TW200804936A - Vertical alignment mode liquid crystal alignment agent and vertical alignment mode liquid crystal display device - Google Patents

Abstract

The present invention provides a vertical alignment mode liquid crystal alignment agent that shows a high voltage holding ratio and a good coating property to substrate. The vertical alignment mode liquid crystal alignment agent is made of polymer which includes from amic acid repeating unit and/or imide repeating unit. The group of the above-mentioned repeating unit being from diamine contains the after-mentioned two groups, for example, one is at least one selected from dodecanoxyl-2,4-diaminobenzene or a specific diamine with steroid structure, and the other is another kind of specific diamine like 1,4-bis(aminemethyl)-bicyclo[2.2.1] heptane.

Description

200804936 Nineth, the invention relates to a vertical alignment type liquid crystal alignment agent and a liquid crystal display element having a vertical alignment type liquid crystal alignment film. More specifically, it relates to a vertical alignment type liquid crystal alignment agent which exhibits good printability and is excellent in various electrical characteristics, and a liquid crystal display element having a vertical alignment type liquid crystal alignment film. [Prior Art] At present, as a liquid crystal display element, a TN type liquid crystal display element having a so-called TN type (Twisted ί Nematic) liquid crystal cell is known, which is formed on the surface of a substrate on which a transparent conductive film is provided with poly-proline, polyfluorene A liquid crystal alignment film formed of an imide or the like is used as a substrate for a liquid crystal display element, and two substrates are arranged to face each other, and a nematic liquid crystal layer having positive dielectric anisotropy is formed in the gap to form a sandwich structure. The unit cell, the long axis of the liquid crystal molecules is continuously twisted 90 degrees from one substrate to the other substrate. Further, an STN (Super Twisted Nematic) type liquid crystal display element and a ? vertical alignment type liquid crystal display element having a higher contrast ratio than the TN type liquid crystal display element and having less viewing angle dependency have been developed. The STN-type liquid crystal display device uses a chiral agent in which a photoactive material is mixed in a nematic liquid crystal as a liquid crystal, and uses birefringence generated by causing a long axis of liquid crystal molecules to be continuously twisted by 180 degrees or more between substrates. effect. In recent years, the development of new liquid crystal display elements has also been active. As one of them, a horizontal electric field type liquid crystal display element has been proposed in which two electrodes for driving liquid crystals are arranged in a comb shape on one side substrate to generate a substrate. 200804936 Parallel electric field, controlling liquid crystal molecules. This element is generally called a planar switching type (IPS type) and is known to have excellent wide viewing angle performance. And recently, the use of an optical compensation film has further improved the wide viewing angle performance, and it has a remarkable feature of obtaining a wide viewing angle which is comparable to a cathode ray tube which has no tone inversion and color tone change. As a liquid crystal display element other than the above, it is proposed that a liquid crystal molecule having a negative dielectric anisotropy is vertically aligned on a substrate, and is referred to as a MVA (Multi domain Vertical Alignment) type or a PVA (Patterned V ertica 1 A1 ignment) type. Alignment type liquid crystal display element. These ΜVA type or PVA type liquid crystal display elements are not only excellent in viewing angle and contrast, but also need not be subjected to rubbing treatment in forming a liquid crystal alignment film, and are excellent in terms of manufacturing engineering. Conventionally, as these liquid crystal alignment films, polyacetamide or a dehydrated ring-closed polyimine is used for many liquid crystal display elements in any of various display modes because of heat resistance, affinity with liquid crystals, or mechanical strength. . At present, a liquid crystal alignment film of a vertical alignment type liquid crystal display element is formed by applying a liquid crystal alignment agent onto a substrate as described in Patent Document 1. As a basic property, it is necessary to have a vertical alignment property which enables vertical alignment of liquid crystals. In recent years, with the expansion of the vertical alignment type liquid crystal display element, the demand for improvement in display quality and productivity improvement by the vertical type liquid crystal alignment film has been increasing. The characteristics required for the alignment film are also various. Among them, as the most important characteristics, as described in Patent Documents 1 to 4, an improvement in high voltage holding performance and good coating property to a substrate can be cited. In order to achieve high voltage holding performance, it is known that the polyimine used in the alignment film has a high sulfhydryl imidization ratio as described in Patent Document 5. However, since the solubility of the hydrazine imidization is lowered in the solvent, the range of the solvent which can be used is limited, and as a result, it is difficult to achieve good coatability. As described above, the improvement of the imidization ratio of the high voltage holding property can be caused, and the coating property is greatly deteriorated, which is a trade-off relationship. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2002-32705 (Patent Document 2) Japanese Laid-Open Patent Publication No. Hei. SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION An object of the present invention is to provide a high voltage holding characteristic while having a good substrate. A coated vertical alignment type liquid crystal alignment agent. Another object of the present invention is to provide a vertical alignment type liquid crystal display element having a liquid crystal alignment film formed of the above liquid crystal alignment agent of the present invention and exhibiting high voltage holding characteristics. Other objects and advantages of the invention will be apparent from the description which follows. Means for Solving the Problems According to the present invention, the above objects and advantages of the present invention, the first, the proline repeating unit represented by the formula (I-1) of 200804036 and the quinone imine represented by the following formula (I-2) a polymer of at least one repeating unit of the repeating unit, Q1 in the above formula (I-1) and Q2 in the above formula (I-2) each having the following formulas (II-1) and (II-2) At least one of a divalent organic group and at least one of a divalent organic group represented by the following formula (III 1).

HOOC COOH / \ / \ P1 , / \ --^HNOC CONH-Q1* (1 -Ί) This base machine has a value of four acid carboxylic acid four-fold construction table Q1 and) ο MHC CUH ο 团 基 , , machine ο nncG Η ο If// There is an amine II composition of N valence / / _ | _ - \ two Ρ 2: Ν ·

2 Q shows that the base has a price of four acid 竣 40% of the structure of the base of the valence of the amine 2 2 and -8- 200804936

(In the above formula, X is a single bond, 〇-, -CO-, -COO-, 〇(]〇-, -NHC〇-, -C〇NH·, ·3_, methyl group, carbon number Is an alkylene group of 2 to fluorene or a phenyl group of the benzene group. R is a monovalent organic group having a carbon atom number of 10 to 20, an alicyclic skeleton having an alicyclic skeleton having 4 to 40 carbon atoms, or a carbon number. a monovalent organic group of 6 to 20 fluorine atom, R 2 is a divalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms or a fluorine atom having 5 to 30 carbon atoms; Valence organic group) - X2 - R3 - X2 - (III - 1) (In the above formula, X2 is a methyl group or an alkylene group having 2 to 20 carbon atoms, and R3 has an aromatic ring skeleton, An organooxane skeleton, a divalent organic group represented by -R-(〇-C2H4)n-〇-R- (R represents an alkylene group having 2 to 5 carbon atoms, and η represents 1 to 100), -R-(〇-C3H6)n-〇-R· represents a divalent organic group (R represents an alkylene group having 2 to 5 carbon atoms, η represents 1 to 50), and has a carbon number of 4 to 4 a divalent organic group of 40 alicyclic cyclic skeleton, wherein each of the plurality of oxime 2 present in the formula may be the same or different) 200804936 According to the present invention, the above objects and advantages of the present invention, and second, are achieved by a vertical alignment type liquid crystal alignment agent characterized in that P1 in the above formula (I-1) and P2 in (I-2) contain At least one of the tetravalent organic groups represented by the following formulas (IV-1) to (IV-6),

(I V — 1)

(wherein R5, R6, R7, R8 and R9 are each independently a hydrogen atom or a monovalent organic group). According to the present invention, the above objects and advantages of the present invention, and third, are achieved by a vertical alignment type liquid crystal alignment agent characterized in that P2 in the above formula (I-1) and P2 in (I-2) are relative to All tetravalent organic groups-10-200804936 (pi+p2) contain 50% by mole or more of at least one of the tetravalent organic groups represented by the above formulas (IV-5) and (IV-6). According to the present invention, the above object and advantages of the present invention, in a fourth aspect, are achieved by a vertical alignment type liquid crystal alignment agent, characterized in that the divalent organic group represented by the above formula (III-1) contains the following formula (V - 1) at least one of divalent organic groups represented by each of (V-5),

-^Rh

(V-1) (¥-2), Rb^^*Rb, (V-3) / (V-4)

Ra r ip, (V — 5) A Rb—Si—O—Si* • Rb— (wherein Ra represents a hydrogen atom or a monovalent organic group, and Rb is an alkylene group having 1 to 20 carbon atoms) A plurality of Ra and Rb may be the same or different, and P is an integer of 1 to 99, and q is an integer of 1 to 20. According to the present invention, the above objects and advantages of the present invention, in a fifth aspect, are achieved by a vertical alignment type liquid crystal alignment agent, characterized in that the polymer is a repeating unit of lysine represented by the above formula (I-1) The total amount of the quinone imine repeating unit represented by the above formula (I-2), wherein the quinone imine repeating unit accounts for 40 mol% or more of the quinone imidized polymer. According to the present invention, the above objects and advantages of the present invention, the sixth aspect, are achieved by a vertical alignment type liquid crystal alignment agent of -11-200804936, characterized in that it further contains 1 to 50 parts by weight with respect to 100 parts by weight of the polymer. At least one epoxy group-containing compound selected from the group consisting of compounds having at least two epoxy groups in the molecule represented by the following formulas (VI-1) and (VI-2),

(In the formula, s is an integer of 2 to 6, and t is an integer of 1 to 4, and T is an organic group having an s-valent value, and is an organic group having a t-valence). According to the present invention, the above objects and advantages of the present invention are attained by a vertical alignment type liquid crystal display device characterized by comprising a vertical alignment type liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention. EFFECTS OF THE INVENTION The vertical liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention is excellent in vertical alignment property, and is an optimum liquid crystal alignment film which can have high voltage holding performance and excellent substrate coating properties. The liquid crystal display element of the present invention can be effectively used for various devices, and can be suitably used, for example, as a display device such as a desktop computer, a watch, a desk clock, a mobile phone, a counter display screen, a word processor, a personal computer, or a liquid crystal television. [Embodiment] -12-

200804936 BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The vertical alignment type liquid crystal alignment agent (hereinafter, also referred to as a bright liquid crystal alignment agent) of the present invention, as described above, is a polymer including a repeating unit containing a valeric acid heavy and/or a quinone imine. A polymer of an amine acid repeating unit (hereinafter, also referred to as "polyglycine polymerization" is produced, for example, by using a tetracarboxylic acid dianhydride and a diamine compound in an organic solvent. In addition, a polymer containing a quinone imine repeating unit ( The following is a "deuterated imidized polymer") which is obtained by partially dehydrating a polyamic acid polymer acid. The polymer containing a repeating unit of guanidinium amide and/or quinone imine used in the present invention may be The polyaminic acid and the ruthenium iodide polymer may be used as a polymer containing an acid repeating unit and a quinone imine repeating unit in the same polymer. Hereinafter, the polyproline polymer of the present invention, 醯亚The preparation of the aminated polymer is described. [Tetracarboxylic acid dianhydride] As the tetracarboxylic dianhydride which can be used for the polyamine and/or the polyimine polymer which constitutes the liquid crystal alignment agent of the present invention, four can be exemplified. Carboxylic acid dianhydride, the following (IV - y) represents a reaction of cyclobutane tetracarboxylic acid "the present compound contains a chelating compound,"), also known as a guanamine repeating single polymer having a guanamine which can be used in a method of acid polymerization such as butane Anhydride

-13- 200804936 (wherein R5, R6, R7 and R8 are each independently a hydrogen atom, a halogen atom or a monovalent organic group), 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1, 2,4,5-cyclohexanetetracarboxylic acid dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1 , 2,4-tricarboxycyclopentyl acetic acid dianhydride, bicyclo[2,2,1]heptane-2,3,5,6-tetracarboxylic dianhydride, 3,5,6-tricarboxynorbornane 2-acetic acid dianhydride, tetracyclo[4,4,0,12,5,17,10]dodecane-3,4,8,9-tetracarboxylic dianhydride, 2,3,4,5- Tetrahydrofuran tetracarboxylic acid dianhydride, dicarboxylic acid dianhydride R9 represented by the following formula (IV-6°)

(wherein R9 is a hydrogen atom or a monovalent organic group), 5-(2,5-dioxotetrahydrofuran)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, double ring [2,2,2]-oct-4-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2,2,2]-oct-7-ene-2,3,5,6 - an aliphatic or alicyclic tetracarboxylic dianhydride such as a tetracarboxylic dianhydride or a compound represented by the following formulas (1) and (2); 14- 200804936

ο ο (wherein R1C) and R12 represent a divalent organic group having an aromatic ring, I R" and R13 represent a hydrogen atom or an alkyl group, and a plurality of R11 and R13 may be the same or different); Tetraic acid dianhydride, 3,3',4,4'-diphenyl ketone tetracarboxylic acid dianhydride, 3,3',4,4'-diphenylstilbene tetracarboxylic acid dianhydride, 1,4,5 , 8-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic acid dianhydride, 3,3', 4,4'-dimethyldiphenylnonanetetracarboxylic acid dianhydride, 3,3',4,4'-tetraphenylnonanetetracarboxylic acid dianhydride, 1,2,3,4-furan tetracarboxylic acid Diacid anhydride, 4,4'-bis(3,4.dicarboxyphenoxy) • Diphenyl sulfide dianhydride, 4,4′·bis(3,4-dicarboxyphenoxy)diphenylphosphonium Diacid anhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene di phthalic anhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, di(phthalic acid)benzenephosphine oxide dianhydride, ethylene glycol-di(hydrogen trimellitate), propylene Alcohol-di(hydrogen trimellitate), 1,4-butanediol-di(hydrogen trimellitate), 1,6-hexanediol-di(hydrogen trimellitate), 1, 8-octanediol-di(dehydrated phenyl•15-200804936 triester), 2,2-bis(4-hydroxyphenyl)propane-di(hydrogen trimellitate), the following formula (3) An aromatic tetracarboxylic acid dianhydride such as a compound represented by (6). They may be used alone or in combination of two or more. /CH3

0 is a cyclobutane tetracarboxylic acid dianhydride represented by the above formula (IV-1°), and may be -16-200804936, for example, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2-di Methyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2-diethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-two Methyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-diethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-two Chloro-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-i,2,3,4-cyclobutanetetracarboxylic acid dianhydride 0

The dicarboxylic acid dianhydride represented by the above formula (IV-6°) may, for example, be 1,3,3&,4,5,91)-hexahydro-5-(tetrahydro-2,5-dioxo. -3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&,4,5,913-hexahydro-5-methyl-5-(tetrahydro- 2,5·dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&,4,5,91>-hexahydro- 5-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3& 4,5,91)-hexahydro-7-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3 - Diketone, 1,3,3&,4,5,91)-hexahydro-7-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2 -c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furan Naphthyl)-naphthalene [1,2<]-furan-1,3-dione, 1,3,3&,4,5,91)-hexahydro-8-ethyl-5-(tetrahydro-2, 5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&,4,5,9-hexahydro-5,8 -Dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione. Wherein, with respect to all of the tetracarboxylic dianhydride, it is preferred to contain 50 mol% or more of a cyclobutane tetracarboxylic acid dianhydride represented by the above formula (IV-1), for example, a 1,2,3,4-ring Butane tetracarboxylic acid dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2·diethyl-1,2,3,4-ring Butane tetracarboxylic acid dianhydride, 1,3- -17- 200804936 dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3·diethyl-1,2,3 , 4-cyclobutane tetracarboxylic acid dianhydride, 1,3-dichloro-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1, 2,3,4-cyclobutanetetracarboxylic acid dianhydride; bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic dianhydride; 1,2,3,4-cyclopentane IV carboxylic acid

Diacid anhydride; 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride; tetracarboxylic acid diacid field represented by the above formula (IV-6), for example, 1,3,3a,4,5,9b- Hexahydro-5-(tetrahydro-2,5-monooxy-3-furanyl)-naphthalene [i,2-c]·furan-1,3-dione, l,3,3a,4,5 , 9b-hexahydro-5.methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, l ,3,3a,4,5,9b-hexahydro-5-ethyl·5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[l,2-c]-furan- 1,3-diketone, 1,3,3&,4,5,91)-hexahydro-7-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2<]-furan-1,3-dione, l,3,3a,4,5,9b-hexahydro-7-ethyl-5-(tetrahydro-2,5-dioxo- 3-furyl)-naphthalene [l,2-c]-furan·ι,3-dione, hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl Furan-l,3-dione, l,3,3a,4,5,9b-/\ hydrogen-8_ethyl-5-(tetrahydro-2,5•dioxo-3-furanyl)·na [1,2 - c ] _ furan-1,3 -dione, [,3,3 a,4,5,9 b -hexahydro-5,8-dimethyl-5-(tetrahydro-2 ,5-dioxo-3-furanyl)·naphthalene [uc]-furan-1,3-dione; 2,3,5 -two The at least one tetracarboxylic acid dianhydride of carboxycyclopentyl acetic acid dianhydride is more preferably 7 〇 mol% or more from the viewpoint of improving performance. In the repeating unit represented by the above formulas (I-1) and (1-2) The group represented by the above formula (Π~丨), (Π~2) and (III-1) represented by (^ and Q2 is a group derived from a monoamine' corresponding to removal of two amine groups from a diamine In the above formula (II-1), the alkyl group having 10 to 20 carbon atoms represented by R1 may, for example, be n-decyl, n-dodecyl or n-pentadecane. a monovalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms, and may be derived, for example, as a monovalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms. An alicyclic skeleton of a cycloalkane such as cyclobutane, cyclopentane, cyclohexane or cyclodecane; a bridged ring skeleton such as norbornene or adamantane; a steroid skeleton such as cholesterol or cholestyl alcohol; a monovalent organic group or the like. The above monovalent organic group having an alicyclic skeleton may be optionally substituted by a halogen atom, preferably a fluorine atom. Examples of the monovalent organic fluorene of a fluorine atom having 6 to 20 carbon atoms include straight-chain alkyl groups having 6 to 20 carbon atoms such as n-hexyl, n-octyl and n-decyl groups; cyclohexyl groups and rings; An alicyclic hydrocarbon group having 6 to 20 carbon atoms such as an octyl group; a hydrogen atom of an organic group such as an aromatic hydrocarbon group having 6 to 20 carbon atoms such as a phenyl group or a biphenyl group, or a fluorine atom or a fluorine atom Alkyl substituted group. Further, in the above formula (II-1), the group represented by X1 is a single bond, ·0-, -CO-, -C〇〇-, -OCO-, -NHCO-, -CONH-, -S-, a methylene group, an alkylene group having 2 to 6 carbon atoms or a phenyl group, wherein, as a particularly preferred one, a group of -〇-, -CO-, -COO-, -〇C〇·ecoin can be cited. group. Specific examples of the diamine having a group represented by the above formula (II-1) include tetradecyloxy-2,4-diaminobenzene and fifteen-epoxy-2,4. A monoaminobenzene, a hexadecanthoyloxy-2,4-anthracene, an octadecyloxy-2,4-diaminobenzene, a compound represented by the following formulas (7) to (21). -19- 200804936 oco

CHa H3Cch{ch2)3chC"CH3 ch3 (7)

Oco—k«Λί

CH3 CH3 1 ^CHa H ( CH2)2CH=C ch3 (9)

CH3 H3〇CH(CH2)2 CH=C^ CHa CHs

H(CHzhCn /CH3 ch3 (11) coo-

Ch3 H39 CH(CH2>2 ch=c zCH3 ch3 !3C CHl H2ir, ^-NH2 (13)

:H ( CH2)3CH (12) ch3 /CHa ch3 (14) CH3

H ( CH2)3CH ^*ch3 ch3 (15)

H2N h2n h2n

〇〇〇-〇-〇〇〇-ό (19)

H2N\ {^^COOH^^OOO

(2 0) (2 1) In the above formula (II-2), the divalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms represented by R2 may, for example, be -20. - 200804936 There are alicyclic skeletons derived from cyclohexane, such as cyclobutane, cyclopentane, cyclohexane, cyclodecane, etc.; norbornane, adamantane, etc., having a bridged ring skeleton; cholesterol, cholesteric A divalent organic group such as a steroid skeleton such as an alkanol. The above divalent organic group having a lipid ring skeleton may be optionally substituted by a halogen atom, preferably a fluorine atom. Specific examples of the diamine having a group represented by the above formula (II-2) include compounds represented by the following formulas (22) to (26).

^ch3

Q-co H2N

In the poly-proline polymer and/or polyimine polymer of the present invention, the ratio of the divalent organic group represented by each of the above formulas (II-1) and (Π-2) is from the viewpoint of vertical alignment. It is considered that 'relative to the amount of all diamines, preferably 7 mol% or more, more preferably more than mol%. Next, in the above formula (III-1), as the divalent organic group having an aromatic ring containing an aromatic 21-200804936 represented by R3, for example, a phenyl group, a biphenyl group, a naphthyl group, Methyldiphenyl, oxydiphenyl. Any of these hydrogens containing an aromatic ring in the aromatic ring skeleton may be optionally substituted by halogen or an alkyl group having 1 to 5 carbon atoms. The divalent organic group having an organic siloxane skeleton may, for example, be tetramethyldimethoxyalkyl or the like. Further, the divalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms may, for example, be derived from cyclopentane, cyclopentane, cyclohexane or cyclodecane. An alicyclic skeleton; a divalent organic group having a bridged ring skeleton such as norbornene or a Donkey Kong. The above divalent organic group having an alicyclic skeleton may be optionally substituted by a halogen atom, preferably a fluorine atom. The specific example of the diamine having the group represented by the above formula (III) is preferably 1,4-bis(aminomethyl)-bicyclo[2,2,1]heptane, 1, 4-bis(aminopropyl)-bicyclo[2,2,1]heptane, isophoronediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-di(amino) Methyl)cyclohexane, 1,3-bis(aminopropyl)cyclohexane, m-xylenediamine, p-xylenediamine, 3,3'-(hexamethyltrioxane-1,3 -diyl)di(propylamine), a compound represented by the following formulas (27), (28), etc. Η2Ν · CH2CH2{〇-CH2CH2+0-CH2CH2· NH2 (27) Η2Ν· CH2CH2CH2+0-CH2CH2l 〇-CH2CH2CH2·ΝΗ2 (28) (In the above formula, η is an integer of 1 to 100.) In the polyproline polymer and/or polyimine polymer of the present invention, the above formula (III-1) represents The ratio of the divalent organic group is preferably 2% or more, more preferably 5% or more, relative to the total amount of the diamine, from the viewpoint of improving the solubility of the polymer solution-22-200804936. In the present invention In the synthesis of polyaminic acid polymers and/or polyimine polymers used, Other diamine compounds may be used in combination within the scope of the effects of the present invention. As other diamine compounds, for example, p-phenylamine, 2-methyl-1,4-phenylenediamine, 2-ethyl- 1,4-phenylenediamine, 2,5 · dimethyl-1,4-phenylenediamine, 2,5-diethyl-anthraquinone, 2,3,5,6•tetramethyl- 1,4-phenylenediamine, m-phenylenediamine, 4,4,-diaminodiphenylmethane, 4,4,_diaminodiphenylethane, 4,4'-diaminodiphenyl Thioether, 4,4,-diaminodiphenylanthracene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2,-bis(trifluoromethyl)-4 , 4,-diaminobiphenyl, 2,2,-diethyl-4,4,-diaminobiphenyl, 3,3'-dimethyl-4,4,diaminobiphenyl, 3,3,_bis(trifluoromethyl)·4,4-amino-amine, 3,3-diethyl-4,4′-diaminobiphenyl, 4,4-diaminobenzene Toluidine aniline, 4,4-diaminodiphenyl ether, hydrazine, % diaminone, 2,2'-dimethyl-4,4'-diaminobiphenyl, 5-amino-1 · (4, _ amine basic group) -1,3,3-dimethyl-imprinted, 6-amino-aminophenyl) · ι 3,3_ spring dimethyl indane, 3,4 ' - two amine Diphenyl ether, 3,3,-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4,diaminobenzophenone, 2,2•2 [4· (4·Aminophenoxy)phenyl]propane, 2,2·bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2·bis(4-aminophenyl) ) propane, 2,2-di(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]anthracene, anthracene, ketone (4.amine) Phenoxy group) benzene, 1,3-bis(4-aminophenoxy)benzene, iota, 3-bis(3.aminophenoxy)benzene, 9,9-bis(4-aminobenzene) Base)-10-hydroquinone, 2,7-diaminopurine, 9,9-bis(4-amino-23-200804936 phenyl) 3⁄4, 4,4'-methyl-di(2-chloro Aniline), 2,2,5,5,·tetrachloro-4,4,diaminobiphenyl, 2,2,-dichloro-4,4,diamino,5,·dimethyl Oxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 1,4,4,-(p-phenylphenylidene)diphenylamine, 4,4 '-(m-phenylphenylisopropylene)diphenylamine, 2,2'-bis[4-(4-amino-2trifluoromethylphenoxy)phenyl]hexafluoropropane, 4, 4'-Diamino-2,2,-bis(trifluoromethyl)biphenyl 4,4,-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl, heart (4-n-heptylcyclohexylphenoxy-2,4-diamine An aromatic diamine such as benzene; 1,3-propanediamine, butanediamine, pentanediamine, hexamethylenediamine, heptanediamine, octanediamine, decanediamine, 4,4-diaminoheptyldiamine, etc. Aliphatic diamine; 2,3·diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2 , 3-dicyanopyrazine, 5,6-diamino 2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 2, 4-Diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-di Amino-6-phenyl-1,3,5-triazine, 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-three Pyrazine, 4,6-diamino-2-vinyl-s-triazine, 2,4-diamino-5-phenylthiazide, 2,6-diaminopurine, 5,6-diamine 1,3 - dimethyl uracil, 3,5 -diamino-1,2,4-triazole, 6,9-diamino-2-ethoxy acridine lactate, 3, 8-Diamino-6-phenylphenanthridine, 1,4-diaminopyridazine, 3,6-diaminoacridine, bis(4·aminobenzene) ) Of diphenylamine molecule having two amine groups and a diamine Level 1 nitrogen atom other than the stage 1 group; the following compounds of formula (29) and (30) can be exemplified. These diamine compounds may be used singly or in combination of two or more kinds. -24- 200804936

2 (2 9)

(wherein y is an integer of 2 to 12, and z is an integer of i to 5). Among them, preferred examples thereof include p-phenylenediamine, 2-methyl-1,4-phenylenediamine, 2-ethyl-1,4-benzenediamine, and 2,5-dimethyl group.丨, phenylenediamine, Φ 2,5-diethyl-1,4-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 4,4, _ Aminodiphenylmethyl, 2,2-monomethyl-4,4'-diaminobiphenyl, 2,2'-di.(trifluoromethyl)-4,4 '-diamine linkage Benzene, 2,2,-diethyl-4,4'-diamino-based, 3,3-methyl-4,4'-diaminobiphenyl, 3,3'-diethyl- 4,4 '-diaminobiphenyl, 3,3 '-bis(trismethyl)-4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 4, 4,-Diaminobenzophenone, 2,2-bis(4-aminophenyl)propane, 2,2, bis(4-aminophenyl)hexafluoropropane, 2,6-diaminopyridine , 3,4 · diaminopyridine, etc. ® [Synthesis of poly-proline] The tetracarboxylic acid diacid and the ratio of the poly-proline synthesis reaction are preferably relative to the amine group of 1 equivalent of the diamine, so that the anhydride group of the tetradecanoic acid diacid is 0.2. A ratio of ~2.0 equivalents is more preferably made to a ratio of 〜·8 to 12 equivalents. The synthesis reaction of polylysine is carried out in an organic solvent, preferably at a temperature of from _2 〜 to 150 °, more preferably at a temperature of from 〇 to i 〇〇 °c. Here, 'as an organic solvent, as long as it can dissolve the synthesized polyaminic acid, -25-200804936, it is not particularly limited, and examples thereof include i-methyl-2-pyrrolidone and N,N-dimethylacetamide. , aprotic polar solvents such as N,N-dimethylformamide, dimethylhydrazine, 7-butyrolactone, tetramethylurea, hexamethylphosphonium triamine; m-cresol, xylenol, A phenolic solvent such as phenol or halogenated phenol. 1〜30重量重量的重量。 The amount of the total amount of the tetracarboxylic acid dianhydride and the diamine compound (n) relative to the total amount of the reaction solution (α + /3) is 0. 1~30% by weight the amount. Further, in the range in which the produced polyamine acid is not precipitated, the alcohol, the ketone, the anthracene' ether, and the halogenated hydrocarbon in which the poor solvent of the polyamic acid is further used in the above-mentioned solvent may be used. , hydrocarbons, etc. Specific examples of such a poor solvent include methanol, ethanol, isopropanol, cyclohexanol, 4-hydroxy-4-methylpentanone, ethylene glycol, propylene glycol, hydrazine, 4-butanediol, and the like. Glycol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl S isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, A Methyl oxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol n-propyl ether, ethylene Alcohol 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, and the like. As described above, a reaction solution in which polylysine was dissolved was obtained. Then, -26-200804936, 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 to obtain a polyamic acid. Further, the poly-proline is redissolved in an organic solvent, and then precipitated with a poor solvent, and the poly-proline is purified by performing one or several processes. [Synthesis of ruthenium iodide polymer] The ruthenium iodide polymer constituting the liquid crystal alignment agent of the present invention can be synthesized by dehydration ring closure of the above polyglycine. The ruthenium iodide polymer used in the present invention may also be a partially dehydrated ring-closing Φ polymer having a ruthenium iodide ratio of less than 100%. The "yttrium imidation ratio" as used herein means the ratio of the ratio of the repeating unit having a quinone ring or an isoindole ring in all repeating units of the polymer expressed as a percentage. The polyaminic acid polymer and/or the ruthenium iodide polymer used in the present invention preferably has a ruthenium amination ratio of 40% or more, and more preferably 70% or more from the viewpoint of voltage retention. The dehydration ring closure of polylysine may be carried out by (1) heating poly-proline, or (ii) dissolving poly-proline in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution and heating as needed. A method of synthesizing it by condensation. φ In the above method (1) of heating poly-proline, the reaction temperature is preferably from 50 to 200 ° C, more preferably from 60 to 170 ° C. When the reaction temperature is less than 50 °C, the dehydration ring-closure reaction cannot be completed. If the reaction temperature exceeds 200 °C, the molecular weight of the obtained quinone imidized polymer may decrease. On the other hand, in the method of adding a dehydrating agent and a dehydration ring-closure catalyst to the polyaminic acid solution of the above (ii), an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent is determined according to the desired imidization ratio of -27-200804936, preferably 0. 01 to 20 moles relative to the repeating unit of 1 mole of polyamic acid. Further, as the dehydration ring-closure catalyst, a tertiary amine such as pyridine, trimethylpyridine, lutidine or triethylamine can be used. However, it is not limited to these. The amount of the dehydration ring-closing catalyst to be used is preferably (Κ01 to 10 mol) with respect to the dehydrating agent used for 1 mol. The more the amount of the dehydrating agent and the dehydration ring-closure agent, the higher the niobium amination rate. The organic solvent used in the dehydration ring-closure reaction may, for example, be the same organic solvent as exemplified as the solvent used in the synthesis of polylysine. Further, the reaction temperature of the dehydration ring-closure reaction is preferably from 0 to 180 ° C. It is preferably 10 to 150 ° C. Further, the ruthenium iodide polymer can be purified by performing the same operation as the polyaminic acid purification method on the reaction solution thus obtained. [End Modification Polymer] The present invention The polyglycolic acid/quinone imidized polymer may also be a terminal modified polymer having a molecular weight adjusted. By using the terminal modified polymer, the coating of the liquid crystal alignment agent can be improved without impairing the effects of the present invention. The characteristics of the coating, etc. The terminal modified polymer can be added to the reaction system by adding a monobasic acid anhydride, a monoamine compound, a monoisocyanate compound, etc. in the synthesis of polyfluorene® amine acid. Among them, as the monobasic acid anhydride, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecane Further, as the monoamine compound, for example, aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, and n- Monoalkylamine, n-dodecylamine, n-tridecylamine, -28- 200804936 n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecaneamine, n-octadecylamine, Further, as the monoisocyanate compound, for example, phenyl isocyanate or naphthyl isocyanate may be mentioned. [Logarithmic Viscosity of Polymer] Polylysine and/or yttrium obtained as above The aminated polymer preferably has a logarithmic viscosity (W 1 η) 〇. 〇 5 〜 1 0 d 1 / g 'more preferably 0 · 0 5 〜 5 d 1 / g. Logarithmic viscosity in the present invention (7) In) 値 is determined by using N-methyl-2-pyrrolidone as a solvent at a concentration of 0.5 g/100 ml at 30 ° C.値 obtained by the following formula (1) _ addition (solution flow time / solvent flow time) % = - one (weight concentration of polymer) [polymerization yield of ruthenium iodide] The ruthenium imidization ratio in the present invention is preferably from 50 to 100%, more preferably from 65 to 100%, particularly preferably from 75 to 100%, from the viewpoint of improving voltage retention performance. The hydrazine imidization rate is obtained by dissolving the hydrazine imidized polymer in a reduced pressure of 60: C, and dissolving it in deuterated dimethyl hydrazine, using tetramethyl decane as a reference, in the chamber. 1H-NMR was measured at a temperature, and 値 was obtained by the formula shown by the following formula (ii): 醯 imidization ratio (%) = (1 - Α1/Α2χ α ) χ 100 ...... (ii) A1: Peak area derived from NH proton (10 ppm) A2: Peak area derived from aromatic ring protons (7 to 8 ppm) α: Relative to i NH matrix-29 in polymer precursor (polyglycine) - , 200804936, the ratio of the number of protons derived from the aromatic ring. [Vertically oriented liquid crystal alignment agent] In order to obtain the liquid crystal alignment agent of the present invention, it is preferred to dissolve the above polyamic acid polymer and/or ruthenium iodide polymer in an organic solvent. Further, 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. Examples of the organic solvent constituting the liquid crystal alignment agent of the present invention include N-methyl-2-pyrrolidone, r-butyrolactone, r-butyrolactam, N,N-•dimethylformamide, and N. , N-dimethylacetamide, 4-hydroxy-4-methyl-2. pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethoxylate Ethyl propionate, 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 dimethyl ether, ethylene 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 Wait. Among them, a preferred solvent composition is a composition obtained by combining the above solvents, and the composition is not precipitated in the alignment agent, and the surface tension of the alignment agent is in the range of 30 to 40 mN/m. The solid content concentration in the liquid crystal alignment agent of the present invention is selected in consideration of viscosity, volatility and the like, and is preferably in the range of 1 to 10% by weight. That is, the liquid crystal alignment agent of the present invention is applied to the surface of the substrate to form a resin film as a liquid crystal alignment film. When the solid content concentration is less than 1% by weight, the thickness of the resin film is too small, so that a good liquid crystal alignment cannot be obtained. When the content of the solid -30-200804936 is more than 5% by weight, the thickness of the resin film is too thick, so that a good liquid crystal alignment film cannot be obtained, and the viscosity of the liquid crystal alignment agent is increased, and the coating property is deteriorated. Further, the particularly preferable solid content concentration range differs depending on the method used for coating the substrate with the liquid crystal alignment agent. For example, when it is a spin coating method, it is particularly preferably in the range of 1 · 5 to 4 · 5 % by weight. In the case of the printing method, the solid content concentration is preferably in the range of 4 to 10% by weight, so that the viscosity of the solution falls within the range of 10 to 50 mPa.s. When the ink jet method is employed, it is particularly preferable that the solid content concentration is in the range of 2 to 5% by weight, so that the viscosity of the solution falls within the range of 5 to 15 mPa, s. The liquid crystal alignment agent of the present invention may further contain an epoxy group-containing compound represented by the following formulas (VI-1) and (VI-2) within a range not impairing the physical properties of the object.

Rc-tO I

<? (VI - 1) (VI-2) (In the forced formula, s is an integer of 2 to 6, ! is an integer of i to 4, rc is an organic group of s, and organic of Rd·t Group). Examples of the seed-containing epoxy group-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol monoglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and neopentyl. Glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl-31- 200804936 oil ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 1,3,5 ,6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-P-phenylenediamine, N,N,N',N,-tetraglycidyl Base-m-xylylenediamine, N,N,N,,N'-tetraglycidyl-2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2-di[ 4-(N,N-diglycidyl-4-aminophenoxy)phenyl]propane, hydrazine, hydrazine, hydrazine, N5-tetraglycidyl-4,4'-diaminodiphenyl A hospital, 1,3 -di(N,N-diglycidylaminomethyl)cyclohexane, 1,4-bis(N,N-diglycidylaminomethyl)cyclohexane, 1 ,3-di(N,N-diglycidylaminomethyl)benzene, N,N,N',N'-tetra# glycidyl-m-m-xylene Amine. The content of the epoxy group-containing compound is preferably from 1 to 50 parts by weight, more preferably from 5 to 45 parts by weight, per 100 parts by weight of the polymer. Further, in the liquid crystal alignment agent of the present invention, a compound containing a functional decane may be contained in a range which does not impair the target physical properties from the viewpoint of improving the adhesion to the surface of the substrate. As such a functional decane-containing compound, for example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, and 2-amine can be mentioned. Propyltriethyloxy decane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-moon-glycolyl)-3-aminopropyl Methyl-methoxylate, 3-propylpropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyltriethoxydecane, N-triethoxydecylpropyltriethylenetriamine, N-trimethoxydecylpropyltriethylenetriamine, 10 -trimethoxydecyl-1,4,7-triazadecane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxy-32- 200804936 decane Base-3,6-diazaindolyl acetate, 9-triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxy Baseline, N-benzyl-3-aminopropyltriethoxysulfate, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyl Triethoxy decane, N-bis(oxyvinyl)-3-aminopropyltrimethoxy sand, N-bis(oxyvinyl)-3-aminopropyltriethoxydecane, 3- (N-allyl-N-glycidyl)aminopropyltrimethoxydecane, 3-(N,N-diglycidyl)aminopropyltrimethoxydecane, and the like. [Manufacture of display element using liquid crystal alignment agent] The liquid crystal display element using the vertical alignment type liquid crystal alignment agent of the present invention can be produced, for example, by the following method. (1) Applying a liquid crystal alignment agent of the present invention to a substrate provided with a patterned transparent conductive film by a method such as a roll coating method, a spin coating method, a printing method, an inkjet method, or the like, followed by coating The surface is heated to form a coating film. Here, as the substrate, for example, glass such as float glass or soda lime glass; a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether oxime or polycarbonate carbonate can be used. As the transparent conductive film provided on one side of the substrate, an ITO film made of tin oxide (Sn〇2), a NESA film (registered trademark of PPG, USA), or indium tin oxide (In2〇3 — Sn〇2) can be used. Wait. These transparent conductive film patterns can be formed by photolithography and a method of using a mask in advance. In the application of the liquid crystal alignment agent, in order to further improve the adhesion between the surface of the substrate and the resin film, for example, a compound containing a functional decane, a compound containing a functional titanium, or the like may be applied in advance. The heating temperature after coating the liquid crystal -33- 200804936 is preferably 80 to 300 ° C, more preferably 120 to 250 ° C. Further, in the liquid crystal alignment agent of the present invention, after the application, the organic solvent is removed to form a resin film as an alignment film, and when the imidization is not completely performed, the dehydration ring closure can be further carried out by further heating to form further ruthenium iodization. Resin film. The thickness of the formed resin film is preferably 0.001 to Ιμπι, more preferably 0.005 to 0.5/zm. (2) Two substrates in which a vertical liquid crystal alignment film is formed as described above are produced, and two substrates are arranged to face each other through a gap (cell gap), and the peripheral portions of the two base plates are bonded together with a sealant. The liquid crystal gap is filled into the cell gap separated by the surface of the substrate and the sealant, and the injection hole is closed to form a liquid crystal cell. Then, a polarizer is disposed on the outer surface of the liquid crystal cell, that is, on 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 which is a curing agent and a spacer can be used. Examples of the liquid crystal include nematic liquid crystal and disc liquid crystal. Among them, a nematic liquid crystal is preferable, and for example, a Schiff base liquid crystal, an oxidized even nitrogen liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, or a combination can be used. Phenylcyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, cubane liquid crystal, or the like. Further, cholesteric liquid crystals such as cholesteryl choline, cholesteryl phthalate, and cholesteryl carbonate may be added to these liquid crystals, and the trade names "C-15" and "CB-15" (manufactured by Merck) may be added. It is used by selling chiral agents and the like. Further, an iron-34-.200804936 electro-optical liquid crystal such as p-methoxybenzylidene-P-amino-2-methylbutylcinnamate may also be used. In addition, as a polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing film called a ruthenium film obtained by absorbing iodine while extending the polyvinyl alcohol may be immersed in a cellulose acetate protective film. A polarizing plate made of a plate or a film itself. EXAMPLES Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited to the examples. # Further, various measurements in the examples and comparative examples were carried out in the following manner. (1) Evaluation of the vertical alignment property When the vertical alignment type liquid crystal display element produced by the above method is applied without a voltage and when an AC voltage (peak-peak) of 8 V is applied, the liquid crystal display element is vertically viewed by a crossed Nicol prism. It was visually observed that when there was no light leakage or the like and the display was white, the evaluation was "good". (2) Measurement of voltage holding ratio ® A voltage of 5 V was applied to the liquid crystal display element at 60 ° C, the voltage application time was 60 μsec, the application period was 16.7 μs, and then the voltage was released to 16.7. The voltage holding ratio after milliseconds. (3) The solubility of the polymer was adjusted to have a viscosity of 15 to 25 mPa·sec (solid content concentration of 6·〇% by weight to 8·0% by weight), and the solvent composition was ··all the amount of the solvent was i〇〇, r _butyrolactone: N-methyl-2-pyrrolidone: butyl cellosolve = 40 · · (60 - A): A (weight ratio -35-200804936, visual observation of turbidity, in the poor solvent butyl cellosolve When it is 30 or more, it is evaluated as "good" in the case of no turbidity. (4) Printability evaluation is a good liquid in the "polymer solubility evaluation" of the above (3), and the printing solution is used for printing. After coating and baking, the film was visually observed. The evaluation of the coating film without depression or unevenness of coating was "good synthesis examples 1 to 25, and comparative synthesis examples 1 to 6. The compositions shown in Tables 1 and 2 were The order of the diamine, tetracarboxylic acid II|#, denoted as "anhydride") was added to N-methyl-2-pyrrole, and a solution having a solid content concentration of 20% by weight was prepared, and it was allowed to stand for 4 hours. A poly-proline polymer was obtained. The mopyridine shown in Table 1 was added to the total amount of the poly-proline acid polymer relative to the obtained poly-proline acid. After the acid anhydride, it was heated at 11 ° C for 4 hours to carry out dehydration. After the precipitate was reprecipitated in diethyl ether, it was recovered and dried under reduced pressure to a logarithmic viscosity and a ruthenium imidation rate as shown in Tables 1 and 2. Bismuth (A-1)~(A-25) and (a-1)~(a-6).

The content A is dissolved, and it is well coated. An acid anhydride (I-reaction of the paraffin 60 〇C anti-polymer ear number. Dry, aminated poly-36-.200804936

醯imitized polymer 1~1 I < CNJ 1 < A-3 inch 1 < uo 1 c VO 1 c A-7 oo ! < ON ! < o T < \ < 1 * 1 < csi I! < 醯i-imidized polymer 醯 imidization rate wn oo JO oo oo oo VQ 醯 imidization polymer logarithmic viscosity 〇〇o 卜 oo 卜 oo MD acetic anhydride (mole number) VO S CN VO o4 s Pyridox (mole number) CN wo o4 VO Anhydride (mmol) 1-2(100) 1-2(100) T-2(100) T-2(100) 1-2(100 ) 7-2(100) 1-2(100) T^2(100) T-2(100) T-2(100) T-K20), T-2(80) 1-2(50), T-4(50) diamine compound (mmol) Dl(10), D-5(20), D-10(70) Dl(lO), D-5(10), D-6(10), D -10(70) Dl(10), D-5(20), D-6(20), D-10(50) Dl(10), D-5(10), D-6(10), D -10(70) Dl(10), D-6(20), D-10(70) : Dl(10), D-6(20), D-10(70) Dl(10), D-6 (20), D-10(50), D-ll(20) Dl(10), D-6(20), D-10(50), D-ll(20) Dl(10), D-6 (20), D-7(20), D-10(50) Dl(10), D-6(20), D-12(70) Dl(lO), D-6(20), D-10 (40), D>12(30) Dl(lO), D-6(20), D-10(50), D-13(20) Synthesis example oo m inch VO v〇卜 OO σ\ O t— 4 CN .200804936

CO y '< I < T < in i 'i 1 <ν〇丁< T < οο ι—Ι 1 < σ\ T < 1 c 1 < 1 c 1 C 1 < 1 < oo oo gg oo vq VO l〇as ΙΟ vq r-; r-; ON c4 u〇r4 ι〇〇4 un CN c^ m oi cs l〇w^i o4 un o4 CN Cvj w^> O4 l〇o4 〇j to i cn S g cn 〇yTy h N gN o OO oo ci HI ·<1—-< VO S v-^ 弇Q <〇1 i Q o Q r < Q § VO VO © c— § OO ss 2 o 2 CNl \ ir—( QQ ά t Q ά QQQQQ ά τ·Η AQ s 豸g 豸go § i—4 芬转ά ά Ν〇ά W^> Ό ώ oo Q 1 < Q Bu Q VO Q v〇Q oo Q VO Q , H δ & Finish Q δ CN QQQQ ά QQQQQQQ i—^ Q CO inch [to i2 Γ^· OO 2 S 200804936

醯i-imidized polymer a-1 a-2 CO Γ a-4 a-5 a-6 醯i-imidized polymer 醯 imidization rate οο o 〇〇〇醯i-imidized polymer logarithmic viscosity 〇〇CO Acetic anhydride (mole number) pppp pyridine (mole number) mpppp anhydride (mmol) T-2 (100) T-2 (100) T-2 (100) T-3 (50), T-5 (50) T-3(50), T-5(50) T-3(50), T-5(50) Diamine compound (mmol) Dl(15), D-10(85) Dl(lO), D- 10(50), D-13(40) Dl(20), D-5(20), D-10(60) Dl(20), D-5(20), D-10(60) D-3 (30), D-9(10), D-10(60) D-4(30), D-9(10), D-10(60) Comparative Synthesis Example τ—^ CS] cn inch vn

σ\ CO 200804936 In Tables 1 and 2, for the diamine compound and the acid anhydride, the numbers in parentheses indicate the content ratio, and the symbols in the table have the following meanings: &lt;Diamine compound&gt; D - 1 : Formula (10) above Diamine D-2 represented by the above formula (11): diamine D-3 represented by the above formula (14): diamine D-5: 1, 4 represented by the above formula (20) - bis(aminomethyl)-bicyclo[2·2·1]heptane φ D- 6 : 1,3-bis(aminomethyl)-cyclohexane D-7 : m-xylenediamine D — 8 : 3,3′-(tetramethyldioxane-1,3-diyl)di(propylamine) D-9: diamine represented by the above formula (28) (average molecular weight: 1000) D - 1 0 : p-phenylenediamine D — 11: 4, 4, diaminodiphenylmethane D-12: 4,4'-diaminodiphenyl ether D-13: 2,2'-dimethyl-4 , 4'-Diaminobiphenyl® <Tetracarboxylic acid dianhydride> Τ A 1: 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride Τ A 2: 2,3,5-tricarboxyl ring Amyl phthalic acid anhydride Τ-3: 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride 4:1,3,3&amp;,4,5,913-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2&lt; ]-furan-1,3-dione oxime-5: pyromellitic dianhydride-40-200804936 Example 1 The ruthenium iodide polymer (a-1) obtained in Synthesis Example 1 was dissolved in r - In a mixed solution of butyrolactone/N-methyl-2-pyrrolidone/butyl cellosolve (weight ratio 40/30/30), 20 parts by weight of polyethylene glycol diglycidyl ether is dissolved relative to 100 parts by weight of the polymer. (Molecular weight: about 400; additive A), a solution having a solid concentration of 6 wt% was prepared. The solution was visually observed to obtain a turbid transparent solution, and thus it was confirmed that it showed good solubility. Subsequently, the film-forming composition of the present invention was prepared by filtration using a filter having a pore size of 0.2 /z m. Then, the printability was evaluated, and no unevenness or unevenness in coating was observed on the coating film, and it was confirmed that the film had good printability. Then, the film-forming composition of the present invention was prepared in the same manner as above except that the solid content concentration was 4%. Next, the film-forming composition was applied onto a transparent conductive film made of an ITO film provided on one surface of a glass substrate having a thickness of 1 mm by a spin coater, and dried at 200 ° C for 60 minutes to form a dry film thickness of 0.08 μ. The film of m. Next, on each of the outer edges of the liquid crystal alignment film of the liquid crystal alignment film coating substrate of the pair of transparent electrode/transparent electrode substrates, an epoxy resin adhered to an alumina ball having a diameter of 3.5 // m is applied. After the mixture is mixed, the liquid crystal alignment film faces are gradually combined and pressure-bonded, and the adhesive is cured. Next, the nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Ltd.) was filled between the substrates through the liquid crystal injection port, and then the liquid crystal injection port was closed with an acrylic photocurable adhesive, and bonded to both sides of the substrate. A polarizer is used to produce a liquid crystal display element. The vertical alignment property of the obtained liquid crystal display element was evaluated to be good. And measured the electric -41- 200804936 pressure retention rate, more than 99%, showing good electrical office retention performance. The results are summarized in Table 3. Examples 2 to 67, Comparative Examples 1 to 1 1 A film-forming composition having a solid content concentration of 6% was prepared in the same manner as in Example 1 according to the formulations shown in the following Tables 3 and 4, and the solubility and printing were evaluated. Sex. Further, a film-forming composition having a solid concentration of 4% was prepared in the same manner to prepare a liquid crystal display element. Then, the vertical alignment property and the measured voltage retention ratio were evaluated, and the results are shown in Tables 3, 4 and 5. -42- 200804936

Table 3 Solid content voltage holding ratio Example Polymer additive (% by weight) Solubility printability Vertical alignment (%) 1 A-1 Additive A (10) Good good and good> 99 2 A-1 Additive · Good good and good> 99 3 A-1 Additive C(10) Good & Good &gt;99 4 A-1 Additive C(40) Good Good &Good&gt;99 5 A-1 Additive D(20) Good & Good &gt;99 6 A-1 Additive E(10) Good Good &Good&gt;99 7 A-1 Additive F(10) Good Good &Good&gt;99 8 A-1 Additive F(30) Good Good Good &gt;99 9 A-2 Additive BU〇) Good Good &Good&gt; 99 10 A-2 Additive C(20) Good Good &Good&gt;99 11 A-2 Additive D(10) Good Good &Good&gt;99 12 A-2 Additive E(10) Good Good &Good&gt;99 13 A-2 Additive F(10) Good Good & Good 99 14 A-3 Additive D(10) Good Good &Good&gt;99 15 A-3 Additive D(10) Good Good &Good&gt;99 16 A-3 Additive F(10) Good Good &Good&gt;99 17 A-4 Additive E(10) Good & Good &gt;99 18 A-5 Additive A _Good good and good&gt;99 19 A-5 Additive C(10) Good good and good&gt;99 -43- 200804936 20 A-5 Additive 1X40) Good good and good&gt;99 21 A-5 Additive F(20) Good good and good&gt; 99 22 A-6 Additive A(10) Good Good &Good&gt;99 23 A-6 Additive B(5) Good Good &Good&gt;99 24 A-7 Additive D(10) Good Good &Good&gt;99 25 A-7 Additive D( 40) Good and good &gt;99 26 A-7 Additive E(30) Good & Good &gt;99 27 A-7 Additive F(10) Good Good &Good&gt;99 28 A-8 Additive A(20) Good Good &Good&gt;99 29 A-9 Additive B(10) Good Good &Good&gt;99 30 A-10 Additive D(20) Good Good &Good&gt;99 31 A-ll Additive A(20) Good Good &Good&gt;99 32 A-ll Additive B (10 Good and good &gt;99 33 A-ll Additive B(10) Good & Good &gt;99 34 A-ll Additives _ Good Good &Good&gt;99 35 A-ll Additive D(5) Good Good &Good&gt;99 36 A-ll Additives) Good and good &gt;99 37 A-12 Additive F(10) Good and good Good &gt;99 38 A —13 Additive D(10) Good Good &Good&gt;99 39 A-13 Additive D(10) Good Good &Good&gt;99 40 A-13 Additive E(10) Good Good &Good&gt;99 41 A-13 Additive F(5) Good Good & Good 99 T14 A-14 Additive A(20) Good Good &Good&gt;99 -44- 200804936

43 A-14 Additive D(10) Good & Good &gt;99 44 A-15 Good & Good &gt;99 45 A -16 Additive D(10) Good Good &Good&gt;99 46 A -16 Additive E(30) Good Good &Good&gt;99 47 A-17 Additive B(30) Good & Good &gt;99 48 A-17 Additive D(5) Good Good &Good&gt;99 49 A-17 Additive D(10) Good Good &Good&gt;99 50 A-17 Additive E(30) Good Good &Good&gt;99 51 A-18 Additive F(10) Good Good &Good&gt;99 Table 4 Solid Composition Voltage Retention Examples Polymer Additives (% by Weight) Solubility Printability Vertical Alignment (%) 52 A-19 Additive F (20) Good and good &gt;99 53 A-20 Additive D(10) Good Good &Good&gt;99 54 A-20 Additive W0) Good Good &Good&gt;99 55 A-21 Additive A(10) Good Good &Good&gt;99 56 A-21 Additive B(20) Good & Good &gt;99 57 A-21 Additive D(10) Good Good &Good&gt;99 58 A-22 Additive B(10) Good Good &Good&gt;99 59 A-22 Additive D(20) Good Good &Good&gt;99 60 A-22 Tim Agent D (40) Good Good &Good&gt;99 61 A-22 Additive E (30) Good Good &Good&gt;99 -45- 200804936 62 A-23 Additive E(30) Good & Good &gt;99 63 A-24 Additive (10) Good and good · Bad 98 64 A-25 Additive A(10) Good Good Good 96 65 A - 25 Additive D(10) Good Good Good 94 66 A-25 Additive E(10) Good Good Good 93 67 A-25 Additive F(20) Good Good and good 96 Table 5 Solid content voltage retention ratio Comparative example Polymer additive (% by weight) Solubility printability Vertical alignment (%) 1 a-1 Additive B (10) Not good _ Good 99 2 a-1 Additive C(10) No Good _ Good &gt;99 3 a-1 Additive EG〇) Not good one good &gt;99 4 a-1 Additive E(10) Bad - Good &gt;99 5 a-2 Additive D(10) Bad _ Good &gt;99 6 a- 2 Additive F(10) Not good one good 99 7 a-3 Additive Da〇) Good good good 93 8 a-4 Additive _ Good good good 90 9 a-5 Additive A(30) Good good good 92 10 a-5 Additive E ( 10) Good good and good 93 11 a-6 Add C⑽ 91 Good Good Good Good Table 3, Table 4 and Table 5, the additives, the numbers in parentheses represent

The content ratio, the symbols in the table have the following meanings: -46- 200804936 &lt;Additives&gt; Additive A: Polyethylene glycol diglycidyl ether (molecular weight about 400) Additive B: 1,6-hexanediol diglycidyl ether additive C : N,N,N',N'-tetraglycidyl-2,2'-dimethyl-4,4'-diaminobiphenyl additive D: N,N,N',N'-four Glycidyl-4,4'-diaminodiphenylmethane additive E: 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane φ Additive F : N, N, N ',N'-tetraglycidyl-m-xylylenediamine [Simple description of the diagram] 〇 [Main component symbol description] ΛΕ 〇y ϊ vn -47·

Claims (1)

200804936 X. Patent application scope: 1. A vertical alignment type liquid crystal alignment agent characterized by comprising a repeating unit of a proline having the following formula (I-1) and a quinone imine represented by the following formula (I-2) The polymer of at least one repeating unit of the repeating unit, Q1 in the above formula (I-1) and Q2 in the above formula (I-2) contain each of the following formulas (II-1) and (II-2) At least one of a divalent organic group and at least one of the divalent organic groups represented by the following formula (III-1), HOOC COOH / \ / pi / \-^HNOC CONH -Q1 The amine sulphide plant has a price of four. The acid bismuth plant has a four-base machine o=c. It has a price list of two P1 tables Q1 and /N\ cyo o nnc \\ 2 QIN , ▲ P2 CHO (where p2 Represents a tetravalent organic group constituting a tetracarboxylic acid, and Q2 represents a divalent organic group constituting a diamine); -48- 200804936 (In the above formula, X1 is a single bond, -0-, -CO-, -COO-, -OCO-, -NHC〇-, •C〇NH_, -S_, methyl group, carbon number a 2 to 6 alkyl or phenyl group, R 1 is an alkyl group having 10 to 20 carbon atoms, a monovalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms, or a carbon number of a monovalent organic group of 6 to 20 fluorine atoms; R 2 is a divalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms or a divalent fluorine atom having 5 to 30 carbon atoms; Organic group); (I I I -1) (In the above formula, X2 is a methyl group or an alkylene group having 2 to 20 carbon atoms, and R3 has an aromatic ring skeleton, an organic decane skeleton, and 1-(0-(:2114)^〇-1 The divalent organic group represented by ^ (11 represents an alkylene group having 2 to 5 carbon atoms, n represents 1 to 1 fluorene), Κ-(〇·ί: 3Η6)η-〇-ίΙ- a monovalent organic group (R represents a stretching group having 2 to 5 carbon atoms, η represents 1 to 50), and a divalent organic group having an alicyclic ring skeleton having 4 to 40 carbon atoms. Each of the plurality of X2s present may be the same or different.) 2. The vertical alignment type liquid crystal alignment agent of the first aspect of the patent application, wherein Ρ1 and (I-2) in the above formula (I-1) Ρ2 contains at least one of the tetravalent organic groups represented by the following formulas (IV-1) to (IV-6), R5 R5 R7 R8 -49- 200804936 XX XX: (IV-2) (IV-3)· (IV-4) (IV-5) (IV-6) (wherein R5, R6, R7, R8 and R9 are each independently; valence organic group). 3. The vertical alignment type liquid crystal according to item 2 of the patent application range contains P2 in the above formula (I-1) and P2 in (I-2) contains 50 mol% or more relative to the group (P, P2). At least one of the tetravalent organic groups represented by the above formula (IV). 4. The vertical alignment type liquid crystal of the first aspect of the patent application is formulated with the divalent organic group represented by the above formula (III-1) At least one of a divalent organic group represented by 矣(V_5)> a hydrogen atom or a direct agent, wherein ί a tetravalent organic 5) and (IV-6) agent, wherein ί (V-1)~ , -50- 200804936 R〇r. -2&gt; (V-3) Rb^^Rb~(V—3) (V - 4) (V-5) (wherein, Ra represents a hydrogen atom or a monovalent organic group, Rb·alkylene group having 1 to 2 carbon atoms, and each of Ra and Rb may be the same or different, and p is An integer from 1 to 99, q is an integer from i to 20). 5. The vertical alignment type liquid crystal alignment agent of claim 1, wherein the polymer is a repeating unit of a proline which is represented by the above formula (I) and a formula represented by the above formula (I-2) The total amount of the amine repeating unit, the quinone imine repeating unit accounts for 40 mol% or more of the quinone imidized polymer. 6. The vertical alignment type liquid crystal alignment agent of claim 1, further comprising 1 to 50 parts by weight, based on 100 parts by weight of the polymer, each selected from the group consisting of the following formulas (VI-1) and (VI-2) At least one of the group consisting of a compound having at least two epoxy groups in the molecule, comprising an epoxy group-containing compound, -51- 200804936 Rd —N &lt;? (VI-2) (In the formula, s is an integer of 2 to 6, an integer of 1 to 4 is an s-valent organic group, and Rd is a t-valent organic group. group). A vertical alignment type liquid crystal display element characterized by having a vertical alignment type liquid crystal alignment film formed by a vertical alignment type liquid crystal according to any one of claims 1 to 6. , Rc 3 please ] Agent -52- 200804936 VII. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Μ 〇 /\\\ 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: