TW201120098A - Liquid-crystal alignment material, liquid-crystal alignment film, liquid-crystal display device, compound and a method for producing this compound - Google Patents

Abstract

The present invention provides a liquid-crystal alignment film, a liquid-crystal alignment material, a liquid-crystal display device having liquid-crystal alignment film, a compound and a method for producing this compound. The aforementioned liquid-crystal alignment material can form the liquid-crystal alignment film that maintains good liquid crystal alignment property and electrical characteristics, has excellent weather resistance and suppresses the increasing of residual DC voltage. The aforementioned liquid-crystal alignment material contains (A) at least a polymer selected from a group consisting of polyamic acid and polyimide and (B) a compound represented by formula (1).

Description

201120098 VI. OBJECTS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a liquid crystal alignment agent 'liquid crystal alignment film, liquid crystal display element' compound, and a method for producing the same. More specifically, the present invention is excellent in liquid crystal alignment, and even if it is continuously driven for a long time, the liquid crystal alignment film can be deteriorated to a small extent, and high-quality display can be performed and the afterimage can be driven even when driven for a long time. Eliminate short-time liquid crystal display elements. [Prior Art] The 'liquid crystal display element' is widely used for liquid crystal display devices such as mobile phones and liquid crystal televisions because of its advantages of low power consumption, ease of miniaturization, and flattening. The display mode of such a liquid crystal display device has been disclosed as having a twisted nematic type (Twisted according to the change of the liquid crystal molecules).

Liquid crystal display of liquid crystal cells such as Nematic 'TN type), super twisted nematic (sUper Twisted Nematic; STN type), in-pione switching type (IPS type), vertical alignment type (Vemcal Alignment; VA type) element. In any of the display modes, the alignment state of the liquid crystal molecules is controlled by the liquid crystal alignment film. Therefore, the properties of the liquid crystal alignment film and the liquid crystal alignment agent formed of the liquid crystal alignment film material have an influence on the characteristic performance of the liquid crystal display element. The material of the liquid crystal alignment agent is known as a resin material such as polylysine, polyimine, and polyurethane, especially a liquid crystal alignment agent containing polyamine or polyamine-4-201120098 amine. The liquid crystal alignment film to be formed is excellent in heat resistance 'mechanical strength' and liquid crystal affinity, and is used for many liquid crystal display elements (see Patent Documents 1 to 6). When such a liquid crystal display element is used for a television application or the like and is continuously driven for a long period of time, the liquid crystal alignment film is deteriorated by exposure to heat and light for a long period of time, and display quality is deteriorated. Therefore, in the case of continuous driving for a long period of time, the display quality is not deteriorated, and a material which can provide a crosslinked structure is being studied (see Patent Document 7). However, the liquid crystal display element using such a material has a small degree of deterioration in electrical characteristics such as voltage holding ratio, but has a drawback that the residual DC voltage 値 becomes large as the driving time becomes long. In view of such a situation, it is desired to develop a liquid crystal alignment film capable of forming a good liquid crystal alignment property and electrical characteristics while maintaining long-term continuous driving while having excellent weather resistance and suppressing an increase in residual DC voltage. Liquid crystal alignment agent. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 5] US Patent No. 5,958, 873 [Patent Document 6] Japanese Laid-Open Patent Publication No. SHO 62-165628 (Patent Document 7) Japanese Patent Application Laid-Open No. Hei. No. Hei. Disclosure of the Invention The present invention has been made in view of the above circumstances, and an object thereof is to provide a liquid crystal alignment performance and electrical characteristics which can be maintained even when driving for a long period of time, while having excellent weather resistance and suppressing A liquid crystal alignment agent, a liquid crystal alignment film, a liquid crystal display element having a liquid crystal alignment film, a compound, and a method for producing a compound, which have a residual DC voltage and which have a liquid crystal alignment film. The invention for solving the above problems is a liquid crystal alignment agent containing [A] at least one polymer selected from the group consisting of polylysine and polyimine, and [B] the following formula (1) The compound represented.

In the formula (1), R is each independently a hydrogen atom, a methylol group, an alkoxymethyl group having 2 to 7 carbon atoms, -CH2?Y or -CH2?Z. Y is a group having a cyclic hindered amine structure. Z is a group having a hindered phenol structure. However, at least one R is a radical having a cyclic hindered amine structure or a hindered phenol structure. By containing the [A] polymer and the [B] compound, the liquid crystal alignment agent can maintain good liquid crystal alignment properties and electrical characteristics even when subjected to continuous driving for a long period of time, and has excellent weather resistance and suppression. A liquid crystal alignment film having an increased DC voltage. 201120098 The cyclic hindered amine structure of Y is preferably a group represented by the following formula (2a), and the hindered phenol structure of Z is preferably a group represented by the following formula (3 3).

(2a) In the formula (2a), R1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 13 carbon atoms or 1, 3-dimethoxybutyl. RM~RV are each independently an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 13 carbon atoms. X1 is a single bond, a carbonyl group or a *-CONH-. Among them, the linkage with * is linked to the piperidine ring. X2 to X5 are each independently a single bond, a carbonyl group, *-CH2-CO- or *-CH2-CH(OH)-. Among them, the linkage with * is linked to the piperidine ring. X6 is a single bond, -C0-, methylene or an alkyl group having 2 to 6 carbon atoms. 201120098

OH

In the formula (3a), RVI is a hydrocarbon group having 4 to 16 carbon atoms. RV11 is a hydrogen atom or a hydrocarbon group having 1 to 16 carbon atoms. X7 is a single bond, -C0_, a methylene group or an alkylene group having 2 to 6 carbon atoms. η is an integer of 0 to 3. By having the specific structure described above, the cyclic hindered amine structure or the hindered phenol structure can maintain electrical characteristics and further improve weather resistance. The [Β] compound contained in the liquid crystal alignment agent is preferably (b 1) a compound represented by the following formula (lx) and (b2) a compound represented by the following formula (2) and/or formula (3); The reaction product of the compound.

R\ Rx \ / N

I I Rx Rx (1x)

Rx— In the formula (lx), Rx is each independently a hydrogen atom, a methylol group or a oxymethyl group having 2 to 7 carbon atoms. Wherein at least one R* is an alkoxymethyl group having a methyl group having 2 to 7 carbon atoms. Y - OH (2) In the formula (2), Y is a group represented by the above formula (2a). 201120098 Z——OH (3) In the formula (3), Z is a group represented by the above formula (3a). The compound [B] can be easily obtained by reacting the above (bl) compound with the (b 2) compound. The above Y is preferably at least one selected from the group consisting of groups represented by the following formulas (2a-1) to (2a-2), and Z is preferably selected from the following formula (33-l)~ At least one of the groups consisting of the groups represented by (3a-2).

(2a-1) (2a-2)

(3a-1)

(3a-2) -9 201120098 Since the [B] compound has the above specific group, the solidity of the liquid crystal alignment film is increased, and the weather resistance is more excellent. The use ratio of the [B] compound is preferably 0.1 part by mass or more and 100 parts by mass or less based on 1 part by mass of the [A] polymer. The weather resistance can be further improved by containing the above specific amount of the [B] compound. A liquid crystal alignment film formed of the liquid crystal alignment agent and a liquid crystal display element having the liquid crystal alignment film are also suitably included in the present invention. The liquid crystal display element ' can be suitably used for various devices, such as clocks, portable game machines, word processors, notebook computers, car navigation systems, cameras, portable information terminals, digital cameras, mobile phones, various displays, Display devices such as LCD TVs. The present invention includes a compound represented by the following formula (1).

In the formula (1), R each independently represents a hydrogen atom, a methylol group, an alkoxymethyl group having 2 to 7 carbon atoms, -CH2〇Y or -CH2〇Z. Y is a group having a cyclic hindered amine structure. Z is a group having a hindered phenol structure. Wherein at least one R is a group having a cyclic hindered amine structure or a hindered phenol structure. This compound can be suitably used as a component of a liquid crystal alignment agent or the like which forms a liquid crystal alignment film. -10-201120098 The present invention comprises a process for producing a compound which has a step of reacting a compound represented by the following formula (1x) with a compound represented by the following formula (2) and/or (3).

In the formula (lx), Rx is each independently a hydrogen atom, a methylol group or an alkoxymethyl group having 2 to 7 carbon atoms. Among them, at least one R1 is a methylol group or an alkoxymethyl group having 2 to 7 carbon atoms. Y——OH (2) In the formula (2), Y is a group having a cyclic hindered amine structure. Z——OH (3) In the formula (3), Z is a group having a hindered phenol structure. Further, the aryl group having 6 to 20 carbon atoms represented by the above R1, the aralkyl group having 7 to 13 carbon atoms, the alkyl group having 1 to 6 carbon atoms represented by Rn to Rv, and the number of carbon atoms Some or all of the hydrogen atoms which are an aryl group of 6 to 12 and an aralkyl group having 7 to 13 carbon atoms may be substituted. According to the present invention, it is possible to provide a liquid crystal which can maintain good liquid crystal alignment performance and excellent weather resistance even when continuous driving is performed for a long period of time, and suppresses residual DC. The liquid crystal alignment agent of the alignment film, the liquid crystal alignment film, and the liquid crystal display element having the film and the compound are manufactured. The liquid crystal display element of the present invention can perform high-quality display even when driven for a long period of time, display performance. Degradation is small, so it is effectively used in various devices', for example, suitable for use in timepieces, portable word processors, notebook computers, car navigation systems, camera information terminals, digital cameras, mobile phones, various displays, video, etc. Display device. [Embodiment] Hereinafter, embodiments of the present invention will be described in detail. &lt;Liquid crystal alignment agent&gt; The liquid crystal alignment agent of the present invention contains at least one polymer (hereinafter referred to as "complex") of [A] selected from the group consisting of polyamidomines, and [B] The compound represented by the above formula (1) (hereinafter referred to as "[B] compound"). Further, the liquid crystal alignment agent of the present invention may contain an optional component as long as it does not impair the [A] poly[B] compound and optionally The composition is described in detail. <A polymer> The polyamine acid as the [A] polymer can be obtained by reacting a tetracarboxylic acid diamine, and the polyamidene can pass through the polyglycolic acid ring. In the following, a detailed voltage-increasing liquid crystal matching method is applied to the tetracarboxylic dianhydride and the diamine. Because of this, there may be a machine, a 'portable liquid crystal, and a poly" [A], which is also called a fruit. Compound, dianhydride and dehydration closure-12- 201120098 [tetracarboxylic dianhydride] tetracarboxylic dianhydride, for example, butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic acid Dihydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid Dihydride, 1 3-Dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic acid Acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, l,3,3a,4,5,9b·hexahydro-5 -(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5, 9b-six Hydrogen-5-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,33 ,4,5,91&gt;-hexahydro-5-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[l,2-c]-furan-1,3 -dione, 1,3,3a,4,5,9b-hexahydro-7-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2&lt; ]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)- Naphtho[1,2-c]-furan-1,3-dione, l,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-di Oxy-3-furanyl)-naphtho[1,2&lt;]-furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-ethyl-5-(four Hydrogen-2,5-dioxo-3-furan )-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5-(tetrahydro- 2,5-dioxo-3-furyl)-naphtho[1,2-c]-furan-1,3-dione, bicyclo[2.2.2]-oct-7-ene-2,3,5 ,6-tetracarboxylic dianhydride, 3-oxabicyclo[3 _ 2 . 1 ]octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2 ',5 '-dione) , -13- 201120098 5-(2,5-Dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxyl 2-carboxymethylnorbornane-2: 3,5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.0'6]undecane-3,5,8,10-tetra a ketone, a compound represented by the following formula (T-1), formula (T-2), pyromellitic dianhydride, 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride, 3 , 3',4,4'-biphenylphosphonium tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3 , 3',4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylnonane tetracarboxylic dianhydride, 3,3',4,4 '-Tetraphenylnonane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide Anhydride '4,4'-bis(3,4-dicarboxyphenoxy)diphenylphosphonium dianhydride, 4,4'-bis(3,4-dihydrophenyloxy)diphenylpropane Anhydride '3,3',4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2·,3 , 3'-biphenyltetracarboxylic dianhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, inter-phenylene-bis (triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride bis(triphenylphthalic acid)-4,4 diphenyl Methane dianhydride, ethylene glycol • bis(benzene trimellitic anhydride), propylene glycol-bis(benzene trimellitic anhydride), 1,4-butanediol-bis(benzene trimellitic anhydride), 1,6-hexanediol - bis (benzene trimellitic anhydride), iota, 8-octanediol-bis(benzene trimellitic anhydride), 2,2-bis(4-hydroxyphenyl)propane-bis(benzene trimellitic anhydride) and the following formula (T-3) to a compound represented by (T-6). These tetracarboxylic dianhydrides may be used singly or in combination of two or more. -14- 201120098 ο ο

(Τ-1) (Τ-2) In the above formula, each of R3 and R3 is independently a divalent organic group having an aromatic ring. R2 and R4 are each independently a hydrogen atom or an alkyl group.

(Τ-3)

-15- 201120098 ?H3 /Ch3 ch3 ch(ch2)3ch,

o The compound represented by the above formula (T-1) and (T-2) may, for example, be a compound represented by the following formula (T-1 - 1) to (Τ-2 - 1). -16- 201120098 ο ο

ο ο Among these tetracarboxylic dianhydrides, selected from butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2, 3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,33 ,4,5,91)-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, l ,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]-furan- 1,3 -dione, 1,3,3a,4,5,9b-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene And [1,2-(:]-furan-1,3-dione, bicyclo[2.2.2]-oct-7-ene-17- 201120098-2,3,5,6-tetracarboxylic dianhydride' 3-oxabicyclo[3.21]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2,5,-dione), 5-(2,5-dioxotetrahydro- 3-furyl)-3-methyl-3-cyclohexene-oxime, 2·dicarboxylic anhydride, 3,5,6·tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6 - dianhydride, 4,9-dioxatricyclo[5.3.1.02.6]undecane-3,5,8,10-tetraketone' pyromellitic dianhydride, 3,3',4,4 '-Biphenyl ketone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl Tetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, the above formula (Tl-1)~(T- At least one of the groups consisting of the compounds represented by the formula (τ - 2 - 1) (hereinafter referred to as "specific tetracarboxylic dianhydride"), from the viewpoint of exhibiting good liquid crystal alignment It is preferred to consider a specific tetracarboxylic dianhydride, preferably selected from the group consisting of 1,2,3,4-cyclobutane tetracarboxylic dianhydride and 2,3,5-tricarboxycyclopentyl acetic acid dianhydride. , i,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-(:]-furan-1, 3-diketone, 1,3,33,4,5,91?-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1, 2-c]-furan-1,3-dione, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3,_(tetrahydrofuran-2,,5,_ Diketone), 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2 -carboxymethylnorbornane_2 : 3,5 : 6 · dianhydride, 4,9-dioxatricyclo[5·3·1·〇2'6]undecane_3,5,8, 10_tetraketone, pyromellitic dianhydride and the above formula (Τ-1 - 1) At least one of the groups of compounds represented. The use ratio of the specific tetracarboxylic dianhydride is preferably 50% by mole or more, more preferably 60% by mole or more, and particularly preferably 8% by mole or more, based on the total of the tetracarboxylic dianhydride. It is preferred to use only specific tetracarboxylic dianhydrides. • 18- 201120098 Diamines, for example, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4 '-Diaminodiphenyl sulfide, 4,4'-diaminodiphenyl hydrazine, 4,4'-diaminobenzimidamide, 4,4'-diaminodiphenyl ether, 1,5-Diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2 , 2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,3'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 5-amine 1-(4'-aminophenyl)-1,3,3-trimethylindoline, 6-amino-1-(4'-aminophenyl)-1,3,3- Trimethylindoline, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-di Aminobenzophenone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoro Propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]anthracene, 1,4-bis(4-amine Benzophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroquinone '2,7-Diaminopurine, 9,9-dimethyl-2,7-diaminopurine, 9,9-bis(4-aminophenyl)anthracene, 4,4'-methylene - bis(2-chloroaniline), 2,2',5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino- 5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-(p-phenylene isopropylidene) bis ( Aniline), 4,4'-(m-phenylphenylidene)bis(aniline), 2,2'-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl Hexafluoropropane, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-bis[(4-amino-2-trifluoromethyl)benzene Oxy]-octafluorobiphenyl, 3,5-diaminobenzoic acid, 1,4-bis-(4-aminophenyl-19-201120098 base)-piped, and the following formula (D-1) An aromatic diamine such as a compound represented by the formula (D-5); CH, I ch3 h2n h2n

(D-1) (D-2) CH3

(D-3) -20- 201120098

(D-5) In the formula (D-4), y is an integer of 2 to 12. In the above formula (D-5), z is an integer of 1 to 5 repeating units. 1,1-M-xylylenediamine, 1, 3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylene Diamine, nonamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadiene diamine, hexahydro-4,7-extension Methyldiamine, tricyclo[6.2.1.0'7]-undecenedimethyldiamine, 4,4'-methylenebis(cyclohexylamine), 1,3-bis(aminomethyl) An aliphatic diamine such as cyclohexane and 1,4-bis(aminomethyl)cyclohexane; and an alicyclic diamine; 2,3-diaminopyridine, 2,6-diaminopyridine, 3, 4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyridinium, 5,6-diamino-2,4-dihydroxypyrimidine, 2,4-Diamino-6-dimethylamino-1,3,5-tri-trap, 1,4-bis(3-aminopropyl)piped, 2,4-diamino-6- Isopropoxy-1,3,5-trin, 2,4-diamino-6-methoxy-1,3,5-tri-trap, 2,4-diamino-6-phenyl- 1,3,5-tripper, 2,4-diamino-6-methyl-s-triad, 2,4-diamino-1,3,5-tri-trap, 4,6-diamine Benzyl-2-vinyl-s-triterpene, 2,4-diamino-5- Thiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5-diamino-1,2,4-triazole, 6,9 -diamino-2-ethoxyacridol lactate, 3,8- -21 - 201120098, - slightly = a certain acridine, diamine, 6-phenylphenanthridine, 1,4-diamino Piper, 3,6---------- 3 6-diamine bis(4-aminophenyl)aniline, 3,6-diaminocarbazole, oxime-methyl 0'-anthracene-amino group Azole' Ν·ethyl-3,6-diaminocarbazole, oxime-phenyl·3' t仗隹f guanamine basic azole, hydrazine, Ν'-bis(4-aminophenyl)-benzidine , -diyl)-hydrazine, hydrazine, -dimethyl-benzidine, wherein the chemical substance Z· represented by the following formula (D-6) has two and is represented by the following formula (D-7) a diamine of a compound such as a primary amine group and a nitrogen atom other than the primary amine group;

Xa-R5 (D-6) ΝΗ, h2n- cultivating, η ting i-valent organic formula (D-6), R5 is a group having a composition selected from the group consisting of pyridine, pyrimidine, and pipe traps Nitrogen atomic ring structure @ group.乂8 is a divalent organic group. H2n

(D-7) . , 峨 11 In the formula (D-7), R6 is a 2-bucket group having a nitrogen atom-containing cyclic structure selected from the group consisting of pyridine, pyrimidine, dioxane, and a pipe trap. Xb is each independently a divalent organic group. Substituted phenylenediamine of a compound represented by the following formula (D-8); h2n

R7—R8 (D-8) NH2 〇C〇 In the formula (D-8), R7 is a Ο—, a COO — -22- 201120098 NHCO — *, — CONH-* or CO—. However, the connection key with * is connected to R8. R8 is a monovalent organic group having a skeleton or a group selected from the group consisting of a steroid skeleton, a trifluoromethylphenyl group, a trifluoromethoxyphenyl group, and a fluorophenyl group, or a carbon number of 6 to 30. Alkyl. A diaminoorganosiloxane such as a compound represented by the following formula (D-9). These diamines may be used singly or in combination of two or more. R9 R9 H2N—(CH2)^-Si-(〇—Si^-(CH2^-NH2 (D-9) R9 R9 In the formula (D-9), R9 is independently a carbon atom of 1 to 12 The hydrocarbon group P is each independently an integer of 1 to 3. q is an integer of 1 to 20. The above aromatic diamine, a diamine having a single primary amine group in the molecule and a nitrogen atom other than the primary amine group, and a single The benzene ring which the substituted phenylenediamine has may be substituted by one or two or more alkyl groups (preferably methyl groups) having 1 to 4 carbon atoms. Further, the steroid in the above formula (D-8) The skeleton refers to a skeleton formed of a cyclopentamethylene-perhydrophenanthrene nucleus or one or more of the carbon-carbon bonds thereof, which is a double bond. Among these diamines, it is preferred to contain a selected one selected from the group consisting of p-phenylenediamine. , 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'- Diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,7-diaminopurine, 4,4'-diaminodiphenyl Ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9-bis(4-aminophenyl)anthracene, 2,2-bis[4-(4- -23- 201120098 Amino Phenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(p-phenylenediphenylene)bis(aniline), 4 , 4'-(meta-phenyldiisopropylidene)bis(aniline), 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy) Biphenyl, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), anthracene, 3-bis(aminomethyl)cyclohexane, the above formula (D- 1 (D-5) each represented by a compound, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-di Amino oxazole, hydrazine, Ν'-bis(4-aminophenyl)-benzidine, anthracene, Ν'-bis(4-aminophenyl)-indole, Ν'-dimethylbenzidine, the above In the compound represented by the formula (D-6), the compound represented by the following formula (D-6-1) and the compound represented by the above formula (D-7) have the following formula (D-77-1). Twelve of the compounds represented by the above formula (D-8) Alkoxy-2,4-diaminobenzene, pentadecyloxy-2,4-diaminobenzene, cetyloxy-2,4-diaminobenzene, octadecyloxy-2 ,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, pentadecyloxy-2,5-diaminobenzene, hexadecyloxy-2,5-diamine a benzene, an octadecyloxy-2,5-diaminobenzene, and a compound represented by the following formula (D-8-1) to (D-8-9), represented by the above formula (D-9) At least one of the group consisting of 1,3-bis(3-aminopropyl)-tetramethyldioxane in the compound (hereinafter referred to as "specific diamine"). -24- 201120098

(D-7-1) -25- 201120098

H2n

(D-8-1) (D-8-2) (D-8-3) (D-8-4)

H2n (D-8-5) -26- 201120098

The amount of the above-mentioned diamine used for synthesizing the polyamic acid in the liquid crystal alignment agent is preferably 50 mol% or more preferably 60 mol% or more, and particularly preferably 80, based on the entire diamine. Mole% is most preferably only a specific diamine. [Synthesis of Poly-Proline] The poly-proline in the liquid crystal alignment agent can be obtained by allowing the above-mentioned di dianhydride to react with a diamine. The ratio of the use of the E dianhydride to the diamine to be supplied to the polyaminic acid synthesis reaction is preferably 0.2 equivalent to 2 equivalents per equivalent of the If group contained in the diamine, and is 0.3 equivalents per side. ~1.2 equivalents. The synthesis reaction of polylysine is preferably carried out in an organic solvent at a temperature of preferably from 20 ° C to 150 ° C, more preferably from 0 ° C to 100 ° C. The time is preferably from 0.1 hours to 24 hours, and more preferably 0.5 hours - said: % to . And the carboxylic acid carboxylic acid amount of amine is better reaction reaction 12 small -27- 201120098. The organic solvent may, for example, be an aprotic polar solvent, a phenol or a derivative thereof, an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon or a hydrocarbon. Examples of the aprotic polar solvent include N.methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, and dimethylammonium. R-butyrolactone, tetramethylurea, hexamethylphosphonium triamine, and the like. Examples of the phenol derivative include m-methylphenol, xylenol, and halogenated phenol. Examples of the alcohol include methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, and 1,4-butylene. Glycol, triethylene glycol, ethylene glycol monomethyl ether, and the like. The ketone may, for example, be acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone. The above ester may, for example, be ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate or malonic acid. Diethyl ester and the like. The ether may, for example, be diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol II. Methyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether 'diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate Ester, diethylene glycol monoethyl ether acetate, tetrahydrofuran, and the like. Examples of the halogenated hydrocarbons include dichloromethane '1,2-dichloroethane' 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene and the like. -28- 201120098 The hydrocarbon may, for example, be hexane, heptane, octane, benzene, toluene, xylene, isoamyl propionate, isoamyl isobutyrate or diisoamyl ether. Among these organic solvents, one or more selected from the group consisting of an aprotic polar solvent and a phenol and a derivative thereof (the first group of organic solvents), or an organic solvent selected from the above first group is preferably used. One or more and one or more mixtures selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons (the second group of organic solvents). The use ratio of the organic solvent of the second group is preferably 50% by mass or less, more preferably 40% by mass or less, and particularly preferably 30% by mass based on the total of the organic solvent of the first group and the second group. %the following. As described above, a reaction solution formed by dissolving polyamic acid can be obtained. The reaction solution may be directly supplied to the preparation of the liquid crystal alignment agent, or the polyphthalic acid contained in the reaction solution may be separated and supplied to the preparation of the liquid crystal alignment agent, or the separated polyamic acid may be refined. The preparation of a liquid crystal alignment agent is supplied. When the poly (proline) is dehydrated and closed to form a polyimine, the reaction solution may be directly supplied to the dehydration ring closure reaction, or the polylysine contained in the reaction solution may be separated and supplied to the dehydration ring closure reaction, or The separated polyamic acid is refined and then supplied to a dehydration ring closure reaction. The separation of the polyamic acid can be carried out by injecting the above reaction solution into a large amount of a poor solvent to obtain a precipitate, and then drying the precipitate under reduced pressure, or decompressing the organic solvent in the reaction solution using an evaporator. The distillation method is carried out. Further, the method of dissolving the polylysine in an organic solvent and then precipitating it with a poor solvent may be carried out by one or several times using a vaporizer for vacuum distillation. Method, refined poly-proline. [Synthesis of Polyimine] The polyimine which may be contained in the liquid crystal alignment agent can be obtained by subjecting a polyamic acid to a dehydration ring closure obtained by reacting a tetracarboxylic dianhydride with a diamine. The tetracarboxylic dianhydride and the diamine which can be used for the synthesis of the polyimine are exemplified by the same compound as the tetracarboxylic dianhydride and the diamine which can be used for the synthesis of the polyamic acid. The preferred types and use ratios of the tetracarboxylic dianhydride and the diamine are the same as those for the synthesis of polyamic acid. The polyimine may be a fully ruthenium imide obtained by dehydrating and ring-closing a glycine structure of a polyamic acid as a raw material, or may be a closed-loop only part of a proline structure. The obtained proline acid structure and a part of the quinone imine compound coexist with the quinone ring structure. The ruthenium imidization ratio of the polyimine in the liquid crystal alignment agent is preferably 30% or more, and more preferably 40% or more. The above ruthenium iodization ratio is a percentage of the total number of ruthenium ring structures relative to the total number of phthalic acid structures and the number of quinone ring structures of the polyimine. At this time, a part of the quinone ring may also be an isoindole ring. The rate of hydrazine imidation can be known by the j-HMR of polyimine. In addition, the ruthenium amide ratio in the present specification is obtained by sufficiently drying the polyimine at room temperature under reduced pressure, and then dissolving it in deuterated dimethyl hydrazine and using tetramethyl decane as a reference material. The j-NMR was measured at room temperature, and the measurement result was determined by the following formula (2). -30- 201120098 醯 imidization rate (%) = { 1 —(AVA2)x α }χ100 (2) In the above formula (2), Α1 is the peak area from the NH matrix near the chemical shift of 10 ppm. A2 is derived from other proton products, and α is a proton of one group relative to the polyamidiamine precursor (polyglycine), and the ratio of the number of other protons. The dehydration ring closure of the polyamic acid for synthesizing the above polyimine is carried out by (1) heating the poly-proline, or (ii) adding the dehydrating agent to the solution and adding a dehydrating ring to the solution. And according to the method of heating required. (1) The reaction temperature in the method is preferably from 50 ° C to 200 ° C and from 60 ° C to 170 ° C. When the reaction temperature is less than 50 °C, the dehydration shutdown does not proceed sufficiently, and if the reaction temperature exceeds 200 °C, the molecular weight of the imine decreases. The reaction time is preferably 1.0 hour to 24 hours and more preferably 1.0 hour to 12 hours. In the method (ii), the dehydrating agent may, for example, be an acid anhydride such as acetic anhydride or trifluoroacetic anhydride. The amount of the dehydrating agent to be used is preferably 0.01 mol to 20 mol of the dehydration ring-closure catalyst, and examples thereof include a tertiary amine such as pyridine, trimethylpyridylpyridine or triethylamine. Use of a dehydration ring-closing catalyst The organic solvent used for the dehydration ring-closure reaction is preferably 0.01 mol to 10 mol of the dehydrating agent used for 1 mol, and an organic solvent exemplified as an organic solvent used in the synthesis of poly. The reaction temperature for dehydration is preferably from 0 ° C to 180 ° C, and more preferably from 10 ° C to the current peak of NH, which can be dissolved in the chemical agent, and the ring reaction is better. , Anhydride, C for 1 ear. Acridine, two amount, phase ear. It can be lysine closed loop 150 〇C. -31 - 201120098 Reaction time, preferably from 1.0 hour to 1 20 hours, and more preferably from 2.0 hours to 30 hours. The polyimine obtained in the method (i) may be directly supplied to a liquid crystal alignment agent, or the obtained polyimine may be purified and then supplied to a liquid crystal alignment agent. On the other hand, in the above method (ii), a reaction solution containing polyienimine can be obtained. The reaction solution may be directly supplied to the preparation of the liquid crystal alignment agent, or may be supplied to the liquid crystal alignment agent after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, or may be separated from the polyimine and then supplied to the liquid crystal alignment agent. The preparation, or the separation of the separated polyimine, may be followed by the preparation of a liquid crystal alignment agent. The dehydrating agent and the dehydration ring-closure catalyst are removed from the reaction solution, and a method such as solvent replacement can be employed. The separation and purification of the polyimine can be carried out in the same manner as described for the separation and purification method of polylysine. The poly-proline or polyimine which may be contained in the liquid crystal alignment agent may be a terminal-modified polymer having a molecular weight adjusted. By using the terminal-modified polymer, the coating properties and the like of the liquid crystal alignment agent can be further improved without impairing the effects of the present invention. Such a terminal-modified polymer can be obtained by adding a molecular weight modifier to a polymerization reaction system when synthesizing polyamic acid. The molecular weight modifier 'for example, a monoanhydride, a monoamine compound, a monoisocyanate compound, etc. are mentioned. The above monoanhydride may, for example, be maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl succinic anhydride Wait. -32- 201120098 The above monoamine compound may, for example, be aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine n-undecylamine , n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecaneamine, n-octadecylamine, n-icosylamine, and the like. The monoisocyanate compound may, for example, be phenyl isocyanate or naphthyl isocyanate. The use ratio of the molecular weight modifier is preferably 20 parts by mass or less, and more preferably 1 part by mass or less, based on 100 parts by mass of the total of the tetracarboxylic dianhydride and the diamine used in synthesizing the polyamic acid. . The polylysine or polyimine obtained as above preferably has a solution viscosity of 20 mPa's to 800 mPa's when forming a solution having a concentration of 10% by mass, and more preferably a solution having 30 mPa's to 500 mPa_s. Viscosity. In addition, the solution viscosity (mPa, s) of the polymer in the present specification is 10 weights prepared for a good solvent (for example, r-butyrolactone, N-methyl-2-pyrrolidone, etc.) using the polymer. % concentration of polymer solution, enthalpy measured at 25t using an E-type rotational viscometer. The [A] polymer in the liquid crystal alignment agent is preferably only a polyimine or a mixture of a polyimine and a polyamic acid. The ruthenium imidization ratio when only the polyimine is used as the [A] polymer is preferably 70% or less, and more preferably 30% to 60%. On the other hand, the average oxime imidization ratio when polyiminoimine and polyglycine are mixed as the [A] polymer is preferably 70% or less, more preferably 10% to 60%, and particularly preferably 15% ~ 55%. The average ruthenium imidization ratio is -33-201120098 The number of quinone imine ring structures (PI -I), the number of valeric acid structures (PI _ A), and poly-polyimine contained in the liquid crystal alignment agent. The number of guanamine structures of valine (PA-A), and the enthalpy calculated according to the following formula (1). Average oxime imidization rate (%) = _(ΡΙ-Ό_ (PI - I) + (PI - A) + (PA-A)

XlOO (1) &lt;[B] compound&gt; The compound [B] in the liquid crystal alignment agent is a compound represented by the above formula (1). R in the formula (1) has a cyclic hindered amine structure or a hindered phenol structure, and the number of substituted R is preferably from 1 to 3. In the present invention, the hindered amine structure means a structure having a plurality of substituents which exhibit steric hindrance on two carbon atoms adjacent to the nitrogen atom of the cyclic amine structure. The substituent which exhibits a steric hindrance may, for example, be an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 13 carbon atoms. R in the above formula (1) is each independently a hydrogen atom, a methylol group, an alkoxymethyl group having 2 to 7 carbon atoms, -CH2〇Y or -CH2〇Z. Y is a group having a cyclic hindered amine structure. Z is a group having a hindered phenol structure. However, at least one R is a group having a cyclic hindered amine structure or a hindered phenol structure. The hindered amine structure of Y is preferably a group represented by the above formula (2). The alkyl group having 1 to 6 carbon atoms represented by R1 in the above formula (2a) may be linear. Or any of the branched forms' and may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, etc. The number of carbon atoms represented by Ri in the above formula (2a) is 6~ The aryl group of 20 may, for example, be phenyl, 3-fluorophenyl, 3-chlorophenyl, 4-chlorophenyl, 4-isopropylphenyl, 4-n-butylphenyl, 3-chloro-4. Methylphenyl, 4-pyridyl, 2-phenyl-4-quinolinyl '2-(4,-tris-butylphenyl)-4-quinolinyl, 2-(2'-thiophenyl) In the above formula (2a), the aralkyl group having 7 to 13 carbon atoms represented by R1 in the above formula (2a) may, for example, be a benzyl group or a phenethyl group. The combination of Ri and X1 (i.e., the moiety of R1 - X1 -) may, for example, be methyl, ethyl, n-propyl, isopropyl, n-butyl '2-butyl, isobutyl, tert-butyl , formazan, ethenyl, phenyl, benzyl, 1,3 -dioxybutyl, 4-pyridylcarbonyl, benzene Indenyl, 2-phenyl-4-quinolinyl, 2-(4'-tris-butylphenyl)-4-quinolinyl, 2-(2'-thiophenyl)-4-quinolinyl Formula 1 CONH-Ph (wherein Ph is phenyl, 3-fluorophenyl, 3-chlorophenyl, 4-chlorophenyl, 4-isopropylphenyl, 4-n-butylphenyl or 3- The group represented by chloro-4-methylphenyl group, etc. The alkyl group represented by R1 to Rv in the above formula (2) having 1 to 6 carbon atoms is exemplified as the number of carbon atoms represented by the above R1. The group exemplified as the alkyl group having 1 to 6 is an aryl group having 6 to 12 carbon atoms represented by Rn to Rv in the above formula (2a), preferably a portion having an aromatic ring of an aryl group or A group in which all hydrogen atoms are substituted by a fluorenyl group or an alkoxy group having 1 to 4 carbon atoms, and examples thereof include a phenyl group, a 4-methylindenylphenyl group, and a 3,4,5-trimethoxyphenyl group. -35- 201120098 The aryl fluorenyl group having 7 to 13 carbon atoms represented by Rn to Rv in the above formula (2a), and some or all of the hydrogen atoms of the aromatic ring of the aralkyl group may be a fluorenyl group or Examples of the group substituted with an alkoxy group having 1 to 4 carbon atoms include, for example, a unit group. R11 in the above formula (2a) a combination of X2, R111 and X3, 1^ and X4, ^ and X5 (i.e., a portion of Ru-X2-, R1&quot;-X3-, RIV-X4- or RV-X5-), for example, methyl group, B Base, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, phenyl, benzyl, benzhydryl, 4-methylbenzyl benzhydryl, 2 - Hydroxy-2-phenylethyl, 2-oxo-2-(3,4,5-trimethoxyphenyl)ethyl and the like. As the compound represented by the above formula (2a), a compound in which R1 is a hydrogen atom, R11 to Rv are both a methyl group, and X and X5 are each a single bond is preferable. Further, in the present invention, having a hindered phenol structure means that steric hindrance is exhibited in the ortho position (position 2 and/or position 6) of the phenolic hydroxyl group in the formula (1). Examples of the substituent which exhibits a steric hindrance include, for example, a tertiary butyl group, a 1-methyl pentene group, an octyl thiomethyl group and the like. Further, when the substituent is located at both the 2-position and the 6-position, the substituents are each independent. The hindered phenol structure of the above Z is preferably a group represented by the above formula (3). Preferred examples can be exemplified by having a (3,5-di-3-butyl-4-hydroxyphenyl group) group. A compound having a carbon number of 4 to 16 represented by RVI in the above formula (3a) is preferably a secondary butyl group, a 1-methyl pentylene group, an octyl thiomethyl group, and 36- 201120098 More preferably a tertiary butyl group. The hydrocarbon group having 1 to 16 carbon atoms represented by Rvn in the above formula (3a) is preferably a tertiary butyl group, a 1-methylpentadecyl group or a octyl group. The thiomethyl group 'and more preferably a tertiary butyl group. The ft. and Rvn in the above formula (3a) are preferably ortho to the phenolic hydroxyl group (positions 2 and 6). X7 in the above formula (3a) Preferably, it is a methylene group. The compound [B] is preferably a reaction product of a 1 molar (bl) compound and an X mole (b2) compound (wherein X satisfies 〇 &lt; x &lt; n). Wherein η is the number of the methylol group or the alkoxymethyl group having 2 to 7 carbon atoms of the above (bl) compound. (bl) The compound represented by the above formula (lx) represented by Rx An alkyl group having a carbon number of 6 It is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group, an ethyl group, an n-butyl group or an isobutyl group, and particularly preferably a methyl group. Such a compound (bl) may, for example, be an 11 ^', 1^川'', 1^''-hexa(alkoxymethyl) melamine and other alkoxymethylated melamine. As a commercial item, CYMEL3 00, CYMEL301, CYMEL303, CYMEL3 50 ' CYMEL3 70, CYMEL3 25, CYMEL3 27, CYMEL703, CYMEL712, MYCOAT715, CYMEL701 'CYMEL28 5, CYMEL232, CYMEL235, CYMEL236, CYMEL23 8 , CYMEL21 1 , CYMEL254, MYCOAT212, CYMEL202, MYCOAT5 08 (MITSU - CYTEC), etc. -37- In the organic solvent which can be used for the above-mentioned reaction, the organic solvent exemplified as the organic solvent used in the synthesis of the polyamic acid is exemplified. The aprotic organic solvent is preferably, for example, N-methyl-2. Pyrrolidone, acetonitrile, dimethyl sulfoxide, N,N-dimethylacetamide, hydrazine, hydrazine-dimethylformamide' hydrazine, Ν'-dimethylimidazolidinone, dimethyl Ruthenium, r-butyrolactone, tetramethylurea The ratio of the use ratio of the organic solvent to the total weight of the compound (b 1) and the compound (b2) in the reaction solution is preferably 1% by mass or more, and more preferably. It is a ratio of 5 mass% to 50 mass%. The temperature at the time of the reaction is preferably from 20 ° C to 2 50 ° C, and more preferably from 50 ° C to 180 ° C. The reaction time is preferably from 0.1 to 72 hours, and more preferably from 0.5 to 48 hours. Thus, a solution containing the preferred [B] compound can be obtained. The solution may be directly supplied to the preparation of the liquid crystal alignment agent, or the [B] compound may be separated and purified from the reaction solution to be supplied to the liquid crystal alignment agent. The method of separating and purifying the [B] compound from the reaction solution may, for example, be a liquid-liquid extraction method, a column chromatography method, a distillation method, or recrystallization. A preferred [B] compound is a compound having a methylol group or an alkoxymethyl group having 2 to 7 carbon atoms which is a compound (b) and reacts with the compound (b2), and has a compound (b). a hydroxymethyl group or an alkoxymethyl group having 2 to 7 carbon atoms and a group R1 derived from the compound (b2). Therefore, the liquid crystal alignment agent can form a compound of the [B], and can maintain a good liquid crystal alignment property and an electric property of 38-201120098 even when driven continuously for a long period of time, while suppressing an increase in residual DC voltage. Liquid crystal alignment film. More preferably, the above Y is at least one selected from the group consisting of groups represented by the above formulas (2a-1) to (2a_2), and more preferably Z is selected from the above formula ( At least one of the groups consisting of the groups represented by 3a-1)~(3a-2). The use ratio of the [B] compound in the liquid crystal alignment agent is preferably 0.1 part by mass to 100 parts by mass, more preferably 0.5 part by mass to 50 parts by mass, per 100 parts by mass of the [A] polymer, and particularly preferably 1 part by mass to 30 parts by mass. &lt;Optional Component&gt; The liquid crystal alignment agent contains the above-mentioned [A] polymer and [B] compound, and may contain another polymer or a compound having at least one epoxy group in the molecule as needed (hereinafter, referred to as "ring" The oxygen compound ") is an optional component such as a functional decane compound, a polyfunctional (meth) acrylate, or a melamine compound (other than the [B] compound). Hereinafter, each component will be described in detail. [Other Polymers] The above other polymers can be used to improve solution properties and electrical properties. Other polymers may, for example, be polyphthalates, polyesters, polyamines, polyoxyalkylenes, cellulose derivatives, polyacetals, polystyrene derivatives, poly(styrene-phenyl-n-butylene Diimine derivatives, poly(meth)acrylates, and the like. The use ratio of the other polymer in the liquid crystal alignment agent of the present invention is preferably 100% by mass or less, more preferably 80% by mass or less, and particularly preferably 3% by mass based on 100 parts by mass of the [A] polymer. the following. The best is not included -39- 201120098 There are other polymers. [Epoxy compound] The epoxy compound can be used from the viewpoint of further improving the adhesion to the surface of the liquid crystal alignment film substrate to be formed. Preferred epoxy compounds include, for example, ethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 1,3,5,6-tetraglycidyl-2. , 4-hexanediol, hydrazine, hydrazine, hydrazine, Ν'-tetraglycidyl-m-xylylenediamine, 1,3-bis(indole, hydrazine-diglycidylaminomethyl)cyclohexane , Ν, Ν, Ν', Ν'-tetraglycidyl-4,4'-diaminodiphenylmethane, hydrazine, hydrazine-diglycidyl benzylamine, hydrazine, hydrazine-diglycidyl- Aminomethylcyclohexane or the like. The formulation ratio of the epoxy compound is preferably 40 parts by mass or less, and more preferably 0.1 part by mass to 30 parts by mass, per 1 part by mass of the [Α] polymer. [Sandane compound] From the viewpoint of further improving the printability of the liquid crystal alignment agent, the above functional decane compound can be used. The functional decane compound may, for example, be 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane or 2-aminopropyltriethyl Oxoxane, Ν-(2-aminoethyl)-3-aminopropyltrimethoxydecane, Ν-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane , 3-decyl propyl trimethoxy decane, 3- ureidopropyl triethoxy decane, N ethoxycarbonyl 3-aminopropyl trimethoxy decane, N-ethoxycarbonyl-3 -Aminopropyltriethoxydecane, N-triethoxydecylpropyltrisethyltriamine, N-trimethoxy-40- 201120098 decylpropyltriethylamine, 10- Trimethoxydecyl-1,4,7-triazadecane, 10-triethoxyindolyl-1,4,7-triazadecane, 9-trimethoxyindolyl-3,6 - diazaindolyl acetate, 9-triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl-3.aminopropyltrimethoxydecane, N- Benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N- Double Ethyl) -3-aminopropyl trimethoxy Silane, N- bis (oxyethyl elongation) -3-aminopropyl group Silane triethylamine and the like. The proportion of the functional decane compound to be used is preferably 2 parts by mass or less, and more preferably 0.02 parts by mass to 0.2 parts by mass, per 100 parts by mass of the [A] polymer. [Polyfunctional (meth) acrylate] From the viewpoint of further improving the weather resistance of the liquid crystal alignment agent, the above polyfunctional (meth) acrylate can be used. Examples of the polyfunctional (meth) acrylate include ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, hydrazine, and 6-hexanediol dimethacrylate. Vinegar, 1,9-nonanediol diacrylate '丨, 9-nonanediol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polypropylene glycol diacrylic acid Ester, polypropylene glycol dimethacrylate, bisphenoxyethanol oxime diacrylate, bisphenoxyethanol oxime dimethacrylate, trimethylol propyl tripropionate, trimethylolpropane three Methacrylate, pentaerythritol triacrylate, neopentyl alcohol trimethacrylate, pentaerythritol tetrapropyl acrylate, neopentyl alcohol tetramethacrylate, dipentaerythritol pentaacrylate Ester, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylic acid-41 - 201120098 ester, dipentaerythritol hexamethacrylate, tris(2-propenyloxyethyl) phosphate , tris(2-methylpropenyloxyethyl) phosphate, and the like. Commercially available products include, for example, ARONOX M-210, ARONOXM-240, ARONOXM-6200 'ARONOXM-309 'ARONOX-400, ARONOX-402, ARONOX-405, ARONOX-450, ARONOX-1310, ARONOX-1600' ARONOX - 1 960, ARONOX - 7100, ARONOX - 803 0, ARONOX - 8 060, ARONOX - 8100, ARONOX - 8 5 30, ARONOX - 8 5 60, ARONOX - 905 0 ' ARONOXTO — 1450 (above, East Asia Synthetic Company), KAYARAD HDDA, KAY ARAD HX-220, KAYARAD R-604, UX-220 1 'UX- 23 0 1, UX-3 204, UX- 3 30 1, UX-4101' UX-6101' UX-7101' UX - 8101' MU - 2100 'MU - 4001, KAYARAD TMPTA, KAYARAD DPHA' KAYARAD DPCA - 20, KAYARAD DPCA - 30, KAYARAD DPCA - 60, KAYARAD DPCA- 120, KAYARAD MAX- 3510 (above, 曰本化制药公司), VISCOAT260, VISCOAT312, VISCO AT3 3 5 HP, VISCOAT295, VISCOAT300, VISCOAT360, VISCOATGPT, VISCOAT3PA, VISC〇AT400 (above 'Osaka Organic Chemical Industry Co., Ltd.), NEW FRONTIER R - 1150 (above 'First Industrial Pharmaceutical Company), KAYARAD DPHA - 40H (above, 曰本化药Division) and so on. The proportion of the polyfunctional (meth) acrylate to be used is preferably 1 part by mass or less, and more preferably 50 parts by mass or less, relative to '100 parts by mass of the [A] polymer. -42- 201120098 [Melamine compound (except for [B] compound)] The above melamine compound may, for example, be the above (b 1) compound. The use ratio of the melamine compound is preferably 100 parts by mass or less, and more preferably 50 parts by mass or less based on 100 parts by mass of the [A] polymer. &lt;Preparation method of liquid crystal alignment agent&gt; The liquid crystal alignment agent is prepared by preparing the above [A] polymer, [B] compound, and optionally a component, preferably a solution composition dissolved in an organic solvent. . The organic solvent may, for example, be N-methyl-2-pyrrolidone, r-butyrolactone, 7*-butylide, hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine-dimethyl diol. Indoleamine, 4-hydroxy-4-methyl-2-pentanone, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol monomethyl ether, ethylene Alcohol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethyl Diol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, two Isobutyl ketone 'isoamyl propionate' isoamyl isobutyrate, diisoamyl ether, ethylene carbonate, propylene carbonate, and the like. They may be used singly or in combination of two or more. The solid content concentration of the liquid crystal alignment agent (the ratio of the total mass of the liquid crystal alignment agent excluding the organic solvent to the total mass of the liquid crystal alignment agent) is appropriately selected in consideration of viscosity, volatility, etc., and is preferably 1 mass - 43- 201120098 % ~ιο质量%. When the liquid crystal alignment agent is applied onto the surface of the substrate and the organic solvent is removed to form a coating film which is formed into a liquid crystal alignment film, when the solid content concentration is less than 1% by mass, the thickness of the coating film is too small to be obtained. In the case of a good liquid crystal alignment film, on the other hand, when the solid content concentration exceeds 10% by mass, it may occur that the thickness of the coating film is too thick and it is also difficult to obtain a good liquid crystal alignment film, or the viscosity of the liquid crystal alignment agent may occur. The increase causes the coating characteristics to deteriorate. A more preferable solid content concentration range differs depending on the method used for coating the liquid crystal alignment agent on the substrate. For example, when the spin coating method is employed, it is preferably in the range of 1.5% by mass to 4.5% by mass. When the printing method is employed, it is preferably in the range of 3 mass% to 9 mass%, and the solution viscosity is preferably in the range of 12 mPa_s to 50 mPa's. When the ink jet method is employed, it is preferably in the range of 1 mass% by mass, and the solution viscosity is preferably in the range of 3 mPa·s to 15 mPa's. The temperature at which the liquid crystal alignment agent is prepared is preferably from 10 ° C to 50 ° C, and more preferably from 20 ° C to 30 ° C. &lt;Liquid Crystal Alignment Film 'The method for forming the liquid crystal display element and the method for producing the liquid crystal display element&gt; The liquid crystal alignment film formed of the liquid crystal alignment agent is also suitable for inclusion in the present invention. The liquid crystal alignment film of the present invention is formed by coating the liquid crystal alignment agent on a substrate, and then heating the coated surface to form a substrate. Further, the liquid crystal display element of the present invention has the liquid crystal alignment film. Hereinafter, a method of forming a liquid crystal alignment film of the present invention and a method for producing a liquid crystal display element - 44 - 201120098 will be described in detail. (1: 1) When manufacturing a TN type, STN type or VA type liquid crystal display element, 'the two substrates on which the patterned transparent conductive film is provided are paired, and preferably passed through an offset printing method, a spin coating method, or an ink jet method. In the printing method, the liquid crystal alignment agents of the present invention are applied to the surfaces of the respective transparent conductive films, respectively, and then the respective coated surfaces are heated to form a coating film. Here, as far as the substrate is concerned, glass such as float glass or soda glass; polyethylene terephthalate, polybutylene terephthalate, polyether maple, polycarbonate, alicyclic olefin, etc. can be used. A transparent substrate formed of plastic. For the transparent conductive film provided on one side of the substrate, a tin oxide film (NESA film formed by SnOO (registered trademark of PPG, USA), and an ITO film formed of indium oxide-tin oxide (In2〇3—Sn〇2) can be used. The method of obtaining the patterned transparent conductive film may, for example, be a method of forming a pattern by photolithography after forming a transparent conductive film having no pattern, or a method of using a photomask having a desired pattern when forming a transparent conductive film. When the liquid crystal alignment agent is applied, in order to improve the adhesion between the surface of the substrate and the transparent conductive film and the coating film, it is possible to apply a functional decane compound or a functional titanium compound to the surface of the substrate to form a coating film. After the application of the liquid crystal alignment agent, preheating (prebaking) is preferably carried out in order to prevent the liquid from dropping downward, etc. The prebaking temperature is preferably 30 ° C to 200 ° C, more preferably 4 0 ° C ~ 1 50 ° C, and particularly preferably 40 ° C ~ 1 0 0 ° C. Pre-baking time, preferably 0.1 minutes ~ 1 minute, and more preferably 0.5 minutes ~ 5 minutes. 45- 201120098 Then, in order to completely eliminate The solvent and, if necessary, the imidization of the polyhydrazine, the calcination (post-baking), the post-baking temperature, preferably 80 ° C ° C, and more preferably 1 2 0 ° C ~ 2 5 0 ° C The post-baking time is preferably 5 minutes, and more preferably 10 minutes to 100 minutes. Although the liquid crystal alignment is removed to remove the organic solvent after coating to form a liquid crystal alignment film, in the liquid crystal alignment agent When the polymer contained is polyaminic acid or a polyimine having a quinone ring structure and a guanidine structure, it may be further heated after the coating film is formed, and a dehydration ring-closing reaction is carried out to form a ruthenium-based coating. The film thickness of the formed coating film is preferably from 0.001 mm to 1 / zm and is from 0.005 / zm to 0.5 / / m. (1 - 2) When printing an IPS type liquid crystal display element, it is preferably through printing. The liquid crystal of the present invention is applied to the surface of the base conductive film on which the patterned transparent conductive film is provided in a comb shape, and the opposite substrate on which the conductive film is not provided, by a method, a spin coating method, or an inkjet printing method, respectively. Then, each coated surface is heated to form a coating film. The substrate used for the conductive film is transparent and conductive. The method of patterning the film, the principle of the substrate, and the heating method after applying the liquid crystal alignment agent are the same as those of the above-mentioned film formed by the same method, and are the same as the above (1 to 1). In the case of the liquid crystal display element of the liquid crystal display element f type manufactured by the method of the present invention, the coating film formed as described above can be directly used as the liquid crystal alignment film, but it may be supplied and used as desired after performing the treatment described below. On the other hand, in the manufacture of liquid amic acid -300 ~ 200 agent permeable coating other than VA type at the same time in a more better offset to the side of the agent plate, before the penetration of 1) phase cold VA with honing crystal display -46 - 201120098 When the device is shown, a liquid crystal alignment film is formed by performing a honing treatment on the coating film formed as described above. The honing treatment can be carried out by rubbing the surface of the coating film formed as described above in a predetermined direction by using a roll wound with a cloth such as nylon, rayon or cotton. Thereby, the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film. Further, the liquid crystal alignment film formed as described above is subjected to, for example, a part of the liquid crystal alignment film shown in JP-A-6-2 2 2 3 6 6 or JP-A-6-281 A process of irradiating ultraviolet rays to change a pretilt angle of a liquid crystal alignment film partial region or a photoresist film formed on a portion of a surface of a liquid crystal alignment film as disclosed in Japanese Laid-Open Patent Publication No. Hei 5-107544, The honing treatment is performed in the different directions of the grinding treatment, and then the treatment for removing the photoresist film 'the liquid crystal alignment film has different liquid crystal alignment ability in each region' can improve the visual field characteristics of the obtained liquid crystal display element. (3) Two sheets of the substrate on which the liquid crystal alignment film was formed were prepared, and liquid crystal was placed between the two substrates arranged in the opposite direction to produce a liquid crystal cell. Here, when the coating film is subjected to the honing treatment, the two substrates are arranged to face each other such that the honing directions in the respective coating films are at a predetermined angle to each other, for example, orthogonal or antiparallel. For the production of the liquid crystal cell, for example, the following two methods can be cited. The first method is a conventionally known method. First, two substrates are disposed opposite each other with a gap (cell gap) therebetween, and the respective liquid crystal alignment films are opposed to each other, and the peripheral portions of the two substrates are bonded together using a sealant. Together, the liquid crystal cell can be manufactured by injecting a liquid crystal into the cell gap which is divided by the surface of the substrate and the sealant, and then closing the injection hole. The first method is a method in which 〇DF (0ne Dr〇p Fi(1) method is applied to a predetermined portion on one of two substrates in which a liquid crystal alignment film is formed, for example, an ultraviolet curable sealing material is applied, and then a liquid crystal is applied. The liquid crystal is dropped on the alignment film surface, and then the other substrate is bonded to the liquid crystal alignment film, and then the entire surface of the substrate is irradiated with ultraviolet rays to cure the sealing agent, whereby the liquid crystal cell can be produced. It is desirable to further heat the liquid crystal cell as described above to a temperature at which the liquid crystal used is in an isotropic phase, and then slowly cool to room temperature ' thereby removing the flow alignment when the liquid crystal is injected. Then 'passing on the outside of the liquid crystal cell The liquid crystal display element can be obtained by bonding a polarizing plate to the surface. The sealing agent ′ includes, for example, an alumina ball as a separator and an epoxy resin containing a curing agent. Examples of the liquid crystal include, for example, nematic liquid crystal and A smectic liquid crystal or the like. Among them, a nematic liquid crystal is preferred. In the case of a VA type liquid crystal cell, a negative dielectric anisotropy is preferred. The liquid crystal may, for example, be a dicyanobenzene liquid crystal, a helium trap liquid crystal, a Schiff's salt liquid crystal, an oxidized azo liquid crystal, a biphenyl liquid crystal, or a phenylcyclohexane liquid crystal. In the case of a TN type liquid crystal cell or an STN type liquid crystal cell, a nematic liquid crystal having a positive dielectric anisotropy is preferred. Examples of such a liquid crystal include a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, and an ester. Liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, dioxin-based liquid crystal, bicyclooctane-48-201120098 liquid crystal, cubic liquid crystal, etc. Further, in the above liquid crystal It is also possible to add a chiral agent such as chlorinated cholesterol, cholesterol decanoate, cholesterol carbonate or the like as a cholesteric liquid crystal (MERCK, "C-15", "CB-15"); p-nonoxybenzene A strong dielectric liquid crystal such as methylene-p-amino-2-methylbutyl cinnamate or the like is used. The polarizing plate bonded to the outer surface of the liquid crystal may be exemplified by a cellulose acetate protective film. The scale obtained by absorbing iodine while stretching and aligning vinyl alcohol A polarizer formed of a polarizing film of a "ruthenium film" or a polarizer formed by the ruthenium film itself. &lt;Compound&gt; The compound of the present invention is represented by the above formula (1). A component such as a liquid crystal alignment agent of a liquid crystal alignment film. The detailed description of the method for producing the compound and the compound has been described in the description of the [Β] compound contained in the liquid crystal alignment agent, and therefore will not be described here. EXAMPLES Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited by the description of the examples. <Synthesis Example of [Α] Polymer> [Synthesis Example 1] As a tetracarboxylic acid 98 g (0.50 mol) of an anhydride, 2,3,4-cyclobutane tetracarboxylic dianhydride and 1 10 g (0.50 mol) of pyromellitic dianhydride, and 200 g (1.0 mol) as a diamine 4,4'-Diaminodiphenylmethane, dissolved in a mixed solvent of 230g N_ -49- 201120098 methyl-2-pyrrolidone and 2 1 0 0 gr - butyrolactone at 40 ° The reaction was carried out for 3 hours under c, and then 1 3 5 0 gr -butyrolactone was added to obtain a mass of 10 Solution - polyamide acid (1 PA). The solution had a solution viscosity of 125 mPa-s. [Synthesis Example 2] 200 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 210 g (1.0 mol) of 2,2' as a diamine -Dimethyl- 4,4'-diaminobiphenyl, dissolved in a mixed solvent of 370 g of N-methyl-2-pyrrolidone and 3300gr - butyrolactone, and carried out at 40 ° C for 3 hours The reaction gave a solution containing 10% by mass of poly-proline (PA-2). The solution had a solution viscosity of 160 mPa_s. [Synthesis Example 3] 10 10 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic dianhydride and 160 g (0.50 mol) 1,3,3 &amp; 5,91)-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[l,2-c]-furan-1,3-dione , with 94 g (0.87 mol) of p-phenylenediamine as a diamine, 25 g (0.10 mol) of 1,3 -bis(3-aminopropyl)tetramethyldioxane and 9.6 g (0.015 mol) 3,6-bis(4-aminophenoxy)cholesterane, and 8.1 g (0.03 mmol) of octadecylamine as a monoamine, dissolved in 960 g of N-methyl-2-pyrrolidine The ketone was reacted at 60 ° C for 6 hours to obtain a solution containing polylysine. A small amount of the obtained polyaminic acid solution was taken, and N-methyl-2-pyrrolidone was added thereto to form a solution having a polyglycine concentration of 1% by mass, and the measured solution viscosity was 60 rnPa.s. -50-201120098 Next, 2700 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and further 400 g of pyridine and 410 g of acetic anhydride were further added, and dehydration ring closure was carried out at 110 ° C for 4 hours. After the dehydration ring-closure reaction, the solvent in the system is replaced with a new r-butyrolactone (by this operation, the pyridine and acetic anhydride used in the dehydration ring-closure reaction are discharged to the outside of the system. The same applies.) About 15% by mass of a solution of a polyamidiamine (PI-1) having a ruthenium iodide ratio of about 95%. A small amount of the obtained polyimine solution was added, and r-butyrolactone was added to form a solution having a polyamidene concentration of 1% by mass, and the measured solution viscosity was 70 mPa's. [Synthesis Example 4] 110 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic dianhydride and 160 g (0.50 mol) 1, 3, 33, 4, 5, 91^hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2&lt;]-furan-1,3-dione, as two 95 g (0.88 mol) of p-phenylenediamine, 32 g (0.10 mol) of 4,4-diamino-2,2-bis(trifluoromethyl)biphenyl and 6.4 g (0.010 mol) 3 of amine. 6-bis(4-aminophenoxy)cholesterane, and 8.1 g (0.03 mol) octadecylamine as a monoamine, dissolved in 960 g of N-methyl-2-pyrrolidone The reaction was carried out for 9 hours at 60 ° C to obtain a solution containing polyamic acid. A small amount of the obtained polyaminic acid solution was taken, and N-methyl-2-pyrrolidone was added thereto to form a solution having a polyglycine concentration of 10% by mass, and the measured solution viscosity was 58 mPa·s. Next, 270 g of N-methyl-2-pyrrolidone was added to the obtained polyaminic acid solution, and 400 g of pyridine and 410 g of acetic anhydride were further added, and dehydration was carried out at 11 〇-51 - 201120098 ° C for 4 hours. closed loop. After the dehydration ring closure reaction, the solvent in the system was subjected to solvent replacement with a new 7.butyrolactone to obtain a polyimine (PI-2) solution containing about 15% by mass of a ruthenium iodide ratio of about 95%. . A small amount of the obtained polyimine solution was added, and T-butyrolactone was added to form a solution having a polyimine concentration of 10% by mass, and the measured solution viscosity was 69 mPa's. [Synthesis Example 5] ll 〇 g (〇.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic dianhydride and 43 g (0.40 mol) as a diamine Phenylenediamine and 52 g (0.10 mol) of 3(3,5-diaminophenoxy)cholesterane, dissolved in 8 3 Og N-methyl-2-pyrrolidone at 60 ° C A 6 hour reaction was carried out to obtain a solution containing polylysine. Taking a small amount of the obtained polyaminic acid solution', N-methyl-2-pyrrolidone was added thereto to form a solution having a polyglycine concentration of 10% by mass, and the measured solution viscosity was 60 mPa's. To the obtained polyaminic acid solution, 1900 g of N-methylpyrrolidone was added and 40 g of pyridine and 51 g of acetic anhydride were further added to carry out dehydration ring closure at 11 ° C for 4 hours. After the dehydration ring-closing reaction, 'solvent substitution of the solvent in the system with a new N-methyl-2-pyrrolidone' yields 0 with about 15% by mass of polyimine (pI) having a ruthenium iodide ratio of about 50%. —3) Solution. A small amount of the obtained polyimine solution was added, and N-methyl-2-lahydroacridone was added to form a solution having a polyamidene concentration of 1% by mass. The measured solution viscosity was 47 mPa's. [Synthesis Example 6] -52- 201120098 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic dianhydride, and 4 g (0.45 g) as a diamine Molar) p-phenylenediamine and 26 g (0.05 mol) of 3(3,5-diaminophenoxy)cholesterane' dissolved in 750 g of N-methyl-2-pyrrolidone at 60 ° C The reaction was carried out for 6 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyaminic acid solution was taken, and N-methyl-2-pyrrolidone was added thereto to form a solution having a polyglycine concentration of 10% by mass, and the measured solution viscosity was 58 mPa_s. Next, 1 800 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 40 g of pyridine and 51 g of acetic anhydride were further added, and dehydration ring closure was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was subjected to solvent replacement with a new N-methyl-2-pyrrolidone to obtain a polyimine (PI) containing about 15% by mass of a ruthenium iodide ratio of about 50%. — 4) Solution. A small amount of the obtained polyimine solution was added, and N-methyl-2-pyrrolidone was added to form a solution having a polyamidene concentration of 10% by mass, and the measured solution viscosity was 69 mPa's. &lt;Synthesis of [B] compound&gt; [Example 1] After dissolving 320 g of formalin, 8 mL of 1 N sodium hydroxide, and 20 g of melamine at 35 ° C, the mixture was allowed to stand at room temperature for a day and night to attract the precipitated six. The crystals of methylol melamine were washed with methanol and vacuum dried to obtain a purified product of 48 g of hexamethylol melamine. Next, 250 mL of tetrahydrofuran and 120 g of the following compound (B1 - 1) were added to the hexamethylol melamine, and the mixture was heated to 70 ° C, and then reacted with 1 mL of 0.5 N hydrochloric acid water-53-201120098 for 8 hours, and then used for hydrazine. The 5 N aqueous sodium hydroxide solution was neutralized to complete the reaction. Next, the reaction liquid was poured into 2 L of water, and the obtained precipitate was filtered, and the precipitate was purified using a ruthenium rubber column using chloroform/ethanol as a developing solvent to obtain a compound (B-1) having an average degree of substitution of 2 (B- 1). The average degree of substitution was analyzed by GPC.

(B1 - 1) H〇" [Example 2] A group having a steroid skeleton was obtained by using 43 g of the following compound (B2-1) in place of the compound (Β1 - Γ, and the same procedure as in Example 1). The compound with an average degree of substitution of 1 (Β~2).

&lt;Preparation of Liquid Crystal Aligning Agent&gt; [Example 3] A polyglycine (ΡΑ-丨) solution containing a [Α] polymer and a solution containing polyimine (ΡΙ-1) were mixed to make a polyfluorene Amino acid (ΡΑ-丨): polymerase (?1 -1) = 80:20 (quality ratio), and added 7 butyl vinegar '-54- 201120098 N-methyl-2-pyrrolidone And a glycol-containing mono-n-butyl ether, and a total of 10 parts by mass of the compound (B-1) as a compound [B], based on the total of the loo parts by mass of the polymer contained in the [B] compound contained therein. The solution is stirred well to form a solvent composition of 7 - butyrolactone: N-methyl-2 · pyrrolidone: ethylene glycol mono-n-butyl ether = 71: 17: 12 (mass ratio), solid concentration It is a 6.0% by mass solution. The solution was filtered using a sieve having a pore size of 1 μm to prepare a liquid crystal alignment agent. Further, ruthenium, osmium, iridium, Ν'-tetraglycidyl-4,4'-diaminodiphenylmethane was used as the epoxy compound. [Examples 4 to 7 and Comparative Examples 1 to 5] A liquid crystal alignment agent was prepared in the same manner as in Example 3 except that the type and amount of the compound to be blended were the types and amounts described in Table 1, respectively. Further, F_1 in Table 1 represents hexamethoxymethylol melamine (CYMELC 3 00, MITSUI-CYTEC). Further ''one' indicates an unused component'. [Example 8] Adding N-methyl-2-pyrrolidone and ethylene to a solution containing polyethylenimine (PI-3) as a polymer [A] Alcohol-mono-n-butyl ether, and further, 10 parts by mass of the compound (B-D solution) as a compound of [B] is added to the total of 100 parts by mass of the polymer in terms of [B] compound contained therein After arbitrarily, a solution having a solvent composition of N·methyl B ratio slightly ketone··ethyl ketone-mono-n-butyl ether = 50:50 (quality ratio) solid content concentration of 6.0% by mass was used. The pore diameter was 1 V. The solution of m was filtered to prepare a liquid crystal alignment agent. -55-201120098 [Examples 9 to 1 2 and Comparative Examples 6 to 1 0] The types and amounts of the compounds to be formulated were respectively the types described in Table 1. In the same manner as in Example 8, a liquid crystal alignment agent was prepared in the same manner as in Example 8. In addition, Ε-1 in Table 1 represents a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (ARONOXM402, East Asia) Synthetic company) &lt;Manufacturing of liquid crystal display element&gt; Printing using liquid crystal alignment film (Japan Photo Printing Co., Ltd.) The liquid crystal alignment agents prepared in Examples 3 to 7 and Comparative Examples 1 to 5 were coated on the transparent electrode surface of a glass substrate with a transparent electrode formed of a ruthenium film, and at 80°. The heated plate of C was heated for 1 minute (pre-bake) to remove the solvent, and then heated on a hot plate at 200 ° C for 10 minutes (post-baking) to form a coating film having an average film thickness of 60 0 A. The honing machine of the wire cloth roller has a roller rotation number of 500 rpm, a sample table moving speed of 3 cm/sec, a fluff squeezing length of 0.4 mm, and a sanding treatment to impart liquid crystal alignment energy. Then, it is carried out in ultrapure water. Ultrasonic washing was performed for 1 minute, followed by drying in a dust-free oven at 100 ° C for 10 minutes to obtain a substrate having a liquid crystal alignment film. These operations were repeated to obtain a pair of (two sheets) substrates having a liquid crystal alignment film. Next, in the above On each of the outer edges of the substrate having the liquid crystal alignment film, an epoxy resin adhesive having an alumina ball of 5.5 vm in diameter is applied, and the liquid crystal alignment film faces are opposed to each other, and the adhesive is laminated and the adhesive is applied. Curing After filling the nematic liquid crystal (MERCK's MLC-622 1 ) between a pair of substrates by a liquid crystal injection port, the liquid crystal injection port is sealed with an acrylic photocurable adhesive-56-201120098, thereby fabricating a liquid crystal cell. Using a liquid crystal alignment film printing machine (Japan Photo Printing Co., Ltd.), the liquid crystal alignment agents prepared in Examples 8 to 12 and Comparative Examples 6 to 1 were coated on a glass substrate with a transparent electrode formed of an ITO film. The transparent electrode surface was heated on a hot plate at 80 ° C for 1 minute (pre-bake) to remove the solvent, and then heated on a hot plate at 200 ° C for 10 minutes (post-bake) to form a coating film having an average film thickness of 600 A. . This operation was repeated to obtain a pair (two sheets) of substrates having a liquid crystal alignment film. Next, on each of the outer edges of the pair of substrates having the liquid crystal alignment film, an epoxy resin adhesive having a diameter of 5.5# m is applied, and then the liquid crystal alignment film faces are opposed to each other and overlapped. 'and cure the adhesive. Then, the liquid crystal injection port was used to fill the liquid crystal (MERCK, MLC-6608) between the pair of substrates, and then the liquid crystal injection port was sealed with an acrylic photocurable adhesive to produce a liquid crystal cell. &lt;Evaluation&gt; The liquid crystal display element produced using the prepared liquid crystal alignment agent was subjected to the following evaluation. The results are shown in Table 1. [Evaluation of weather resistance] For a liquid crystal cell, a voltage of 5 V was applied at an interval of 60 μsec and a distance of 167 ms at 70 ° C, and then T〇Y〇TECHNICA company "VHR _ 1 " The voltage holding ratio (initial voltage holding ratio (VHR, N)) after the release of the application to 167 ms was measured. Next, with respect to the liquid crystal cell in which the initial voltage holding ratio was measured, light irradiation was performed for 500 hours using a weather resistance tester using a carbon arc as a light source. For the liquid crystal cell after light irradiation, the voltage holding ratio (voltage holding ratio (VHRaf) after light irradiation) was measured again in the same manner as in the above-mentioned -57-201120098. When the maintenance ratio of the voltage holding ratio was 90% or more, the weather resistance was judged to be good, and when the temperature was less than 90%, the weather resistance was judged to be poor. [Evaluation of Residual DC Voltage] For the liquid crystal cell produced as described above, the DC voltage 値 (initial DC voltage) in the liquid cell was measured by a scintillation erasing method. Next, a voltage of DC 丨 7 V was applied to the liquid crystal cell at 100 ° C for 20 hours. For the liquid crystal cell after the application of the voltage, after 15 minutes passed after the release of the direct current power source, the D C voltage 液晶 in the liquid crystal cell was measured again by the scintillation erasing method. At this time, the D obtained by subtracting the initial 〇 c voltage 値 from the DC voltage after the application of the voltage is used as the residual DC voltage. The case where the residual DC voltage 値 was less than 500 mV was evaluated as "+", and the case where 500 00 mV or more was evaluated as "one". -58- 201120098 [I ¥ evaluation gffl H m ϋ + + -l· + + + + + + + + + + + 1 weatherability maintenance rate (%) r- cs ON r- CO ON cn Home Ο home cn σ&lt ; oo p oS OO oo ON OO oo OO CO Os r- CO ON ON cs a\ ON C-; ON inch inch £S inch ON OO oo vd oo \〇oo oo oo VO CO voltage retention rate after light irradiation VHRaK%) &lt;T) CN ON CN cn ON OO CS ON cn σν cn Os inch oo oo oo wn oo oo ss oo ON ON r&lt;i CO O v〇os ι_ H CO ON os » i \o oo cn oo oo oo oS Wo oo Initial voltage hold rate VHRin(%) oo σ&lt; cys ir\ ON ON σ&lt; CTn 〇\ ON S ON s ON 00 ON ^sO oo ON oo oo ON ON OO ON _·. κ ON ON ON ON Os s ON CO ON ON oo ON oo oo On ON o oo o § Os Composition of other constituents ooo Ο oooooooooooooooo Category II 1 1 l 1 1 [X. 1 1 1 I 1 1 1 1 1 &lt; ω 1 1 1 &lt; π mass parts ooor-Η ooooo different oooooo another oo [Β] compound mass parts o Ο o T-^ oooooo vy-t different 0 1 * o ί * ooooo kind|·_&lt; I PO 1 i 1 PQ B-2 ί Β-2 I CQ 1 1 1 1 1 1 PQ B-2 1 &lt; 1 PQ B-2 4 1 PQ 1 1 1 1 1 [Α]Polymer mass parts 80/20 80/20 70/30 1 80/20 j 80/20 80/20 80/20 70/30 80/20 1 80/20 or · oo 0 1 &lt; oooooo 骚ilmil W- II 1 &lt; 1 &lt;N 1 » ·Η 1 ι Η 1 ΡΑ-1/ΡΙ-2 ι—H 1 —H ! r 1 ι i 1 1 CS 1 PA—1 /PI —2 1 PA — 2/PI—2 fH 1 1 ( 1 PI-3 PI —3 PI-4 PI-4 PI-4 PI-3 PI-3 PI-4 PI—4 PI-4 Liquid Crystal Aligning Agent Example 3 Example 4 Example 5 π Example 6 Example 7 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Example 8 Example 9 Example 10 Example 11 Example 12 Comparison Example 6 Comparison Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 s-201120098 As is clear from the results of Table 1, the liquid crystal alignment agent of the present invention is capable of maintaining good electrical characteristics while having excellent weather resistance and suppressing an increase in residual DC voltage. Liquid crystal alignment film. Industrial Applicability According to the present invention, it is possible to provide a liquid crystal which can maintain good liquid crystal alignment performance and electrical characteristics while maintaining continuous DC voltage increase while maintaining long-term continuous driving. A liquid crystal alignment agent for an alignment film, a liquid crystal alignment film, a liquid crystal display element having a liquid crystal alignment film, a compound, and a method for producing a compound. Therefore, the liquid crystal display element of the present invention can perform high-quality display and has less deterioration in display performance even when driven for a long period of time, and thus can be effectively used for various devices, for example, for watches, portable game machines, word processors. Display devices such as notebook computers, car navigation systems, video cameras, portable information terminals, digital cameras, mobile phones, various displays, and LCD TVs. [Simple description of the diagram] None. [Main component symbol description] 6$ 〇 &gt;»\\ -60-

Claims (1)

201120098 VII, the scope of application for patents: Select] A amines 1) 醯ί Polygraph and lower acid Β 1 amine 醯 poly ' self-polymerization has a kind of suitable (less 'to the agent to the middle of the group of crystal group liquid Speciation of composition and composition of matter RR Ν· Ν Ί \ ΝI R RI N IR ——R In the formula (1), R is independently a hydrogen atom, a hydroxymethyl group, and the number of carbon atoms is 2~ 7 alkoxymethyl, -CH 2 〇 Y or -CH 2 〇 Z; Y is a group having a hindered amine structure; Z is a group having a hindered phenol structure, however, At least one R is a group having a cyclic hindered amine structure or a hindered phenol structure. 2. The liquid crystal alignment agent according to claim 1, wherein the above-mentioned Y has a cyclic hindered amine structure of the following formula (2a) The group represented by Z, which has a hindered phenol structure, is a group represented by the following formula (3a). -61- 201120098 In the formula (2a), R1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 13 carbon atoms or 1 , 3-dioxybutyl: Rn~Rv are each independently an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 13 carbon atoms; X1 Is a single bond, a carbonyl group or *-CONH-, wherein a linkage bond with * is attached to the piperidine ring; X2 to X5 are each independently a single bond, a carbonyl group, * - CH2 - CO - or * - ch2 -CH ( OH)-, wherein the linkage bond with * is attached to the piperidine ring; X6 is a single bond, a C0-, methylene group or an alkylene group having a carbon number of 2 to 6 'OH Rv, in the formula (3a), RV1 is a hydrocarbon group having 4 to 16 carbon atoms; Rvn is a hydrogen atom or a hydrocarbon group having 1 to 16 carbon atoms; and X7 is a single bond, a CO-, a methylene group or a carbon atom. The number is 2 to 6 alkylene; η is an integer of 0 to 3. 3. The liquid crystal alignment agent of claim 2, wherein the [Β] compound is (bl) a compound represented by the following formula (1Χ) and (b2) the following formula (2) and/or formula (3) Reaction product of the indicated compound, -62 - 201120098 (1x) In the formula (lx), Rx is each independently a hydrogen atom, a methylol group or an alkoxymethyl group having 2 to 7 carbon atoms, but at least one is a methylol group or a carbon atom is 2~ 7 alkoxymethyl, Y - OH (2) In the formula (2), Y is a group represented by the above formula (2a), Z - OH (3) wherein - Z is the above a group represented by the formula (3a). The liquid crystal alignment agent of claim 2, wherein the γ is at least one selected from the group consisting of groups represented by the following formulas (2*-1) to (2a-2). Z is at least one selected from the group consisting of groups represented by the following formulas (3a-1) to (3a-2): Η (2a-1) -63- 201120098 5. The liquid crystal alignment agent according to any one of claims 1 to 3, wherein the use ratio of the [B] compound is 〇. 1 part by mass or more with respect to 100 parts by mass of the [A] polymer. Below the mass. A liquid crystal alignment film which is formed by a liquid crystal alignment agent according to any one of claims 1 to 3. A liquid crystal display element which has a liquid crystal alignment film as in claim 6 of the patent application. 8. - A compound represented by the following formula (1)' -64- 201120098 In the formula (1), R is each independently a hydrogen atom, a methylol group, an alkoxymethyl group having 2 to 7 carbon atoms, -CHiOY or -CH2〇Z; and Y is a group having a cyclic hindered amine structure. Z is a group having a hindered phenol structure, but at least one R is a group having a cyclic hindered amine structure or a hindered phenol structure. 9. A process for producing a compound according to claim 8 which has a step of reacting a compound represented by the following formula (1x) with a compound represented by the following formula (2) and/or (3). In the formula (lx), Rx is each independently a hydrogen atom, a methylol group or an alkoxymethyl group having 2 to 7 carbon atoms 'but 'at least one R1 is a methylol group or a carbon number of 2 to 7 Alkoxymethyl 'Y-OH (2) In the formula (2), Y is a group having a cyclic hindered amine structure; Z - OH (3) In the formula (3), Z is a hindered phenol structure Group. -65 - 201120098 ' IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: