetate, propylene glycol monoethyl ether, Methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3- Methoxy-N,N-dimethylpropane decylamine, 3-ethoxy-N,N-dimethylpropane decylamine, 3-butoxy-N,N-dimethylpropane decylamine, and the like. These can be used alone or in combination. Further, even if the solvent of the polyamine acid cannot be dissolved, it may be used in the above solvent as long as it is a range in which the produced polyamic acid does not precipitate. Further, the water in the organic solvent hinders the polymerization reaction and further causes hydrolysis of the produced polylysine, and the organic solvent is preferably dried as far as possible. When the tetracarboxylic dianhydride and the diamine component are reacted in an organic solvent, for example, a solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic dianhydride component is added as it is, or A method in which a tetracarboxylic dianhydride component is dispersed or dissolved in an organic solvent, and a method of adding a diamine component to an organic solvent as a solution in which a tetracarboxylic dianhydride component has been dispersed or dissolved is exemplified. As a method, a method of adding a tetracarboxylic dianhydride component and a diamine component alternately, etc., any of these methods can be used. Further, when the tetracarboxylic dianhydride component or the diamine component is formed of a plurality of compounds, the reaction can be carried out in a state of being mixed beforehand, or the reaction can be carried out in an individual order, or the individual reaction can be carried out. The low molecular weight body is subjected to a mixing reaction to become a high molecular weight body. The polycondensation temperature at this time may be any temperature of from -20 to 150 ° C, preferably from -5 to 100 ° C. Further, the polycondensation reaction can be carried out at any concentration of -34 to 201226390, but when the concentration is too low, the polymer becomes difficult to obtain; when the concentration is too high, the viscosity of the reaction solution becomes excessively agitated. If it is difficult, the tetracarboxylic dianhydride and the s ten concentration in the reaction solution are preferably 1 to 5 〇 mass%, more preferably 5 to 3 0. The initial stage of the reaction is carried out at a commercial concentration, and then an organic solvent may be added. In the polymerization reaction of polyamic acid, the ratio of the total number of moles of the combination of the tetracarboxylic dianhydride and the diamine component (the total number of moles of the diamine component of the tetracarboxylic dianhydride and the diamine component) is preferably Oja〗.? . The same as the polymerization reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the acid produced becomes. Further, a polyglycolate is a reaction between a tetracarboxylic acid diester and a diamine component as described above, or a tetracarboxylic acid diester and a diamine component, and a reaction is carried out in the presence of a condensing agent or a base. get. The above method can also be obtained by synthesizing polylysine in advance and esterifying the carboxylic acid in valeric acid with a polymer. Specifically, for example, the reaction of the tetracarboxylic acid diester dichloride with two in the presence of a base and an organic solvent is carried out at -20 to 150 ° C to 405 ° C for 30 minutes to 24 hours. Preferably, it is a 1~ synthesizable polyphthalate. As the base, pyridine, triethylamine or 4-dimethylpyridine can be used, and in order to carry out the reaction stably, pyridine is preferred. The addition of the base is easy to remove, and it is easy to obtain a high molecular weight body or the like, and the tetracarboxylic acid diester dichloride is preferably 2 to 4 moles. Further, the tetracarboxylic acid diester and the diamine have a high molecular weight and a uniform diamine component mass% in the presence of a condensing agent. Media. Counting moles of tens of moles / usually shrinking polyamine dichloride by means of appropriate or suitable, by means of the amine compound preferably 〇 4 hours, the amount of amide is added, in other words, When the relative component is -35- 201226390, in the polycondensation reaction, as the base, triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl) can be used. Carboximide hydrochloride, N,N'-carbonyldiimidazole, dimethoxy-1,3,5-tri-n-methyl-m-propofolin, 〇-(benzotriazol-1-yl) )-N,N,N',N'-tetramethylurea tetrafluoroborate, 0-(benzotriazol-1-yl)-oxime, hydrazine, Ν', Ν'-tetramethylurea Fluorophosphate, diphenyl (2,3-dihydro-2-thio-3-benzoxazolyl)phosphonic acid, 4-(4,6-dimethoxy-1,3,5-tri Ind-2-yl) 4-methoxymorpholine chloride-η-hydrate and the like. Further, in the method of using the above condensing agent, the reaction proceeds efficiently by adding a Lewis acid as an additive. The Lewis acid is preferably lithium halide such as lithium chloride or lithium bromide. The amount of the Lewis acid to be added is preferably 〇" to 1.0 mol" relative to the diamine or tetracarboxylic acid diester which causes the reaction. The solvent used in the above reaction may be the same solvent as that used in the above-mentioned synthesis of polyamic acid. The solubility of the monomer and the polymer is preferably Ν-methyl- 2-pyrrolidone, γ-butyrolactone, and the like, and these may be used alone or in combination of two or more. The concentration at the time of synthesis is a tetracarboxylic acid derivative such as a tetracarboxylic acid diester dichloride or a tetracarboxylic acid diester and a second in the reaction solution insofar as the polymer is less likely to be precipitated and a high molecular weight body is easily obtained. The total concentration of the amine component is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass. Further, in order to prevent hydrolysis of the tetracarboxylic acid diester dichloride, it is preferred to use a solvent for the synthesis of the polyphthalate to be dehydrated as much as possible, preferably in a nitrogen atmosphere to prevent external gases. Mix in.

36-201226390 The polyimine of the present invention is obtained by dehydrating and ring-closing the above polyamic acid. In the polyimine of the present invention, the dehydration ring closure ratio of the valine group is not necessarily 100%, and can be arbitrarily adjusted depending on the purpose or purpose. As a method for imidizing polyphosphonium amide, for example, a solution in which a solution of polyproline is heated as it is is imidized, and a catalyst is added to a solution of polylysine. Amination. The temperature at which the polyaminic acid is thermally imidized in the solution is from 100 to 400 t, preferably from 120 to 250 ° C, and the water formed by the imidization reaction is removed to the outside of the system. The method carried out is suitable. The catalyst of the polyaminic acid is imidized, and the basic catalyst and the acid anhydride are added to the solution of the poly-proline, and the ratio is -2 0 to 25 (TC, preferably 0 to 180 °) The amount of the alkaline catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the prolyl group; the amount of the anhydride is 1 to 5 of the amidate group. 0 moles, preferably 3 to 30 moles. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Further, pyridine is preferred because it has a moderate basicity for carrying out the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyrogallic anhydride. Among them, when acetic anhydride is used, purification after completion of the reaction is changed. It is easy to use, and it is preferable to control the imidization ratio of the imidization of the catalyst by adjusting the amount of the catalyst, the reaction temperature, and the reaction time. Further, as described above, by using polyamine The acid ester is heated at a high temperature' and promotes the dealcoholization to close the ring, and the polyimine is also obtained. -37- 201226390 尙, agglomerated by poly-proline, polylysine, etc. When the reaction solution of the imine precursor or the polyimine is recovered by collecting the produced polyamine, polyphthalate, polyimine or the like, the reaction solution may be placed in a weak solvent to precipitate. Examples of the weak solvent used for precipitation include methanol, acetone, hexane, butyl cyanisol, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, and the like. The precipitated polyimide precursor or polyimine in a weak solvent can be dried at room temperature or under normal pressure or reduced pressure after being subjected to filtration and recovery, and the precipitated polycondensate is recovered. When the imine precursor or the polyimine is repeated for 2 to 10 times to be redissolved in an organic solvent and subjected to reprecipitation recovery, impurities in the polymer can be reduced. As a weak solvent at this time, for example, for example When three or more kinds of weak solvents selected from the above are used, such as alcohols, ketones, hydrocarbons, etc., since the efficiency of purification is further improved, it is preferably contained in the liquid crystal alignment agent of the present invention. Polyimine, polyamidomate, etc. The molecular weight of the precursor or the polyimine, and the weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method, in consideration of the strength of the coating film obtained, the workability at the time of formation of the coating film, and the uniformity of the coating film. Preferably, it is 5,000 〜1, 〇〇〇, 〇〇〇, more preferably 10,000 〜1 50,000 ° The polyimine precursor of the above polylysine, polyphthalate, etc. of the present invention and poly phthalate The amine can be used together with a solvent to form a liquid crystal alignment agent. The so-called liquid crystal alignment agent is a solution for forming a liquid crystal alignment film, and is a solution for dispersing or dissolving a polymer component for forming a liquid crystal alignment film in an organic solvent.尙, the so-called liquid crystal alignment film, used to make the liquid crystal alignment

•38- 201226390 Directional film. Then, in the present invention, at least one selected from the above-mentioned polymer component, the polyimine precursor such as polylysine or polylysine of the present invention, and polyimine is selected in the present invention. In the liquid crystal alignment agent, all of the polymer components contained in the present invention may be the polyimine precursors such as polylysine or polylysine of the present invention or polyimine, or may be mixed with other polymerizations. The present invention is used in the polyimine precursor or polyimine of the above polylysine, polyphthalate or the like of the present invention. When the polymer component contains another polymer, the content of the other polymer in the total amount of the polymer component is from 0.5% by mass to 50% by mass, preferably from 1% by mass to 30% by mass. By forming a mixture of a plurality of polymers, the characteristics of the liquid crystal alignment agent or the liquid crystal alignment film can be improved. As such a polymer, for example, a diamine component which reacts with a tetracarboxylic dianhydride component, for example, a polyamine obtained by using a diamine other than the diamine represented by the above formula [1] of the present invention. Amine acid, polyphthalate or polyimine. In the liquid crystal alignment agent, at least one selected from the above-mentioned polyamidamine precursors such as polylysine, polylysine, and polyimine, and other polymers which are mixed as necessary. The content of the polymer component is preferably from 1% by mass to 20% by mass, more preferably from 3% by mass to 15% by mass, even more preferably from 3 to 10% by mass, based on the total amount of the polymer component. The solvent to be used in the liquid crystal alignment agent of the present invention is not particularly limited as long as it is an organic solvent that dissolves the polymer component. As such a specific example, for example, hydrazine, dimethyl-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2 -pyrrolidone, N-ethylpyrrole

S -39- 201226390 ketone, N-vinylpyrrolidone 'dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethine, γ-butyrolactone, 3-methoxy-N , N-dimethylpropane decylamine, 3-ethoxy-N,N-dimethylpropane decylamine, 3-butoxy-N,N-dimethylpropane decylamine, 1,3-dimethyl Base-imidazolidinone, ethyl amyl ketone, methyl decyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, Diglyme, 4-hydroxy-4-methyl-2-pentanone, and the like. These can be used alone or in combination. The liquid crystal alignment agent of the present invention may contain components other than the above. In this case, there is a solvent or a compound which improves film thickness uniformity or surface smoothness when a liquid crystal alignment agent is applied, and a compound which improves the adhesion between the liquid crystal alignment film and the substrate. Specific examples of the solvent (weak solvent) for improving the uniformity of the film thickness or the smoothness of the surface, for example, isopropyl alcohol, methoxymethylpentanol, methyl ceramide, ethyl ceramide, butyl Celluloid, methyl cyanoacetate, ethyl cyproterone acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol Monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether , diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, two Propylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl-40- 201226390 ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diiso Ketone, methylcyclohexene, propyl ether, dihexyl ether, 1-hexanol, η-hexane, η-pentane, η-octane, diethyl ether, methyl lactate, ethyl lactate, Methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate Ester, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1- Methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol II Acetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propane A solvent having a low surface tension, such as an alcohol, methyl lactate, ethyl lactate, η-propyl lactate, η-butyl lactate or isoamyl lactate. These weak solvents can be used in one type or in a mixture of plural kinds. When the solvent is used, it is preferably 5 to 80% by mass, more preferably 20 to 60% by mass based on the total amount of the solvent contained in the liquid crystal alignment agent. The compound which improves the uniformity of the film thickness or the surface smoothness is, for example, a fluorine-based surfactant, a polyfluorene-based surfactant, or a nonionic surfactant. More specifically, for example, F - Τ ο p EF 3 0 1 , EF3 03, EF352 (manufactured by Tokem Products Co., Ltd.), MEGAFACE F171, F173, R-30 (manufactured by DIC Corporation), Fluorad FC43 0, FC431 (Sumitomo 3M Company), AashiGuard AG710, Surflon S-3 8 2, SC101, SC 102 'SC 103 'SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.). The ratio of use of the surfactant is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the resin component contained in the liquid-41-201226390 crystal alignment agent. Specific examples of the compound which enhances the adhesion between the liquid crystal alignment film and the substrate include, for example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, and 2-aminopropyl. Trimethoxy decane, 2-aminopropyltriethoxy decane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl) 3-aminopropylmethyldimethoxydecane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyl Trimethoxy decane, N-ethoxycarbonyl-3-aminopropyltriethoxy decane, N-triethoxymercaptopropyltriethylenetriamine, N-trimethoxydecylpropyltri Ethylene triamine, 10-trimethoxydecyl-1,4,7-trioxane, 10-triethoxyindolyl-1,4,7-trioxane, 9-trimethoxyindenyl -3,6-dimercaptoacetate, 9-triethoxyindolyl-3,6-dimercaptoacetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N-double (oxyethylene)-3·Aminopropyltrimethoxydecane, N-bis(oxyethylene)-3-aminopropyltriethoxydecane, ethylene glycol diglycidyl ether, polyethylene glycol diminish Glycerol ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2·dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, 1^,1^,:^,,>^' -tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, meaning: ^:^'々'-tetraglycidyl-4 , 4'-Diaminodi-42-201226390 The compound of the genus (5) sex sand chamber or the compound containing an epoxy group. Further, in addition to the adhesion between the substrate and the film, it is possible to prevent the deterioration of the electrical characteristics of the backlight. The liquid crystal alignment treatment agent may further contain a phenoplast-based additive as described below. The specific phenolic plastic additive is as follows, but is not limited to this configuration. [Chem. 23]

(In the formula, Me is shown as a methyl group). When the compound is used to improve the adhesion to the substrate, the amount of use is preferably from 1 to 30 parts by mass, more preferably from 1 to 20 parts by weight based on 100 parts by mass of the polymer component contained in the liquid crystal alignment agent. Parts by mass. When the amount of use is less than 1 part by mass, the effect of improving the adhesion cannot be expected; if it is more than 30 parts by mass, the alignment of the liquid crystal may be deteriorated. In the liquid crystal alignment treatment agent of the present invention, in addition to the above, the dielectric properties of the liquid crystal alignment film may be changed so as not to impair the effects of the present invention, and dielectric properties may be added.质质-43-201226390 Electrical substances, in addition, for the purpose of improving the hardness or density of the film formed into a liquid crystal alignment film, crosslinkable compounds can be added. The liquid crystal alignment agent of the present invention can be used as a liquid crystal alignment film which is not subjected to alignment treatment when it is applied onto a substrate, calcined, and then subjected to alignment treatment by rubbing treatment or light irradiation, or when it is used for vertical alignment or the like. Since the liquid crystal alignment film of the present invention contains the polyimine precursor or polyimine formed using the diamine of the present invention, there is no pinhole formation or unevenness of the film thickness at the edge portion. Moreover, the storage of electric charges is not easy to occur, and the stored charge is eliminated quickly. The substrate is not particularly limited as long as it has high transparency, and a glass substrate or a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used. Further, it is preferable to use a substrate on which an ITO electrode or the like for driving a liquid crystal is formed, from the viewpoint of simplification of the procedure. Further, in the case of the reflective liquid crystal display element, if it is only a single-sided substrate, an opaque material such as a germanium wafer or the like may be used. In this case, a material such as aluminum or the like may be used. Further, in a high functional element such as a TFT type element, an element such as a transistor formed between an electrode for driving a liquid crystal and a substrate can be used. The coating method of the liquid crystal alignment agent is not particularly limited, but industrially, there are generally methods such as screen printing, lithography, quick-drying printing, and injection. As another coating method, there are also a dipping, a roll coater, a slit coater, a spin coater, etc., and these may be used depending on the purpose. The liquid crystal alignment agent is applied to the substrate and calcined, and is heated by a heating means such as a hot plate, a hot air circulation furnace or an infrared furnace at 50 to 30 (TC, preferably 80 to 250 ° C to evaporate the solvent). A film can be formed. The thickness of the coating film formed after calcining -44 - 201226390 is too unfavorable in terms of power consumption of the liquid crystal display element, and if it is too thin, there is a liquid crystal display element. In the case where the reliability is lowered, it is preferably 5 to 300 nm, more preferably 10 to 100 nm. When the liquid crystal is horizontally aligned or tilted, the film after calcination is irradiated by rubbing or polarized ultraviolet rays. In the liquid crystal display element of the present invention, a liquid crystal cell is produced by a known method using a liquid crystal alignment film of the present invention, and a liquid crystal display element is produced. For example, the liquid crystal layer provided in the opposite direction, the liquid crystal layer disposed between the substrates, and the liquid crystal alignment layer formed by the liquid crystal alignment agent of the present invention are provided between the substrate and the liquid crystal layer. The liquid crystal display element of the liquid crystal cell of the film is not particularly limited as long as it is a substrate having high transparency, and a transparent electrode for driving liquid crystal is usually formed on the substrate. The substrate is, for example, the same as the substrate described in the above liquid crystal alignment film. Further, the liquid crystal alignment film is formed by applying calcination by applying the liquid crystal alignment agent of the present invention to the substrate. The liquid crystal material constituting the liquid crystal layer of the liquid crystal display element of the present invention is not particularly limited, and a liquid crystal material used in a conventional vertical alignment method can be used, for example, MLC-2003, MLC-6608 manufactured by Mok Corporation. MLC-6609, etc. When an example of liquid crystal cell fabrication is exemplified, one pair of substrates on which a liquid crystal alignment film has been formed may be prepared, and a spacer such as beads may be dispersed on a single substrate. a liquid crystal alignment film, and the liquid crystal alignment film surface is bonded to the inside to bond the other substrate, and the liquid crystal is injected under reduced pressure to be sealed, or The liquid crystal alignment film surface on which the spacer has been dispersed is a method in which the liquid crystal is dropped, and the substrate is bonded and sealed. The thickness of the spacer is preferably 1 to 30 μm, more preferably 2 to ΙΟμπι. In the above, the liquid crystal display element produced by using the liquid crystal alignment agent of the present invention is excellent in reliability, and can be suitably used for a large-screen, high-definition liquid crystal television, etc. [Embodiment] [Embodiment] The examples are described in more detail, but the present invention is not limited to the examples. [Synthesis of Diamine] The abbreviations used below are as follows. DMF: hydrazine, hydrazine - dimethylformamide THF: tetrahydrofuran RT : room temperature (25t) (Synthesis Example 1) Synthesis of 1-(4-aminophenyl) '5-amino D porphyrin [Diamine-1] of the following formula 201226390 [Chem. 24] NH2

h2N^nXX

[Dlamlne-1] (first step) Synthesis of 1-(4-nitrophenyl)-5-nitroporphyrin [Chem. 25] N〇2

DMF RT

_ - 0jNiJO Sodium hydride (purity 55%) 9.30 g (213 mmol) and dehydrated DMF 100 mL were placed in a 500 mL two-necked flask, and a 5-nitroporphyrin DMF solution was stirred while stirring under a nitrogen atmosphere ( 5-Nitroporphyrin: 35.0 g (213 mmol), DMF: 100 mL) was dripped at not more than 30 °C. After the completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours. A solution of 4-fluoronitrobenzene in DMF (4-fluoronitrobenzene: 33.0 g (234.5 mmol), DMF: 100 mL) was added dropwise to the reaction solution under a nitrogen atmosphere. Stir at room temperature for 6 hours. After the completion of the reaction, the reaction solution was stirred while slowly injecting 100 mL of pure water to precipitate a solid. The precipitated solid was filtered and dissolved again in DMF, and poured into 500 mL of pure water to reprecipitate, and the solid was again filtered and recovered. The obtained solid was dispersed and washed with methanol and η-hexane, and dried in vacuo to obtain an orange solid 54.7 g (yield: 90%). (Second step) Diamine-indole synthesis-47- 201226390 [化26]

N〇2 ό Pd/c h2 EtOHRT NH2 [Diamine-1] 15.0 g of i_(4_nitrophenyl)-5-nitroindole derived from the first step was weighed in a 300 mL four-necked flask ( 52.6 mmol) and i〇 mass carbon 1 _50 g, and 1 5 OmL of ethanol was added. After being sufficiently substituted with nitrogen, a hydrogen gas atmosphere was obtained, and the mixture was vigorously stirred at room temperature. After completion of the reaction, palladium carbon was filtered using a glass filter, and the filtrate was passed through a rotary evaporator to remove the solvent. The obtained residue was dissolved in acetone, and the activated carbon was temporarily stirred, and the activated carbon was filtered, and acetone was removed by a rotary evaporator, followed by a mixed solution of η-hexane and ethyl acetate (2:3 by mass). Crystallization gave 10.5 g of a pale purple solid of the desired diamine (diamine-1) (yield: 89%). This structure was confirmed by 1 H-NMR spectrum of the nuclear magnetic resonance spectrum of the intramolecular hydrogen atom. The measurement data is as follows. 1 H NMR (400 MHz, [D6]-DMSO) 5 : 6.8 7 - 6.2 3 (Arom at i cH, 7H), 4.77-4.68 (s-br, 2H), 4.39-4.38 (s-br, 2H), 3,62-3,5 8 (t, 2H), 2.8 9-2.8 7 (t, 2H) (Synthesis Example 2) ^(4-Aminophenyl)-2-methyl- represented by the following formula Synthesis of 5-month female based Π[Diamine-2] (racemic mixing) -48 - 201226390 [化27]

(First step) Synthesis of 1-(4-nitrophenyl)-2-methyl-5-nitroporphyrin [Chem. 28]

2. Sodium hydride (purity 55%) 2.45 g (56.1 mmol) and dehydrated DMF 100 mL were placed in a 500 mL two-necked flask, and 2-methyl-5-nitroporphyrin was stirred while stirring under a nitrogen atmosphere. The DMF solution (2-methyl-5-nitroporphyrin: l〇.〇g (56.1 mmol), DMF: 50 mL) was dropped at a temperature not exceeding 30 °C. After the completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours. A DMF solution of 4-fluoronitrobenzene (4-fluoronitrobenzene: 8.7 g (61.7 mmol), DMF: 5 OmL) was added dropwise to the reaction solution, and the mixture was stirred at room temperature for 6 hours under a nitrogen atmosphere. After the completion of the reaction, while stirring the reaction solution, 100 mL of pure water was slowly injected to precipitate a solid, and the precipitated solid was filtered and dissolved again in DMF, and poured into 500 mL of pure water to reprecipitate, and the solid was again filtered and recovered. The obtained solid was subjected to dispersion washing with methanol and n-hexane, and dried in vacuo to give 14.4 g of an orange solid (yield: -49 - 201226390 8 6%). (Second step) Synthesis of Diamine-2 [Chem. 29] no2 0 J〇>- [Diamine-2] ή

Pd/c h2

EtOH.RT

H2N was weighed in a 3 〇OmL four-necked flask to obtain i_(4_nitrophenyl)-2-methyl-5-nitroindole 哄咐l〇.〇g (56.1 mmol) obtained in the first step and 10% by mass of palladium carbon 1. 〇〇g 'Isoethanol was added to 1 5 Om L, and it was sufficiently substituted with nitrogen to form a hydrogen gas atmosphere, and the mixture was vigorously stirred at room temperature. After completion of the reaction, palladium carbon was filtered using a glass filter, and the filtrate was removed by a rotary evaporator. The obtained residue was dissolved in acetone, and the activated carbon was temporarily stirred, and the activated carbon was filtered, and acetone was removed by a rotary evaporator, followed by a mixed solution of η-hexane and ethyl acetate (2:3 by mass). Crystallization gave 7.03 g of a slightly pink solid of the desired diamine (diamine-2) (yield: 89%). This structure was confirmed by 1H-NMR spectroscopy. The measurement data is as follows. 1H NMR (400 MHz, [D6]-DMSO) 5: 6.86-6.84 (d, 2H), 6.5 6-6.22 (Aromatic-H, 7 Η), 4.7 7 - 4.6 8 (s - br, 2H), 4.39 -4.3 8(s-br, 2H), 4.83-4.81 (m, 1H), 3, 42-3, 3 8 (dd, 1H), 2.89-2.87 (dd, 1 H) 1 · 4 8 -1 · 4 7 (s, 3H) (Synthesis Example 3) 1-(4-Aminophenyl)-2,3,3-trimethyl-5-amino-50-201226390 哄引哄琳[Diamine-3 Synthesis (racemic mixing) [Chem. 30]

(First step) Synthesis of 1-(4-nitrophenyl)_2,3,3-trimethyl-5-nitroporphyrin [Chem. 31]

2.61 g (48.5 mmol) of sodium hydride (purity 55%) and 100 mL of dehydrated DMF were placed in a 50 mL two-necked flask, and 2,3,3-trimethyl-5-nitrate was stirred while stirring under a nitrogen atmosphere. The porphyrin-containing DMF solution (2,3,3-trimethyl-5-nitroporphyrin: 10.0 g (48.5 mmol), DMF: 50 mL) was dropped at a temperature of not more than 30 °C. After the completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours. A 4-fluoronitrobenzene-containing DMF solution (4-fluoronitrobenzene: 7.52 g (53.3 mmol), DMF: 50 mL) was added dropwise to the reaction mixture, and the mixture was stirred at room temperature for 6 hours under a nitrogen atmosphere. After the completion of the reaction, 100 mL of pure water was slowly poured while stirring the reaction solution to precipitate a solid. The precipitated solid was filtered and dissolved again in DMF, and poured into 500 mL of pure water to reprecipitate, and the solid was again filtered and recovered. The obtained solid was dispersed and washed with methanol and η-hexane -51 - 201226390, and dried in vacuo to give an orange solid 13.5 g (yield: 8 5%) 〇 (second step) Diamine-3 Synthesis [32]

10.0 g (30.5 mmol) of 1-(4-nitrophenyl)·2,3,3-dimethyl-5-nitroporphyrin obtained in the first step was weighed in a 300 mL four-necked flask and 10% by mass of palladium carbon 1 〇〇g, 150 mL of ethanol was added thereto, and after sufficiently substituted with nitrogen, a hydrogen gas atmosphere was obtained, and the mixture was vigorously stirred at room temperature. After completion of the reaction, palladium carbon was filtered using a glass filter, and the filtrate was removed by a rotary evaporator. The obtained residue was dissolved in acetone, and the activated carbon was temporarily stirred, and the activated carbon was filtered, and acetone was removed by a rotary evaporator, followed by a mixed solution of η-hexane and ethyl acetate (2:3 by mass). Crystallization gave 7.50 g (yield: 92%) of a pale purple solid of the desired diamine. This structure was confirmed by iH-NMR spectroscopy. The measurement data is as follows. 'H NMR (400 MHz, [D6]-DMSO) 5 : 6.8 6 - 6.2 2 (Aromat i cH, 7H), 4.74-4_66 (s-br, 2H), 4.41-4.39 (s-br, 2H), 4.23 -4.21 (m, 1H), 1.48-1.14 (s, 9H) -52 - 201226390 (Synthesis Example 4) 1-(4-aminophenyl)-6-amino group 1,2 represented by the following formula Synthesis of 3,4-tetrahydroquinoline [Diamine-4] [Chem. 33]

(First step) Synthesis of 6-(tert-butoxycarbonyl)aminoquinoline [Chem. 34]

In a 20 mL four-necked flask, 5.00 g (34.7 mmol) of 6-n-quinoline was dissolved in THF 100 mL, and 7.5 7 g (3 4.7 mmol) of tert-butyl dicarbonate was added thereto, and the mixture was refluxed for 20 hours under a nitrogen atmosphere. After completion of the reaction, THF was removed by a rotary evaporator, ethyl acetate was added, and the mixture was washed with purified water and saturated brine, and dried with anhydrous magnesium sulfate. After removing anhydrous magnesium sulfate by filtration, the solvent was removed using a rotary evaporator, and the residue was recrystallized from a mixed solvent of ethyl acetate and hexane-hexane (1: 4 by volume) to give white solid 7.29 g ( 86%). (Second step) Synthesis of 6-(tert-butoxycarbonyl)amino-1,2,3,4-tetrahydroquinoline-53- 201226390 [Chem. 35] rV, Pd/CH~CrS B〇C Boc was taken in a 100 mL two-necked flask to obtain 5.00 g (20.4 mm 〇l) of 6-(tert-butoxycarbonyl)aminoquinoline obtained in the first step and 10% by mass of palladium carbon ruthenium. After 50 mL of methanol was sufficiently substituted with nitrogen, it was allowed to stand in a hydrogen gas atmosphere and vigorously stirred at 60 °C. After completion of the reaction, palladium carbon was filtered using a glass filter, and the filtrate was removed by a rotary evaporator. The obtained residue was dissolved in acetone, and the activated carbon was temporarily stirred, and the activated carbon was filtered, and acetone was removed by a rotary evaporator, followed by a mixed solution of η-hexane and ethyl acetate (2:3 by mass). Crystallization gave 3.65 g of a white glassy solid (yield: 72%) » (Second step) 1-(4-nitrophenyl)-6-amino-1,2,3,4-tetrahydroquine Synthesis of porphyrins [Chem. 36] ΗΝΧ» I Boc Y=58%

NaH 〇2N 〇f

HCJ

DMF RT RT 20h Sodium hydride (purity 55%) 615.615g (i4.immol), dehydrated DMF 20 mL was added to a 100 mL two-necked flask, and the mixture was stirred under a nitrogen atmosphere. 6-(tert-butoxycarbonyl)amino-1,2,3,4-tetrahydroquinoline in DMF (6-(tert-butoxycarbonyl)amino--54 - 201226390 1,2 3,4-tetrahydroquinoline: 3.50 g (14.1 mmol), DMF: 20 mL) was dripped at not more than 30 °C. After the completion of the dropwise addition, the mixture was stirred for 2 hours. 4-Fluoronitrobenzene in DMF solution (4-fluoronitrobenzene: 2.19 g (15.5 mmol), DMF: 20 mL) was added dropwise to the reaction solution, and the mixture was stirred at room temperature for 20 hours under a nitrogen atmosphere. After the completion of the reaction, the reaction solution was stirred while slowly injecting 3 mL of pure water to precipitate a solid. The precipitated solid was filtered and dissolved again in DMF, poured into 100 mL of pure water to reprecipitate, and the solid was again filtered and recovered. Dispersion washing was carried out using η-hexane, and dried in vacuo to give a yellow solid. A 4 Ν hydrochloric acid-ethyl acetate solution was added to the solid, and the mixture was stirred at 40 ° C for 2 hours. Pure water was added to the reaction solution, the aqueous layer was recovered, neutralized with sodium hydrogencarbonate, extracted with ethyl acetate, and washed with water and saturated brine, dried over anhydrous magnesium sulfate. After removing the magnesium sulfate, the solvent was removed using a rotary evaporator, and the residue was subjected to column chromatography (1:1 volume ratio of ethyl acetate and dichloroethane) to obtain a yellow solid of 2.2 g. Rate: 5 8%) Synthesis of hydrazine (fourth step) 1-(4-aminophenyl)-6-amino-1,2,3,4-tetrahydroquinoline [Diamine-4] ]

NH2

Pd/C, H2

EtOH

RT 1 - (4· -55-201226390 nitrophenyl)-6-amino-1,2,3,4-tetrahydroquinoline 10.0 g obtained in the third step in a 500 mL four-necked flask (37.1 mmol), 100% by mass of palladium carbon 1. 〇〇g, 300 mL of ethanol was added, and the mixture was sufficiently substituted with nitrogen to form a hydrogen gas atmosphere, and the mixture was vigorously stirred at room temperature. After completion of the reaction, palladium carbon was used as a glass filter. Filtration was carried out and the filtrate was removed using a rotary evaporator. The obtained residue was dissolved in acetone, and the activated carbon was temporarily stirred, and the activated carbon was filtered, and acetone was removed by a rotary evaporator, followed by a mixed solution of η-hexane and ethyl acetate (5:1 by mass). Crystallization gave 7.30 g of a pale purple solid of the desired diamine (diamine-4) (yield: 82%). This structure was confirmed by 1H-NMR spectroscopy. The measurement data is as follows. *HNMR (4 0 0 Μ H z, [ D 6 ] - DMS Ο) δ · 6.8 5 - 6.3 5 (A r ο mati c-Η, 7H), 5.00-4.98 (s-br, 2H), 4.59- 4.58 (s-br, 2H), 3, 94-3, 9 3 (m, 2H), 2.89-2.87 (m, 2H), 2.66-2.64 (m, 2H) (Synthetic Comparative Example Aminophenyl)- Synthesis of 5-amino D-inducing [Diamine-5] [Chem. 38]

(First step) Synthesis of 1-(4-nitrophenyl)-5-nitroguanidine -56- 201226390 [Chem. 39]

O^N

NaH DMF RT, 2hr 〇, Ν〇Ρ

N〇2 0 Sodium hydride (purity 55%) 4.48 g (l〇1.8 mmol) and dehydrated DMF 50 mL were placed in a 500 mL two-necked flask, and 5-nitroguanidine was stirred while stirring under a nitrogen atmosphere. The DMF solution (5-nitroguanidine: 15.0 g (92.5 mmol), DKlF··100 mL) was dropped at a temperature not exceeding 30 °C. After the completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours. A 4-fluoronitrobenzene DMF solution (4-fluoronitrobenzene: 13.1 g (92.5 mmol), DMF: 100 mL) was added dropwise to the reaction solution, and the mixture was stirred at room temperature for 6 hours under a nitrogen atmosphere. After the completion of the reaction, the reaction solution was stirred while slowly injecting 100 mL of pure water to precipitate a solid, and the precipitated solid was filtered and dissolved again in DMF to be injected into 5 mL of pure water to reprecipitate, and the solid was again filtered. Recycling. The obtained solid was subjected to dispersion washing with methanol and n-hexane, and dried under vacuum to obtain 25.0 g (yield: 95%) of a yellow solid (first step) 1-(4-aminobenzene) Synthesis of 5-amine-based ruthenium [Diamine-5]-57- 201226390 [Chemical 40] 0 >〇> [Diamine-5] N〇2 ό

Pd/c h2

EtOH, Reflux H2N 1⁄4 (4 _ nitrophenyl)-5-nitroindole 20.0 g (70.6 mmol), 10 mass % palladium obtained in the first step in a 500 ml L four-necked flask Carbon (2.00 g) was added to 300 mL of ethanol, and the mixture was sufficiently substituted with nitrogen to form a hydrogen gas atmosphere, followed by reflux for 42 hours. After completion of the reaction, palladium carbon was filtered using a glass filter, and the filtrate was removed by a rotary evaporator. The obtained residue was dissolved in acetone, the activated carbon was temporarily stirred, the activated carbon was filtered, and acetone was removed by a rotary evaporator, and then the residue was washed with η-hexane to obtain the desired diamine (Diamine_5). 15.0 g of a slightly pink solid (yield: 9 5%). This structure was confirmed by 1H-NMR spectrum. The measured data is as follows. 'H NMR (400MHz, [D6]-DMSO) 5 : 7.2 5 - 6.2 8 (A r 0 mati c-Η, 9H), 5.20 (s-br, 2H), 4.56 (s-br, 2H) Synthesis of Proline and Polyimine and Modulation of Liquid Crystal Aligning Agent] The abbreviations of the compounds used below are as follows. Further, the composition of the polymer synthesized in each of the examples and the comparative examples and the composition of the liquid crystal alignment agent are shown in Tables 1 and 2. <tetracarboxylic dianhydride> -58- 201226390 CBDA: 1,2,3,4-cyclobutane tetracarboxylic dianhydride TDA: 3,4-dicarboxy-1,2,3,4-tetrahydrogen -1-naphthalene succinic acid dianhydride CBDE: 1,2,3,4-cyclobutane tetracarboxylic acid dimethyl ester

<Diamine> P-PDA : 1,4-phenylenediamine DDM: 4,4-diaminodiphenylmethane C16DAB: 4-hexadecyloxy-1,3-diaminobenzene H2n

ΧΤΗ: p-PDA ΗίΝχταΝΗ2

DDM

a ηΆβΚ»χχ C16DAB <condenser> DMT-MM : 4-(4,6-dimethoxy-1,3,5-trian-2-yl)4-methoxymorpholine chloride -η-Hydrate<Organic Solvent> Ν Μ P : Ν-Methyl-2-pyrrolidinium γ-BL : γ· Butyrolactone BC : Butyl cyanoside DPM: Dipropylene glycol monomethyl ether -59-201226390 <Measurement of Molecular Weight> The molecular weight of the polymer obtained by the polymerization reaction was measured by a GPC (normal temperature gel permeation chromatography) apparatus, and polyethylene glycol, poly The number average molecular weight and the weight average molecular weight were calculated from the conversion of ethylene oxide. GPC device: manufactured by Shodex Co., Ltd. (GPC-101) Pipe column: made by Shodex (series of KD 803, KD 805)

Column temperature: 50 °C Dissolution: 30 mmol/L of N,N-dimethylformamide (as an additive for lithium bromide-hydrate (LiBr.H2〇), 30 mmol/L of phosphoric acid. Anhydride crystals (〇 -phosphoric acid), l〇mL/L of tetrahydrofuran (THF)) Flow rate: 1.0 mL/min. calibrated line Standard sample: TSK standard polyethylene oxide manufactured by TOSOH Co., Ltd. (molecular weight: about 900,000, 150,000, 100,000, 30 , 000), and polyethylene glycol manufactured by Polymer Laboratories (molecular weight: about 1 2,000 '4,000, 1,000) = <Measurement of oxime imidization rate> The ruthenium imidization ratio of polyimine is as follows The measurement was carried out. 20 mg of polyimine powder was placed in an NMR sample tube (NMR sample tube standard manufactured by Kusano Scientific Co., Ltd.), and 0.53 mL of heavy argon dimethyl hydrazine (DMSO-d6 '〇.〇5% TMS mixture) was added. The ultrasound is applied to dissolve completely. Proton NMR at 500 MHz was measured using a JEOL DATUM (NMR) NMR analyzer (JNW-ECA500). The imidization rate of ruthenium is determined by using protons whose structure has not changed before and after imidization as the reference proton, and the peak of this proton is accumulated and appears near 9.5~10.0Ppm. The proton peak accumulation of the NH group of proline is determined by using the following formula.尙, in the above formula, X is the proton peak cumulative 値 from the NH group of the proline, y is the peak cumulative 値 of the reference proton, and α is when the polyproline (〇 imidization is 〇%) The ratio of the number of reference protons relative to one of the ruthenium protons.

Ruthenium amination rate (%) = (l-〇fX/y) xlOO (Example 1) Synthesis of polyamidic acid using CBDA/Diamine-1 In a 50 mL four-necked flask, as a diamine component, it was added to the synthesis. Example 1 Diamine·1 1 · 50 g (6.6 5 mm ο 1) 'NMP 1 5.3 g > was cooled to about 10 ° C. Add CBDA 1.22 g (6.20 mmol), and return to room temperature. The reaction was carried out for 6 hours under a nitrogen atmosphere to obtain a solution having a concentration of polyamine acid (PAA-1) of 15% by mass. 15.0 g of this polyaminic acid (PAA-1) solution was transferred to a 50 mL Erlenmeyer flask, and 15.0 g of NMP and 7.50 g of BC were added and diluted to prepare a polyglycine (PAA-1) of 6 mass%, and NMP was A solution of 74% by mass and BC of 20% by mass gives the liquid crystal alignment agent-1 of the present invention. The polyamino acid had an average molecular weight of 12,300 and a weight average molecular weight of 33,100. (Example 2) Synthesis of polyamino acid using CBDA/Diamine-2 In a 50 mL four-necked flask, Diamine-2 1.50 g (6.25 mmol) obtained in Synthesis Example 2 was added as a diamine component, and NMP was added. 15. 〇g, cooled to about l ° ° C, added CBDA 1.14g (5.80mmol) 'return to room -61 - 201226390 temperature, and allowed to react under nitrogen atmosphere for 6 hours to get poly-proline (pa A - 2) A solution having a concentration of 15% by mass. 15.0 g of this poly-proline (PAA-2) solution was transferred to a 50 mL Erlenmeyer flask, and 15.0 g of NMP and 7.50 g of BC were added and diluted to obtain a polyamine acid (PAA-2) of 6 mass%, and NMP was A solution of 74% by mass and bC of 20% by mass gave the liquid crystal alignment agent-2 of the present invention. The polyamino acid had an average molecular weight of 13,700 and a weight average molecular weight of 35,600. (Example 3) Synthesis of polyaminic acid using CBDA/Diamine-3 As a diamine component in a 50 mL four-necked flask, Diamine-3 obtained by Synthesis Example 3 was added to 1.50 g (5.8 0 mm). 1) 'NMP 14.3g, cooled to about 1 〇 ° C, added CBDA 1.02g (5.20mmol), returned to room temperature, and allowed to react under nitrogen atmosphere for 6 hours to obtain poly-proline (pa A - 3 ) A solution having a concentration of 15% by mass. 15.0 g of this polyaminic acid (PAA-3) solution was transferred to a 50 mL Erlenmeyer flask, and 15.0 g of NMP and 7.50 g of BC were added and diluted to obtain a polyamine acid (PAA-3) of 6 mass%, and NMP was A solution of 74% by mass and BC of 20% by mass gives the liquid crystal alignment agent-3 of the present invention. The polyamino acid had an average molecular weight of 11, and had a weight average molecular weight of 31,300. (Example 4) Synthesis of polyamino acid using CBDA/Diamine-4 In a 50 mL four-necked flask, Diamine-4 obtained in Synthesis Example 4 was added as a diamine component 1.50 g (6-25 mmol), NMP 15.0. g, cooled to about 10 ° C, added CBDA 1.14g (5.80mmol), returned to room -62- 201226390 temperature, and allowed to react under nitrogen atmosphere for 6 hours to obtain the concentration of poly-proline (PAA-4) 15% by mass solution. 15.0 g of this poly-proline (PAA-4) solution was transferred to a 50 mL Erlenmeyer flask, and 15.0 g of NMP and 7.50 g of BC were added and diluted to obtain a polyamine acid (PAA-4) of 6 mass%, and NMP was A solution of 74% by mass and BC of 20% by mass gives the liquid crystal alignment agent-4 of the present invention. The polyamino acid had a number average molecular weight of 14,200 and a weight average molecular weight of 3,600 » (Comparative Example 1) Synthesis of polyamino acid using CBDA/Diamine-5 in a 50 mL four-necked flask as a diamine component. Diamine-5 1 . 5 0 g (6.7 5 mmo 1) 'NMP 15.4g obtained by the synthesis of Comparative Example 1 was added. After cooling to about 10 ° C, CBDA 1.23 g (6.25 mmol) was added and returned to room temperature. The reaction was carried out for 6 hours under a nitrogen atmosphere to obtain a solution having a concentration of polyamine acid (p AA - 5 ) of 15% by mass. 15.0 g of this polyaminic acid (PAA-5) solution was transferred to a 50 mL Erlenmeyer flask. 'NMP 15.0 g and 7.50 g of BC were added and diluted to obtain a polyamine acid (PAA-5) of 6 mass%, and NMP was A solution of 74% by mass and BC of 20% by mass was obtained as a liquid crystal alignment agent-5 to be compared. The polyamine has a number average molecular weight of 1,2,300 and a weight average molecular weight of 32,100. (Example 5) Synthesis of soluble polyimine using CBDA/Diamine-1 and C16DAB In a 50 mL four-necked flask, Diamine-1 2 obtained by synthesizing -63-201226390 Example 1 was added as a diamine component. .OOg (8.88 mmol), C16DAB 0.774 g (2.22 mmol), NMP 27.2 g, cooled to about 10 ° C, added 1.81 g (10.3 mmol) of CBDA, returned to room temperature, and allowed to react under nitrogen for 6 hours. A solution having a concentration of polyamine acid (PAA-6) of 15% by mass was obtained. To 20 g of a polyaminic acid (PAA-6) solution, 30.0 g of NMP was added and diluted, and 2.19 g of acetic anhydride and 0.90 g of pyridine were added, and the reaction was carried out at 40 ° C for 3 hours. After the reaction solution was cooled to room temperature, it was slowly poured into 180 mL of methanol cooled to about 10 ° C while stirring to precipitate a solid. The precipitated solid was recovered, and further dispersed and washed twice in methanol (1 mL), and dried under reduced pressure at 100 ° C to obtain a micro-purple powder of polyimine (SPI-1). The polyimine had a number average molecular weight of 9,200 and a weight average molecular weight of 23,500. Further, the sulfhydrylation rate was 8 1%. 18.0 g of γ-BL was added to 2.00 g of polyimine (SPI-1), and the mixture was stirred at 50 ° C for 20 hours. The polyimine was completely dissolved at the end of the stirring. Further, 8.0 g of γ-BL and 12.0 g of BC were added to the solution, and the mixture was stirred at 50 ° C for 20 hours to obtain a polyamidimide (SPI-1) of 5% by mass and γ-BL of 6.5 mass%, BC. It is 30% by mass of the liquid crystal alignment agent-6. (Example 6) Synthesis of soluble polybendimimine using CBDA/Diamine-2, C 1 6DAB

In a 50 m L four-necked flask, Diamine-2 obtained by the synthesis of Example 2 was added as a diamine component, 2.00 g (8.36 mmol), C16DAB.

-64- 201226390 0.728g (2.09mmol) ' NMP 6.3g, cooled to about 10 ° C, force D into CBDA 1.90g (9.71mmol), returned to room temperature, and allowed to react under nitrogen atmosphere for 6 hours to obtain poly A solution of 15% by mass of proline (PAA-7). To 20 g of a polyaminic acid (PAA-7) solution, 30.0 g of NMP was added and diluted, and 2.12 g of acetic anhydride and 0.88 g of pyridine were added, and the reaction was carried out at 40 ° C for 3 hours. After cooling the reaction solution to room temperature, it was slowly poured into 160 mL of methanol cooled to about 10 ° C while stirring to precipitate a solid, and the precipitated solid was recovered, and further totaled in methanol 100 mL. The mixture was washed, and dried under reduced pressure at 100 ° C to obtain a micro-purple powder of polyimine (SP 1-2). The polyimine had a number average molecular weight of 9,800 and a weight average molecular weight of 24,200. Further, the sulfhydrylation rate was 80%. 18.0 g of γ-BL was added to 2.00 g of polyimine (SPI-2), and the mixture was stirred at 50 ° C for 20 hours. The polyimine was completely dissolved at the end of the stirring. Further, 8.0 g of γ-BL and 12.0 g of BC were added to the solution, and the mixture was stirred at 50 ° C for 20 hours to obtain phthalocyanine (SPI-2) of 5% by mass and γ-BL of 6.5 mass%, BC. It is 30% by mass of liquid crystal alignment agent·7. (Example 7) Synthesis of soluble polyimine using CBDA/Diamine-3 and C16DAB In a 50 mL four-necked flask, Diamine-3 obtained in Synthesis Example 3 was added as a diamine component. 2.00 g (7.47 mmol) C16DAB 0.65 1 g (1.87 mmol), NMP 24.7 g, cooled to about 10 ° C, and then poured into -65-201226390 CBDA 1.51 g (8.68 mmol), returned to room temperature, and allowed to react under nitrogen atmosphere 6 In an hour, a solution of a concentration of polyamine acid (PAA-8) of 15% by mass was obtained. To 20 g of a polyamine acid (PAA-8) solution, 30.0 g of NMP was added and diluted, and 2.00 g of acetic anhydride and 0.83 g of pyridine were added, and the reaction was carried out at 40 ° C for 3 hours. After the reaction solution was cooled to room temperature, it was slowly poured into 160 mL of methanol cooled to about 10 ° C while stirring to precipitate a solid. The precipitated solid was recovered, and further dispersed and washed twice in methanol (100 mL), and dried under reduced pressure at 100 ° C to obtain a micro-purple powder of polyimine (SPI-3). The polyimine had a number average molecular weight of 9,500 and a weight average molecular weight of 22,200. Further, the sulfhydrylation rate was 8 1%. 18.0 g of γ-BL was added to 2.00 g of polyimine (SPI-3), and the mixture was stirred at 50 ° C for 20 hours. The polyimine was completely dissolved at the end of the stirring. Further, 8.0 g of γ-BL and 12.0 g of BC were added to the solution, and the mixture was stirred at 50 ° C for 20 hours to obtain a bismuthimide (SPI-3) of 5% by mass and γ-BL of 6.5 mass%, BC. It is 30% by mass of the liquid crystal alignment agent-8. (Example 8) Synthesis of Soluble Polyimine Using CBDA/Diamine-4 and C16DAB Diamine-4 2.00 g (8.36 mmol) obtained in Synthesis Example 4 was added as a diamine component to a 50 mL four-necked flask. , C16DAB 0.728g (2.09mmol), NMP 6.3g, cooled to about 10 ° C, added 1.90g (9.71mmol) of CBDA, returned to room temperature, and reacted under the nitrogen atmosphere for 201226390 for 6 hours to obtain polydecylamine. A solution of 15% by mass of acid (PAA-8). To 20 g of a polyproline (PAA-8) solution, 30.0 g of NMP was added and diluted, and 2.12 g of acetic anhydride and .88 g of pyridinium were added, and the reaction was allowed to proceed at 40 ° C for 3 hours. After cooling the reaction solution to room temperature, it was slowly poured into 180 mL of methanol which had been cooled to about 10 ° C while stirring to precipitate a solid, and the precipitated solid was recovered, and further totaled in methanol 100 mL. The mixture was washed, and dried under reduced pressure at 100 ° C to obtain a micro-purple powder of polyimine (SPI-4). The polyimine has a number average molecular weight of 10,200 and a weight average molecular weight of 28,900. Further, the sulfhydrylation rate was 82%. 18.0 g of γ-BL was added to 2.00 g of polyimine (SPI-4), and the mixture was stirred at 50 ° C for 20 hours. The polyimine was completely dissolved at the end of the stirring. Further, 8.0 g of γ-BL and 12.0 g of BC were added to the solution, and the mixture was stirred at 50 ° C for 20 hours to obtain phthalocyanine (SPI-4) of 5% by mass and γ-BL of 65% by mass. 30% by mass of liquid crystal alignment agent-9. (Comparative Example 2) Synthesis of Soluble Polyimine Using CBDA/Diamine-5 and C16DAB Diamine-5 2.00 g (8.96 mmol) obtained in Synthesis Comparative Example 1 was added as a diamine component to a 50 mL four-necked flask. ), C16DAB 0.78 1 g (2.24 mmol), NMP 27.3 g, cooled to about 10 ° C, added CBDA 2.04 g (10.4 mmol), returned to room temperature, and allowed to react under nitrogen for 6 hours to obtain polydecylamine. The concentration of the acid (PAA-9) is 15% by mass of the solution -67-201226390. 30.0g of NMP was added to 20g of polylysine (PAA-9) solution for dilution, and 2.20g of acetic anhydride and .91g of pyridinium were added to react at 40 ° C, but gelation started after a little time. It became impossible to stir. Unable to modulate soluble polyimine (SPI-5). Therefore, the liquid crystal alignment agent -1 〇 of the comparison object cannot be prepared. (Example 9) <Synthesis of polyaminic acid using CBDA/Diamine-1 and DDM> Diamine-1 2.50 g obtained in Synthesis Example 1 was added as a diamine component in a 50 mL four-necked flask ( Ll.lmmol), DDM 0.943g (4_77mmol), NMP 17.9g, γ-BL 17.9g, cooled to about 10 ° C, added CBDA 2.89g (14.8mmol), returned to room temperature, and under nitrogen atmosphere After reacting for 6 hours, a solution of a concentration of polyamine acid (PAA-10) of 15% by mass was obtained. 30.0 g of this polyaminic acid (PAA-10) solution was transferred to a 100 mL Erlenmeyer flask, and NMP 28.0 g, γ-BL 2.20 g, and BC 15.0 g were added and diluted to prepare polyglycine (PAA-10). A solution of 6 mass%, NMP of 54% by mass, γ-BL of 20% by mass, and BC of 20% by mass gave a polylysine solution (BL-PAA1) for blending. The polyamine had a number average molecular weight of 10,400 and a weight average molecular weight of 29,100. <Synthesis of Soluble Polyimine of C16DAB Using TDA/p-PDA>

In a 50 mL four-necked flask, p-PDA 2.00 g (1 8.5 mmol) of 'C16DAB 0.7 1 8 g (2.0 6 mm ο 1), NMP-68-201226390 3 5.4 g was added as a diamine component, and cooled to about At 10 ° C, 6.12 g (20.4 mmol) of TDA was added, and the reaction was carried out at 40 ° C for 20 hours under a nitrogen atmosphere to obtain a solution of a concentration of polyglycine (paA-15) of 20% by mass. To 40.0 g of a polyaminic acid (PAA-15) solution, 93.3 g of NMP was added for dilution, and 9.51 g of acetic anhydride and 7.36 g of pyridine were added, and the reaction was allowed to proceed at 40 ° C for 3 hours. After the reaction solution was cooled to room temperature, it was slowly poured into 500 mL of methanol which had been cooled to about 10 ° C while stirring to precipitate a solid. The precipitated solid was recovered, and further dispersed and washed twice in 300 mL of methanol, and dried under reduced pressure at 100 ° C to obtain a white powder of polyimine (SP 1-6). The polyimine had a number average molecular weight of 9,500 and a weight average molecular weight of 20,900. Further, the sulfhydrylation rate was 85%.

80.5 g of γ-BL was added to 7.00 g of polyimine (SPI-6), and the mixture was stirred at 50 ° C for 20 hours. The polyimine was completely dissolved at the end of the stirring. Further, 29.2 g of γ-BL was added to the solution, and the mixture was stirred at 50 ° C for 20 hours to obtain a solution of a solution of phthalocyanine (SP 1-6) of 6 mass% and γ-BL of 94 mass%. Polyimine solution (BL-SPI). <Preparation of blended liquid crystal alignment agent> 40 g of the prepared polyglycine solution (BL-PAA1) was separately weighed into a 200 mL Erlenmeyer flask, and the prepared polyimine solution for blending was added. (BL-SPI) 10 g of Og was stirred under a nitrogen atmosphere for 20 hours to obtain a blended liquid crystal alignment agent BL-1. (Example 1 0) -69-201226390 <Synthesis of Polylysine Using CBDA/Diamine-2 and DDM> In a 50 mL four-necked flask, the synthesis example 2 was added as a diamine component. Diamine-2 2.50g (10. 4mmol), DDM 0.887g (4.47mmol), NMP 17.3g, γ-BL 17.3g, cooled to about 10 ° C, added CBDA 2.7 2g (13.9mmol), returned to room temperature after The reaction was allowed to proceed for 6 hours under a nitrogen atmosphere to obtain a solution of a polyamine acid (PAA-1 1 ) concentration of 15 mass%. 30.0 g of this polyaminic acid (PAA-11) solution was transferred to a 100 mL Erlenmeyer flask, and NMP 28.0 g, γ-BL 2.20 g, and BC 15.0 g were added and diluted to prepare polylysine (PAA-11). A solution of 6 mass%, NMP of 54 mass%, γ-BL of 20 mass%, and BC of 20 mass% was obtained, and a polylysine solution (BL-PAA2) for blending was obtained. The polyamine has a number average molecular weight of 11,200 and a weight average molecular amount of 31,000. <Preparation of blended liquid crystal alignment agent> 40 g of the prepared polyglycine solution (BL-P A Α 2) was separately weighed into a 200 mL Erlenmeyer flask, and was added in the same manner as in Example 9. The blended polyimine solution (BL-SPI) of the method was stirred for 20 hours under a nitrogen atmosphere to obtain a blended liquid crystal alignment agent BL-2. (Example 11) <Synthesis of polyaminic acid using CBDA/Diamine-3 and DDM> Diamine-3 2.50 g obtained in Synthesis Example 3 was added as a diamine component in a 50 mL four-necked flask. (9.35 mmol), DDM 0.794 g (4.01 mmol), NMP 16.2 g, γ-BL 16.2 g, cooled to about

-7〇- S 201226390 l〇°C 'Add 2.43g (12.4mmol) of CBDA, return to room temperature and react for 6 hours under nitrogen atmosphere to obtain the concentration of poly-proline (pa A-12) 15% by mass. Solution. 30.0 g of this polyaminic acid (PAA-12) solution was transferred to a 100 mL Erlenmeyer flask, and NMP 28.0 g, γ-BL 2.20 g, and BC 15.0 g were added for dilution to prepare polyglycine (PAA-12). A solution of 6 mass%, NMP of 54% by mass, γ-BL of 20% by mass, and BC of 20% by mass gave a polylysine solution (BL-P A A3) for blending. The polyamine has a number average molecular weight of 1,3,600 and a weight average molecular weight of 36,000. &lt;Preparation of blended liquid crystal alignment agent&gt; The prepared blended polylysine solution (BL-PAA3) was separately weighed 4 〇g in a 200 mL Erlenmeyer flask, and the same method as in Example 9 was used. The prepared blended polyimine solution (BL-SPI) 10 Og was stirred under a nitrogen atmosphere for 20 hours to obtain a blended liquid crystal alignment agent BL-3. (Example 12) &lt;Synthesis of polyaminic acid using CBDA/Di amine-4 'DDM&gt; In a 50 mL four-necked flask, Diamine-4 2.50 g obtained in Synthesis Example 4 was added as a diamine component. (10.4mmol), DDM O.88 7g (4.47mmol), NMP 17.3g, γ-BL 17.3g, cooled to about 10 ° C, added 2.72g (13.9mmol) of CBDA, returned to room temperature after nitrogen atmosphere The reaction was allowed to proceed for 6 hours to obtain a solution of a polyamine acid (PAA-13) concentration of 15% by mass. 30.0 g of this polyaminic acid (PAA-13) solution was transferred to a 100 mL triangle-71 - 201226390 flask, and NMP 28.0 g, γ-BL 2.20 g, and BC 15.0 g were added for dilution to prepare polylysine (PAA). -13) A solution of 6 mass%, NMP of 54 mass%, γ-BL of 20 mass%, and BC of 20 mass%, and a polylysine solution (BL-P A A4) for blending was obtained. The polyamine has a number average molecular weight of 1,2,500 and a weight average molecular weight of 30,800. &lt;Preparation of blended liquid crystal alignment agent&gt; 40 g of the prepared polyglycine solution (BL-P A A4) was separately weighed into a 200 mL Erlenmeyer flask, and the same method as in Example 9 was used. The prepared blended polyimine solution (BL-SPI) 10 Og was stirred under a nitrogen atmosphere for 20 hours to obtain a blended liquid crystal alignment agent BL-4. (Comparative Example 3) &lt;Synthesis of polyaminic acid using CBDA/Diamine-5 and DDM&gt; In a 50 mL four-necked flask, D iami n+e obtained by synthesizing Comparative Example 1 was added as a diamine component. 5 2 · 50 g (1 1 · 2 mm ο 1) , DD Μ 0.952 g (4.80 mmol), NMP 18.1 g, γ-BL 18.1 g, cooled to about 10 ° C, and added CBDA 2.92 g (14.9 mmol) After returning to room temperature, the reaction was allowed to proceed for 6 hours under a nitrogen atmosphere to obtain a solution of a polyamine acid (PAA-14) concentration of 15% by mass. 30.0 g of this polyaminic acid (PAA-14) solution was transferred to a 100 mL Erlenmeyer flask, and NMP 28.0 g, γ-BL 2.20 g, and BC 15.0 g were added and diluted to prepare polylysine (PAA-14). A solution of 6 mass%, NMP of 54% by mass, γ-BL of 20% by mass, and BC of 20% by mass gave a polylysine solution (BL-PAA5) for blending. The polyamino acid had a number average molecular weight of -72 to 201226390 of 13,600 and a weight average molecular weight of 37,700. &lt;Preparation of blended liquid crystal alignment agent&gt; 40 g of the prepared polyglycine solution (BL-P A A4) was separately weighed into a 200 mL Erlenmeyer flask, and was added in the same manner as in Example 9. The blended polyimine solution (BL-SPI) of the method was stirred for 20 hours under a nitrogen atmosphere to obtain a blended liquid crystal alignment agent BL-5. (Example 13) <PAE for blending> 6.35 g (24.4 mmol) of CBDE and 250 g (23.1 mmol) of p-PDA as a diamine component, C16DAB 0.8 96 g (2.57 mmol), NMP were added to a 100 mL four-necked flask. 71,5g, triethylamine oxime. 60g (5.90mmol) « Cooled to about 10 ° C, added DMT-MM 21.3g (77.1mm 〇l), returned to room temperature and allowed to react under nitrogen atmosphere for 24 hours. A solution having a concentration of polyacetate (PAE-1) of 12% by mass was obtained. To the polyacetic acid (PAE-1) solution, 81.2 g of NMP was added, and while stirring, the mixture was slowly poured into 1.0 L of methanol which had been cooled to about 1 Torr to precipitate a solid. The precipitated solid was recovered, and further washed with a total of 500 mL of methanol for 2 times, and dried under reduced pressure at 10 ° C to obtain a white powder of polyamine (PAE-1). The polyperurethane had a number average molecular weight of 12,300 and a weight average molecular weight of 27,000. To the 7.00 g of the polyperurate (PAE-1), 80.5 g of γ-BL was added, and the mixture was stirred at 5 ° C for 20 hours. The polyimine was completely dissolved at the end of the stirring. Further, 29.2 g of γ-BL was added to the solution, and 5 (TC agitation of 20 -73 to 201226390 hours) was used to prepare a solution in which the polyglycolate (PAE-1) was 6 mass% and the γ-BL was a quantity %. A blending polyglycolate solution (BL-PAE) was obtained. &lt;Preparation of blended liquid crystal alignment agent&gt; A blended proline solution (BL) prepared in the same manner as in Example 9. -PAA1) Weigh 40g of the prepared polyglycolate solution (BL-PAE) lO.Og in a 200 mL Erlenmeyer flask, and stir for 20 hours under an atmosphere to obtain a blended liquid crystal alignment agent BL-6. (Example 14) 40 g of a blended polyamidoguanidine (BL-PAA2) prepared in the same manner as in Example 10 was weighed and placed in a 200 mL Erlenmeyer flask, and a blending polyamine prepared in the same manner as that of f 13 was added. The ester solution (BL 10.〇g, stirred under a nitrogen atmosphere for 20 hours to obtain a blending liquid | Agent BL-7. (Example 15) Polyamine prepared for blending in the same manner as in Example 11 S (BL-PAA3) was weighed and weighed 40 g in a 200 mL Erlenmeyer flask, and a blending polyglycolate solution (BL 10.·〇g, stirred under a nitrogen atmosphere for 20 hours) was added in the same manner as that of f 13 . Blending the liquid wicking agent BL-8. (Example 1 6) The blending polyamine 94 having the same preparation as in Example 12 was added to a nitrogen solution. Example P AE) Alignment solution (PAE) The alignment solution-74-201226390 (BL-ΡΑΑ4) was weighed and weighed 4 〇g in a 200 mL Erlenmeyer flask, and a blending polyamine solution (BL-PAE) prepared in the same manner as in Example 13 was added. The mixture was stirred for 20 hours under a nitrogen atmosphere to obtain a blended liquid crystal alignment! IBL - 9 〇 (Comparative Example 4) A blending polylysine solution (BL-PAA5) scale prepared in the same manner as in Comparative Example 3 was used. 40 g of a polyacetate solution (BL-PAE) prepared in the same manner as in Example 13 was added to a 200 mL Erlenmeyer flask, and the mixture was stirred for 20 hours under a nitrogen atmosphere to obtain a blended liquid crystal. The alignment agent BL-10 (Comparative Example). (Test Example 1) Varnish (Liquid Crystal Alignment Agent) Printability Test Using the alignment film prepared by using the liquid crystal alignment agents prepared in Examples 1 to 16 and Comparative Examples 1 to 4 Machine ("angstromer" manufactured by Nippon Photo Printing Co., Ltd.) performs quick-drying printing on a washed Cr plate for coating. Approximately 1. OmL of the liquid crystal alignment agent was dropped on the anilox roller, and after 10 runs were performed, the printing machine was stopped for 1 minute to dry the printing plate. Then, one piece of the Cr substrate was printed. The substrate was placed on a hot plate at 70 ° C for 5 minutes to perform pre-drying of the coating film and the film state was observed. The observation was carried out by visual observation and optical microscopy ("ECLIPSE ME600" manufactured by Nikon Corporation) at 50 times. When the pinhole was not observed, it was good, and when the pinhole was observed, it was bad; and when the film thickness of the edge portion was not uneven, it was good, and when the film thickness at the edge portion was uneven, it was evaluated as -75-201226390. . The results are shown in Table 3. [Production of Liquid Crystal Cell] The liquid crystal alignment agents prepared in Examples 1 to 16 and Comparative Examples 1 to 4 were prepared as follows. The liquid crystal alignment agent was spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at 80 ° C for 70 seconds, and then calcined on a hot plate of 22 (TC) for 10 minutes. A coating film having a film thickness of 1 〇〇nm was formed. Regarding the liquid crystal alignment treatment by rubbing, the coating film surface was rubbed with a roll diameter of 120 mm, and the roll was rotated at a number of 100 rpm and the roll traveling speed was 50 mm/sec. The substrate having the liquid crystal alignment film was obtained by rubbing under the condition of a pressure of 33 mm. A substrate having a liquid crystal alignment film having such a liquid crystal alignment treatment was prepared, and a spacer of 6 μm was dispersed therein. After the liquid crystal alignment film of the film is applied to the film surface, the sealing agent is printed thereon, and the other substrate is bonded to the substrate with the liquid crystal alignment film surface and the rubbing direction is orthogonal (ΤΝ-type liquid crystal cell). The sealing agent is hardened to form an empty cell. The empty cell is injected into the liquid crystal MLC-2〇〇3 (manufactured by Mok Corporation) in the case of a ruthenium type cell, and the injection port is sealed. A ΤΝ-type liquid crystal cell was obtained. (Test Example 2) Before high temperature aging test Determination of post ion density

The liquid crystal cell produced by the method described in the above [Production of Liquid Crystal Cell] was measured for ion density in an initial state, and ion density was maintained at 100 ° C -76 - 201226390 for 30 hours (high temperature aging). Determination. In the ion density measurement, the ion density when a triangular wave having a voltage of ±10 V and a frequency of 0.01 Hz was applied to the liquid crystal cell was measured. The measurement temperature was 8 (TC). The measurement device used was a 6 2 4 5 liquid crystal physical property evaluation device manufactured by TOYO Corporation. The results are shown in Table 3. (Test Example 3) Before and after the high temperature aging test Storage charge (RDC) measurement For the prepared liquid crystal cell, the DC voltage was applied from 0 V to 1.0 V at a temperature of 23 ° C at a temperature of 23 ° C, and the flicker amplitude level at each voltage was measured to prepare a flicker amplitude. The calibration line with the applied DC voltage. After 5 minutes of grounding, the external voltage (V5Q) and the DC voltage of 5.0 V ' when the applied luminance is half is measured, and the flashing amplitude level is measured after 1 hour. The calibrated action of the calibration curve is used to estimate RD C (flicker reference method). After that, the DC voltage is made 0V, and the RDC is calculated by the same method to determine the relaxation of RDC. How will it be measured? The RDC is shown in the column of “DCon lh (storage) and RDC (mitigation) after DCoff l〇min in Table 3. 尙, the data of RDC shown in Table 3 is to set the liquid crystal cell to 1 〇0. °C for 30 hours (high temperature aging) (Test Example 4) Evaluation of the alignment property The observed liquid crystal cell was visually observed, and the alignment state of the liquid crystal was observed. When the liquid crystal was in a defect-free alignment, it was good; when an alignment defect was generated, it was defective. The results are shown in Table 3. -77-201226390 As a result, Examples 1 to 4 and Comparative Example 1 were evaluated as a homopolymer (polyglycine) of a diamine and CBDA, but compared with the unused Comparative Example 1 of the diamine compound of the invention, the storage of RDCs of Examples 1 to 4 using the diamine compound of the present invention (RDC値 after DCon 1 time) and relaxation (RDC値 after DCoff 10 minutes) were remarkably small Further, since it is a single polylysine, a large difference is not confirmed in printability; compared with Comparative Example 1, the initial state of Examples 1 to 4 and the ion density after high temperature aging are both small, practically Then, in Examples 1 to 4, the liquid crystal was aligned without defects, but in Comparative Example 1, the liquid crystal was defective, and the alignment was inferior to those in Examples 1 to 4. Examples 5 to 8 and Comparative Example 2 is used as an evaluation of soluble polyimine In the case of Examples 5 to 8 of the diamine of the invention, soluble polyimine was produced, and phase separation or precipitation at the time of printing was not produced, and pinholes and film unevenness were not obtained, and the printability was good. In Examples 5 to 8, the storage and relaxation of RDC were both remarkably small. Then, the ion density after the initial state and high temperature aging was small, which was practically no problem. On the other hand, Patent Document 3 diamine was used. In Comparative Example 2 of Diamine-5, soluble polyimine was not produced. Further, in Examples 5 to 8, the liquid crystal was aligned without defects. Examples 9 to 12 and Comparative Example 3 were soluble polyimine and used. In the evaluation of the blending material of the polyamine of the diamine of the present invention, since the diamine of the present invention is excellent in compatibility with the soluble polyimine, it is not produced in the liquid crystal alignment agents of Examples 9 to 12. The phase separation or precipitation at the time of printing does not cause pinholes and film unevenness, and the printability is good. On the other hand, in Comparative Example 3 -78 to 201226390, the soluble polyimine was localized and separated from the poly-proline, and was separated in the printing test, and the printability at the edge portion was poor. Further, in Examples 9 to 12, the storage and relaxation of the RDC were remarkably small as compared with Comparative Example 3. Then, compared with Comparative Example 3, the initial state of Examples 9 to 12 and the ion density after high temperature aging were small, which was practically no problem. Further, the liquid crystals of any of Examples 9 to 12 were aligned without defects. Examples 13 to 16 and Comparative Example 4 are evaluations of a blending material of a polyglycolate and a polyamine having a diamine of the present invention because of the phase of the diamine of the present invention and a polyphthalate. Since the solubility is excellent, in the liquid crystal alignment agents of Examples 13 to 16, no phase separation or precipitation at the time of printing occurred, and pinholes and film unevenness were not obtained, and the printability was good. On the other hand, in the case of the liquid crystal alignment agent of Comparative Example 4, as in Comparative Example 3, the phase separation property was poor, and there was a tendency to separate during printing, and the printability at the edge portion was poor. Further, in Examples 13 to 16, the storage and relaxation of the RDC were remarkably smaller than in Comparative Example 4. Then, compared with Comparative Example 4, the initial state of Examples 13 to 16 and the ion density after high temperature aging were both small, which was practically no problem. Further, the liquid crystals of any of Examples 1 to 3 were aligned without defects. As a result of the above, it was confirmed that the liquid crystal alignment agent and the liquid crystal alignment film of the diamine of the present invention are excellent in printability, and a liquid crystal alignment film having a small storage charge and a relaxed charge charge can be obtained. -79 - 201226390 [Table 1] Polymer name Acid dianhydride or acid diester diamine component PM-1 CBDA (0.93) Diarriine-l (l.OO) —— PAA-2 CBDAC0.93) Dianiine-2 (1.00 ) PAA-3 CBDA (0.93) Diamine-3 (1.00) — PAA-4 CBDA (0.93) Dkrine^l.OO) . — PM-5 CBDA (0.93) Dianiine-5(1.00) — SR-1 CBDA ( 0.93) Dianiine-1(0.80) C16DAB(0.3 SR-2 CBDA(0.93) Diamine-2(0.80) C16DAB(0.^ SR-3 CBDA(0.93) Diamine-3(0.80) C16DAB(0.2) SFM CBDA(0.93 Diairin&amp;-4(0.80) C16DAB(0.^ SH-5 CBDA(0_93) Diamine-5(0.90) C16DAB(0.1) PAA-10 CBDA(0.93) Diamine-1(0.70) DDM(0.30) PAA-11 CBDA(0.93) Dkmin&amp;*2(0.70) DDM(0.30) PM-12 CBDA(0.93) Diamin&amp;-3(0.70) DDM(0.30) PM-13 CBDA(0.93) Diarnine-4(〇.7〇) DDM (0.30) PM-14 CBDA (0.93) Diamine-5 (0.70) DDM (0.30) SPI-6 TDA (0.99) p-PDA (0.90) C16DAB (0.1) PAE-1 CBDH0.95) p-PDA (0.90) C16DAB(0.1) *In the brackets, it is shown as a molar ratio. -80- 201226390 [Table 2] Liquid crystal alignment agent polymer component solvent (% by mass) Solid content (%) Example 1 1 PAA-1 NMPC740) BCC20.0 ) - 6.0 Example 2 2 PM-2 NMPC74.0) BCX20.0) - 6.0 Example 3 3 PM-3 NMK74.0) BC(20.0) - 6.0 Example 4 4 PAA-4 NMPC740) BC(2〇.〇) - 6.0 Comparative Example 1 5 PM -5 NMPC74.0) BC(20.0) - 6.0 Example 5 6 SPI-1 v-BU65.0) BC(30.0) - 5.0 Example 6 7 SH-2 V-Hi65.0) BCOO-O) - 5.0 Example 7 8 SR-3 v-Hj(65.0) BC(30.0) - 5.0 Example 8 9 SPI-4 y-BL(65.0) BCX3a〇) - 5.0 Comparative Example 2 10 Yin-5 Unable to adjust Example 9 BL -1 PM-KX0.80) SH-6(0.20) NMP(43.2!) 7-BU348) Bcaao) 6.0 Example 10 BL-2 PAA-lKO.80) SK〇_20) NMP (43.2J 7-BLC34 .8) Bcaao) 6.0 Example 11 KL-3 PM-12C0.80) SR-6(0.20) NMP(43.2!) 7-^(34.8) BO16.0) 6.0 Example 12 BL-4 PM-13( 0.80) ^-6(0.20) NMK43.25 γ-BU34.8) Bai6.0) 6.0 Comparative Example 3 BL-5 PM-14(0.80) SR-6(020) NMP(43.2) 7-BU34.8) Bcaao) 6.0 Example 13 BL-6 PAA-KX0.80) PAE-K0.20) NMPC43.25 T^L(34.8) Bai6.0) 6.0 Example 14 BL-7 PAA-lKO.80) PAE-1 (0^0) NMK43.2) 7-BU34.8) BC(16.0) &0 Example 15 BL-8 PAA-12(0.80) PAE-K0.20) NMK43.2D 7—BU34.8) Bcaao 6.0 Example 16 BL-9 PAA-13 (0.8 0) PAE-KO20) NMP (43.^ 7—BLj(34.8) BC(16.0) 6.0 Comparative Example 4 BL-10 PM-14(0.80) PAE-K0.20) NMF&lt;43.^ 7^BU34.8 ) Bcaao) 6.0 * The brackets are shown as Moerby. -81 - 201226390 m 3] Liquid crystal alignment printable ion density (pC) RDC(V) 100X: 30h After the pinhole edge film thickness is uneven Initial Loot: After 30 h DCon lh (storage) DCoff lOmin (moderate) Example 1 Good Good Good 68 92 0.25 0 Example 2 Good Good Good 58 87 0.25 0 Example 3 Good Good m 59 86 0.27 0 Example 4 Good mm 62 86 0.23 0 Comparative Example 1 Bad mm 75 96 0.60 0.32 Example 5 Good mm 44 55 0.30 0 Example 6 Good mm 43 57 0.28 0 Example 7 Good good good 52 56 0.31 0 Example 8 mmm 49 54 0.28 0 Comparative Example 2 Failure to act as a unit cell Example 9 鲥mm 45 76 0.18 0 Example 10 m Good m 43 72 0.20 0 Example 11 mmm 43 78 0.18 0 Example 12 Good mm 41 79 0.20 0 Comparative Example 3 Poor bad Xiang Xiang bad Xiang _ 56 92 .0.44 0.23 Example 13 Good m Good 55 87 0.22 0 Example 14 m mm m 53 82 0.21 0 Example 15 mmm 52 90 0.23 0 Example 16 Good mm 53 89 0.22 0 Comparative Example 4 Adverse failure 62 103 0.45 0.18 [Industrial Applicability] With the liquid crystal alignment agent of the diamine of the present invention, the printability is good, and a liquid crystal alignment film having a small storage charge and a moderate relaxation of stored charges can be obtained. Therefore, the liquid crystal display element produced by using the liquid crystal alignment agent of the present invention can be used as a highly reliable liquid crystal display device, and is suitably used for a TN (Twisted Nematic) liquid crystal display element, an STN liquid crystal display element, a TFT liquid crystal display element, and a VA liquid crystal. A display element, an IPS liquid crystal display element, an OCB (Optically sel f-Compensated Birefringence) liquid crystal display element, or the like is represented by various means. -82-

Claims (1)

201226390 VII. Application for Patent Park 1. A diamine characterized by the following formula [1] [Chemical 1] Re (In the formula [1], two of Ri to R9 are a 1-stage amine group', and the residue is a hydrogen atom or a monovalent organic group other than the amine group, which may be the same or different, and η is · 1 or 2'. The hydrogen atom of the saturated hydrocarbon moiety of the ring may be substituted by a halogen atom or a monovalent organic group other than the amine group). 2. If you apply for the diamine in the first paragraph of the humiliation range, it is as shown in the following formula [2], [Chemical 2] (In the formula [2], 'ρ is an integer of &amp; Q~3, and R1Q is a one-valent organic group other than an amine group' -(R丨❶)n pentad $ is a substituent having R, . And may be the same or different 'q show ® Λ 0 〇 ~ 4 integer, Rn is shown as a one-valent organic group other than the amine group, _ (RX ~ $ has q substituents Rll, and can be the same respectively Or different, η is 1 or 2, and the hydrogen atom forming the saturated hydrocarbon moiety of the ring may be -83-201226390 substituted by an organic group other than a halogen atom or an amine group.) 3. As claimed in the second item of claim 2 An amine, which is represented by the following formula [3], [Chemical 3] (In the formula [3], η is 1 or 2, m is an integer of 0 to 2 (η+1), R12 is a one-valent organic group other than a fluorine atom or an amine group, and _(R12)m is shown to have m Substituents R i 2, and may be the same or different, respectively. 4. The diamine of claim 3, wherein R12 is a hydrocarbon group having 1 to 6 carbon atoms. 5. The diamine of claim 4, wherein R12 is a methyl group. 6. For the diamine of claim 1, the n=1. 7. For the application of the diamine of the first paragraph of the patent, which is represented by the following formula Μα] ~ [4-d], -84- 201226390 [Chemical 4] A polyimine precursor which is obtained by reacting at least one selected from tetradecanoic acid and a derivative thereof with a diamine component containing a 1 g 2 1 amine of the patent application. 9. If the patented range 8th polyimide precursor, the towel, the total molar amount of the tetracarboxylic acid and its derivative is set to 100 mol%, the patent range of the first item of the diamine It is 5 to 95% by mole. 1 0. A polyimine which is obtained by imidating a polybendimimine precursor of claim 8 of the patent application. 1 1 · A liquid crystal alignment agent characterized by comprising a polyimine precursor of the patent application model 8; a polyfluorene precursor of claim 9 and a patent application scope 10 At least one selected from the group consisting of polyimides. A liquid crystal alignment film which is obtained by coating and calcining a liquid crystal alignment agent of the stomach of the patent application in a substrate. 13. A liquid crystal display device is characterized in that it has a liquid crystal alignment film which is applied for the 12th item. -85- 201226390 IV. Designated representative map: (1) The representative representative of the case is: No (2) The symbol of the symbol of the representative circle is simple: No 201226390 If there is a chemical formula in the case, please disclose the chemical formula that best shows the characteristics of the invention. :no