TW201030059A - Liquid crystal aligning agent - Google Patents

Abstract

Provided is a liquid crystal aligning agent capable of forming a liquid crystal alignment film the surface of which is rarely scratched or abraded when rubbed, and which exhibits excellent liquid crystal aligning properties and enables the production of liquid crystal cells having high voltage holding ratios and low ion densities. The liquid crystal aligning agent contains either a polyimide precursor or a polyimide, said polyimide precursor and polyimide being substances obtained by reacting a diamine component with a tetracarboxylic acid derivative. The liquid crystal aligning agent is characterized in that the diamine component contains a diamine represented by formula (1) [wherein X is an oxygen atom or a sulfur atom; Y1 and Y2 are each independently a single bond, -O-, -S-, -OCO-, or -COO-; and R1 and R2 are each independently a C1-3 alkylene group].

Description

201030059 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a liquid crystal alignment treatment agent for producing a liquid crystal alignment film. In particular, the present invention relates to a liquid crystal alignment treatment agent used in a liquid crystal alignment film produced by a rubbing treatment step. [Prior Art] The liquid crystal alignment film is a phase difference plate of a liquid crystal display element or a polymerizable liquid crystal, and is used to control the alignment direction of liquid crystal molecules to form a film. The method of simply forming a liquid crystal alignment film is formed on a substrate. A polymer film such as polyimine which is rubbed on the surface by a cloth and subjected to a so-called rubbing treatment is widely used in the industry. The rubbing treatment generates dust due to grinding of the liquid crystal alignment film or scratches the liquid crystal alignment film, and there is a problem that the display quality is lowered. Therefore, one of the characteristics required for the liquid crystal alignment β film is friction resistance. A method of obtaining a liquid crystal alignment film which is hard to cause a rubbing scratch or a rubbing flaw is known as a method of adding various additives to a polyimide or a polyimide precursor (see, for example, Patent Documents 1 and 2). Further, a polyimine structure having excellent friction resistance has been proposed (see, for example, Patent Documents 3 and 4). In recent years, the use of one of the liquid crystal display elements has a tendency to be rubbed with more friction. By performing a strong rubbing treatment, the purpose is to make the liquid crystal alignment state more uniform and stronger. Accordingly, the requirements relating to the frictional resistance of the liquid crystal to the film -5 - 201030059 are also high. CITATION LIST PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT DISCLOSURE OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION An object of the present invention is to provide a liquid crystal alignment treatment agent which can obtain a liquid crystal alignment film which is less likely to cause friction scratches or rubbing scratches and which is excellent in friction resistance. [Means for Solving the Problem] The present inventors have actively studied the above-mentioned objects, and found that a novel liquid crystal alignment treatment agent capable of obtaining a liquid crystal alignment film excellent in friction resistance is completed by the present invention based on the above findings. The following points are as follows: 1. A liquid crystal alignment treatment agent which is a liquid crystal alignment treatment agent containing any one of a polyimine precursor obtained by reacting a diamine component with a tetradecanoic acid derivative or a polyimine. The above diamine component contains a diamine represented by the following formula (1): -6 - 201030059 [Chemical Formula 1]

(In the formula (1), X is an oxygen atom or a sulfur atom, and Y1 and Y2 are each independently a single bond '-S_, -OCO- or -COO-, and R1 and R2 are each independently a C 1 to 3 alkylene group. ). 2. The liquid crystal alignment treatment agent according to Item 1, wherein the formula (1 ❹ ) has the same structure as -R2_Y2_. 3. The liquid crystal alignment treatment agent according to the above item 1, wherein Y1 and Y2 in the formula (1) are a single bond. The liquid crystal alignment treatment agent according to any one of the above items 1 to 3 wherein X in the formula (1) is an oxygen atom. The liquid crystal alignment treatment agent according to any one of the above items 1 to 4, wherein the tetracarboxylic acid derivative is tetracarboxylic dianhydride, tetracarboxylic acid monoanhydride 'φ tetracarboxylic acid, dicarboxylic acid II An alkyl ester or a dicarboxy chlorodialkyl ester. The liquid crystal alignment agent according to any one of the above items 1 to 5, further comprising a fluorine-based surfactant, a ruthenium-based surfactant or a non-ionic surfactant. The liquid crystal alignment treatment agent according to any one of the above items 1 to 6, which further contains a functional decane-containing compound or an epoxy group-containing compound. The liquid crystal alignment agent of the liquid crystal alignment treatment agent, wherein the solid content concentration in the liquid crystal alignment treatment agent is U0% by mass based on the total amount (100% by mass) of the liquid crystal alignment treatment agent. A liquid crystal alignment film obtained by the liquid crystal alignment treatment agent according to any one of items 1 to 8 above. A liquid crystal display device characterized by comprising the liquid crystal alignment film of the above item 9. A bisaminophenylalkylurea or a bisaminophenoxyalkylurea which is represented by the following formula (1-7), formula (1-8), formula (Ι-b) or formula (1) C) means: [Chemical 2].

Η Η

(In the formula (Ι-b), R12 and R22 each represent an alkylene group having a carbon number of 1 to 3, and in the formula (1-c), R13 and R23 are each independently a carbon number of 1 to 3) . 12. A bisaminophenylalkylurea or a bisaminophenoxyalkylurea, -8 - 201030059

According to the liquid crystal alignment agent of the present invention, it is possible to reduce scratches or scratches on the surface of the film during the rubbing treatment, and to obtain a liquid crystal alignment film having good liquid crystal alignment. Further, the liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent of the present invention has a high voltage holding ratio of the liquid crystal cell and a low ion density, so that a high quality liquid crystal display element can be produced. [Embodiment] <Specific Diamine Compound> The liquid crystal alignment treatment agent of the present invention contains a polyimine precursor such as polyglycolic acid or polyglycolate or a polyimine which is characterized by the following formula ( 1) A diamine component represented by a specific diamine as a raw material for its synthesis: • 9 - (1) 201030059 [Chemical 4]

In the formula (1), 'X is an oxygen atom or a sulfur atom, and γ1 and γ2 are each independently a single bond, -0-, -S-, -OCO- or -COO-', and R1 and R2 are each independently a carbon number of 1 to 3. The alkyl group. In the formula (1), when X is an oxygen atom, it is a ureido group. When it is a sulfur atom, it is a thiourea group (hereinafter, a ureido group and a thiourea group are collectively referred to as a (thio)ureido group). ® Oxygen and sulfur atoms are atoms with high electrical negativeity. Further, there are two electron-donating hydrogen atoms on the nitrogen atom. Accordingly, the oxygen or sulfur atom of the (thio)urea group is relatively self-aggregated by non-covalent bonding with two hydrogen atoms of other (thio)ureido groups. In the present invention, X in the formula (1) is preferably an oxygen atom. It is considered that when oxygen atoms or sulfur atoms are compared, the oxygen negative degree of oxygen atoms is higher, so the urea structure is more likely to have stronger self-aggregation than the thiourea structure. The liquid crystal alignment treatment agent of the present invention is a (thio)ureido group having a specific diamine derived from a specific structure of the above formula (1) in a polymer chain. According to this, the frictional resistance is improved by the electrostatic interaction of the (thio)urea groups existing in the polymer chain having a specific structure. In this respect, the present invention is different from the method used in the field of liquid crystal alignment films in which a crosslinking agent is bonded to a polymer chain to improve friction resistance. Further, in the formula (1), R1 and R2 each independently represent an alkylene group having 1 to 3 carbon atoms, and the structure may be either a straight chain or a branched chain. Specific examples thereof are methyl group, ethyl group, trimethyl group, methyl group-10-201030059 ethyl group, and 2-methyl group ethyl group. Among them, from the viewpoint of liquid crystal alignment, 'it is better to have a free-rotating part, and a small structure', specifically, a methyl group, an extended ethyl group, and a three-form type (1) in which 'Y1 and γ2 are independent. Is a single bond, _〇_, or -COO-. Further, the structure of γ ΐ and Υ 2 is preferably soft and has a small steric hindrance, a single bond, -〇- or -s-, from the viewpoint of liquid crystal alignment. The so-called formation of a film having a high film density and formation of stronger is preferably that the structure between the (thio)ureido group and the benzene ring is symmetrical with respect to the center 'and preferably -Rl-Yl- and -R2 -, the maker. The compound represented by the formula (1) is preferably 'from the formula (1) to the formula (1-C): (h2n is compatible with friction and the steric hindrance stretches the methyl group -S- ' -OCO- and friction-resistant structure, and the liquid crystal alignment film (sulfur)urea 2 is the same structure (1 -a

(In the formula (l_a), 'R11 and R21 are equal in carbon number.

Number 1~3

In the formula (l_b), R12 and R22 are different from each other in the number of carbon atoms -11 - 201030059 alkyl group) [chemical 7] Ο - 0-r < n person n, r η2ν η η *13 and 23-°-Q νη2 (1-c) 2 3 (In the formula (1-C), R13 and R23 are each independently an alkylene group having 1 to 3 carbon atoms)

In the formula (1), the bonding position of the amine group on the benzene ring is not particularly limited, but from the viewpoint of liquid crystal alignment, a 3-aminophenyl structure or a 4-aminophenyl structure is preferred. It is preferably a 4-aminophenyl structure. Specifically, the formula (1) is preferably any one of the following formula (1-1), formula (1-2) or formula (1-3), and is preferably a formula (1-1). [化8]

Η Η

(1-2) (1-3)

In the formulae (1-1), (1-2) and (1-3), the meanings of Y1, Y2, R1 and R2 are the same as defined in the formula (1). The specific examples of the formula (1) are listed below in the formula (1 - 4 ) to the formula (1 - 15). -12- 201030059

[Chemistry 9]

The compounds of the formulae (1-7) to (1-11) are the novel compounds first provided by the present invention, and of course, the polyimine precursors or polyimines obtained using the above are also novel compounds. Further, the diamine compound other than the formula (1-7) to (1 -1 1 ) is a known compound, but the polyimine precursor or the polyimine obtained using the diamine compound is a novel compound. . -13-201030059 <Synthesis method of diamine> The amine represented by the formula (1) can be synthesized, for example, as follows. The diamine compound represented by the formula (1) of the present invention is composed of an aniline skeleton, a separating portion (W'R2), a linking group (Υ'Υ2), and a (thio)ureido group, and the synthesis method thereof is not particularly limited. It can be synthesized, for example, by the method described below. [化10]

(1)

In the formula (1), 'X is an oxygen atom or a sulfur atom, and γΐ and Υ2 are each independently a single bond, -0-, -S-, -OCO- or -COO-, and R1 and r2 are each independently a carbon number of 1 to 3 The alkyl group. Further, the bonding position of the amine group on the benzene ring is not particularly limited. 〇'Y1_RWR2_Y20 (2) Θ 02Ν Η Η Ν〇2 The compound represented by the formula (1) of the present invention is synthesized by the dinitro compound represented by the formula (2) (in the above formula (2) , r1, R2, Υ1, Υ2, and X have the same meanings as in the formula (1), and are then obtained by converting a nitro group to an amine group. The method for reducing the dinitro group is not particularly limited, and palladium-carbon, platinum oxide, Raney nickel, iron, tin chloride, platinum black, rhodium-alumina, or platinum sulfide carbon is usually used as a catalyst in acetic acid. In a solvent such as ethyl ester, toluene, tetrahydrofuran, diketone or alcohol, a method of reducing by hydrogen, hydrazine, hydrogen chloride or -14" 201030059 ammonium chloride is used. The method for synthesizing the dinitro compound represented by the formula (2) is not particularly limited, and it can be synthesized by any method. Specific examples thereof can be synthesized, for example, by using the method shown in the following reaction scheme (3). [化 12]

❹ In the reaction scheme (3), the dinitro compound represented by the formula (2) can be obtained by using a nitrobenzene compound (α), (α ') and (thio)carbonyl group in the presence of a base in an organic solvent. The compound (a generic term of a carbonyl compound and a thiocarbonyl compound) (β) is synthesized to be reacted. Among the above nitrobenzene compounds (α) and (α'), .... The oxime 1 and the oxime 2 are the same as the formula (1), and the amine group represented by ΝΗ2 can also form a salt such as a hydrochloride (ΝΗ2 · HC1). Specific examples thereof include nitrobenzylamine or a hydrochloride thereof; 2-(nitrophenyl)ethylamine or a hydrochloride thereof; 3-(nitrophenyl)propylamine or a hydrochloride thereof. Further, the substitution position of the nitro group on the benzene ring is appropriately selected depending on the substitution position of the target diamine compound obtained. Further, the compound shown here is an example thereof, and is not particularly limited thereto. In the (thio)carbonyl compound (β), the X system is the same as the formula (1), and the oxime is an organic group having a valence of 1 to 2. The (thio)carbonyl compound (β) is exemplified by, for example, -15-201030059 carbon ruthenium chloride, thiocarbonium chloride, diphenyl carbonate, diphenyl thiocarbonate, bis(nitrophenyl) carbonate 'bis(nitro) Phenyl) thiocarbonate, dimethyl carbonate, dimethyl thiocarbonate, diethyl carbonate, diethyl thiocarbonate, ethylene carbonate, thiocarbonate, 1,1'-mercapto -1H - imidazole, 1,1'-thiocarbonyl bis-1H-imidazole, and the like. Further, a carbonyl compound (?) may be substituted with carbon oxide ("carbon oxide or carbon dioxide"). Further, the compound shown here is an example thereof, and is not particularly limited thereto. In the above reaction scheme (3), in order to obtain a compound having a structure centered on the (thio)ureido group, the nitrobenzene compound (α) and (α ') may be the same, and in order to obtain an asymmetric compound, Preferably, the nitrobenzene compound (α) is subjected to an equimolar reaction with respect to the (thio)carbonyl compound (β), and then a nitrobenzene compound (α') having a structure different from that of the nitrobenzene compound (α) is further added. The base is exemplified by basic organic compounds such as triethylamine, diisopropylethylamine, DMΑΡ(4-Ν, Ν-dimethylaminopyridine); inorganic base compounds such as sodium hydroxide and potassium carbonate; A metal hydride such as sodium. Further, the compound shown here is an example thereof, and is not particularly limited thereto. The organic solvent is a solvent which has little influence on the reaction. Specifically, an aromatic solvent such as toluene or xylene; an aliphatic hydrocarbon solvent such as hexane or heptane; and dichloromethane, 1, may be used alone or in combination. a halogen solvent such as 2-dichloroethane; an ether solvent such as tetrahydrofuran or 1,4-dioxane; dimethylformamide, hydrazine, hydrazine-dimethylacetamide, hydrazine-methylpyrrolidone , a protic polar solvent such as dimethyl sub-grinding. Again, the amount used is any amount. -16- 201030059 The diamine synthesized as described above may be used as a polyamide or polyurea in addition to a polyimine precursor such as polyglycolic acid or polyamidomate or polyimine. Raw materials, which can be utilized as raw materials for various electronic materials. <Polyimine precursor or polyimine> The polyimine precursor system contained in the liquid crystal alignment agent of the present invention is a diamine component and a tetracarboxylic acid containing the above specific diamine as an essential component. The derivative is obtained by reaction. The diamine component used to obtain the polyimine precursor may be only a specific diamine represented by the formula (1), and other diamines may be used. When used in combination with other diamines, the ratio of the specific diamine represented by the formula (1) may be any enthalpy, but in order to obtain sufficient friction resistance, in all the diamine components (100% by mole), The ratio is preferably 10% by mole or more, more preferably 30% by mole or more, and still more preferably 5% by mole or more. On the other side, in terms of the optimum pretilt angle or the decrease in accumulated charge, the proportion of the special female component is preferably less than 9% of the total diamine component. The diamine used for the specific diamine oxime represented by the formula (1) is not particularly limited, but may be represented by the following formula (4). R3 R4 HN—R5—NH (4) In the above formula (4), R 5 represents a divalent organic group, and ampules 3 and R 4 each independently represent a hydrogen atom or a monovalent organic group. -17- 201030059 Specific examples of R5 can be exemplified by the following divalent organic groups.

CH3

-p- [B-15] [ B-16 ] [B-17] [B-18] x)g_ [B-19] [ B-20 ] [B-21 ] [ B-22 ] [ B-23 ]

201030059

[Chemistry 16]

H3CYCH3 f3c cf3

[B-37 ] [ B-38 ] [ B-39 ]

201030059 [Chemistry 18]

[Β-48] [B-49] [B-50]

[B-56 ]

[B-58 ] F

[Β-60]

20- 201030059 [Chem. 20] ^3〇.CH3 F3〇vCF3

[B-63 ] O II

[B-66 ] (ch2)2-c-(ch2)2-ch3 [B-67 ] [B-65 ] CH3 -(CH2)4-C-(CH2)3-ch3 [B-68 ] ❹ [ 21]

[B-72 ] ch3 ch3 [B-73 ] —(CH2)3—Si—0-Si-(CH2)3—^^Q-(CH2)n·

[B-64 ] one (CH2)n- n=2~12 CH3 n = 3 ~12 [B-75 ] ch3 ch3 [B-74 ] -21 - 201030059 [Chem. 22]

\(ch2) η = 2~12 [Β-76 ] 12 [Β-77 3

[Chem. 23]

0~21 丨(CH2)nCH3 [B-83] η = 0~21 [Β-82 ]

[Β-84]

0~21 η = 0~21^ (CH2)nCH3 〇~O~〇-〇(CH2)nCH3 [Β-85] η = 0~21

[Β-86]

B-87] 0(CH2)nCH3 : 0~21(CH2)nCH3 -22- 201030059 [Chemical 24] 2~19 =0~21 Corpse~\\ y~〇(CH2)nCH3 〇(CH2)nCH3 [ B-89] Bu. ·€Κ>: ❿

=0~21 0(CH2)nCH3

[B-92 ] °O^〇-〇CF3 [B-93 ] [Chem. 25]

23- 201030059 [Chem. 26]

B-100] [B-101] [Chem. 27]

[B-102]

COOH XX [B-103]

COOH

〇-c〇〇H _H(ry_)~COOH -COOH [B-104]

COOH

[B-105] COOH HOOC ❿

B-108] COOH 0(CH2)3C00H

[B-106] HOOC [B-107] COOH [B-109]

COOH

o(ch2)3c〇〇h [B_110 -24- 201030059 [化28] ❹ h3cx/(ch2)2C〇〇h B-111 ]

CH3 [B-116] [B-117] [c?2〇rjxxr j^cr^o In the formula [B-112] and [B-113], -OCO-, -CONH-, -NHC〇_,

The two 'CH Qs each independently represent -COO--, -O-, -CO- or -NH-. In the above formula (4), one or all of R is a formula [b_8〇] to a formula [b_101]. , can increase the pretilt angle of the liquid crystal. When the liquid crystal is vertically aligned, it is preferred to use a diamine of the above formula (4) wherein R5 has any of the formulas [B-80] to [B-101]. The diamine content in the case of using the diamine is preferably from 5 to 90 mol%, more preferably from 10 to 80 mol%, based on the entire diamine. On the other hand, 'making the pretilt angle small, it is preferable to use r5 of the above formula (4) to have the formula [B-1] to the formula [B-79] and [B-102] to the formula [B-118]. Diamine of any configuration. In addition, at least one of R3 and R4 in the formula (4) is preferably a monovalent organic group, more preferably a methyl group. The tetra--25-201030059 carboxylic acid derivative which reacts with the specific amine component represented by the formula (1) containing the specific diamine component represented by the formula (1) or the diamine represented by the above formula (4) is not particularly limit. The tetracarboxylic acid derivative in the present invention is exemplified by tetracarboxylic dianhydride, tetracarboxylic acid monoanhydride, tetracarboxylic acid, dialkyl dicarboxylate (expressed by the following formula (5-d)), dicarboxy ruthenium chloride The alkyl ester (represented by the following formula (5-e)) or the like is not limited as long as it can be reacted with a diamine. The tetracarboxylic acid derivative is represented by the following formula (5-a) to (5-e), and R7 represents an alkyl group. Specific examples of R6 include the following [A-1] to [A-47]. [化29]

(5-d) (5-e) [Chem. 30]

[A-4] [A-5] [A-6]

[A-7 ] [ A-8 ] [ A-9 ] [A-10] [A-11] [ A-12 〔 [Α-13] [ Α-14 ] [Α-15 ] [Α-16 ] -26- 201030059 [化31]

[Α-17] [Α-18] [Α-19] [Α-20] [Α-21 ]

ΖΚ><: TC XX

[Α-22] [ Α-23 ] [ Α-24 ] [Α-25] [Α-26]

[Α-33]

[Α-39 ] »°ΐΧ [Α-34 ]

[Α-37] 0CC [Α-40 ] -27 201030059 [化33] ccc [A-41 ] [ A-42 ] [A-43] xccc h3c h3c [A-44 ] [ A-45 ] [A- 46] [ A-47 ] In the above, R6 is of the formula [A-6], the formula [A·16], the formula [eight_18]~the formula [A-22], the formula [A-25], the formula [ A-37] and the tetracarboxylic acid derivative of the formula [A-38], i.e., a polyimine which has a high ruthenium imidation ratio, is preferable because it has high solubility in an organic solvent. Further, the tetracarboxylic acid derivative to be used has an alicyclic structure or an aliphatic structure of 1% by mol or more, preferably 20 mol% or more, having the alicyclic structure or the aliphatic structure of the formula [A-1] to the formula [A-25]. In the case of R6, it is preferable because the voltage maintenance ratio can be increased. Further, when R6 is a tetracarboxylic acid derivative selected from the group consisting of the formula [A-1], the formula [A-16], and the formula [A-19] in the alicyclic structure or the aliphatic structure, It is preferred because a liquid crystal alignment film having a faster charge relaxation can be obtained. On the other hand, if the total amount of the tetracarboxylic acid derivative to be used is 10 mol% or more, preferably 20 mol% or more, the aromatic tetracarboxylic acid derivative is improved in liquid crystal alignment and the accumulated electric charge is lowered. Therefore, it is better. A method of reacting the above diamine component (hereinafter referred to as diamine) with a tetracarboxylic acid derivative component (hereinafter simply referred to as a tetracarboxylic acid derivative) to obtain a polyimine precursor or a polyimine can be obtained by a known method obtain. An example of the case of using tetracarboxylic dianhydride will be described below. The tetracarboxylic acid derivative used in the production of the liquid crystal alignment treatment agent of the present invention is not particularly limited in the polymerization reaction method of the diamine. In general, polyglycine can be obtained by polymerization in an organic solvent. Further, a carboxylic acid group of polyglycine can be esterified using a conventional esterifying agent to obtain a polyphthalate. The polyamido acid can then be formed into a polyimine by dehydration ring closure. The method of mixing a tetracarboxylic acid derivative and a diamine component in an organic solvent is exemplified by stirring a solution of dispersing or dissolving a diamine in an organic solvent, directly adding a tetracarboxylic acid derivative or dispersing or dissolving it. A method of adding an organic solvent; a method of adding a diamine to a solution obtained by dispersing or dissolving a tetracarboxylic acid derivative in an organic solvent; and a method of alternately adding a tetracarboxylic acid derivative and a diamine. Further, when at least one of the tetracarboxylic acid derivative component and the diamine is composed of a plurality of compounds, the plurality of components may be subjected to polymerization in a state of being mixed in advance, or the polymerization may be carried out in an orderly manner. The temperature at which the tetracarboxylic acid derivative and the diamine are polymerized in an organic solvent is usually 0 to 150 ° C, preferably 5 to 100 ° C, more preferably 10 to 80 ° C ® . When the temperature is higher, the polymerization reaction ends earlier, but when it is too high, there is a case where a high molecular weight polymer cannot be obtained. Further, the polymerization reaction can be carried out at any concentration to carry out 'but when the feed concentration is too low, it is difficult to obtain a polymer having a high molecular weight. When the feed concentration is too high, it is difficult to uniformly stir the reaction liquid because the viscosity of the reaction liquid is too high. It is 1 to 50% by mass, more preferably 5 to 30% by mass. The polymerization reaction is carried out at a high concentration in the initial stage, and then an organic solvent may be added. The feed concentration herein means the concentration of the total mass of the tetracarboxylic dianhydride component and the diamine component. The organic solvent to be used in the above reaction is particularly limited as long as it can dissolve the produced polyamine -29-201030059 acid and polyglycolate (hereinafter referred to as polyglycolic acid). Specific examples are, for example, N,N-dimethylformamidine dimethylacetamide, N-methyl-2-pyrrolidone, N-methylhexamethylene ruthenium, tetramethylurea, pyridine , dimethyl mill, hexamethyl γ-butyrolactone and the like. These may be used singly or in combination. The solvent in which the polylysine is dissolved may be used in the above solvent in a range in which the formed polyester is not precipitated. Further, since the water in the organic solvent interferes with the polymerization reaction to cause hydrolysis of the produced polylysine (ester), it is preferably used by drying and dehydrating. The ratio of the tetracarboxylic acid to the diamine used in the polymerization to obtain the polyamic acid is preferably 1: 0.8 to 1: 1.2, and the closer to 1: 1, the larger the molecular weight of the obtained polyamic acid. If the molecular weight of the polyester) is too small, the strength of the coating film obtained therefrom may be obtained. Conversely, if the molecular weight of the polyamic acid (ester) is too large, the viscosity of the manufactured liquid crystal alignment treatment agent is too high to form a coating film. When the uniformity of the coating film is deteriorated. Accordingly, the polyglycolic acid (ester) used in the clarifying agent of the present invention has a weight average molecular weight of 2,000 to 500,000 » more preferably 5,000 to 300,000. In the present invention, although a tetracarboxylic acid derivative is used to obtain a polyamic acid, the diamine is a diamine represented by the above formula (4) which is represented by the above formula (1). When a dicarboxylic acid derivative of the formula (4 diamine) is used, R6 in the above formula (5-5-e) is represented by the formula [A-1], the formula [A-2], and the formula [A- 16], the formula is that there is no amine, N, N-decalamine, quinone, and, in addition, pro-amine (and further into an organic solvent than the acid derivative of the molar ratio of lysine) It is better to be a biological and diamine and its basis according to its working crystal alignment. (a) to (a), [A-18], 201030059, [A-19], [A-25], [A-26], the formula [A-27], the formula [A-32], the formula [A-35], the formula [A-3 8] or the formula [A-47], and the above-mentioned specific diamine The diamine of the formula (4) is preferably used as the formula [Β·6], the formula [B-7], the formula [Β·8], the formula [Β-16], the formula [Β-17], the formula [ Β-20], formula [Β-21], formula [Β-29], formula [Β-30], formula [Β-32], formula [Β-33], formula [Β-40], formula [Β -44], formula [Β-45], formula [Β-48], formula [Β-56], formula [Β-57], formula [Β-58], formula [Β-61], formula [Β- 62], the formula [Β-63], the formula [Β-76], the formula [Β-80], the formula® [Β-82], the formula [Β-83], the formula [Β-84], the formula [Β- 85], the formula [Β-86], the formula [Β-87], the formula [Β-93], the formula [Β-104], the formula [Β-114], [Β-115] or the formula [Β-118], wherein the 'tetracarboxylic acid derivative is preferably R6 in the above formula (5-a) is the formula [A-1], the formula [A-2], the formula [ A-16], formula [A-18], formula [A-19], formula [A-25], formula [A-26], formula [A-27] or formula [A-32], as for formula ( 4) The diamine, wherein R5 is preferably of the formula [B7], the formula [Β·8], the formula, the formula [B-20], the formula [B-21], the formula [B-29], the formula [B- 30], formula [B-32], formula [B-61], formula [B-76], formula [B-80], formula [B-82], formula [B-83], formula [B- 84], formula [B-85], formula [B-104], formula [B-114], formula [B-115], or formula [Bl 18]. The polylysine thus obtained may also be as follows The repeating unit of the formula (6) indicates that the polyperurethane can also be represented by the following formula (7).

-31 - 201030059 In the above formulas (6) and (7), Ra, Rb, and R. When diamine derived from the above formula (1) or formula (4) is used, when diamine represented by formula (1) is used, 113 and Rb are hydrogen, and Rc is -phenylene-YLnH-CX-HN- R2-Y2-phenylene-' When a diamine represented by the formula (4) is used, Ra is R3, Rb is R4, and Re is R5»R5 has the meaning of the above formula (5-a)~(5-e In the tetracarboxylic acid derivative represented by the same, R5 is the same. R in the formula (7) is derived from the group of the esterifying agent to be used. The polyamic acid or polyglycolate obtained as described above may be used as it is in the liquid crystal alignment treatment agent of the present invention, but a dehydrated ring-closed polyimine may also be used. However, depending on the structure of the polyglycolic acid, it is difficult to be used in the liquid crystal alignment treatment agent because it is insolubilized by the imidization reaction. In this case, it is also possible to carry out the ruthenium imidization in the range in which the prolyl acid group in the poly-proline (ester) is not imidized, and the imidization is carried out in a range in which the solubility is moderate. The ruthenium imidization reaction of poly (propyl) acid by dehydration ring closure is generally carried out by heat-imiding the solution of poly-proline acid directly, and adding the catalyst to the solution of poly-proline (ester) The chemical oxime is imidized, but the chemical ruthenium imidization at a lower temperature is less likely to cause a decrease in the molecular weight of the obtained polyimine. The chemical polyimidization can be carried out by stirring a polyglycolic acid in an organic solvent in the presence of a basic catalyst and an acid anhydride. The reaction temperature at this time may be -20 to 250 ° C', preferably 〇 to 180 ° C, and the reaction time may be 1 to 100 hours. The amount of the alkaline catalyst is 0.5 to 30 moles of polyamine, preferably 2 to 20 moles, and the amount of the anhydride is polyamine (ester-32-201030059) 1 to 50 moles, preferably 3 to 30 moles. When the amount of the basic catalyst or acid anhydride is small, the reaction does not proceed sufficiently, and if it is too much, it is difficult to completely remove the reaction after completion of the reaction. The basic catalyst used in the imidization can be exemplified by pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like, wherein pyridine is preferably maintained in a moderately alkaline state during the reaction. . Further, the acid anhydride may, for example, be acetic anhydride, trimellitic anhydride, pyromellitic anhydride or the like. Among them, the use of acetic anhydride is preferred because it is easier to purify after completion of the reaction. As the organic solvent, a solvent used in the polymerization of the aforementioned polyaminic acid can be used. The rate of hydrazine imidation by chemical hydrazine imidation can be controlled by adjusting the amount of catalyst, the reaction temperature, and the reaction time. The polyimine solution thus obtained remains in the solution because the added catalyst remains. Therefore, in order to be used in the liquid crystal alignment treatment agent of the present invention, the polyimine solution is preferably poured into a weak solvent under stirring. The polyimine precipitate is recovered and used. The weak solvent used for the precipitation of polyimine is not particularly limited, and can be exemplified by methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, Toluene, benzene, etc. By pouring into a weak solvent, the polyimine of the sinking chamber is filtered, washed and recovered, and then dried under normal pressure or reduced pressure, and then heated to a powder. Further, the powder may be dissolved in a good solvent, and the reprecipitation operation may be repeated 2 to 10 times to purify the polyimine. When the primary precipitation recovery operation cannot remove impurities, it is preferred to repeat the purification step. When the weak solvent in the purification step is repeated, it is preferred to further increase the purification efficiency by mixing or sequentially using three or more kinds of weak solvents such as an alcohol or a ketone 'hydrocarbon. -33- 201030059 Also, the precipitation recovery and purification can be carried out in the same manner as polyglycolic acid. This precipitation recovery and purification are preferably carried out when the solvent for polymerization of poly-proline is contained in the liquid crystal alignment agent or when unreacted monomer components or impurities are present in the reaction solution. The ruthenium imidization ratio of the polyimine contained in the liquid crystal alignment agent of the present invention is not particularly limited. Any enthalpy can be set as long as the solubility of the polyimine is considered. The molecular weight of the polyimine contained in the liquid crystal alignment treatment agent of the present invention is not particularly limited, but the molecular weight of the polyimine is too small, and the strength of the obtained coating film is insufficient, and conversely, the molecular weight of the polyimide. When the resin is too large, the viscosity of the liquid crystal alignment agent to be produced is too high, and the workability at the time of forming the coating film and the uniformity of the coating film may be deteriorated. Accordingly, the weight average molecular weight of the polyimine used in the liquid crystal alignment agent of the present invention is preferably from 2,000 to 500,000, more preferably from 5,000 to 300,000. <Liquid Crystal Alignment Treatment Agent> The liquid crystal alignment treatment agent of the present invention contains any of the polyimine precursors or polyimine obtained as described above, and usually dissolves the polymers in an organic solvent. Coating solution. The polymer contained in the liquid crystal alignment agent of the present invention may contain a polymer having another structure in addition to the above-mentioned polyimine precursor or polyimine. The organic solvent contained in the liquid crystal alignment agent of the present invention is not particularly limited as long as it dissolves the polymer contained therein. Specific examples of the organic solvent are hydrazine, hydrazine-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methyl caprolactone, - 34- 201030059 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl hydrazine, tetramethylurea, pyridine, dimethyl hydrazine, hexamethyl arsenide, γ - Butyrolactone, 1,3-dimethyl-pyrimidinone, and the like. These may be used alone or in combination of two or more. Further, even if it is a solvent in which the polymer cannot be dissolved alone, it may be mixed in the liquid crystal alignment agent of the present invention as long as it does not precipitate the polymer. In particular, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1 -ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl Ethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, A solvent having a low surface tension such as N-propyl lactate, N-butyl lactate or isoamyl lactate is mixed therein to increase the uniformity of coating film to the substrate. Therefore, the solvents may be used singly or in combination of plural kinds. ® In the liquid crystal alignment treatment agent of the present invention, a solvent having a low surface tension is also suitably used, but the amount thereof is preferably from 5 to 80% by mass, more preferably from 20 to 60%, based on the total amount of the solvent contained in the liquid crystal alignment treatment agent. quality%. The liquid crystal alignment agent of the present invention may contain various additives in addition to the above polymer and organic solvent. The additives for improving post-film uniformity and surface smoothness are exemplified by a fluorine-based surfactant, a rhodium-based surfactant, a nonionic surfactant, and the like. More specifically, for example, F-Top EF301, EF303, EF352-35-201030059 (manufactured by TOKEMU PRODUCTS), Megafack F 1 7 1, F173, R-30 (manufactured by Dainippon Ink Co., Ltd.), Florad FC43 0, FC431 (manufactured by Sumitomo 3M), Asahi Guard AG710, SURFLON S-3 82, SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.). The use ratio of the surfactant is preferably from 1 to 2 parts by mass, more preferably from 0.01 to 1 part by mass, per part by mass of the polymer component contained in the liquid crystal alignment agent. Specific examples of the additive for improving the adhesion between the liquid crystal alignment film and the substrate are a compound containing a functional decane, an epoxy group-containing compound, and the like. Examples are, for example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, N- (2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-ureidopropyl Trimethoxy decane, 3-ureidopropyltriethoxy decane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyl@yl Triethoxydecane, N-triethoxydecylpropyltriethylamine, N-trimethoxydecylpropyltriethylamine, 10-trimethoxydecyl-1,4 , 7-triazadecane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6-diazaindolyl acetate , 9-triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyl Triethoxy decane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N-bis(oxyethyl)-3 -aminopropyltrimethoxy Alkane, -36- 201030059 N-bis(oxyethyl)-3-aminopropyltriethoxydecane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether , tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo Neopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, hydrazine, hydrazine, hydrazine, Ν'-tetraglycidyl-m-xylene Amine, 1,3-bis(indole, hydrazine-diglycidylaminomethyl)cyclohexane, hydrazine, hydrazine, hydrazine, Ν'-tetraglycidyl-4,4'-diaminobenzene Methane and the like. When the compound is added, it is preferably from 0.1 to 3 parts by mass, more preferably from 1 to 20 parts by mass, per 1 part by mass of the polymer component contained in the liquid crystal alignment agent. When the amount is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected, and when it exceeds 30 parts by mass, the liquid crystal alignment property may be deteriorated. In addition to the above, the liquid crystal alignment agent of the present invention may be added with a polymer component other than the polymer as long as the effect of the present invention is not impaired, and may be added to change the dielectric constant or conductivity of the liquid crystal alignment film. A dielectric material or a conductive material of an isoelectric property may be added, and a cross-linking compound or the like which is intended to increase the film hardness or density when the liquid crystal alignment film is formed may be added. The solid content concentration in the liquid crystal alignment agent of the present invention can be appropriately changed depending on the film thickness of the intended liquid crystal alignment film. However, it is possible to obtain a suitable film thickness of the liquid crystal alignment film based on the formation of a coating film having no defect. 1 to 2 0% by mass is more preferably, more preferably 2 to 10% by mass. The liquid crystal alignment treatment agent of the present invention is applied to a substrate, and after being fired, it is subjected to alignment treatment by rubbing treatment or light irradiation, or when it is used for vertical alignment or the like, it can be used as a liquid crystal alignment film without alignment treatment. In this case, the substrate using -37-201030059 is not particularly limited as long as it is a substrate having high transparency, but a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used, but in terms of process simplification, It is preferable to use a substrate which forms an ITO electrode or the like for driving a liquid crystal. Further, in the reflective liquid crystal display device, an opaque substance such as a germanium wafer can be used as the single-sided substrate. In this case, a material such as aluminum or the like can be used as the electrode. The coating method of the liquid crystal alignment agent is not particularly limited, but industrially, it is usually carried out by screen printing, offset printing, soft printing, ink jet, or the like. Other coating methods are dipping, roll coating, slit coating, spin coating, etc., and it is preferred to use them according to the purpose. The firing of the substrate coated with the liquid crystal alignment agent can be carried out at any temperature of 100 to 3 50 ° C, preferably at a temperature of 150 to 300 ° C, more preferably at a temperature of 180 to 250 ° C. When the liquid crystal alignment agent contains polyamic acid or polyphthalate, the conversion rate of the polyimine is changed by the baking temperature, but the liquid crystal alignment treatment agent of the present invention is not necessarily 1% by weight. The need for imidization. Therefore, the firing time can be set to an arbitrary time. However, when the firing time is too short, the display failure is caused by the influence of the residual solvent, so it is preferably from 5 to 60 minutes, more preferably from 1 to 40 minutes. When the thickness of the coating film after firing is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element. When the thickness is too thin, the reliability of the liquid crystal display element may be lowered, so it is preferably 5 to 300 nm, more preferably 10 ~l〇〇nm. When the liquid crystal is subjected to horizontal alignment or oblique alignment, the fired coating film is treated by rubbing or polarized ultraviolet irradiation or the like. In the liquid crystal display device of the present invention, the substrate to which the liquid crystal alignment film is attached is obtained from the liquid-38-201030059 crystal of the present invention, and the liquid crystal cell is produced as a liquid crystal display element by a conventional method. An example of the production of a liquid crystal cell is exemplified by preparing a pair of substrates on which a liquid crystal alignment film is formed, and dispersing a spacer on a liquid crystal alignment film of one substrate so that the liquid crystal alignment film surface is inside and bonded to another substrate. A method of injecting a liquid crystal and encapsulating under reduced pressure, or a method of laminating a substrate and encapsulating the liquid crystal after the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacer is dispersed. 〇 The thickness of the separator at this time is preferably from 1 to 30 μm, more preferably from 2 to ΙΟμιη. As described above, the liquid crystal display device produced by using the liquid crystal alignment treatment agent of the present invention can be preferably used for high-precision liquid crystal televisions with excellent reliability and large screen. EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the invention should not be construed as limited. The abbreviations used in the following examples and comparative examples are as follows: BABU: 1,3-bis(4-aminobenzyl)urea BAPU: 1,3-bis(4-aminophenethyl)urea DA-3: 1,3-bis(3-aminobenzyl)urea DA-4 : 1-(4-aminobenzyl)-3-(4-aminophenethyl)urea DA-5 : 1,3-double (2-(4-Aminophenoxy)ethyl)urea DA-6: 1,3-bis(3-(4-aminophenoxy)propyl)urea DA-7: 1,5'- Bis(4-Aminophenoxy)pentane CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride-39- 201030059 PMDA: pyromellitic dianhydride BODA: bicyclo[3,3, 0] Octane-2,4,6,8-tetraresidic acid dianhydride CA-4: 1,3-dicarbomethoxy-2,4-bis(chloro-friendly)cyclobutane CA-5: 2 , 5-dicarbomethoxyterephthalic acid di-enriched P-PDA: p-phenylenediamine Further, in the synthesis example, the so-called W-NMR means a nuclear magnetic resonance spectrum of an intramolecular hydrogen atom. [Synthesis Example] Synthesis of 4_Aminophenethyl)urea [BAPu] 〇2N-Qpv-NH2'HCI [C] Η Η IT 〇2Ν€Τ-ΝδΝ^Ν02 rJr, Η

Η H

[BAPU] In a hydrazine-substituted hydrazine, a 2-neck flask was replaced with a nitrogen-substituted four-necked flask, 4-(4-stone 1 4-nitrolaizide hydrochloride [C] (52·54, 259 mm〇l), carbonic acid double ) (1 8 77 interesting) [D] (3 7.53g, l23tnm〇1) and THF (0 hydrofuran, and added with ethylamine (74.9〇g, 74〇mmo〇 stirrer / armor) Aminopyridine (3. 〇1g, 24.7mm〇l), and simmered in stone. The reaction was followed by HPLC (high-speed liquid chromatography), -40. 201030059 After the reaction was over, the reaction solution was added to pure water. (9L), stirring for 30 minutes. Subsequently, filtration was carried out, and washed with pure water (1 L) to obtain a crude product as a white solid. The obtained white solid was washed with methanol (48 8 g) in an ultrasonic apparatus. After purification, filtration and drying were carried out to give a white solid, dinitro compound [E] (yield 42.3 g, yield 96%). Ή-NMR (400 MHz. DMS0-d6, «5 ppm): 8.11-8.08 (4H , m). 7.43-7.40 (4H.m). 5.89(2H, t), 3.24-3.19(4H, q), 2.76(4H, t). ❿ Compound [E] (42.32g, 1 18mmol), a mixture of 5% palladium-carbon (5% Pd/C) (4.23 g) and 1,4-dioxane (203 1 g) After the replacement, the mixture was replaced with hydrogen, and stirred at room temperature in the presence of hydrogen. The reaction was followed by HP LC, and after the reaction was completed, the catalyst was filtered with diatomaceous earth. Then, the solvent of the filtrate was distilled off under reduced pressure to obtain white. The crude product was solid. To the obtained crude product was added 2-propanol (85 g), which was subjected to dispersion washing with an ultrasonic apparatus, followed by filtration and drying to obtain a white solid diamine compound [BAPU] (yield 31.9 g, Yield 91%) φ Ή-NMR (400 MHz. DMS0-d6. 5 ppm): 6.85-6.82 (4H, m), 6.51-6.48 (4H, m), 5·78(2Η, t), 4.83 ( 4H, s), 3.14-3.09 (4H, m). 2.50-2.45 (4H, m) [Synthesis Example 2] Synthesis of 1,3-bis(4-aminobenzyl)urea [BABU] -41 - 201030059 [化36]

^Y"nh2-hci一^^ 02N A

[F] T 〇2Nj〇r^N〇2

Ν〇2 again [G] Λ. η2νΌ^η ηΌ.ΝΗ2 [BABU]

4-nitrohexylamine hydrochloride [F] (25. 〇〇g' 133 mmol), bis(4-nitrophenyl) carbonate was added to a nitrogen-substituted four-necked flask at room temperature [ D] (1 9.20g '63 · lmmol ) and THF ( 750g ) ' and added triethylamine (38.32g, 379mmol) and 4-N,N-dimethylamine oxime (1.54g, 12.6mmol) ) 'Stirring with a magnetic stirrer. The reaction was followed by HP LC. After completion of the reaction, the reaction solution was added to purified water (4.5 L) and stirred for 30 minutes. Subsequently, filtration was carried out, and washed with pure water (500 mL) to obtain a crude product as a pale yellow solid. The obtained pale yellowish white solid was washed with methanol (300 g) by an ultrasonic apparatus, and then filtered and dried to obtain a dinitro compound [G] (yield: 19-01 g, yield 91%) as a pale yellow solid. 1H-NMR (400MHz, DMS0-d6, δ ppm): 8.22-8.19 (4H.m), 7.53-7.50 (4H.m), 6.82 (2H, t), 4.36 (4H, d). A mixture of the compound [G] (16.00 g, 48.4 mmol), 5% carbon (5% Pd/C) (1.60 g) and 1,4-dioxane (800 g) was replaced with nitrogen and then hydrogen. Displacement, stirring at room temperature in the presence of hydrogen -42- 201030059. The reaction was followed by HPLC, and after completion of the reaction, the catalyst was filtered with diatomaceous earth. Subsequently, the solvent of the filtrate was distilled off under reduced pressure to give a crude product as a white solid. 2-propanol (128 g) was added to the obtained crude product, and the mixture was subjected to dispersion washing with an ultrasonic apparatus, followed by filtration and drying to obtain a yellow-white solid diamine compound [BABU] (yield 12.19 g, yield 93%) ). Ή-NMR (400MHz, DMS0-d6, <5 ppm): 6. 92-6.88 (4H, m), 6.51-6.48 (4H, m), 6.03 (2H, t), 4.9K4H, s), 4.02 (4H, d) 〇❹ [Synthesis Example 3] Synthesis of 1,3-bis(3-aminobenzyl)urea [DA-3]

[化37] o2n 丫〉"Ί . HC|_ [Η] xn x, .N〇2 ο2ν

3-Nitrobenzylamine hydrochloride [H] (10.Og, 53_0 mmol), bis(4-nitrophenyl) vinegar [D] was added to a nitrogen-substituted four-necked flask at room temperature. (7.68 g, 25.3 mmol) and THF (384 g) were added thereto, and triethylamine (15.33 g, 152 mmol) and 4-N,N-dimethylaminopyridine (〇_62g' 5.05 mmol) were added and stirred. The reaction was followed by HPLC. After completion of the reaction, the reaction solution was added to purified water (2.3 L) and stirred for 30 minutes. Subsequently, filtration was carried out and washed with pure water (·5() 0 ηηί) -43-201030059 to obtain a crude product of a white solid. The obtained white solid was dispersed and washed in 2-propanol (50 g) by an ultrasonic apparatus, and then filtered and dried to obtain a dinitro compound [I] as a white solid (yield: 7.04 g, yield: 84%) . Ή-NMR (400MHz, DMS0-d6, 5 ppm): 8.06-8.05 (4H, m). 7.68C2H, d), 7.56-7.55 (2H, m), 6.84 (2Η, t), 4.32 (4H , d). A mixture of the compound [I] (7.04 g, 21.3 mmol) '5% pin-carbon (5% Pd/C) (0.7 g) and 1,4-dioxane (3 50 g) was replaced with nitrogen, and then It was replaced with argon gas and stirred at room temperature in the presence of hydrogen. The reaction was followed by HPLC, and after completion of the reaction, the catalyst was filtered with diatomaceous earth. Subsequently, the filtrate was subjected to distillation under reduced pressure to give a crude product as a white solid. 2-propanol (60 g) was added to the crude product, and the mixture was subjected to dispersion washing with an ultrasonic apparatus, followed by filtration and drying to obtain a diamine-based compound [DA-3] (yield 4.04 g, yield) 81%). Ή-NMR (400MHz, DMS0-d6, 5ppm): 6.93(2H, t), 6.46-6.45 (2H.m), 6.42-6.34(4H, m), 6.20(2H, t), 5_01 (4H, s ), 4.07 (4H, d). [Synthesis Example 4] Combination of 1-(4-aminobenzyl)-3-(4-aminophenethyl)urea [DA_4] 201030059 [Chem. 38]

[L]

Add 4-nitroguanylamine hydrochloride m (s〇.00g, 265mmol), 卩 ratio steep (2〇97g, 265mmol) and chloromethane in a four-necked flask with a chain nitrogen replacement at room temperature. (75 μg), allowing the solution to cool below ι. After a solution of dichloromethane (15 〇g) containing chlorophenyl formate [j] (53.43 g, 265 mmol) was added thereto, the reaction temperature was raised to 23 ° C and stirred for 1 hour, and then heated to reflux. After completion of the reaction, the reaction solution was cooled to room temperature, and dichloromethane (500 g) and a 10% by mass aqueous hydrochloric acid solution (10 g) were added and filtered. The filtrate was stirred at room temperature and the precipitated solid was filtered. The solid was washed with methanol (200 g) and dried to yield Compound (K) (yield 3 3.26 g, yield 4%). On the other hand, a saturated aqueous solution of sodium hydrogencarbonate (500 g) was added to the filtrate, and the organic layer was washed with saturated brine (500 g) and dried over magnesium sulfate. Subsequently, the solvent was distilled off and the solvent was distilled off to obtain a white crude product. The crude product was recrystallized from methanol (2 g) to further afford a compound [K] as a white solid (yield: 20% yield: 20%). 1H-NMR (400MHz, CDCI3, 5ppm): 8.8.28-8.24(4H, m). 7.55-7. 53(2H, m), 7.37-7.34(2H, m), 5.64(1H, t), 4.59 (2H, d). -45- 201030059 Add 2-(4-nitrophenyl)ethylamine hydrochloride [C] (30.29g '150mmol), compound [K] (45.18) to a nitrogen-substituted four-necked flask at room temperature. g, 142 mmol) and THF (2260 g) were reacted with triethylamine (43.23 g, 427 mmol) and 4-N,N-dimethylaminopyridine ( 1.74 g, 14.2 mmol). The reaction was followed by HPLC, and after completion of the reaction, the reaction solution was added to pure water (1 〇L), and stirred for 30 minutes. Subsequently, filtration was carried out, and washed with pure water (2 L) to obtain a crude product as a white solid. The obtained white solid was washed with 2-propanol (300 g), and then filtered and dried to give a white solid, dinitro compound [L] (yield: 43.9 g, yield: 90%). 1H-NMR (400MHz, DMS0-d6, 5 ppm): 8.19-8.14(4H, m), 7.52-7.44 (4H.m), 6.620H, t). 6.120H, t), 4.31 (2H.d) , 3.33(2H.m). 2.86(2H, t) ° Compound [L] (50.00g, 145mmol), 5% palladium-carbon (5%Pd/C) (5.0g) and 1,4-dioxin The mixture of the alkane (l〇〇〇g) was replaced with nitrogen, then replaced with hydrogen, and stirred at room temperature in the presence of hydrogen. The reaction was followed by HPLC, and after completion of the reaction, the catalyst was filtered with diatomaceous earth. After @, the filtrate was evaporated under reduced pressure to give a crude white solid. 2 -propanol (330 g) was added to the crude product, and the mixture was washed with an ultrasonic device, and then filtered and dried to obtain a diamine-based compound [DA-4] (yield 37.0 g, yield 90%). ^-NMR (400MHz, DMS0-d6, 5 ppm): 6.90-6.87 (2H, m), 6.84-6.82 (2H, m), 6.51-6.47 (4H, m), 6.08OH. t), 5.73 (1H , t), 4.9 (2H, s), 4.84 (2H, s), 3.99 (2H, d). 3.15-3.10 (2H, m), 2.51-2.46 (2H, m). [Synthesis Example 5] -46- 201030059 Synthesis of I,3-bis(2-(4-aminophenoxy)ethyl)urea [DA·5]

[化39]

[M step excitation] j〇tf o2n IP}

Synthesis of Compound [P] from Reaction Step A Nitroic acid (27.69 g, 1 99 mmol), potassium carbonate (5 5 · 0 1 g, 3 9 8 mmo 1 ) was added to a four-necked flask at room temperature under a nitrogen atmosphere. And N,N-dimethylformamide (hereinafter referred to as DMF) (140g) 'heated to

65 ° C. A solution of N-(2-bromoethyl)benzimidimine (50.57 g, 199 mmol) in DMF (140 g) was added dropwise. After the completion of the reaction, the reaction solution was added to ice water (224 〇g) to obtain a yellow solid. After filtration, washed with water, and dried to give a yellow-white solid compound [yield] (yield 44.2 g, yield 71%) ). 1H-NMR (400MHz, CDCI3, <5 ppm): 8.19-8.16 (2H.m), 7.90-7.87 (2H.m). 7. 77-7. 74 (2H.m), 6.96-6.94 (2H m), 4.33(2H.t), 4.14(2H, t) 化合物 A compound of hydrazine-hydrate (81.00 g, 1.28 mol) added to a four-necked flask at room temperature under nitrogen atmosphere [o] After (40.OOg, -47-201030059 l28mmol) of ethanol (93〇g) solution, it was heated and refluxed. After completion of the reaction, the precipitated solid was dissolved in distilled water (93 Og), and then extracted four times with 1,2-dichloroethane (500 g). After the organic layer was combined, it was washed with water (500 g) twice, dried over magnesium sulfate, filtered, and evaporated to give a yellow solid compound [P] (yield: 16.5 g, yield 51%) 1H-NMR (400 MHz CDCI3> δ ppm) : 8. 22-8.20 (2H, m), 6.99-6. 96 (2H, m). 4·09(2Η, t), 3.15(2H, t), 1.26(2H, brs ). Synthesis of Compound [P] from Reaction Step B In a four-necked flask, 1,2-dimethoxyethane (hereinafter referred to as DME) (150 g) was poured at room temperature under a nitrogen stream, and 60% was added thereto. Sodium hydride (16.24 g, 3 72 mmol). Subsequently, a solution of 2-MEA (22.73 g, 372 mmol) in DME (50 g) was slowly added dropwise. Next, a solution of 1-fluoro-4-nitrobenzene (50.00 g, 354 mmol) in DME (50 g) was added dropwise. After completion of the reaction, the reaction solution was added to distilled water (1250 g), and extracted with dichloromethane (400 g) three times. The organic layer was combined, dried over magnesium sulfate, and filtered, and evaporated to give crystals of crystals of compound (P) (yield: 46.1 g, yield 71%). 1H-NMR (400MHz, CDCI3, 5 ppm): 8.22-8.20 (2H.m), 6.99-6.96 (2H, m), 4.09(2H, t). 3.15(2H, t), 1.26(2H. brs) . Add bis(4-nitrophenyl)carbonate [D] (7.95 g, 26.1 mmol), triethylamine (15.87 g, 157 mmol), 4-1 to a nitrogen-substituted four-necked flask at room temperature. ^,1^-dimethylamino group|] is more steep (〇.64 ru, 5.23 mmol) and THF (280 g) and stirred. A solution of the compound [P] (10.Og, 54.9 mmol) in THF (40 g) containing the compound 201030059 was added thereto, and the reaction was further carried out. The reaction was followed by HP LC. After completion of the reaction, the reaction solution was added to purified water (1.9 L) and stirred for 30 minutes. Subsequently, it was filtered, washed with pure water (500 mL) to obtain a crude product as a yellow solid. The obtained crude product was washed with 2-propanol (60 g), and dried to give a di-nitro compound [Q] as a yellow solid (yield: 6.78 g, yield 68%). Q 1H-NMR (400 MHz, CDCI3) , 5ppm): 8.21-8.18(4H, m), 6.97-6. 93(4H, m). 4.83(2H, t), 4.15(4H, q), 3.68(4H, q). Four necks containing a mixture of compound [Q] ( 6.73 g, 17.2 mmol), 5% palladium-carbon (5% Pd/C) (0.67 g) and 1,4-dioxane (33 7 g) were replaced with nitrogen. After the flask was replaced with hydrogen, it was stirred at room temperature in the presence of hydrogen. The reaction was followed by HPLC, and after completion of the reaction, the catalyst was filtered with diatomaceous earth. Subsequently, the filtrate was evaporated under reduced pressure to give a crude product as a yellow solid. 2-propanol (48 g) was added to the crude product, and the mixture was washed with a ® ultrasonic device, and then filtered and dried to obtain a diamine-based compound [DA-5] (yield 3.43 g, yield of white powder). Rate 60%) 〇Ή-NMR (400MHz, DMS0-d6, 5 ppm): 6. 67-6.63 (4H, m), 6.51-6.48 (4H.m), 6.18(2Η, t), 4.60( 4H, brs), 3.79(4H, t), 3.30(4H, q). [Synthesis Example 6] Synthesis of 3-bis(3-(4-aminophenoxy)propyl)urea [DA-6] -49- 201030059 [Reaction step C]

[Reaction step

m o2n

Synthesis of Compound [τ] from Reaction Step C To a four-necked flask was added 4-nitroso (25.79 g '185 mm), potassium carbonate (49.70 g, 185 mmol) and DMF (130 g) at room temperature under a nitrogen atmosphere. ) 'heated to 65. (: A solution of N-(3-bromopropyl)benzimidimine (49.7 g, 185 mmol) in DMF (130 g) was added dropwise thereto. After the reaction was completed, the reaction solution was added to ice water (2080 g). In the middle, a yellow solid was obtained, which was filtered, washed with water, and then dried to give a yellow white solid compound [s] (yield 59.5 g yield 98%). 1H-NMR (400 MHz, CDCI 3. 5ρρπ): 8.8 .17-8.15(2H, m), 7.89-7.84 (2H, m). 7.76-7. 73(2H, m), 6. 86-6.84(2H, m). 4.13(2H, t), 3. 93(2H, t), 2.27- 2·20(2Η, m) 化合物 Adding hydrazine-hydrate (116.0g' 1.85mol) to a compound in a four-necked flask at room temperature under nitrogen atmosphere [S ] (60.50g' 18 5mmol) in ethanol (9〇8g) solution, then 'heated back.' -50- 201030059 After the reaction is completed, the precipitated solid is dissolved in distilled water (908g), and 1,2-dichloride is used. The ethane (5 〇〇g) was extracted four times. After the organic layer was combined, it was washed with water (500 g) twice and dried over magnesium sulfate. Yield 36.0 g, yield 99%) 0 Ή-NMR (400 MHz, CDCI 3, 5 ppm): 8.20-8. 17 (2H, tn), 6. 98-6. 94 (2H. m), 4.18- 4_ 15 (2H, m), 3.40-3. 37 (2H, m), 2. 20-2.14 (2H, m ), 2.03-2. 20 (2H, m).

G Synthesis of Compound [T] from Reaction Step D At room temperature under a nitrogen stream, 1,2-dimethoxyethane (hereinafter referred to as DME) (188 g) was placed in a four-necked flask, and 60% was added thereto. Sodium hydride (14.52 g, 3 3 3 mmol). Subsequently, a solution of DME (94 g) containing 3-amino-1-propanol (25.0 〇g, 33 3 mmol) was slowly added dropwise. Next, a 01 ugly (948) solution containing flufluoro-4-5 schylbenzene (46.968, 333 〇 1111 〇 1) was added dropwise. After completion of the reaction, the reaction solution was added to distilled water (5 64 g) φ, and extracted with dichloromethane (500 g) three times. The organic layer was combined, dried over magnesium sulfate, filtered, and evaporated to give the compound (t) (yield: 60.72 g, yield 93%). 1H-NMR (400MHz, CDCI3, d ppm): 8.20-8.17 (2H, m), 6. 98-6. 94 (2H, m), 4.18- 4_15(2H, m), 3.40-3.37 (2H, m ), 2.20-2_14(2H, m), 2·03-2·20(2Η, m). Compound (T) (60.72 g, 310 mmol) and bis(4-nitrophenyl)ester [D] (35.87 g, 1 18 mmol) were added to a nitrogen-substituted four-necked flask at room temperature. Triethylamine (47.72 g, 47 2 mmol), 4-N,N-dimethylaminopyridine (1.44 g, 11.8 mmol) and THF (720 g) were stirred. The reaction was followed by HP LC, and after completion of the reaction, the reaction -51 - 201030059 solution was added to pure water (4.3 L) and stirred for 30 minutes. Subsequently, it was filtered, washed with pure water (1 L) to give a crude product as a yellow solid. The obtained crude product was washed with 2-propanol (400 g) and then dried to give a di-nitro compound [U] as a yellow solid (yield: 38.1 g, yield 77%). 1H-NMR (400 MHz, DMS0-d6, 5 ppm) : 8.18-8.14 (4H. m). 7.11-7.08 (4H, m). 5.96(2H, t). 4.07(4H. 5). 3.11 (4H, q), 1.84-1.78(4H. m ). The compound [U] (26.00 g '62.1 mm )l), 5% palladium-carbon (5%? (1/(:) (2-6 g)) and 1,4-dioxane (160 g) / ethanol were replaced with nitrogen. After a mixture of (160 g) in a four-necked flask, the mixture was replaced with hydrogen. The mixture was stirred at room temperature in the presence of hydrogen. The reaction was followed by HPLC. After the reaction was completed, the precipitated solid was dissolved, and after replacing with nitrogen, acetonitrile was added. 1500 g) and DMF (150 g) were heated and allowed to dissolve completely. Subsequently, the catalyst was filtered with diatomaceous earth, and then the filtrate was distilled off under reduced pressure to obtain a crude product as a white solid, which was added to the crude product. 2-propanol (160 g), which was subjected to dispersion washing with an ultrasonic device. Subsequently, it was filtered and dried to obtain a diamine-based compound [DA-6] as a white solid (yield: 7.7 g, yield: 7 9 %) ^H-NMR (400MHz, DMS0-d6, <5 ppm): 6.65-6.61 (4H, m). 6.51-6.47 (4H.m), 5.90(2H.t). 4.58(4H, s). 3.8K4H, t), 3.13-3.08 (4H, m). 1.77-1.70 (4H, m) [Example 1] In a 50 ml four-necked flask equipped with a stirring device and a nitrogen introduction tube

0.60 g (2.0 mmol) of BAPU and 1.9 5 g (1 8.0 m m ο 1 ) p-PDA -52-201030059 were added, and 30 g of N-methyl-2-pyrrolidone was added, and the mixture was stirred and dissolved while blowing nitrogen gas. 3-7 g (18.9 mmol) of CBDA was added while stirring the diamine solution, and then N-methyl-2-pyrrolidone was added to adjust the solid content to 12% by mass, and the mixture was stirred at room temperature for 4 hours in a nitrogen atmosphere. A polylysine (P1) solution was obtained. The viscosity of the polyaminic acid solution at 25 ° C was confirmed to be 316 mPa_s by an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.). To the 6.26 g of the polyaminic acid solution, 9.94 g of N-methyl-2-pyrrolidinone and 6.54 g of butyl cellosolve were added to obtain a liquid crystal alignment treatment agent having a P1 concentration of 6.0% by mass. (friction resistance) The liquid crystal alignment treatment agent obtained above was filtered through a filter of Ι.Οηηι, and then spin-coated on a glass substrate to which a transparent electrode was attached, and dried on a hot plate at 80 ° C for 5 minutes, at 230 After firing at ° C for 30 minutes, a polyimide film having a film thickness of 100 nm was obtained. The polyimide film was rubbed with a crepe cloth (roll diameter: 120 mm, number of revolutions of 100 rpm, moving speed of 20 mm/sec, and amount of stretching of 0 to 4 mm). The surface state of the surface of the film was observed using a confocal laser microscope, and the presence or absence of abrasion residue and the presence or absence of scratches were observed at 10 times magnification. The results are shown in Table 2. (Production of Liquid Crystal Cell) The liquid crystal alignment agent obtained above was filtered through a 1.0 μm filter, and then spin-coated on a glass substrate to which a transparent electrode was attached, and dried on a hot plate at 80 ° C for 5 minutes, at 230 The mixture was fired at ° C for 30 minutes to obtain a polyimide film having a film thickness of -53 - 201030059 lOOnm. After rubbing with a cloth (roll diameter: 120 mm, rotation number: 300 rpm, moving speed: 20 mm/sec, and pushing amount: 0.2 mm), the polyimide film was subjected to ultrasonic irradiation for 1 minute in pure water and dried at 80 ° C for 10 minutes. minute. Prepare two substrates to which the liquid crystal alignment films are attached, and provide 6 μm of the spacer on the liquid crystal alignment film surface of one of the substrates, and then combine the rubbing directions of the two substrates in antiparallel to seal the periphery but leave the liquid crystal At the inlet, a cell having a liquid crystal cell gap of 6 μm was produced. Liquid crystal (MLC-2041, manufactured by Merck) was vacuum-injected into the cell at room temperature, and the injection port was sealed to complete the antiparallel liquid crystal cell. (Liquid alignment property) The alignment state of the above liquid crystal cells was observed with a polarizing microscope, and it was confirmed that the uniform alignment was performed without defects. (Pretilt angle) Using a measuring apparatus (TBA107, manufactured by AutroNic-MELCHERS GmbH), the liquid crystal cell was measured by a crystal rotation method to measure the pretilt angle of the liquid crystal after heating at 110 ° C for 30 minutes. (Voltage Maintaining Rate) A voltage of 4 V was applied to the liquid crystal cell produced in the same manner as in the above (manufacturing of the liquid crystal cell) by 60 ps, and the voltage after 16.67 ms was measured, and the difference from the initial enthalpy was calculated as the voltage holding ratio. At the time of measurement, the temperature of the liquid crystal cell was set to 90 ° C, and the measurement was performed at each temperature. -54-201030059 (Ion Density) The liquid crystal cell produced in the same manner as the above (manufactured by the liquid crystal cell) was measured for ion density using a 6254 liquid crystal physical property evaluation device manufactured by Toyo Kogyo Co., Ltd. The measurement system applied a triangular wave of 10 V and 0.01 Hz, and an area corresponding to the ion density of the obtained waveform was calculated by the triangle approximation as the ion density. In the measurement, the temperature of the liquid crystal cell was measured at 60 ° C. [Example 2] 2.39 g (8.0 mmo 1 ) of BAPU and ruthenium were fed into a 50 ml four-necked flask equipped with a stirring apparatus and a nitrogen introduction tube. 7 g (8 · Ommo 1 ) p-PDA, 30 g of N-methyl-2-pyridinone was added, and stirred and dissolved while blowing nitrogen gas. 2.92 g ( 14.9 mmol) of CBDA was added while stirring the diamine solution, and N-methyl-2-pyrrolidone was further added to have a solid concentration of Ο 12% by mass, and the mixture was stirred at room temperature under a nitrogen atmosphere. After 2 hours, a polylysine (P2) solution was obtained. The viscosity of the polyaminic acid solution at 25 ° C was confirmed to be 281 mPa · s with an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.). To the 16.12 g of the polyaminic acid solution, 9.61 g of N-methyl-2-pyrrolidone and 6.43 g of butyl cellosolvin were added to obtain a liquid crystal alignment agent having a P2 concentration of 6.0% by mass. [Example 3] In a 50 ml four-necked flask equipped with a stirring device and a nitrogen introduction tube, -55-201030059 was fed into 2.68 g (9.0 mmol) of BAPU and 30 g of N-methyl-2-pyrrolidone while blowing nitrogen gas. Stir and dissolve. While stirring the diamine solution, 1.69 g (8.6 mmol) of CBDA was added, and N-methyl-2-pyrrolidone was further added to adjust the solid content to 12% by mass, and the mixture was stirred at room temperature for 6 hours in a nitrogen atmosphere. A polylysine (P3) solution was obtained. The viscosity of the polyaminic acid solution at 25 ° C was 2 0 6 mP a · s ° and the addition of 5.10 g 2-Pyrrolidone and 4.94 g of butyl cellosolve gave a liquid crystal alignment treatment agent having a P3 concentration of 6.0% by mass. [Example 4] 2.62 g (9.7 mmol) of BABU and 25 g of N-methyl-2-pyrrolidone were fed into a 50 ml four-necked flask equipped with a stirring apparatus and a nitrogen gas introduction tube, and stirred and dissolved while blowing nitrogen gas. While stirring the diamine solution, 1.85 g (9_4 mmol) of CBDA was added, and then N-methyl-2-pyrrolidone oxime was added to a concentration of 10% by mass, and the mixture was stirred at room temperature under a nitrogen atmosphere. In hours, a solution of poly-proline (P4) was obtained. It was confirmed by an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.) that the polyamic acid solution had a viscosity of 1 7 3 mP a · s at 25 ° C. 5.10 g of N-A was added to the polyglycine solution at 13.90 g. Base-2-pyrrolidone and 4.75 g of butyl cellosolve gave a liquid crystal alignment agent having a P4 concentration of 6.0% by mass. -56-201030059 [Example 5] 2.54 g (8.5 mmol) of BAPU and 30 g of N-methyl-2-pyrrolidone were fed into a 50 ml four-necked flask equipped with a stirring device and a nitrogen introduction tube, while blowing nitrogen gas. Stir and dissolve. While stirring the diamine solution, 1.69 g (7.7 mmol) of PMDA was added, and N-methyl-2-pyrrolidone was further added to adjust the solid content to 10% by mass, and the mixture was stirred at room temperature for 4 hours in a nitrogen atmosphere. A polylysine (P5) solution was obtained. The viscosity of the polyproline solution at 13t was 138.6mPa·s. Pyrrolidone and 4.94 g of butyl cellosolve gave a liquid crystal alignment agent having a P5 concentration of 6.0% by mass. [Example 6] In a 50 ml four-necked flask equipped with a stirring device and a nitrogen introduction tube, 2.43 g (9.0 mmol) of BABU and 30 g of N-methyl-2-pyrrolidone were fed, and the mixture was stirred and dissolved while blowing nitrogen gas. . While stirring the diamine solution, 1.88 g (8.6 mmol) of PMDA was added, and N-methyl-2-pyrrolidone was further added so that the solid content concentration became 1% by mass, and the mixture was stirred at room temperature for 3 hours in a nitrogen atmosphere. A polylysine (P6) solution was obtained. The viscosity of the polyaminic acid solution at 25 ° C was confirmed to be 2 7 6 mPa a · s with an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.). To 10.75 g of the polyaminic acid solution, 8.56 g of N-methyl-2-pyrrolidone and 4.83 g of butyl cellosolve were added to obtain a liquid crystal alignment agent having a P6 concentration of 4.5% by mass to 57 to 201030059. [Example 7] 3.58 g (12_0 mmol) of BAPU and 30 g of N · methyl-2-pyrrolidone were fed into a 50 ml four-necked flask equipped with a stirring device and a nitrogen introduction tube, and stirred and dissolved while blowing nitrogen gas. . 2.86 g (1 1.4 mmol) of BODA was added while stirring the diamine solution, and N-methyl-2-pyrrolidone was further added so that the solid content concentration became 12% by mass, and the mixture was stirred at 50 ° C in a nitrogen atmosphere. In hours, a solution of poly-proline (P7) was obtained. It was confirmed by an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.) that the polyamic acid solution had a viscosity of 630 mPa*s at 25 ° C. 12.2 g of the polyaminic acid solution was added with 12.8 Og of N-methyl-2-pyrrole. The ketone and 6.32 g of butyl cellosolve gave a liquid crystal alignment agent having a P7 concentration of 6.0% by mass.

[Example 8] Q 3.24 g (12.0 mmol) of BABU and 25 g of N-methyl-2-pyrrolidone were fed into a 50 ml four-necked flask equipped with a stirring apparatus and a nitrogen introduction tube, and stirred and dissolved while blowing nitrogen gas. . While stirring the diamine solution, 2.99 g (11.9 mmol) of BODA was added, and N-methyl-2-pyrrolidone was further added so that the solid content concentration became 15% by mass, and the mixture was stirred at 50 ° C in a nitrogen atmosphere. A polylysine (p8) solution was obtained for 24 hours. The polyamic acid solution (manufactured by Toki Sangyo Co., Ltd.) was confirmed to have a viscosity of 498 mPa·s at 25 °C. -58-201030059 12.0 g of N-methyl-2-pyrrolidone and 550 g of butyl cellosolve were added to 9.95 g of the polyaminic acid solution to obtain a liquid crystal alignment agent having a P8 concentration of 6.0% by mass. [Example 9] Into a 50 ml four-necked flask equipped with a stirring device and a nitrogen introduction tube, 2.31 g (8.54 mmol) of DA-3 and 24_3 g of N-methyl-2-benzazeone were fed while blowing nitrogen gas. Stir and dissolve. While stirring the diamine solution, 1.66 g (8.46 mmol) of CBDA was added, and N-methyl-2-pyrrolidone was further added so that the solid content concentration became 10% by mass, and the mixture was stirred at room temperature for 4 hours in a nitrogen atmosphere. A polylysine (P9) solution was obtained. The viscosity of the polyaminic acid solution at 25 ° C was 155 mPa·s as determined by an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd.). To 16.80 g of this polyaminic acid solution, 7.57 g of N-methyl-2-pyrrolidone and 6.09 g of butyl cellosolve were added to obtain a liquid crystal alignment agent having a P9 concentration of 6.0% by mass. [Example 10] 2.84 g (9.98 mmol) of DA-4 and 2 9 · 5 g of N-methyl-2-pyrrolidone were fed into a 50 ml four-necked flask equipped with a stirring apparatus and a nitrogen introduction tube, and were blown. Stir and dissolve with nitrogen. While stirring the diamine solution, 1.66 g (9.53 mmol) of CBDA was added, and N-methyl-2-pyrrolidone was further added so that the solid content concentration became 10% by mass, and the mixture was stirred at room temperature for 4 hours in a nitrogen atmosphere. A polylysine (P10) solution was obtained. The viscosity of the polyaminic acid solution at 206 °C was 206 mPa·s ° at 17.25 g of the polyaminic acid solution, and 7.75 g of N- was added to the polyglycine solution at an E-type viscosity of -59-201030059 (manufactured by Toki Sangyo Co., Ltd.). Methyl-2-pyrrolidone and 6.22 g of butyl cellosolve gave a liquid crystal alignment treatment agent having a P10 concentration of 5.5% by mass. [Example 11] 3.50 g ( 9.48 mmol ) of DA-6 and 2 9.5 g of N-methyl-2-pyrrolidone were fed into a 50 ml four-necked flask equipped with a stirring apparatus and a nitrogen introduction tube while blowing nitrogen gas. Stir and dissolve. While stirring the diamine solution, 1.76 g (8.9 7 mmol) of CBDA was added, and N-methyl-2-pyrrolidone was further added so that the solid content concentration became 10% by mass, and the mixture was stirred at room temperature under a nitrogen atmosphere. In hours, a solution of poly-proline (P11) was obtained. The viscosity of the polyaminic acid solution at 25 ° C was 150 mPa · s by an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd.). To 18.88 g of this polyaminic acid solution, 5.26 g of N-methyl-2-pyrrolidine and 6.03 g of butyl cellosolve were added to obtain a liquid crystal alignment agent having a P11 concentration of 6.0% by mass. [Example 12] 0.53 g (1.6 mmol) of DA-5 and 1.56 g (14. 4 mmol) of p-PDA were fed into a 50 ml four-necked flask equipped with a stirring apparatus and a nitrogen introduction tube, and 30.9 g of N-methyl group was further added. The -2-pyrrolidone was stirred and dissolved while blowing nitrogen gas. While stirring the diamine solution, 2.82 g (1 5 - 4 mmol) of 201030059 CBDA was added, and N-methyl-2-pyrrolidone was further added so that the solid content concentration became 10% by mass, and the mixture was stirred at room temperature under a nitrogen atmosphere. In hours, a solution of poly-proline (P12) was obtained. The viscosity of the polyamic acid solution at 25 ° C was confirmed to be 160 mPa · s by an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd.). 6.03 g of N-methyl-2-pyrrolidone and 6.llg of butyl cellosolve were added to the polyaminic acid solution to obtain a liquid crystal alignment treatment agent having a P12 concentration of 6.0% by mass. [Example 13] 7.00 g (24.44 mmol) of D A-7 and 3.1 3 g (1 0.4 8 mmol ) of ΒΑΡϋ ' were fed into a 1000 ml four-necked flask equipped with a stirring apparatus and a nitrogen introduction tube, and the inside of the flask was replaced with nitrogen. . Next, 359.90 g of dehydrated hydrazine-methyl-2-pyrrolidone and 6.63 g of pyridine were fed into a syringe, and stirred at 25 ° C with a magnetic stirrer to completely dissolve BAPU and DA-7. Subsequently, 9.34 g (> 31.44 mm〇l) CA-4 was added while the reaction liquid was water-cooled while stirring with a magnetic stirrer. The addition was carried out using a funnel in 30 seconds. Subsequently, the funnel used was washed with 100.0 g of dehydrated N-methyl-2-pyrrolidone, and the inside of the reaction vessel was replaced with nitrogen, and stirring was continued for 3 hours under water cooling. Then, the reaction solution was poured in a small amount of methanol in a five-fold weight of the reaction solution, and stirring was continued for 1 hour. Subsequently, the precipitate obtained by filtration was stirred with five times by weight of methanol for 1 hour, and then the filtered precipitate was recovered. Subsequently, the same operation was carried out using five times by weight of methanol, and the obtained precipitate was dried at 100 ° C under reduced pressure for 24 hours to obtain 14.59 g of a polyphthalate (P13). 2.26 g of the obtained solid component was completely dissolved with -61 - 201030059 20.3 6 g of N-methyl-2-pyrrolidone. Next, 2.12 g of N-methyl-2-pyrrolidone and 10.60 g of butyl cellosolve were added to the solution to obtain a liquid crystal alignment agent having a P13 concentration of 6.0% by mass. [Example 14] Into a 30 ml four-necked flask equipped with a stirring device and a nitrogen introduction tube, 4.0 0 g (1 3.9 7 mmo 1 ) DA-7 and 1 · 7 8 g (5.9 9 mm ο 1 ) BAPU were fed. The inside of the flask was replaced with nitrogen. Next, 2 0 2.93 g of dehydrated N-methyl-2-pyrrolidone and 3.79 g of pyridine were fed through a syringe, and stirred at 25 ° C with a magnetic stirrer to completely dissolve BAPU and DA-7. Subsequently, the reaction liquid was cooled with water, and 1.27 g (3.99 mm) of CA-5 and 4.15 g (13.96 mmol) of CA-4 were added while stirring with a magnetic stirrer. The addition was carried out using a funnel in 30 seconds. Subsequently, the funnel used for the addition was washed with 10. g of dehydrated N-methyl-2-pyrrolidone, and the inside of the reaction vessel was replaced with nitrogen, and stirring was continued for 3 hours under water cooling. Next, the reaction solution was poured into a small amount of methanol in a five-fold weight of the reaction solution, and stirring was continued for 1 hour. Subsequently, the precipitate obtained by filtration was stirred with five times by weight of methanol for 1 hour, and then the precipitate was filtered. Subsequently, the same operation was carried out using five times by weight of methanol, and the obtained precipitate was dried at 100 ° C under reduced pressure for 24 hours to obtain 8.8 7 g of polyamine ester (P14). 2.27 g of the obtained solid component was completely dissolved with 20.45 g of N-methyl-2-pyrrolidone. Next, 2.13 g of N-methyl-2-pyrrolidone and 10.65 g of butyl cellosolve were added to the solution to obtain a liquid crystal alignment agent having a P14 concentration of 6.0% by mass. 201030059 [Comparative Example 1] 2.17 g (20.0 mmol) of p-PDA was fed into a 50 ml four-necked flask equipped with a stirring device and a nitrogen introduction tube, and then 25 g of N-methyl-2-pyrrolidone was added thereto while blowing nitrogen gas. Stir and dissolve. While stirring the diamine solution, 3.77 g (19.2 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was further added, and N-methyl-2-pyrrolidone was further added to make the solid concentration 12 The mass% was stirred at room temperature for 4 hours to obtain a polyaminic acid solution. The viscosity of the polyaminic acid solution at 25 ° C was confirmed to be 602.3 mPa*s by an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd.). 7.89 g of the obtained polyaminic acid solution was added to a 50 ml Erlenmeyer flask filled with a stir bar, and 6.29 g of N-methyl-2-pyrrolidone and 3.55 g of butyl cellosolve were added, and stirred by a magnetic stirrer. In a minute, a liquid crystal alignment treatment agent having a polyamine concentration of 5.5% by mass was obtained. [Comparative Example 2] ® 1 O.OOg (34.92 mmol) of DA-7 was fed into a 1 000 ml four-necked flask equipped with a stirring device and a nitrogen introduction tube, and the inside of the flask was replaced with nitrogen. Next, 304 g of dehydrated N-methyl-2-pyrrolidone and 6.1 g of pyridine' were fed in a syringe and stirred at 25 ° C with a magnetic stirrer to completely dissolve DA-7. Then, 9.34 g (3 1 ·43ηιιηο1 ) CA-4 was added while stirring the reaction liquid through water cooling with a magnetic stirrer. The addition was carried out using a funnel in 30 seconds. Then, the funnel used in the addition of 20 g of dehydrated hydrazine-methyl-2-pyrrolidone was removed. The inside of the reaction vessel was replaced with nitrogen, and stirring was continued for 3 hours under water cooling. Then, the reaction solution was stirred for 1 hour with a small amount of -63-201030059 by stirring the saturated solution in five times the weight of the reaction solution. Subsequently, the precipitate obtained by filtration was stirred with five times by weight of distilled water for 1 hour, and then the precipitate was filtered. Subsequently, the same operation was carried out using five times by weight of ethanol, and the obtained precipitate was dried under a reduced pressure of under pressure for 24 hours to obtain 14.82 g of a solid component. 3.99 g of the obtained solid component was completely dissolved with 3 5.90 g of N-methyl-2-pyrrolidone. Then, 6.91 g of N-methyl-2-pyrrolidone and 19.36 g of butyl cellosolve were added to the solution to obtain a liquid crystal alignment agent having a polyglycolic acid concentration of 5.5% by mass. [Comparative Example 3] 7.00 g (24.44 mmol) of DA-7 was fed into a 1 000 ml four-necked flask equipped with a stirring apparatus and a nitrogen introduction tube, and the inside of the flask was replaced with nitrogen. Next, 249.3 g of dehydrated N-methyl-2-pyrrolidone and 4.6 g of pyridine were fed in a syringe, and stirred at 25 ° C with a magnetic stirrer to completely dissolve DA-7. Subsequently, the reaction liquid was subjected to water cooling, and 1.56 g (4.88 mmol) of CA-5 and 6·8 8 g (1 7 · 12 mmol) of CA-4 were added while stirring with a magnetic stirrer. Adding the system using a funnel in 30 seconds. Subsequently, the funnel used for the addition was washed with 100 g of dehydrated N-methyl-2-pyrrolidone, and the inside of the reaction vessel was replaced with nitrogen, and stirring was continued for 3 hours under water cooling. Next, the reaction solution was poured into a small amount of methanol in a five-fold amount of the reaction solution, and stirring was continued for 1 hour. Subsequently, the precipitate obtained by filtration was stirred with five times by weight of methanol for 1 hour, and the filtered precipitate was collected. Subsequently, the same operation was carried out using five times by weight of methanol, and the obtained precipitate was dried at 100 ° C under reduced pressure for 24 hours to obtain 11.15 g of a solid component. Among the obtained solid components, -64-201030059 10.06 g was completely dissolved in 90.5 4 g of N-methyl-2-pyrrolidone. Next, 5.63 g of N-methyl-2-pyrrolidone and 44.97 g of butyl-solvent were added to the solution to obtain a liquid crystal alignment agent having a polyacetamide concentration of 6.0% by mass. Table 1 shows the amounts of the raw materials (diamines, etc.) used in Examples 1 to 14 and Comparative Examples 1 to 3, the codes of the obtained polylysines (P1, etc.), and the N-methyl groups of the polyamido acids. The viscosity of the 2-pyrrolidone solution. Further, the polyamines and polyphthalates of Comparative Examples 1 to 3 were not accompanied by codes (indicated by a blank column in Table 1). In addition, "one" in Table 1 indicates that the viscosity was not measured. In the same manner as in Example 1, liquid crystal cells were prepared using the liquid crystal alignment film treating agents obtained in Examples 2 to 4, Examples 7 to 13, Comparative Example 1, and Comparative Example 2, and friction resistance and liquid crystal were measured. Orientation, pretilt angle, voltage maintenance rate and ion density. Further, in the same manner as in Example 1, the friction resistance and the liquid crystal alignment property were measured for Example 5, Example 6, Example 14 and Comparative Example 3. The results obtained are shown in Table 2. -65- 201030059 [Table i] Polylysine or polyphthalate diamine tetracarboxylic acid derivative [mmol] Viscosity (mPa · s) Formula (1) [mmol] Other [mmol] Example 1 Ρ1 BAPUP.01 p-PDA丨18.01 CBDA[18.91 316 Example 2 Ρ2 BAPU『8.0] p-PDA[8〇l CBDA[ 14.91 281 Example 3 Ρ3 BAPU『9.〇l Not used CBDA『8.61 206 Example 4 Ρ4 BABU[ 9.71 Not used CBDA [9.4] 173 Example 5 Ρ5 BAPUr8.5] PMDA not used "7.71 139 Example 6 Ρ6 BABU [9.0] PMDA not used "8.61 276 Example 7 Ρ7 BAPUr 12.01 Not used ΒΟϋΑΓ 11.41 630 Example 8 Ρ8 BABUr 12.01 Not used BODAr 11.91 498 Example 9 Ρ9 DA-3 "8.51 CBDAr8.5 not used] 155 Example 10 Ρ10 DA-4[10.0] CBDA not used "9.51 206 Example 11 Ρ11 DA-6 丨9.51 Using CBDA "9.〇l 150 Example 12 Ρ12 DA-5 丨1.6] p-PDA " 14.41 CBDA "15.41 160 Example 13 Ρ13 BAPU [0.51 DA-7 [24.41 CA-4P1.41 Example Η Ρ 14 BAPU [ 6.0] DA-7 "14.〇l CA-4[14.0], CA-5f4.0] Competition Example 1 p-PDA not used 丨20.01 CBDAf 19.21 602 Comparative Example 2 DA-7 not used P4.91 CA-4P1.41 _ Comparative Example 3 Not used DA-71^4.41 CA-4『17.H, CA-5“4.91 _

-66- 201030059 [Table 2] Polyamide or polyphthalate friction resistance pretilt angle (°) Voltage maintenance ratio (%) Ion density (pC/cm2) Alignment residue scratching Example 1 Ρ1 Less ^ ΤΤΓ 1111* 1.32 92.9 138 Good Example 2 Ρ2 Μ /\s\ ^rrr 1111 1.94 96.1 67 Good Practice 3 Ρ3 Sister>firr ΙίΜ 2.45 97.3 81 Good Practice 4 Ρ4 Μ ΊΉΤ* / Μ, 2.25 96.9 59 Good Example 5 Ρ5 • fm* Ws Arrr ~ Ι11 Γ JWS Not determined Not determined Not determined Good example Ρ & 6 > £πχ Μ Μ J \ \Ν Not determined Not determined Not determined Good Example 7 Ρ7 Μ ΑττΓ 1 r 0.87 95.0 110 Good Example 8 Ρ8 Less Αττΐ IH1: j\ \\ 0.74 92.3 172 Good Example 9 Ρ9 ΑττΤ m -fTTf-1ΤΙΙ: J i ΝΝ 1.68 96.9 103 Good Example 10 Ρ10 Μ ^\\\ ιιιι: J » 2.17 97.2 42 Good Example 11 Ρ11 ΑπΤ. Μ -fnr IIH J \ 1.46 96.4 281 Good Example 12 Ρ12 Less /fnrr II11! /» \\ 1.24 92.6 207 Good Example 13 Ρ13 Less Arrr ΠΠ 1.67 96.8 52 Good Example 14 Ρ14 less than πν. 1IM /1 No measurement, no measurement, no measurement, good comparison, comparative example 1, a large number of 1.05, 90.7, 259, good comparative example 2, a large amount, 0.95, 95.2, 133, good comparative example 3, no measurement, no measurement, no measurement, no good industrial use, and use of the liquid crystal alignment treatment of the present invention. As the agent, a liquid crystal alignment film which is excellent in friction resistance, liquid crystal alignment property, and strong rubbing treatment can be obtained. Further, since the liquid crystal alignment film of the present invention has a high voltage holding ratio and a low ion density, it can be used as a liquid alignment display element which can be used as a photoalignment liquid as a vertical alignment of -67-201030059 which does not require rubbing treatment. In addition, the specification, the scope of the patent application, and the entire disclosure of the Japanese Patent Application No. 2008-285860, filed on Jan.

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Claims (1)

201030059 VII. Patent application scope: 1. A liquid crystal alignment treatment agent which is a liquid crystal alignment treatment containing any of a polyimine precursor or a polyimine obtained by reacting a diamine component with a tetracarboxylic acid derivative. And a diamine component containing the diamine represented by the following formula (1): [Chemical Formula 1] (1) ❹ (In the formula (1), 'X is an oxygen atom or a sulfur atom, and γΐ and Y2 are each independently a single bond, ·〇_, -S-, _〇co_ or -C〇〇_, Ri and R2 Each is independently an alkylene group having a carbon number of 1 to 3. 2 _ The liquid crystal alignment treatment agent of the first aspect of the patent application, wherein in the formula (1), -Ι^-Υ1- and -R2-Y2- have the same structure. 3. The liquid crystal alignment treatment agent according to claim 1 or 2, wherein in the formula (1), Y1 and Y2 are single bonds. 4. The liquid crystal alignment treatment agent according to any one of claims 1 to 3, wherein in the formula (1), X is an oxygen atom. The liquid crystal alignment treatment agent according to any one of claims 1 to 4, wherein the tetracarboxylic acid derivative is tetracarboxylic dianhydride, tetracarboxylic acid monoanhydride, tetracarboxylic acid, dicarboxylic acid dioxane Ester, or dicarboxymethyl chlorodialkyl ester. 6. The liquid crystal alignment agent according to any one of claims 1 to 5, further comprising a fluorine-based surfactant, a ruthenium-based surfactant, or a nonionic surfactant. 7. The liquid crystal alignment of any one of claims 1 to 6, which further contains a functional decane-containing compound or an epoxy group-containing compound. 8. The liquid crystal alignment treatment agent according to any one of claims 1 to 7, wherein the solid content concentration in the liquid crystal alignment treatment agent is 1 to 1% by mass relative to the total amount of the liquid crystal alignment treatment agent (1% by mass). 20% by mass. A liquid crystal alignment film obtained by the liquid crystal alignment treatment agent according to any one of claims 1 to 8. A liquid crystal display element characterized by having a liquid crystal alignment film of claim 9 of the patent application. A bisaminophenylalkylurea or a bisaminophenoxyalkylurea which is represented by the following formula (1-7), formula (1-8), formula (Ι-b) or formula (1) -c ) means: • 70- 201030059 [Chemical Formula 2] Η Η (In the formula (l_b), R12 and R22 represent an alkyl group having a carbon number of each other, and in the formula (1-c), each of R13 and R23 is an alkyl group). 12. A bisaminophenylalkylurea or a diamine group is represented by the following formula (1-9) to formula (1-1 1 ): (1-7) (1-8) (10) (1- c) F with the same carbon number 1: carbon number 1~3 ί oxyalkylurea-71 - 201030059 [Chemical 3] (1-9) H2N h2n (1-10) h2n (1-11) 72- 201030059 IV. Designated representative map: (1) The representative representative of the case is: None (2) The symbol of the representative figure is simple: No 201030059 V If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: (Chemical 1) -4-