TW200949388A - Liquid crystal aligning agent and liquid crystal display element - Google Patents

Abstract

The present invention provides a liquid crystal aligning agent which can provide a liquid crystal aligning film with high level properties required for liquid crystal aligning film, particularly with good adherence for sealing agent, and has a property that in the production of a liquid crystal display element, in the case which is suitable for one drop fill (ODF) method, liquid crystal is wet spread at high speed; the present invention also provides a liquid crystal display element which has good electric properties and showing high display quality. The above crystal aligning agent comprises (a) at least one polymer selected from the group consist of a polyamic acid and an imide polymer thereof, and (b) a compound comprising 2 epoxy groups and 1 or more of fluorine atom in the molecule. The above liquid crystal display element comprises a liquid crystal aligning film formed by the above liquid crystal aligning agent.

Description

200949388 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a liquid crystal alignment agent and a liquid crystal display element. [Prior Art] At present, as a liquid crystal display element, a TN type liquid crystal display element having a so-called TN type (twisted nematic) liquid crystal cell is known, which is formed of polylysine on the surface of a substrate provided with a transparent conductive film. A liquid crystal alignment film formed of a polyimine or the like is provided as a substrate for a liquid crystal display element, and two of the substrates are provided in a β-direction, and a nematic liquid crystal layer having positive dielectric anisotropy is formed in the gap. In the cell of the sandwich structure, the long axis of the liquid crystal molecules is continuously twisted by 90 degrees from one substrate to the other. Furthermore, an STN (Super Twisted Nematic) type liquid crystal display element and a small viewing angle dependence IPS (in-plane switching) type liquid crystal display element and VA (vertical alignment) capable of achieving high contrast compared with a TN type liquid crystal display element have been developed. ) Liquid crystal display element, optical compensation curved (OCB) type liquid crystal display element excellent in viewing angle dependence and excellent in high-speed response of video images (refer to Patent Documents 1 to 3 and Non-Patent Document 1) »

Dβ is a material of a liquid crystal alignment film in these liquid crystal display elements. Organic films such as polyimine, polyamide, and polyester, particularly polyimine, have been known for their heat resistance and affinity with liquid crystals. It is excellent in mechanical strength, electrical properties, etc., and is used in most liquid crystal display elements (refer to Patent Document 4). Usually, in order to produce a liquid crystal display element, it is necessary to pass a step of filling a liquid crystal into a gap between two substrates (cell gap) in which a liquid crystal alignment film is formed. In the liquid crystal charging, a vacuum injection method in which a liquid crystal is interposed between liquid crystal display element substrates by using a pressure difference between atmospheric pressure and vacuum is generally used. However, it is necessary to flow liquid crystal into the inter-substrate gap of only 3 to 6 μm in 200949388. More time, so the manufacturing steps take a long time, and for the very large panels, the manufacturing process needs to be shortened. As a new liquid crystal charging method for solving the above problems in the vacuum injection method, a liquid crystal dropping method (ODF method) has been developed. When the necessary amount of liquid crystal is dropped on the substrate on which the liquid crystal alignment film is formed and bonded to another substrate under vacuum, the sealing agent for sealing the liquid crystal is UV-cured, so that the entire panel can be filled with liquid crystal. Technology (refer to Patent Document 5). This technology © is a technology that is expected to significantly reduce the time required for the liquid crystal charging step. However, if the 〇DF step is applied to a substrate having a previously known liquid crystal alignment film, the diffusion speed of the liquid crystal molecules on the liquid crystal alignment film is not fast enough, and the time for shortening the liquid crystal charging step is not sufficiently good. Further, in recent years, due to the tendency of the liquid crystal display element to be thinned and the display area to be enlarged, an area where the primitive is not formed on the outer edge of the substrate has been performed (commonly referred to as "frame area" between practitioners in the field). The narrowing technique is the study of the application of the framework narrowing technique. If the application frame is narrowed, the technique is required to reduce the coating area of the sealant for bonding the two glass substrates, and thus the adhesive strength between the substrates tends to decrease. Further, recently, in order to further narrow the frame, a technique of applying a sealant to a liquid crystal alignment film formed on a substrate to bond is performed. At this time, the adhesion strength of the liquid crystal alignment film to the substrate and the sealant becomes a big problem. In particular, it is known that the interface bonding strength between the organic film and the sealant tends to be smaller than the interface bonding strength between the glass substrate and the sealant. As described above, in order to further narrow the frame, it is necessary to improve the liquid crystal alignment film-sealant. The bond strength (adhesion) of the interface. 200949388 However, as an investigation of the adhesion of a liquid crystal alignment film, there are many examples of adhesion to a glass substrate or a transparent conductive film, and there is basically no example of adhesion to a sealant. The examples of the adhesion of the adhesive and the various reports required for the performance of the liquid crystal alignment film are still unknown. [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. Hei. No. Hei. No. Hei. [Patent Document 5] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 8] Japanese Laid-Open Patent Publication No. Hei No. Hei 5-107544 - Non-Patent Document [Non-Patent Document 1] SID' 94 Digest ρ· 927 (1994) ® [Invention] It is an object of the present invention to provide A liquid crystal alignment agent in which liquid crystal can rapidly wet and spread properties when a liquid crystal dropping method (ODF) is applied in the manufacture of a liquid crystal display element. Another object of the present invention is to provide a liquid crystal alignment agent capable of forming a liquid crystal alignment film having various properties required for a liquid crystal alignment film while having particularly excellent adhesion to a sealant. Still another object of the present invention is to provide a liquid crystal display element which is excellent in electrical properties and exhibits high display quality. Other objects and advantages of the present invention can be seen from the following description. According to the present invention, the above objects and advantages of the present invention, first, achieved by a liquid crystal alignment agent comprising (a) at least one polymerization selected from the group consisting of polylysine and its ruthenium iodide polymer And (b) a compound having two epoxy groups and one or more fluorine atoms in the molecule. Second, it is achieved by a liquid crystal display element having a liquid crystal alignment film formed of the above liquid crystal alignment agent. When the liquid crystal alignment film is formed of the liquid crystal alignment agent of the present invention, the time for the liquid crystal charging step using the ODF method can be sufficiently shortened. Further, the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention has a high level of various properties required as a liquid crystal alignment film, and is particularly excellent in adhesion to a sealant. The liquid crystal alignment agent of the present invention can be applied to various liquid crystal display elements such as TN type, STN type, VA type, IPS type, OCB type, ferroelectricity, and antiferroelectricity. The liquid crystal display device of the present invention is excellent in electrical properties and exhibits high display quality. The liquid crystal display element of the present invention can be effectively applied to various devices such as a display device which can be applied to computers, watches, desk clocks, counting displays, word processors, personal computers, liquid crystal televisions and the like. [Embodiment] The liquid crystal alignment agent of the present invention contains (a) at least one polymer selected from the group consisting of polylysine and its quinone imidized polymer, and (b) two epoxy groups in the molecule. A compound having one or more fluorine atoms (hereinafter referred to as "epoxy compound having a fluorine atom"). Hereinafter, various components contained in the liquid crystal alignment agent of the present invention will be described. 200949388 (a) Polymer The (a) polymer contained in the liquid crystal alignment agent of the present invention is at least one selected from the group consisting of polyglycolic acid and its quinone imidized polymer. <Polyamic acid> The above polylysine can be synthesized by reacting a tetracarboxylic dianhydride with a diamine. [tetracarboxylic dianhydride]

四 The tetracarboxylic dianhydride used in the synthesis of the polyamic acid used in the present invention may, for example, be butane tetracarboxylic dianhydride or 12,3,4-cyclobutanetetracarboxylic dianhydride or 1, 2-Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, hydrazine, 3·Dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4·cyclobutane tetracarboxylic dianhydride 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexane tetraresic acid dianhydride, 3,3',4,4'-dicyclohexyltetradecene Acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2 3,4 5 • tetraazafuran tetracarboxylic acid Dihydride, 1,3,3&,4,5,915-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[l,2-c]-furan·1, 3·dione, l,3,3a4,5,9b hexachloro$methyl-5-(tetrahydro-2,5·dioxo-3·furanyl)·naphthalene [丨2 '”.j - u Tianran-1,3-dione, 1,3,3&,4,5,91»-hexahydro-5-ethyl-5-(tetrahydro-25~_ 幽ζ'5·~oxo_ 3_furyl)-naphthalene [l,2-c]-furan-1,3-dione, l,3,3a,4 5 ^ Hydrogen-7-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)naphthalene t1,2 c-furan-dione, l,3,3a,4,5,9b -hexahydro-7-ethyl-5-(tetrahydro-2 5 - &, -~ deutero-3-furanyl)-naphthalene [l,2-c]-furan·1,3-dione, l,3,3a,4 5 α 丄',9b•hexahydro-8-methyl-5-(tetrahydro-,-dioxo-furanylnaphthalene^. 'furfuran-1,3-two Ketone, 1,3,3&,4,5,91)-hexahydro-8-ethyl-5-(tetrahydro-25~,-~oxo-3-furan 200949388)-naphthalene [l,2 -c]-furan-indole, 3-dione, 1,3,3&,4,5,91>-hexamethylene-5-(tetrahydro-2,5-dioxo-3-furanyl) -naphthalene [1,2-(:]-fluorenone, 5-(2,5-dioxotetrahydrofuranyl)_3.methyl-, cyclohexanoic anhydride, bicyclo[2.2_2]-oct-7-ene_ 2,3,5,6-tetracarboxylic dianhydride, cyclo[3_2.1]octane-2,4-dione-6-spiro-3,-(tetrahydrofuran-2, 5 〇5_(2,5 · Dioxotetrahydro__3_furanyl)_3_methyl-nonylcyclohexanic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2:3,5:6-methylpyran-1 , 3-carboxy 3, oxabis ''dione), ' 1,2. Xuan, Carboxy 4, 9. Oxabicyclo[5.3.1.02,6]undecane-3,5,8,1〇 -tetraketone Bian said formula - (T and (T - aliphatic or compounds represented by each of anhydrides II); helmet four carboxylic acids of formula I)

(In the formula (τ-D and (τ-Π), R1 and K3 each represent a divalent organic group having an aromatic ring 'R2 and R4 each represent a hydrogen atom or an alkyl group, and a plurality of R2 and R4 present may be the same , can also be different); pyromellitic dianhydride, 3,3',4,4,-benzophenone tetraphthalic acid dianhydride, 3,3,4,4'-monophenylphosphonium tetrahydro acid anhydride 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetraphthalic acid dianhydride, 3,3',4,4'-diphenyl acid tetradecanoic acid , 3,3',4,4'-dimethyldiphenylnonanetetracarboxylic dianhydride, 3,3,4,4,4-tetraphenylnonanetetracarboxylic dianhydride, 1,2,3,4 -furan tetracarboxylic dianhydride, 4,4,_bis(3,4-diphenylphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dis-pentylphenoxy 200949388 Diphenylphosphonium dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene di-ortho Phthalic anhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, bis(phthalic acid) benzene Phosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, Phenyl-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4 , 4'-diphenylmethane dianhydride, ethylene glycol-bis(hydroper trimellitate), propylene glycol-bis(hydroper trimellitate), 1,4-butanediol-bis (dehydrated benzene) Triester), 1,6-hexanediol-bis(anhydrotrimellitic acid ester), 1,8-octanediol-bis(anhydrotrimellitic acid ester), 2,2-bis(4- An aromatic tetracarboxylic dianhydride such as a compound represented by the following formula (T-1) to (T-4) of hydroxyphenyl)propane-bis(hydrogen trimellitate). They may be used alone or in combination. The above combination is used.

-10- 200949388

The tetracarboxylic dianhydride used in the synthesis of the polyamic acid used in the present invention is preferably one selected from the group consisting of butane four from the viewpoint of exhibiting good liquid crystal alignment properties of the formed liquid crystal alignment film. Dicarboxylic anhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1, 2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydrogen) -2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&,4,5,91)-hexahydro- 8-methyl_5_(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-indolyl]-furan-1,3-dione, 1,3,3&,4 ,5,91>-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-(;]-furan-1 , 3-dione, bicyclo[2.2.2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo[3.2.1]octane-2,4- Two-11 - 200949388

Keto-6-spiro-3'-(tetrahydrofuran-2',5,-dione), 5-(2,5-dioxotetrahydro-3-(furanyl)-3-methyl-3-cyclohexane Alkene-indole, 2_dicarboxylic anhydride, 3,5,6-tricarboxyl_2_carboxynorbornane-2:3,5:6·dianhydride, 4, phenodioxatriene [^丨^11 Alkane-3,5,8,1〇-tetraketone, pyromellitic dianhydride, 3,3,,4,4,_benzophenone tetracarboxylic acid monohydride, 3,3',4,4'- a base selenium tetracarboxylic dianhydride, 2,2,3,3,-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, a compound represented by the above formula At least one of the group consisting of the compound represented by the following formula (Τ_5) to (τ-7) and the compound represented by the following formula (τ_8) in the compound represented by the above formula (Τ - II) ( Hereinafter referred to as "specific tetracarboxylic dianhydride 1")

(Τ-5) (Τ-6)

The above specific tetracarboxylic dianhydride is more preferably selected from the group consisting of 1,2,3,4·cyclobutane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, and 1,3. 3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-(:]-furan-1,3-anthracene, L,3,3a,4,5,9b-/,chloro-8-methyl-5-(tetrachloro-2,5-monooxy-3-indolyl)-naphthalene [1,2<]- Furan-1,3-diketone '3_oxabicyclo[3.2.1]octane-12- 200949388

-2,4-dione-6-spiro-3,-(tetrahydrofuran-2,5'-dione), tetrahydro-3-furanyl)-3-methyl-3-cyclohexene-I, 2-dicarboxylate carboxy-2-carboxynorbornane-2:3,5:6-dianhydride, 4,9 [5.3.1.02'6]undecane-3,5,8,10-tetraone, At least-2,3,5-tricarboxycyclopentyl acetic acid dianhydride in a group consisting of compounds represented by pyromellitic acid (T-5). The η residual acid bismuth used in the synthesis of the polylysine used in the present invention is from 2 to 2 mol% of the anhydride, preferably 10 mol% or more with respect to the entire tetracarboxylic dianhydride. The tetracarboxylic dianhydride of the specific tetracarboxylic dianhydride 1 is more preferably contained, and particularly preferably contains 50% by mole or more. [Diamine] The diamine used in the synthesis of the polyamic acid used in the present invention may, for example, be an aromatic diamine, an aliphatic diamine, an alicyclic diamine or a diamine organooxane. Examples of the aromatic diamine include a compound represented by the following formula (D-I) to (1)-IV), an aromatic diamine having a fluorine atom, and another fluorene aromatic diamine. (R6)a1

(D-II) -13- 200949388

(EHIII)

(D-IV ) Ο (In the formula (DI), R5 is an alkyl group having 6 to 30 carbon atoms, or a group having a group selected from the group consisting of pyridine, pyrimidine, triterpene, piperidine, and piperene a monovalent organic group having a cyclic structure of a nitrogen atom, X1 being a single bond, -〇_*, -COO_*, _〇CO_*, -NHCO.*, -CONH-* or _c〇-* (with The connection key is connected to R5), R6 is a hospital base having 1 to 4 carbon atoms, and al is an integer of 0 to 3,

In the formula (D-II), 'R7 is a divalent organic group having a nitrogen atom-containing cyclic structure selected from the group consisting of pyridine, pyrimidine, triterpene, piperazine, and a pipe trap, and each of χ2 is _0-*, -COO- *, -OCO-*, -NHCO-*, -CONH-* or _C0_* (where the connection key is connected to R7), the presence of multiple Χ2 can be the same 'may be different, R8 is each a carbon atom The number is 1 to 4, and a2 is an integer of 0 to 4, and R9 in the formula (D-III) is a monovalent organic group having a steroid skeleton, and X3 is a single bond, 〇_*, - COO-*, _〇c〇·*, -NUCC)·*,·〇〇Νϋ-* or -CO-* (where the connection key is connected to R9), Rl() is a carbon number of 1~ 4 alkyl, a3 is an integer of 0 to 3, -14- 200949388 R11 in the formula (D-IV) is a divalent organic group having a steroid skeleton 'X4 is each -Ο-*, -COO-* , -OCO-*, -NHCO-*, -CONH-* or -CO-* (wherein the "*', the linkage is linked to R11), and each of R12 is an alkyl group having 1 to 4 carbon atoms. Each of a4 is an integer of 0 to 4), and R6, R8, R1G, and R12' in the above formulas (D-1) to (D-IV) are preferred. The methyl group, a1, a2, a3, and a4 are each preferably 0 or 1', and more preferably 0. The compound represented by the above formula (D-1) may, for example, be dodecyloxy-2,4-di. Aminobenzene, pentadecyloxy-2,4-diaminobenzene, cetyloxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, ten Dialkoxy-2,5-diaminobenzene, pentadecyloxy-2,5-diaminobenzene, cetyloxy-2,5-diaminobenzene, octadecyloxy- 2,5-diaminobenzene, a compound represented by the following formula (D-1);

The compound represented by the above formula (D - II) may, for example, be a compound represented by the following formula (D-2).

(D-2 is a monovalent organic group having a steroid skeleton of R9 in the above formula (D-III), and examples thereof include a 3-cholesteryl group, a 3-cholesteryl group, and a 3-lanethyl group. Specific examples of the compound represented by the above formula (D-III) include, for example, the following formulas (D-3) to (D-8) each representing -15-200949388.

Compounds, etc.

-16- 200949388 As the divalent organic group having a steroid skeleton of R11 in the above formula (D-IV), for example, cholestane-3,6-diyl, cholestene-3,6-diyl may be mentioned , a cholestane-3,3-bis(ι,4-phenylene) group, and the like. Specific examples of the compound represented by the above formula (D-IV) include compounds represented by the following formulas (D-9) to (D-11), and the like.

The aromatic diamine having a fluorine atom may, for example, be a compound represented by the formula (D-V), -17-200949388 h2n

(DV) (In the formula (D - V), R13 represents a monovalent organic group having a group selected from the group consisting of a trifluoromethylphenyl group, a trifluoromethoxyphenyl group, and a fluorophenyl group; , X5 is -〇-*, -coo-*, -OCO-*, -NHCO-*, -CONH-* or -CO-* (with "*,' connection key and connection", Ri4 is carbon An alkyl group having an atomic number of 1 to 4, a5 is an integer of 〇~3), 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2_bis (4) _Aminophenyl)hexafluoropropane, 2,2'-bis(trifluoromethyl)-4,4,-diaminobiphenyl, 3,3,_bis(trifluoromethyl)-4,4 '-Diaminobiphenyl, 2,2,_bis[4_(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4,-diamino-2, 2, bis(trifluoromethyl)biphenyl, 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl, etc. as the above formula (D- R14 in V) is preferably a methyl group, and a5 is preferably ruthenium or 1, more preferably 0. 具体 As a specific example of the compound represented by the above formula (D - V), for example, the following formula (D - 12) ~ (D - 14) each represented by a compound or the like.

(D-12)

-18 - .200949388

H2N NH2 (D-14) The aromatic diamine having a fluorine atom is preferably a compound represented by the above formula (D-V) and 2,2,-bis(trifluoromethyl)-4. 4,-Diaminobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane and 2,2-bis(4-aminophenyl)hexafluoropropane, The particularly preferable aromatic aryl diamine having a fluorine atom can be exemplified by the compounds represented by the above formulas (D-12) to (D-14) and 2,2'-bis(trifluoromethyl)-4,4. , _diaminobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane and 2,2.bis(4-aminophenyl)hexafluoropropane. Examples of the other aromatic diamine include p-phenylenediamine, m-phenylenediamine, 4,4,-diaminodiphenylmethane, 4,4,diaminodiphenylethane, and 4,4. ,-Diaminodiphenyl sulfide, 4,4,-diaminodiphenyl maple, 3,3'-dimethyl-4,4,-diaminobiphenyl, 4,4,-di Aminobenzamide, 4,4'-diaminodecyl diphenyl ether, 1,5-.diaminonaphthalene, 2,2,-dimethyl-4,4'-diaminobiphenyl, 3,3'-Dimethyl-4,4,-diaminobiphenyl, 5-amino-b (4'-aminophenyl)-13,3-trimethylindan, 6-amino group -丨_(4,aminophenyl)-1,3,3-trimethylindan, 3,4,-diaminodiphenyl ether, 3,3,-diaminobenzophenone, 3 , 4'-diaminobenzophenone, 4,4,-diaminobenzophenone, 2,2·bis[4·(4-aminophenoxy)phenyl]propane, 2,2-double [4-(4-Aminophenoxy)phenyl]anthracene, i,4.bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1, 3_bis(3-aminophenoxy)benzene, 4,4-bis(4-aminophenoxy)biphenyl, 9,9-bis(4-aminophenyl)-1〇-hydroquinone , 2,7-diaminopurine, 9,9-dimethyl-2 , 7-diaminopurine, -19- 200949388 9,9-bis(4-aminophenyl)anthracene, 4,4'-methylene-bis(2-chloroaniline), 2,2',5 , 5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3 '-Dimethoxy-4,4'-diaminobiphenyl, 4,4'-(p-phenylene isopropylidene)diphenylamine, 4,4'-(m-phenylene isopropylidene Diphenylamine, 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2, 3-dicyanopyridine, 5,6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1, 4-bis(3-aminopropyl) piperazine, 2,4-diamino-6-isopropoxy fluorene-1,3,5-tri-trap, 2,4-diamino-6-- Oxy-1,3,5-tri-trap, 2,4-diamino-6-phenyl-1,3,5-trin, 2,4-diamino-6-methyl-3-tri Plowing, 2,4-diamino-1,3,5-three tillage, 4,6-diamino-2-vinyl-s-three tillage, 2,4-diamino-5-phenylthiazole , 2,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5-diamino-1,2,4-triazole, 6,9-di Amino-2-ethoxyl Acridine lactate, 3,8-diamino-6-phenylphenanthridine, 1,4-diaminopiperidine, 3,6-diaminoacridine, bis(4-aminophenyl)benzene Amine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminosostazole, N-phenyl-3, 6-decanediamine-based, N,N'-bis(4-aminophenyl)benzidine, N,N'-bis(4-aminophenyl)-N,N'-dimethyl linkage An aniline, a compound represented by the following formula (D-15) and (D-16), etc.,

(D-15) -20- 200949388

>νη2 (D-16) (Y in the formula (D-15) is an integer of 2 to 12, and Ζ in the formula (D-16) is an integer of 1 to 5). Examples of the aliphatic diamine include hydrazine, hydrazine, hydrazine, propylenediamine, butanediamine, pentanediamine, hexamethylenediamine, heptanediamine, octylamine, and hydrazine. Amine, 1,3_bis(aminomethyl)cyclohexane, 14-bis(aminomethyl)cyclohexyl, hexahydro-4,7-methylene dimethylene diamine, tricyclic [ 6 2 丨〇 2, 勹 undecene dimethyl diamine, etc.: As the above alicyclic diamine, for example, diamine cycloheximide, isophorone diamine, tetrahydrodicyclopentadiene And a compound represented by the following formula (D Θ - VI), etc., as the above-mentioned diamine organo oxoane, etc.

H2N-f-CH2^ (D-VI) (In the formula (D-VI), each of R15 represents a hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R15 groups may be the same or different, and each of P is - 21 - 200949388 1 to 3 integers, q is an integer from 1 to 20). Specific examples of the compound represented by the above formula (D-VI) include, for example, 1,3-bis(3-aminopropyl)-tetramethyldioxane. The diamine used in the synthesis of the polyamic acid used in the present invention preferably contains a compound selected from the group consisting of the above formulas (D-I) to (D-IV); the above aromatic having a fluorine atom Group diamine; p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 1,5-diamino group in the above other aromatic diamines Naphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,7-diaminostilbene, 4,4'-diaminodiphenyl ether, 2,2-dual [ 4-(4-Aminophenoxy)phenyl]propane, 9,9-bis(4-aminophenyl)anthracene, 4,4'-(p-phenylene diisopropylidene)diphenylamine, 4,4'-(m-phenylene diisopropylidene)diphenylamine, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy) Biphenyl, 2,6-diaminopyridine, 3,4·diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N,N' - bis(4-aminophenyl)benzidine and the above formulas (D-15) and (D_16) a compound; 1,4-diaminocyclohexane and 1,3-bis(aminomethyl)cyclohexane in the above aliphatic diamine; 4,4-methylene in the above alicyclic diamine At least one of the group consisting of bis(cyclohexylamine); and 1,3-bis(3-aminopropyl)-tetramethyldioxane in the above diamine organooxane (hereinafter A diamine called "specific diamine 1"). The diamine used in the synthesis of the polyamic acid used in the present invention is preferably -22-200949388, which is preferably contained in an amount of 5 mol% or more of the specific diamine 1 as described above with respect to all diamines. 1 〇 mol% or more, more preferably 2 〇 mol% or more, particularly preferably 50 mol% or more. Further, the 'diamine used in the synthesis of polylysine when the liquid crystal alignment agent of the present invention is used for forming a liquid crystal alignment film for vertical alignment preferably contains a compound selected from the above formula (D-III) and the above The diamine of at least one of the groups represented by the formula (D - iV) (hereinafter referred to as "specific diamine 2-1") adheres to the sealant 0 from the formed vertical alignment liquid crystal alignment film. From the viewpoint of the property, it is preferable to further contain at least one selected from the aromatic diamine having a fluorine atom (hereinafter referred to as "specific diamine 2 - 2") together with the specific diamine 2- 1 . amine. When the liquid crystal alignment agent of the present invention is used to form a liquid crystal alignment film for vertical alignment, the diamine used in the synthesis of polylysine preferably has a specific content of 8 to 40 mol% relative to the entire diamine as described above. The diamine of diamine 2_1 preferably contains 10 to 30 mol%. The diamine at this time preferably contains 0.2 to 40 mol% of the diamine of the specific diamine 2-2 with respect to the entire diamine, and more preferably contains 3 to 10 mol%. [Synthesis of Polylysine] The polylysine used in the present invention can be synthesized by reacting the above-described tetracarboxylic dianhydride with a diamine. The ratio of use of the tetracarboxylic dianhydride to the diamine compound for the synthesis reaction of the polyamic acid is preferably 0.5 to 1 for the acid anhydride group of the tetracarboxylic dianhydride relative to 1 equivalent of the amine group contained in the diamine compound. The ratio of 2 equivalents is more preferably made to be a ratio of 0.7 to 1.2 equivalents. The synthesis reaction of polylysine is preferably carried out in an organic solvent at a temperature of preferably from -20 to -23 to 200949388 at 150 ° C, more preferably from 0 to 100 ° C, more preferably from 0.5 to 2 hours. Good to carry out 2~1 0 hours. Here, the organic solvent is not particularly limited as long as it is a solvent capable of dissolving the synthesized polyamic acid, and examples thereof include N-methyl-2-pyrrolidone and N,N-dimethylacetamide. An aprotic polar solvent such as hydrazine, dimethyl dimethyl phthalamide, dimethyl sulfoxide, γ-butyrolactone, tetramethyl urea, hexamethylphosphonium triamine; m-methylphenol, xylenol, A phenolic solvent such as phenol or halogenated phenol. The amount (α) of the organic solvent is preferably such that the total amount (β) of the tetracarboxylic dianhydride and the diamine compound is from 0.1 to 30% by weight based on the total amount (α + β) of the reaction hydrazine solution. In addition, when the organic solvent is used in combination with the following poor solvent, the above-mentioned "amount of the organic solvent" means the total amount of the organic solvent and the poor solvent. In the organic solvent, the produced polyamine acid is not precipitated. In the range, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like which are generally considered to be poor solvents for polylysine may be used in combination. As a specific example of such a poor solvent, For example, methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol oxime monomethyl ether, ethyl lactate, butyl lactate, acetone , methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxy propionate, diethyl oxalate , diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol n-propyl ether 'ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene two Alcohol ether acetate, diglyme, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether Diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene , o-dichlorobenzene, hexane, heptane, octane, benzene, -24- 200949388 toluene, xylene, isoamyl propionate, isoamyl isobutyrate, isoamyl ether, etc. When the organic solvent is as above When the poor solvent is used in combination, the use ratio of the poor solvent is preferably 50% by weight or less, more preferably 20% by weight or less, and particularly preferably 10% by weight based on the total amount of the organic solvent and the poor solvent. As described above, a reaction solution in which polyamic acid is dissolved is obtained. The reaction solution may be directly supplied to a liquid crystal alignment agent, or may be separated from a polyamic acid contained in the reaction solution and then supplied to a liquid crystal alignment agent. The preparation or the preparation may also be carried out by refining the separated polyamic acid and then supplying the liquid crystal alignment agent. The separation of the poly-proline may be carried out by introducing the above reaction solution into a large amount of poor solvent to obtain a precipitate. Method for drying the precipitate under reduced pressure Alternatively, the reaction solution may be subjected to distillation under reduced pressure in an evaporator, and the solution may be further dissolved in an organic solvent by one or several times, and then precipitated by a poor solvent, or by evaporation. The polyacetin can be purified by a step of distilling off under reduced pressure. <醢i-imidized polymer> The oxime imidized polymer used in the present invention can be reacted with a dicarboxylic acid dianhydride and a diamine. The obtained polyglycine is dehydrated and closed to synthesize it. [Tetracarboxylic dianhydride] The tetrahydro acid dianhydride used in the synthesis of the quinone imidized polymer used in the present invention may be exemplified by the above polyamic acid. The same compound as the tetradecanoic acid dianhydride used in the synthesis. Among them, an alicyclic tetracarboxylic dianhydride is preferred. The tetracarboxylic acid monoanhydride used in the synthesis of the ruthenium iodide polymer used in the present invention Preferably, the alicyclic tetracarboxylic dianhydride is selected from the group consisting of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3&,4,5,91)-hexahydro-5- ( Tetrahydro-2,5-dioxo-25- 200949388-3--3-furyl)-naphthalene [l,2-c]-furan-1,3-dione, l,3,3a,4,5,9b -six -8-Methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-isan•1,3-dione, 3-oxabicyclo [3.2.1] Octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxotetrahydro-3- Furyl)-3-methyl·3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6·tricarboxy-2-carboxynorbornane-2:3,5:6-dianhydride and At least one of the group consisting of 4,9-dioxatricyclo[5.3.1'02'6]undecane-3,5,8,10-tetraketone (hereinafter referred to as "specific tetracarboxylic acid II" Anhydride 2") of a tetracarboxylic dianhydride. As the specific tetracarboxylic dianhydride 2, preferably ruthenium is 2,3,5-tricarboxycyclopentyl acetic acid dianhydride. The tetracarboxylic dianhydride used in the synthesis of the quinone imidized polymer used in the present invention preferably contains 10 mol% or more of the specific tetracarboxylic dianhydride 2 as described above with respect to all the tetracarboxylic dianhydride. The tetracarboxylic dianhydride preferably contains 20 mol% or more, and particularly preferably contains 50 mol% or more. The diamine used in the synthesis of the quinone imidized polymer used in the present invention may be the same as the diamine used in the synthesis of the above polyamic acid. The preferred diamine should also be understood in the same manner as in the synthesis of poly-proline. [Synthesis of a ruthenium iodide polymer] The ruthenium iodide polymer used in the present invention can be preferably synthesized by dehydration ring closure of a polyglycine prepared by reacting a tetracarboxylic dianhydride with a diamine as described above. . The synthesis of the precursor polyamic acid of the ruthenium iodide polymer can be carried out in the same manner as the synthesis of the polyamic acid used in the present invention. The dehydration ring-closing reaction of polylysine may be (i) by heating poly-proline, or (ii) by dissolving poly-proline in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution according to It is carried out by heating method -26- 200949388. The reaction temperature in the method of heating poly-proline in the above (i) is preferably 50 to 200 ° C, more preferably 60 to 170 ° C. When the reaction temperature is less than 50 °C, the dehydration ring-closure reaction may not proceed sufficiently. If the reaction temperature exceeds 20 CTC, the molecular weight of the obtained ruthenium-imided polymer may decrease. The reaction time is preferably from 1 to 120 hours, more preferably from 2 to 30 hours. In the method of adding a dehydrating agent and a dehydrated closed-loop catalyst to the polyamic acid solution of the above (ii), as the dehydrating agent, an acid anhydride such as acetic anhydride, phthalic anhydride or trifluoroacetic anhydride can be used. The amount of the dehydrating agent is preferably 0.01 to 20 moles per 1 mole of the repeating unit of the polyaminic acid. Further, as the dehydration ring-closure catalyst, a tertiary amine such as pyridine, trimethylpyridine, dimethylpyridine or triethylamine can be used. However, it is not limited to these. The amount of the dehydration ring-closing catalyst is preferably 0.01 to 10 mols per mol of the dehydrating agent used. In addition, examples of the organic solvent used in the dehydration ring-closure reaction include organic solvents exemplified as the organic solvent used in the synthesis of polyglycolic acid. Further, the reaction temperature of the dehydration ring-closure reaction is preferably from 〇 to 〇 180 °C', more preferably from 1 Torr to 150 °C. The reaction time is preferably from 0.5 to 30 hours, more preferably from 2 to 1 hour. The ruthenium iodide polymer obtained in the above method (i) can be directly used for the preparation of a liquid crystal alignment agent, or the obtained ruthenium iodide polymer can be refined and used for a liquid crystal alignment agent. Formulated. Further, in the above method (ii), a reaction solution containing a ruthenium-imided polymer was obtained. The reaction solution can be directly used for the preparation of a liquid crystal alignment agent, or can be used for the preparation of a liquid crystal alignment agent after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution. It can be used for the preparation of liquid crystal with -27-200949388, or it can also be used for the preparation of liquid crystal alignment agent after refining the separated ruthenium-imiding polymer. The dehydrating agent and the dehydration ring-closing catalyst are removed from the reaction solution, and a method such as solvent replacement can be employed. The separation and purification of the ruthenium iodide polymer can be carried out in the same manner as described above for the separation and purification method of polyglycine. The ruthenium iodide polymer used in the present invention may be a complete ruthenium imide of a lysine structure in which the precursor polyamic acid has a dehydration ring structure, or may be a partial valerate structure dehydration ring closure. The proline sulphate structure and the quinone imine ring coexist with a ruthenium imide having a lower quinone imidization ratio. The ruthenium imidization ratio of the ruthenium iodide polymer used in the present invention is preferably 40% or more, more preferably 80 to 90%. Here, the "rhodium imidization ratio" means the total amount of the proline structure and the quinone ring in the ruthenium iodide polymer, and the ratio of the number of the quinone ring is expressed by a percentage. At this time, a part of the quinone ring may also be an isoindole ring. The ruthenium imidization ratio of the ruthenium iodide polymer can be obtained by dissolving the ruthenium iodide polymer in a suitable deuterated solvent (for example, deuterated dimethyl hydrazine), using tetramethyl decane as a reference material. The 1H-NMR measured at room temperature can be determined by the following formula (i).醯imination rate (%) = (1 - Α^Α^οΟχ 100--(i) (In equation (i), A1 is the peak area of the proton derived from the NH group near 10 ppm, and A2 is the source Regarding the peak area of other protons, α is a proton of one NH group in the pro-imidized polymer precursor (polyglycolic acid), and the number of other protons). [End-modified polymer] The above polylysine and its quinone imidized polymer may also be a terminal modified polymer having a molecular weight adjusted. This terminal modified type polymerization -28-200949388 can be used in the synthesis of polyamic acid. The synthesis is carried out by adding a suitable molecular weight modifier such as a monoanhydride, a monoamine compound or a monoisocyanate compound to the reaction system. Here, examples of the monoanhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, and rhodium. a succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl succinic anhydride, etc. Further, examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, and Pentylamine, n-hexylamine, n-heptylamine, n-octylamine, positive Amine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, hydrazine, pentadecylamine, n-hexadecylamine, n-heptadecaneamine, positive Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate. The use ratio of these molecular weight modifiers is relative to polyamic acid. The total amount of the tetracarboxylic dianhydride and the diamine used in the synthesis is preferably 20 mol% or less, more preferably 10 mol% or less. [Solid viscosity] The above polylysine and its quinone imine The polymer, when separately formulated into a solution having a concentration of ❹ 10% by weight, preferably has a solution viscosity of 20 to 800 mPa_s, more preferably a solution viscosity of 30 to 500 mPa, s. Solution viscosity of the above polymer (mPa) *s) is a 10% by weight polymer solution formulated with a good solvent for the polymer (for example, N-methyl-2-pyrrolidone, γ-butyrolactone, etc.), rotated with a Ε type値 measured by a viscometer at 25 ° C. (b) epoxy compound having a fluorine atom contained in the liquid crystal alignment agent of the present invention (b) The epoxy compound having a fluorine atom is a compound -29-200949388 having two epoxy groups and one or more fluorine atoms in the molecule. The fluorine atom is preferably used as an epoxy compound having a fluorine atom. The perfluoroalkyl group is present, more preferably as a trifluoromethyl group. (b) The number of perfluoroalkyl groups in the epoxy compound having a fluorine atom is preferably from 1 to 4, more preferably from 1 to 2. b) The epoxy group having a fluorine atom is preferably a compound represented by the following formula (B): Λ Ν-R-CF3 ( Β ) ❹ (wherein R is a divalent organic group). R in the above formula (Β) is preferably a divalent organic group having one or more alicyclic or aromatic rings. The alicyclic ring is preferably an alicyclic ring having 3 to 20 carbon atoms, and examples thereof include a cyclopentane ring and a cyclohexane ring. The aromatic ring is preferably an aromatic ring having 6 to 20 carbon atoms, and examples thereof include a benzene ring, a naphthalene ring, and an anthracene ring. The total number of carbon atoms of the divalent R is preferably from 1 to 20, more preferably from 2 to 12. As a specific example of (b) an epoxy compound having a fluorine atom,

D exemplifies, for example, 1-(diglycidylaminomethyl)-4-trifluoromethylbenzene, 1-(diglycidylaminomethyl)-3·trifluoromethylbenzene, 4-(bi-) Glycerylaminomethyl)-4'-trifluoromethylbiphenyl, 4-(diglycidylaminomethyl)-4'-(trifluoromethyl)-diphenyl ether, N,N- Diglycidyl-4-trifluoromethylaniline, N,N-diglycidyl-3-trifluoromethylaniline, 4-(diglycidylamino)-4'-trifluoromethylbiphenyl , 4-(diglycidylamino)-4'-(trifluoromethyl)-diphenyl ether, 4-(diglycidylamino)-4'-(trifluoromethyl)-diphenyl Methane, 1-(diglycidylamino)-5- -30- 200949388 trifluoromethylnaphthalene, 2-(diglycidylamino)-6-trifluoromethylnaphthalene, 1-(bi-shrink) Glycerylaminomethyl)-4-trifluoromethylcyclohexane, 1-(diglycidylamino)-4-trifluoromethylcyclohexane, 1-(diglycidylamino)- 3-trifluoromethylcyclohexane, 1-(diglycidylamino)-2-trifluoromethylcyclopentane, 1-(diglycidylaminomethyl)-4-trifluoromethoxy Benzobenzene, 1-(diglycidyl) Aminomethyl)-3-trifluoromethoxybenzene, 4-(diglycidylaminomethyl)-4'-trifluoromethoxybiphenyl, 4-(diglycidylamino) -4'-(Trifluoromethoxy)-diphenyl ether, hydrazine, hydrazine-diglycidyl-4-trifluoromethyl methoxyaniline, hydrazine, hydrazine-diglycidyl-3-tri Fluoromethoxyaniline, 4-(diglycidylamino)-4'-trifluoromethoxybiphenyl, 4-(diglycidylamino)-4'-(trifluoromethoxy)- Diphenyl ether, 4-(diglycidylamino)-4'-(trifluoromethoxy)diphenylmethane, 1-(diglycidylamino)-5-trifluoromethoxy Naphthalene, 2-(diglycidylamino)-6-trifluoromethoxynaphthalene, 1-(diglycidylaminomethyl)-4-trifluoromethoxycyclohexane, 1-(two Glycidylamino)-4-trifluoromethoxycyclohexane, 1-(diglycidylamino)-3-trifluoromethoxycyclohexane, 1-(diglycidylamino) Mercapto)-4-trifluoromethoxycyclohexane, 1-(diglycidylamino)-2-trifluoromethoxycyclopentane, and the like. Among them, preferred is 1-(diglycidylaminomethyl)-4-trifluoromethylbenzene, hydrazine, hydrazine-diglycidyl-4-trifluoromethylaniline, 1-(diglycidylamine) Methyl)-4-trifluoromethylcyclohexane, 1-(diglycidylamino)-4-trifluoromethylcyclohexane, 1-(diglycidylaminomethyl)-4 -trifluoromethoxybenzene, hydrazine, hydrazine-diglycidyl-4-trifluoromethoxyaniline, 1-(diglycidylaminomethyl)-4-trifluoromethoxycyclohexane, and 1-(diglycidylamino)-4-trifluoromethoxycyclohexane, particularly preferably selected from the group consisting of 1-(diglycidyl-31 - 200949388-aminomethyl)-4-trifluoromethyl One or more of the group consisting of benzene, N,N-diglycidyl-4-trifluoromethylaniline and 1-(diglycidylaminomethyl)-4-trifluoromethylcyclohexane. The use ratio of the (b) epoxy group-containing epoxy compound in the liquid crystal alignment agent of the present invention is preferably from 1 to 40 parts by weight, more preferably 〇·5, based on 100 parts by weight of the (a) polymer. It is preferably 30 to 30 parts by weight, particularly preferably 1 to 20 parts by weight. The use of such a range does not cause the disadvantages of insufficient affinity, poor mechanical strength, and poor electrical properties associated with the formed liquid crystal alignment film, and it is possible to use ODF liquid crystal charging in the manufacturing steps of the liquid crystal display element. In the mode, the liquid crystal wet extensibility is more excellent, and therefore it is preferable. Further, when (b) a part of the epoxy compound having a fluorine atom is used instead of the epoxy compound described below, the above content ratio is understood to be (b) the content ratio of the epoxy compound having a fluorine atom. The total ratio of the content ratio to other epoxy compounds. In the liquid crystal alignment agent of the present invention, a part of the epoxy group Q having a fluorine atom in the above (b) may be replaced with another epoxy compound, insofar as the effects and advantages of the present invention are not impaired. Examples of such other epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether. , neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6 -tetraglycidyl-2,4-hexanediol, hydrazine, hydrazine, hydrazine, Ν'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidyl) Aminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N-diglycidyl--32- 200949388 Benzylamine, N,N-diglycidylaminomethylcyclohexane, and the like. In the liquid crystal alignment agent of the present invention, when a part of (b) an epoxy compound having a fluorine atom is replaced with another epoxy compound, the use ratio of the other epoxy compound is (b) The total amount of the epoxy atom-containing epoxy compound and the other epoxy compound is preferably 90% by weight or less, more preferably 85% by weight or less, still more preferably 80% by weight or less, and particularly preferably 50% by weight or less. In the liquid crystal alignment agent of the present invention, it is preferred not to use other epoxy compounds φ <Other components> The liquid crystal alignment agent of the present invention contains the above (a) polymer and (b) an epoxy compound having a fluorine atom as an essential component, but may optionally contain other components. As such other additives, for example, a functional decane compound or the like can be mentioned. The functional decane compound may be added in order to improve the adhesion of the formed liquid crystal alignment film to the surface of the substrate. Examples of such a functional decane compound include, for example, 3-aminopropyltrimethoxydecane, 3-aminomercaptopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, and 2-amino group. Propyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, Ν(2-aminoethyl)-3-aminopropylmethyldi Methoxydecane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, Ν-ethoxycarbonyl-3-aminopropyltrimethoxydecane, Ν-ethoxycarbonyl -3_Aminopropyltriethoxydecane, Ν-triethoxydecylpropyltriethylenetriamine, N-trimethoxydecylpropyltriethylenetriamine, 1〇·Trimethoxy矽alkyl-1,4,7-triazadecane, 10-triethoxynonanyl hydrazine, ? Triazane, 9-trimethoxydecyl-3,6-diazadecyl acetate, 9-triethoxy-33- 200949388 decyl-alkyl-3,6-diazaindole Acetate, N-benzyl-3.Aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxy Baseline, N-phenyl-3-aminopropyltriethoxydecane, N-bis(oxyvinyl)-3-aminopropyltrimethoxydecane, N-bis(oxyvinyl)-3 - Aminopropyltriethoxydecane, and the like. The use ratio of these functional decane compounds is preferably 2 parts by weight or less, more preferably 0.2 parts by weight or less based on 100 parts by weight of the (a) polymer. <Liquid crystal alignment agent> The liquid crystal alignment agent of the present invention is preferably obtained by dissolving the above (a) polymer and (b) an epoxy group having a fluorine atom and optionally adding other components in an organic solvent. Formulated in a solution state. The organic solvent which can be used in the liquid crystal alignment agent of the present invention may, for example, be a solvent exemplified as a solvent used in the synthesis reaction of the specific polyaminic acid. Further, it is also possible to appropriately select a poor solvent which is exemplified as a combination of the synthesis reaction of the specific polyaminic acid. As a particularly preferable organic solvent which can be used in the liquid crystal alignment agent of the present invention, for example, N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactone, hydrazine, hydrazine-dimethyl group can be mentioned. Formamide, hydrazine, hydrazine-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methoxypropionate Ester, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve), ethylene glycol Ethyl ether, ethylene glycol ethyl ether acetate, diglyme, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol Monoethyl ether acetate, isoamyl propionate, isoamyl isobutyrate, isoamyl ether, and the like. They can be used alone or in combination of two -34- 200949388. In the liquid crystal alignment agent of the present invention, the solid content concentration (the ratio of the total weight of the liquid crystal alignment agent other than the solvent to the total weight of the liquid crystal alignment agent) is appropriately set in consideration of viscosity, volatility, etc., preferably 1 to 10 parts by weight. The range of %. That is, the liquid crystal alignment agent of the present invention is applied to the surface of the substrate, and then the solvent is removed to form a coating film as a liquid crystal alignment film, but when the solid content concentration is less than 1% by weight, the thickness of the coating film is too small. However, it is difficult to obtain a good liquid crystal alignment film. When the solid content concentration exceeds 10% by weight, there is a case where the thickness of the coating film is too thick and it is difficult to obtain a good liquid crystal alignment film, or the viscosity of the liquid crystal alignment agent increases. This causes a deterioration in coating performance. Further, a particularly preferable solid content concentration range differs depending on the method used when the liquid crystal alignment agent is applied to the substrate. For example, when the spin coating method is employed, it is particularly preferably in the range of 1.5 to 4.5% by weight. When the printing method is employed, it is particularly preferable that the solid content concentration is in the range of 3 to 9 % by weight, so that the solution viscosity can be made to fall within the range of 12 to 50 mPa_s. When the ink jet method is employed, it is particularly preferable that the solid content concentration of ruthenium is in the range of 1 to 5 % by weight, so that the viscosity of the solution can be made to fall within the range of 3 to 15 mPa·s. The temperature at which the liquid crystal alignment agent of the present invention is formulated is preferably 〇 ° C to 200 ° C, more preferably 20 ° C to 60 ° C. <Liquid Crystal Display Element> The liquid crystal display element of the present invention has a liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention as described above. The liquid crystal display element of the present invention can be produced, for example, by the following method. -35- 200949388 First, the liquid crystal alignment agent of the present invention is applied to a substrate provided with a patterned transparent conductive film by an appropriate coating method such as a roll coating method, a spin coating method, a printing method, or an inkjet method. One side of the conductive film is heated at a temperature of, for example, 40 to 250 ° C for 0.1 to 120 minutes to form a coating film. The thickness of the coating film is preferably 0.001 to Ιμηη' as the thickness of the solvent to be removed, and more preferably 0.005 to 0 · 5 μm. 〇 As the substrate, for example, glass such as float glass or soda lime glass or polyterephthalic acid can be used. As the transparent conductive film such as ethylene glycol ester, polybutylene terephthalate, ruthenium polyether oxime, polycarbonate or poly(alicyclic olefin), as the transparent conductive film, a NESA film made of Sn02 can be used. ITO film made of In203-Sn02. The formation of the pattern-like transparent conductive film may be a method of forming a pattern by photolithography after forming a transparent conductive film without a pattern, and forming a pattern transparently by using a photomask having a desired pattern when forming the transparent conductive film. A method of conducting a film or the like. In the application of the liquid crystal alignment agent, in order to further improve the adhesion between the substrate and the transparent conductive film and the coating film, a functional decane compound, titanate or the like may be applied to the substrate and the transparent conductive film in advance. When the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention is used for a horizontal alignment type liquid crystal display element, the formed coating film surface is then subjected to a roll wrapped with a cloth made of a fiber such as nylon, rayon, cotton or the like. Grinding treatment of direction friction. By this sanding treatment, the liquid crystal molecules can be imparted to the coating film to form a liquid crystal alignment film. Further, the liquid crystal alignment film which is formed by the liquid crystal alignment agent of the present invention is a liquid crystal alignment film as shown in the patent document 6 (Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. And a part of the surface of the liquid crystal alignment film is formed on the surface of the liquid crystal alignment film, as shown in the patent document 8 (JP-A-5-1075 44) After the polishing process is performed in a different direction from the previous polishing process, the resist film is removed, so that each region of the liquid crystal alignment film has a different liquid crystal alignment energy treatment, and the field performance of the obtained horizontal liquid crystal display element can be improved. When the liquid crystal alignment film is applied to a vertical alignment type liquid crystal display element, such a polishing process may not be performed. 0 Two substrates on which the liquid crystal alignment film was formed were prepared, and liquid crystal cells were produced by arranging liquid crystal between the two substrates. For the manufacture of liquid crystal cells, the following two methods can be listed. The first method is a previously known method. First, the two substrates are disposed to face each other through the gap (cell gap) so that the respective liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded together with a sealant to the cells surrounded by the substrate surface and the sealant. After the liquid crystal is filled in the gap and the injection hole is closed, the liquid crystal cell can be obtained.第二种 The second method is called the 〇DF (〇ne Drop Fill) method. Applying, for example, an ultraviolet curable sealant material to a predetermined portion of one of the two substrates forming the liquid crystal alignment film, and then dropping the liquid crystal on the liquid crystal alignment film surface, and bonding the other substrate to make the liquid crystal alignment film relatively The liquid crystal cell can be obtained by irradiating ultraviolet light to the entire surface of the substrate to cure the sealant. When the liquid crystal alignment agent of the present invention is used in the 0DF method, it is possible to form a liquid crystal alignment film having excellent liquid crystal moisture spreadability, which has an advantage of contributing to a drastic reduction in processing time in the liquid crystal charging step. When either method is used, it is necessary to subsequently heat the liquid crystal cell to -37-200949388. After the liquid crystal is at an isotropic phase temperature, it is slowly cooled to room temperature to remove the flow alignment during charging. Then, the liquid crystal display element of the present invention can be obtained by laminating a polarizing plate on the outer surface of the liquid crystal cell. Here, as the above-mentioned sealant, for example, an epoxy resin containing an alumina ball as a spacer and a curing agent can be used. As the liquid crystal, for example, a nematic liquid crystal, a dish-shaped liquid crystal, or the like can be used. When a liquid crystal display element having a TN type liquid crystal cell or an STN type liquid crystal cell is produced, a liquid crystal (positive liquid crystal) having positive dielectric anisotropy in a nematic liquid crystal is preferable, and for example, a biphenyl liquid crystal can be used. A phenylcyclohexane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, a biphenylcyclohexane liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, or a cuba liquid crystal. Further, in these liquid crystals, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl phthalate, and cholesteryl carbonate may be further added; and sold under the trade names "C-15" and "CB-15" (manufactured by MERCK Co., Ltd.). A chiral agent; used for ferroelectric liquid crystals such as decyloxybenzylidene-p-amino-2-methylbutyl cinnamate. On the other hand, in the case of a vertical alignment type liquid crystal cell, a liquid crystal (negative liquid crystal) having a negative dielectric anisotropy in a nematic liquid crystal is preferably used, and a diamino benzene liquid crystal or a germanium well liquid crystal may be used. Schiff base liquid crystal, oxidized azo liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, and the like. The polarizing plate used for the outer side of the liquid crystal cell may be a polarizing plate obtained by sandwiching a polarizing film called "H film" obtained by stretching and dispersing polyvinyl alcohol and absorbing iodine, in a cellulose acetate protective film, or a film made by itself. A polarizing plate. -38- 200949388 The liquid crystal display element of the present invention thus produced exhibits excellent display quality without display failure caused by uneven alignment of liquid crystal. [Examples] In the following synthesis examples, the solution viscosity of the polymer solution was measured by an E-type viscometer at 25 °C. The ruthenium imidization ratio of the ruthenium iodide polymer is obtained by dissolving the ruthenium iodide polymer under sufficient pressure at room temperature, and then dissolving it in deuterated dimethyl quinone, using tetramethyl decane as a reference material. From the measured 1 H-NMR, the above formula (1) was used. <Synthesis of Polylysine> Synthesis Example 1 10 g (0.50 mol) of pyromellitic dianhydride as tetracarboxylic dianhydride and 1,2,3,4-cyclobutane tetracarboxylic dianhydride 98 g (0.50 mol), dissolved in 200 g of N-methyl-2-leoleol and 2060 g of γ-butane with 4,4'-diaminodiphenyl ether as a diamine (1.0 mol) The mixed solvent of the ester composition is at 4 Torr. After the reaction was carried out for 3 hours, I 3 50 g of γ-butyrolactone was added to obtain a solution of about 39 〇〇g of a polyglycolic acid (A-1) containing 10% by weight. The solution viscosity of the polyamic acid solution was 200 mPa·s® Synthesis Example 2 98 g (0.50 mol) of 1,2,3,4·cyclobutane tetracarboxylic dianhydride as tetracarboxylic dianhydride and both Pyromellitic dianhydride 11〇g (〇5〇莫耳), and 4,4′-diaminodiphenylmethane 2〇〇g (1〇mol) as a diamine dissolved in 23〇gN_甲After reacting at 40 ° C for 3 hours in a mixed solvent of ketone-2-carrolidone and 2〇6〇g γ-butyrolactone, 135 〇g γ-butyrolactone was added to obtain about 4000 g of 1 A solution of 〇% by weight of polyaminic acid (Α-2). The solution viscosity of the poly-aramidic acid-39-200949388 solution was 125 mPa.s. Synthesis Example 3 200 g (1.0 mol) of 1,2,3,4-ring as tetracarboxylic dianhydride and 44'·200 g (1.0 mol) as diamine were dissolved in 230 g of N-methyl-2. In a mixed solvent of pyridone lactone, 1300 g of γ-butyrolactone was added at 4 ° C to obtain a solution of about 39 〇〇 8; ; acid (Α - 3 ). ❹ mP a· s ° of the polyaminic acid solution Synthesis Example 4 ι, 2, 3, 4-ring 200 g (1.0 mol) as tetracarboxylic dianhydride, and 2, 2, - as diamine Two-year benzene 210 g (1.0 mol) was dissolved in a mixed solvent consisting of 37 〇g of N-methyl-2-γ-butyrolactone at 40. (3, 4000 g of a solution containing 10% by weight of polyaminic acid a-amino acid solution was obtained, and the viscosity of the solution was 16 〇mPa.s. 〇Synthesis Example 5 2,3,5-tricarboxylate as a tetracarboxylic dianhydride 220 g (1.0 mol), dissolved in 4,4,. 200 g (1.0 mol) as a diamine in a mixed solvent consisting of 24 g of N-methyl-2-pyridolactone, under 4〇»c About 4700 g of a solution containing poly-proline (A_5) was added to the γ-butyrolactone to prepare a solution having a polyglycine concentration of 10 and a solution viscosity of 38 mPa·s. Synthesis Example 6 Butane tetracarboxylic dianhydride II After reacting the aminodiphenyl ether L-alkanone with 2020g Y-line for 4 hours, the viscosity of the 10% by weight polyamine solution is 210 butane tetracarboxylic dianhydride-4,4'-diaminopyrrolidone and 3300g was reacted for 3 hours, 4 solution. The polyfluorene I cyclopentyl acetic acid dianhydride • diaminodiphenyl ether cyano ketone and 2200g γ-line reaction for 4 hours, a small amount of the solution, weight% Solution, measured -40-200949388 2,3,5-tricarboxycyclopentyl acetic acid dianhydride 110 g (0.50 mol) and 1,3,3a,4,5,9b-hexahydrogen as tetracarboxylic dianhydride -8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl -Naphthalene [l,2-c]-furan-l,3-dione 160g (0.50 mol), with p-phenylenediamine as a diamine 95g (0.88 mol), 2,2-bis (trifluoro Methyl)-4,4-diaminobiphenyl 32 g (0.1 Torr), 3,6-bis(4-aminobenzylideneoxy)cholane (a compound represented by the above formula (D-1), The same as below) 6.4g (0. 〇l〇 Mo) and octadecyloxy-2,5-diaminobenzene 4.0g (0.015 mol) dissolved in 960g N-methyl-2-pyrrolidone, at 60 The reaction was carried out for 9 hours at a temperature of ° C. A small amount of the obtained polyaminic acid solution was added, and N-methyl-2-pyrrolidone was added to prepare a solution having a polyglycine concentration of 1% by weight, and the solution viscosity was determined to be 58 mPa. , s. 2740g of N-methyl-2-pyrrolidone, 400g of pyridine and 410g of acetic anhydride were added to the obtained polyamic acid solution, and the dehydration ring-closure reaction was carried out for 4 hours under ll〇t. After dehydration ring closure reaction, the system was passed through The solvent is replaced with a new γ-butyrolactone (by this operation, the pyridine and acetic anhydride used in the oxime imidization reaction are removed to the outside of the system. The same applies hereinafter) to obtain about 25 〇〇g of yttrium. % 醯 imidization rate is about 95 % 醯iminated polymer (B- 〇 solution. A small amount of this solution was added, butyrolactone was added to form a solution having a ruthenium polymer concentration of 10% by weight, and the solution viscosity was determined to be 69 mPa·s. Synthesis Example 7 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride 110 g (0.50 mol) and 1,3,3a,4,5,9b-hexahydro·8·A -5-(tetrahydro-2,5-oxo-3-furanyl)-naphthalene [i,2-c]-furan-indole, ;dione 16 〇g (〇5〇莫耳)' And p-phenylenediamine as a diamine 96g (0.89 mol), bis(aminopropyl) tetramethyl-decane 25g (0.10 mol) and 3 6_bis (4-aminobenzidine) -41- 200949388 base) Cholesterane 13g (〇.020 mol) and as a monoamine Ν·8-yard amine 8_lg (0.030 mol) dissolved in 960g N-methyl-2-pyrrolidone at 60° The reaction was carried out for 6 hours under C. Take a small amount of the obtained poly-proline solution, add methyl-2-pyrrolidone, and prepare a solution having a concentration of polyamidic acid of 1% by weight, and measure the viscosity of the solution to 60 mPa_s. Then, the obtained polyamine 2700 g of N-methyl-2-pyrrolidone was added to the acid solution, and 400 g of pyridine and 410 g of acetic anhydride were further added to carry out a dehydration ring-closure reaction at ll ° C for 4 hours. After dehydration ring closure reaction, 'solvent was replaced with a new γ-butyrolactone solvent to obtain about 2400 g of a ruthenium iodide polymer containing 15% by weight of ruthenium iodide (About 95%) (B- 2) solution. A small amount of this solution was taken, and γ-butyrolactone was added to prepare a solution having a concentration of ruthenium iodide polymer of 10% by weight, and the viscosity of the solution was determined to be 7 〇 mPa-s. Synthesis Example 8 220 g (1.0 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, and 110 g (0.99 mol) and 3 as p-phenylenediamine as a diamine. 6-bis(4-aminobenzylideneoxy)cholestane 6.4 g (0-010 mol) was dissolved in 〇3 04 0 g of N-methyl-2-pyrrolidone and reacted at 60 ° C for 6 hours to obtain A poly-proline solution with a solution viscosity of approximately 260 mPai. Then, 2700 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 400 g of pyridine and 310 g of acetic anhydride were further added, and a dehydration ring-closure reaction was carried out for 4 hours under ii〇-C. After the dehydration ring closure reaction, the solvent in the system was replaced with a new γ-butyrolactone to obtain about 290 g of a ruthenium iodide polymer containing 10% by weight of a ruthenium iodide ratio of about 89% (B_3). The solution has a solution viscosity of 300 mPa.s. Synthesis Example 9 -42- 200949388 2,3,5-tricarboxycyclopentylacetic acid dianhydride g (〇·50 mol) and 1,3,3&, 4,5,91> as tetracarboxylic dianhydride ;-Hexahydro-8-methyl-5-(tetrahydro-2,5-oxo 3 furanyl^naphthalene^,]-.]·furan I,]·dione i6〇g (〇5〇莫耳As an amine, p-phenylenediamine 89g (〇82 mole), 2,2,_bis(trifluoromethyl)4,4-aminobiphenyl 32g(3)1〇mol" diaminobenzhydryloxy -4-(4-trifluoromethylbenzylideneoxy)-cyclohexane (compound represented by the above formula (d-14)) 25 g (〇.〇59 mol) and octadecyloxy_2 5,5-aminobenzene 4. (^ (0.0 ^ Moer) dissolved in 218 〇g N methyl · 2 pyrrolidone in 〇 60 C into fj 6 hours reaction. Take a small amount of the resulting poly-proline solution, add N - The solution viscosity of the solution of methyl-2-pyridylpyrrolidone formulated as a polyglycine concentration of 1% by weight was 11〇mPa.s. 15〇〇g in the obtained polyaminic acid solution was obtained. Adding 3000 g of N-methyl-2-pyrrolidone to it and adding 221 g of pyridine and 228 g of acetic anhydride, and performing a dehydration ring-closure reaction at 110 ° C for 4 hours. The solvent in the system was subjected to solvent replacement with a new γ-butyrolactone to obtain a solution of about 2500 g of a ruthenium imidized polymer (B-4) having a ruthenium iodide ratio of about 92% by weight of about 92%. The solution viscosity of this solution was 130 mP a·s. Synthesis Example 10 110 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride as a diamine pair Phenyldiamine 43g (0.40 moles) and 3-(3,5-diaminobenzylideneoxy)cholestane 52g (0.10 moles) are dissolved in 83 0g N-methyl-2-pyrrolidone, The reaction was carried out for 6 hours at 60 ° C. A small amount of the obtained polyaminic acid solution was added, and N-methyl-2-pyrrolidone was added to prepare a solution having a polyglycine concentration of 1% by weight. The viscosity of the solution was 6〇. mPa.s Then, 190 gram of N-methyl-2-43-200949388 pyrrolidone was added to the obtained polyaminic acid solution, and 40 g of pyridine and 51 g of acetic anhydride were further added, and dehydration was carried out at U 〇 ° C for 4 hours. Closed-loop reaction. After the dehydration ring-closing reaction, the solvent in the system is replaced with a new N-methyl-2-pyrrolidone to obtain about 1200 g of 15% by weight of ruthenium amide. 50% solution of ruthenium iodide polymer (B-5). A small amount of this solution was added, and N-methyl-2-pyrrolidone was added to prepare a solution having a concentration of 10% by weight of the ruthenium polymer. The solution viscosity was 47 mPa*s. Synthesis Example 1 1 2 2,3,5-tricarboxycyclopentyl acetic acid dianhydride 110 g (0.50 mol) as tetracarboxylic dianhydride, and p-phenylene as diamine Amine 49g (0.45 moles) and 3-(3,5-diaminobenzylideneoxy)cholestane 26g (0.05 moles) are dissolved in 7 50g of N-methyl-2.pyrrolidone at 60° The reaction was carried out for 6 hours under C. Take a small amount of the obtained polyaminic acid solution, add N-methyl-2-pyrrolidone, and prepare a solution having a polyglycine concentration of 1% by weight. The measured solution viscosity is 58 m P a · s ° and then To the polyaminic acid solution, 1 800 g of N-methyl-2-indolylpyrrolidone was added, and further 40 g of pyridine and 51 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone to obtain about 〇〇μg of a ruthenium iodide containing 15% by weight of a ruthenium iodide of about 50%. A solution of the polymer (B-6). A small amount of this solution was taken, and N-methyl-2-pyrrolidone was added to prepare a solution having a ruthenium-imided polymer concentration of 10% by weight, and the solution viscosity was determined to be 85 mPa_s. Synthesis Example 1 2 2,3,5-tricarboxycyclopentylacetic acid dianhydride-44-200949388 110 g (0.50 mol) as a tetracarboxylic dianhydride, and 38 g of p-phenylenediamine as a diamine (〇35) Molar), 4,4-diaminodiphenylmethane 2 (^(〇.1 mol) and 3-(3,5-diaminobenzylideneoxy)cholestane 26 g (0.05 mol) Dissolved in 750g of N-methyl-2-pyrrolidone and reacted at 60 °C for 6 hours. Take a small amount of the obtained polyamic acid solution 'addition of N-methyl-2-pyrrolidone to form polyamine The solution having an acid concentration of 1% by weight was measured to have a solution viscosity of 60 mPa·s. Then, 1 800 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 40 g of pyridine and 51 g of acetic anhydride were further added. After 4 hours of dehydration ring closure reaction at ll 〇 ° C. After the dehydration ring closure reaction, the solvent in the system was replaced with a new γ-butyrolactone solvent to obtain about 1150 g containing 15% by weight of ruthenium amide. A solution of about 50 ° / 醯 imidized polymer (B-7). A small amount of this solution was added, γ-butyrolactone was added, and a solution having a concentration of 10% by weight of the ruthenium polymer was determined. Solution viscosity 87 mP as. Synthesis Example 1 3 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic dianhydride 77 g (0.34 mol), and p-phenylenediamine as a diamine 30 g (0-27) The compound represented by the above formula (D-3) 34 g (0.0 7 mol) was dissolved in 560 g of N-methyl-2-pyrrolidone, and the reaction was carried out at 60 ° C for 4 hours. The proline solution was added with N·methyl-2-pyrrolidone to form a solution having a polyglycine concentration of 10% by weight, and the viscosity of the solution was determined to be 137 mP a·s. Then, the obtained polyaminic acid solution was obtained. Add 1300g of N-methyl-2-pyrrolidone, add 27g of pyridine and 35g of acetic anhydride, and carry out dehydration ring-closure reaction at 110 ° C for 4 hours. After dehydration ring closure reaction, by using the solvent in the system with new N- The solvent was replaced with benzyl-2-pyrrolidone to obtain a solution of about 7 l g of a ruthenium iodide polymer-45-200949388 (B-8) containing 13% by weight of a ruthenium iodide ratio of about 50%. The solution was added with N-methyl-2-pyrrolidone to prepare a solution having a ruthenium-imided polymer concentration of 10% by weight, and the measured solution viscosity was 98 mPa·s. 1 4 74 g (0.33 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 27 g (0.25 mol) of p-phenylenediamine as diamine, and the above formula (D) -33) The compound represented by 33 g (0.07 mol) and the compound of the above formula (D-12), 7 g (0.02 mol), are dissolved in 560 g of N-methyl-2-pyrrolidone oxime, and are carried out at 60 ° C. Hour response. A small amount of the obtained polyaminic acid solution was taken, and N-methyl-2-pyrrolidinium was added to prepare a solution having a polyglycine concentration of 1% by weight, and the solution viscosity was determined to be 124 mP a.s. Then, 1300 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 26 g of pyridine and 34 g of acetic anhydride were further added thereto at 11 Torr. (: 4 hours of dehydration ring closure reaction. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone solvent to obtain about 660 g of 17% by weight of ruthenium amide. a solution of 5〇% of the ruthenium iodide polymer (B-9). A small amount of this solution is added, and N·methyl-2-pyrrolidone is added to prepare a solution having a concentration of ruthenium iodide polymer of 1% by weight. The measured solution viscosity was 90 mPa·s. Synthesis Example 15 25 g (0.34 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetradecanoic dianhydride, and p-benzene as an amine 25 g of diamine (〇25 mol), compound of the above formula (D-3) 25 g (〇〇5 mol) 2,2,_trifluoromethyl • 4,4 aminobiphenyl 5 〇g (〇 〇2mol) and 4 trifluoromethylbenzyl methoxy)cyclohexyl-3,5-diaminobenzoate 7. 〇g (〇_〇2 mol) dissolved in -46- 200949388 560g In N-methyl-2-pyrrolidone, the reaction was carried out at 60 ° C for 4 hours. A small amount of the obtained polyaminic acid solution was added, N-methyl-2-pyrrolidone was added, and a solution having a polyglycine concentration of 10% by weight was prepared, and the solution viscosity was determined to be 110 mPa·s. Then, the obtained polyamine was obtained. To the acid solution, 1 300 g of N-methyl-2-pyrrolidone was added, and further 27 g of pyridine and 34 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone to obtain about 7 〇〇g of yttrium imine containing 16% by weight of hydrazine imidization rate of about 50%. A solution of the polymer (B-10). A small amount of this solution was added, and N-methyl-2-pyrrolidone was added to prepare a solution having a ruthenium-imided polymer concentration of 10% by weight, and the solution viscosity was determined to be 87 mPai. Synthesis Example 1 6 (2,3,5-tricarboxycyclopentylacetic acid dianhydride as a tetracarboxylic dianhydride, 69 g (0.31 mol), and p-phenylenediamine 20 g (0.19 mol) as a diamine, the above Compound (31 g (0.06 mol) represented by formula (D-3) and compound 26g (0.06 mol) represented by the above formula (D-〇12) are dissolved in 560 g of N-methyl-2-pyrrolidone at 60 ° C The reaction was carried out for 4 hours. A small amount of the obtained polyaminic acid solution was added, and N-methyl-2-pyrrolidone was added to prepare a solution having a polyglycine concentration of 10% by weight, and the solution viscosity was measured to be 119 mPa·s. Then, 1 300 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 24 g of pyridine and 32 g of acetic anhydride were further added, and a dehydration ring-closure reaction was carried out for 4 hours at ll °C. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone to obtain about 650 g of a ruthenium-imiding polymer containing 16% by weight of a ruthenium iodide ratio of about 50%. 47- 200949388 (B-11) solution. A small amount of this solution was added, and N-methyl-2-pyrrolidone was added to prepare a solution having a ruthenium iodide polymer concentration of 10% by weight, and the solution viscosity was determined to be 84 mPa-s. Example 1 <Preparation of Liquid Crystal Aligning Agent> The solution containing the polyaminic acid (A-1) obtained in the above Synthesis Example 1 is converted into polyglycine (A-1) in an amount corresponding to 80 parts by weight and contained. The solution of the oxime imidized polymer-1) obtained in the above Synthesis Example 6 is mixed in an amount corresponding to 20 parts by weight in terms of 醯φ imidized polymer (B-1), and added thereto as having a fluorine atom. 10 parts by weight of an epoxy compound (diglycidylaminomethyl)-4-trifluoromethylbenzene, followed by a mixed solvent of N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) (mixing ratio NMP : BC = 50 : 50 (weight ratio)), and a solution having a solid content concentration of 3% by weight was prepared. This solution was filtered through a filter having a pore size of Ιμηη to prepare a liquid crystal alignment agent. This liquid crystal alignment agent was evaluated as follows. <Evaluation of Moisture Spreadability> Ο The above-prepared liquid crystal alignment agent was applied onto a transparent electrode surface of a glass substrate with a transparent electrode made of a ruthenium film by a spin coater, and prebaked on a hot plate at 80 ° C After 1 minute, it was post-baked on a hot plate at 200 ° C for 10 minutes to form a coating film having an average film thickness of 600 Å. 5 pL of liquid crystal (MLC-622 1 manufactured by MERCK Co., Ltd.) was dropped on the coating film, and the contact angle between the coating film and the liquid crystal was measured, and the contact angle was 12.4°. In addition, the inventors found that the liquid crystal dropping method (ODF method) was employed. The time required for the liquid crystal charging step depends on the affinity of the liquid crystal alignment film to the liquid crystal. Further, it is known from experience that when the contact angle is 13 or less, the wetness spread of the liquid -48-200949388 crystal is good. At this time, the time required for the liquid crystal charging step can be sufficiently shortened. <Production of ΤΝ-type liquid crystal cell> Using the liquid crystal alignment agent prepared above, and the above <Evaluation of liquid crystal wet extensibility> In the same manner, a coating film having an average film thickness of 60 Å was formed on the transparent electrode surface of a glass substrate having a transparent electrode made of a ruthenium film. The 0 coating film was polished by a grinding machine equipped with a roller wound with a rayon cloth at a roller speed of 500 rpm, a table moving speed of 3 cm / sec, and a fluffing length of 0.4 mm. A liquid crystal alignment film is formed by imparting liquid crystal alignment energy thereto. These operations were repeated to obtain a pair (two pieces) of substrates having a liquid crystal alignment film on the surface of the transparent electrode. Then, an epoxy resin adhesive having an alumina ball having a diameter of 5·5 μm is applied to each outer edge of the surface of the pair of substrates having the liquid crystal alignment film, and then the polishing direction of each liquid crystal alignment film surface is applied. At 90°, it is relatively heavy and combined, and the adhesive is cured. Then, the liquid crystal injection port was used to charge the liquid crystal (MLC-622 1 manufactured by MERCK Co., Ltd.) to the substrate, and then the liquid crystal injection port was sealed with an acrylic photocurable adhesive to produce a liquid crystal cell. <Evaluation of Liquid Crystal Alignment> When the voltage of 5 V was turned on and off (applied and released) at room temperature by a polarizing microscope, the presence or absence of an abnormal region was observed, and the liquid crystal alignment property was evaluated as "good" when there was no abnormal region. The liquid crystal alignment of the above liquid crystal cell is "good". <Evaluation of Voltage Retention Rate> At 60 ° C, a voltage of 5 V was applied to the liquid crystal cell manufactured above at a time span of 167 msec, and the voltage application time was 60 μm, and then -49- 200949388 The voltage holding ratio after the voltage is released to 167 milliseconds, the voltage holding ratio of the liquid crystal cell is 99.0%. The voltage holding ratio was measured by the "VHR-1" type manufactured by TOYO Corporation. <Measurement of residual voltage> A direct current voltage of 17.0 V was applied to the liquid crystal cell produced above at 100 ° C for 20 hours. Immediately after the application of the DC voltage was released, the temperature was allowed to stand at room temperature for 15 minutes, and then the residual voltage in the liquid crystal cell was determined by the scintillation elimination method. At this time, when the residual voltage was 800 mV or less, the residual voltage was evaluated as "good". The residual voltage of the liquid crystal cell was "good". Examples 2 to 1 2 were respectively used to contain the polymer shown in Table 1. The solution is a solution containing a polyphthalic acid and a solution containing a ruthenium iodide polymer, and the kind and amount of the epoxy compound having a fluorine atom are as shown in Table 1, respectively, and Example 1 The liquid crystal alignment agent was prepared and evaluated in the same manner. The results are shown in Table 1. In addition, in Table 1, the abbreviations of the types of the epoxy compound having a fluorine atom are as follows. E-1: 1-( Diglycidylaminomethyl)_4_trifluoromethylbenzene E-2: 1-(diglycidylaminomethyl)_4·trifluoromethylcyclohexane. Comparative Examples 1 to 6 were used separately. A solution containing the polymer shown in Table 2 was used as a solution containing a polyglycine and a solution containing a ruthenium iodide polymer, and only the epoxy group-containing epoxy group shown in Table 2 was used. Ν,Ν,Ν',Ν'-tetraglycidyl-4,4'-diaminodiphenylmethane A liquid crystal alignment agent was prepared in the same manner as in Example 1 except that the epoxy group-containing compound having a fluorine atom was used, and evaluation was carried out in the range of -50 to 200949388. The results are shown in Table 2. Table 1

Liquid crystal alignment agent evaluation result Polyphosphonium imide amide polymerized epoxy compound having fluorine atom liquid crystal contact angle liquid crystal alignment voltage retention ratio (%) Residual voltage type type and amount (parts by weight) 〇 Example 1 A -1 B-1 E-1 10 12.4 Good 99.0 Good Example 2 A-1 B-2 E-1 10 11.7 Good 99.4 Good Example 3 A-1 B-3 E-1 10 11.9 Good 99.4 Good Example 4 A-1 B-4 E-1 10 12.1 Good 99.4 Good Example 5 A-2 B-1 E-1 10 12.0 Good 99.2 Good Example 6 A-3 B-1 E-1 10 12.3 Good 99.2 Good Example 7 A-4 B-1 E-1 10 12.0 Good 99.2 Good Example 8 A-5 Β·1 E-1 10 11.6 Good 99.0 Good Example 9 A-1 B-1 E-1 20 12.1 Good 99.1 Good implementation Example 10 Α·1 B-1 E-1 30 11.8 Good 99.0 Good Example 11 A-1 B-1 E-2 10 12.3 Good 98.9 Good Example 12 A-1 B-1 E-2 30 11.5 Good 98.8 Good Liquid crystal alignment agent evaluation result Polyamine type 醯imination polymer type Amount of fluorine atom-free epoxy compound (parts by weight) Liquid crystal contact angle (.) Crystal alignment voltage retention ratio (%) Residual voltage comparison example 1 Α·1 B-1 10 15.4 Good 99.0 Good Comparative Example 2 A-1 B-1 20 14.8 Good 99.2 Good Comparative Example 3 A-1 B-2 10 14.7 Good 99.0 Good Comparative Example 4 A-1 B-3 10 15.2 Good 99.1 Good Comparative Example 5 A-2 B-1 10 14.8 Good 99.0 Good Comparative Example 6 A-3 B-1 10 14.6 Good 99.1 Good -51 - 200949388 Implementation Example 1 3 &lt;Preparation of Liquid Crystal Aligning Agent&gt; The ruthenium iodide polymer obtained in the above Synthesis Example 10 was obtained in an amount equivalent to 1 part by weight in terms of the ruthenium iodide polymer (B-5). a solution of B-5) to which 5 parts by weight of 1-(diglycidylaminomethyl)-4-trifluoromethylbenzene as an epoxy compound having a fluorine atom is added, and N-methyl group is further added thereto. A mixed solvent composed of -2-pyrrolidone (NMP) and butyl cellosolve (BC) (mixing ratio NMP: BC = 50:50 (weight ratio)) was formulated into a solution having a solid content concentration of Q 2.5 wt%. This solution was filtered through a filter having a pore size of 1 μm to prepare a liquid crystal alignment agent. This liquid crystal alignment agent was evaluated as follows. &lt;Evaluation of liquid crystal wet extensibility&gt; The liquid crystal alignment agent prepared above was used, and the liquid crystal used was MLC-6608 manufactured by MERCK Co., Ltd., and was the same as the evaluation of liquid crystal wet extensibility in Example 1. The contact angle of the coating film with the liquid crystal was measured. The results are shown in Table 3. &lt;Evaluation of adhesion of liquid crystal alignment film&gt; The above-prepared liquid crystal alignment agent was applied onto one surface of a rectangular glass substrate by spin coating, and prebaked on a hot plate at 80 ° C for 1 minute and then at 200 ° The hot plate of C was post-baked for 10 minutes to form a coating film having an average film thickness of 600 Å. The same operation was repeated to obtain a pair of (two pieces) rectangular glass substrates having a coating film on one side. One of the substrates having the formed coating film was taken, and 0.1 mg of a sealant (an ultraviolet curable sealant containing 2.0% by weight of a spherical separator having a diameter of 3.5 μm) was dropped on a substantially central portion of the coating film surface. The other substrate is superposed on the other side of the substrate so that the surface of the coating film is opposed to each other. The two substrates are pressed one by one by pressing -52-.200949388 and the coating film faces are reversed in the horizontal plane, so that the two substrates are dropped by the sealant. A cross shape is formed for the joint portion. By this operation, the sealant was extruded and expanded into a circular shape having a diameter of 4.8 to 5.2 mm. Then, it was irradiated with ultraviolet rays having a 365 urn bright line and a strength of 1 〇 W mW for 30 seconds, and then heated in an oven at 120 ° C for 1 hour to cure the sealant, thereby preparing a test article for evaluation of adhesion. A tensile compression tester (model "SDWS — 0201 - 100SL") manufactured by Ida Manufacturing Co., Ltd. was used, and the test article was adhered as follows. The test piece is mounted on a 3-shaped gantry such that one of the substrates is horizontally positioned on the gantry through the two ends of the outer portion of the cross-shaped contact portion (center portion), and the other substrate is not in contact with the gantry to be positioned on the gantry The underside. Then, a three-shaped pressing jig was attached to the mounted test piece so that only the both end portions on the outer side of the cross-shaped contact portion (center portion) in the lower substrate were pressed downward. In this state, pressure is applied to the jig for pressing from the upper direction, and the two glass substrates bonded by the coating film and the sealant are biased toward the separated side. At this time, the force required to break the adhesive interface of the substrate (Fsai) was also observed. In addition, a test piece for evaluation of adhesion was prepared in the same manner as above, and a adhesion test was performed in the same manner as above. The force (Fref) required to break the adhesion interface of the substrate. The enthalpy of Fsam divided by Fref is shown in Table 3. In addition, the above Fsam and Fref are calculated by calculating the average 値 of 5 points. &lt;Production and Evaluation of VA Type Liquid Crystal Cell&gt; In the <Production of &lt;TN Type Liquid Crystal Cell of Example 1>, 'The liquid crystal used was not produced by the -53-200949388 grinding process, and the liquid crystal used was produced by MERCK Corporation. In the same manner as in the production of the &lt;TN type liquid crystal cell in the first embodiment, the VA type liquid crystal cell was produced in the same manner as in the first embodiment. The liquid crystal alignment property and the voltage holding ratio were similar to those in the first embodiment. Evaluation of residual voltage. The evaluation results are shown in Table 3. Example 1 4 to 4 6 A solution containing the polymer shown in Table 3 was used as a solution containing a quinone imidized polymer, and a ring having a fluorine atom. Type of oxy compound The liquid crystal alignment agent was prepared and evaluated in the same manner as in Example 1 except that the amounts of Q were as shown in Table 3. The results are shown in Table 3. In addition, the epoxy group having a fluorine atom in Table 3 was used. The abbreviations of the species are the same as those in Table 1. Comparative Examples 7 to 2 7 A solution containing the polymer shown in Table 4 was used as a solution containing a quinone imidized polymer, and only the use shown in Table 4 was used. Amount of fluorine-free atom-containing epoxy compound 1^,1^,1^',]^'-tetraglycidyl-4,4'-diaminodiphenylphenylmethane instead of a ring having a fluorine atom A liquid crystal alignment agent was prepared and evaluated in the same manner as in Example 13 except that the oxy compound was used. The results are shown in Table 4 〇-54- 200949388 Table 3

Evaluation result of the liquid crystal alignment agent The liquid crystal contact angle of the epoxy group having a fluorine atom with the imidized polymer type [·) Adhesion liquid crystal alignment voltage retention ratio (%) of the liquid crystal alignment film Residual voltage type (parts by weight) Example 13 B-5 E-1 5 12.3 0.40 Good 99.3 Good Example 14 B-5 E-1 10 12.3 0.42 Good 99.0 Good Example 15 B-6 E-1 5 11.8 0.50 Good 99.3 Good Example 16 B-6 E-1 10 11.6 0.52 Good 99.2 Good Example 17 B-7 E-1 5 11.6 0.59 Good 99.4 Good Example 18 B-7 E-1 10 11.4 0.62 Good 99.1 Good Example 19 B-5 E-1 20 11.8 0.45 Good 99.0 Good Example 20 B-5 E-1 30 12.1 0.48 Good 98.6 Good Example 21 B-5 E-2 5 11.9 0.41 Good 99.3 Good Example 22 Β·5 E-2 10 11.7 0.43 Good 99.3 Good implementation Example 23 Β-6 E-2 5 12.3 0.48 Good 99.1 Good Example 24 Β-6 E-2 10 11.9 0.50 Good 99.0 Good Example 25 Β-7 E-2 5 12.1 0.57 Good 99.3 Good Example 26 Β·7 E-2 10 12.2 0.59 Good 99.2 Good Practice 27 B-5 E-2 20 11 .6 0.44 Good 99.0 Good Example 28 B-5 E-2 30 11.7 0.46 Good 98.5 Good Example 29 B-6 E-2 20 11.7 0.53 Good 99.1 Good Example 30 B-6 E-2 30 12.3 0.55 Good 98.5 Good Example 31 B-8 E-1 5 11.4 0.67 Good 99.4 Good Example 32 B-8 E-1 10 11.3 0.71 Good 99.2 Good Example 33 B-8 E-1 20 11.4 0.75 Good 99.1 Good Example 34 B -8 E-1 30 11.2 0.76 Good 99.0 Good Example 35 B-9 E-1 5 11.3 0.74 Good 99,0 Good Example 36 B-9 E-1 10 11.1 0.79 Good 99.0 Good Example 37 B-9 E -1 20 10.7 0.80 good 98.9 good example 38 B-9 E-1 30 10.6 0.85 good 98.7 good example 39 B-10 E-1 5 9.0 0.84 good 98.8 good example 40 B-10 E-1 10 8.8 0.86 Good 98.7 Good example 41 B-10 E-1 20 8.4 0,90 Good 98.5 Good example 42 B-10 E-1 30 8.3 0.92 Good 98.4 Good example 43 B-ll E-1 5 10.8 0.83 Good 98.8 Good Example 44 B-ll E-1 10 10.7 0.85 Good 98.8 Good Example 45 B-ll E-1 20 10.4 0.86 Good 98.4 Good Example 46 B-ll E- 1 30 10.3 0.90 Good 98.6 Good -55- 200949388 Table 4

Night crystal alignment agent parity result 醯i-imidized polymer type The amount of epoxy group-free epoxy compound (parts by weight) Liquid crystal contact angle 黏 Liquid crystal alignment film adhesion liquid crystal alignment voltage retention ratio (%) Residual voltage comparison Example 7 B-5 5 15.5 0.37 Good 99.1 Good Comparative Example 8 B-5 10 15.6 0.37 Good 99.1 Good Comparative Example 9 B-5 20 15.3 0.38 Good 99.3 Good Comparative Example 10 B-5 30 15.3 0.39 Good 95.8 Poor Comparative Example 11 B-6 5 14.8 0.43 Good 97.9 Poor Comparative Example 12 B-6 10 14.7 0.43 Good 96.1 Bad Comparative Example 13 B-6 20 14.6 0.45 Good 99.1 Good Comparative Example 14 B-7 5 14.8 0.53 Good 99.2 Good Comparative Example 15 B- 7 10 14.8 0.54 Good 99.4 Good Comparative Example 16 B-8 5 14.0 0.43 Good 99.1 Good Comparative Example 17 B-8 10 13.7 0.43 Good 98.7 Good Comparative Example 18 B-8 20 13.7 0,41 Good 98.2 Bad Comparative Example 19 B- 9 5 13.6 0.51 Good 98.9 Good Comparative Example 20 B-9 10 13.8 0.52 Good 98.5 Good Comparative Example 21 B-9 20 13.7 0.53 Bad 98.7 Good Comparative Example 22 B-10 5 12.2 0.56 Good 98.4 Good ratio Comparative Example 23 B-10 10 12.4 0.58 Bad 98.1 Bad Comparative Example 24 B-10 20 12.1 0.57 Good 98.4 Bad Comparative Example 25 B-11 5 13.5 0.55 Good 98.5 Bad Comparative Example 26 B-11 10 13.4 0.59 Good 98.3 Good Comparative Example 27 B-11 20 13.4 0.60 Bad 98.2 Bad [Simplified illustration] None. [Main component symbol description] iffi 〇 J\\\ -56-

Claims (1)

200949388 VII. Patent application scope: 1. A liquid crystal alignment agent, comprising: (a) at least one polymer selected from the group consisting of polylysine and its quinone imidized polymer, and (b) a compound having two epoxy groups and one or more fluorine atoms in the molecule. 2. The liquid crystal alignment agent of claim 1, wherein the component (a) is selected from the group consisting of tetracarboxylic dianhydride and a compound selected from the group consisting of the following formulae (D-III) and (D-IV) At least one polymer of a group consisting of polylysine and its quinone imidized polymer obtained by reacting at least one of two groups of compounds, which is formed by a group of compounds, for forming a vertical alignment Liquid crystal alignment film, (R1〇)a3 (D-IV) R9 in the formula (D-III) is a monovalent organic group having a steroid skeleton 'X3 is a single bond, -0_*, -COO-*, -OCO-*, -NHCO-* , -CONH-* or - CO-* (with the connection key connected to R9), R1() is the base of the carbon number 1~4 'a3 is an integer of 〇~3' (D-IV R11 in the formula is a divalent organic group having a steroid skeleton '-57-. 200949388 X 4 are each -Ο - *, -C Ο 〇- *, - qc 〇_ *, - NHC Ο - *, - C 〇Ν Η - * or - co-* (where the connection key of "*, ' is connected to R11), each of R12 is a hospital base having 1 to 4 carbon atoms, and each a4 is an integer of 〇4. 3. The liquid crystal alignment agent of claim 2, wherein the diamine is a diamine further containing an aromatic diamine having a gas atom. 4. The liquid crystal alignment agent according to claim 2 or 3, wherein The tetracarboxylic dianhydride is a tetracarboxylic dianhydride containing 2,3,5-tricarboxycyclopentylacetic acid dioxime. The liquid crystal alignment agent of any one of claims 1 to 4 Wherein the above component (b) is a compound represented by the following formula (B) , Λ 1 ~, \ /N-R-CF3 (B) In the formula (B), R is a divalent organic group. ❹ 6. The liquid crystal alignment agent of claim 5, wherein the above formula (B) The liquid crystal alignment agent of any one of Claims 1 to 6 which contains 0.01 to 40 parts by weight with respect to 100 parts by weight of the component (a). Component (b) 8. A liquid crystal display element characterized by having a liquid crystal alignment film formed by the liquid crystal alignment agent according to any one of claims 1 to 7. -58-.200949388 IV. Designated representative Figure: (1) The representative representative of the case is: No. (2) The symbol of the symbol of the representative figure is simple: 〇a 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: ❹ Sister