TW201038623A - Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

Disclosed is a liquid crystal aligning agent which can provide a liquid crystal alignment film that is insusceptible to film chipping during a rubbing processing and exhibits only a small reduction in a voltage holding ratio even after the liquid crystal alignment film is exposed to a back light for a long period. Specifically disclosed is a liquid crystal aligning agent characterized by comprising a component (A) and a component (B), wherein the component (A) is a compound having such a structure that a group represented by formula [i] is bound to an aromatic ring and the component (B) is at least one polymeric compound selected from a group consisting of a polyimide and a polyimide precursor. In formula [i], X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

Description

201038623 VI. Description of the Invention: [Technical Field] The present invention relates to a liquid crystal alignment agent containing a polyimide and/or a polyimide precursor, a liquid crystal alignment film, and a liquid crystal display element. [Prior Art] Liquid crystal display elements have been widely used in today's applications as thin and lightweight display devices. In the liquid crystal display device, a liquid crystal alignment film is used to determine the alignment state of the liquid crystal. Further, the liquid crystal alignment film is produced by applying a certain alignment treatment to the surface of the polymer film formed on the electrode substrate, except for a part of the vertical alignment type liquid crystal display element. As the polymer used for the liquid crystal alignment film, polyimine, polyamine, polyamidimine or the like is known, and a liquid crystal alignment agent which dissolves these polymers or the precursor in a solvent is generally used. As a precursor of polyimine, polylysine is generally used. ^ As a method of aligning the polymer film formed on the electrode substrate, the most popular method is to apply a rubbing treatment by applying a pressure to the surface of the film by a cloth such as a crucible. However, in the step of the rubbing treatment, a part of the film may be peeled off, or a scratch caused by the rubbing treatment may occur on the surface of the liquid crystal alignment film, causing a problem of so-called "film reduction", which may become a characteristic of the liquid crystal display element. One of the reasons for the decrease or the decrease in yield. For the problem of film reduction caused by such rubbing treatment, it has been proposed to use at least one polymer of polyaminic acid or polyimine, and to use a liquid crystal alignment agent containing a specific heat crosslinkable compound of -5 to 201038623. (Method, for example, refer to Patent Document 1), or a method of using a liquid crystal alignment agent containing a compound containing an epoxy group (for example, refer to Patent Document 2), or a method of improving frictional resistance by using a curing agent. Further, in recent years, large-screen and high-definition liquid crystal televisions have been widely used, and liquid crystal display elements in such applications are required to have long-term use characteristics that can withstand harsh environments. Therefore, the liquid crystal alignment film used herein must have higher reliability than the past. The electrical characteristics of the liquid crystal alignment film are required, and the initial characteristics are also required to be good. For example, it is required to have excellent light resistance for long-term backlight exposure. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei 9- No. Hei. . That is, the problem to be solved by the present invention is to provide a liquid crystal alignment agent which has less film reduction by rubbing treatment and which has less reduction in voltage holding ratio even after long-time exposure to backlight, and further provides resistance to strictness. A highly reliable liquid crystal display element for long-term use in harsh environments. The gist of the present invention is as follows. (1) A liquid crystal alignment agent' characterized by containing -6- of the component (A)

201038623 A polymer compound selected from the group consisting of polyimine and polyimine precursors having a structure of the formula β) bonded to the aromatic ring. [Chemical 1] X〆. "^ [i] (X is a hydrogen atom or a group having 1 to 3 carbon atoms.) (2) X in the liquid crystal alignment| ® ] described in the above (1) is a hydrogen atom. (3) The liquid (A) component in the liquid described in the above (1) or (2) is at least one selected from the group consisting of the chemical compounds represented by the following formula [1]. [Chemical 2]

[wherein, Xi, X2, and 3 each independently represent an alkyl group of a hydrogen atom of ~3, Y2, and any hydrogen atom independently representing an aromatic ring may also be a hydroxyl group, a carbon atom, or a carbon number of 1 to 3. The alkoxy or vinyl group may be a single bond, all or a part may also be bonded to form a saturated hydrocarbon group having a cyclic number of 1 to 10' and any hydrogen atom may also be derived from -NH-'-N(CH3)- or The base shown in [3]. I compound and (B group at least one ί! ί, wherein the formula [i crystal alignment agent, 3 and the formula [2] [2] or a carbon number of 1 ring, the aromatic 3 alkyl group, halogen 5 The substitution of jin. The substitution of the fluorine atom of the carbon atom of the Z1 table structure 201038623 [Chemical 3] - Pi_Qi - P2 - [3] (wherein, P! and p2 each independently represent an alkyl group having 1 to 5 carbon atoms, and Qi represents an aromatic 4) is an integer of 2 to 4, and t2 and t3 are each independently an integer of 1 to 3, and a and b are each independently an integer of 1 to 3. (4) The liquid crystal alignment agent as described in the above (3) And a liquid crystal alignment agent according to the above (3) or (4), wherein Y in the formula [1], wherein X2 and X3 in the formula [2] are a hydrogen atom. And the liquid crystal alignment agent of any one of the above (1) to (5), wherein (A) is selected as the liquid crystal alignment agent of any one of the above-mentioned (1) to (5). At least one compound grouped from the following compounds.

(A) The liquid crystal alignment agent according to any one of the above-mentioned (1), wherein the component (A) is at least one compound selected from the group consisting of the following compounds. -8- 201038623 [化5]

The liquid crystal alignment agent according to any one of the above-mentioned (1), wherein the component (B) is selected from the group consisting of a diamine component and a tetracarboxylic acid dioxane. At least one polymer compound in the group consisting of an amine acid and a polyimine obtained by subjecting the polyamic acid to dehydration ring closure. (9) The liquid crystal alignment agent according to any one of the above (1) to (8), further comprising an organic solvent. (10) The liquid crystal alignment agent according to any one of the above (1) to (9), wherein the mass (concentration of the solid content) other than the organic solvent is from 1 to 20% by mass. (1 1 ) A liquid crystal alignment film obtained by using the liquid crystal alignment agent according to any one of the above (1) to (1). (12) A liquid crystal display device comprising the liquid crystal alignment film according to (11) above. The liquid crystal alignment agent of the present invention is a liquid crystal alignment film which is less cut by a film subjected to rubbing treatment and which has a small decrease in voltage holding ratio even after exposure to a backlight for a long period of time. As a result, the liquid crystal display element having the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention can be used as a highly reliable liquid crystal television or the like which is high-definition in a large screen. The liquid crystal alignment agent of the present invention is a compound (the following compound) having a structure in which the group represented by the formula [i -9 - 201038623] is bonded to the aromatic ring, and the component (B) is selected from the group consisting of poly(A). At least one polymer compound (hereinafter also referred to as a substance) in which an amine and a polymer are grouped. In the formula [i], X represents a hydrogen atom or a carbon atom number 1 to and wherein X is a hydrogen atom, the pretilt angle of the uniform liquid crystal alignment crystal can be maintained, and can be quickly removed at the same time. Liquid crystal charge is preferred. The liquid crystal alignment agent of the present invention generally contains (A) an under-ingred component which is a solution state in which these are dissolved in an organic solvent < (A) component> (A) component is a specific compound having the above formula bonded to an aromatic ring The structure of the formula [i] (-CH2 is bonded to the structure of the aromatic ring, so that it is easy to react with the polyimine and the polymerization, and the specific compounds are easy to each other. It is presumed that the present invention is achieved. In the specific compound, at least one compound which is grouped by the compound represented by the following formula [1] [2] is f: also known as a specific quinone imine precursor is a specific polymerization 3 alkyl group. Next, the reaction of the liquid display element with the (B) [i] group of -O-based cis-proline acid is also a compound and the formula -10 - 201038623 [Chem. 7]

In the formula, X, X2, and X3 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and Yl, Y2, and Y3 each independently represent an aromatic ring. Any hydrogen atom of the aromatic ring may be substituted with a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, a halogen fluorene atom, a oxy group having 1 to 3 carbon atoms or an ethylene group. ζ 〗 〖 indicates that a single bond, all or a part may also be combined to form a cyclic structure of a divalent saturated hydrocarbon group having 1 to 10 carbon atoms, and any hydrogen atom may be substituted by a fluorine atom - ΝΗ-, -N (CH3)-, a group represented by the formula [3]. Ti is an integer of 2 to 4, and t2 and t3 are each independently an integer of 1 to 3, and a and b are each independently an integer of 1 to 3. [Chem. 8] —Pi—QfP2— [3] In the formula [3],? And P2 each independently represent an alkyl group having 1 to 5 carbon atoms, and Qi represents an aromatic ring. The CH2-OX! group, the -CH2-OX2 group and the -CH2-OX3 gene of the formula [1] and the formula [2] are directly bonded to the aromatic ring, and thus Y, 'Y2, and Y3 each independently represent an aromatic ring. Examples of the specific examples thereof include a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, an anthracene ring, an anthracene ring, an anthracene ring, an anthracene ring, a phenanthrene ring, a benzonaphthalene ring, a pyrrole ring, an imidazole ring, and an oxazole ring. Thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring-11 - 201038623, pyrazoline ring, isosinoline ring, indazole ring, anthracene ring, thiadiazole ring, pyridazine ring, dioxet ring , 哩 院 院 院 ring, San Wah ring, 卩 卩 卩 环 、 、 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯, phenothiazine ring, acridine ring, oxazole ring and the like. Specific examples of the preferred aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, an anthracene ring, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, an isoquinoline ring, and an anthracene ring. An azole ring, a pyridazine ring, a pyrazine ring, a benzimidazole ring, a benzimidazole ring, an anthracene ring, a quinone ring, an acridine ring or the like. More preferably, it is a benzene ring, a naphthalene ring, a pyridinium ring or an oxazole ring, and most preferably a benzene ring or a pyridine ring. Further, the hydrogen atom of these aromatic rings may be substituted by a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, a spectrin atom, an alkoxy group having 1 to 3 carbon atoms or a vinyl group. 12 and t3 in the formula [2] are preferably an integer of 1 or 2. Further, a and b are preferably 1 or 2. X in the formula [1] and oxime 2 and oxime 3 in the formula [2] each independently represent one selected from the group consisting of a hydrogen atom, CH3, C2H5, and C3H7, and the smaller the carbon number, the polyimine and The binding reaction of poly-proline is easier, or the compound is easy to react with each other. On the other hand, when the carbon number is large, the reactivity of the -CH2-OX! group, the -CH2-OX2 group and the -CH2-OX3 group is lowered, and the storage stability of the solution containing the compound is increased. In the case where X! and X3 in the formula [1] and X2 and x3 in the formula [2] are hydrogen atoms, the uniform liquid crystal can be kept downward, and the pretilt angle of the liquid crystal can be increased, and the liquid crystal can be accumulated quickly. The charge removal of the liquid crystal display element is preferred. When all or a part of Z in the formula [2] is bonded to form a cyclic valence of 12 to 201038623, a carbon atom having 1 to 10, preferably 1 to 5, a divalent saturated hydrocarbon group Any hydrogen atom may be replaced by a fluorine atom. Examples of z include an alkylene group having 1 to 碳 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, an alkylene group and an alicyclic hydrocarbon group, and having 1 carbon atom. ~10 base. Further, a group in which any hydrogen atom of the above-mentioned group is substituted by a fluorine atom may be mentioned. In the formula [3], (^ is an aromatic ring, but as such a specific example, a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, an anthracene ring, an anthracene ring, an anthracene ring, an anthracene ring, a phenanthrene ring, a forced ring Benzonaphthalene ring, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, indazole ring, anthracene ring, thiophene Diazole ring, pyridazine ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, thiline ring, phenanthroline ring, anthracene ring, quinolin a porphyrin ring, a benzothiazole ring, a phenothiazine ring, an acridine ring, an oxazole ring, etc. Specific examples of a preferred aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, an anthracene ring, and a pyrrole ring. Imidazole ring, pyrazole ring, pyridine Q ring, pyrimidine ring, quinoline ring 'isoquinoline ring, indazole ring, pyridazine ring, pyrazine ring, benzimidazole ring, benzimidazole ring, anthracene ring, quinolin A porphyrin ring, a fluorene ring, etc., more preferably a benzene ring, a naphthalene ring, a pyridine ring, an oxazole ring, an anthracene ring or the like. In the present invention, a compound selected from the formula [1] and the formula [2] can be used. At least one combination of groups Specific examples of the specific compound to be used in the present invention include compounds of [p1] to [P45], but are not limited thereto. -13- 201038623 [Chemical 9]

OH [P1]

HO HO ^X; [P4]

OH OH

OH

OHHO-v^k^-〇H ho-^t^-oh OH [P7] [化 10] c2h5o

CP8]

OCH3 OCH3 h3co- -och3

CH3 [PI 3] [pio]

OH hct'^t^oh

OH ho^Coh [P11] H0>w<0H H3C^_^-〇-CH3 [PI 2]

[PI 4]

14- 201038623 [化11] h3co-v ch^^och: ho-Oc-^-oh H3C0^~^ CH3 N-OCH: [P19]HsCO'YY^Y'OCHs csH7〇^OCHs C3H7O [P22] HO H3C0 •^YYYV^OH 〇2Η50-ν ch3 r-1)0j h〇-^-cQ-<HO; , OH CzHsO-^ CH3^-' 〇〇2Η5 OH 〇C2Hs

HhPT^Ch〇H He/ , OH [P24] [P21]

〇ch3 c2h5o»t^丫, OC2H5 OCH3 HO^ ^OH OCH3, OC2H5 [P26] o [Chemical 12]

HO_

[P30]

❹

[P33] [P34] [P35]

[Chem. 13]

-15- 201038623 [Chem. 14] [P41] [P42] CP43] ch3 :〇^ΤφΓΝ1〇ρ>〇Η3 h3cc/ ,〇ch3

H3CO H3CO〆, 〇CH3 [P45]

OH OH

OH OH [P48] [P44]

OH HO'

OH CH3 ch3 ch3 ch3 [P46] [P47] The specific compound of the above component (A) is preferably a compound represented by [P15], [Pl7], [P19], [P29], [P31] or [P41]. Among them, compounds represented by [P15], [P17], [P29], [P31] and [P41] are preferred. <(B) Component> The component (B) is a specific polymer, and the specific polymer is as defined above. The polyimine precursor in the present invention means polyamic acid and/or polyphthalate. As the specific polymer, polyimide and polyglycolic acid are preferred. In the present invention, a method of synthesizing a specific polymer is not particularly limited. The specific polymer is generally obtained by reacting a diamine component with a tetracarboxylic dianhydride component. Generally, at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic acid and a derivative thereof is reacted with a diamine component-16-201038623 of one or more kinds of diamine compounds to obtain a formula [5]. The repeating unit of the structural formula of the polyamine is shown. The method of converting the carboxyl group of polyproline into an ester is used to obtain a polyamidate. Further, a method of imidizing the above polyamic acid into a polyimine is used. [化15]

In the formula [5], 1^ is a tetravalent organic group, and R2 is a divalent organic group 'η represents a positive integer. The tetracarboxylic acid component and the diamine component of the raw material can be appropriately selected depending on the necessity. The tetracarboxylic acid and its derivatives are tetracarboxylic acid, tetracarboxylic acid dihalide and tetracarboxylic dianhydride. Among them, tetracarboxylic dianhydride is also preferred because it has high reactivity with a diamine compound. Specific examples of the above Ri include the following structures of eight-丨 to eight-46. -17- 201038623 [化16] Al Α·2 h3c ch3 Α·3 h3c ch3 it Α·4 H3C CH3 '-____ h3c ch3 Α·5 Α*6 文Α-7 Introduction 88 XX Α.9 XX ΑΊΟ xc All Α.12 me Α.13 体A* 14 Π(:=: Α·1δ Α·16 re A. 17 ΑΊ8 ch3 Α19 A-20 Α-21 v ch3 Α-22 Μ A-23 χχ. Α -24 X>C Α-25 re A-26 XX Α_27 Α*28 A-29 Α-30 -18- 201038623 [Chem. 17] A-31 A-32 A-33 xrcc A-34 XTCC A-35 Xr \X A-36 ^cc A.37 A-38 F3C CF3 χΛχ A-39 A-40 OCC A-41 OOC A-42 A-43 A_ 44 ch3 D%tC h3c A-45 CH3 h3c A-46 ic again Specific examples of R2 include the structures of B-1 to B-1 1 3 described later.

-19- 201038623 [Chem. 18] Β·1 B.2 XX B-3 xna Β'4 B-5 ,xrxxCH3 B-6 -b Β.7 B-8 JX B-9 XT Β-10 〇-ch3 B -ll XX, B-12 h3c. _〇-ch3 善Β·13 ch3 XK"CH3 B-14 zhong α B-15 Β-16 B-17 ΒΊ8 Β-19 B-20 B-21 xr Β-22 XT&quot B-23 % B-24 Β-25 QrOr B-26 H3c ch3 B-27 CH3 -tfb- h3c Β-28 f3c B-29 ira Β·30 ira Β-31 jm B-32 θχχ B-33 -20 - 201038623 [化19] Ο

Β-34 oV Β-35 Β·36 Β·37 h3c ch3 Β-38 f3c cf3 ira B-39 FaC CFS Β·40 Η .N. Β-41 B-42 # Β-43 Β-44 B-45 Β ·46 Β-47 q^TMb B-48 Β-49 V Β-50 6. B-51 iX -21 - 201038623 [Chem. 20] Β·52 B-53 Β,54 Φο B-55 jya0xr Β-56 iTCUX B-57 Xr°xy°XX Β-58 B_59 Β-60 F B-61 H3c CH3 jT person. XX Β-62 HsC CHj xxo0xaxr Β·63 f3c cf3 Β-64 B-65 Β*6β -(CHJn- n = 2~12 B,67 ch3 —(CH2)2-C-(CH2)2-ch3 Β- 68 CH3 —(CH2)4-C-(CH2)3~ ch3 B*69 ch3 ch3 a CH2-C - (CH2)2-C—(CH2}2 - Β*70 ch3 ch3 —CHa'C—(CH2 ) 2_C—(CH2)3~ Η H Β·71 ch3 -, ten ch2)5 -22- 201038623 [Chem. 21]

Β·72 ch3 ~(CH2)4-C-(CH2)5- Η B-73 I(CH^-O - (ch2)2-o-(ch2)3- Β·74 CHg ch3 —(CH^s -Si_0-甲一(CH2)3—ch3 ch3 B-75 n = 3~12 Β-76 n = 2~12 B-77 OjCrwXXXT n = 2~12 Β-78 points n = 2~12 B- 79 WK>- n = 2^12 Β-80 YjC - (CH2)nCH3 n = 5 ～19 B-81 XX n = 5~19 Β·82 Ns^^>-0~O-(cH2)nCH3 n = 0~21 B-83 (^-(CH^CHa n = 0 to 21 Β·84 n = 0 to 21 B-85 n = 0~21 Β-86 n = 0~21 B-87 ^^~^ O_(Z)—(Z)~(cH2)nCH3 n = 0~21 Β·88 ^~N〇-^-^-〇(CH2)nCH3 n = 0~21 B-89 3-^^-^) -〇(CH2)nCH3 n = 2~19 Β-90 >-(3-(3-〇(CH2)nCH3 n = 0 〜21 B-91 ^_A〇-(3~0-〇(cH2)nCH3 n = 0 ～21 Β*92 B-93 V^^〇-C^~C^_ocF3 -23- 201038623 [化22]

-24- 201038623 [Chem. 23]

B-102 ^^COOH B103 s^s^COOH uC B-104 ^^-COOH B105 ΒΊ06 B-107 COOH HOOC B.108 HOOC B-109 / -qb- Q-〇-cooh COOH / COOH B110 0{CH2 )3C00H Bill HgC^iCH^COOH 0(CH2)3COOH H〇X^ TA0h ΒΊ12 jCrVTa COOH B-113 iTt^Cr COOH

In the above B-112 and B-113, 'Q means _c〇〇·, _〇c〇_, -CONH-, -NHCO-, -CH2-' _〇_, or _NH_. The method for producing a specific polymer, for example, a tetracarboxylic acid component containing at least one of the tetracarboxylic dianhydrides represented by the formula [6] and at least one of the diamine compounds containing the formula [7] The diamine component is subjected to polycondensation in an organic solvent such as Ν_methylpyrrolidone, hydrazine, hydrazine, -dimethylacetic acid amine, hydrazine, hydrazine, _:methylformamide or y-butyl vinegar. The method of reaction. -25- 201038623 [Chem. 24] Ο Ο

H2n-r2-nh2 [7] Further, Ri in the formula [6] has the same meaning as defined in the formula [5], and specific examples thereof are the above A-1 to A-46. Further, R2 in the formula [7] has the same meaning as defined in the formula [5], and specific examples thereof are the above-mentioned B-1 to Β_Π3. The tetracarboxylic dianhydride used for obtaining a specific polymer and its derivative are not particularly limited. The tetracarboxylic dianhydride may be used alone or in combination of two or more. Among them, when the voltage holding property is emphasized, it is preferred to use a tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure such as A-1 to A-25 and A-46. In particular, it is preferred to use at least one selected from the group consisting of A-1 to A-6, A-8, A-16, A-18 to A-24, and A-46. Further, at least 10 to 100 mol% of the tetracarboxylic dianhydride component is effective for voltage holding characteristics when it is a tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure. Further, when the liquid crystal alignment property or the accumulated charge is lowered, it is preferred to use an aromatic acid dianhydride such as A-26 to A-45. In particular, it is preferred to use at least one selected from the group consisting of 27, A-32, A-34, and A-39 to A-43. Further, when at least 20 to 100 mol% of the dianhydride component is an aromatic acid dianhydride, it is effective for liquid crystal alignment or storage charge reduction. The preferred composition ratio (m〇l%) of the tetracarboxylic acid dianhydride having an alicyclic structure or an aliphatic structure in the tetracarboxylic dianhydride component in combination with the aromatic acid dianhydride is 10% in the former. 80% 〗 〖, the latter is 20 to 90 mol%. -26- 201038623 In particular, when tetrafluorocarboxylic dianhydride is used, at least one selected from the group consisting of A-6, A-16, A-18, A-19 to A-22, and A_46 is used. The solubility of the polymer becomes high, and the solubility of the polymer is dehydrated and closed, and the solubility in the case of soluble polyimine is preferable.

The diamine represented by the formula [7] is not particularly limited, and only one type may be used in the present invention, but a plurality of kinds may be used. Among them, when a part or all of the diamine component used for obtaining a specific polymer is B-80 to B-101 or the like, the pretilt angle of the liquid crystal can be improved. Further, as the diamine component for increasing the pretilt angle of the liquid crystal, a diamine compound represented by the following formula can be exemplified. [Chem. 25]

I and 'wherein, A4 is an alkyl group having a carbon number of 3 to 20 which may be substituted by a fluorine atom, A3 is a 1,4 ring-extension hexyl group, or a 1,4-phenylene group, and a2 is an oxogen Q, or -COO-* (However, the bond position with "*" is combined with a3), Αι is an oxygen atom, or -COO-* (but the bond position with '*' is combined with (CH2) a2 ). Further, 3! is an integer of 0 or 1, and a2 is an integer of 2 to 10, and a3 is an integer of 0 or 1. When the liquid crystal is particularly vertically aligned, the diamine component is preferably used in an amount of 5 to 100 mol%, more preferably 10 to 80 mol%, b-80 to B-101, or the like. When the tetracarboxylic acid component is polymerized with the diamine component, the reaction temperature may be any temperature of from -2 °C to 150 °C, preferably from -5 °C to 100 °C. -27- 201038623 The degree of polymerization of a particular polymer is affected by the ratio of raw materials charged. Therefore, the ratio of the total number of moles of the compound constituting the tetracarboxylic acid component to the total number of moles of the diamine compound constituting the diamine component is preferably 0.8 to 1.2, preferably 0.9 to 1.1. The closer the molar ratio is to 1. 〇, the greater the degree of polymerization of the resulting polymer. As a method of imidizing polylysine, it is generally a thermal imidization by heating, and a catalyst imidization using a catalyst, but the imidization of the imidization reaction at a relatively low temperature is carried out. It is preferred that the molecular weight of the obtained polyimine is less likely to occur. The catalyst is imidized so that the polyglycolic acid can be stirred in an organic solvent in the presence of an alkaline catalyst and an acid anhydride. The reaction temperature at this time is -2 0 ° C to 2 50 ° C, preferably 0 to 180 ° C. The higher the reaction temperature, the faster the imidization proceeds, but when it is too high, the molecular weight of the polyimine is sometimes lowered. The amount of the alkaline catalyst is 醯. 5~3 0 moles, preferably 2 to 20 moles, and the amount of the anhydride is 1 to 50 moles of the amidate group, preferably For 3 to 3 〇 Mo Er times. When the amount of the basic catalyst or acid anhydride is small, the reaction does not proceed sufficiently, and if it is too large, it is difficult to completely remove the reaction after completion of the reaction. The basic catalyst may, for example, be pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine. Among them, pyridine is preferred because it has a moderate alkalinity in the reaction. Further, the acid anhydride may be acetic anhydride, trimellitic anhydride or pyromellitic anhydride. In the case where acetic anhydride is used, purification after completion of the reaction is easily carried out, which is preferable. The organic solvent is not particularly limited as long as it can dissolve the polyamic acid. Specific examples thereof include hydrazine, Ν'-dimethylformamide, and N,N'-di. Methylacetamide, N-methyl-2_pyrrole-28 - 201038623 alkanone, N-methyl caprolactam, dimethyl hydrazine, tetramethyl urea, dimethyl hydrazine, hexamethyl Maple, 7-butyrolactone and the like. The imidization ratio by the imidization of the catalyst can be controlled by the amount of the catalyst and the reaction temperature and reaction time. The produced polyimine can be obtained by recovering a precipitate obtained by putting the above reaction solution into a poor solvent. In this case, the poor solvent to be used is not particularly limited, and examples thereof include methanol, acetone, hexane, ethylene glycol butyl ether, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene. Water, etc. The polyimine which is precipitated by the lean solvent is filtered, and then dried under normal pressure or reduced pressure, and then heated or dried to become a powder. When the polyimine powder is further dissolved in an organic solvent, and the reprecipitation operation is repeated 2 to 10 times, the polyimine can be purified. This purification step may preferably be carried out when the precipitation recovery operation cannot remove impurities. The molecular weight of the specific polyimine used in the present invention is not particularly limited, and the weight average molecular weight is preferably 2,000 to 200,000, more preferably 4,000, from the viewpoints of ease of handling and stability of properties at the time of film formation. Q ~ 50,000. The molecular weight can be determined by GPC (gel permeation chromatography) &lt;liquid crystal alignment treatment agent&gt; The liquid crystal alignment treatment agent of the present invention is generally a specific compound of the above (A) component and a specific polymer of the component (B). It is obtained by mixing with other components mentioned later in an organic solvent as needed. The specific compound may be one type or a combination of plural types. The mixing method is, for example, a method in which the component (B) is dissolved in a solution of an organic -29-201038623 solvent, and the component (A) is added as needed. The organic solvent to be used in this case is not particularly limited as long as it is a solvent for dissolving polyimine. This specific example is as follows. For example, N,N'-dimethylformamide, hydrazine, hydrazine, -dimethylacetamide, hydrazine-methyl-2-pyrrolidone, hydrazine-methyl caprolactam, 2-pyrrolidone, Ν-Ethylpyrrolidone, Ν-vinylpyrrolidone, dimethyl arylene, tetramethyl urea, pyridine, dimethyl maple, hexamethyl sulfoxide, r-butyrolactone, 1,3-dimethyl- Imidazolinone, dipentene, ethylpentyl ketone, methyl fluorenone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropanone, cyclohexanone, ethyl carbonate, ethyl carbonate Ester, diglyme, 4-hydroxy-4-methyl-2-pentanone, and the like. These solvents can be used in combination of two or more types. When the polyimine is dissolved in an organic solvent, heating can be carried out for the purpose of promoting the dissolution of the polyimide. When the heating temperature is high, the molecular weight of the polyimide may decrease. Therefore, the temperature is preferably 30 to 100 ° C, preferably 50 to 9 ° C. The concentration of the polyimine solution is not particularly limited, and the concentration of the polyimine in the solution is preferably 1 to 2% by mass, preferably 3 to 15% by mass, particularly preferably 3 to 10% by mass. . The specific compound may be directly added to the solution of the polylysine and the solvent-soluble poly@imine, but it is preferably added in a suitable solvent to a concentration of 〇1 to 50% by mass, preferably 5 to 20% by mass. The solvent of the above polyimine is mentioned as this solvent. <Other components> The liquid crystal alignment treatment agent of the present invention may contain a specific polymer, specifically g-30-

In addition to the compound, the solvent may be used as a solvent for improving the film thickness uniformity or surface smoothness when the treatment agent is applied, or a substance for improving the adhesion between the liquid crystal alignment film and the substrate. These are mixed with a specific polymer and added to the specific compound, or added after the solution. [Solvent for improving film thickness uniformity or surface smoothness] Examples of the solvent for improving film thickness uniformity or surface smoothness include the following. For example, isopropyl alcohol, methoxymethylpentanone, methyl ethyl glycol, butyl 赛苏苏, methyl sarbuta acetate, acetic acid ester, butyl carbitol, ethyl Carbitol, ethyl carbitol glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, butyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl glycol-tert- Butyl ether, dipropylene glycol monomethyl ether, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether Alcohol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropionic acid monopropyl acid, 3-methyl-3-methoxybutyl acetate vinegar, methyl ether, 3-methyl- 3-methoxybutanol, diisopropyl ether, ether, diisobutylene, pentyl acetate, butyl butyrate, butyral butanone, methylcyclohexene, propyl ether 'dihexyl ether , Xinxieyuan, η-octane, diethyl ether, methyl lactate ethyl lactate, ethyl acetate, η-butyl acetate, propylene glycol monoethyl ether cloth liquid crystal materials, can be used in some Mixed concrete , Glycol Alcohol, Kesailusu Acetate, Ethylene Glycol Monoether Ether, Propanol, Diacetate Mono, Dipropylene Diethylene Monoethylene Tripropylene Glycol Ethyl Isobutyl Ether, Second Hospital, η -methyl valerate, pyruvate-31 - 201038623 methyl ester, ethyl acetonate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-methoxypropionic acid Ethyl ester, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, i-methoxy-2-propanol, 1 -ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-丨_单甲Ethyl ether-2-acetate, propylene glycol-b-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, lactic acid A solvent having a low surface tension such as η-propyl ester, n-butyl lactate or isoamyl lactate. These solvents can be used after using one type or a mixture of plural types. When the solvent is used, the solvent contained in the liquid crystal alignment agent is preferably from 5 to 80% by mass, preferably from 20 to 60% by mass. [Substance for improving film thickness uniformity or surface smoothness] Examples of the film thickness uniformity or surface smoothness include a fluorine-based surfactant, a polyfluorene-based surfactant, and a nonionic surfactant. More specifically, for example, F-topEF301, EF3 03, EF352 (manufactured by Dokampa), Megafac F171, F173, R-30 (made by Dainippon Ink Co., Ltd.), 卩111〇 (1?€ 430, ? 431 (Sumitomo 3 "Company"), Asahiguard AG7 1 0, Surflon S-3 82, SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.), etc. The ratio of use of these substances is included in the liquid crystal alignment The amount of the component (B) of the treating agent is preferably 0.01 to 2 parts by mass, more preferably -32 to 201038623, preferably 0 to 0 1 to 1 part by mass. [Improving the adhesion between the liquid crystal alignment film and the substrate. Specific examples of the substance which improves the adhesion between the liquid crystal alignment film and the substrate include a functional decane-containing compound or a compound containing an epoxy group. For example, 3-aminopropyltrimethyl Oxydecane, 3-aminopropyltriethoxy Decane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, Ν-(2-aminoethyl)-3-aminopropyltrimethoxydecane, hydrazine- (2-Aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, oxime-ethoxy Carbocarbonyl-3-aminopropyltrimethoxydecane, Ν-ethoxycarbonyl-3-aminopropyltriethoxydecane, Ν-triethoxycarbenylpropyltriethylidene triamine , Ν-trimethoxymethyl methacrylate propyl triethylamine, 10-trimethoxymethyl sulfonyl-I, 4,7-triazadecane, 10-triethoxymethyl sulfonyl-Q 1,4,7-triazanonane, 9-trimethoxycarbamido-3,6-diazaindolyl acetate, 9-triethoxycarbamido-3,6-diaza Heteroalkyl acetate, Ν-benzyl-3-aminopropyltrimethoxy decane, Ν-benzyl-3-aminopropyltriethoxy decane, Ν-phenyl-3-amine Propyltrimethoxydecane, fluorenyl-phenyl-3-aminopropyltriethoxydecane, fluorene-bis(oxyethylidene)-3-aminopropyltrimethoxydecane, hydrazine-bis(oxygen) Base extension B 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-hexane-33- 201038623 diol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 1 , 3,5,6-tetraepoxypropyl-2,4-hexanediol, 1\[,:^,:^',;^'-tetraepoxypropyl-111-xylenediamine, 1,3-bis(indenyl diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraepoxypropyl-4,4'-diaminodiphenylmethane, and the like. When 100 parts by mass of the specific polymer component contained in the liquid crystal alignment agent is added, it is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass. When the amount is not more than 0.1 part by mass, the adhesion improving effect is not obtained, and when the amount is more than 30 parts by mass, the alignment property of the liquid crystal may be deteriorated. In the liquid crystal alignment treatment agent of the present invention, in addition to the above, the polymer component other than the specific polymer or the electrical properties such as the dielectric constant or the conductivity of the liquid crystal alignment film can be added without impairing the range of the effect of the present invention. Further, a substance to be changed (such as a dielectric or a conductive material) may be added to improve the film hardness or density when the liquid crystal alignment film is used (a substance which changes electrical characteristics) as a liquid crystal alignment film. Specific examples of the substance in which the charge of the liquid crystal cell of the liquid crystal alignment film is removed by the movement of the charge are exemplified by an amine such as Μ 1 to Μ 1 5 8 (hereinafter also referred to as an added amine). The addition of the amine may be directly added to the solution of the specific polymer, and it is preferably added in a suitable solvent to a solution having a concentration of 0.1 to 1% by mass, preferably 1 to 7% by mass. The solvent of the above polyimine is mentioned as this solvent. -34- 201038623 [Chem. 26] H3C>ir called έτΝΗζ M1 M2 M3 M4 M5

CH3 HsN M6 M7 M8 M9 M10

M11 M12 M13 M14 M15 [Chem. 27]

M16 M17 M18 M19 M20

M26 M27 M28 M29 -35- 201038623 [28]

NH NH2 ^-NHz

N-N

N-N *NH, M31 M32 M33 M34

[化29]

M55 M56 M57 M58 -36- 201038623 [化30] h2n* H3Cs M59

M65 M64

HsCY^N f^N HsC'v^NN^A^NHz N^Is^NH, ^N-k^NH2 WNA^NH2 o nh2 M68 M69

M72 M70 M71 [化31]

M81 M82 M83 M84 -37- 201038623 [化32], νη2, CH, :: 碎αα» M88 M87 M85 M86

NH2 0 (3⁄4 M91

CO ch3 M92

CO N NH2 5 M93

.NH, X, M96 s-

[化33] Q 0^nh ch3 mi

Nh2 cl

M100 h2Nj00 M101

Cf3 •nh2 s^^hh m〇4 M105 2 ch3 M106

Nh2 M108 H2N^c〇 M109 -38- 201038623 [Chem. 34]

M122 M123 M124 M125 [化35]

M134 M135 M136 M137 M138 39- 201038623 [化36]

Cn CH3 h3c^ch3 nh2 ^)-nh2 M141 M142 M143 H,C M139 M140

Br HzHy M145 M146 M147 OQVc M148 M150 M151 [Chem. 37]

H2H^O hn^.NH M152 M153 M154 M155 M156 The concentration of the solid component in the liquid crystal alignment agent of the present invention can be appropriately changed by the film thickness of the intended liquid crystal alignment film, but a coating film capable of forming a defect-free film can be formed. Further, as a liquid crystal alignment film having a suitable film thickness, it is preferably 1 to 20% by mass, preferably 2 to 10% by mass. Here, the solid content is the mass of the component which removes the solvent by the liquid crystal alignment treatment agent. &lt;Liquid Crystal Alignment Film/Liquid Crystal Display Element&gt; The liquid crystal alignment treatment agent of the present invention is applied to a substrate, and then subjected to alignment treatment by rubbing treatment or light irradiation, or in alignment with a vertical alignment or the like. It can be used as a liquid crystal alignment film by treatment. The substrate is not particularly limited as long as it has high transparency, and a glass-40-201038623 substrate or a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used. In particular, when a substrate such as an ITO electrode to be driven by a liquid crystal is used, it is preferable from the viewpoint of simplifying the process. Further, when the reflective liquid crystal display device is only a single-sided substrate, an opaque such as a germanium wafer may be used, and in the case of the electrode, a material that reflects light such as aluminum may be used. The coating method of the liquid crystal alignment agent is not particularly limited, and is generally industrially a Q method by screen printing, offset printing, letterpress printing, jetting or the like. As other coating methods, there are dipping, roll coating, slit coating, rotor, etc., and these can be used for the purpose. After the liquid crystal alignment treatment agent is applied onto the substrate, the firing may be carried out by heating means such as a hot plate at 50 to 300 ° C, preferably at 80 to 250 ° C. A coating film is formed. When the thickness of the coating film after firing is too thick, it is disadvantageous in the power-consuming surface of the liquid crystal display, and if it is too thin, the reliability of the liquid crystal display element may be lowered, so it is preferably 5 to 3 0 0 nm, more preferably 1 0 to 1 0 0 nm. When the liquid crystal is horizontally aligned or tilted, the coating film after the firing is treated by rubbing or polarized ultraviolet rays or the like. In the liquid crystal display device of the present invention, a substrate having a liquid crystal alignment film is obtained from the liquid crystal alignment agent of the present invention by the above method, and a liquid crystal cell is produced by a known method as a component. An example of a method for producing a liquid crystal cell is a pair of substrates on which a liquid crystal alignment film is to be formed, a spacer is spread on a liquid crystal alignment film of a single substrate, and a liquid crystal alignment film surface is formed inside, and another single substrate is bonded. A method in which a liquid crystal is injected under reduced pressure and sealed, or a method in which a liquid crystal is dropped onto a liquid crystal alignment film surface of a spacer, and a substrate is bonded to each other to be closed. The thickness of the spacer at -41 - 201038623 at this time is preferably from 1 to 30 μm, more preferably from 2 to 1 〇 V m. The liquid crystal display device produced by using the liquid crystal alignment agent of the present invention is excellent in reliability, and can be suitably used for a large-screen, high-definition liquid crystal television or the like. [Embodiment] [Examples] Hereinafter, the present invention will be described in more detail with reference to examples (synthesis examples) and comparative examples, but the present invention is not construed as being limited thereto. &lt;Synthesis Examples 1 to 4 4, Examples 1 to 2 7 and Comparative Examples 1 to 6 &gt; Abbreviations and symbols used in the examples (synthesis examples) and comparative examples are as follows. Further, the measurement of the molecular weight of the polyimine and the measurement of the imidization ratio were carried out according to the following methods. &lt;tetracarboxylic dianhydride&gt; A-1 : 4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride A-2: 1,2,3,4-cyclobutane Alkanetetracarboxylic dianhydride A - 3 : pyromellitic dianhydride A-4: bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride A-5: 2, 3,5-tricarboxycyclopentyl acetic acid-ι,4: 2,3-dianhydride-42 - 201038623 [Chem. 38]

&lt;February&gt; B-2: 1,3-diamino-4-octadecyloxybenzene B-4: p-phenylenediamine B-5: 4-{4-(4- Heptylcyclohexyl)phenoxy}-1,3-diaminobenzene B-8 : 4,4'-diaminodiphenylmethane B-1 3 : 3 , 5 -diaminobenzoic acid B- 14 : m-phenylenediamine B - 1 5 : diamine compound B-16 represented by the following formula B - 15 : 1,3-diamino-5- { 4-[trans-4-( Trans-4-n-pentylcyclohexyl)cyclohexyl]phenoxymethyl}benzene [39]

(Specific compound) -43- 201038623 The meanings of P15, P17, P29, P31 and P41 are as described above. [40]

&lt;Amine compound&gt; c -1 : 3-aminomethylpyridine C - 2 : 3-aminopropyl imidazole (organic solvent) Ν Μ P : N -methyl-2-pyrrolidone BCS: butyl raceway SU GBL: γ-butyrolactone &lt;Molecular weight determination of polyimine&gt; The molecular weight of the polyimine in the synthesis example can be a room temperature colloidal permeation chromatography (GPC) apparatus manufactured by Senshu Scientific Co., Ltd. (SSC-7200) ),

Shodex column (KD-803, KD-8 05) is measured as follows: Column temperature: 50 °c Dissolution: Ν, N '-dimethylformamide (as additive, lithium bromide - hydration (L i B r · Η 2 Ο ) is 30 mm ο 1 / L, phosphoric acid • anhydrous crystals (〇- -44- 201038623 phosphoric acid) is 30 mm〇l/L, tetrahydrofuran (THF) is 10 ml/L) : 1.0 m 1 /min Standard curve for standard samples: TSK standard polyethylene oxide (total molecular weight of approximately 9000,000, 150,000, 1〇〇, 〇〇〇, 30,000) manufactured by Tosoh Corporation, and Polyethylene B by Polymer Laboratory Glycol (molecular weight of about 12,000, 4,000, 1,000). Q <Measurement of imidization ratio> The imidization ratio of the polyimine in the synthesis example was measured as follows. 20 mg of polyimine powder was placed in an NMR sample tube (NMR sampling tube standard Φ 5 manufactured by Kusano Scientific Co., Ltd.), and 0.53 ml of dimethyl hydrazine (DMSO-d6 &gt; 0.05% TMS mixture) was added thereto, and ultrasonic waves were applied thereto. Make it completely soluble. This solution was measured for proton NMR at 500 MHz by an NMR measuring instrument (JNW-ECA500) manufactured by JEOL Ltd. The imidization ratio is determined by using protons having a structure unchanged before and after imidization as the reference proton Q, using the peaks of the protons and the protons of the NH group derived from proline from 9.5 to 10. The peaks are accumulated and found by the following formula. Amination rate (%) = (1 - α · X / y) xl 〇〇 In the above formula, X is the proton peak accumulation 値 from the NH group of the proline, and y is the peak accumulation of the reference proton 値 ' α For the case of polyproline (imidization ratio 〇%), the proton number ratio of the proton of one proton of the thiol group of valeric acid is -45 - 201038623. (Synthesis Example 1) A - 4 (1 3.5 g ' 5 4 mm ο 1 ), B-4 (5.4 g, 50 mmol), and B-5 (8.2 g, 22 mmol) were mixed in NMP (80_lg), After reacting at 40 ° C for 3 hours, A - 2 (3 · 3 g, 17 mm ο 1 ) and hydrazine (41.8 g) were added, and the reaction was carried out at 40 ° C for 3 hours to obtain a polyaminic acid solution. After the NMP was diluted to 6% by mass in the polyamic acid solution (1 〇 4.2 g), acetic anhydride (12.5 g) and pyridine (9.7 g) as an imidization catalyst were added, and the mixture was carried out at 80 ° C. Hour response. The reaction solution was poured into methanol (1,300 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (A). The polyimine had an imidization ratio of 55%, a number average molecular weight of 19,100, and a weight average molecular weight of 54,300. (Synthesis Example 2) A-4 (127.6 g, 510 mmol), B-13 (51.8 g '340 mmol), and B-5 (129.4 g' 340 mmol) were mixed in ΝΜΡ (1096 g) at 8 (TC) After 5 hours of reaction, 'A-2 (33.0 g, 168 mmol) and NMP (272 g)' were added to react at 40 ° C for 3 hours to obtain a polyaminic acid solution. The polyaminic acid solution (5 1 0.2 g ) was obtained. After adding Ν Μ P to 6% by mass, acetic anhydride (54_3 g) and pyridine (42.2 g) were added as a catalyst, and the reaction was carried out at 80 ° C for 3 hours. The reaction solution was poured into methanol (6500 ml). In the middle of the furnace, the precipitate of the obtained -46-201038623 was separated. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (B). The imidization ratio was 57%, the number average molecular weight was 22,800, and the weight average molecular weight was 79,200 ° (Synthesis Example 3) A-4 (127.6 g, 5 1 Ommol), B-13 (51.8 g, 340 mmol), and B -5 (129.4 g, 3 4 0 mm ο 1 ) was mixed in NMP (1 096 g o ), and after reacting at 80 ° C for 5 hours, A-2 (33.0 g, l68 mmol) and NMP (272 g) were added. 40 ° C for 3 After the hourly reaction, a polyaminic acid solution was obtained. After the NMP was added to the polyamic acid solution (1 〇 1.2 g) and diluted to 6% by mass, acetic anhydride (2 1.4 g) and pyridine were added as an imidization catalyst. (16.0 g), the reaction was carried out for 3 hours at 90 ° C. The reaction solution was poured into methanol (65 0 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol at 1 〇〇. The polyimine powder (C) was obtained by drying under reduced pressure at ° C. The imidization ratio of the polyimine was 81%, the number average molecular weight was 2,400, and the weight average molecular weight was 65,400 (Synthetic Example 4). Mix A-4 (3 7.3 g, 148.8 mmol), B-13 (21_lg, 138.9 mmol), and B-16 (25.9 g, 5 9.5 mm ο 1 ) in NMP (2 0 3 . 5 g ) After reacting at 80 ° C for 5 hours, A-2 (9.5 g, 48.3 mmol) and NMP (171.4 g) were added, and 401 was allowed to carry out -47-201038623 for 6 hours to obtain a polyaminic acid solution. After the NMP was added to the polyamic acid solution (15.6 g) and diluted to 6% by mass, acetic anhydride (27.0 g) and pyridin (20.9 g) were added as an imidization catalyst at 90%. (: The reaction was carried out for 3.5 hours. The reaction solution was poured into methanol (丨6〇〇ml) to 'subtract the precipitate obtained by separation. The precipitate was washed with methanol and reduced at 1 °C. After pressure drying, a polyimine powder (D) was obtained, which had an imidization ratio of 80%, a number average molecular weight of 21,200, and a weight average molecular weight of 64,500. (Synthesis Example 5) A-1 (3 0.3 g &gt; lOO.Ommol), B - 4 (9.7 g &gt; 9 0.0 mm ο 1 ), and B-2 (3.8 g, 10 mmol) were mixed in NMP (246.7 g) at 5 After a 24 hour reaction at 〇 ° C, a polyaminic acid solution was obtained. After adding NMP to the polyamic acid solution (120.8 g) and diluting to 6 mass%, acetic anhydride was added as an imidization catalyst (3 5 . Og) and pyridine (16. 2g) &gt; 3 hours of reaction at 35t. The reaction solution was poured into methanol (1 420 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol at 1 The polyimine powder (E) was obtained by drying under reduced pressure at 00 ° C. The imidization ratio of the polyimine was 83%, the number average molecular weight was 12,700, and the weight average molecular weight was 29,200. (Synthesis Example 6) A-2 (11. 8g, 60.0mmol), Ad (11.5g' 52.8mmol), and B-8 (23.8g, 120.0mmol) were added to -48 in NMP (266'4g). The mixture was mixed at 201038623 and reacted at room temperature for 5 hours to prepare a polyaminic acid solution (F) having a number average molecular weight of 11,7 〇〇 'weight average molecular weight of 29,400. 7) A-2 (39.2 g, 200.0 mmol) and B-4 (20.5 g, 190.0 mmol) were mixed in NMP (537.9 g), and reacted at room temperature for 0.5 hours to prepare a polyaminic acid solution ( G) The polyamine has a number average molecular weight of 13,600 and a weight average molecular weight of 38,400. (Synthesis Example 8) A-5 (22.2 g, 99.0 mmol), B-8 (19. 8 g, 100.Ommol) The mixture was mixed in NMP (168.1 g), and reacted at 40 ° C for 15 hours to obtain a polyaminic acid solution (Η). The polyamine acid had a number average molecular weight of 25,500 and a weight average molecular weight of 92,100. Example 9) A-5 (22_2 g, 99.0 mm 0.1.) and B-8 (19. 8 g '100.Ommol) were mixed in NMP (168.lg), and reacted at 40 ° C for 15 hours. Polylysine solutionAfter adding the NMP to the polyamic acid solution (50.0 g) and diluting to 4.5% by mass, acetic anhydride (6.0 g) and pyridine (4·7 g) were added as an imidization catalyst at 1 〇0 °C. It was allowed to react for 3 hours. The reaction solution was poured into methanol (620 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol to dryness under reduced pressure at -49 to 201038623 at 00 ° C to obtain a polyimine powder (I). The polyamidimide had an imidization ratio of 64%, a number average molecular weight of 21,200, and an average weight average molecular weight of 75,900. (Synthesis Example 1 〇) A-5 (3.3 g, 15 mmol), B-4 (1.3 g, 12 mmol), and B-15 (1.5 g '3 mmol) were mixed in NMP (24.5 g) at 40 ° C The reaction was carried out for 8 hours to obtain a polyaminic acid solution. After adding NMP to the polylysine solution (20.0 g) and diluting it to 6 mass%, acetic anhydride (2.5 g) and pyridine (1.9 g) were added as an imidization catalyst, and the reaction was carried out at 9 Torr for 3 hours. The reaction solution was poured into methanol (300 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (J). The polyimine has an imidization ratio of 50%, a number average molecular weight of 18, 100, and a weight average molecular weight of 52,300. (Synthesis Example U) A-5 (4.5 g, 20 mmol), B-14 (1.5 g, 14 mmol),

B-5 (2.3 g, 6 mmol) was mixed in N Μ P (3 3 · 0 g ), and reacted at 40 ° C for 8 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (30.0 g) and diluting it to 6% by mass, acetic anhydride (3-7 g) and pyridine (2.9 g) were added as an imidization catalyst, and the reaction was carried out at 9 (TC for 3 hours). The reaction solution was poured into methanol (3,70 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C - 50 - 201038623 to obtain a polyimine powder. (κ) The imidization ratio of the polyimine is 51% 'the number average molecular weight is 18,600, and the weight average molecular weight is 72,600. (Synthesis Example 1 2 ) A-4 ( 85.1 g, 3 40 mmol ) ' B- 13 (39.6 g, 260 mmol) and B16 (60.9 g '140 mmol) were mixed in NMP (556.3 g), and after reacting at 80 ° C for 5 hours, A-2 (1 1.5 g, 58 mmol) and NMP were added. (231.4 g), a polyamine acid solution was obtained after a reaction for 3 hours at 40 ° C. NMP was added to the polyaminic acid solution (200 g · 0 g) and diluted to 6 mass%, and then imidized. The catalyst was added with acetic anhydride (2 6.4 g) and pyridin (1 3 · 7 g), and the reaction was carried out at 100 ° C for 2.5 hours. The reaction solution was poured into methanol (2500 ml), and the filtrate was separated. The precipitate was washed with methanol, and dried under reduced pressure at 10 ° C to obtain a polyimine powder (L). The imidization ratio of the polyimine was 7 1 Q %. The number average molecular weight was 2 1,300 00, and the weight average molecular weight was 54,700 (Synthesis Example 13) A-4 (112.6 g, 450 mmol), B-4 (19. 5 g, 1 80 mmol), B-13 ( 18.3, 120 mmol) , B-5 (114.2g, 300mmol) was mixed in NMP (7 9 3 · 5 g ), and after reacting for 5 hours at 80 ° C, A-2 (28.6g, 145mmol) and NMP (3) were added. 78.5 g), a polyamine acid solution was obtained after a reaction at 40 ° C for 3 hours. The polyaminic acid solution ( -51 - 201038623 3 〇 O.Og) was added to NMP and diluted to 6 mass%, and then used as a sub- The amination catalyst was added with acetic anhydride (3 1. 3 g) and pyridine (2 4.2 g), and the reaction was carried out at 80 ° C for 4 hours. The reaction solution was poured into methanol (3 700 ml), and the mixture was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (Μ). The polyamidimide had an imidization ratio of 52%, a number average molecular weight of 1,980, and a weight average molecular weight of 53,800. (Synthesis Example 14) Α-4 (138.2 g, 552 mmol), B-13 (39.6 g, 260 mmol), and B-5 (74.2 g - 1 95 mmol) were mixed in NMP (8 1 9 g). After reacting at 80 ° C for 5 hours, A-2 ( 18.1 g, 92 mmol) and NMP (3 46 g) were added, and the reaction was carried out at 40 ° C for 3 hours to obtain a polyaminic acid solution. After adding NMP to the polyaminic acid solution (500.0 g) and diluting to 6 mass%, acetic anhydride (68.1 g) and pyridine (35.2 g) were added as an imidization catalyst at 10 The reaction was carried out at 0 ° C for 2.5 hours. The reaction solution was poured into methanol (6200 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried at a reduced pressure of 1 Torr (TC) to obtain a polyimine powder (N). The imidization ratio of the polyimine was 68%, and the number average molecular weight was 22. 100, the weight average molecular weight was 77,200. The liquid crystal alignment treatment agents (1) to (27) were prepared as follows, and the friction resistance was evaluated for each of the liquid crystal alignment treatment agents as follows. The results are summarized in Table 1. 201038623 [Evaluation of Friction Resistance] The liquid crystal alignment agent of the present invention obtained above was spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate of 8 CTC for 5 minutes, followed by a hot air circulation at 22 ° C. The film was fired in an oven for 30 minutes to form a coating film having a film thickness of 1 〇〇 nm. The coating film was rubbed on a roll having a roll diameter of 120 mm, and the roll was rotated at several rpm, and the roll was rotated at a speed of 50 mm/sec. The substrate having the liquid crystal alignment film was obtained by rubbing under the condition of 0. 4 mm. The surface of the liquid crystal alignment film near the center of the substrate was observed at a random magnification of 100 times by a laser microscope at a magnification of 100 times. Observation field The 6.5 mm square range was confirmed as the average of the amount of frictional damage and friction slag (attachment), and the frictional resistance was evaluated. The results are shown in Table 1 below, and the evaluation criteria are determined as follows. Q Evaluation Standard A: Friction Or rubbing slag 20 or less B: frictional or friction slag is 2 〇 ~ 40 C: frictional or friction slag is 40~60 D: frictional or friction slag is more than 60 (Example 1) The polyimine powder (a) (5.2 g) obtained in Example 1 was added with NMP (29_5 g), and stirred at 80 ° C for 3 hours to dissolve. The solution was added to the solution of P15 at a temperature of -53 - 201038623. The NMP solution (5.2 g) (as a P15, 〇.52 g), NMP (3.4 g), and BCS (43.3 g) were stirred at room temperature for 2 hours to obtain a liquid crystal alignment treatment agent (1). 2) NMP (2 7.3 g) was added to the polyimine powder (B) (5.6 g) obtained in Synthesis Example 2, and it was stirred at 70 ° C for 30 hours to dissolve it. C- was added to the solution. 1 5.0 mass% NMP solution (5.6 g) (0.28 g as C-1), NMP (8_lg), and BCS (46.6 g) were stirred at 50 ° C for 15 hours. P 1 was added to the solution. 5液晶. 〇 mass % NMP solution (5.6 g) (as Ρ15 is 〇.56 g), and the liquid crystal alignment treatment agent (2) was obtained by stirring at room temperature for 2 hours. (Example 3) In the synthesis example 2 The obtained polyimine powder (b) (5.6 g) was added to NMP (27. 3 g), and stirred at 70 ° C for 30 hours to dissolve. To this solution was added a C-1 solution of 5.0 mass% N MP (5.6 g) (0.28 g as C-1), NMP (8.1 g), and BCS (46.6 g), and stirred at 5 ° C for 15 hours. . To the solution, a pi5 mass% NMP solution (3.9 g) of pi5 (as a P15 of 39.39 g) was added, and the liquid crystal alignment treatment agent (3) was obtained by stirring at room temperature for 2 hours. (Example 4) The polyimine powder (B) (5.6 g) obtained in Synthesis Example 2 was added to NMP (27.3 g) at -54 to 201038623, and the mixture was stirred at 70 ° C for 30 hours. To this solution, a 5.0% by mass NMP solution of C-1 was added as 'C-1 was 0.28 g) 'NMP (8.1 g), and BCS (5 〇 °C was stirred for 15 hours. P 1 5 was added to the solution. The NMP solution (2.8 g) (0.28 g as P15) was stirred for 2 hours to obtain a liquid crystal alignment agent (4). ^ (Example 5) The polyimine powder obtained in Synthesis Example 2 (B) ) NMP ( 27.3g), 30 hours at 70 ° C. The solution was added with C -1 5.0% by mass Ν Μ P solution I was C-1 0.28 g) ' NMP ( 8. 1 g And BCS (5 搅拌 ° C for 15 hours of stirring. Add pi 5 NMP solution (1.7 g) (as p 1 5 is 0.17 g) to the solution, and obtain a liquid crystal alignment treatment agent by stirring for 2 hours. 〇 (Example 6)

The polyimine powder (C) obtained in Synthesis Example 3 was placed in NMP (35_2 g), and stirred at 70 ° C for 30 hours. To the solution, a 5.0 mass% NMP solution I of C-1 was added, and C-1 was 0.36 g), NMP (10. 4 g)' and BCS were stirred at 50 ° C for 15 hours. To the solution, a solution of p 1 5 % NMP (7.2 g) (0.72 g as P15) was added, and the mixture was stirred for 2 hours to obtain a liquid crystal alignment treatment agent (6): and dissolved: 5.6 g) (for 46.6 g). At 10.0% by mass: by adding (5 · 6 g) at room temperature: while dissolving: 5.6g) (for 46.6g), at 0.0% by mass: by (7 · 2 g) at room temperature : while dissolving: 7.2 g) (as (60.0 g), 10.0 mass by using the polyimine powder (D) obtained in Synthesis Example 4 at room temperature -55-201038623 (Example 7) 5.2 g) Add NMP (25_4g), stir it at 70 ° C for 30 hours to dissolve it. Add C - 1 of 5 - 0 mass % Ν Μ P solution (5.2 g ) to the solution (as C-1 is 0.26) g), NMP (7_5g), and BCS (43_4g), stirred at 50 ° C for 15 hours. Add 10.0 mass % NMP solution (5.2 g) of PI 5 (as a PI 5 of 0.5 2 g) to the solution. The liquid crystal alignment treatment agent (7) was obtained by stirring at room temperature for 2 hours. (Example 8) A liquid crystal alignment treatment agent (8) was obtained in the same manner as in Example 7 except that P 1 5 was changed to P3 1 . (Example 9) The obtained in Synthesis Example 7 Polyacrylic acid (G) (1 5_〇g) was added to NMP (5.0 g) and BCS (5.0 g), and stirred at room temperature for 2 hours. To the solution was added 10.0 mass% NMP solution of P15 (1 _5 g). (As P 1 5 is 0.15 g), the liquid crystal alignment treatment agent (9) is obtained by stirring at room temperature for 2 hours. (Example 1 〇) P 1 5 is changed to P 1 7 and Examples (9) The liquid crystal alignment treatment agent (1 1 ) was obtained in the same manner as in Example 9 except that P 1 5 was changed to P29 (Example 1 1). 1 2) The same liquid crystal alignment treatment agent (1 2 ) as in Example 9 except that P15 was changed to PM.

G (Example 1 3) The polyimine powder obtained in Synthesis Example 5 (E into GBL (45.0 g)' was stirred at 50 ° C for 20 hours, and the solution was added to GBL (33.3 g) at room temperature. To the polyimine solution. Secondly, in the solution (F) (100.Og) of the synthesis example (6), add GBL (112.5 g) q 3 7 · 5 g ) to stir at room temperature for 2 hours to obtain a poly The polyimine solution (20. g) was mixed with the polyglycolic acid name, and the mixture was stirred at room temperature for 20 hours, and the polyglycine mixed solution. Finally, the mixed solution 1 〇 〇 mass % GBL solution (6.0 g) (as P15 was stirred at room temperature for 2 hours to obtain a liquid crystal alignment treatment (Example 14). The polylysine obtained in Synthesis Example 8 was obtained. (η) modulate and obtain the obtained , (5 · 0 g) to dissolve it. After stirring for a while, obtain the poly phthalic acid, and BCS (proline solution; § liquid (80.0 g) to obtain P 1 5 of 〇_6g) was added to the polyimine, and a solution of -57-201038623 NMP (8.5g) and P17 of 10.0% by mass NMP was added by the agent (1 3 ) ° (2 0 · 〇g ) (1.5 g) (0.15 g as P17) and BCS (20.0 g) were obtained by stirring at room temperature for 2 hours to obtain a liquid crystal alignment treatment agent (1 4 ). (Example 1 5) The polymerization obtained in Synthesis Example 9 The quinone imine powder (I) (5.0 g) was added to NMP (2 8.3 g), and it was stirred and dissolved at 70 ° C for 30 hours. To the solution was added P 1 7 of 10 0% by mass of NMP solution (2.5). g) (0.25 g as P17), NMP (11.7 g), and BCS (33.3 g) were obtained by stirring at room temperature for 2 hours to obtain a liquid crystal alignment agent (15). (Example 1 6) Synthesis Example 1 0 obtained polyimine powder (J) (5 · 0g) was added to NMP (28. 3g), and dissolved in 7 (TC for 30 hours). 10.0% by mass of NMP solution (2.5g) of P17 was added to the solution. (as 0.25 g of P17), NMP (11.7 g), and BCS (33.3 g), the liquid crystal alignment treatment agent (16) was obtained by stirring at room temperature for 2 hours. (Example 1 7) The polyimine powder (K) (5.0 g) obtained in Example 1 was added to NMP (28. 3 g), and it was stirred and dissolved at 70 ° C for 30 hours, and a P0.0 solution of 10.0% by mass of NMP was added to the solution ( 2_5g) (0_25g as P17), NMP (ll_7g), and BCS (33.3g) were obtained by stirring at room temperature for 2 hours to obtain a liquid crystal alignment treatment agent (1 7 ). -58- 201038623 (Example 1 8 ) In the polyimine powder (L) (10.Og) obtained in Synthesis Example 12, Ν Μ P (4 8.8 g) was added, and the mixture was stirred at 70 ° C for 30 hours to dissolve it. -1 mass% NMP solution (10.Og) (0.5 g as C-1) 'NMP (22.8 g) &gt; BCS (75.0 g) was stirred at 50 ° C for 15 hours. To the solution, a 10.0% by mass NMP solution (5.0 g) of P17 (0.5 g as P17) was added, and the liquid crystal alignment treatment agent (18) was obtained by stirring at room temperature for 2 hours. (Example 1 9) NMP (48.8 g) was added to the polyimine powder (Μ) (10.0 g) obtained in Synthesis Example 13, and the mixture was stirred at 70 ° C for 30 hours to be dissolved. To this solution was added C-2 5.0 mass% NMP solution (l〇.〇g) (0.5 g as C-2) 'NMP (22.8 g), BCS (75.0 g), and Q was carried out at 50 ° C for 20 hours. Stir. To the solution, a P0.0 solution of 10.0% by mass of NMP (5.0 g) (0.5 g as P17) was added, and a polyimine solution (〇) was obtained by stirring at room temperature for 2 hours. Next, NMP (48.8 g) was added to the polyimine powder (N) (10 μg) obtained in Synthesis Example 14, and the mixture was stirred at 7 ° C for 30 hours to be dissolved. To the solution was added a C-2 5.0 mass% NMP solution (5.9 g) (as C-2 was 〇.6 g) 'NMP (26.9 g) &gt; BCS (75.Og) at 50. (: stirring was carried out for 20 hours. To the solution was added 0.07 mass% Ν Μ P solution ( 5. 〇g ) of p 1 7 (as p17, 〇. 5 g), and stirred at room temperature for 2 hours - 59 - 201038623, the polyimine solution (p) was obtained, and the above polyimine solution (〇) (30.0 g) and polyimine solution (P) (30.0 g) were mixed, and liquid crystal alignment treatment was obtained by stirring for 20 hours. (Example 9) NMP (9.8 g) was added to the polyimine powder (A) (2.0 g) obtained in Synthesis Example 1, and stirred at 80 ° C for 30 hours to dissolve. To the solution, a P0.0 solution of 10.0% by mass of NMP (l.g) (as P17 was 0_lg), NMP (3.9 g), and BCS (16.7 g) were added, and liquid crystal alignment was obtained by stirring at room temperature for 2 hours. Treatment agent (20). (Example 2 1 ) To the polyimine powder (B) (2.0 g) obtained in Synthesis Example 2, Ν Μ P ( 9.8 g ) was added for stirring at 70 ° C for 30 hours. The solution was dissolved in NMP (2.9 g) and BCS (16.7 g), and stirred at 5 (TC for 15 hours). A solution of 10.0 mass% NMP (2_0 g) of p7 was added to the solution (as P17). 〇.2g), at room temperature The liquid crystal alignment treatment agent (2 1 ) was obtained by stirring for 2 hours. (Example 2 2 ) The polyimine powder (B ) ( 2 · 0 g ) obtained in Synthesis Example 2 was added with A NMP (9.8 g), The solution was dissolved by stirring at 70 t for 30 hours. To this solution, a 5.0% by mass NMP solution (2.0 g) of C-1 (O.lg as C-1), NMP (1.5 g), and BCS (16.7 g) were added. Stir at 5 (TC-60 - 201038623 for 1 hour). Add 1 p · 7 〇 mass % Ν Μ P solution (1.4g) (as P17 is 0.14g) in this solution, by room The mixture was stirred for 2 hours to obtain a liquid crystal alignment treatment agent (22). (Example 2 3) The polyimine powder (B) (2.0 g) obtained in Synthesis Example 2 was added to NMP (9.8 g) at 70 t: The solution was dissolved by stirring for 30 hours. NMP (2.9 g) and BCS (16.7 g) were added to the solution, and the mixture was stirred at 5 Torr for 15 hours. 1 〇·〇% by mass of NMP solution of p丨7 was added to the solution. (l.Og) (O.lg as P17) was obtained by stirring at room temperature for 2 hours to obtain a liquid crystal alignment treatment agent (2 3 ). (Example 2 4 ) Polyazide obtained in Synthesis Example 2 Amine powder (B) (2.0 g) was added to NMP (9.8 g). 70 ° C for 30 hours with stirring to dissolve. To this solution, a 5.0 mass% NMP solution (2.0 g) of C-1 (as o.g.), NMP (2.3 g), and BCS (16.7 g) were added to the solution, and the mixture was stirred at 50 ° C for 15 hours. To the solution, a P 1 70.0% by mass NMP solution (0.6 g) (0.06 g as P17) was added, and the liquid crystal alignment treatment agent (24) was obtained by stirring at room temperature for 2 hours. (Example 25) NMP (9.8 g) was added to the polyimine powder (C) (2.0 g) obtained in Synthesis Example 3, and the mixture was stirred at 70 ° C for 30 hours to be dissolved. In 201038623, the solution was added with C-1 5.0% by mass NMP solution (2, 〇g) (as οι is O.lg), NMP (1.9g), BCS (16.7g), and stirred at 50 ° C for 15 hours. . To the solution, a P 1 7 0 0 0% by mass NMP solution (l-〇g) (as P.sub.17.) was added, and a liquid crystal alignment treatment agent (2 5 ) was obtained by stirring at room temperature for 2 hours. . (Example 2 6) NMP (9.8 g) was added to the polyimine powder (D) (2.0 g) obtained in Synthesis Example 4, and the mixture was stirred at 70 ° C for 30 hours to be dissolved. To the solution was added C-1 of a 5_0% by mass NMP solution (2.0 g) (as οι to O.lg), NMP (1.9 g), and BCS (16.7 g), and the mixture was stirred at 50 ° C for 15 hours. To the solution, a P 1 70.0% by mass NM P solution (l-〇g) (O.lg as P17) was added, and a liquid crystal alignment treatment agent (26) was obtained by stirring at room temperature for 2 hours. (Example 2 7) Polyethyleneimine powder (E) (2.0 g) obtained in Synthesis Example 5 was added to GBL (18.0 g), and stirred and dissolved at 50 ° C for 20 hours. To the solution was added GBL (1 3.3 g), and the mixture was stirred at room temperature for 2 hours to obtain a polyimine solution. Next, GBL (112.5 g) and BCS (3 7.5 g) were added to the polyamic acid solution (F) (100.0 g) obtained in Synthesis Example (6), and stirred at room temperature for 2 hours to obtain a polyaminic acid solution. Further, the above polyimine solution (20.0 g) and polylysine solution (80.0 g) were mixed, and after stirring at room temperature for 20 hours, a polyimine and a polyaminic acid mixed solution - 62 - 201038623 were obtained. Finally, a 10.0 mass% GBL solution (6.9 g) of P17 (as a P17 of 6 g) was added to the mixed solution, and a liquid crystal alignment treatment agent (27) was obtained by stirring at room temperature for 2 hours. (Comparative Example 1) NMP (32.2 g) was added to the polyimine powder (A) (6.6 g) obtained in Synthesis Example 1, and stirred and dissolved at 80 ° C for 30 hours. NMP (16.1 g) and BCS (55.0 g) were added to the solution, and the liquid crystal alignment treatment agent (2 8 ) was obtained by stirring at room temperature for 2 hours. (Comparative Example 2) NMP (22.5 g) was added to the polyimine powder (b) (4.6 g) obtained in Synthesis Example 2, and the mixture was dissolved in 7 (TC) for 30 hours, and C-1 was added to the solution. 50% by mass Ν Μ P solution (4 · 6 g ) (as C -1 is 〇.23g ), NMP ( 6.7g ), and BCS ( 38.4g ) by 1 5 at Q 5 0 °C After the mixture was stirred for an hour, a liquid crystal alignment agent (2 9 ) was obtained. (Comparative Example 3) A liquid crystal alignment treatment agent (3) was obtained in the same manner as in Comparative Example 2 except that the polyimine powder (C) obtained in Synthesis Example 3 was used. (Comparative Example 4) A liquid crystal alignment treatment agent (3 Å) was prepared in the same manner as in Comparative Example 2 except that the polyimine powder obtained in Synthesis Example 4 was used. -63- 201038623 (Comparative Example) 5) Adding r-BL (18.0 g) to the polyimine powder (E) (2.0 g) obtained in Synthesis Example 5, stirring and dissolving at 5 (TC for 20 hours), adding GBL (8.3 g) to the solution, And BCS (5.0 g) was obtained by stirring at room temperature for 2 hours to obtain a liquid crystal alignment treatment agent (3 2 ). (Comparative Example 6) Polyisamic acid (G) (15.0 g) obtained in Synthesis Example 7 was added. NMP ( 5.0 g ) and BCS (5.〇g) 'The liquid crystal alignment treatment agent (33 ) was obtained by stirring at room temperature for 2 hours. -64 - 201038623 [Table 1]

Polyimine polyamine amide compound specific compound friction resistance Example 1 A P15 A Example 2 B Cl P15 A Example 3 B Cl P15 A Example 4 B Cl P15 A Example 5 B Cl P15 B Example 6 C Cl P15 A Example 7 D Cl P15 A Example 8 D Cl P31 B Example 9 G P15 A Example 10 G P17 A Example 11 G P29 A Example 12 G P41 B Example 13 EF P15 A Implementation Example H P17 A Example 15 I P17 A Example 16 J P17 A Example 17 K P17 A Example 18 L Cl P17 A Example 19 Μ, Ν C-2 P17 A Example 20 A P17 A Example 21 B P17 A Example 22 B Cl P17 A Example 23 B P17 A Example 24 B Cl P17 B Example 25 C Cl P17 A Example 26 D Cl P17 A Example 27 EF P17 A Comparative Example 1 AD Comparative Example 2 B Cl D Comparative Example 3 C Cl D Comparative Example 4 D Cl D Comparative Example 5 ED Comparative Example 6 GD -65- 201038623 (Examples 2 8 to 3 8 and Comparative Examples 7 and 8) For the above Examples and Comparative Examples Each of the liquid crystal alignment treatment agents is rotatably coated with ITO After the glass substrate 'for 5 minutes and dried on a hot plate of 80 ° c, in the 2 1 0 ° C hot air circulation type oven baked for 1 hour, to produce a film thickness of 1 m square 〇n liquid crystal alignment film. Two sheets of the liquid crystal alignment film were prepared, and a spacer of 6 μm was spread on the surface of the liquid crystal alignment film, and then a sealant was printed thereon, and the sealant was cured to form a hollow cell. In the empty cell, liquid crystal MLC-6608 (manufactured by Merck Japan Co., Ltd.) was injected by a reduced pressure injection method, and the injecting port was closed to obtain a nematic liquid crystal cell. When each liquid crystal cell was observed by a polarizing microscope, the liquid crystal exhibited uniform vertical alignment, and no alignment defect or the like was observed. The voltage holding ratio at the time of production of the liquid crystal cell and the voltage holding ratio after UV-vis irradiation (light resistance) were evaluated for each liquid crystal cell, and the results are summarized in Table 2. &lt;Voltage retention rate at the time of liquid crystal cell production&gt; The liquid crystal cell produced above was subjected to a voltage of 1 V at a temperature of 80 ° C for 60 μs, and after 1 6.6 7 ms and after 50 ms. The voltage and voltage can be maintained as a voltage holding ratio. As a result, the voltage holding ratio at 16.67 ms was 97.0%, and the voltage holding ratio at 50 ms was 94.2%. And the measurement was carried out using a VHR-1 voltage holding ratio measuring device manufactured by Dongyang Technica Co., Ltd., and was set at a voltage of ±1 V, Pulse Width: 60 jas, Flame Period: 16.67 ms or 50 ms. -66-201038623 &lt;Voltage retention after UV-vis irradiation&gt; The same measurement was carried out after each liquid crystal cell having the above voltage holding ratio was measured to emit light of 50 J/cm 2 in terms of 365 nm. Further, UV-vis (high-pressure mercury lamp) irradiation was carried out using a table-top type UV hardening device (HCT3B28HEX-1) manufactured by SEN LIGHT CORPORATION. As a result, the voltage holding ratio at 16.67 ms was 92.3%, and the voltage holding ratio at 50 ms was 88.9 %. 〇[Table 2] Polyimine liquid crystal alignment treatment amine compound specific compound mmm _%) After liquid crystal cell formation UV. Vis after irradiation 16.67 50.00 16.67 50.00 Example 28 B 2 C-1 Ρ 15 97.0 94.2 92.3 88.9 Example 29 B 3 C-1 Ρ 15 97.0 94.4 88.0 82.1 Example 30 B 4 C-1 Ρ 15 97 Λ 94.2 87.2 80.1 Example 31 K 17 Ρ 17 97.1 94.3 89.1 86.8 Example 32 L 18 C-1 Ρ 17 97.4 94.8 92.5 90.7 Example 33 Μ,Ν 19 C-2 Ρ17 97.3 94.8 92.1 90.1 Example 34 Β 22 C-1 Ρ 17 97.3 94.7 92.0 90.2 Example 35 Β 23 C-1 Ρ 17 97.4 94.6 92.1 90.0 Example 36 Β 24 C-1 Ρ 17 97.2 94.7 91.9 89.4 Example 37 C 25 C-1 Ρ 17 97.5 94.8 92.8 91.3 Example 38 D 26 C-1 Ρ 17 97.7 94.8 93.0 91.8 Comparative Example 7 A 28 96.7 94.0 83.8 75.3 Comparative Example 8 Β 29 C-1 96.8 94.1 84.1 75.0

&lt;Example 3 9 to 5 4 and Comparative Examples 9 to 2 0 &gt; Each liquid crystal alignment treatment agent was prepared as follows. The composition of each of the obtained liquid crystal alignment treating agents is summarized in Table 3. Further, liquid crystal cells were produced using each of the liquid crystal alignment treatment agents -67 - 201038623, and the respective inclination angles, frictional resistances, and R D C 〇 are summarized as shown in Table 4 below. The abbreviations used in the examples and comparative examples are as follows. &amp;, unless otherwise stated, the abbreviation is as described above. (specific compound)

P13, P17, P46, P47, P31 and P49 have the same meanings as described above. [化41]

Η OH H HO^VV&quot;〇H P-13 ?H3 OH oh :Η〇^φηφτ〇Η ch3 6h3 ch3 ch3 P-46 P-47

t0H P-49 P-31 (two limbs) Bl : 2,4-diamino-N,N-diallylaniline B-3: 4-(trans-4-pentylcyclohexyl)benzamide Amine-2',4'-phenylenediamine B-6: 4-aminobenzylamine B-7: 3-amine basic methylamine B-9: 1,3-diamino-4 -dodecyloxy-benzene B-10: 1,3-diamino-4-tetradecyloxybenzene B-11: 1,4-bis(4-aminophenoxy)pentane B- 12 : 4,4'·diaminodiphenylamine-68- 201038623 [Chem. 42]

NH〇

Β-7

Η2Ν^ Βν6 Η2Νγ^τΝΗ2 HjNy^NHa ^0-C12H25 ^O-ChHm Β-9 Β-10

&lt;Production of Liquid Crystal Cell&gt; The liquid crystal alignment agent was spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 80 ° C for 5 minutes, and then 1 〇 on a hot plate at 210 ° C. The film was fired in minutes to form a coating film having a film thickness of 7 Onm. The coating film was rubbed on a friction device having a roll diameter of 120 mm, and rubbed under the conditions of a roll rotation speed of 1000 rpm, a roll speed of 50 mm/sec, and a press-in amount of 0.3 mm to obtain a substrate with a liquid crystal alignment film. . Two substrates with a liquid crystal alignment film are prepared, and a spacer of 6 /im is spread on the liquid crystal alignment film surface of the one film, and then the other substrate is bonded to the surface of the liquid crystal alignment film by the upper printing sealant. After the rubbing direction is straight, the sealant is hardened to produce a hollow cell. In this empty cell, liquid crystal MLC-2003 (manufactured by Merck Japan Co., Ltd.) was injected by a reduced pressure injection method, and the injection port was closed to obtain a twisted nematic liquid crystal cell. &lt;Measurement of pretilt angle&gt; The produced twisted nematic liquid crystal cell was heated at 105 ° C for 5 minutes _ 69 - 201038623 and then the pretilt angle was measured. The pretilt angle is measured using a crystal rotation method. &lt;Measurement of accumulated charge (RDC)&gt; The twisted nematic liquid crystal cell produced by the method described in the above &lt;Production of Liquid Crystal Cell&gt;, the DC voltage is from 0 V at a temperature of 23 ° C 0. 1 V interval is applied to 1 .〇V, and the flashing amplitude level at each voltage is measured to make a standard curve. After grounding for 5 minutes, after adding an alternating voltage of 3.0 V for 1 hour and a DC voltage of 5.0 V, the flicker amplitude level after only the DC voltage was 0 N was measured, and the RDC was calculated against the previously prepared standard curve. (The calculation method of this RDC is called the scintillation reference method.) Among them, RDC (before OFF) indicates that the AC voltage of 3.0 V for 1 hour and the DC voltage of 5.0 V are added, and RD C (after 10 minutes) indicates The accumulated charge after 10 minutes after the AC voltage was set to OFF &lt;Evaluation of friction resistance&gt; The liquid crystal alignment agent of the present invention obtained as described above was spin-coated on a glass substrate with a transparent electrode at 80 ° C After drying on a hot plate for 5 minutes, it was fired in a hot air circulating oven at 210 ° C for 1 minute to form a coating film having a film thickness of 100 nm. The surface of the coating film was rubbed with a screw having a roll diameter of 1 〇 mm by a number of 100 rpm, a light speed of 50 mm/sec, and a press-in amount of 0 mm to 5 mm to obtain a substrate with a liquid crystal alignment film. -70- 201038623 The surface of the liquid crystal alignment film near the center of the substrate was observed at a random laser microscope set at a magnification of 1 〇〇, and the observed frictional damage was observed in the range of about 6 · 5 mm. And the average enthalpy of the amount of rubbing (attachment) to evaluate the frictional resistance. The evaluation criteria are as follows: The evaluation criteria q 〇: frictional or friction slag is 20 or less △: frictional or frictional slag is 20 to 60 X: frictional or frictional slag is 60 or more (Example 3 9 ) as acid For the dianhydride component, 30.03 g (100 mmol) of A-1 was used as the diamine component, and 9.73 g (90 mmol) of B-4, 3.77 g (10 mmol) of B-2, and NMP 247 g were used for 40 hours at 40 °C for 3 hours. After Q, a polyaminic acid solution is obtained. 50 g of the polyaminic acid solution was diluted to 5 wt% with NMP, 17.6 g of acetic anhydride as an imidization catalyst was added, 8.2 g of pyridine was added, and the reaction was carried out at 40 ° C for 3 hours to prepare a soluble polyfluorene. Imine resin solution. This solution was poured into 0.6 L of methanol, and the resulting precipitate was separated by filtration and dried to give white-soluble polyimine (SPI-1). As a result of measuring the molecular weight of the soluble polyimine, the number average molecular weight was 1,3,430 and the weight average molecular weight was 26,952. The imidization ratio was 85%. The polyimine powder lg was dissolved in GBL 11.8 g, BCS 4.8 g - 71 - 201038623 to obtain a uniform polyimine solution. To the solution of the solution, 3 g of P 1 7 was added, and the mixture was stirred at room temperature for 5 hours as a liquid crystal alignment treatment agent. (Example 40) As a tetracarboxylic dianhydride component, 9.80 g (50 mmol) of A-2 and 9.60 g (44 mmol) of A-3 were used, and as a diamine component, 19-8 g (100 mmol) of B-8 and NMP222 g were used. The polyaminic acid solution (PA A-1 ) was obtained after 5 hours of reaction at room temperature. The polyamine had a number average molecular weight of 11,153 and a weight average molecular weight of 29,487. To 10 g of this solution, 10.5 g of NMP and 7.5 g of BCS were added, and the mixture was stirred at room temperature for 20 hours to obtain a uniform liquid crystal alignment treatment agent. For a solution in which the mass ratio of SPI-1 to PAA-1 was 2:8, 〇.〇3g of P17 was added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment treatment agent. (Example 4 1) For a solution in which the mass ratio of SPI_1 to PAA-1 was 2:8, 0.03 g of P19 was added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment treatment agent. (Example 42) For a solution in which a mass ratio of SPI-1 to PAA-1 was mixed to 2:8, 10 g of 0_〇3 g of P13 was added, and stirring was carried out for 5 hours at room temperature to obtain a liquid crystal alignment treatment agent. -72- 201038623 (Example 43) For a solution of 1 〇g of a mixture of SPI-1 and PAA-1 to a mass ratio of 2:8, 〇3 g of P 4 9 was added, and stirring was carried out for 5 hours at room temperature. A liquid crystal alignment treatment agent was obtained. (Example 44) 0 For a solution of 1 〇g in which the mass ratio of SPI-1 to PAA-1 was 2:8, 〇3 g of P 4 8 was added, and stirring was carried out for 5 hours at room temperature to obtain a liquid crystal alignment. Treatment agent. (Example 4 5) For a solution in which the mass ratio of SPI-1 to PAA-1 was 2:8, 3 g of P46 was added, and 5 g of P46 was added thereto, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment treatment agent. 〇 (Example 46) For a solution in which the mass ratio of SPI-1 to PAA-1 was mixed to 2:8, 〇3 g of P47 was added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment treatment agent. (Example 4 7 ) 3 0.03 g (100 mmol) of A-1, 8.56 g (80 mmol) of B-4, and 5.85 g (20 mmol) of B-9, NMP 252 g at -50 °C - 201038623 A 24-hour reaction prepares a polyaminic acid solution. 50 g of the polyaminic acid solution was diluted to 5 mass% by NMP, and then 8.0 g of pyridine as an imidization catalyst and acetic anhydride 1 7.2 g' were added at 40 ° C for 3 hours. This solution was poured into 0.6 L of methanol. The precipitate obtained by filtration was separated and dried to give a white polyimine powder (SPI-2). The solvent-soluble polyimine obtained had a number average molecular weight of 9,111' and a weight average molecular weight of 1,085. Further, the imidization ratio was 83%. For mixing 3?1-2- with? A mass ratio of 8-8-1 to a solution of 2:8, 10 g, was added to P 3 g of P 1 7 and stirred at room temperature for 5 hours to obtain a liquid crystal alignment treatment agent. (Example 4 8 ) As a tetracarboxylic dianhydride component, 8.18 g (42 mm )l) of A-2, 1.63 g (7.5 mmol) of A-3, and 1.22 g (10 mmol) of B- as a diamine component were used. 7. 5.08 g (25 mmol) of hydrazine·1, 6.11 g (15 mmol) of hydrazine-3, and NMP 88.96 g were reacted at room temperature for 24 hours to obtain a polyaminic acid solution. To 9 5 · 8 g of the polyaminic acid solution, 228.5 g of NMP was added and diluted, and acetic anhydride 7.5 g and 6.4 g of pyridine were added, and the mixture was reacted at 5 ° C for 3 hours to imidize. The reaction solution was cooled to room temperature, and then poured into methanol 1 2 5 9 · 1 m 1 to recover the precipitated solid matter. Further, the solid matter was washed several times with methanol, and then dried under reduced pressure at a temperature of 1 °C to obtain a white powder of soluble polyimine (s P I - 3 ). The polyimine had a number average molecular weight of 18,195 and a weight average molecular weight of 57,063. Further, the imidization ratio was 93%. To the 1.2 g of GBL, the polyimine powder -74-201038623 was added to 10.8 g of GBL, and the mixture was stirred at a temperature of 50 ° C for 24 hours. At the end of the agitation, the polyimine was completely dissolved. After cooling 12 g of the solution to 23 ° C, 2 g of GBL and 6 g of BCS were added, and the mixture was stirred at a temperature of 50 ° C for 20 hours. After the completion of the stirring, the mixture was cooled to 23 ° C to obtain a uniform liquid crystal alignment treatment agent. 〇 For this solution, 〇g was added, and 0.07 g of P 17 was added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment treatment agent. 〇 (Example 4 9 ) As the tetracarboxylic dianhydride component, 13.53 g (69 mmol) of A-2, 6.54 g (30 mmol) of A-3 was used, and 8.13 g (40 mm ο 1 ) was used as the diamine component. Bl, 3.6 7 g (30 mm ο 1 ) of B-6, 8 · 7 7 g (30 mmol) of B-9, NMP 161.8 g was reacted at room temperature for 24 hours to obtain a polyaminic acid solution. To the emulsion of 34.81 g of the polyamic acid solution, 62.65 g of NMP was added and diluted, and Q·5 5 g of acetic anhydride and 2.1 g of pyridine were added, and the mixture was imidized by a reaction at a temperature of 50 ° C for 3 hours. After the reaction solution was cooled to room temperature, it was poured into methanol 3 6 6.8 m 1 to recover the precipitated solid matter. Further, the solid matter was washed with methanol several times, and then dried under reduced pressure at a temperature of 1 ° C to obtain a white powder of polyimine (SP1-4). The polyimine had a number average molecular weight of 12,016' and a weight average molecular weight of 35,126. Further, the imidization ratio was 90%. 1.2 g of GBL was added to 1.2 g of the polyimine powder, and the mixture was stirred at a temperature of 75-201038623 at 50 °C for 24 hours. At the end of the agitation, the polyimine was completely dissolved. After cooling 12 g of this solution to 23 ° C, 2 g of GBL and 6 g of BCS were added, and the mixture was stirred at a temperature of 50 ° C for 20 hours. After the completion of the stirring, the mixture was cooled to 23 ° C to obtain a uniform liquid crystal alignment treatment agent. To the solution, 3 g of P17 was added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment treatment agent. (Example 50) As the tetracarboxylic dianhydride component, 13.33 g (68 mmol) of A-2, 6.54 g (30 mmol) of A-3, and 3.81 g (10 mm ο 1 ) of B were used as the diamine component. -5, 8. 3 g (40 mmol) of Β·1, 7.6 4 g (50 mmol) of B-6 and NMP 151.7 g were reacted at room temperature for 24 hours to obtain a polyaminic acid solution. To the polyamic acid solution 3 3.3 8 g, 59.61 g of NMP was added and diluted, and 5.26 g of acetic anhydride and 2.24 g of pyridine were added, and the reaction was carried out at a temperature of 50 ° C for 3 hours and imidized. After the reaction solution was cooled to room temperature, it was poured into methanol 3 5 1 · 7 ml, and the precipitated solid matter was collected. Further, the solid matter was washed with methanol several times, and then dried under reduced pressure at a temperature of 100 ° C to obtain a white powder of polyimine (SP1-5). The polyimine has a number average molecular weight of 10,111' and a weight average molecular weight of 3夂65 3 . Further, the imidization ratio was 90%.

1.2 g of GBL was added to 1.2 g of the polyimide pigment, and the mixture was stirred at a temperature of 5 ° C for 24 hours. At the end of the agitation, the polyimine was completely dissolved. After cooling 12 g of this solution to 23 ° C, 2 g of GBL and 6 g of BCS-76-201038623 were added, and the mixture was stirred at a temperature of 50 ° C for 20 hours. After the completion of the stirring, the mixture was cooled to 23 ° C to obtain a uniform liquid crystal alignment treatment agent. To the solution of 1 〇 g, P 3 g of P 1 7 was added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment treatment agent. (Example 5 1 ) 6.68 g (35 mmol) of a-2, _ 3.27 g (15 mmol) of A-3, and 2.44 g (〇20 mmol) of B-7 were used as the diamine component. A polyaminic acid solution (PAA-2) was obtained by reacting 3.04 g (1 5 mm ο 1 ) of B1, 6.11 g (15 mmol) of hydrazine-3, and NMP 87.0 g at room temperature for 24 hours. The polyamine has a number average molecular weight of 15,5, and a weight average molecular weight of 47,210. To 10 g of this solution, 10.5 g of NMP and 7.5 g of BCS were added, and the mixture was stirred at room temperature for 20 hours to obtain a uniform liquid crystal alignment treatment agent. To the solution, 3 g of P17 was added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment treatment agent. (Example 52) For a solution of a mixture of SPI-3- and PAA-4 having a mass ratio of 3:7 to 10 μg, 〇.〇3 g of P1 7 was added, and stirring was carried out for 5 hours at room temperature to obtain a liquid crystal alignment treatment agent. . (Example 5 3 ) As the tetracarboxylic dianhydride component, 4.05 g (18 mm )l) of A-3, -77-201038623 was used as the diamine component, and 5.15 g (1 8 mmo 1 ) of B-ll and 0.75 g were used. (2 mmol) of B-2 and NMP 73.07 g were reacted at room temperature for 16 hours to obtain a 12 mass% polyamine acid solution. The polyamic acid had a number average molecular weight of 12,180 and a weight average molecular weight of 25,160. 50 g of this polyaminic acid solution was diluted with NMP 115 g and BCS 50 g to obtain a polyaminic acid solution (PAA-3). To the solution, 0.03 g of P17 was added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment treatment agent. (Example 54) As the tetracarboxylic dianhydride component, 7.15 g (37 mmol) of A-2 and 3.00 g (10 mmol) of A-1 were used, and 7.97 g (40 mmol) of B-12 was used as the diamine component. 1 .9 8 g (1 Ommol) of B-8 and NMP181g were reacted at room temperature for 16 hours to obtain a 10% by mass poly-proline solution. The polyamic acid had a number average molecular weight of 12,180 and a weight average molecular weight of 30,160. The polyamic acid solution 100.Og was diluted with NMP 230 g and BCSIOOg to obtain a polyaminic acid solution (PAA-4). For a solution of a mixture of PAA-3- and PAA-4 having a mass ratio of 2:8 to 1 8 g, 〇 3 g of P 1 7 was added and stirred at room temperature for 5 hours to obtain a liquid crystal alignment treatment agent. (Comparative Example 9) 30.03 g (100 mmol) of A-1 was used as the tetracarboxylic dianhydride component, and 9.73 g (90 mmol) of B-4 and 3.77 g (-78-201038623 lOmmol) of B- as a diamine component were used. 2. In NMP247g, a poly-proline solution was obtained after 3 hours of reaction at 40 degrees. The polyphthalic acid solution was diluted to 5 wt% by NMP, and then as an imidization catalyst, acetic anhydride was added. .6 g and 8.2 g of pyridine were reacted at 40 ° C for 3 hours to prepare a soluble polyimine resin solution. This solution was poured into methanol of L·6 L, and the obtained precipitate was separated by filtration and dried to give white soluble polyimine (S P I -1 ). As a result of measuring the molecular weight of the soluble polyimine, the number average molecular weight was 13,430, and the weight average molecular weight was 26,952. Further, the imidization ratio was 85%. The polyimine powder lg was dissolved in GBL 11.8 g and BCS 4.8 g to obtain a homogeneous polyimine solution. (Comparative Example 10) The mass ratio of SPI-1 to PAA-1 was mixed to 2:8, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment treatment agent. ❹ (Comparative Example 1 1) The mass ratio of SPI-2 to PAA-1 was mixed to 2:8, and stirred at room temperature for 5 hours to obtain a liquid crystal alignment treatment agent. (Comparative Example 1 2) As the tetracarboxylic dianhydride component, 8.18 g (42 mmol) of A-2 and 1.63 g (7.5 mmol) of A-3' were used as the diamine component, and 1.22 g (10 mmol) of B-7 was used. , 5 · 0 8 g ( 2 5 mm ο 1 ) of Bl, 6.11 g ( -79- 201038623 1 5 mmol ) of B-3, NMP 88.96g, obtained a polyamine acid solution after 24 hours of reaction at room temperature . To 95.8 g of this polyaminic acid solution, 228.5 g of NMP was added and diluted, and 15. g of acetic anhydride and 6.4 g of pyridine were added, and the mixture was subjected to a reaction at 50 ° C for 3 hours to imidize. After the reaction solution was cooled to room temperature, it was poured into 1 2 5 9.1 ml of methanol to recover a precipitated solid. Further, the solid matter was washed with methanol several times, and then dried under reduced pressure at a temperature of 〇〇 ° C to obtain a white powder of soluble polyimine (SPI-3). The polyimine had a number average molecular weight of 18,195 and a weight average molecular weight of 57,063. Further, the imidization ratio was 93%. 1.2 g of GBL was added to 1.2 g of the polyimine powder, and the mixture was stirred at a temperature of 50 ° C for 24 hours. At the end of the agitation, the polyimine was completely dissolved. After cooling this solution to 2 °g to 23 ° C, 2 g of GBL and 6 g of BCS were added, and the mixture was stirred at a temperature of 50 ° C for 20 hours. After the completion of the stirring, the mixture was cooled to 23 ° C to obtain a uniform liquid crystal alignment agent. (Comparative Example 1 3) As a tetracarboxylic dianhydride component, 13.53 g (69 mmol) of A-2 and 6.54 g (30 mol) of A-3 were used, and as a diamine component, 8-13 g (40 tn m ο 1 ) of B1 was used. 3-6 μg (3 0 mm ο 1 ) of B-6, 8.77 g (30 mmol) of B-9, and NMP 161.8 g were reacted at room temperature for 24 hours to obtain a polyaminic acid solution. To the emulsion of 34.81 g of the polyamic acid solution, 62.65 g of NMP was added and diluted, and 5 · 15 g of acetic anhydride and 2 · 19 g of pyridine were added, and the mixture was imidized at a temperature of 50 ° C for 3 hours. -80 - 201038623 The reaction solution was cooled to room temperature and then poured into 3 6 6.8 m 1 to recover the precipitated solid. Further, the solid form was washed several times, and then dried under reduced pressure at a temperature of 100 Å to give a white powder of imine (SPI-4). The polyimine had a number of 12,016 and a weight average molecular weight of 35,126. Also, Asia is 90%. 1.2 g of the polyimine powder was added to GBL l.8 g of 50 ° C for 24 hours. At the end of the agitation, the polyphthalocyanine dissolves. After cooling 12 g of this solution to 23 ° C, 6 g of GBL was added, and the mixture was stirred at a temperature of 50 ° C for 2 hours. After the end of the stirring, 2 3 ° C, a uniform liquid crystal alignment treatment agent was obtained. (Comparative Example 1 4) As a tetracarboxylic dianhydride component, 13.33 g (68 mmol) of 6.54 g (30 mmol) of A-3 and 1,0 mmol of a diamine component were used as B-5, 8·1 3 g (40). Mp ο 1 ) of B 5 Ommol ) of B-6, NMP 151.7 g, after 24 hours at room temperature to obtain a polyaminic acid solution. The polyamic acid solution 3 3 . NMP 59-61 g was diluted and added with 5.26 g of acetic anhydride and reacted at a temperature of 5 ° C for 5 hours to imidize. After the reaction solution was cooled to room temperature, it was poured into /351.7 ml, and the precipitated solid matter was recovered. Further, the solid was washed several times, and then dried under reduced pressure at a temperature of 10 ° C to give a white powder of imine (SPI-5). The polyimine is in the same amount, and the aminization rate of the poly(p-Amine molecular weight) is obtained by methanol in methanol. At the temperature, the amine is completely 2 g, BCS, and cooled to A-2, 3.81 g ( 7.64 g (hour reaction 3 8) g was added to \24g, and the molecular weight of the poly(fluorene) in methanol was -81 - 201038623 to 10,11 1 , and the weight average molecular weight was 3 3,65 3. The yield of imidization was 90%. 1.2 g of polyimine powder was added to 10.8 g of GBL, and stirred at a temperature of 5 ° C for 24 hours. At the end of the stirring, the polyimine was completely dissolved. After cooling the solution to 2 2 ° C, the solution was cooled. GBL 2 g and BCS 6 g were added, and the mixture was stirred at a temperature of 50 ° C for 20 hours. After the completion of the stirring, the mixture was cooled to 23 ° C to obtain a uniform liquid crystal alignment treatment agent. (Comparative Example 1 5 ) As a tetracarboxylic dianhydride component, 6.86 g (35 mmol) of A-2, 3-27 g (15 mmol) of A-3, 2.44 g (20 mmol) of B-7, 3,04 g (15 mmol) of B, 6.1 1 g (15 mmol) were used as the diamine component. B-3, NMP 87.0 g was reacted at room temperature for 24 hours to obtain a polyaminic acid solution (PAA-2). The number average molecular weight of the polylysine was 15,539 The weight average molecular weight was 47,210. 8 Μ P 1 0.5 g and BCS 7.5 g were added to 8 g of the solution, and stirred at room temperature for 20 hours to obtain a uniform liquid crystal alignment treatment agent. (Comparative Example 1 6) Mixed SPI-3 and The mass ratio of PAA-4 was 3:7, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment treatment agent. (Comparative Example 1 7) As a tetracarboxylic dianhydride component, 4.05 g (18 mmol) of A-3 was used. 82-201038623 As a diamine component, 5.15 g (18 mmol) of B-ll, 0.75 g (2 mmol) of B-2, and NMP 73.07 g were used for 16 hours at room temperature to obtain 12% by mass of polylysine. The polyamino acid had a number average molecular weight of 12,180 and a weight average molecular weight of 25,160. 50 g of the polyaminic acid solution was diluted with NMP 1 15 g and BCS 50 g to obtain a polyaminic acid solution (PAA-3). ^ (Comparative Example 1 8) ❹ As a tetracarboxylic acid diterpene component, 9.80 g (50 mmol) of A-2, 9.60 g (44 mxnol) of A-3, and 19.8 g (100 mmol) of B- as a diamine component were used. 8. NMP 222g was reacted at room temperature for 5 hours to obtain a polyaminic acid solution (PAA-1). The polyamine has a number average molecular weight of 11,153' and a weight average molecular weight of 29,487. To 8 g of this solution, 10.5 g of NMP and 7.5 g of BCS were added, and the mixture was stirred at room temperature for 20 hours to obtain a uniform liquid crystal alignment treatment agent. Q To this solution, 1 〇g, p 1 7 0.03 g was added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment treatment agent. (Comparative Example 1 9) As the tetracarboxylic dianhydride component, 7.15 g (37 mmol) of A-2 and 3.00 g (10 mmol) of A-1 were used, and as the diamine component, 7.97 g (40 mmol) of B-12 and 1.98 were used. g (1 Ommol) of B-8 and NMP18lg were reacted at room temperature for 16 hours to obtain a 1% by mass poly-proline solution. The polyamine has a number average molecular weight of 12,180 and a weight average molecular weight of -83 to 201038623 of 30,160. The polyaminic acid solution 100.Og was diluted with NMP 230 g and BCSIOOg to obtain a polyaminic acid solution (PAA-4). To the solution of 〇g, 3 g of P17 was added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment treatment agent. (Comparative Example 20) The mass ratio of PAA-3 to PAA-4 was mixed to 2:8, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment treatment agent. -84- 201038623 [Table 3]

Imidization ratio (%) of the specific compound in the polymer []. Example 39 SPI-1 P17 85 Example 40 SPI-1/PPA-1 [2/81 P17 Example 41 SPI-l/PPA- l[2/8] P19 Example 42 SPI-l/PPA-l [2/8] P13 Example 43 SPI-l/PPA-l [2/8] P49 Example 44 SPI-l/PPA-l [ 2/8] P31 Example 45 SPI-l/PPA-l [2/8] P46 Example 46 SPI-1/PPA-1 [2/81 P47 Example 47 SPI-2/PPA-l [2/81 P17 Example 48 SPI-3 P17 93 Example 49 SPI-4 P17 90 Example 50 SPI-5 P17 90 Example 51 PPA-2 P17 Example 52 SPI-3/SPI-4 [3/7] P17 Example 53 PAA-3 P17 Example 54 PAA-3/PAA-4[2/8] P17 Comparative Example 9 SPI-1 Μ J \ w 85 Comparative Example 10 SPI-l/PAA-lf2/8] M y\\\ Comparative Example 11 SPI-2/PAA-l [2/8] M y\\\ Comparative Example 12 SPI-3 M / &gt; 93 Comparative Example 13 SPI-4 Charm &gt; i NS 90 Comparative Example 14 SPI-5 te 90 Comparative Example 15 PAA-2 te J \ w Comparative Example 16 SPI-3/SPI-4[3/7] M / \ \\ Comparative Example 17 PAA-3 M j\\\ Comparative Example 18 PAA-1 P17 Comparison Example 19 PAA-4 P17 Comparative Example 20 PAA-3/PAA-4[2/8] te ^w\ -85- 201038623 [Table 4] Tilt angle [% increase rate] RDC (OFF RDC (after 10 minutes OFF) Friction resistance Example 39 7_3 "2〇1 0.3 0.03 〇 Example 40 3.6 Γ 201 0.3 0 〇 Example 41 3.5 [16] 0.3 0.05 〇 Example 42 3.7 [231 0.3 0 Δ Example 43 3.9 [30] 0.3 0 〇 Example 44 3.9 [30] 0.3 0 〇 Example 45 4.2 [4〇1 0.3 0.01 Δ Example 46 3.5 [16] 0.3 0 Δ Example 47 3_4 [21] 0.25 0.03 〇Example 48 8.5 [13] 0.5 0.08 〇 Example 49 3.0 "131 0.45 0 〇 Example 50 7.7 Π 91 0.5 0.09 〇 Example 51 7.5 "211 0.8 0.07 〇 Example 52 6.0 [251 0.5 0 〇 Example 53 4.6 [281 0.25 0 〇 Example 54 3.5 "25] 0.2 0 〇 Comparative Example 9 6.1 0.3 0.2 X Comparative Example 10 3 0.3 0.1 X Comparative Example 2.8 2.8 0.25 0.18 X Comparative Example 12 7.5 0.5 0.3 Δ Comparative Example 13 2.4 0.45 0 〇 Comparative Example 14 6.5 0.5 0.32 Δ Comparative Example 15 6.2 0.8 0.2 〇 Comparative Example 16 4.8 0.5 0.1 Δ Comparative Example 17 3.6 0.25 0 Δ Comparative Example 18 1.3 [〇1 0.15 0 〇 Comparative Example 19 1-2 [〇1 0.11 0 〇 Comparative Example 20 2.8 0.2 0 Δ -86- 201038623 [Industrial Applicability] By using the liquid I of the present invention, and even if Long back &gt; less reduced liquid crystal alignment film, the I element is shown by excellent reliability, Ϊ television screen and other LCD. In the description 1 of 2008 No. 2008-334248, there is a content. As the 曰J k alignment agent of the present invention, after the exposure of the film treated by the rubbing is reduced by 3, the liquid crystal obtained by the voltage holding ratio I can be obtained. The liquid crystal of the alignment film is included in the disclosure of Japanese Patent Application No. 1, the scope of the patent application, and the Abstract of the Abstract of 〇 -87-

Claims (1)

201038623 VII. Patent application scope: 1 · A liquid crystal alignment agent characterized by containing a compound having the structure of the formula (i) bonded to the aromatic ring and the component (B) selected from the group (A) At least one polymer compound in which the quinone imine and the polyimine precursor are grouped; [X1] xx〇N^ [i] (X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms). 2. The liquid crystal alignment agent of claim 1, wherein X in the formula [i] is a hydrogen atom. 3. The liquid crystal alignment agent according to claim 1 or 2, wherein the component (A) is at least one selected from the group consisting of a compound represented by the following formula [1] and a compound represented by the formula [2]; [wherein, Χι, Χ2, and X3 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and Υ, Y2, and Y3 each independently represent an aromatic ring, and any hydrogen atom of the aromatic ring may be a hydroxyl group or a carbon. An alkyl group having 1 to 3 atoms, a halogen atom, an alkoxy group having 1 to 3 carbon atoms or a vinyl group; and a single bond, all or a part of a carbon atom which is bonded to form a cyclic structure a saturated hydrocarbon group of ~1 fluorene, any hydrogen atom may be substituted by a fluorine atom - Ν Η -, -88- 201038623 -N(CH3)- or a group of the formula [3]; [Chemical 3] - P^Q^P2 — [ 3 ] (wherein, P! and P2 each independently represent an alkyl group having 1 to 5 carbon atoms, Q represents an aromatic ring) "is an integer of 2 to 4, and t2 and t3 are each independently an integer of 1 to 3 , a and b are each independently an integer of 1 to 3. 4. The liquid crystal alignment agent of the third aspect of the patent application, wherein the oxime in the formula [1] and the X2 and X3 in the formula [2] are a hydrogen atom. 5. The liquid crystal alignment agent of claim 3 or 4, wherein Y in the formula [1], and the oxime 2 and Y3 in the formula [2] are each independently a benzene ring or a pyridyl ring. For example, the scope of patent application is 1 To the liquid crystal alignment agent according to any one of item 5, wherein the component (A) is a compound selected from the following groups of at least one compound. ❹ [Chemical Formula 4] The liquid crystal alignment agent according to any one of the items 1 to 5, wherein the component (A) is at least one compound selected from the group consisting of the following compounds. -89- 201038623 [化5] 8. The liquid crystal alignment agent according to any one of claims 1 to 7, wherein the component (B) is selected from the group consisting of polyamines obtained by reacting a diamine component with a tetracarboxylic dianhydride component. And at least one polymer compound of the polyimine obtained by dehydration ring closure of the polyamic acid. 9. The liquid crystal alignment agent according to any one of claims 1 to 8, which further contains an organic solvent. 10. The liquid crystal alignment agent according to any one of the items 1 to 9, wherein the mass of the organic solvent to be removed (the concentration of the solid component) is 1 to 20% by mass. A liquid crystal alignment film which is obtained by using a liquid crystal alignment agent according to any one of claims 1 to 10. A liquid crystal display element characterized by comprising a liquid crystal alignment film according to item 11 of the patent application. -90- 201038623 IV. Designated representative map: (1) The designated representative figure of this case is: None (2), the symbol of the representative figure is simple: no ❹ 201038623 5. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none