TWI356068B - Liquid crystal alignment agent and liquid crystal - Google Patents

Description

1356068 IX. 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 widely known, and a liquid crystal alignment film is formed as a liquid crystal on a surface of a substrate on which a transparent conductive film is provided. a substrate for a display element, wherein two of the substrates are disposed opposite each other, and a nematic liquid crystal layer having positive dielectric anisotropy is formed in the gap to form a cell of a sandwich structure, and a long axis of the liquid crystal molecule is from one substrate to another The substrate is continuously twisted by 90 degrees. And 'STN (Super Twisted Nematic) type liquid crystal display element and IPS (in-plane switching) type liquid crystal display element with high contrast ratio compared with TN type liquid crystal display element, VA (Vertical Alignment) The liquid crystal display element has an OCB (Optically Compensatory Bend) type liquid crystal display element which is excellent in viewing angle dependence and excellent in high-speed response of a video picture. As the liquid crystal alignment agent material in these liquid crystal display elements, polylysine, polyimine, polyamine, polyester, etc. are known. In particular, a liquid crystal alignment film made of polyacrylic acid or polyimine is excellent in heat resistance, mechanical strength, affinity with liquid crystal, and the like, and is used in many liquid crystal display elements. A liquid crystal alignment film formed of polyacrylic acid or polyimine, which can be formed by forming a film mainly composed of a polymer obtained from tetracarboxylic dianhydride and diamine on a substrate, using rayon or the like. A suitable cloth material is rubbed (grinding method), or when the film has a group which can be induced by radiation-induced isomerization, an irradiation ray (photoalignment method) or the like is used to produce a liquid crystal alignment energy I S1 1356068. Moreover, it has been reported that at least a part of the tetracarboxylic dianhydride raw material is prepared by using 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, and the poly-proline or polyimine is in liquid crystal alignment and electrical properties. It is excellent in various properties (see Patent Documents 1 to 5) and is suitable as a liquid crystal alignment film. However, in recent years, there has been an urgent need to lower the price of various liquid crystal panels, so that it is required to shorten the step time and improve the yield of products in each step of the production of alignment films, which is higher than in the past. In particular, in the coating step of the liquid crystal alignment agent solution, it is required to improve the uniformity of the coating film. However, the conventionally known liquid crystal alignment agent cannot meet such a high standard. [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A-62-165628 (Patent Document 3) Japanese Laid-Open Patent Publication No. JP-A-62-165628 (Patent Document 3) Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid crystal alignment which is excellent in various properties such as liquid crystal alignment property and electrical performance, and has improved coatability. Agent. The inventors of the present invention conducted intensive studies to achieve the above object, and found that 'the 2,3,5-tricarboxyl ring used as a raw material of poly-proline or polyimine, at least 1356068 part of tetracarboxylic dianhydride. There is a correlation between the stereostructure of pentyl acetic acid dianhydride and the coatability of the obtained liquid crystal alignment agent, and the present invention has been completed. That is, the above object of the present invention, firstly, is achieved by a liquid crystal alignment agent containing at least one polymer selected from the group consisting of polyfluorene@acid and ruthenium imide of the polyamic acid. The polyamino acid is prepared by reacting a tetracarboxylic dianhydride containing 2,3,5-tricarboxycyclopentyl acetic acid dianhydride with a diamine, and is characterized by the above 2,3,5·tricarboxycyclopentane. The exces content of the acetic acid dianhydride is 90% or more. The above object of the present invention, and secondly, is achieved by a liquid crystal display element having a liquid crystal alignment film produced from the above liquid crystal alignment agent. [Effect of the Invention] According to the liquid crystal alignment agent of the present invention, a good liquid crystal alignment film having no unevenness in printing and pores even when printed in a short step time can be obtained. Further, the liquid crystal alignment agent of the present invention is excellent in various properties such as liquid crystal alignment properties and electrical properties. The liquid crystal alignment agent of the present invention can be applied to VA (vertical alignment) type, IPS (in-plane switching) type, and optical compensation bending (OCB) by selecting the liquid crystal to be used in addition to the TN type and STN type liquid crystal display. Type, ferroelectric type and anti-ferroelectric liquid crystal display elements. Further, the liquid crystal display element of the present invention can be effectively used for various devices such as display devices for computers, watches, clocks, counting display panels, word processing machines, personal computers, liquid crystal televisions, and the like. [Embodiment] <2,3,5-Tricarboxycyclopentylacetic acid dianhydride> I S1 1356068 The 2,3,5·di residue cyclopentyl acetic acid dianhydride used in the present invention has a body content of 90 %the above. The stereo structure of the 2,3,5-tris-resin cyclopentyl acetic acid dianhydride is known as an exo body represented by the following formula (A) and an end steroid represented by the following formula (B).

The exo body content is defined as the ratio (%) of the ex0 of the exo and end0 bodies in the 2,3,5-tricarboxycyclopentyl acetate dianhydride as a raw material. The ex steroid content is preferably 95% or more, more preferably 99% or more. The ex steroid content can be determined by 1 Η-NMR of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 1 3 c _ Ν μ R knows. Such a stereostructured 2,3,5-tricarboxycyclopentyl acetic acid dianhydride can be obtained, for example, by the following method. That is, first, hydroxydicyclopentadiene obtained by hydrolyzing dicyclopentadiene is used as a raw material, at least in the initial stage of the reaction (from the start of the reaction to preferably 1356068 for at least 30 minutes, more preferably at least 1 hour). Further preferably, the oxygen is controlled at a temperature of less than 50 ° C, preferably at a temperature below 45 ° C, to control the stereostructure of 2,3,5-tricarboxycyclopentyl acetic acid. The temperature in the process is controlled below 50 ° C. ' For example, a nitric acid oxidation method using ammonium vanadate as a catalyst can be used. The 2,3,5-tricarboxycyclopentyl acetic acid obtained here is suitable for analysis. After the method is refined, it is supplied to the next step. The 2,3,5-tricarboxycyclopentyl acetic acid which controls the stereostructure is dehydrated and closed under the condition, and the 2-cyclopentyl acetic acid dianhydride which controls the stereo structure can be obtained. A known dehydrating agent such as propionic anhydride can be used for the dehydration ring-closure reaction, and a dehydration ring-closure catalyst can be used in the dehydration reaction, and further refining such as recrystallization can be further carried out as needed. The exo body content can be obtained by the above method. High condition optimization In essence, the e X steroid is 1% by mole of 2,3,5-triacetic acid dianhydride. _ <Other tetrahydro acid dianhydride> The poly-proline or the guanidine imide used in the present invention a substance obtained by reacting a stereostructure of 2,3,5-tricarboxycyclopentylacetic acid di dianhydride with a diamine. In the present invention, the poly-proline or its quinone imidization process can be used as exo Other tetradecanoic acid dianhydrides of 2 cyclopentyl acetic acid dianhydride having a body content of 90% or more, such as butane tetracarboxylic dianhydride and 1,2,3,4-cyclobutane tetracarboxylic acid 2 hours), it can be prepared here, preferably the oxidation reaction, etc., preferably passes the acid and then passes through a 3,5-tricarboxyl group such as acetic anhydride below 60 ° C, preferably not once or If the reaction carboxycyclopentyl group is prepared from a tetracarboxylic acid containing an anhydride, the 3,5-tricarboxyl group can be exemplified by: 1,2-dimethyl 1S3 1356068-based-1,2,3 , 4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3, 4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane Carboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-di Cyclohexyltetracarboxylic dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3a,4,5 , 9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&amp; ,4,5,91)-hexahydro-5-methyl-5-(tetrahydro-2,5-dioxo-3-indolyl)-naphthalene[l,2-c]-furan-1, 3-diketone, 1,3,3&amp;,4,5,91)-hexahydro-5-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l ,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-methyl-5-(tetrahydro-2,5-dioxo-3 -furyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&amp;,4,5,91?-hexahydro-7-ethyl-5-(tetrahydrogen) -2,5-dioxo-3-furyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&amp;,4,5,915-hexahydro-8-A -5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-(:]-furan-1,3-dione, 1,3,3&amp;,4,5 ,91)-hexahydro-8-ethyl-5-(tetrahydro-2,5-dioxo-3-furyl)-naphthalene[l,2-c]-furan-1,3 -di 1,3,3a,4,5,9b-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2- (:]-furan-1,3-dione, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, bicyclo [2.2. 2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'- (tetrahydrofuran-2',5'-dione), 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride , 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.0'6]undecane- 3,5,8,10-tetraketone, a compound represented by any one of the following formulas (T-I) and (T-II), such as a fat-ΙΟ Ι 51 1356068 family or an alicyclic tetracarboxylic dianhydride;

(wherein R1 and R3 each independently represent a group having an aromatic ring, R2 and R4 each independently represent a hydrogen atom or a plurality of R2 and R4 in the plural of an alkyl group may be the same, or may be pyromellitic acid Anhydride, 3,3',4,4'-benzophenonetetracarboxylic acid 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylate ,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxy 3,3',4,4'-dimethyldiphenylnonane tetracarboxylic acid Dihydride, 3,3',4&quot; decane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4 dicarboxyphenoxy)diphenyl sulfide dianhydride, 4 , 4'-bis(3,4-diyl)diphenylphosphonium dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)dicarboxylic anhydride, 3,3',4,4' - perfluoroisopropylidene phthalic acid 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3',2,3'-biphenyltetracarboxylic acid (o-phenylene) Formic acid) phenylphosphine oxide dianhydride's p-phenylene-bis(tribenzoic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) II I have two valences, the same score is 4 different) . - dianhydride, acid dianhydride, acid dianhydride, plant-tetraphenyl, -bis (3,4-carboxyphenoxyphenylpropane g dianhydride, dianhydride, bis-phenylene phthalate, double (three- 11 - 1356068 Phenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, ethylene glycol-double (dehydrated trimellitate), propylene glycol-bis(hydroper trimellitate), 1,4-butanediol-bis(dehydrated trimellitic acid' ester), 1,6-hexanediol-double ( Dehydrated trimellitate), 1,8-octanediol-bis(dehydrated trimellitate), 2,2-bis(4-hydroxyphenyl)propane-bis(dehydrated trimellitic acid' An ester), an aromatic tetracarboxylic acid such as a compound represented by the following formula (T-1) to (T-4), a dianhydride, etc. These tetracarboxylic dianhydrides may be used alone or in combination of two or more.

-12- 1356068

CH,

Ο

Among them, from the viewpoint of enabling liquid crystal alignment which is excellent in performance, butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and 1,3-dimethyl are preferable. Base-oxime, 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,3,3&amp;,4,5,91?- Hexahydro-5-(tetrahydro-2,5-dioxo-3-furan IS] -13- 1356068 yl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3 ,3&amp;,4,5,915-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-(;]-furan-1, 3-diketone, 1,3,3a,4,5,9b-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene 1,2-c]furan-1,3-dione, bicyclo[2.2.2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo[3.2. 1] Octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxotetrahydro-3-furanyl) 3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6-dianhydride, 4 , 9-dioxatricyclo[5.3.1.0''6] deca-al-3,5,8,10-tetraketone, pyromellitic dianhydride, 3,3',4,4'-benzophenone Tetracarboxylic dianhydride, 3,3' , 4,4'-diphenylphosphonium tetracarboxylic dianhydride, 2,3',2,3'-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, the above The compound represented by the following formula (T-5) to (T-7) in the compound represented by the formula (T-I) and the following formula (T-8) in the compound represented by the above formula (Τ-II) represent compound of,

(T-5) (T- 6) (T-7) 1 S1 1356068

As a particularly preferable '1 2 3 4 - cyclobutane tetracarboxylic dianhydride, 1,3, 33, 4, 5, 91?. hexahydro_5_(tetrahydro-2,5-dioxo- 3_furyl)naphthalene [l,2-c]pyran-1,3_dione, 13,33,4,591)_hexahydro-8methyl5_(tetrahydro-2,5-oxo-3_ Furyl)-naphthalene [1,2-c]furan rl,3-dione, 3-oxabicyclo[3.2.1]octane-24•dione 6 spiro-3' (tetrahydrofuran-2,,5, Diketone), 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3_cyclohexene 1,2-dicarboxylic acid 1,3,5,6-tricarboxyl -2-carboxynorbornane-2:3, 5:6-dianhydride, 4,9-dioxabicyclo[5·3·1·〇2,6]decane-3,5,8, 1〇_tetraketone, pyromellitic dianhydride, and a compound represented by the above formula (Τ-5). In the preparation of the poly-proline or its quinone imide used in the present invention, when 2,3,5-tricarboxycyclopentyl acetic acid dianhydride having an ex 〇 content of 90% or more and other tetracarboxylic acids When the dianhydride is used at the same time, the amount of the other tetracarboxylic dianhydride is preferably '60 mol% or less, more preferably 3 〇 mol% or less of the total tetracarboxylic dianhydride. &lt;Diamine&gt; Examples of the diamine which can be used in the production of the polyacrylic acid or the oxime imide of the present invention include p-phenylenediamine, m-phenylenediamine, and 4,4 '-diaminodiphenyl. Methane, 4,4,diaminodiphenylethane, 4,4,-diaminodiphenyl sulfide, 4,4,-diaminodiphenylanthracene, 3,3'-dimethyl 4,4'-diaminobiphenyl, 4,4,-diaminobenzilide, 4,4,-diaminodiphenyl ether, 1,5-di m 1356068 aminonaphthalene, 2 , 2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl -4,4'-diaminobiphenyl, 3,3'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 5-amino-1-(4-aminophenyl) )-1,3,3-trimethylindan, 6-amino-1-(4'-aminophenyl)-1,3,3-trimethylindan, 3,4'-diamine Diphenyl ether, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone' 2,2-double [4- (4-Aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl) ) hexafluoropropane, 2,2-double [ 4-(4-Aminophenoxy)phenyl]Maple, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene' 1, 3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroquinone, 2,7-diaminopurine, 9,9-dimethyl- 2,7-diaminopurine, 9,9-bis(4-aminophenyl)anthracene, 4,4'-methylene-bis(2-chloroaniline), 2,2',5,5' -tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-di Methoxy-4,4'-diaminobiphenyl, 1,4,4'-(p-phenylene isopropylidene)diphenylamine, 4,4'-(m-phenylene isopropylidene) Diphenylamine, 2,2'-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-diamino-2,2'-double Aromatic diamines such as (trifluoromethyl)biphenyl, 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl; 1,1-m-phenylene Dimethylamine, 1,3-propanediamine, butanediamine, pentanediamine, hexamethylenediamine, heptanediamine, octanediamine, decanediamine, 1,4-diaminocyclohexane, isophor Ketodiamine, tetrahydrodicyclopentadiene diamine, hexahydro-4,7-methyl quinone di Aliphatic and alicyclic diamines such as diamine, tricyclo[6.2.1.02,7]undecene dimethyldiamine, 4,4,-methylenebis(cyclohexylamine); 2,3 - Diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 16-1356068 2.4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrazine ,5,6-Diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-tri-trap, 14-bis(3-aminopropyl)峨哄, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2.4-diamino-6-methoxy-1,3,5-tri-trap, 2,4-diamino -6-phenyl-1,3,5-trin, 2,4-diamino-6-methyl-3-trin, 2,4-diamino-135_ Plowing, 4,6-diamino-2-vinyl-s-trin, 2,4-diamino-5-phenylthiazole, 2,6-diaminoguanidine 5,6-diamine -1,3-dimethyluracil, 35-diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridine lactate, 38-diamino-6 -Phenylphenanthridine, 1,4-diaminopiperidinium, 3,6-diaminoacridine, bis(4-aminophenyl)phenylamine, 3,6-diaminosostazole, N -Methyl-3,6-diaminopyrazole, N-ethyl-3,6-diaminocarbazole, N-phenyl -3,6-diaminosostazole, N,N'-bis(4-aminophenyl)benzidine, compound h2n p5.Pi NH represented by the following formula (D-I): R5-R6 (Dl )

(In the formula (D-I), R5 represents a divalent organic group selected from the group consisting of -0, -COO-, -OCO-, -NHCO, -CONH-, and -CO-, and R6 represents one or more. a monovalent hydrocarbon group having 1 to 40 carbon atoms in the unsaturated bond, wherein a part or all of a hydrogen atom of the monovalent hydrocarbon group may be substituted by a fluorine atom), a compound represented by the following formula (D-II),

(D-II) (In the formula (D-II), R7 represents a monovalent organic group having a cyclic structure containing a nitrogen atom selected from the group consisting of a pyridine, a pyrimidine 'tripper, a piperidine, and a sorghum, and the 乂1 table- 17- 1356068 shows a divalent organic group), a compound represented by the following formula (D-ΠΙ), η2νΌ X2—R®-X2 -C- (D-III) (in the formula (D-III), R8 is 2 a valence organic group, χ2 indicates that a plurality of ruthenium 2 having a cyclic structure containing a nitrogen atom selected from the group consisting of pyridinium, chewing steepness, triterpene, piperidine, and a pipe trap may be the same or different ), a compound represented by the following formula (D-IV),

(D-IV) (In the formula (D~IV), 'R9 is a smoky group having 1 to 12 carbon atoms, and a plurality of valleys may be the same 'may be different', and may be an integer of 丨~3, △ a compound represented by the following formula (D-1) to (D-5),

i -18 - 1356068

(y in the formula (D-4) is an integer of 2 to 12', and z in the formula (D-5) is an integer of 1 to 5). -19- 1356068 wherein 'preferably, para-phenylene, 4,4,-diaminodiphenylmethane, 4,4,-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2, 2,-Dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4,-diaminobiphenyl, 2,7-diamino fluorene , 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9-bis(4-aminophenyl)anthracene , 22_bis[4_(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(p-phenylene di Isopropyl)diphenylamine, 4,4', (m-phenylene diisopropylidene) diphenylamine, I,4-cyclohexanediamine, 4,4'-methylenebis(cyclohexylamine) ), bis-(mono)-aminobenzene oxy)benzine, 4,4'-bis(4-aminophenoxy)biphenyl, a compound represented by the above formula (9) to (13), 2,6 -diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl_3 ,6_diaminocarbazole':^-ethyl-3,6-diaminocarbazole, 1^phenyl-3,6-diamino

a compound represented by the following formula (D-6) in the compound, a compound represented by the following formula (D-7) in the compound represented by the above formula (D-ηη),

Or dodecyloxy-2,4. diaminobenzene, pentadecyloxy-2,4-diaminobenzene, hexadecyloxy-2 in the compound represented by the above formula (D-1) 4_Diaminobenzene, octadecyloxy-2,4·diaminobenzene, dodecyloxy-2, diaminobenzene, pentadecyloxy-2,5-diaminobenzene , cetyloxy-2,5-diamino 1356068 benzene, octadecyloxy-2,5-diaminobenzene, and a compound represented by the following formula (D-8)~(D-13).

CH3 ch3

The dim-21- 1356068 amine used in the preparation of the poly-proline or the oxime imide of the present invention preferably contains at least a part of a diamine having a fluorene skeleton, particularly preferably a group of the above formula (D-I). Group R6 is a diamine having a group of a steroid skeleton. &lt;Polyamic acid&gt; The ratio of use of the tetracarboxylic dianhydride to the diamine compound to which the polyproline acid synthesis reaction which can be used in the present invention is used is preferably 1 equivalent of the amino group contained in the diamine compound. The acid anhydride group of the tetracarboxylic dianhydride is in a ratio of 0.2 to 2 equivalents, more preferably in a ratio of 0.3 to 1.2 equivalents. The synthesis reaction of poly-proline is preferably carried out in an organic solvent, preferably at a temperature of from -20 ° C to 150 ° C, more preferably from 0 to 100 ° C, preferably for 5 to 2 hours. 'Better 2~1 0 hours. Here, the organic solvent is not particularly limited as long as it can dissolve the synthesized polyaminic acid, and examples thereof include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N. - aprotic polar solvents such as dimethylformamide, N,N-dimethylimidazolidinone, dimethylhydrazine, γ-butyrolactone, tetramethylurea, hexamethylphosphonium triamine; A phenolic solvent such as methyl phenol, xylenol, phenol or halogenated phenol. The amount (a) of the organic solvent is preferably such that the total amount (b) of the tetra-residual dianhydride and the diamine compound is 〇·1 to 5 Ό% by weight based on the total amount (a + b) of the reaction solution, It is preferably made in an amount of 5 to 30% by weight. Further, in the above organic solvent, a solvent alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, or a hydrocarbon may be used in combination with a polyglycine in a range in which the produced polyamine acid is not precipitated. Classes, etc. Specific examples of such a poor solvent include methanol, ethanol 'isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, and lactic acid. Ethyl ester, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, -22- 1356068 cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, Ethyl ethoxypropionate, 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 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, tetrahydrofuran, dichloromethane, 1,2-dichloroethane '1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, Hexane, heptane, octane, benzene, toluene, xylene, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether and the like. When a poor solvent as described above is used in combination in an organic solvent at the time of production of polylysine, the use ratio thereof can be appropriately set within a range in which the produced polyaminic acid is not precipitated, and it is preferably in all the solvents. 50% by weight or less. The reaction solution in which polylysine was dissolved was obtained as above. Then, the reaction solution is poured into a large amount of a poor solvent to obtain a precipitate, and the precipitate is dried under reduced pressure, or the reaction solution is evaporated under reduced pressure with an evaporator to obtain a polyamine. Further, the poly-proline can be purified by repeating the step of dissolving the polyamine in an organic solvent once or several times, then precipitating it with a poor solvent, or distilling off under reduced pressure with an evaporator. &lt;Ruthenium imide of polyglycolic acid&gt; The ruthenium imide of polyglycolic acid (polyphosphonium amine) which can be used in the present invention can be obtained by using the polyplycine as described above. The amino acid structure is dehydrated and closed to prepare. The dehydration ring of polylysine may be (1) 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-23-1356068 and It is carried out according to the method of heating required. 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 200 °C, the molecular weight of the obtained polyimine may decrease. The reaction time in the method of heating the polyamic acid is preferably from 0.5 to 48 hours, more preferably from 2 to 20 hours. On the other hand, in the method of adding a dehydrating agent and a dehydration ring-closure catalyst to the polyamic acid solution of the above (ii), as the dehydrating agent, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used. The amount of the dehydrating agent is preferably from 0.01 to 20 moles per 1 mole of the prolyl acid structural unit. As the dehydration ring-closing 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 moles per mole of the dehydrating agent used. The organic solvent used in the dehydration ring-closure reaction may, for example, be an organic solvent exemplified as a solvent used in the synthesis of polylysine. The reaction temperature of the dehydration ring-closing reaction is preferably from 0 to 180 ° C, more preferably from 10 to 150 ° C, and the reaction time is preferably from 0.5 to 20 hours, more preferably from 1 to 8 hours. By carrying out the same operation as the separation and purification method of polylysine by the reaction solution thus obtained, the polyimine can be separated and purified. The quinone imide used in the present invention may also be a ruthenium imide having a lower ruthenium amination ratio which is only a part of the proline structure. The ruthenium imide of the ruthenium imide used in the present invention is preferably 80% or more, more preferably 1 S1 - 24 to 1356068 85% or more. Here, the "yttrium imidation ratio" means the total number of methionine units and ruthenium rings in the phase, and the oxime ring is expressed in % by oxime. At this time, a part of the quinone ring may also be an amine ring. The imidization ratio can be determined by dissolving the oxime imide in a suitable form and using tetramethyl decane as a reference, and measuring ιΗ at room temperature by the formula represented by the following formula (1). Ruthenium amination rate (%) = (1 - AVA2xa )xl00 ···((In equation (1), A1 is the origin of the NH peak area found at 10 ppm' A2 is the peak area derived from other protons, α It is a ruthenium matrix in polylysine before the relative ring reaction, and other ratios.) When the liquid crystal alignment agent of the present invention is used, 2,3,5-tricarboxycyclopentylacetate is used as the exo body content. When the anhydride and other tetracarboxylic acid dimerimide are used, as the other tetracarboxylic dianhydride, other tetracarboxylic dianhydrides containing a fatty acid dianhydride are preferred. In this case, the particularly preferred alicyclic four is: 1,3. ,3&,4,5,91)-hexahydro-5-(tetrahydro-2,5-dioxo-3-linked [l,2-c]pyran- l,3-dione, • six Hydrogen_8_methyl-2,5-oxo-3-furanyl)-naphthalene[12^]furan-13-dione, cyclo[3_2.1]octane-2,4-dione-6- Spiro-3,-(tetrahydrofuran-2,5-5(2,5-dioxotetrahydro-3-(furanyl)_3_methyl_3_cyclohexene anhydride, 3,5,6-dicarboxyl 2-carboxynorbornane-2:3,5:6-dianhydride-oxabicyclo[5.3.1.02,6]decane/35,8,1〇·tetraketone. When the liquid crystal alignment agent of the present invention Used in the ratio of inclusions for the number of aggregates is different NMR, and 1) a cyclic tetracarboxylic dianhydride prepared from more than 90% of an anhydride of a dehydrated closed proton: mentyl)-naphthalene g - 5 - (tetrahydro 3-oxo double, - Dicarboxylic acid dianhydride of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride having a diketone), -1,2-dicarboxy or 4,9-ex steroid content of 90% -25 - 1356068 or more In the case of a polyimine obtained by diamine, as the diamine, a compound represented by the above formula (D-I), particularly preferably dodecyloxy-2,4-diaminobenzene or pentadecyloxy is preferably used. Benzyl-2,4-diaminobenzene, hexadecyloxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, dodecyloxy-2,5 -diaminobenzene, pentadecyloxy-2,5-diaminobenzene, cetyloxy-2,5-diaminobenzene, octadecyloxy-2,5-diaminobenzene a compound represented by the above formula (D-8) to (D-13). In this case, other diamines may be used in combination with the compound represented by the above formula (D-1). Preferred diamines among other diamines used herein include, for example, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 1,5. -diaminonaphthalene, 2,2'.dimethyl-4,4'-diaminobiphenyl, 2,2,-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,7-Diaminoguanidine, 4,4,-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9-bis ( 4_Aminophenyl)anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(p-phenylene diisopropylidene)diphenylamine, 4,4'-(m-phenylene diisopropylidene)diphenylamine, 1,4-cyclohexanediamine, 4, 4'-methylenebis(cyclohexylamine), 1,4-bis(4-aminophenoxy)benzene, 4,4,_bis(4-aminophenoxy)biphenyl, the above formula ( D-1) a compound represented by ~(D-3), 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine , hydrazine, Ν'-bis(4-aminophenyl)benzidine, a compound represented by the above formula (D-6) in the compound represented by the above formula (D-II) The compound represented by the above formula (D-7) in the compound represented by the above formula (D-III). When the liquid crystal alignment agent of the present invention is used, a polyphthalocyanine prepared from a tetracarboxylic dianhydride and a diamine containing 2,3,5-tricarboxycyclopentyl acetic acid dianhydride having an exo body content of 90% -26- or more is used. In the case of the amine, the diamine represented by the above formula (D-1) in the diamine to be used is preferably 0.5% by weight or more, and more preferably 1% by weight or more based on the entire diamine. &lt;Terminal-modified poly-proline, quinone imine.&gt; The poly-lysine or its quinone imide may be a terminal-modified polymer having a molecular weight adjusted. Such a terminal-modified polymer can be synthesized by adding a monobasic acid anhydride, a monoamine compound, a monoisocyanate compound or the like to a reaction system during the synthesis of poly-proline. Here, examples of the monobasic acid anhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl group. Succinic anhydride and the like. Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-nonylamine, rutheniumamine, and diasterium. Amine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecaneamine, n-octadecylamine, n-icosylamine, and the like. The monoisocyanate compound may, for example, be phenyl isocyanate or naphthyl isocyanate. &lt;Solid viscosity of polyaminic acid and its ruthenium iodide&gt; The above polylysine was formulated into a 10% by weight solution of Ν-methyl-2-pyrrolidone, using a 旋转-type rotational viscometer at 25 ° C The viscosity of the solution to be measured is preferably from 20 to 800 mPa_s, more preferably from 30 to 500 mPa, s. The yttrium imide of the above polyaminic acid is formulated into a 10% by weight solution of γ-butyrolactone, and the viscosity of the solution measured by a rotary viscous viscometer at 25 ° C is preferably 20 to 800 mPa, s, More preferably 30 to 500 mPa's. 1356068 &lt;Other components&gt; The liquid crystal alignment agent of the present invention contains at least one selected from the group consisting of polyacrylic acid and sulfonium imide as an essential component, and may be in a range that does not impair the effects of the present invention. Contains other ingredients. Examples of such other components include, for example, a polymer other than the above-mentioned polyaminic acid and its quinone imide (hereinafter referred to as "other polymer"), a compound having at least one epoxy group in the molecule, and a functional decane. Compounds, etc. The above other polymer may be used in order to further improve the solution characteristics of the liquid crystal alignment agent of the present invention and the electrical properties of the resulting liquid crystal alignment film. Examples of such other polymers include, for example, polylysine other than polyamic acid, ruthenium imide, polyphthalate, polyester, polyamine, cellulose derivative, polyacetal, and the like. Polystyrene derivatives, poly(styrene-phenylmaleimide) derivatives, poly(meth)acrylates, and the like. When the liquid crystal alignment agent of the present invention contains other polymers, the use ratio thereof is preferably 80% by weight or less, more preferably less than 50% by weight based on the total amount of the polymer. The compound having at least one epoxy group in the molecule (hereinafter simply referred to as "epoxy compound") may be used as an epoxy compound in order to improve the adhesion of the obtained liquid crystal alignment film to the surface of the substrate. Examples of the compound having two or more epoxy groups in the molecule include, for example, a glycidyl ether of a polyhydric alcohol, a glycidylamine compound, and the like. Examples of the glycidyl ether of the above polyhydric alcohol include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether. -28- 1356068 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, etc.; as the glycidylamine compound, for example, 'N, N, N', N'-tetraglycidyl-m-xylylenediamine , 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'· • Diaminobiphenyl Methane, N,N-diglycidyl-benzylamine, N,N-diglycidyl-aminomethylcyclohexane, and the like. • As the epoxy compound, a glycidylamine compound is preferred. The proportion of the epoxy group to be used is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight, based on 1 part by weight of the total amount of the polymer. The above functional decane compound may, for example, be 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane or 2-aminopropyltriethyl Oxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane , 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethyloxy decane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3- Aminopropyltriethoxydecane, N-triethoxydecylpropyltriethylenetriamine, N-trimethoxydecylpropyltriethylenetriamine, 10·trimethoxydecane-1, 4,7-triazadecane, 10-triethoxydecyl-1,4,7-triazanonane '9-trimethoxydecylalkyl-3,6-diazaindolyl acetic acid Ester, 9-triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyl Triethoxy decane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyl-29- 1356068 triethoxydecane, N-double Oxyethylene) -3-aminopropyl trimethoxy Silane, N- bis (oxyethylene) -3-aminopropyl triethoxy silane-like. The mixing ratio of these functional decane compounds is preferably 2 parts by weight or less based on 100 parts by weight of the total amount of the polymer. &lt;Liquid Crystal Aligning Agent&gt; The liquid crystal alignment agent of the present invention is preferably at least one selected from the group consisting of the above polylysine and its quinone imide, and optionally other components are preferably dissolved in an organic solvent. Composed of The organic solvent constituting the liquid crystal alignment agent of the present invention may, for example, be a solvent exemplified as a solvent used in the polyamido acid synthesis reaction. Further, it is also possible to appropriately select a poor solvent which can be used in combination as a synthetic reaction of polylysine. In the liquid crystal alignment agent of the present invention, the solid content concentration (refer to the ratio of the total weight of the components other than the liquid crystal alignment agent solvent to the total weight of the liquid crystal alignment agent) is selected in consideration of viscosity, volatility, and the like. It is preferably in the range of 1 to 10% by weight. In other words, the liquid crystal alignment agent of the present invention is applied to the surface of the substrate to form a coating film as a liquid crystal alignment film. When the solid content concentration is less than 1% by weight, the thickness of the coating film is too small, so that it is difficult to obtain a good liquid crystal alignment. When the solid content concentration exceeds 10% by weight, the thickness of the coating film is too thick, and it is also difficult to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent is increased by 1 to cause deterioration of coating properties. The particularly preferable solid content concentration range differs depending on the method used to apply the liquid crystal alignment agent to the substrate. For example, when the spin coating method is employed, the concentration of the particularly good solid content is in the range of 1.5 to 4.5% by weight. When the printing method is used, the range of the solid content is 3 to 9% by weight. It can make the solution viscosity fall within the range of 12~50 mPa.s. When the ink jet method is employed, it is particularly preferable that the solid content concentration is in the range of 1 to 5 % by weight, so that the solution viscosity 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 prepared is preferably 〇 ° C to 200 ° C, more preferably 20 ° C to 60 ° C. Preferred examples of the organic solvent to be used in the liquid crystal alignment agent of the present invention include N-methyl-2-pyrrolidone, r-butyrolactone, r-butyrolactone, and N,N-dimethylformamide. , N,N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, B Ethyl oxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl race), ethylene glycol dimethyl 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 single Ethyl acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, and the like. These solvents may be used singly or in combination of two or more. &lt;Liquid Crystal Display Element&gt; The liquid crystal display element obtained by using the liquid crystal alignment agent of the present invention can be produced, for example, by the following method. (1) The liquid crystal alignment agent of the present invention is applied onto one surface of a substrate on which a patterned transparent conductive film is provided by a roll coating method, a spin coating method, a printing method, an inkjet method, etc. 'Next, by applying the coated surface Heating forms a coating film. Here, as the substrate, glass such as float glass or soda lime glass can be used; -31 - 1356068 polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, A transparent substrate made of plastic such as polycyclocarbon. As the transparent conductive film provided on one side of the substrate, an NEA film made of tin oxide (Sn02) (registered with the same standard as PPG, USA) and an I TO film made of indium oxide-tin oxide (Ιιΐ2〇3 - Sn〇2) can be used. Wait. Further, the pattern of formation of these transparent conductive films is a photolithography method or a method in which a mask is used in advance. At the time of coating the liquid crystal alignment agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional decane-containing compound, a functional titanium-containing compound, or the like may be applied to the surface of the substrate in advance. After the liquid crystal alignment agent is applied, preheating (prebaking) is preferably performed for the purpose of preventing the coating agent liquid from sagging or the like. The prebaking temperature is preferably from 30 to 300 ° C, more preferably from 40 to 200 ° C, and particularly preferably from 50 to 150 ° C. Then, the aging (post-baking) step is carried out for the purpose of completely removing the solvent and the like. The ripening (post-baking) temperature is preferably from 80 to 300 ° C, more preferably from 120 to 250 ° C. The liquid crystal alignment agent of the present invention is formed by removing the organic solvent to form a coating film as a liquid crystal alignment film. When the liquid crystal alignment agent of the present invention contains a polymer having a proline structure, it can be further dehydrated and closed by heating. A coating film which is further imidized is formed. The thickness of the coating film to be formed is preferably 0.001 to Ιμηι, more preferably 0.005 to 0.5 μηηβ. (2) Next, the coating film surface formed as described above is applied by a roll wrapped with a cloth such as nylon, rayon, cotton or the like. Grinding treatment in a certain direction of friction. Thus, the alignment energy of the liquid crystal molecules is generated on the coating film to form a liquid crystal alignment film. In addition, the liquid crystal alignment -32 - 1356068 film formed by the liquid crystal alignment agent of the present invention is carried out, for example, in Patent Document 6 (Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. In the case where the ultraviolet ray is partially irradiated to change the pretilt angle, or as shown in the patent document 8 (Japanese Laid-Open Patent Publication No. Hei No. 5-107544), the surface of the liquid crystal alignment film after the sanding treatment is partially formed. After the protective film is subjected to a rubbing treatment in a direction different from the previous rubbing treatment, the protective film is removed, and the liquid crystal alignment of the liquid crystal alignment film can be changed, whereby the field of view characteristics of the liquid crystal display element can be improved. (3) fabricating two substrates on which the liquid crystal alignment film is formed, and placing the two substrates oppositely through the gap (cell gap) so that the polishing directions of the respective liquid crystal alignment films are perpendicular or anti-parallel to each other, and the sealant is used for the peripheral portions of the two substrates. The liquid crystal is filled in the interstitial space divided by the surface of the substrate and the sealant, and the injection hole is closed to form a liquid crystal cell. Then, a polarizing plate is bonded to the outer surface of the liquid crystal cell, i.e., the transparent substrate side constituting the liquid crystal cell, to obtain a liquid crystal display element. Here, as the sealant, for example, an alumina ball-containing epoxy resin or the like as a curing agent and a spacer can be used. Examples of the liquid crystal include a nematic liquid crystal and a disk-shaped liquid crystal. Among them, a nematic liquid crystal is preferable, and for example, a Schiff base liquid crystal, an oxidized azo liquid crystal, a biphenyl liquid crystal, or a phenylcyclohexane can be used. Liquid crystals, ester liquid crystals, terphenyl liquid crystals, biphenyl cyclodecane liquid crystals, pyrimidine liquid crystals, dioxane liquid crystals, bicyclooctane liquid crystals, cubane liquid crystals, and the like. Further, in these liquid crystals, cholesteric liquid crystal such as cholesteryl cholesteryl, cholesteryl phthalate or cholesteryl carbonate may be further added; under the trade names "C · 15", I S1 -33 - 1356068 &quot;CB -15" (manufactured by Merck) chiral agent; methyl-p-amino-2-methylbutyl cinnamate and other ferroelectricity evaluation as a polarizing plate attached to the outer surface of the liquid crystal, enol extended A polarizing plate or a polarizing plate which is obtained by absorbing iodine at the same time and which is obtained by sandwiching the protective film of acetaminophen. [Examples] Hereinafter, the present invention will be more specifically described by the examples. The present invention is not limited to the examples. The brewing imidization ratio, voltage holding ratio, and liquid repellency of the examples and the aminated polymer were evaluated by the following methods. [醯imination rate] The imidization ratio of ruthenium iodide is obtained by dissolving ruthenium imide (deuterium imide 4 at a temperature under reduced pressure) and dissolving it in deuterated dimethyl sulfoxide as a reference substance at room temperature. 1H-NMR was measured and found. [Solid viscosity] The solution viscosity of the polymer, when it is polyamic acid, a % by weight solution of Ν-methyl-2-pyrrolidone, which is formulated as a quinone imine. The % by weight of γ-butyrolactone solution was measured at 25 ° C. [Voltage retention rate] During the time span of 167 ms, the voltage applied to the liquid crystal was applied at a voltage of 60 μm. Seconds, then the determination of p-methoxyphenyl phthalocyanine, etc., to illustrate the preparation of the poly(ethylene film) polarizing film ruthenium film itself, but in the comparative example, the ruthenium phthalate alignment agent of the ruthenium polymer) In the tetramethyl group, the above formula (1) was used to formulate 10 weights: when the polymer was polymerized, the voltage retention rate after the voltage was released from 5 volts to -34 - 1356068 167 milliseconds was applied by the 旋转-type rotating adhesive element. The measuring device used VHR-1 manufactured by Dongyang Technology Co., Ltd., and the voltage holding ratio was 95% or more, and it was judged as "good". Synthesis of -2,3,5-tricarboxycyclopentylacetic acid dianhydride &gt; Synthesis Example 1 (1) Synthesis of hydroxy-dicyclopentadiene A 3-liter three-necked flask was charged with 153 g of water and 72 g of 78% sulfuric acid. , heated to 60 ° C. 76 g of dicyclopentadiene was added thereto, and reacted for 6 hours at 1 Torr with rapid stirring. The reaction mixture was cooled to room temperature and allowed to stand until the layer was separated. 76 g of toluene was added thereto, and after heating to 55 ° C, 76 g of water, 7.6 g of sodium hydrogencarbonate and 7.6 g of sodium chloride were added, and further stirring was continued at 55 ° C for 30 minutes. After standing until layering again, the organic layer was taken out' Concentration under reduced pressure to remove toluene. To the residue was added 40 g of water, heated to 75 ° C ', heated to 100 ° C, and azeotropically removed by distillation under reduced pressure to give 7 8 g of hydroxy-dicyclopentadiene. The crude product was subjected to vacuum distillation at a temperature of 150 t: or less to obtain 60 g of purified hydroxy-dicyclopentadiene. (2) Oxidation of hydroxydicyclopentadiene to 3 liters The flask was charged with 67.5 % of nitric acid and ammonium vanadate 'heated to 43 ° C. 54 g of the above-mentioned synthesized hydroxydicyclopentane was added dropwise thereto. At this time, the temperature of the reaction solution during the dropwise addition was maintained at 42 to 45. (: ° After the end of the dropwise addition, the reaction was carried out at 4 3 ° C for 2 hours) and the reaction was continued at 4 8 t for 8 hours. At 62 ° Concentrated under reduced pressure at C, the remaining about 8 g of the solution was further reacted at 5 ° C for 8 hours. The reaction mixture was cooled to 1 ' to crystallize for 1 hour. To the crystal-containing slurry was added 67.5 % of nitric acid. And the crystals of IS1 -35-1356068 were recovered. The crystals recovered on the filter were dried under reduced pressure with a filter to obtain 46 g of crude crystals containing 2,3,5-tricarboxycyclopentyl acetic acid. Add 16 g of ultrafine to the filter. The pure water was stirred at 6 (TC) to dissolve the crystals remaining in the filter (crystals remaining on the filter which could not be recovered), and an aqueous solution containing 2,3,5-tricarboxycyclopentyl acetic acid was recovered. (3) Acid precipitation of 2,3,5-tricarboxycyclopentyl acetic acid to 46 g of crude crystals containing 2,3,5-tricarboxycyclopentyl acetic acid and recovered 2,3,5- To the aqueous solution of the crude crystal of tricarboxycyclopentyl acetic acid, 5.8 g of ultrapure water was added, and the mixture was stirred at 75 ° C to dissolve the crystal. While maintaining the internal temperature of the reactor at 75 ° C, 5 1.4 g of 35% hydrochloric acid was added dropwise to the solution over 30 minutes. After the completion of the dropwise addition, the reaction was continued at 75 ° C for 2 hours. The reaction mixture was then cooled to -3 ° C and allowed to stand for 10 hours to precipitate crystals. The supernatant was discarded, and the residual slurry was transferred to a centrifugal filter device, and 24 g of methyl isobutyl ketone was added. The solid component and the supernatant were separated by centrifugation, the supernatant was discarded, the crystal-containing slurry was recovered, and the slurry was again transferred to a centrifugal filter device, and the same operation as above was repeated twice, and the obtained crystal was subjected to methylation. Wash with butyl ketone. Thus, a methyl isobutyl ketone slurry containing 38 g of 2,3,5-tricarboxycyclopentyl acetic acid containing acid was obtained. (4) Anhydride formation of 2,3,5-tricarboxycyclopentyl acetic acid. To a 2-liter flask was placed 118 g of acetic anhydride under a nitrogen atmosphere, and then 33 g of the purified crystal of 2,3,5-tricarboxycyclopentylacetate obtained above was added. The mixture was heated to 90 ° C and allowed to react under nitrogen for 3 hours. The internal temperature of the reactor was once cooled to 45 ° C and the internal temperature was maintained at 60 ° C under -36 - 1356068, and concentrated under reduced pressure, and about 100 ml of the distillate was discarded. Further, 20 g of acetic anhydride was further added under the conditions of an internal temperature of 60 ° C or lower, and further concentrated under reduced pressure at an internal temperature of 60 ° C or lower, and about 18 ml of the distillate was discarded. The reaction mixture was stirred while being purged with nitrogen, and cooled to 7 ° C, and stirred at this temperature for 10 hours to crystallize the crystal. Then, the crystal-containing slurry was filtered under pressure with nitrogen to obtain a crude crystal. Then, the above crude crystals and 67 g of methyl isobutyl ketone cooled to -5 ° C were placed in a 2-liter flask which was internally purged with dry nitrogen and cooled to -5 °C. The slurry was stirred at an internal temperature of 5 ° C for 2 hours under a nitrogen stream. The slurry was filtered under pressure with nitrogen, and the obtained solid material was washed with 12 g of methyl isobutyl ketone. The solid matter inside the filter was dried under reduced pressure at 60 ° C with a filter. The inside of the desiccator was ventilated with argon gas, and 22 g of crystals were recovered by a screening procedure under argon gas. Then, the outlet of the filter was closed, and 332 g of acetone was added to the filter, and the mixture was heated to 30 ° C to dissolve the crystals remaining inside the filter. 20 g of acetone and 22 g of crystals recovered beforehand were added to the filter, and a condenser was attached to the filter to heat the inside to 55 °C. After dissolving the solid matter under reflux, adjust the internal temperature of the filter to 50 °C »open the outlet at the lower part of the filter for filtration' and then add 12 g of acetone to the filter to rinse the inside of the filter. The filtrate and rinse were transferred to a 2 liter flask, heated to 60 ° C, and about 350 kg of acetone was distilled off. Then, the temperature inside the flask was cooled to -3 °C under a nitrogen flow. The crystal was aged at this temperature for 1 hour to precipitate crystals. The obtained slurry was pre-cooled, transferred to a filter, filtered under pressure with nitrogen, and 16 g of acetone cooled to 0 ° C was added to wash the crystals. The crystal -37- 1356068 remaining in the filter was dried under reduced pressure at 40 °C together with the filter. 18 g of 2,3,5-tricarboxycyclopentylacetic acid dianhydride crystals were recovered from the filter. (5) Analysis of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride to 2,3,5 prepared above The crystal of tricarboxycyclopentyl acetic acid dianhydride was measured by iH-NMR and 13C-NMR, and the exo content was about ΙΟΟ%. 1!! An NMR spectrum and a 13C_NMR spectrum are shown in Figures 1 and 2, respectively. Further, according to the results of two-dimensional NMR (HH - COS Y, HH - NOES Y ' HMBC, HMQC) pattern measurement, the specific maps belong to the following.

&lt;Synthesis of oxime imidized polymer&gt; Synthesis Example 2 Exo-2,3,5-tricarboxycyclopentyl acetic acid dianhydride prepared in the above Synthesis Example 1 as tetracarboxylic dianhydride (hereinafter It is called "〇-1^八_AH")ll〇g(〇.50 莫耳) and 1,3,3&,4,5,91)-hexahydro-8-methyl-5-(four Hydrogen-2,5-dioxo-3-furanyl)-naphthalene [1,2-(:]-furan-1,3-dione 160g (0.50 mole), p-phenylenediamine as diamine 95g (〇.88 mol), 2,2-bis(trifluoromethyl)-4,4-diaminobiphenyl 32 g (0.10 mol), 3,6-bis(4-aminobenzonitrile) Cholestane (compound represented by the above formula (D-1)) 6.4 g (〇.〇i〇mole) and octadecyloxy-2,5-diaminobenzene-38- 1 S] 1356068 4.0 g (0.015 mol) was dissolved in 960 g of N-methyl-2-pyrrolidone and allowed to react at 60 ° C for 9 hours to obtain a polyaminic acid solution. A small amount of the obtained poly-aramidic acid solution was used to determine the polymer. The viscosity of the solution, the viscosity of the solution was 58 mP a·s. 2740g of N-methyl-2-pyridinone, 396g of pyridine and 409g of acetic anhydride were added to the obtained poly-proline solution to make it dehydrated at 110 °C. 4 hours, after the reaction The solvent in the system was replaced with a new γ-butyrolactone solvent (in this operation, the pyridine and acetic anhydride used in the oxime imidization reaction were removed to the outside of the system) to obtain a solid content concentration of about 24 〇Og. A solution of yttrium imidized polymer (as a "noniminated polymer (A-1)") having a weight % and a ruthenium iodide ratio of about 94%. The ruthenium iodide polymer (A-1) The solution viscosity was 69 mPa-s. Synthesis Example 3 Exo-TCA-AH 112g (0.50 mol) and 1,3,3&, 4,5,91&gt;-hexahydro-8 as tetracarboxylic dianhydride -Methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione 157 g (0.50 mol)' as two Amine p-phenylenediamine 96g (0.8 9 moles), diaminopropyl tetramethyldioxane 25g (0.10 moles) and 3,6-bis(4-aminobenzylideneoxy) cholesta 13 g (0.020 mol) of decane and 8.1 g (0.030 mol) of N-octadecylamine as a monoamine were dissolved in 960 g of N-methyl-2-pyrrolidone, and allowed to react at 60 ° C for 6 hours. A polylysine solution is obtained. A small amount of the obtained polyaminic acid solution is used to determine the solution viscosity of the polymer, which is 60. mPa s Then, 2700 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 396 g of pyridine and 409 g of acetic anhydride were further added thereto, and the mixture was dehydrated and closed at 110 ° C for 4 hours. After the reaction, the solvent in the system was replaced with a new γ-α- IS] 1356068 butyrolactone (in this operation, the pyridine and acetic anhydride used in the oxime imidization reaction were removed to the outside of the system) to obtain about 1900 g of a ruthenium iodide polymer having a solid content concentration of 15% by weight and a ruthenium iodide ratio of about 95% (as a "ruthenium iodide polymer (A-2)") solution. The solution viscosity of the substance (A-2) was 77 mPai. Synthesis Example 4 Exo-TCA-AH 112g (0.50 mole) as a tetracarboxylic dianhydride as a diamine compound of p-phenylenediamine 43g (0.40 mole) and 3-(3,5-diaminobenzene Methyloxy) cholestyramine 52 g (0.10 mol) was dissolved in 830 g of N-methyl-2-pyrrolidone, and allowed to react at 60 ° C for 6 hours to obtain a polyaminic acid solution. A small amount of the obtained polyaminic acid solution was taken to determine the solution viscosity of the polymer, which was 2100 mPa's. Then, i900 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 thereto, and the mixture was dehydrated and closed at 1 1 ° C for 4 hours. After the reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone (in this operation, the pyridine and acetic anhydride used in the oxime imidization reaction were removed to the outside of the system). About 14 g of a solution of a ruthenium iodide polymer having a solid content concentration of 15% by weight and a ruthenium iodide ratio of about 50% as a "ruthenium iodide polymer (A-3)". Synthesis Example 5 Exo-TCA-AH U2g (0.50 mol) as a tetracarboxylic dianhydride, p-phenylenediamine 49 g (0.45 mol) and 3 _(3,5--fl female) as a diamine compound Basic methyl oxo) 26 g (0.05 mol) was dissolved in 75 〇g N-methyl-2-pyrrolidone and allowed to react at 6 ° C for 6 hours to obtain a polyaminic acid solution. A small amount of the obtained polyaminic acid solution was used to determine the solution viscosity of the polymer, and -40 - 1356068 was 2000 mPa.s. Then, 1800 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 40 g of pyridine and 5 lg of acetic anhydride were further added thereto, and the mixture was dehydrated and closed at 1 1 Torr for 4 hours. After the reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone (in this operation, the pyridine and acetic anhydride used in the oxime imidization reaction were removed to the outside of the system) to obtain about 1,500 g. A solution of a ruthenium iodide polymer having a solid content concentration of 15% by weight and a ruthenium iodide ratio of about 50% as a "ruthenium iodide polymer (A-4)"). Synthesis Example 6 Exo-TCA-AH 112g (0.50 mole) as a tetracarboxylic dianhydride as a diamine compound, p-phenylenediamine 38g (0.35 mole), 4,4,-diaminodiphenyl 20 g (0.1 mol) of methane and 26 g (0.05 mol) of 3-(3,5-diaminobenzimidyloxy)cholestane are dissolved in 750 g of N-methyl-2-pyrrolidone. The reaction was carried out at 0 ° C for 6 hours to obtain a polyaminic acid solution. The solution viscosity of the polymer was determined by taking a small amount of the obtained polyamic acid solution to be 2000 mPa. S 〇 Then, 1800 g of Ν·methyl-2-pyrrolidone was added to the obtained poly phthalic acid solution, and 40 g of pyridine and 51 g of acetic anhydride were further added. The mixture was dehydrated and closed at 11 (TC) for 4 hours. After the reaction, the solvent in the system was replaced with a new n-methyl-2-indole behenone (in this operation, the oxime imidization reaction was carried out). The pyridine and acetic anhydride used in the solvent are removed to the outside of the system) to obtain about 5% by weight of a ruthenium iodide polymer having a solid content concentration of 15% by weight and a ruthenium iodide ratio of about 50% (which is used as &quot a solution of ruthenium imidized polymer (A _ 5 ) ”) &lt;Synthesis of poly-proline&gt; I S3 -41 - 1356068 Synthesis Example 7 1,2,3,4 as tetracarboxylic dianhydride - cyclohexane tetracarboxylic dianhydride 98 g (0.50 mol) and pyromellitic dianhydride 109 g (〇.50 mol), as a diamine compound 4,4,-diaminodiphenylmethane I 98 g ( 1.0 mol) was dissolved in a mixed solvent consisting of 203 g of N-methyl-2-pyrrolidine and 2060 g of γ-butyrolactone, and reacted at 40 ° C for 3 hours, and then added 1 3 50 g Γ-丁内A solution of about 3 600 g of a polyglycine having a solid content concentration of 10% by weight as polylysine (B-1) was obtained. The solution viscosity of the polyglycine (B-1) was 15 mPa·s. Synthesis Example 8 1,2,3,4-cyclobutanetetracarboxylic dianhydride as a tetracarboxylic dianhydride 196 § (1.0 mol) as a diamine compound of 2,2,-dimethyl-4 , 4,-diaminobiphenyl 212g (l. oxime) was dissolved in a mixed solvent consisting of 37 〇g N-methyl-2-pyrrolidone and 3300 g γ-butyrolactone at 4 〇〇 The reaction was carried out for 3 hours to obtain about 3 700 g of a solution of polyglycine (as poly-proline (B-2)) having a solid content concentration of 1% by weight. The solution of the poly-proline (B-2) The viscosity was l60 mPa·s. Example 1 The polyamidonic acid (B-1), r-butyrolactone obtained in Synthesis Example 7 of the ruthenium iodide polymer (Ai) obtained in the above Synthesis Example 2 , N-methyl-2-pyrrolidone and butyl racelusate (Al) : (B-1) = 20:80 (weight ratio) and solvent composition of r-butyrolactone: N-methyl -2-pyrrolidone: butyl sirolimus = 71 : 17 : 12 (weight ratio) for mixing, and then for 1 〇〇 by weight The total amount of the polymer is 5 parts by weight of hydrazine, hydrazine, hydrazine, Ν'-tetraglycidyl • 42-1356068 -4,4,-diaminodiphenylmethane, and a solution having a solid concentration of 3.5 liters is prepared. After the solution is sufficiently stirred, the liquid crystal alignment agent is prepared by using a filter having a pore size of ΐμ®. The liquid crystal alignment agent is coated with a liquid crystal alignment agent (manufactured by Sakamoto Co., Ltd.) with a film made of a ruthenium film. The transparent electrode surface of the glass of the transparent electrode was heated on a hot plate at 80 ° C for 1 minute, and then heated on a hot plate at 200 ° C for 10 minutes to form a film having an average film thickness of 1000. This coating film was observed with a microscope having a magnification of 20 times, and uneven printing and pores were not observed, and the printability was good. Then, using a sander equipped with a roller wound with a nylon cloth, the coating film is polished to form a liquid crystal alignment under the conditions of a roller rotation speed of rpm, a table moving speed of 3 cm/sec, and a pile extrusion length of 0. The film was repeatedly subjected to the same operation as described above to prepare two (a pair of) substrates having a liquid-oriented film. On the outer edges of the pair of substrates having the liquid crystal alignment film, an epoxy resin adhesive having a diameter of 5 · 5 μηι is added, and the liquid crystal alignment film surface is relatively recombined and pressed to cure the adhesive. . The nematic liquid crystal (manufactured by Merck 'MLC· 62 2 1 ) was filled into the gap of the substrate through the liquid crystal injection port, and then the injection port was closed with an acrylic photocurable adhesive to form a liquid crystal display element. At a temperature of 70 ° C, a rectangular visual observation element of 30 Hz and 3.0 V in which 6.0 V alternating current (peak-to-peak) was superimposed was applied to the obtained liquid crystal display element, and no display defect was observed in the liquid crystal display element. Further, the liquid crystal display element has good voltage retention. The amount of 5% is filtered, and the printed substrate is then coated with a r 500 4 mm ο crystal, so that the company liquid crystal 500 wave, 15] -43- 1356068 Example 2 In addition to the use of Synthetic Example 3 A liquid crystal alignment agent was prepared in the same manner as in Example 1 except that the aminated polymer (A _ 2) was used instead of the ruthenium iodide polymer (A-1) to form a coating film on the surface of the substrate. The coating film was observed in the same manner as in Example 1. No unevenness in printing and pores were observed, and the printability was good. Further, a liquid crystal display element was produced using the substrate on which the liquid crystal alignment film was formed, and observed in the same manner as in Example 1, and no display defect was identified. The liquid crystal display element has good voltage retention. Examples 3 to 4 Operations on the surface of the substrate were carried out in the same manner as in Example 1 or Example 2, except that polylysine (B-2) obtained in Synthesis Example 8 was used instead of polyglycine (B-1). A coating film is formed on each of them. When the coating film was observed in the same manner as in Example 1, no printing unevenness and pores were observed, and the printability was good. Further, liquid crystal display elements were produced on the substrates on which the liquid crystal alignment films were formed, and as in the case of Example 1, no display defects were identified. These liquid crystal display elements have good voltage retention. Example 5 100 parts by weight of the oxime imidized polymer (A-3) obtained in Synthesis Example 4 and 0.2 parts by weight of N,N,N',N'-tetraglycidyl-4,4'-di Aminodiphenylmethane is dissolved in a mixed solvent of N-methyl-2-pyrrolidone and butyl sarbuta, and the solvent composition is N-methyl-2-pyrrolidone: butyl 赛路苏 = 50: 5 0 ( The weight ratio was adjusted to a solution having a solid content concentration of 4% by weight, and the solution was filtered through a filter having a pore size of 1 μm to prepare a liquid crystal alignment agent. In the same manner as in Example 1, the liquid crystal alignment agent was used to form a coating film on the surface of the substrate at -44 to 1356068, and no uneven printing and good paintability were observed on the coating film. Further, a bamboo display element was produced in the same manner as in Example 1 except that a nematic liquid crystal (Merck MLC-660 1 ) was used as the liquid crystal, and no display defect was identified. This liquid crystal has good voltage retention. Examples 6 to 7 In addition to the oxime imidized polymer shirts obtained in Synthesis Examples 5 to 6 or (A-5) in place of the oxime imidized polymer (A-3), the operation was carried out on the substrate. A coating film was formed on the surface, and it was observed that uneven printing and pores were observed, and the printability was good. Further, a liquid crystal display element was produced by each of the substrates on which the alignment film was formed, and it was observed in Example 5 that no display defect was recognized. These liquid crystal display elements are all excellent in retention. As is apparent from the above examples, the liquid crystal alignment agent of the present invention is excellent in liquid crystal electrical properties, and at the same time, coatability is improved. Although the reason why the presenting agent exerts such a beneficial effect is unclear, the stereostructure of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride is the same as that of polylysine or its ruthenium imide. The molecular chain torque is uniform and the solubility of the polymer is increased. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a j-NMR spectrum (full spectrum) of exo-2,3,5-tribasic acetic acid dianhydride prepared in Synthesis Example 1. Fig. 2 is a 1H-NMR chart (partially enlarged view) of exo-2,3,5-tribasic acetic acid dianhydride prepared in Synthesis Example 1. , hole, printing company system; liquid crystal display element I (A - 4) Example 5 is not the same, the liquid crystal similar voltage twisting and: Ming liquid crystal: speculation, can,, by: Base ring 〖 环 Cyclopentyl-45 - 1356068 Fig. 3: 13C_NMR spectrum (high chemical shift region) of exo-2,3,5-tricarboxycyclopentyl acetic acid dianhydride prepared in Synthesis Example 1. Fig. 4 is a 13C_NMR spectrum (low chemical shift region) of ex〇_2,3,5-tricarboxycyclopentylacetic acid dianhydride prepared in Synthesis Example 1. [Main component symbol description] Μ . /\\\

-46-

Claims (1)

1356068 X. Patent Application Range: 1. A liquid crystal alignment agent containing at least one polymer'. The polymer is selected from the group consisting of polylysine and ruthenium imide of the polyamic acid. The polylysine is prepared by reacting a tetracarboxylic dianhydride containing 2,3,5-tricarboxycyclopentyl acetic acid dianhydride with a diamine, and is characterized by the above 2,3,5-tricarboxycyclopentyl acetic acid. The exo body content of the dianhydride is 90% or more. 2. The liquid crystal alignment agent of claim 1, wherein the diamine contains a diamine having a quinone skeleton. 3. The liquid crystal alignment agent of claim 1, wherein the diamine contains a compound represented by the following formula (D-I), (DI) In the formula (D-I), R5 represents a divalent organic group selected from the group consisting of -0, -COO-, -OCO-, -NHCO-, -CONH-, and -CO-, and R6 represents 1 One or more unsaturated bonds may have a monovalent hydrocarbon group having 1 to 40 carbon atoms, and a part or all of the hydrogen atoms of the monovalent hydrocarbon group may be substituted with a fluorine atom. 4. The liquid crystal alignment agent of claim 3, wherein the group R6 in the formula (D-ϊ) is a group having a fluorene skeleton. The liquid crystal alignment agent according to any one of claims 1 to 4, further comprising a compound having two or more epoxy groups in the molecule. 6. A liquid crystal aligning agent as claimed in claim 5, wherein the compound having two or more epoxy groups in the molecule is -47-1356068 is a glycidylamine compound. A liquid crystal display element characterized by having a liquid crystal alignment film produced by the liquid crystal alignment agent according to any one of claims 1 to 6. S S3 -48-