TW200841093A - Agent for alignment treatment of liquid crystal and liquid crystal display element using the same - Google Patents

Abstract

Disclosed is an agent for the alignment treatment of a liquid crystal, which has a highly stabilized pretilt angle. Also disclosed is a liquid crystal display element which has less change in a pretilt angle and also has excellent display reliability. The agent for the alignment treatment of a liquid crystal comprises at least one polymer selected from the group consisting of polyamic acid and polyimide and a crosslinkable compound having at least two oxetane groups represented by the formula [I] in the molecule.

Description

[Technical Field] The present invention relates to a liquid crystal alignment treatment agent for producing a liquid crystal alignment film, and a liquid crystal display element using the same. [Prior Art] In the liquid crystal display element, the liquid crystal alignment film serves to align the liquid crystal in a certain direction. Now, it is applied to the main liquid crystal alignment film in the industry by polycondensation of the polyimide precursor. A polyimine-based liquid crystal alignment treatment agent prepared by a solution of an amino acid or a polyimide reaction is applied to a substrate to form a film, and when the liquid crystal is aligned in a parallel direction or obliquely aligned with respect to the substrate surface, after film formation, The surface extension treatment is performed by rubbing. In addition, it has also been proposed to replace the honing treatment by an anisotropic photochemical reaction such as polarized ultraviolet ray irradiation. In recent years, it has been reviewed for industrialization, and the liquid crystal alignment film is also used to control the angle of the liquid crystal with respect to the substrate. That is, the tilt angle of the liquid crystal is controlled. However, since the liquid crystal display element is improved in performance and its use range is expanding year by year, not only the predetermined tilt angle but also the stability of the tilt angle is more important. From the viewpoint of the stability of the tilting angle, in the production step of the liquid crystal alignment film, it is proposed to contain a polyimine-based liquid crystal alignment treatment agent for the purpose of obtaining a certain inclination angle regardless of the honing condition. A compound having two or more epoxy groups in the molecule (for example, refer to the patent literature). Further, in the manufacturing step of the liquid crystal display device, in order to improve the alignment uniformity of the liquid crystal-5-200841093, there is a case where the liquid crystal is sealed and then heat-treated to cause the liquid crystal to be isotropy once, but the tilt angle is stable. When the degree of lowness is low, the tilt angle of the target size or the deviation of the tilt angle may not be obtained after the assimilation processing. In particular, in order to obtain high brightness, a liquid crystal display element using a backlight having a large amount of heat or a liquid crystal display element used in an in-vehicle use, such as a car navigation system and an instrument panel, may be used or placed in a long-time ambient temperature environment. In such a case, when the inclination angle is gradually changed under such severe conditions, the initial display characteristics may not be obtained, or the display may be uneven. [Problem to be Solved by the Invention] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid crystal alignment treatment agent which is excellent in stability of a tilt angle even in a high-temperature environment for a long period of time, and provides a tilt. A liquid crystal display element having a small change in angle and excellent reliability of display. Further, with the recent increase in the density of pixels in the liquid crystal display element, the high dimensionality of the surface structure of the substrate (the large unevenness of the surface), the variation in the honing strength in the liquid crystal display surface is larger than that of the prior art, and occurs. In the weaker part, the alignment regulation force of the liquid crystal becomes weaker, and some display defects occur. Therefore, in addition to the stability of the lift angle, it is also an object of the present invention to provide a liquid crystal alignment treatment agent which does not deteriorate the alignment property of the liquid crystal regardless of the honing condition. 200841093 [Means for Solving the Problem] That is, the present invention is an invention having the following gist. (1) A liquid crystal alignment treatment agent comprising the following (A) component and (B) component, (A) at least one polymer selected from the group consisting of polyproline and polyimine. (B) A crosslinkable compound having at least two oxetanyl groups represented by the following formula [1] in the molecule. [Chemical 1]

(2) The liquid crystal alignment treatment agent according to the above (1), wherein the component (B) is a compound represented by the following formula [2]

[Chemical 2]

(In the formula [2], Χι means N, NH, C0, 0, S, S02, Si' 1/2

A siloxane, a polyoxyalkylene, or an organic group having a carbon number of 1 to 20' may also contain a hetero atom (N, 0, s, Si) in the organic group; χ2 and χ3 each independently represent a single bond, ΝΗ , CO, hydrazine, S, S02, or an organic group having 1 to 20 carbon atoms, which may also contain a hetero atom (N, hydrazine, S, Si); γι and Y2 200841093 each independently represent a carbon number of 1~ An organic group of 20, the organic group may also contain a hetero atom (Ν, 0, S, Si); m, η each independently represent an integer of 0 to 2 ,, and m + n represents an integer of 2 to 20 ). (3) The liquid crystal alignment treatment agent according to the above (1), wherein the component (B) is a compound represented by the following formula [3],

(In the formula [3], X2 and X3 each independently represent a single bond, NH, C0, 0, S, S02, or an organic group having 1 to 20 carbon atoms, and the organic group may also contain a hetero atom (N, 0). , S, Si); 丫1 and Y2 each independently represent an organic group having 1 to 20 carbon atoms, and the organic group may also contain a hetero atom (N, 0, S, Si); Zi represents a single bond, NH, N (CH3), NHCO, CONH, NHCONH, CO, COO, 0, S, S02, CF2, C(CF3)2, Si(CH3)2, OSi (ch3) 2, Si (ch3) 20, OSi (ch3) 20, or an alkyl group having 1 to 10 carbon atoms; m and n each independently represent an integer of 0 to 10, and m + n represents an integer of 2 to 10). (4) The liquid crystal alignment treatment agent according to the above (1), wherein the component (B) is a compound represented by the following formula [4] [Chemical Formula 4] W(4) -8- 200841093 (In the formula [4], Χι Represents NH, N (CH3), NHCO, CONH, NHCONH, CO, COO, OCO, 0, S, S〇2, CF2, C(CF3)2, Si(CH3) 2, 〇Si (CH3) 2, Si (CH3) 20 or 0Si(CH3)20; 丫! and Y2 each independently represent an alkyl group having 1 to 10 carbon atoms. (5) The liquid crystal alignment treatment agent according to (1) above, wherein (B) The composition is a compound represented by the following formula [5]

W匕5]

[5] (In the formula [5], Xi is N, an aliphatic ring having 1 to 20 carbon atoms, an aromatic ring having 1 to 20 carbon atoms or an alkylene group having 1 to 20 carbon atoms; Y! and Y2 are each independently The ground represents an alkyl group having 1 to 10 carbon atoms; m and η each independently represent an integer of 0 to 2 0, and m + n represents an integer of 2 to 20). (6) The liquid crystal alignment agent according to any one of the above (1), wherein the component (B) is contained in an amount of 0.1 to 150 parts by mass based on 100 parts by mass of the component (A). (7) The liquid crystal alignment agent according to any one of (1) to (6) above which further contains an organic solvent. (8) The liquid crystal alignment treatment agent according to the above (7), wherein the organic solvent contains 5 to 8 % by mass of a solvent having a low surface tension in the total organic solvent. (9) A liquid crystal alignment film obtained by the liquid crystal alignment treatment agent according to any one of the above (1) to (8). (10) A liquid crystal display device comprising the liquid crystal alignment film described in the above (9). [Effects of the Invention] By using the liquid crystal alignment treatment agent of the present invention, a liquid crystal alignment film having excellent stability of a tilt angle even in a high-temperature environment for a long period of time can be obtained, and a liquid crystal display element having the liquid crystal alignment film can be trusted. Excellent sex. Further, the liquid crystal alignment treatment agent of the present invention is particularly suitable for use in honing treatment because it is difficult to hinder the elongation of the polymer by honing, and the alignment property of the liquid crystal is not lowered for weak honing conditions. use. [Best Mode for Carrying Out the Invention] < (A) Component: Polyproline and Polyimine] The liquid crystal alignment treatment agent of the present invention contains a group of polyglycine and polyimine The specific structure of the at least one polymer selected, the polyamic acid and the polyimine is not particularly limited, and is, for example, a polyamic acid or a polyphthalamide contained in a conventional liquid crystal alignment treatment agent. Amines are also available. Polylysine can be obtained by a reaction of a derivative of a tetracarboxylic acid or a tetracarboxylic acid with a diamine. The method for producing the polyamine and the polyimine of the component (A) used in the present invention is not particularly limited, and generally, one or more selected from the group consisting of tetracarboxylic acid and a derivative thereof are used. The tetracarboxylic acid component is reacted with a diamine component formed from one or more kinds of diamine compounds to obtain a polyfluorene-10-200841093 aminic acid, which is subjected to amination of the polyamic acid to form a poly Method of quinone imine In this case, the obtained polyglycolic acid ' can be a homopolymer or a copolymer by appropriately selecting a tetracarboxylic acid component and a diamine component of the raw material. Here, the tetracarboxylic acid and its derivative are a tetracarboxylic acid, a tetracarboxylic acid dihalogen, and a tetracarboxylic dianhydride, and among them, a tetracarboxylic dianhydride is preferred because it has high reactivity with a diamine compound. Specific examples thereof include pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, naphthalenetetracarboxylic acid, 2,3,6,7_ Terpene tetracarboxylic acid, 1,2,5,6-nonanetetracarboxylic acid, 3,3,4,4,biphenyltetracarboxylic acid, 2,3,3,,4,-biphenyltetracarboxylic acid, double (3,4-dicarboxyphenyl)ether, 3,3,4,4,-benzophenone tetradecanoic acid, bis(3,4-dicarboxyphenyl) maple, bis(3,4-di Carboxyphenyl) Azolla, 2,2_bis(3,4-dicarboxyphenyl)propane, anthracene, :,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyl Phenyl)propane, bis(3,4-dicarboxyphenyl)dimethyl decane 'bis(3,4-dicarboxyphenyl)diphenyl decane, 2,3,4,5-pyrrolidinetetracarboxylic acid , 2,6-bis(3,4-dicarboxyphenyl)pyridine, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane, 3,3,4,4 , _ diphenyl sulfonium tetracarboxylic acid, 3,4,9,1 fluorene tetracarboxylic acid, diphenyl-; i, 2,3,4-cyclobutane tetracarboxylic acid, oxodisium tetra Carboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentene tetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 1, 2,3,4-Tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2-dimethyl-1,2, 3,4-cyclobutanetetracarboxylic acid, 1,3-dimethylcyclobutanetetracarboxylic acid, 12,3,4-cycloheptanetetracarboxylic acid 2,3,4,5-tetraazaindole Citrate, 3,4-diphenyl-1-cyclohexyl number 200841093 acid, 2,3,5-tricarboxycyclopentyl acetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydrogen 1-naphthylsuccinic acid, bicyclo[3,3,0]octane-2,4,6,8-tetraresidic acid, bicyclo[4,3,0]nonane-2,4,7,9-tetra Carboxylic acid, bicyclo[4,4,nonane]nonane-2,4,7,9-tetracarboxylic acid, bicyclo[4,4,0]nonane-2,4,8,10-tetracarboxylic acid, three Ring [6.3.0.0 < 2,6 > ]-[-alkane-3,5,9,11-tetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, bicyclo[2,2 , 2] oct-7-ene-2,3,4,5·tetracarboxylic acid, tetracyclo[6,2,1,1,0,2,7]dodecane-4,5,9,1 0 A tetracarboxylic acid such as tetracarboxylic acid. Further, examples thereof include dihalides of tetracarboxylic acid and tetracarboxylic dianhydride. In particular, as a liquid crystal alignment film, from the viewpoint of transparency of the coating film, alicyclic tetracarboxylic acid and such dianhydrides and such dicarboxylic acid diacid halides are preferred, particularly 1 , 2,3,4_cyclobutane tetracarboxylic acid, 2,3,5-tricarboxycyclopentyl acetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid Bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic acid, and dihalides of such tetracarboxylic acids and dianhydrides of tetracarboxylic acids are preferred. The tetracarboxylic acid and the derivative thereof, which are exemplified above, may be used alone or in combination of two or more kinds depending on the characteristics of liquid crystal alignment, voltage retention, and charge accumulation in the liquid crystal alignment film. The diamine used in the synthesis reaction of polylysine is not particularly limited. Specific examples thereof include anthracene-phenylenediamine, 2,3,5,6-tetramethyl-anthracene-phenylenediamine, 2,5-dimethyl-anthracene-phenylenediamine, and m-benzene. Diamine, 2,4·dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4- Diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminobenzyl alcohol, 4,4 '- -12- 200841093 Diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'- _* amine Base, 3,3' - _*-based 4,4'- _aminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'- Difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diamine Biphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,35-diaminodiphenylmethane , 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl Ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl , 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldiphenylamine, 3,3'-sulfonyldiphenylamine, double (4-Aminophenyl)decane, bis(3-aminophenyl)decane, dimethyl-bis(4-aminophenyl)decane, dimethyl-bis(3-aminophenyl)decane , 4,4'-thiodiphenylamine, 3,3'-thiodiphenylamine, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'- Diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl Amine, N-methyl(3,3'-diaminodiphenyl)amine, N-methyl(3,4'-diaminodiphenyl)amine, N-methyl (2,2' _Diaminodiphenyl)amine, N-methyl(2,3'-diaminodiphenyl)amine, 4,4'-diaminobenzophenone, 3,3'-diamino Benzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2'-diaminobenzophenone, 2,3'-diaminodiphenyl Methyl ketone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2, 6-diamino group , 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis(4-aminophenyl)ethane, 1,2-bis(3-aminophenyl)ethane 1,3_bis(4-aminophenyl)propane, 1,3-bis(3-aminophenyl)propane, -13- 200841093 1,4-bis(4-aminophenyl)butane , 1,4-bis(3-aminophenyl)butane, bis(3,5-diethyl-4-aminophenyl)methane, 1,4-bis(4-aminophenoxy) Benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1, 4-bis(4-aminobenzyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'-[1,4-phenylene bis(methyl)methyl Aniline, 4,4'-[1,3-phenylenebis(methyl)diphenylamine, 3,4'-[1,4-phenylenebis(methyl)diphenylamine, 3, 4'-[1,3-phenylenebis(methyl)diphenylamine, 3,3'-[1,4-phenylenebis(methyl)diphenylamine, 3,3'-[ 1,3-phenylene bis(methyl)diphenylamine, 1,4-phenylene bis[(4-aminophenyl)methanone], 1,4-phenylene bis[(3- Aminophenyl)methanone], 1,3-phenylene bis[(4-aminophenyl) Ketone 1 ], 1,3-phenylene bis[(3-aminophenyl)methanone], 1,4-phenylene bis(4-aminobenzoate), 1,4·benzene Bis(3-aminobenzoate), 1,3-phenylene bis(4-aminobenzoate), 1,3-phenylene bis(3-aminobenzoate) , bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)terephthalate, bis(4-aminophenyl)isophthalate, double (3-Aminophenyl)isophthalate, N,N'-(1,4-phenylene)bis(4-aminophenylguanamine), N,N'·( 1,3- Phenyl)bis(4.aminoamidoamine), N,N'-(1,4-phenylene)bis(3-aminophenylguanamine), hydrazine, Ν'- (1,3· Phenyl) bis(3-aminophenylguanamine), hydrazine, Ν'-bis(4-aminophenyl)terephthalamide, hydrazine, Ν'-bis(3-aminophenyl) Parathylene phthalamide, hydrazine, Ν'-bis(4-aminophenyl)m-xylylene amide, hydrazine, Ν'-bis(3-aminophenyl)m-xylyleneamine, 9 , 10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy)diphenylanthracene, 2,2'-bis[4-(4-aminobenzene) Phenyl] -14 - 200841093 propane, 2,2'-bis[4_(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis(4-aminophenyl)hexa Qibin, 2,2'-bis(3-aminophenyl)hexachloropropane, 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2'- Bis(4-aminophenyl)propane, 2,2'-bis(3-aminophenyl)propane, 2,2'-bis(3-amino-4-methylphenyl)propane, 3.5- Diaminobenzoic acid, 2,5-diaminobenzoic acid, 1,3-bis(4-aminophenoxy)propane, 1,3-bis(3-aminophenoxy)propane, 1, 4-bis(4-aminophenoxy)butane, 1,4-bis(3-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1 , 5-bis(3-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7-bis(3-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane 1,8-bis(3-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)decane, 1,9-bis(3-aminophenoxy)anthracene Alkane, 1,1 0-bis(4-aminophenoxy)decane, 1,1 fluorene-(3-aminophenoxy)decane, 1,11-(4-aminophenoxy)undecane, amine Aromatic diamines such as phenoxy)undecane, 1,12-(4-aminophenoxy)dodecane, 1,12-(3-aminophenoxy)dodecane; 4-aminocyclohexyl)methane, alicyclic diamine such as bis(4-amino-3-methylcyclohexyl)methane; iota, 3-diaminopropane, 1,4-diaminobutane 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane An aliphatic diamine such as 1,10-diaminodecane, 1,11-diaminoundecyl ester or 1,12-diaminododecyl ester. Further, examples of the diamine side chain include an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a hetero ring, and a large cyclic substituent formed therefrom. The diamine represented by the following formulas [A1] to [A20] is exemplified as the -15-200841093. [{匕6]

H2N

[A1]

(In the formulae [A1] to [A5], 1^ represents an alkyl group having 1 or more and 22 or less carbon atoms or a fluorine-containing alkyl group). -16- 200841093 [化7]

[A6] CA7]

(In the formula [A6] to [A9], R2 represents COO, OCO, CONH, CH2, 0, C0, or NH; and R3 represents a hydrogen atom, an alkyl group having a carbon number of 1I^ or a fluorine-containing alkyl group). NHCO, on 22

17- 200841093 (In the formula [A10] to [All], R4 represents 〇, 〇CH2, CH20, COOCH2, or CH2OCO; R5 represents an alkyl group having 1 to 22 or less carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a Fluoroalkoxy). [fW]

(In the formula [A12] to [A14], R5 represents COO, OCO, CONH, NHCO, COOCH2, CH2OCO, CH20, OCH2, or CH2; and R7 represents an alkyl group having 1 or more and 22 or less carbon atoms, an alkoxy group, or a fluorine-containing group. Alkyl or fluoroalkoxy). -18- 200841093

UtlQl Η2Ν^8Ό^9 Ci nh2 Η2ΝΧ>»ΟΌ^ NHCO NH ; 醯 base, (in the formula [A15]~[A16], R8 represents COO' OCO, CONH, COOCH2, CH2OCO, CH20, OCH2, CH2, Ο Or r9 represents a fluoro group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a methyl ethyl fluorenyl group, an ethyl ethoxy group, a hydroxyl group, or a carboxyl group). -19- 200841093 W 匕 11]

Base oxane and the like. [A2 1] Further, a diamine represented by the following formula [A21]: [12] /ch3\ch3 H2N-(CH2)3-deca----(CH2)3_NH2\CH3/mCH3 (Formula [A2] In 1], m represents an integer of 1 to 10). The diamine can be used in one type or in a mixture of two or more types depending on the liquid crystal alignment property, the liquid-retentive property of the liquid crystal alignment film, and the charge retention property. Among the synthetic raw materials of polylysine shown above, the use of a raw material having a hydroxyl group or a carboxyl group can improve the reaction efficiency of polyperuric acid or polyimine with a crosslinkable compound to be described later. Specific examples of such a raw material include 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2, 4 -diaminobenzyl alcohol, 3,3'. dihydroxy-4,4,-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,5_ Diaminobenzoic acid, 2,5-diaminobenzoic acid, diamine represented by the formula [A22] to [A25], etc. [Chem. 13]

[A2 2] [A2 3]

ΓΑ 2 4]

-21 - 200841093

(In the formula [A22] to [A25], R1() represents COO, OCO, CONH, NHCO, CH2, Ο, CO, or NH).

[A2 7] (In the formula [A26] and [A27], Rn represents COO, OCO, CONH, NHCO, COOCH2, CH2OCO, CH20, OCH2, CH2, Ο, or NH; R12 represents a hydroxyl group or a carboxyl group). The organic solvent to be used in the synthesis of the polyamic acid is not particularly limited as long as it is a polylysine which is produced by dissolution. Specific examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethyl Azulene, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethylarylene, 7-butyrolactone, isopropanol, methoxymethylpentanol, dipentene, ethylamino ketone, A Ketrinone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve Acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetic acid Ester, propylene glycol monoterpene ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether-22- 200841093, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol single B Acid ester monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3·methyl-methoxy Butyl acetate, tripropyl Alcohol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, dibutyl ether, diisobutyl Ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, η-pentane, η-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, lactic acid Methyl ester, ethyl lactate, methyl acetate, ethyl acetate, η-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxyacetonate, 3-ethoxy Methyl ethyl pyruvate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, 3-methoxypropane Butyl acrylate, diglyme, 4-hydroxy-4-methyl-2-pentanone; these may be used singly or in combination. Further, even in the range in which the produced polyamine acid is not precipitated in the range in which the polyamic acid is not dissolved, it can be used in the above solvent. Further, since the water in the organic solvent hinders the polymerization reaction and becomes a cause of further hydrolysis of the produced polyamic acid, the organic solvent is used as far as possible for dehydration. A method for reacting a tetracarboxylic acid and a derivative thereof in an organic solvent in the synthesis of polyamic acid, and a solution in which a diamine is dispersed or dissolved in an organic solvent, and a tetracarboxylic acid is directly added thereto a derivative, or a method of adding it after dispersing or dissolving in an organic solvent; instead, adding a diamine to a solution in which tetradecanoic acid and a derivative thereof are dispersed or dissolved in an organic solvent; alternately adding a tetracarboxylic acid and The method of the derivative and the diamine, and the like. These -23· 200841093 may be any method, and when the tetracarboxylic acid and its derivative or diamine are a plurality of compounds, the reaction may be carried out in a premixed state, and the reaction may be carried out individually. Further, a high molecular weight product obtained by subjecting a plurality of low molecular weight substances formed by the reaction to a mixed reaction may be used. The temperature at which the polyamic acid is synthesized may be selected from any temperature of from -2 °C to 15 °C, preferably from -5 °C to 1 °C, and the reaction may be carried out at any concentration. However, if the concentration is too low, it is difficult to obtain a polymer having a high molecular weight. If the concentration is too high, the viscosity of the reaction liquid becomes too high and the stirring is difficult, so it is preferably 1 to 50% by mass, more preferably 5 to 5. 30% by mass. The initial stage of the reaction is carried out at a high concentration, and then an organic solvent may be added. In the synthesis of polyamic acid, the molar ratio of the diamine component to the molar ratio of the tetracarboxylic acid and the derivative thereof is preferably 0.8 to 1.2, more preferably 0.9 to 1.1. As with the usual polycondensation reaction, the closer the molar ratio is to 1 〇, the larger the molecular weight of the produced polyamine. A method for polyimidization of polylysine by means of a heated hydrazine imidization, a catalyst oxime imidization using a catalyst as a general method, and a catalytication of ruthenium imidization at a relatively low temperature The method is preferred because it does not easily cause a decrease in the molecular weight of the obtained polyimine. The imidization of the catalyst oxime can be carried out by mixing the polyamic acid in an organic solvent in the presence of a basic catalyst and an acid anhydride. The reaction temperature at this time is -20 to 250 ° C, preferably 〇 18 〇 ° C. When the reaction temperature is high, the imidization is carried out faster, but if it is too high, the molecular weight of the polyimine is lowered, and the amount of the basic catalyst is 醯·5 to 30 mol times of the proline group. Preferably, it is 2 to 20 moles, and the amount of the acid anhydride is 1 to 5 moles of the valeric acid group, preferably -24 to 200841093 3 to 3 0 moles. When the amount of the basic catalyst or acid anhydride is small, the reaction is not sufficiently carried out, and if too much, it is difficult to be completely removed after completion of the reaction. The basic catalyst may, for example, be pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine, and the pyridine is preferred because it has a moderate basicity for allowing the reaction to proceed. Further, examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic acid. Among them, acetic anhydride is used, and purification after completion of the reaction is preferred. The organic solvent is not particularly limited as long as it is a polyamic acid, and specific examples thereof include hydrazine, Ν'-dimethylformamide, hydrazine, Ν'_dimethylglyoxime, Ν-methyl-2-pyrrolidone, Ν-methyl caprolactam, dimethyl hydrazine, tetramethyl urea, dimethyl hydrazine, hexamethyl sulfoxide, decyl-butyrolactone, and the like. The imidization ratio of the imidization of the oxime by the catalyst is controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time. The produced polyimine is obtained by recovering a precipitate formed by putting the above reaction solution into a weak solvent. In this case, the weak solvent to be used is not particularly limited, and examples thereof include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene. , water, etc. The polyimine precipitated after being injected into a weak solvent, after being filtered, can be made into a powder under normal pressure or reduced pressure at room temperature or by heating, and the polyimine powder is redissolved in an organic solvent. The step of precipitating is repeated 2 to 10 times to purify the polyimine. This purification step is preferred when the primary precipitation recovery operation does not remove impurities. The molecular weight of the specific polyimine used in the present invention is not particularly limited, but from the viewpoints of ease of handling and stability of properties at the time of film formation, -25-200841093, the weight average molecular weight is 2,000 to 200,000. Better, better for 4,00 0~5 0,000. The molecular weight is calculated by GPC (gel permeation chromatography). < (B) Component: Specific Crosslinkable Compound> The liquid crystal alignment treatment agent of the present invention contains at least two oxetines represented by the following formula [1] in addition to the above polymer component. The crosslinkable compound (B) having at least two oxetanyl groups represented by the following formula [1] in the molecule of the crosslinkable compound (B) of the alkyl group (hereinafter referred to as a specific crosslinkable compound) Μ 匕 15 ]

[1] Oxetane, which is known to react with a carboxyl group or a hydroxyl group in the presence of a heat or an acid catalyst, and therefore, a specific crosslinkable compound and a carboxyl group contained in polyglycine or polyimine or The hydroxyl group reacts to form a film that crosslinks between the polymers. Further, the oxetane group, in addition to the reaction with a carboxyl group or a hydroxyl group, also causes a self-polymerization reaction, particularly an oxetane group, since the nucleophilicity is higher than that of the epoxy group, the final conversion ratio can be high. And a polymer with a high degree of polymerization. In other words, the liquid crystal alignment film obtained by using the liquid crystal alignment agent of the present invention is a film having high heat resistance by crosslinking between polymers and polymerization of a oxetane group. -26- 200841093 In addition, because the oxetane group is a 4-membered ring structure, when reacting with a carboxyl group or a hydroxyl group and self-polymerizing, the bonding site contains a methyl group in comparison with the epoxy resin of the 3-member structure. . Therefore, the film obtained by the liquid crystal alignment treatment agent of the present invention is less likely to be stretched or toughened than the film using the epoxy-based crosslinkable compound, so that the elongation of the polymer by honing is less susceptible. Obstruction. Therefore, the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention has improved tilt stability with respect to heat compared with a liquid crystal alignment film containing no crosslinkable compound or a liquid crystal alignment film containing an epoxy crosslinkable compound. Moreover, the alignment of the liquid crystal for weak honing conditions is not lowered. In the liquid crystal alignment agent of the present invention, the oxetane group which the specific crosslinkable compound has is not particularly limited as long as it is two or more, and is preferably 2 to 50, more preferably 2 to 20 pieces. Further, the specific structure of the specific crosslinkable compound is not particularly limited, and examples thereof include a compound represented by the following formula [2].

In the formula [2], X! represents N, NH, C0, 0, S, S02, Si, sesquiterpene oxide, polyoxane, or an organic group having 1 to 20 carbon atoms. The organic group having a hetero atom (N, 0, S, Si) and having a carbon number of 1 to 20 may be an organic group having a cyclic structure. Specific -27·200841093, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclodecane ring, a cyclodecane ring, a ring Monoalkane, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclopentadecane Ring, cycloecosane ring, tricyclohexadecane ring, tricyclotetracosane ring, bicycloheptane ring, decahydronaphthalene ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydrogen Naphthalene ring, anthracene ring, anthracene ring, anthracene ring, anthracene ring, phenanthrene ring, 1,8-benzoin, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quin Physic ring, pyrazoline ring, isoquinoline ring, oxazole ring, anthracene ring, thiadiazole ring, pyridazine ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzoxazole Ring, benzimidazole ring, m-diazepine ring, limonin ring, phenanthroline ring, anthracene ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring, acridine ring, Oxazole ring, piperazine ring, piperidine ring, dioxane , Morpholine ring, azepine ring, diazepine ring, a naphthalene ring spindles, phenazine ring, a phthalazine ring. X2 and X3 each independently represent a single bond, NH, CO, hydrazine, s, S02, or an organic group having 1 to 20 carbon atoms, and the organic group may also contain a hetero atom (N, 0, S, Si). Hey! And Y2 each independently represent an organic group having 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, and the organic group may further contain a hetero atom (N, 0, S, Si). m and η each independently represent an integer of 0 to 20, preferably an integer of 〇 15 , and m + n is an integer of 2 to 20, preferably an integer of 2 to 15. Among the specific crosslinkable compounds represented by the formula [2], preferred is that X1 represents N, NH, CO, hydrazine, sesquioxane, polyoxyalkylene or an organic group having 1 to 10 carbon atoms. The organic group may also contain a hetero atom (N, 〇), -28- 200841093. Further, the organic group having a carbon number of 1 to 10 of X! also includes a cyclohexanyl ring, a benzene ring, a naphthalene ring, and an anthracene ring. a ring of a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a carbazole ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzoxanthene ring, or a quinoxaline ring. Further, X2 and X3 are each independently NH, CO, COO, OCO, 0, CONH, or NHCO; Υι and Y2 each independently represent a yard having a carbon number of 1 to 10; m and η are each independently represented An integer of 〇~20, and m + n is an integer of 2 to 20. When 'X! is a sesquioxane in the formula [2], examples thereof include a structure selected from the general formulas [S1] to [S4]. -29- 200841093

<.>< ^ [S2] .Si, [S3]

iO- [S4] ̄··Si-O—Si^° In the formula [2], when X2 is a polyoxyalkylene, an example of the polyoxyalkylene can be listed as -30-200841093 by the general formula [PI] And at least one structure selected from the group consisting of [P2], [P3], and [P4]. [Chem. 18]

Si Ο - [Ρ 1]

CP2]

[1], 112, 1^, 1^4, and 5 in the formulas [P1] to [P4] are each independently an alkyl group, an alkoxy group having a hydrogen atom, a hydroxyl group, and a carbon number of 1 to 1 fluorene. A selected group of an aliphatic cyclic group or an aromatic ring group. Preferred specific examples of the formula [2] include the structures of the following formulas [3] to [8] [Chem. 19]

[3] In the formula [3], X2 and X3 each independently represent a single bond, NH, CO, hydrazine, S, S02, or an organic group having 1 to 20 carbon atoms, and the organic group may further contain a hetero atom (N). 'O, S, Si); Yi and Y2 each independently represent a carbon number of -31 - 200841093 1 to 20, preferably an organic group having a carbon number of 1 to 15, which may also contain a hetero atom (N, Ο) , S, Si); Ζι means single bond, NH, N (CH3), NHCO, CONH, NHCONH, CO, COO, Ο, S, S02, CF2, C (CF3) 2, Si (CH3) 2, OSi ( CH3) 2, Si(CH3)2〇, OSi(CH3)20, or an alkyl group having 1 to 10 carbon atoms; m and n each independently represent an integer of 0 to 5, preferably an integer of 0 to 3, and m + n represents an integer of 2 to 10, preferably an integer of 2 to 6. Among the specific crosslinkable compounds represented by the formula [3], preferred ones X2 and X3 each independently represent NH, CO, COO, OCO, hydrazine, CONH, or NHCO; Ζ! represents a single bond, CH2, C (CH3) 2, NH, N (CH3), NHCO, CONH, CO, COO, O, S02, C (CF3) i, Si (CH3) 2, OSi (CH3) 2, Si (CH3) 20, OSi (CH3) 20, or an alkyl group having 1 to 5 carbon atoms; Y1 and Y2 are each independently an alkyl group having 1 to 10 carbon atoms; and m and η each independently represent an integer of 0 to 5, preferably an integer of 0 to 3, Further, m + n represents an integer of 2 to 10, preferably an integer of 2 to 6. [Chem. 20]

In the formula [4], X! represents NH, N(CH3), NHCO, CONH, NHCONH, CO, COO, OCO, Ο, S, S02, CF2, C(CF3)2, Si(ch3) 2, OSi ( CH3) 2, Si(ch3) 2〇, or OSi(CH3)2〇; Yi and Y2 each independently represent an alkyl group having 1 to 10 carbon atoms, preferably a group having 1 to 5 carbon atoms. -32- 200841093 Among the specific crosslinkable compounds represented by the formula [4], preferred ones are NH, N(CH3), NHCO, CONH, CO, COO, 〇c〇, 〇, S02, C ( CF3) 2, Si (CH3) 2, 〇Si (CH3) 2, Si(CH3)2〇, or 〇8丨(0:113)2〇; 丫1 and Y2 each independently represent the carbon number i~i〇 Alkyl.

In the formula [5], 1 is N, an aliphatic ring having 1 to 2 carbon atoms, an aromatic ring having 1 to 2 carbon atoms, or an alkylene group having 1 to 20 carbon atoms, preferably N and carbon number. 1 to 15 of an aliphatic ring, an aromatic ring having 1 to 15 carbon atoms or an alkylene group having 1 to 15 carbon atoms, more preferably an aliphatic ring having N, a carbon number of 1 to 10, and a carbon number of 1 to 1. An aromatic ring of hydrazine or an alkylene group having a carbon number of 1 to 10. Υι and Y2 in the formula [5] are each independently an alkyl group having 1 to 10 carbon atoms, and each of them is preferably an alkyl group having 1 to 5 carbon atoms. In the formula [5], m and η represent an integer of 〇-20, and m + n represents an integer of 2 to 20; preferably, m and η represent an integer of 0 to 15, and m + n represents an integer of 2 to 15. More preferably, m and η represent an integer of 〇10, and m + n represents an integer of 2 to 10. Therefore, a preferred combination of Xi, Yi, Y2, m, η is as follows. In the formula [5], Χ is Ν, an aliphatic ring having 1 to 20 carbon atoms, an aromatic ring having 1 to 20 carbon atoms or an alkylene group having 1 to 20 carbon atoms; and 丫1 and Y2 are each -33-

200841093 An alkyl group having 1 to 10 carbon atoms; m and η are integers of 0 to 20, and m + n is an integer. Preferably, Xi is N, an aliphatic ring having 1 to 15 carbon atoms, an aromatic ring having a carbon number or an alkylene group having 1 to 15 carbon atoms; each of Y and Y2 is an alkyl group having 1 to 5; m, η It is an integer from 0 to 15, and m + n is a number from 2 to 15. More preferably, the oxime 1 is N, an aliphatic ring having 1 to 10 carbon atoms, an aromatic ring having a carbon number or an alkylene group having 1 to 10 carbon atoms; each of Yi and Y2 is an alkyl group having 1 to 5; m, η It is an integer of 0 to 10, and m + n is a number of 2 to 10. Specific examples of the aliphatic ring having 1 to 20 carbon atoms and the aromatic ring having 1 to 20 carbon atoms in the above Xi are as follows. The aliphatic ring may, for example, be a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a ring, a ring, a ring, a ring, a ring, a ring, a ring, a ring, and a ring. Courtyard ring, ring 13 courtyard ring, ring 14 courtyard discharge pentadecane ring, cyclohexadecane ring, cycloheptadecane ring, ring 18 ring ring, pentane ring Decane ring, three ring twenty two entertainment double ring Gengyuan ring, norbornene ring, diamond ring. Examples of the aromatic ring include a decahydronaphthalene ring, a benzene ring, a naphthalene ring, a tetra, an anthracene ring, an anthracene ring, an anthracene ring, an anthracene ring, a phenanthrene ring, a 1,8-benzoin naphthalene, an imidazole ring, an oxazole ring, Thiazole ring, pyrazole ring, pyridine ring, spurring ring, 卩 哩 哩 ring, 睦 睦 ring, 哩 ring, 嘿 U ring ring, azine ring, triazine ring, pyrazol ring, three Oxazole ring, 嗓 ring oxime ring, benzimidazole ring, m-diazepine ring 'limon ring, phenanthrene 2~20 1~1 5 carbon number of whole 1~10 carbon number of whole aromatic ring, ring, , cyclopentacyclic, naphthalene ring, oxadiazole benzoxanyl-34-200841093, anthracene ring, quinoxaline ring, benzothiazepine ring, phenothiazine ring, 11 oxadiazine ring, hydrazine A pyridine ring, an oxazole ring, a piperazine ring, a piperidine ring, a dioxane ring, a morphine ring, a hydrazine ring, a dioxin ring, a naphthalene ring, a phenazine ring, a tribute ring, and the like. Among these, preferred are a cyclopropane ring, a cyclohexane ring, a norbornane ring, an adamantane ring, a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, an anthracene ring, an anthracene ring, an anthracene ring, an imidazole ring, Oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, indazole ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring , piperazine ring, piperidine ring. More preferably, it is a cyclohexane ring, a norbornene ring, an adamantane ring, a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, a pyrrole ring, an imidazole ring, a pyridine ring, a pyrimidine ring, an indazole ring, a pyridazine ring, or a trioxane. Ring, triazole ring, pyrazine ring, benzimidazole ring, piperazine ring, piperidine ring. [化23⁄4

In the formula [6], Υι and Υ2 each independently represent an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, and η represents an integer of 1 to 10, preferably an integer of 1 to 5. . [Chem. 23]

In the formula [7], Υ! and Υ2 each independently represent a carbon number of 1 to 1 Å, preferably a carbon number of 1 to 5, and η represents an integer of 1 to 10, preferably -35 to 200841093. An integer from 1 to 5. [Chem. 24]

[8] In the formula [8], Y2 each independently represents an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, and η represents an integer of 1 to 10, preferably 1 to 5 Integer. More specific specific crosslinkable compounds include the compounds of the formulae [9] to [19]. -36- 200841093 msi

[11]

[13]

-37- 200841093 [Chem. 26]

-38- 200841093

The above-mentioned compound is an example of a specific cross-linking compound, and the compound to be used in the liquid crystal alignment agent of the present invention may be one type or a combination of two or more types. (Liquid Crystal Alignment Treatment Agent) The content of the (B) component (sex compound) in the liquid crystal alignment treatment agent of the present invention is 100% by mass based on the poly (amic acid) and/or the (A) component (polymer component). The portion is preferably a ruthenium component, and the film is formed to exhibit a crosslinking reaction, and the alignment property of the liquid crystal is not lowered. More preferably, the film is preferably 1 to 50 parts by mass. The liquid crystal alignment treatment agent of the present invention is not particularly limited. 39- Non-limiting specific cross-linking acid imine. 1~150 hardenability, part, special, but usually 200841093 in the production of liquid crystal alignment film, because A uniform film of 0·01 〜1·〇# m must be formed on the substrate, so that the coating liquid containing the organic solvent in which the components are dissolved in addition to the components (A) and (B) is Preferably. When the liquid crystal alignment agent of the present invention contains the above organic solvent, the content of the organic solvent is preferably from 90 to 99% by mass in the liquid crystal alignment treatment agent from the viewpoint of forming a uniform film by coating, and is preferably 92 to 97% by mass. % is better. On the other hand, the content of the (Α) component is preferably from 0.4 to 9.9% by mass 'particularly preferably from 0.5 to 9.9% by mass, and the content of the (Β) component is preferably from 〜1 to 9.6% by mass, particularly preferably 〇 . 1~9 · 5 mass%. The content of these can be appropriately changed depending on the film thickness of the target liquid crystal alignment film. Specific examples of the organic solvent contained in the liquid crystal alignment agent of the present invention include organic solvents used in the synthesis reaction of the above polyamic acid. Particularly preferred are hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine-dimethylacetamide, hydrazine-methyl-2-pyrrolidone, dimethyl hydrazine, butyrolactone, etc. One type of the organic solvent may be used, or two or more types may be used. Further, in the organic solvent, in order to improve the uniformity of the coating film, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, diethylene glycol diethyl ether, and the like are preferably contained. Ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethyl carbitol acetate, ethylene glycol, ethylene glycol monohexyl ether, methoxy-2-propanol, ethoxylated-2 -propanol, 1 -butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetic acid Ester, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, 4-hydroxy-4.methyl-2·pentanone, 2-(2-ethoxyl) Propyl alcohol) propanol, methyl lactate, lactate-40, 200841093 ethyl ester, η-propyl lactate, η-butyl lactate, isoamyl lactate and other solvents with low surface tension; these solvents are usually used One type or a mixture of two or more types is used. These solvents are generally preferably 80% by mass in an organic solvent, more preferably 60% by mass or less, because the polyacrylic acid or polyimine is generally low in solubility. Further, if it is desired to improve the uniformity of the coating film, it is preferably 5% by mass or more, more preferably 20% by mass or more in the organic solvent. The liquid crystal alignment agent of the present invention may contain an additive component in addition to the (A) component, the (Β) component, and the above organic solvent, within a range not impairing the effects of the present invention. The additive component may, for example, be a compound for improving the adhesion between the liquid crystal alignment film and the substrate, or a surfactant for improving the flatness of the coating film. Specific examples of the compound which improves the adhesion between the coating film and the substrate can be expressed as follows. For example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, N- ( 2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-propylpropyl Dimethoxylate, 3-propylpropyldiethoxylate, N.ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyl Triethoxy decane, N-triethoxydecylpropyltriethylenetriamine, N-trimethoxydecylpropyltriethylenetriamine, 10-trimethoxydecyl-1,4, 7-triazanonane, ίο-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6-diazaindolyl acetate, 9-Triethoxy sulfhydryl-3,6-diazaindolyl acetate, N-nodal-3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyl Triethoxy decane, N-benzene-41 - 200841093 -3-aminopropyltrimethoxy decane, N-phenyl-3-aminopropyltriethoxy decane, N-bis (oxyethylene) )-3-aminopropyl three A functional decane-containing compound such as methoxydecane or N-bis(oxyethylene)-3-aminopropyltriethoxydecane. When the compound of the temple is added, the effect of the dense lifting can be obtained, and from the viewpoint of not lowering the alignment property of the liquid crystal, it is preferably 1 to 30 parts by mass based on 1 part by mass of the component (A). More preferably, it is 1 to 20 parts by mass, and particularly preferably 1 to 10 parts by mass. The surfactant used for improving the flatness of the coating film may, for example, be a fluorine-based surfactant, a polyfluorene-based surfactant, or a nonionic surfactant. More specifically, for example, F-TOP EF301, EF3 03, EF352 (above, TOHKEM PRODUCT), MEGAFAC F171, F173, R-30 (above, manufactured by Otsuka Ink Co., Ltd.), FULORD FC430, F431 (for example) Above, Sumitomo 3M Company, AsahiGuard AG710, Surf Ion S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, Asahi Glass Co., Ltd.). The proportion of the surfactant to be used is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the polymer component. <Liquid Crystal Alignment Film-Liquid Crystal Display Element> The liquid crystal alignment treatment agent of the present invention can be applied onto a substrate, and after firing, it can be subjected to alignment treatment by honing treatment or light irradiation, or can be performed in a vertical alignment application or the like. The alignment treatment is used as a liquid crystal alignment film. In this case, the substrate to be used may be a substrate having high transparency, and -42 to 200841093 is not particularly limited, and a plastic substrate such as a glass substrate, an acrylic substrate or a polycarbonate substrate can be used. Further, it is preferable to use a substrate on which an ITO electrode or the like for liquid crystal driving is formed, from the viewpoint of simplification of the process, and a reflective liquid crystal display element can be opaque using a germanium wafer or the like only on one side of the substrate. For the electrode at this time, a material that reflects light such as aluminum can also be used. The coating method of the liquid crystal alignment agent is not particularly limited, but industrially, it is generally a method of screen printing, offset printing, flexographic printing, ink jetting or the like. Other coating methods are immersion, roll coater, slit coater, spin coater, etc., and can be used according to the purpose. The firing after application of the liquid crystal alignment agent can be carried out at any temperature of 100 to 3 50 ° C, but is preferably 120 to 300 ° C, more preferably 150 to 250 ° C. This baking can be performed in a hot plate, a hot air circulation furnace, an infrared furnace, or the like. The thickness of the coating film after firing is too thick to be detrimental to the power consumption of the liquid crystal display element. If it is too thin, the reliability of the liquid crystal display element may be lowered, so it is preferably 5 to 300 nm. Good for 10~100nm. When the liquid crystal is horizontally aligned or tilted, it is treated by honing or polarized ultraviolet light irradiation. In the liquid crystal display device of the present invention, a substrate having a liquid crystal alignment film is obtained from the liquid crystal alignment treatment agent of the present invention, and a liquid crystal cell is produced by a conventional method to obtain a liquid crystal display element. In the case of an example of the production of a liquid crystal cell, a pair of substrates on which a liquid crystal alignment film has been formed is prepared, and a separator is interposed on the liquid crystal alignment film of one of the substrates, and the other substrate is bonded to the inside of the liquid crystal alignment film. -43- 200841093 A method of sealing after liquid crystal injection under reduced pressure; or a method of sealing a substrate after laminating liquid crystal on a liquid crystal alignment film surface on which a separator is dispersed, and then sealing. The thickness of the separator at this time is preferably from 1 to 30 m, more preferably from 2 to 10 #m. In this way, the liquid crystal display element produced by using the liquid crystal alignment agent of the present invention can be made into a liquid crystal display having excellent tilt stability, suitable for a germanium element, an STN element, a TFT liquid crystal element, and more suitable for vertical. An alignment type liquid crystal display element or the like. [Embodiment] Hereinafter, the present invention will be described in more detail by way of Examples, but it is not limited to these Examples. The abbreviations of the compounds used in this example are as follows. (tetracarboxylic dianhydride)

CBDA: 1,2,3,4-cyclobutanine tetraresin dianhydride BODA: bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride [Chem. 28]

(Diamine) p-PDA : p-phenylenediamine-44- 200841093 DBA : 3,5-diaminobenzoic acid DADPA: 4,4,-diaminodiphenylamine AP18 ·· 4_ (18-base Oxy)-1,3-phenylenediamine PCH : 1,3-diamino-4-[4-(4-heptylcyclohexyl)phenoxy]benzene [29]

H2N

DADPA API 8

(oxetane) oxetane (A) : OXT_221 (manufactured by Toagosei Co., Ltd.) Oxetane (B): OX-SQ-H (manufactured by Toagosei Co., Ltd.) Oxetane (C) ) : ΟΧ-SC (manufactured by Toagosei Co., Ltd.) -45- 200841093 [Chem. 30] Oxetane A (OX Ding-2 2 1)

Oxetane B (OX-SQ-H)

Oxetane C (〇X — SC)

(Epoxy-based cross-linking compound) Epoxy A: YH-4 3 4L (manufactured by Tohto Kasei Co., Ltd.) Epoxy B: Aberdeen GT-401 (4-functional alicyclic epoxy resin) (manufactured by DAICEL Chemical Co., Ltd.) Epoxidized butane tetracarboxylic acid ruthenium-(3-cyclohexenylmethyl) modified ε-caprolactone-46- 200841093 [Chem. 31]

(Organic solvent) NMP : N-methyl-2-pyrrolidone BCS : butyl cellosolve <Molecular weight measurement of polyimine > The molecular weight of polyimine in the synthesis example is a room temperature gel permeation layer The analytical method (GPC) is equipped with a pipe column (KD-803, KD-805) manufactured by Shodex.

Column temperature: 50 °C Dissolution: N,N'-dimethylformamide (30 mmol/L as hydrate (LiBr·H2O), phosphoric acid as dish) 30 mmol/L, tetrahydrofuran (THF) % Flow rate: 1.0ml / minute Standard sample for the production of checkweighing lines: Tosoh Corporation _ Oxygenethane (molecular weight about 90 00,000, 150,000, ), and Polyethylene Laboratories Inc. Polyethylene 12,000, 4,000, 1,000) 〇SENSHU Science (SSC-7200), 'Test additive according to the following method, lithium bromide-love•anhydrous crystal (〇·I 1 0 m 1 / L ) ^ TSK standard polycyclic ring 1,00,000, 3,000 diol (molecular weight about -47- 200841093 &lt;Measurement of yttrium imidation ratio&gt; The ruthenium imidation ratio of the polyimine in the synthesis example was as follows. 20 mg of the polyimide pigment was placed in the NMR sample tube (the NMR sputum column manufactured by Kusano) The sampling tube standard is 0 5mm), 0.53ml of heavy hydrogen hydrazine (DMSO-d6, 〇.〇5% TMS mixture) is added, and the sound wave is completely dissolved. The solution in the sputum column is measured by NMRDATUM NMR. Proton NMR measured by JNW-ECA5 00. The rate of oxime imidization is based on the structure of the acetylation before and after imidization. The proton is determined by the reference proton, and the wave of this proton is calculated by the following formula with the NH sub-peak derived from lysine which appears near 9.5~10. Oppm. Measurement, • Ultra-electronic 500MHz: the quality of the enthalpy based on the unconverted r

醯 imidization rate (%) = ( 1- α · x / y) xlOO In the above formula, x is the mass 値 of the NH group of the proline, y is the peak of the reference proton, α, α is The ratio of the number of protons of the ruthenium proton 1 to the valeric acid when the polyamine amination rate is 〇%). The peak product (the synthesis example 1) makes CBDA (5.1 g, 2 6. Ommol), p-PD A (2 3.4 mm ο 1 ), AP18 (0.98 g, 2.6 mmol) in NMP (in the middle) Mix and react with 2 51 for 6 hours to obtain polylysine

2.53g, 81.5g) solution (A -48- 200841093). The polyaminic acid solution (A) had a number average molecular weight of 22,000 and a weight average molecular weight of 78,900. (Synthesis Example 2) CBDA (3.04 g, 1 5.5 mmo 1 ), p-PD A (1.56 g, 14.4 mmol), and PCH (0.61 g, 1.6 mmol) were mixed in NMP (22.0 g) to 2 51 was allowed to react for 5 hours to obtain a polyaminic acid solution (B). The polyaminic acid solution (B) had a number average molecular weight of 25,000 and a weight average molecular weight of 94,000. (Synthesis Example 3) BODA (16.9 g, 6 8 mmol), p-PD A (8.74 g, 81 mmol), and PCH (3.43 g, 9 mmol) were mixed in NMP (100" g) at 40 °C After reacting for 3 hours, CBDA (4 Ig, 21 mmol) and NMP (52.2 g) were added, and the mixture was reacted at 40 ° C for 3 hours to obtain a polyaminic acid solution (C). The polyamic acid (C) had a number average molecular weight of 20,500 and a weight average molecular weight of 76,500. (Synthesis Example 4) BODA (150.1 g, 6 00 mmol), DBA (60.9 g, 400 mmol), and PCH (152.2 g, 400 mmol) were mixed in NMP (1290 g), and reacted at 80 ° C for 5 hours, and then added. CBDA (38.8 g, 198 mmol) and NMP (32 0 g) were reacted for 4 hours at 4 Torr to obtain a polyaminic acid solution (D). The number average fraction of the polyfluorene acid (D) was -24-200841093, and the weight average molecular weight was 98,500. (Synthesis Example 5) After the NMP was added to the polyaminic acid solution (C) (1 3 0.3 g) obtained in Synthesis Example 3 and diluted to 6 mass%, acetic anhydride (15.6 g) and pyridine (12.1 g) were added as The ruthenium imidization catalyst was reacted at 80 ° C for 3 hours, and the reaction solution was poured into methanol (1 600 ml), and the obtained precipitate was filtered, and the precipitate was washed with methanol at 100 ° C. The polyimine powder (E) was obtained by drying under reduced pressure. The polyamidimide had a ruthenium iodide ratio of 5 4 %, a number average molecular weight of 18,300, and a weight average molecular weight of 453 00. (Synthesis Example 6) After the NMP was added to the polyaminic acid solution (D) (600.2 g) obtained in Synthesis Example 4 and diluted to 6 mass%, acetic anhydride (63.9 g) and pyridine (49.6 g) were added as a ruthenium. The aminated catalyst was reacted at 80 ° C for 3 hours, and the reaction solution was poured into methanol (7700 ml), and the obtained precipitate was filtered, and the precipitate was washed with methanol and decompressed at 1 ° C. Dry to obtain a polyimide pigment (F). The polyamidimide had a ruthenium iodide ratio of 5 7%, a number average molecular weight of 23,000, and a weight average molecular weight of 80,200. (Synthesis Example 7) After the NMP was added to the polyamidic acid solution (D) (101.2 g) obtained in Synthesis Example 4 and diluted to 6 mass%, acetic anhydride (21.3 g) and pyridine (16.5 g) were added as hydrazine. For the imidization catalyst, the reaction solution was poured into methanol (1 300 ml) at 9 (rc) to react 3 small - 50 to 200841093, and the obtained precipitate was filtered, and the precipitate was washed with methanol to The polyilylimide powder (G) was obtained by drying under reduced pressure at 100 ° C. The polyamidimide had a ruthenium iodide ratio of 81%, a number average molecular weight of 20,400, and a weight average molecular weight of 63 000. (Example 1 To the polyproline solution (A) (6.00 g) obtained in Synthesis Example 1, oxetane (A) (O.llg), NMP (4.76 g), BCS (2 · 5 3 g) were added. After stirring, a liquid crystal alignment treatment agent [1] was obtained. The liquid crystal alignment treatment agent [1] obtained above was spin-coated on an ITO surface of a substrate of 3 cm X 4 cm with a ruthenium electrode, and heat-treated at 80 ° C. After 5 minutes of heat treatment at 23 ° C for 30 minutes, a polyimide film having a thickness of 100 nm was obtained. The coating surface was honed by a boring mill with a drum diameter of 120 mm and a rayon cloth. The pm, the moving speed of 40 mm/Sec, and the press-in amount of 0.3 mm were honed to obtain a substrate with a liquid crystal alignment film. Two substrates with the liquid crystal alignment film were prepared, and the liquid crystal alignment film was turned inward. The separator of 5 0/m is combined in a state in which the honing direction is reversed, and an empty box is formed by adhering the sealant to the periphery, and liquid crystal ZLI-2293 is injected into the empty box by a vacuum injection method (Merk Japan Co., Ltd.) In order to obtain an anti-parallel alignment nematic liquid crystal cell after closing the injection port, the tilt angle measuring device (EL) is used for the liquid crystal cell at the initial stage after liquid crystal injection and at each tilt angle after heat treatment at 120 ° C for 5 hours. SIC ON company sampler PAS-301) was measured at room temperature, and the liquid crystal cell after the initial and each heat treatment was observed by a polarizing microscope to confirm the uniformity of the liquid crystal alignment - 51 - 200841093. Further, regarding the liquid crystal cell prepared by the same method as described above except for the honing treatment, the liquid crystal and each tilt angle after heat treatment at 120 ° C for 5 hours were observed, and the liquid crystal distribution was observed and confirmed. As a result of the uniformity, any liquid was poor, and the liquid crystals were uniformly aligned. The measurement results of the tilt angle are shown in Table 1. (Example 2) The polyaminic acid solution obtained in Synthesis Example 1 (A: , After adding oxetane (A) (0.06 g) and NMP (2.35 g), the mixture was stirred to obtain a liquid crystal alignment treatment agent [2]. Using the obtained liquid crystal alignment treatment agent [2], a liquid crystal cell was fabricated. The liquid crystal cell after the initial measurement of the honing treatment, the initial stage of the honing treatment, the heat treatment at 120 ° C for 5 hours, and the liquid crystal cell after each heat treatment were used, and any liquid crystal was used as a result of the uniformity of the alignment of the polarized microcrystals. The boxes are evenly aligned without any matching. Further, regarding the amount of press-in which is the same as the above-described immersion treatment, the liquid crystal cell produced by the same method as described above was measured for liquid crystal and each tilt angle after heat treatment at 120 ° C for 5 hours, and the result of observing the alignment uniformity of the liquid crystal was observed. Any liquid is poor, and the liquid crystals are evenly aligned. All of them were evenly aligned to 0.1 mm, and the initial polarized microscope cartridges were not aligned in the initial injection (4.05 g) (4.05 g), and the BCS Example 1 was similarly tilted after liquid crystal injection, and the liquid observation was confirmed by mirror observation. The liquid crystal was 0.1 mm, and the initial polarization microscope collimator after the injection was not aligned. The measurement results of the tilt angle of -52-200841093 are shown in Table 1. (Example 3) In the polyaminic acid solution (A) (6.00 g) obtained in Synthesis Example 1.

After adding oxetane (B) (0.03 g), NMP (3.61 g), and BCS (2.21 g), the mixture was stirred to obtain a liquid crystal alignment treatment agent [3]. Using the obtained liquid crystal alignment treatment agent [3], a liquid crystal cell was produced in the same manner as in Example 1, and the initial amount after the liquid crystal injection of the honing treatment was measured, and the heat treatment was performed at 10 ° C for 5 hours. After the initial tilting angle and the liquid crystal cell after the heat treatment, the alignment uniformity of the liquid crystal was observed by a polarizing microscope. As a result, no alignment failure was observed in any of the liquid crystal cells, and the liquid crystals were uniformly aligned. Further, regarding the liquid crystal cell produced by the same method as described above except that the press-in amount was set to 0.1 mm, the initial angle after liquid crystal injection and each tilt angle after heat treatment at 150 ° C for 5 hours were measured, and a polarizing microscope was used. As a result of observing the alignment uniformity of the liquid crystal, any of the liquid crystal cells had no misalignment, and the liquid crystals were evenly aligned. The measurement results of the tilt angle are shown in Table 1. (Example 4)

To the polyproline solution (B) (6.00 g) obtained in Synthesis Example 2, oxetane (A) (〇.12g), NMP (3.61g), and BCS (2.4g) were added, followed by stirring. A liquid crystal alignment treatment agent [4] was obtained. Using the obtained liquid crystal alignment treatment agent [4], in the same manner as in Example 1, -53-200841093, the liquid crystal cell was measured, and the amount of press-in which the honing treatment was measured was 〇3 mm, and the initial stage after liquid crystal injection was performed, and at 20 ° C. Each of the tilt angles after the heat treatment for 5 hours was used to observe the uniformity of alignment of the liquid crystals with respect to the liquid crystal cell after the initial treatment and the heat treatment, and any liquid crystal cell was not misaligned, and the liquid crystals were uniformly aligned. The measurement results of the tilt angle are shown in Table 1. (Example 5) In the polyaminic acid solution (B) (6.02 g) obtained in Synthesis Example 2

Then, oxetane (B) (0.03 g), NMP (2.41 g), and BCS (2.10 g) were added, followed by stirring to obtain a liquid crystal alignment treatment agent [5]. Using the obtained liquid crystal alignment treatment agent [5], a liquid crystal cell was produced in the same manner as in Example 1, and the initial stage after liquid crystal injection in which the pressing amount of the honing treatment was 0·3 mm and the heat treatment at 1200 ° C were measured. For each of the tilt angles after the hour, the liquid crystal cell after the initial and each heat treatment was observed by a polarizing microscope to confirm the uniformity of alignment of the liquid crystal, and any liquid crystal cell was not misaligned, and the liquid crystals were uniformly aligned. The measurement results of the tilt angle are shown in Table 1. (Comparative Example 1) NMP (3.06 g) and BCS (2.12 g) were added to the polyamic acid solution (A) (6.9 g) obtained in Synthesis Example 1 and stirred to obtain a liquid crystal alignment treatment agent [ 6]. Using the obtained liquid crystal alignment treatment agent [6], a liquid crystal cell was produced in the same manner as in Example 1 -54-200841093, and the amount of press-in of the honing treatment was measured, and the initial stage after the liquid crystal injection of 3 mm and the temperature of 1 20 ° were measured. C. The respective inclination angles after the heat treatment for 5 hours, as a result of observing the alignment uniformity of the liquid crystal by the polarizing microscope with respect to the liquid crystal cell after the initial stage and each heat treatment, any liquid crystal cell was not misaligned, and the liquid crystals were uniformly aligned. The measurement results of the tilt angle are shown in Table 1. (Comparative Example 2) NMP (2.01 g) and BCS (1.99 g) were added to the polyamic acid solution (B) (6·01 g) obtained in Synthesis Example 2, followed by stirring to obtain a liquid crystal alignment treatment agent. [7]. Using the obtained liquid crystal alignment treatment agent [7], a liquid crystal cell was produced in the same manner as in Example 1, and the initial stage after liquid crystal injection of 0·3 mm of the honing treatment and the heat treatment at 120 ° C were measured. For each of the tilt angles after 5 hours, the liquid crystal cell after the initial and each heat treatment was observed by a polarizing microscope to confirm the uniformity of alignment of the liquid crystal, and any liquid crystal cell was not misaligned, and the liquid crystals were uniformly aligned. The measurement results of the tilt angle are shown in Table 1 ° (Comparative Example 3). In the polyamic acid solution (A) (6.0 〇g) obtained in Synthesis Example 1, epoxy (A) (O.Ug) was added. After stirring with NMP (4.75 g) and BCS (2.5 2 g), a liquid crystal alignment treatment agent [8] was obtained. Using the obtained liquid crystal alignment treatment agent [8], a liquid crystal cell was produced in the same manner as in Example 1 -55-200841093, and the amount of press-in of the honing treatment was measured, and the initial stage after the liquid crystal injection of 3 mm and the temperature of 1 20 ° were measured. In the initial state of the liquid crystal cell, the so-called flow alignment in which the liquid crystal is aligned toward the liquid crystal flow direction during liquid crystal injection is observed in the initial state of the liquid crystal cell, and the flow alignment is not eliminated in each stage after the heat treatment. Further, since the discrimination line occurs due to the heat treatment, the tilt angle of the liquid crystal cell cannot be measured because such a misalignment occurs. Further, in the measurement, in addition to the press-in amount of 0.1 mm, the initial angle after liquid crystal injection of the liquid crystal cell produced by the same method as described above and the tilt angle after heat treatment at 10 ° C for 5 hours were observed in the initial state. Flow alignment, this flow alignment is not eliminated after heat treatment, and the discrimination line occurs, so the tilt angle cannot be measured. The measurement results of the tilt angle are shown in Table 1. (Comparative Example 4) In the polyamic acid solution (A) (6.05 g) obtained in Synthesis Example 1, the force Q was incorporated into epoxy (A) (0.06 g), NMP (4.03 g), and BCS (2.34 g). After stirring, a liquid crystal alignment treatment agent [9] was obtained. Using the obtained liquid crystal alignment treatment agent [9], a liquid crystal cell was produced in the same manner as in Example 1, and the initial stage after the liquid crystal injection of the honing treatment and the heat treatment at 10 ° C for 5 hours were measured. As for the initial liquid crystal cell, the alignment uniformity of the liquid crystal was confirmed by a polarizing microscope. The alignment was poor and the liquid crystal was uniformly aligned. However, after the heat treatment was performed at 12 ° C for 5 hours, a discrimination line occurred. Unable to measure -56- 200841093 The tilt angle of the liquid crystal cell after heat treatment at 1 2 0 °C for 5 hours. Further, in the initial state, the measurement was carried out in the initial state, except that the press-in amount was set to 0.1 mm, and the inclination angles at the initial stage after liquid crystal injection of the liquid crystal cell produced by the same method as described above and after heat treatment at 10 ° C for 5 hours were obtained. Seeing the flow alignment 'this flow alignment is not eliminated after heat treatment, plus the discrimination line occurs, so the tilt angle cannot be measured. The measurement results of the tilt angle are shown in Table 1. (Comparative Example 5) In the polyamic acid solution (A) (6.00 g) obtained in Synthesis Example 1, epoxy (B) (0.06 g), NMP (4.0 2 g), and BCS (2 · 3) were introduced. After 5 g), the mixture was stirred to obtain a liquid crystal alignment treatment agent [1 〇]. Using the obtained liquid crystal alignment treatment agent [10], a liquid crystal cell was produced in the same manner as in Example 1, and the initial stage after liquid crystal injection in which the pressing amount of the honing treatment was 0.3 mm and the heat treatment at 120,000 °C were measured. As for the initial tilt angles, the liquid crystal cell was observed by a polarizing microscope, and the alignment uniformity of the liquid crystal was confirmed. The alignment was poor and the liquid crystal was uniformly aligned. However, after the heat treatment at 120 ° C for 5 hours, a discrimination line occurred. Therefore, the tilt angle of the liquid crystal cell after heat treatment at 1200 ° C for 5 hours could not be measured. Further, in the initial state, the measurement was carried out in the initial state, except that the press-in amount was set to 0.1 mm, and the inclination angles at the initial stage after liquid crystal injection of the liquid crystal cell produced by the same method as described above and after heat treatment at 10 ° C for 5 hours were obtained. When the flow alignment is seen, the flow alignment is not eliminated after the heat treatment, and, in addition, the discrimination line occurs, so the inclination angle cannot be measured. -57- 200841093 The measurement results of the tilt angle are shown in Table i. (Example 6) NMP (1·7·1 g) was added to the polyimine powder (e) (2·9 1 g) obtained in Synthesis Example 5, and the mixture was stirred at 80 ° C for 40 hours to be dissolved. In this solution, oxetane (A) (〇·60 g), Μ Μ P (1 2.2 g), and BCS (25·7 g) were added and stirred to obtain a liquid crystal alignment treatment agent [i丨]. φ Using the obtained liquid crystal alignment treatment agent [11], the liquid crystal cell was produced in the same manner as in Example j except that the liquid crystal was 'MLC-660 8 (manufactured by Merk Japan Co., Ltd.), and then the press-in amount of the honing treatment was measured. - The initial angle after liquid crystal injection of 3 mm and the tilt angle after heat treatment at 1200 °C for 5 hours. As a result of observing the uniformity of alignment of the liquid crystal with a polarizing microscope for the initial and each liquid crystal cell after heat treatment, The liquid crystal cells have no misalignment, and the liquid crystals are evenly aligned. Further, regarding the liquid crystal cell prepared by the same method as the above, except that the press-in amount of the honing treatment was set to 0.1 mm, the tilt angle after the liquid crystal injection was measured and the tilt angle after heat treatment at 10 ° C for 5 hours was measured. As a result of observing the alignment uniformity of the liquid crystal by a polarizing microscope, the liquid crystal cell was not misaligned in any of the liquid crystal cells, and the liquid crystals were evenly aligned. (Example 7) NMP (18.0 g) was added to the polyimine powder (E) (3.05 g) obtained in Synthesis Example 5, and the mixture was stirred at 80 ° C for 40 hours to dissolve, and then oxygen was added to the solution. Heterocyclic butane (A) (〇.31g), NMP (6.55 g) -58-200841093, and BCS (28.0 g) were stirred to obtain a liquid crystal alignment treatment agent [12]. The liquid crystal cell was produced in the same manner as in Example 1 except that the liquid crystal was MLC-660 8 (manufactured by Merk Japan Co., Ltd.), and the amount of press-in of the honing treatment was measured. In the initial stage after the liquid crystal injection of 3 mm and the inclination angle after heat treatment at 10 ° C for 5 hours, the liquid crystal cell after the initial and each heat treatment was observed by a polarizing microscope to confirm the uniformity of alignment of the liquid crystal, and any liquid crystal cell was observed. None of the alignment is poor, and the liquid crystals are evenly aligned. Further, regarding the liquid crystal cell produced by the same method as described above except that the press-in amount was set to 〇1 mm, the respective tilt angles after the liquid crystal injection was measured and the heat treatment at 10 ° C for 5 hours was measured. When the liquid crystal cell was observed by a polarizing microscope to confirm the uniformity of the alignment of the liquid crystal, any of the liquid crystal cells had no misalignment, and the liquid crystals were evenly aligned. The measurement results of the tilt angle are shown in Table 1. (Example 8) NMP (1. 6 g) was added to the polyimine powder (E) (3.0 g) obtained in Synthesis Example 5, and the mixture was stirred at 80 ° C for 40 hours to dissolve the solution. An oxetane (A) (0.15 g), NMP (5·5 1 g), and BCS (26. 3 g) were added thereto, followed by stirring to obtain a liquid crystal alignment treatment agent [13]. The obtained liquid crystal alignment treatment agent [13] was prepared in the same manner as in Example 1 except that the liquid crystal was MLC-660 8 (manufactured by Merk Japan Co., Ltd.), and then the amount of press-in of the honing treatment was measured. In the initial stage after the liquid crystal injection of mm and the inclination of -59 to 200841093 after heat treatment for 5 hours, the liquid crystal cell after the initial and each heat treatment was observed by a polarizing microscope to confirm the uniformity of alignment of the liquid crystal. As a result, any of the liquid crystal cells have no misalignment, and the liquid crystals are evenly aligned. Further, regarding the liquid crystal cell produced by the same method as described above except that the press-in amount was set to 0.1 mm, the tilt angles at the initial stage after liquid crystal injection and after heat treatment at 120 ° C for 5 hours were measured. As a result of observing the alignment uniformity of the liquid crystal by a polarizing microscope, any of the liquid crystal cells had no misalignment, and the liquid crystals were evenly aligned. The measurement results of the tilt angle are shown in Table 1. (Example 9) NMP (18.4 g) was added to the polyimine powder (F) (3.12 g) obtained in Synthesis Example 6, and the mixture was stirred at 80 ° C for 40 hours to dissolve, and then oxygen was added to the solution. Heterocyclic butane (A) (0.31 g), NMP (6.80 g), and BCS (28.6 g) were stirred to obtain a liquid crystal alignment treatment agent [14]. Using the obtained liquid crystal alignment treatment agent [14], a liquid crystal cell was produced in the same manner as in Example i except that the liquid crystal was MLC-660 8 (manufactured by Merk Japan Co., Ltd.), and then the indentation amount of the honing treatment was measured. In the initial stage after the injection of the liquid crystal of mm and the tilt angle after heat treatment at 1200 ° C for 5 hours, the liquid crystal cell after the initial and each heat treatment was observed by a polarizing microscope to confirm the uniformity of alignment of the liquid crystal, and any liquid crystal cell was observed. None of the mismatched 'liquid crystals are evenly aligned. The measurement results of the tilt angle are shown in Table 1. -60-200841093 (Example 1 〇) NMP (1.79 g) was added to the polyimine powder (F) (3.04 g) obtained in Synthesis Example 6, and the mixture was dissolved in 8 (TC for 40 hours). To the solution, oxetane (A) (0.15 g), NMP (5.51 g), and BCS (26.6 g) were added, followed by stirring to obtain a liquid crystal alignment treatment agent [15]. Using the obtained liquid crystal alignment treatment agent [15] In the same manner as in Example 1, except that the liquid crystal was MLC-660 8 (manufactured by Merk Japan Co., Ltd.), the liquid crystal cell was produced in the same manner as in Example 1, and the initial stage after the liquid crystal injection of 0.3 mm of the honing treatment was measured, and 1 2 was measured. The tilt angle after heat treatment at 0 °C for 5 hours, and the liquid crystal cell after the initial and each heat treatment were observed by a polarizing microscope to confirm the uniformity of alignment of the liquid crystal, and any liquid crystal cell was not misaligned, and the liquid crystals were uniformly aligned. The measurement results of the angles are shown in Table 1. (Example 1 1 ) NMP (17.5 g) was added to the polyimine powder (G) (2.98 g) obtained in Synthesis Example 7 at 8 ° C. After stirring for 40 hours to dissolve, oxetane (A) (0.30 g) and NMP (6.61 g) were added to the solution. After the BCS (27. 3g) was stirred, the liquid crystal alignment treatment agent [16] was obtained. The obtained liquid crystal alignment treatment agent [16] was used except that the liquid crystal was MLC-660 8 (manufactured by Merk Japan Co., Ltd.). In the same manner, a liquid crystal cell was produced, and then the initial amount after the liquid crystal injection of 3 mm was measured, and the tilt angle after heat treatment at 10 ° C for 5 hours was measured, and the liquid crystal cell after the initial and each heat treatment was measured. As a result of observing the alignment uniformity of the liquid crystal, the liquid crystal was uniformly aligned, and the liquid crystals were evenly aligned. The measurement results of the tilt angle are shown in Table 1. (Example 1 2 ) NMP (1.77 g) was added to the polyimine powder (G) (3.01 g) obtained in Synthesis Example 7, and after stirring at 80 ° C for 40 hours to dissolve, oxetane was added to the solution ( C) (0.15g), NMP (5.41g), and BCS (26.36g) were stirred to obtain a liquid crystal alignment treatment agent [17]. The obtained liquid crystal alignment treatment agent [17] was used except that the liquid crystal was MLC-660 8 ( Liquid crystal was produced in the same manner as in Example i except for Merk Japan Co., Ltd. Then, the initial stage after the liquid crystal injection of 0.3 mm of the honing treatment and the inclination angle after heat treatment at 1200 ° C for 5 hours were measured, and the liquid crystal cell after the initial and each heat treatment was observed by a polarizing microscope. As a result of the uniformity of alignment of the liquid crystal, any liquid crystal cell has no misalignment, and the liquid crystals are evenly aligned. The measurement results of the tilt angle are shown in Table 1. (Comparative Example 6) NMP (1.71 g) was added to the polyimine powder (E) (2.91 g) obtained in Synthesis Example 5, and the mixture was stirred at 80 ° C for 40 hours to dissolve, and then NMP was added to the solution. (4.18g) and BCS (26.3g) were stirred to obtain a liquid crystal alignment treatment agent [18]. Using the obtained liquid crystal alignment treatment agent [1 8 ], a liquid crystal cell was produced in the same manner as in Example 1 except that the liquid crystal was -62-200841093 MLC-6608 (manufactured by Merk Japan Co., Ltd.), and then the press-in of the honing treatment was measured. 〇 〇 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 The liquid crystal cells have no misalignment, and the liquid crystals are evenly aligned. The measurement results of the tilt angle are shown in Table 1. (Comparative Example 7) NMP (1.79 g) was added to the polyimine powder (F) (3.05 g) obtained in Synthesis Example 6, and after stirring at 80 ° C for 40 hours, NMP was added to the solution. (4.66 g) and BCS (25.4 g) were stirred, and a liquid crystal alignment treatment agent [19] was obtained. Using the obtained liquid crystal alignment treatment agent [19], a liquid crystal cell was produced in the same manner as in Example i except that the liquid crystal was MLC-6608 (manufactured by Merk Japan Co., Ltd.), and then the indentation amount of the honing treatment was measured to be 0 · 3 mm. The initial angle after the liquid crystal injection and the tilt angle after heat treatment at 120 ° C for 5 hours. As a result of observing the alignment uniformity of the liquid crystal by the polarizing microscope with respect to the liquid crystal cell after the initial and each heat treatment, any liquid crystal cell was not aligned. Poor, the liquid crystals are evenly aligned. The measurement results of the tilt angle are listed in Table 1. (Comparative Example 8) In the polyimine powder (G) (3.000 g) obtained in Synthesis Example 7, -63-200841093 was added to NMP (17. 7 g), and the mixture was stirred at 80 ° C for 40 hours to dissolve therein. NMP (4 · 3 5 g ) and BCS (25 · 1 g) were added to the solution, followed by stirring to obtain a liquid crystal alignment treatment agent [20]. Using the obtained liquid crystal alignment treatment agent [20], a liquid crystal cell was produced in the same manner as in Example 1 except that the liquid crystal was MLC-6608 (manufactured by Merk Japan Co., Ltd.), and then a liquid crystal having a press-in amount of 0.3 mm was measured. The initial angle after the injection and the tilt angle after heat treatment at 1200 ° C for 5 hours, and the liquid crystal cell after the initial and each heat treatment were observed by a polarizing microscope to confirm the uniformity of alignment of the liquid crystal, and any liquid crystal cell was not misaligned. The liquid crystals are evenly aligned. The measurement results of the tilt angle are shown in Table 1. (Comparative Example 9) In the polyimine powder (F) (3 · 0 1 g ) obtained in Synthesis Example 6

After adding NMP ( 17.7 g) and stirring at 80 ° C for 40 hours, epoxy (A ) (0.60 g), NMP (8.80 g), and BCS (3 O.Og) were added to the solution and stirred. A liquid crystal alignment treatment agent [21] was obtained. The liquid crystal cell was produced in the same manner as in Example 1 except that the liquid crystal was MLC-660 8 (manufactured by Merk Japan Co., Ltd.), and the amount of press-in of the honing treatment was measured. In the initial stage after liquid crystal injection and the inclination angle after heat treatment at 10 ° C for 5 hours, in the initial state of the liquid crystal cell, the so-called flow alignment in which the liquid crystal is aligned in the liquid crystal flow direction during liquid crystal injection is observed, and heat treatment is performed. This flow alignment was not eliminated in the subsequent stages, and, because of the heat treatment, the discrimination line of -64 - 200841093 occurred because the tilt angle of the liquid crystal cell could not be measured because of such poor alignment. Further, in the measurement, in addition to the press-in amount of 0.1 mm, the initial stage after the liquid crystal injection of the liquid crystal cell produced by the same method as described above and the tilt angle after 12 hours of the TC heat treatment were observed in the initial state. Flow alignment, this flow alignment is not eliminated after heat treatment, and the discrimination line occurs, so the tilt angle of the liquid crystal cell cannot be measured. The measurement results of the tilt angle are shown in Table 1. (Comparative Example 1 〇) Synthesis NMP (17.5 g) was added to the polyimine powder (F) (3·0 0 g) obtained in Example 6, and after 80 ° C was mixed at 80 ° C to dissolve it, epoxy (A was added to the solution). (0.30g) ^ NMP ( 6.71 g ), :BCs (27.5g), and stirred to obtain a liquid crystal alignment treatment agent [22]. The obtained liquid crystal alignment treatment agent [22] is used, except that the liquid crystal is MLC_660 8 ( Merk Japan In the same manner as in the example, the liquid crystal cell was produced in the same manner as in the example. Next, the amount of press-in of the honing treatment was measured, and the initial angle after liquid crystal injection of 3 mm and the tilt angle after heat treatment at 10 ° C for 5 hours were measured. , for the initial and each heat-treated liquid crystal cell, by polarized light As a result of microscopic observation confirming the uniformity of alignment of the liquid crystal, any liquid crystal cell has no misalignment, and the liquid crystals are evenly aligned. Moreover, in addition to the measurement of the press-in amount to 0.1 mm, the liquid crystal of the liquid crystal cell produced by the same method as described above is measured. As a result of the initial angle after the injection and the inclination angle after heat treatment at 1 2 〇 ° C for 5 hours, the flow-65-200841093 alignment was observed in the initial state, and the flow alignment was not eliminated after the heat treatment, and the discrimination occurred. Line, therefore, the tilt angle cannot be measured. The measurement results of the tilt angle are shown in Table 1. (Comparative Example 1 1 ) The polyimine powder (F) ( 3.〇3g) obtained in Synthesis Example 6 was added to NMP. (17. 8g), after stirring at 80 ° C for 40 hours to dissolve, epoxy (A) (0.15g), NMP (5.60g), and Bcs (26.3g) were added to the solution, followed by stirring to obtain a liquid crystal alignment treatment. In the same manner as in Example 1, except that the liquid crystal was MLC-660 8 (manufactured by Merk Japan Co., Ltd.), the liquid crystal cell was produced, and then the pressure of the honing treatment was measured. After the injection of 0.3mm liquid crystal In the initial stage and the inclination angle after heat treatment at 1200 ° C for 5 hours, the liquid crystal cell after the initial and each heat treatment was observed by a polarizing microscope to confirm the uniformity of alignment of the liquid crystal, and any liquid crystal cell was not misaligned. Evenly, the measurement was performed, except that the amount of press-in was 0.1 mm, and the results of the initial stage after liquid crystal injection of the liquid crystal cell produced by the same method as described above and the inclination angle after heat treatment at 120 ° C for 5 hours were measured. In the initial state, the flow alignment was observed, and the flow alignment was not eliminated after the heat treatment. In addition, the discrimination line occurred, so the inclination angle could not be measured. The measurement results of the tilt angle are shown in Table 1. (Comparative Example 1 2 ) -66 - 200841093

NMP (1.71 g) was added to the polyimine powder (F) (2.93 g) obtained in Synthesis Example 6, and after stirring at 80 ° C for 40 hours to dissolve, epoxy (B) was added to the solution. 0.30 g), NMP (5.50 g), and BCS (2 5.7 g) were stirred, and a liquid crystal alignment treatment agent [24] was obtained. The liquid crystal cell was produced in the same manner as in Example i except that the liquid crystal was MLC-660 8 (manufactured by Merk Japan Co., Ltd.), and the amount of press-in of the honing treatment was measured. In the initial stage after the injection of the liquid crystal of mm and the inclination angle after heat treatment at 120 ° C for 5 hours. As for the liquid crystal cell after the initial and each heat treatment, the alignment uniformity of the liquid crystal was confirmed by a polarizing microscope. Poor alignment 'liquid crystals are evenly aligned. Further, as a result of measuring the amount of pressing of the honing treatment to be 0.1 mm, the results of the initial stage after liquid crystal injection of the liquid crystal cell produced by the same method as described above and the inclination angle after heat treatment at 10 ° C for 5 hours were In the initial state, the flow alignment was observed, and the flow alignment was not eliminated after the heat treatment. Further, discriminati ο η 1 ine occurred, so the inclination angle could not be measured. The measurement results of the tilt angle are shown in Table 1. -67- 200841093 Table 1 (Α戚分(B戚分压: 0.3mm Indentation 0.1mm Initial 120〇C/5h Initial 120〇C/5h Example 1 [1] Oxetane (A 5.0 4.9 5.2 5.1 Example 2 [2] Oxetane (A) 5.7 5.6 5.8 5.8 Example 3 [3] Oxetane (B) 5.3 5.3 5.5 5.5 Example 4 [41 Oxetane Alkane (A) 5.3 5.3 Example 5 [5] Oxetane (B) 6.2 6.1 _ Comparative Example 1 [6] Μ j\\\ 6.9 5.8 - - Comparative Example 2 [7] Μ 7.8 7.0 - - Comparison Example 3 [8] Epoxy (A) *1 *2 *1 *2 Comparative Example 4 [9] Epoxy (A) 5.5 *3 *1 *2 Comparative Example 5 [10] Epoxy (B) 5.6 *3 *1 *2 Example 6 [11] Oxetane (A) 84.8 85.4 85.1 85.2 Example 7 [12] Oxetane (A) 85.2 85.6 85.6 85.6 Example 8 [13] Oxetane Alkane (A) 86.2 86.7 86.5 86.5 Example 9 [14] Oxetane (A) 87.9 88.3 - - Example 10 [15] Oxetane (B) 88.4 88.6 - - Example 11 [16] Oxetane (A) 88.1 88.3 - - Example 12 [17] Oxetane (C) 88.5 88.6 • Comparative Example [18] Μ 86.0 88.3 - - Comparative Example 7 [19] Μ y\\ \ 87.4 89.0 - Comparative example 8 [20] No 88.1 89.8 - - Comparative Example 9 Ρ1] Epoxy (A) *1 *2 *1 *2 Comparative Example 10 [22] Epoxy (A) 89.6 89.7 *1 *2 Comparative Example Π [23] Epoxy (A) 89.2 89.8 *1 *2 Comparative Example 241 [241 Epoxy (B) 89.1 89.9 *1 *2 _ : Not evaluated * 1 : Flow alignment was observed in the liquid crystal cell by observation with a polarizing microscope. 2: The liquid alignment and the discrimination line were observed in the liquid crystal cell by observation under a polarizing microscope. : The discrimination line 看到 was observed in the liquid crystal cell by a polarizing microscope (the tilt angle was measured, and the center of the liquid crystal cell was measured and The average 値 of 3 points above and below 1 cm) -68- 200841093 From the above results, there is no change in the orientation of the crystal from the crystal to the film, and the change in the orientation of the crystal with respect to the specific crosslinkable compound ～5, and Comparative Examples 9 to 12, a comparative example of a specific crosslinkable compound, and an industrial useability of the honing treatment, by using a liquid crystal display element of a liquid film excellent in the stability of the oblique angle of the present invention, In the present invention, the TN element, the STN element, and the direct alignment type liquid crystal display element In the entire contents of the application 2006-297244, the liquid crosslinkable compounds obtained by the liquid crystal alignment treatment agent of the present invention are compared with the first to second examples, and the liquids are not contained in the examples 1 to 2 and the comparative examples 6 to 8. Moreover, the inclination angle after the high temperature treatment has a degree of improvement of less than 1 degree. On the other hand, when the epoxy-based crosslinkable compound was used in place of the present invention, a poor alignment was observed, and particularly when such a press-in amount was low, misorientation occurred. The liquid crystal alignment agent can obtain a tilting alignment film of a liquid crystal. Further, since this liquid crystal alignment is excellent in reliability, it is suitable for use in a TFT liquid crystal element, and is more suitable for use in a pendant or the like. The disclosure of the specification, the scope of the patent application, and the disclosure of the Japanese Patent Application, filed on Nov. 1, 2006, is hereby incorporated by reference. -69-

Claims (1)

200841093 X. Patent application scope 1 · A liquid crystal alignment treatment agent characterized by containing the following (A) component and (B) component, (A) component: a group of polyglycine and polyimine At least one selected polymer, (B) component: a crosslinkable compound having at least two oxetanyl groups represented by the following formula [1] in the molecule, [Chemical Formula 1] 2. The liquid crystal alignment treatment agent according to item 1 of the patent application, wherein the component (B) is a compound represented by the following formula [2], [Chemical 2] [2] (In the formula [2], Xi represents N, NH, CO, 0, S, S02, Si, sesquioxane, polyoxyalkylene, or an organic group having 1 to 20 carbon atoms, and this organic group It may also contain a hetero atom (N, Ο, S, Si); X2 and X3 each independently represent a single bond, :^11, (: 〇, 〇, 8, 8 〇 2, or an organic number of 1 to 20) The organic group may also contain a hetero atom (N, 0, S, Si); Y! and Y2 each independently represent an organic group having 1 to 20 carbon atoms, and the organic group may also contain -70-200841093 a hetero atom (N, 0, S, Si); m and η each independently represent an integer of 〇~20, and m + n represents an integer of 2 to 2 0. 3. Liquid crystal alignment as in claim 1 The treatment agent 'wherein the component (B) is a compound represented by the following formula [3], (In the formula [3], X2 and X3 each independently represent a single bond, NH, CO, hydrazine, S, S02, or an organic group having 1 to 20 carbon atoms, and the organic group may further contain a hetero atom (N, 0). , S, Si); Y! and Υ2 each independently represent an organic group having a carbon number of 1 to 20, and the organic group may also contain a hetero atom (Ν, 0, S, Si); Zi represents a single bond, NH, N(CH3), NHCO, CONH, NHCONH, CO, COO, Ο, S, S〇2, CF2, C (CF3) 2, Si (CH3) 2, OSi (CH3) 2, Si (CH3) 2〇, 〇Si(CH3) 2〇, or an alkyl group having 1 to 10 carbon atoms; m and n each independently represent an integer of 〇~l〇, And the m + n table is not an integer of 2 to 10). 4. The liquid crystal alignment treatment agent according to claim 1, wherein the component (B) is a compound represented by the following formula [4], [4] [in the formula [4], Χι means NH, N (CH3), NHCO, CON Η, -71 - 200841093 NHCONH, CO, COO, OCO, 〇, S, S02, CF2, C(CF3)2, Si (ch3) 2, OSi (ch3) 2, Si ( Ch3) 2o, or OSi(CH3)20; Y2 each independently represents an alkyl group having 1 to 10 carbon atoms). 5. The liquid crystal alignment treatment agent according to item 1 of the patent application, wherein the component (B) is a compound represented by the following formula [5], [Chem. 5] [5] (In the formula [5], Xi is N, an aliphatic ring having 1 to 20 carbon atoms, an aromatic ring having 1 to 20 carbon atoms, or an alkylene group having 1 to 20 carbon atoms; and Yi and Y2 are each independently The ground represents an alkyl group having 1 to 10 carbon atoms; m and η each independently represent an integer of 〇~2 0 and m + n represents an integer of 2 to 20). 6. The liquid crystal alignment treatment agent according to any one of claims 1 to 5, wherein the (B) component # content is 0.1 to 150 parts by mass based on 100 parts by mass of the component (A). 7. The liquid crystal alignment treatment agent according to any one of claims 1 to 6, which further contains an organic solvent. 8. The liquid crystal alignment treatment agent according to claim 7, wherein the organic solvent contains 5 to 80% by mass of a solvent having a low surface tension in the total organic solvent. A liquid crystal alignment film obtained by the liquid crystal alignment treatment agent according to any one of claims 1 to 8. 10. A liquid crystal display element characterized by having a liquid crystal alignment film of the ninth application of the patent scope -72-200841093. % m 郁 蠓 -73- 200841093 VII Designated representative map: (1) The designated representative figure of this case is: None (2), the representative symbol of the representative figure is a simple description ·· 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: