TWI466921B - Vertical alignment type liquid crystal aligning agent and vertical alignment type liquid crystal display element - Google Patents

Description

Vertical alignment type liquid crystal alignment agent and vertical alignment type liquid crystal display element

The present invention relates to a vertical alignment type liquid crystal alignment agent and a vertical alignment type liquid crystal display element. More specifically, it relates to a vertical alignment type liquid crystal alignment agent and a vertical alignment type liquid crystal display element which are excellent in electrical performance, have improved afterimage performance in short-time driving and long-time driving.

At present, as a liquid crystal display element, a TN type liquid crystal display element having a so-called TN type (twisted nematic) liquid crystal cell is known, which forms polyacrylamide, polyimine, or the like on the surface of a substrate on which a transparent conductive film is provided. The liquid crystal alignment film is used as a substrate for a liquid crystal display element, and two of the substrates are opposed to each other, and a nematic liquid crystal layer having positive dielectric anisotropy is formed in the gap to form a cell having a sandwich structure, and the long axis of the liquid crystal molecule is One substrate is continuously twisted by 90 degrees to the other substrate; and an STN (Super Twisted Nematic) liquid crystal display element having higher contrast and less viewing angle dependency than the TN liquid crystal display element. The latter STN type liquid crystal display element is used as a liquid crystal in which a photoactive material chiral agent is blended in a nematic liquid crystal, and birefringence is produced by a state in which the long axis of the liquid crystal molecules is continuously twisted by 180 degrees or more between the 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 a liquid crystal are arranged in a comb shape on one side of the substrate to produce a surface with a substrate. Parallel electric fields, thereby controlling liquid crystal molecules (Patent Document 1). This element is generally called an in-plane switching type (IPS type) and is known to have excellent wide viewing angle performance.

As a liquid crystal display element other than the above, a vertical alignment called MVA (Multi-domain Vertical Alignment) type or PVA (Modeled Vertical Alignment) type in which liquid crystal molecules having negative dielectric anisotropy are vertically aligned on a substrate is proposed. Type liquid crystal display element. These vertical alignment type liquid crystal display elements are excellent not only in terms of viewing angle and contrast, but also in the process of forming a liquid crystal alignment film, and are not required to be subjected to polishing treatment or the like, and are therefore excellent in terms of manufacturing steps.

Heretofore, in order to improve the display quality of the vertical alignment type liquid crystal display element, improvement of the liquid crystal alignment agent has been studied from various angles. In particular, in the case of afterimages, attempts have been made to use polylysine polymers having bulky substituents in the side chain and attempts to combine two polylysines and/or polyimines (Patent Document 2 and 3) An attempt to introduce a monomer unit having excellent antistatic properties (Patent Document 4), an attempt to introduce an additive having excellent afterimage attenuation performance (Patent Document 5), and the like to reduce afterimage.

However, the above-mentioned afterimage improving product is mainly a product which reduces the afterimage generated in a short period of time, and does not take into consideration the afterimage performance when driven for a long period of time (for example, 48 hours or longer). In recent years, liquid crystal display elements have been widely used in fields such as television applications, and long-term driving is required to be performed longer than before, and thus the afterimage problem that occurs when driving for a long time is more important. Therefore, there is a need for a vertical alignment type liquid crystal display element which is excellent in afterimage performance in both the short-time driving and the long-time driving, and a liquid crystal alignment agent which can be imparted thereto, but such research has hardly been conducted before.

[Patent Document 1] Japanese Patent Laid-Open No. Hei 7-261181

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2003-295194

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2004-94179

[Patent Document 4] Japanese Patent Laid-Open No. Hei 11-116676

[Patent Document 5] Japanese Patent Laid-Open Publication No. 08-54631

[Patent Document 6] Japanese Patent Laid-Open No. Hei 6-222366

[Patent Document 7] Japanese Patent Laid-Open No. Hei 6-281937

[Patent Document 8] Japanese Patent Laid-Open No. Hei 5-170044

SUMMARY OF THE INVENTION An object of the present invention is to provide a vertical alignment type liquid crystal alignment agent and a vertical alignment type liquid crystal display element which have good vertical alignment and electrical properties, are hard to generate afterimages in both short-time driving and long-time driving.

Further objects and advantages of the present invention will be apparent from the following description.

According to the present invention, the above objects and advantages of the present invention, first, are achieved by a vertical alignment type liquid crystal alignment agent comprising:

(A) at least one selected from the group consisting of polyamic acid obtained by reacting a tetracarboxylic dianhydride with a diamine containing a compound represented by the following formula (1), and a ruthenium iodide polymer thereof Polymer (hereinafter also referred to as "polymer (A)"),

(In the formula (1), A is a monovalent organic group having a steroid skeleton), and

(B) at least one selected from the group consisting of polyglycines obtained by reacting a tetracarboxylic dianhydride with a diamine containing a compound represented by the following formula (2), and a ruthenium iodide polymer thereof Polymer (hereinafter also referred to as "polymer (B)"),

(In the formula (2), B is a steroid skeleton, a trifluoromethylphenyl group, a trifluoromethoxyphenyl group, a fluorophenyl group, an alkyl group having 6 to 10 carbon atoms or a carbon number of 6 The monovalent organic group of the fluoroalkyl group of ～10, and the content ratio of the (A) polymer is from 10 to 90% by weight based on the total amount of the (A) polymer and the (B) polymer.

The above objects and advantages of the present invention are, in a second aspect, achieved by a vertical alignment type liquid crystal display element having a vertical alignment type liquid crystal alignment film formed of the above-described vertical alignment type liquid crystal alignment agent.

According to the present invention, it is possible to provide a vertical alignment type liquid crystal alignment agent and a vertical alignment type liquid crystal display element which have good electrical properties, are hard to generate afterimages in short-time driving and long-time driving.

The vertical alignment type liquid crystal display element of the present invention can be effectively used for various devices, and can be suitably applied to, for example, a desktop calculator, a watch, a desk clock, a mobile phone, a counting display screen, a word processor, a personal computer, a television, etc. Display device.

Vertical alignment type liquid crystal alignment agent

The vertical alignment type liquid crystal alignment agent of the present invention comprises the polymer (A) and the polymer (B) as described above.

Polymer (A)

The polymer (A) contained in the vertical alignment type liquid crystal alignment agent of the present invention is a polyglycine which is obtained by reacting a tetracarboxylic dianhydride with a diamine containing the compound represented by the above formula (1) and At least one polymer of the group consisting of ruthenium imidized polymers.

<polylysine>

[tetracarboxylic dianhydride]

The tetracarboxylic dianhydride used for the synthetic polymer (A) may, for example, be 1,2,3,4-cyclobutanetetracarboxylic dianhydride or 1,2-dimethyl-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-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentane IV Carboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, cis-3,7-dibutyl Cyclohexyl-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 5-(2,5-dioxo Tetrahydro-3-furanyl-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarbonyl-2-carboxynorbornane-2:3,5: 6-dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3 -furyl)-naphthalene [1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-methyl-5-(tetrahydro-2 ,5-dioxo-3-furanyl)-naphthalene[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-ethyl -5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b -hexahydro-7-methyl -5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b -hexahydro-7-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-c]-furan-1,3-dione, 1,3 ,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-c]-furan-1, 3-diketone, 1,3,3a,4,5,9b-hexahydro-8-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2 -c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo- 3-furyl)-naphthalene [1,2-c]-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]oct-2,4- Diketo-6-spiro-3'-(tetrahydrofuran-2',5'-dione), a compound represented by the following formula (TI) or (T-II),

(wherein R ¹ and R ³ represent a divalent organic group having an aromatic ring, R ² and R ⁴ represent a hydrogen atom or an alkyl group, and a plurality of R ² and R ^{4 present} may be the same or different).

Specific examples of the aliphatic tetracarboxylic dianhydride include butane tetracarboxylic dianhydride and the like.

Specific examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, and 3,3',4,4. '-Diphenylphosphonium tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4 '-Diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylnonane tetracarboxylic dianhydride, 3,3',4,4'-tetraphenylnonane IV Carboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'- Bis(3,4-dicarboxyphenoxy)diphenylphosphonium dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4, 4'-perfluoroisopropylidene diphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, pair Phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4' -diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, ethylene glycol-bis(hydroper trimellitate), propylene glycol-double (dehydrated trimellitate), 1,4-butanediol-bis(anhydrotrimellitic acid ester), 1,6-hexanediol-bis(anhydrotrimellitic acid ester), 1,8-octane Glycol-bis(hydrogen trimellitate), 2,2-bis(4-hydroxyphenyl)propane-bis(anhydrotrimellitic acid ester), the following formula (T-1) to (T-4) ) respective compounds and the like.

These tetracarboxylic dianhydrides may be used alone or in combination of two or more.

The tetracarboxylic dianhydride used for the polymer (A) contained in the liquid crystal alignment agent of the present invention is preferably a tetracarboxylic dianhydride containing an alicyclic tetracarboxylic dianhydride, and preferably contains a compound selected from 1, 2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetra 1,2-,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride , 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, cis-3,7-dibutylcyclooctane-1,5 -diene-1,2,5,6-tetracarboxylic dianhydride, 3,5,6-tricarbonyl-2-carboxynorbornane-2:3,5:6-dianhydride, 1,3,3a ,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-c]-furan-1,3-dione, 1, 3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-c]-furan-1 ,3-dione, 1,3,3a,4,5,9b-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [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), the above formula (TI) A group consisting of a compound represented by the following formula (T-5) to (T-7) and a compound represented by the following formula (T-8) in the compound represented by the above formula (T-II); Further, at least one of the tetracarboxylic dianhydrides further preferably contains a compound selected from the group consisting of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 2,3,5-tricarboxycyclopentyl acetic acid dianhydride. At least one of the tetracarboxylic dianhydrides is particularly preferably a tetracarboxylic dianhydride containing 2,3,5-tricarboxycyclopentyl acetic acid dianhydride.

The tetracarboxylic dianhydride used for the synthetic polymer (A) is preferably contained in an amount of 50 mol% or more, more preferably 75 mol% or more of alicyclic tetracarboxylic dianhydride, based on the total tetracarboxylic dianhydride.

[diamine]

The diamine used in the synthesis of the polymer (A) contains the compound represented by the above formula (1). The monovalent organic group having a steroid skeleton represented by A in the above formula (1) is preferably a cholesteryl group or a cholesteryl group.

Specific examples of the compound represented by the above formula (1) include a compound represented by the following formula (1-1) or (1-2).

As the diamine used for the synthetic polymer (A), only the compound represented by the above formula (1) may be used, or other diamines may be contained in addition to the compound represented by the above formula (1). Examples of such other diamines include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, and 4, 4'-Diaminodiphenyl sulfide, 4,4'-diaminodiphenylanthracene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'- Diaminobenzimidanilide, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 5 -amino-1-(4'-aminophenyl)-1,3,3-trimethylindan, 6-amino-1-(4'-aminophenyl)-1,3,3 -trimethylindan, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-di Aminobenzophenone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoro Propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]anthracene, 1,4-bis(4-amine Phenyloxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminobenzene) Base)-10-hydroquinone, 2,7-diaminopurine, 9,9-bis(4-aminophenyl)anthracene, 4,4'-methylene-bis(2-chloroaniline), 2 , 2',5,5'-tetrachloro-4,4'-diaminobiphenyl, 2 , 2'-Dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4 , 4'-(p-phenylene diisopropylidene) bisaniline, 4,4'-(m-phenylene diisopropylidene) bisaniline, 2,2'-bis[4-(4-amine Benzyl-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-double [ An aromatic diamine such as (4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl or bis(4-aminophenyl)benzidine; 1,1-m-xylylenediamine; 1,3-propanediamine, butanediamine, pentamethylenediamine, hexamethylenediamine, heptanediamine, octanediamine, decanediamine, 4,4-diaminoheptyldiamine, 1,4-diamine Cyclohexane, isophoronediamine, tetrahydrodicyclopentadienyldiamine, tricyclo[6.2.1.0 ^2,7 ]undecenedimethyldiamine, 4,4'-methylenebis ( Aliphatic or alicyclic diamines such as cyclohexylamine), 1,3-bis(aminomethyl)cyclohexane; 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4 -diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyridine ,5,6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-three 1,4-bis(3-aminopropyl)per 2,4-Diamino-6-isopropoxy-1,3,5-three 2,4-diamino-6-methoxy-1,3,5-three 2,4-diamino-6-phenyl-1,3,5-three 2,4-diamino-6-methyl-s-three 2,4-diamino-1,3,5-three 4,6-Diamino-2-vinyl-s-three , 2,4-Diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5-diamino- 1,2,4-triazole, 6,9-diamino-2-ethoxyacridine lactate, 3,8-diamino-6-phenylphenanthridine, 1,4-diamine Piper , 3,6-diaminoacridine, bis(4-aminophenyl)phenylamine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N -ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N,N'-bis(4-aminophenyl)benzidine, the following formula ( Compound represented by DI)

(In the formula (DI), R ⁵ is selected from the group consisting of pyridine, pyrimidine, and tri Piperidine and piperazine a monovalent organic group having a cyclic structure containing a nitrogen atom, X ¹ is a divalent organic group, and a compound represented by the following formula (D-II) has two primary amino groups in the molecule. And a diamine of a nitrogen atom other than the primary amine group

(In the formula (D-II), X ² is selected from the group consisting of pyridine, pyrimidine, and tri Piperidine and piperazine a group of divalent organic groups having a cyclic structure containing a nitrogen atom, R ⁶ is a divalent organic group, and a plurality of X ² groups may be the same or different)

Diamino-based organodecane represented by the following formula (D-III)

(In the formula (D-III), R ⁷ represents a hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R ⁷ groups may be the same or different, p is an integer of 1 to 3, and q is 1 to 20. Integer), a compound represented by each of the following formulas (D-1) to (D-5),

(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).

Among them, preferred are p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,7-diamine. Base, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9-bis(4-aminophenyl)芴, 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'-methylene Bis(cyclohexylamine), 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, the above formula (D-1) to ( D-5) each represented by a compound, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6- Diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole And N,N'-bis(4-aminophenyl)benzidine, a compound represented by the following formula (D-6) in the compound represented by the above formula (DI),

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

Or 1,3-bis(3-aminopropyl)-tetramethyldioxane in the compound represented by the above formula (D-III), particularly preferably p-phenylenediamine.

The diamine used in the synthetic polymer (A) preferably contains 1 to 30 mol%, more preferably 5 to 20 mol%, still more preferably 5 to 15 mol%, based on the total amount of the diamine. (1) A compound represented.

The diamine used in the synthesis of the polymer (A) preferably further contains p-phenylenediamine. The content ratio of the p-phenylenediamine at this time is preferably 99% by mole or less, more preferably 70 to 95% by mole, still more preferably 80 to 95% by mole, more preferably the total amount of the diamine. It is 85~95 mol%.

The diamine used in the synthesis of the polymer (A) preferably does not contain the compound represented by the above formula (2).

[polyglycolic acid]

The polylysine which is the polymer (A) contained in the liquid crystal alignment agent of the present invention can be obtained by reacting a tetracarboxylic dianhydride with a diamine containing the compound represented by the above formula (1).

The ratio of use of the tetracarboxylic dianhydride to the diamine supplied to the polyaminic acid synthesis reaction is preferably 0.5 to 2 equivalents based on 1 equivalent of the amine group of the diamine, and the ratio of the acid anhydride group of the tetracarboxylic dianhydride is 0.5 to 2 equivalents. Good to make it a ratio of 0.7 to 1.2 equivalents.

The synthesis reaction of poly-proline is preferably carried out in an organic solvent, preferably at -20 ° C to 150 ° C, more preferably at 0 to 100 ° C, preferably for 1 to 7 hours, more preferably 2~ 7 hours. Here, the organic solvent is not particularly limited as long as it can dissolve the produced polyamic acid, and examples thereof include 1-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N. - dimethylformamide, 3-butoxy-N,N-dimethylpropanamide, 3-methoxy-N,N-dimethylpropanamide, 3-hexyloxy-N, Aprotic compounds such as guanamine compounds such as N-dimethylpropionamide, dimethyl hydrazine, γ-butyrolactone, tetramethyl urea, hexamethylphosphonium triamine; m-methylphenol, dimethyl A phenolic compound such as phenol, phenol or halogenated phenol. The amount (α) of the organic solvent is usually preferably an amount such that the total amount (β) of the tetracarboxylic dianhydride and the diamine compound is from 0.1 to 30% by weight based on the total amount (α + β) of the reaction solution.

In the organic solvent, a solvent alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, a hydrocarbon, or the like may be used in combination with the polyglycine which is not precipitated. . Specific examples of such a poor solvent include methanol, ethanol, isopropanol, cyclohexanol, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol, propylene glycol, and 1,4-butane. Alcohol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, acetic acid Ester, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol n-propyl ether, B 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, digan Alcohol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane Alkane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, isoamyl ether, and the like.

When an organic solvent is used in combination with a poor solvent, the amount of the poor solvent can be appropriately set within a range in which the produced polyaminic acid is not precipitated, and is preferably 10% by weight or less based on the total amount of the solvent. Preferably it is 5% by weight or less.

As described above, a reaction solution in which polyamic acid as the polymer (A) was dissolved was obtained. The reaction solution may be supplied to the liquid crystal alignment agent as it is, or may be prepared by separating the polyamic acid contained in the reaction solution, and then supplying the liquid crystal alignment agent, or the separated polyamic acid may be refined. The preparation of the liquid crystal alignment agent is supplied. The separation of the polyamic acid can be carried out by adding the above-mentioned reaction solution to a large amount of a poor solvent to obtain a precipitate, and drying the precipitate under reduced pressure, or by subjecting the reaction solution to distillation under reduced pressure by an evaporator.

Further, the polyaminic acid can be purified by repeating the step of dissolving the polyamic acid in an organic solvent once or several times, and then precipitating it with a poor solvent or distilling off under reduced pressure with an evaporator.

[醯i-imidized polymer]

The quinone imidized polymer of the polymer (A) contained in the liquid crystal alignment agent of the present invention can be obtained by subjecting the polylysine obtained as described above to dehydration and ring closure to imidize the oxime.

The ruthenium iodide polymer contained in the liquid crystal alignment agent of the present invention may be a fully ruthenium imide of a glycosidic acid structure in which the proline acid material has a dehydration ring structure, or may be a part of the proline structure dehydrated. Closed-loop, a partial ruthenium imide of a proline structure with a quinone ring structure.

The ruthenium iodide polymer contained in the liquid crystal alignment agent of the present invention preferably has a ruthenium iodide ratio of 20% or more, more preferably 25 to 95%.

The above-mentioned ruthenium amination ratio means a total amount of the number of guanamine structures and the number of quinone ring structures in the ruthenium iodide polymer, and the ratio of the number of quinone ring structures is expressed as a percentage. At this time, a part of the quinone ring may also be an isoindole ring. The imidization ratio can be determined by dissolving the ruthenium iodide polymer in a suitable deuterated solvent (for example, deuterated dimethyl hydrazine), using tetramethyl decane as a reference material, and measuring 1H-NMR at room temperature. The measurement result was obtained by the following formula (i).

醯 imidization rate (%) = (1-A ¹ /A ² ×α)×100(i)

(In the formula (i), A ¹ is the peak area derived from the NH proton present near the chemical shift of 10 ppm, A ² is the peak area derived from other protons, and α is the precursor relative to the ruthenium polymer ( One NH matrix in poly-proline), the ratio of the number of other protons).

Dehydration ring closure reaction of polylysine, preferably (i) by heating poly-proline, or (ii) by dissolving poly-proline in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution And according to the method of heating required.

The reaction temperature in the method of heating poly-proline in the above (i) is preferably from 50 to 200 ° C, more preferably from 60 to 170 ° C. The reaction time is preferably from 1 to 7 hours, more preferably from 2 to 7 hours. When the reaction temperature is less than 50 ° C, the dehydration ring closure reaction cannot be sufficiently carried out. When 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 the dehydrating agent and the 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 determined depending on the desired hydrazine imidization ratio, and is preferably 0.01 to 20 moles per 1 mole of the proline structure of the polyglycolic 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-closure catalyst is preferably from 0.01 to 10 mols per mol of the dehydrating agent used. The higher the amount of the above dehydrating agent and the dehydration ring-closure catalyst, the higher the yield of ruthenium. 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 closure reaction is preferably from 0 to 180 ° C, more preferably from 10 to 150 ° C. The reaction time is preferably from 1 to 7 hours, more preferably from 2 to 6 hours.

The polyimine obtained in the above method (i) may be directly supplied to a liquid crystal alignment agent, or may be obtained by refining the obtained polyimine and supplying it to a liquid crystal alignment agent. Further, in the above method (ii), a reaction solution containing a ruthenium iodide polymer is obtained. The reaction solution can be directly supplied to the liquid crystal alignment agent, or can be prepared by removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, and can also be supplied to the liquid crystal alignment agent, and can also be separated into the liquid crystal alignment after the separation of the ruthenium iodide polymer. The preparation of the agent may also be carried out by refining the separated quinone imidized polymer and then supplying it to the liquid crystal alignment agent. The dehydrating agent and the dehydration ring-closure catalyst are removed from the reaction solution, and a method such as solvent replacement can be employed. The separation and purification of the ruthenium iodide polymer can be carried out in the same manner as the above-described separation and purification method as polyglycine.

(Polymer B)

The polymer (B) contained in the vertical alignment type liquid crystal alignment agent of the present invention is a polyglycine prepared by reacting a tetracarboxylic dianhydride with a diamine containing the compound represented by the above formula (2). At least one polymer of the group consisting of ruthenium iodide polymers.

<polylysine>

[tetracarboxylic dianhydride]

The tetracarboxylic dianhydride used in the synthesis of the polymer (B) is the same as the tetracarboxylic dianhydride used in the above synthetic polymer (A).

[diamine]

The diamine used in the synthesis of the polymer (B) contains the compound represented by the above formula (2).

The monovalent organic group having a steroid skeleton represented by B in the above formula (2) is preferably a cholesteryl group or a cholesteryl group. As the monovalent group having a trifluoromethylphenyl group, for example, 4-(4-trifluoromethylphenylmethyloxy)cyclohexyl group can be cited as a monovalent group having a trifluoromethoxyphenyl group. For example, 4-(4-trifluoromethoxyphenylmethaneoxy)cyclohexyl group can be mentioned. Examples of the monovalent organic group having an alkyl group having 6 to 10 carbon atoms include a heptyl group, an octyl group, a decyl group, a fluorenyl group and the like, and a fluoroalkyl group having 6 to 10 carbon atoms. The monovalent organic group may, for example, be 7,7,7-trifluoroheptyl, 8,8,8-trifluorooctyl, 9,9,9-trifluorodecyl, 10,10,10- Trifluoromethyl group and the like.

Specific examples of the compound represented by the above formula (2) include compounds represented by the following formulas (2-1) to (2-7).

As the diamine used for the synthetic polymer (B), only the compound represented by the above formula (2) may be used, or other diamines may be contained in addition to the compound represented by the above formula (2). Examples of such other diamines include a compound represented by the above formula (1) and a diamine exemplified as another diamine which can be used for the synthesis of the polymer (A).

Among them, a compound represented by the above formula (1) or p-phenylenediamine is particularly preferred.

The diamine used in the synthesis of the polymer (B) preferably contains 1 to 50 mol% of the diamine represented by the above formula (2), more preferably 10 to 40 mol%, based on the total amount of the diamine.

The diamine used in the synthesis of the polymer (B) preferably further contains at least one selected from the group consisting of the compound represented by the above formula (1) and p-phenylenediamine. In this case, the content ratio of the compound represented by the above formula (1) is preferably 30 mol% or less, more preferably 5 to 15 mol%, based on the total amount of the diamine. The content ratio of p-phenylenediamine is preferably 95 mol% or less, more preferably 70 to 90 mol%, based on the total amount of the diamine.

The diamine used in the synthesis of the polymer (B) is most preferably a compound represented by the above formula (2), a compound represented by the above formula (1) and p-phenylenediamine, and the ratio thereof is 5 to 15 mol%, respectively. 5 to 15 mol% and 70 to 90 mol%.

[polyglycolic acid]

The polylysine which is the polymer (B) contained in the liquid crystal alignment agent of the present invention can be obtained by reacting a tetracarboxylic dianhydride with a diamine containing the compound represented by the above formula (2).

The reaction method is the same as the synthesis method of the above polyamic acid as the polymer (A).

[醯i-imidized polymer]

The ruthenium iodide polymer of the polymer (B) contained in the liquid crystal alignment agent of the present invention can be imidized by dehydrating and ring-closing the polylysine as the polymer (B) obtained as described above. be made of.

The ruthenium iodide polymer of the polymer (B) contained in the liquid crystal alignment agent of the present invention may be a fully ruthenium imide of a glycosidic acid structure in which the polyglycolic acid raw material has a dehydration ring closure, or may be Only a part of the proline structure is dehydrated and closed, and the proline structure and the quinone ring structure coexist with a part of the quinone imide.

The ruthenium iodide polymer of the polymer (B) contained in the liquid crystal alignment agent of the present invention preferably has a ruthenium amination ratio of 20% or more, more preferably 25 to 75%. The above ruthenium amination ratio can be measured in the same manner as the polymer (A).

The synthesis of the ruthenium iodide polymer as the polymer (B) is carried out in the same manner as the dehydration ring closure reaction of the polyglycolic acid in the polymer (A), or may be carried out after a change familiar to the skilled person.

- terminal modified polymer -

The polymer (A) and the polymer (B) contained in the vertical alignment type liquid crystal alignment agent of the present invention may also be terminal modified polymers each having a molecular weight adjusted. By using the terminal-modified polymer, the coating performance and the like of the vertical alignment type liquid crystal alignment agent can be further improved without impairing the effects of the present invention. Such a terminal-modified polymer can be produced by adding a molecular weight modifier to a polymerization reaction system during the synthesis of poly-proline. Examples of the molecular weight modifier include a monoanhydride, a monoamine compound, and a monoisocyanate compound.

As the above monoanhydride, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl amber may be mentioned. Anhydride, etc. Examples of the above monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-undecylamine, and positive ten. Dialkylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecaneamine, n-octadecylamine, n-icosylamine, and the like. The monoisocyanate compound may, for example, be phenyl isocyanate or naphthyl isocyanate.

The use ratio of the molecular weight modifier is preferably 50 parts by weight or less, and more preferably 30 parts by weight or less based on the total amount of the tetracarboxylic dianhydride and the diamine used in the synthesis of the polyglycolic acid.

- solution viscosity -

The polymer (A) and the polymer (B) obtained as described above preferably have a solution viscosity of 20 to 800 mPa·s, more preferably 30 to 500 mPa·s, when formulated into a solution having a concentration of 10% by weight, respectively. Solution viscosity.

The solution viscosity (mPa ‧ s) of the above polymer is a polymer solution prepared by using a good solvent (for example, N-methyl-2-pyrrolidone) of the polymer at a concentration of 10% by weight, using an E-type rotational viscometer The value measured at 25 °C.

<Other additives>

The vertical alignment type liquid crystal alignment film of the present invention comprises: as the polymer (A), a polyamine acid obtained by using a diamine containing the compound represented by the above formula (1), and a ruthenium imidized polymer thereof. At least one polymer in the group; and as the polymer (B), the polyamine obtained by using the diamine containing the compound represented by the above formula (2), and the ruthenium iodide polymer thereof At least one selected from the group consisting of at least one polymer in the group is an essential component, and may further contain other components as needed.

Examples of such other components include a compound having at least one epoxy group in the molecule (hereinafter referred to as "epoxy compound"), a functional decane compound, and the like.

Examples of the epoxy group compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and neopentyl Alcohol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl Base-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl) Cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N-diglycidyl-benzylamine, N,N-bi-dihydrate Glyceryl-aminomethylcyclohexane or the like.

The use ratio of the epoxy compound as described above is preferably 40% by weight based on the total amount of 100 parts by weight of the polymer (refer to the total amount of the above polymer (A) and the polymer (B), the same applies hereinafter). More preferably, it is 0.1 to 30 parts by weight.

The functional decane compound may, for example, be 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane or 2-aminopropyl. Triethoxy decane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxy Baseline, 3-ureidopropyltrimethoxydecane, 3-glypropylpropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3 -Aminopropyltriethoxydecane, N-triethoxydecylpropyltriethylenetriamine, N-trimethoxydecylpropyltriethylenetriamine, 10-trimethoxydecane-1 ,4,7-triazadecane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6-diazaindole Acid ester, 9-triethoxydecyl-3,6-diazadecyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-amino Propyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N-bis(oxyethylene)- 3-aminopropyl three Silane group, N- bis (oxyethylene) -3-aminopropyl triethoxy silane-like.

The mixing ratio of these functional decane compounds is preferably 2 parts by weight or less, more preferably 0.5 parts by weight or less, based on 100 parts by total of the total amount of the polymer.

<Liquid alignment agent>

The vertical alignment type liquid crystal alignment agent of the present invention is preferably prepared by dissolving the polymer (A) and the polymer (B) as described above and other additives optionally blended as needed in an organic solvent.

The content ratio of the polymer (A) contained in the vertical alignment type liquid crystal alignment agent of the present invention is 10 to 90% by weight based on the total amount of the polymer (A) and the polymer (B). This value is preferably from 25 to 75% by weight.

The polymer (A) and the polymer (B) contained in the vertical alignment type liquid crystal alignment agent of the present invention are each preferably a ruthenium iodide polymer.

The organic solvent which can be used for the liquid crystal alignment agent of the present invention is exemplified as a solvent which is used as a solvent used in the synthesis reaction of polyglycine. Further, a solvent exemplified as a poor solvent which can be used in combination in the polyglutamic acid synthesis reaction can be appropriately selected and used in combination.

Examples of the particularly preferable organic solvent used in the liquid crystal alignment agent of the present invention include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactone, and N,N-dimethylformamide. N,N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethoxy Ethyl propyl 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, B Glycol diethyl 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 Ester, isoamyl propionate, isoamyl isobutyrate, isoamyl ether, and the like. These solvents may be used singly or in combination of two or more. A particularly preferable solvent composition is a composition obtained by combining the above solvents, and has a composition in which the polymer in the alignment agent is not precipitated, and the surface tension of the obtained vertical alignment type liquid crystal alignment agent falls within a range of 25 to 40 mN/m.

The solid content concentration of the vertical alignment type liquid crystal alignment agent of the present invention (the ratio of the total weight of the components other than the solvent in the vertical alignment type liquid crystal alignment agent to the total weight of the alignment agent) is appropriately selected in consideration of viscosity, volatility, and the like, and is preferably selected. It is in the range of 1 to 10% by weight. That is, the vertical alignment type liquid crystal alignment agent of the present invention is applied to the surface of the substrate to form a coating film as a vertical alignment type liquid crystal alignment film. When the solid content concentration is less than 1% by weight, the thickness of the coating film is too small to be difficult. Obtaining a good vertical alignment type liquid crystal alignment film; on the other hand, when the solid content concentration exceeds 10% by weight, the coating film thickness is too thick and it is also difficult to obtain a good vertical alignment type liquid crystal alignment film, and the liquid crystal alignment agent The viscosity increases, resulting in poor coating properties.

The particularly preferable solid content concentration range differs depending on the method used when the vertical alignment type liquid crystal alignment agent of the present invention is applied to a substrate. For example, when a spin coating method is employed, it is particularly preferably in the range of 1.5 to 4.5% by weight. When the printing method is employed, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by weight, so that the solution viscosity can be made to fall within the range of 12 to 50 mPa·s. When the ink jet method is employed, it is particularly preferable that the solid content concentration 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 vertical alignment type liquid crystal alignment agent of the present invention is prepared is preferably from 0 ° C to 200 ° C, more preferably from 20 ° C to 60 ° C.

<Liquid crystal display element>

The liquid crystal display element of the present invention has a liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention as described above.

The liquid crystal display element of the present invention can be produced, for example, by the following steps (1) to (4).

(1) Applying the liquid crystal alignment agent of the present invention to the substrate provided with the patterned transparent conductive film by an appropriate coating method such as an offset printing method, a spin coating method, or an inkjet printing method, and then passing The coated surface is heated to form a coating film. Here, as the substrate, for example, glass such as float glass or soda lime glass; polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, alicyclic poly A transparent substrate made of plastic such as olefin. As the transparent conductive film provided on one surface of the substrate, for example, a NESA film made of tin oxide (SnO ₂ ) (registered trademark of PPG, USA), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ), or the like can be used. . The pattern of these transparent conductive films may be formed by photolithography or a method of using a photomask in advance when forming a transparent conductive film. In the application of the liquid crystal alignment agent, in order to further improve the adhesion between the surface of the substrate and the transparent conductive film and the coating film, a functional decane compound, a functional titanium compound or the like may be applied to the surface of the substrate in advance. After the liquid crystal alignment agent is applied, in order to prevent the coating agent liquid from sagging, etc., it is preferred to perform preheating (prebaking) first. The prebaking temperature is preferably from 30 to 200 ° C, more preferably from 40 to 150 ° C, and particularly preferably from 40 to 100 ° C. The prebaking time is preferably from 1 to 10 minutes, more preferably from 1 to 5 minutes. Then, after the solvent is completely removed, it is preferred to further carry out a heating (post-baking) step. The post-baking temperature is preferably from 80 to 300 ° C, more preferably from 120 to 250 ° C. The post-baking time is preferably from 1 to 60 minutes, more preferably from 5 to 30 minutes. The liquid crystal alignment agent of the present invention forms a coating film as an alignment film by removing the organic solvent as described above, and the polymer (A) or the polymer (B) contained in the liquid crystal alignment agent of the present invention is a polyamic acid. Alternatively, when a ruthenium iodide polymer having a ruthenium ring structure and a proline structure is present, it may be subjected to a dehydration ring-closure reaction by further heating after forming a coating film to form a further yttrium-imided coating film.

The thickness of the formed coating film is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm.

The coating film formed as above is considered to have a film having a different composition in the thickness direction thereof, the polymer (B) is present at a higher ratio near the film surface, and the polymer (A) is higher at the inner portion of the film. The ratio exists. The coating film formed by the liquid crystal alignment agent of the present invention is presumed to have good vertical alignment and electrical properties due to such a special film structure, so that it is difficult to produce afterimages in short-time driving and long-time driving. Liquid crystal display element.

(2) The coating film formed as described above may be used as a vertical alignment type liquid crystal alignment film as it is, and may be coated with a roll of a cloth made of a suitable fiber such as nylon, rayon, cotton or the like. The direction rubbing is used as a liquid crystal alignment film after the rubbing treatment. In addition, a part of the liquid crystal alignment film shown in the patent document 6 (JP-A-H06-222366) or the patent document 7 (JP-A-6-281937) is applied to the coating film. a process of changing the pretilt angle of a part of the liquid crystal alignment film by irradiating the ultraviolet ray, or forming a protective film on a part of the surface of the liquid crystal alignment film as shown in Patent Document 8 (Japanese Laid-Open Patent Publication No. Hei No. 5-105044) The treatment for removing the protective film after the sanding treatment is performed in the different direction of the previous polishing treatment, so that each region of the liquid crystal alignment film has a different liquid crystal alignment energy, which can improve the field of view performance of the obtained liquid crystal display element.

(3) A liquid crystal alignment film obtained as described in the above (1) to (2), which may then be washed as needed. As the washing solvent, for example, water, acetone, methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, methyl ethyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate can be used. , tetrahydrofuran, hexane, heptane, octane, and the like. In order to improve the cleaning efficiency, at least one selected from the group consisting of a method of adding a surfactant to a cleaning solvent, a method of washing with a heating solvent, a method of combining with a brushing, and a method of using ultrasonic waves may be used in combination. After washing, it may be used as a liquid crystal alignment film as it is, or may be further washed with a suitable solvent, and then, if necessary, removed by heating, and then used.

(4) Two substrates on which the liquid crystal alignment film is formed are formed, and the two substrates are placed opposite each other through a gap (cell gap) so that the polishing directions of the respective liquid crystal alignment films are perpendicular or antiparallel to each other in the case of being polished. The peripheral portions of the two substrates are bonded together with a sealant, and liquid crystals are injected into the interstitial space partitioned from the surface of the substrate and the sealant to close the injection holes to form liquid crystal cells. Then, a liquid crystal display element of the present invention can be obtained by laminating a polarizing plate on the outer surface of the liquid crystal cell, that is, the other side surface of each of the substrates constituting the liquid crystal cell.

Here, as the sealant, for example, an epoxy resin containing an alumina ball as a curing agent and a spacer, or the like can be used. Examples of the liquid crystal include a nematic liquid crystal and a dish-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 phenyl ring may be used. An alkane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, a biphenyl cyclohexane liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a cubic liquid crystal, or the like. Further, cholesteric liquid crystals such as cholesteryl cholesteryl, cholesteryl phthalate, and cholesteryl carbonate may be added to these liquid crystals, and sold under the trade names "C-15" and "CB-15" (manufactured by MERCK Co., Ltd.). A chiral agent or a ferroelectric liquid crystal such as p-methoxybenzylidene-p-amino-2-methylbutylcinnamate is used.

The polarizing plate to be bonded to the outer surface of the liquid crystal may be a polarizing plate or an H film formed by sandwiching a polarizing film called "H film" obtained by stretching the polyvinyl alcohol while absorbing iodine. A polarizing plate made by itself.

[Examples]

Hereinafter, the present invention will be more specifically described by way of examples, but the invention is not limited to the examples.

In addition, the viscosity of the polymer solution in the following synthesis examples was a value measured at 25 ° C using an E-type viscometer. The ruthenium imidization ratio of the ruthenium iodide polymer is obtained by dissolving the ruthenium iodide polymer under reduced pressure at room temperature in a deuterated dimethyl hydrazine and using tetramethyl decane as a reference substance. 1H-NMR was measured at room temperature (23 ° C), and the value obtained by the above formula (i) was determined from the measurement results.

<Synthesis Example of Polymer (A)> Synthesis Example 1

21 g (1.0 mol equivalent) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 9.2 g (0.9 mol equivalent) of p-phenylenediamine as a diamine, and the above formula ( 1-1 g of the diamine represented by 1-1) was dissolved in 140 g of N-methyl-2-pyrrolidone, and allowed to react at 60 ° C for 4 hours to obtain a polyglycine having a concentration of 20% by weight. Solution. The polyamic acid solution was prepared into a N-methyl-2-pyrrolidone solution having a polymer concentration of 10% by weight, and the solution viscosity was measured to be 98 mPa·s.

After the polyamic acid solution was diluted with 325 g of N-methyl-2-pyrrolidone, 7.4 g of pyridine and 9.6 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system is subjected to solvent replacement with a new N-methyl-2-pyrrolidone (in this operation, the pyridine and acetic anhydride used in the dehydration ring-closure reaction are removed to the outside of the system. The same applies hereinafter). 160 g of a polymer solution containing 18% by weight of a ruthenium iodide polymer (A-1) having a ruthenium iodide ratio of 51% was obtained.

Synthesis Example 2

In addition to using 19 g (1.0 mole equivalent) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as the tetracarboxylic dianhydride, 7.4 g (0.8 mole equivalent) of p-phenylenediamine and 8.5 g (0.2 mole) were used. In the same manner as in Synthesis Example 1, except that the diamine represented by the above formula (1-1) was used as the diamine, a polyamine acid solution having a concentration of 20% by weight was obtained. The polyamic acid solution was formulated into a N-methyl-2-pyrrolidone solution having a polymer concentration of 10% by weight, and the solution viscosity was measured to be 78 mPa·s.

After the polyamic acid solution was diluted with 325 g of N-methyl-2-pyrrolidone, 6.7 g of pyridine and 8.7 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone to obtain 146 g of a ruthenium iodide polymer having a 19% by weight oxime imidization ratio (A- 2) polymer solution.

Synthesis Example 3

In addition to using 18 g (1.0 mole equivalent) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as the tetracarboxylic dianhydride, 5.9 g (0.7 mole equivalent) of p-phenylenediamine and 8.5 g (0.3 mole) were used. In the same manner as in Synthesis Example 1, except that the diamine represented by the above formula (1-1) was used as the diamine, a polyamine acid solution having a concentration of 20% by weight was obtained. The polyamic acid solution was formulated into a N-methyl-2-pyrrolidone solution having a polymer concentration of 10% by weight, and the measured solution viscosity was 62 mPa·s.

After the polyamic acid solution was diluted with 325 g of N-methyl-2-pyrrolidone, 6.2 g of pyridine and 8.0 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone solvent to obtain 182 g of a ruthenium imidized polymer containing 16% by weight of a ruthenium iodide ratio of 49% (A- 3) polymer solution.

<Synthesis Example of Polymer (B)> Synthesis Example 4

In addition to using 21 g (1.0 mole equivalent) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as the tetracarboxylic dianhydride, 9.2 g (0.9 mole equivalent) of p-phenylenediamine and 5.0 g (0.1 mole) were used. In the same manner as in Synthesis Example 1, except that the diamine represented by the above formula (2-1) was used as the diamine, a polyamine solution having a concentration of 20% by weight was obtained. The polyamic acid solution was formulated into a N-methyl-2-pyrrolidone solution having a polymer concentration of 10% by weight, and the measured solution viscosity was 89 mPa·s.

After the polyamic acid solution was diluted with 325 g of N-methyl-2-pyrrolidone, 7.4 g of pyridine and 9.5 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone to obtain 153 g of a ruthenium iodide polymer containing 19% by weight of a ruthenium iodide ratio (B- 1) polymer solution.

Synthesis Example 5

In addition to using 19 g (1.0 mole equivalent) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as the tetracarboxylic dianhydride, 7.3 g (0.8 mole equivalent) of p-phenylenediamine and 8.9 g (0.2 mole) were used. In the same manner as in Synthesis Example 1, except that the diamine represented by the above formula (2-1) was used as the diamine, a polyamine solution having a concentration of 20% by weight was obtained. The polyamic acid solution was formulated into a N-methyl-2-pyrrolidone solution having a polymer concentration of 10% by weight, and the measured solution viscosity was 89 mPa·s.

After the polyamine acid solution was diluted with 325 g of N-methyl-2-pyrrolidone, 6.64 g of pyridine and 8.57 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone to obtain 196 g of a ruthenium iodide polymer containing 15% by weight of a ruthenium iodide ratio (B- 2) polymer solution.

Synthesis Example 6

In addition to using 17 g (1.0 mole equivalent) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as the tetracarboxylic dianhydride, 5.8 g (0.7 mole equivalent) of p-phenylenediamine and 12 g (0.3 mole equivalents) were used. In the same manner as in Synthesis Example 1, except that the diamine represented by the above formula (2-1) was used as the diamine, a polyamine acid solution having a concentration of 20% by weight was obtained. The polyamic acid solution was prepared into a N-methyl-2-pyrrolidone solution having a polymer concentration of 10% by weight, and the solution viscosity was measured to be 56 mPa·s.

After the polyamic acid solution was diluted with 325 g of N-methyl-2-pyrrolidone, 6.0 g of pyridine and 7.8 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone to obtain 139 g of a ruthenium iodide polymer containing 21% by weight of a ruthenium iodide (B- 3) polymer solution.

Synthesis Example 7

In addition to using 21 g (1.0 mole equivalent) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as the tetracarboxylic dianhydride, 9.2 g (0.9 mole equivalent) of p-phenylenediamine and 4.9 g (0.1 mole) were used. In the same manner as in Synthesis Example 1, except that the diamine represented by the above formula (2-1) was used as the diamine, a polyamine solution having a concentration of 20% by weight was obtained. The polyamic acid solution was formulated into a N-methyl-2-pyrrolidone solution having a polymer concentration of 10% by weight, and the solution viscosity was measured to be 90 mPa·s.

After the polyamic acid solution was diluted with 325 g of N-methyl-2-pyrrolidone, 11 g of pyridine and 14 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone to obtain 183 g of a ruthenium-imiding polymer containing 16% by weight of a ruthenium iodide ratio of 60% (B- 4) polymer solution.

Synthesis Example 8

In addition to using 21 g (1.0 mole equivalent) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as the tetracarboxylic dianhydride, 9.2 g (0.9 mole equivalent) of p-phenylenediamine and 4.9 g (0.1 mole) were used. In the same manner as in Synthesis Example 1, except that the diamine represented by the above formula (2-1) was used as the diamine, a polyamine solution having a concentration of 20% by weight was obtained. The polyamic acid solution was formulated into a N-methyl-2-pyrrolidone solution having a polymer concentration of 10% by weight, and the solution viscosity was measured to be 85 mPa·s.

After the polyamine acid solution was diluted with 325 g of N-methyl-2-pyrrolidone, 15 g of pyridine and 19 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone to obtain 171 g of a ruthenium imidized polymer containing 17% by weight of a ruthenium iodide ratio (B- 5) polymer solution.

Synthesis Example 9

In addition to using 22 g (1.0 mole equivalent) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as the tetracarboxylic dianhydride, 10.2 g (0.95 mole equivalent) of p-phenylenediamine and 2.5 g (0.05 mole) were used. In the same manner as in Synthesis Example 1, except that the diamine represented by the above formula (2-1) was used as the diamine, a polyamine solution having a concentration of 20% by weight was obtained. The polyamic acid solution was formulated into a N-methyl-2-pyrrolidone solution having a polymer concentration of 10% by weight, and the measured solution viscosity was 101 mPa·s.

After the polyamine acid solution was diluted with 325 g of N-methyl-2-pyrrolidone, 7.9 g of pyridine and 10 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone to obtain 165 g of a ruthenium iodide polymer containing 17% by weight of a ruthenium iodide ratio (B- 6) polymer solution.

Synthesis Example 10

In addition to using 19 g (1.0 mole equivalent) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as the tetracarboxylic dianhydride, 7.4 g (0.80 mole equivalent) of p-phenylenediamine, 4.4 g (0.10 mole) was used. Equivalent) Diamine represented by the above formula (2-1) and 4.2 g (0.10 molar equivalent) of the diamine represented by the above formula (1-1) were treated in the same manner as in Synthesis Example 1 except for the diamine. Weight% polyamine solution. The polyamic acid solution was prepared into a N-methyl-2-pyrrolidone solution having a polymer concentration of 10% by weight, and the solution viscosity was measured to be 98 mPa·s.

After the polyamic acid solution was diluted with 325 g of N-methyl-2-pyrrolidone, 6.7 g of pyridine and 8.7 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone to obtain 143 g of a polyimine (B-7) containing 20% by weight of a ruthenium iodide ratio of 52%. A solution of a ruthenium iodide polymer.

Synthesis Example 11

In addition to using 17 g (1.0 mole equivalent) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as the tetracarboxylic dianhydride, 5.9 g (0.70 mole equivalent) of p-phenylenediamine, 4.1 g (0.10 mole) was used. In the same manner as in Synthesis Example 1, except that the diamine represented by the above formula (2-1) and 7.7 g (0.20 mol equivalent) of the diamine represented by the above formula (1-1) were used as the diamine, a concentration of 20 was obtained. Weight% polyamine solution. The polyamic acid solution was formulated into a N-methyl-2-pyrrolidone solution having a polymer concentration of 10% by weight, and the solution viscosity was measured to be 90 mPa·s.

After the polyamic acid solution was diluted with 325 g of N-methyl-2-pyrrolidone, 6.1 g of pyridine and 7.9 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone to obtain 169 g of a polyimine (B-8) containing 18% by weight of a ruthenium iodide ratio of 53%. A solution of a ruthenium iodide polymer.

Synthesis Example 12

In addition to using 17 g (1.0 mole equivalent) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as the tetracarboxylic dianhydride, 5.9 g (0.70 mole equivalent) of p-phenylenediamine, 8.1 g (0.20 mole) was used. In the same manner as in Synthesis Example 1, except that the diamine represented by the above formula (2-1) and 3.8 g (0.10 mol equivalent) of the diamine represented by the above formula (1-1) were used as the diamine, a concentration of 20 was obtained. Weight% polyamine solution. The polyamic acid solution was formulated into a N-methyl-2-pyrrolidone solution having a polymer concentration of 10% by weight, and the measured solution viscosity was 82 mPa·s.

After the polyamic acid solution was diluted with 325 g of N-methyl-2-pyrrolidone, 6.1 g of pyridine and 7.9 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone to obtain 181 g of a polyimine (B-9) containing 16% by weight of a ruthenium iodide ratio of 51%. A solution of a ruthenium iodide polymer.

Synthesis Example 13

In addition to using 17 g (1.0 mole equivalent) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as the tetracarboxylic dianhydride, 5.9 g (0.70 mole equivalent) of p-phenylenediamine, 6.1 g (0.15 mole) was used. In the same manner as in Synthesis Example 1, except that the diamine represented by the above formula (2-1) and 5.8 g (0.15 mol equivalent) of the diamine represented by the above formula (1-1) were used as the diamine, a concentration of 20 was obtained. Weight% polyamine solution. The polyamic acid solution was formulated into a N-methyl-2-pyrrolidone solution having a polymer concentration of 10% by weight, and the solution viscosity was measured to be 85 mPa·s.

After the polyamic acid solution was diluted with 325 g of N-methyl-2-pyrrolidone, 6.1 g of pyridine and 7.9 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone to obtain 187 g of a polyimine (B-10) containing 15% by weight of a ruthenium iodide ratio of 52%. A solution of a ruthenium iodide polymer.

Synthesis Example 14

In addition to using 16 g (1.0 mole equivalent) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as the tetracarboxylic dianhydride, 4.6 g (0.60 mole equivalent) of p-phenylenediamine, 7.5 g (0.20 mole) was used. In the same manner as in Synthesis Example 1, except that the diamine represented by the above formula (2-1) and 7.1 g (0.20 mol equivalent) of the diamine represented by the above formula (1-1) were used as the diamine, a concentration of 20 was obtained. Weight% polyamine solution. The polyamic acid solution was formulated into a N-methyl-2-pyrrolidone solution having a polymer concentration of 10% by weight, and the solution viscosity was measured to be 68 mPa·s.

After the polyamic acid solution was diluted with 325 g of N-methyl-2-pyrrolidone, 5.6 g of pyridine and 7.2 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone to obtain 164 g of a polyimine (B-11) containing 18% by weight of a ruthenium iodide ratio of 51%. A solution of a ruthenium iodide polymer.

Synthesis Example 15

In addition to using 19 g (1.0 mole equivalent) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as the tetracarboxylic dianhydride, 7.4 g (0.80 mole equivalent) of p-phenylenediamine, 4.4 g (0.10 mole) was used. Equivalent) Diamine represented by the above formula (2-1) and 4.2 g (0.10 molar equivalent) of the diamine represented by the above formula (1-1) were treated in the same manner as in Synthesis Example 1 except for the diamine. Weight% polyamine solution. The polyamic acid solution was formulated into a N-methyl-2-pyrrolidone solution having a polymer concentration of 10% by weight, and the measured solution viscosity was 96 mPa·s.

After the polyamine acid solution was diluted with 325 g of N-methyl-2-pyrrolidone, 10 g of pyridine and 13 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone to obtain 154 g of a polyimine (B-12) containing 18% by weight of a ruthenium iodide ratio of 66%. A solution of a ruthenium iodide polymer.

Synthesis Example 16

In addition to using 17 g (1.0 mole equivalent) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as the tetracarboxylic dianhydride, 5.9 g (0.70 mole equivalent) of p-phenylenediamine, 4.1 g (0.10 mole) was used. In the same manner as in Synthesis Example 1, except that the diamine represented by the above formula (2-1) and 7.7 g (0.20 mol equivalent) of the diamine represented by the above formula (1-1) were used as the diamine, a concentration of 20 was obtained. Weight% polyamine solution. The polyamic acid solution was formulated into a N-methyl-2-pyrrolidone solution having a polymer concentration of 10% by weight, and the measured solution viscosity was 91 mPa·s.

After the polyamic acid solution was diluted with 325 g of N-methyl-2-pyrrolidone, 9.2 g of pyridine and 12 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone to obtain 175 g of a polyimine (B-13) containing 17% by weight of a ruthenium iodide ratio of 65%. A solution of a ruthenium iodide polymer.

Synthesis Example 17

In addition to using 17 g (1.0 mole equivalent) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as the tetracarboxylic dianhydride, 5.9 g (0.70 mole equivalent) of p-phenylenediamine, 8.1 g (0.20 mole) was used. In the same manner as in Synthesis Example 1, except that the diamine represented by the above formula (2-1) and 3.8 g (0.10 mol equivalent) of the diamine represented by the above formula (1-1) were used as the diamine, a concentration of 20 was obtained. Weight% polyamine solution. The polyamic acid solution was formulated into a N-methyl-2-pyrrolidone solution having a polymer concentration of 10% by weight, and the solution viscosity was measured to be 80 mPa·s.

After the polyamic acid solution was diluted with 325 g of N-methyl-2-pyrrolidone, 9.1 g of pyridine and 12 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone to obtain 152 g of a polyimine (B-14) containing 18% by weight of a ruthenium iodide ratio of 66%. A solution of a ruthenium iodide polymer.

Synthesis Example 18

In addition to using 17 g (1.0 mole equivalent) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as the tetracarboxylic dianhydride, 5.8 g (0.70 mole equivalent) of p-phenylenediamine, 6.1 g (0.15 mole) was used. In the same manner as in Synthesis Example 1, except that the diamine represented by the above formula (2-1) and 5.8 g (0.15 mol equivalent) of the diamine represented by the above formula (1-1) were used as the diamine, a concentration of 20 was obtained. Weight% polyamine solution. The polyamic acid solution was formulated into a N-methyl-2-pyrrolidone solution having a polymer concentration of 10% by weight, and the measured solution viscosity was 86 mPa·s.

After the polyamic acid solution was diluted with 325 g of N-methyl-2-pyrrolidone, 9.1 g of pyridine and 12 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone to obtain 173 g of a polyimine (B-15) containing 17% by weight of a ruthenium iodide ratio of 66%. A solution of a ruthenium iodide polymer.

Synthesis Example 19

In addition to using 16 g (1.0 mole equivalent) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as the tetracarboxylic dianhydride, 4.6 g (0.60 mole equivalent) of p-phenylenediamine, 7.5 g (0.20 mole) was used. In the same manner as in Synthesis Example 1, except that the diamine represented by the above formula (2-1) and 7.1 g (0.20 mol equivalent) of the diamine represented by the above formula (1-1) were used as the diamine, a concentration of 20 was obtained. Weight% polyamine solution. The polyamic acid solution was prepared into a N-methyl-2-pyrrolidone solution having a polymer concentration of 10% by weight, and the solution viscosity was measured to be 66 mPa·s.

After the polyamine acid solution was diluted with 325 g of N-methyl-2-pyrrolidone, 8.4 g of pyridine and 11 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone to obtain 151 g of a polyimine (B-16) containing 19% by weight of a ruthenium iodide ratio of 64%. A solution of a ruthenium iodide polymer.

Synthesis Example 20

In addition to using 19 g (1.0 mole equivalent) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as the tetracarboxylic dianhydride, 7.4 g (0.80 mole equivalent) of p-phenylenediamine, 4.4 g (0.10 mole) was used. Equivalent) Diamine represented by the above formula (2-1) and 4.2 g (0.10 molar equivalent) of the diamine represented by the above formula (1-1) were treated in the same manner as in Synthesis Example 1 except for the diamine. Weight% polyamine solution. The polyamic acid solution was formulated into a N-methyl-2-pyrrolidone solution having a polymer concentration of 10% by weight, and the solution viscosity was determined to be 95 mPa ̇s.

After the polyamine acid solution was diluted with 325 g of N-methyl-2-pyrrolidone, 13 g of pyridine and 17 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone to obtain 186 g of a polyimine (B-17) containing 15% by weight of a ruthenium iodide ratio of 76%. A solution of a ruthenium iodide polymer.

Synthesis Example 21

In addition to using 17 g (1.0 mole equivalent) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as the tetracarboxylic dianhydride, 5.9 g (0.70 mole equivalent) of p-phenylenediamine, 7.7 g (0.20 mole) was used. In the same manner as in Synthesis Example 1, a diamine represented by the above formula (2-1) and 4.1 g (0.10 mol equivalent) of the diamine represented by the above formula (1-1) were used in the same manner as in Synthesis Example 1. Weight% polyamine solution. The polyamic acid solution was formulated into a N-methyl-2-pyrrolidone solution having a polymer concentration of 10% by weight, and the measured solution viscosity was 89 mPa·s.

After the polyamic acid solution was diluted with 325 g of N-methyl-2-pyrrolidone, 12 g of pyridine and 16 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone to obtain 151 g of a polyimine (B-18) containing 20% by weight of a ruthenium iodide ratio of 76%. A solution of a ruthenium iodide polymer.

Synthesis Example 22

In addition to using 17 g (1.0 mole equivalent) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as the tetracarboxylic dianhydride, 5.9 g (0.70 mole equivalent) of p-phenylenediamine, 3.8 g (0.10 mole) was used. In the same manner as in Synthesis Example 1, except that the diamine represented by the above formula (2-1) and 8.1 g (0.20 mol equivalent) of the diamine represented by the above formula (1-1) were used as the diamine, a concentration of 20 was obtained. Weight% polyamine solution. The polyamic acid solution was formulated into a N-methyl-2-pyrrolidone solution having a polymer concentration of 10% by weight, and the measured solution viscosity was 84 mPa·s.

After the polyamic acid solution was diluted with 325 g of N-methyl-2-pyrrolidone, 12 g of pyridine and 16 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone to obtain 176 g of a polyimine (B-19) containing 16% by weight of a ruthenium iodide ratio of 74%. A solution of a ruthenium iodide polymer.

Synthesis Example 23

In addition to using 17 g (1.0 mole equivalent) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as the tetracarboxylic dianhydride, 5.9 g (0.70 mole equivalent) of p-phenylenediamine, 6.1 g (0.15 mole) was used. In the same manner as in Synthesis Example 1, except that the diamine represented by the above formula (2-1) and 5.8 g (0.15 mol equivalent) of the diamine represented by the above formula (1-1) were used as the diamine, a concentration of 20 was obtained. Weight% polyamine solution. The polyamic acid solution was formulated into a N-methyl-2-pyrrolidone solution having a polymer concentration of 10% by weight, and the measured solution viscosity was 84 mPa·s.

After the polyamic acid solution was diluted with 325 g of N-methyl-2-pyrrolidone, 12 g of pyridine and 16 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone to obtain 162 g of a polyimine (B-20) containing 18% by weight of a ruthenium iodide ratio of 73%. A solution of a ruthenium iodide polymer.

Synthesis Example 24

In addition to using 16 g (1.0 mole equivalent) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as the tetracarboxylic dianhydride, 4.6 g (0.60 mole equivalent) of p-phenylenediamine, 7.5 g (0.20 mole) was used. In the same manner as in Synthesis Example 1, except that the diamine represented by the above formula (2-1) and 7.1 g (0.20 mol equivalent) of the diamine represented by the above formula (1-1) were used as the diamine, a concentration of 20 was obtained. Weight% polyamine solution. The polyamic acid solution was formulated into a N-methyl-2-pyrrolidone solution having a polymer concentration of 10.% by weight, and the solution viscosity was measured to be 68 mPa·s.

After the polyamic acid solution was diluted with 325 g of N-methyl-2-pyrrolidone, 11 g of pyridine and 14 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone to obtain 142 g of a polyimine (B-21) containing 19% by weight of a ruthenium iodide ratio of 76%. A solution of a ruthenium iodide polymer.

Example 1 <Preparation of liquid crystal alignment agent>

The solution of the ruthenium-imidized polymer (A-1) prepared in the above Synthesis Example 1 and the solution of the ruthenium-imidized polymer (B-1) obtained in the above Synthesis Example 4 were polymerized. (A-1) is mixed with the polymer (B-1) at a ratio of 30:70 (weight ratio), to which N-methyl-2-pyrrolidone and butyl cellosolve are added, and further to 100 parts by weight of the polymer (A-1) and the total amount of the polymer (B-1), 20 parts by weight of N,N,N ' ,N ' -tetraglycidyl-m-xylylenediamine as an epoxy compound is added, and is formulated. Solvent ratio N-methyl-2-pyrrolidone: a solution of butyl cellosolve = 50:50 and a solid content concentration of 4% by weight. This solution was filtered through a filter having a pore size of 0.2 μm to prepare a liquid crystal alignment agent.

<Manufacture and evaluation of liquid crystal display elements>

The liquid crystal alignment agent prepared above was applied by spin coating to a transparent electrode surface of a glass substrate having a thickness of 1 mm made of a transparent electrode made of an ITO film, and heated on a hot plate at 80 ° C for 1 minute (prebaking). After the solvent, it was further heated on a hot plate at 200 ° C for 10 minutes (post-baking) to form an average film thickness of 600. Coating film (liquid crystal alignment film). This operation was repeated to produce two (a pair of) substrates having a liquid crystal alignment film.

Then, on each outer edge of the pair of substrates having the liquid crystal alignment film, an epoxy resin adhesive having an alumina ball having a diameter of 3.5 μm is applied, and the liquid crystal alignment film surface is relatively recombined and pressed. The adhesive is then cured. Next, a negative liquid crystal (MLC-6608, manufactured by MERCK Co., Ltd.) was filled between a pair of substrates through a liquid crystal injection port, and then the liquid crystal injection port was closed with an acrylic photocurable adhesive, and a polarizing plate was bonded to both outer surfaces of the substrate. A liquid crystal display element is produced.

The liquid crystal display element manufactured above was evaluated as follows. The results are shown in Table 2.

[Evaluation of vertical alignment]

In the liquid crystal display device produced as described above, when a voltage of 12 V was applied and a peak voltage of 12 V was applied, the display surface was observed by crossed-neon, and the presence or absence of an abnormal region was observed by a polarizing microscope, and no abnormal region was identified. The vertical alignment was evaluated as "good", and the abnormal region was identified, and the vertical alignment was evaluated as "bad".

[Evaluation of voltage retention rate]

A voltage of 5 V was applied to the liquid crystal display element manufactured as above at a temperature of 60 ° C for a period of 167 msec, and the voltage application time was 60 μsec, and then the voltage was released to 167 msec by VHR-1 manufactured by TOYO Corporation. After the hold voltage rate.

[Remaining image performance (short time afterimage) when driving for a short time]

The liquid crystal display element manufactured above was applied with a DC voltage of 5 V for 20 hours at an ambient temperature of 60 ° C, the DC voltage was cut, and left at room temperature for 15 minutes, and then residual DC remaining in the liquid crystal display element was determined by a scintillation elimination method. Voltage. When the residual DC voltage value is less than 500 mV, the short-term afterimage is evaluated as "good", and when it is 500 mV or more, the short-term afterimage is evaluated as "poor".

[After image performance (long-term afterimage) when driving for a long time]

Two liquid crystal display elements were fabricated in the same manner as above, one at room temperature and the other at 100 ° C for 48 hours. Then, a DC voltage of 5 V was applied to each liquid crystal display element at an ambient temperature of 60 ° C for 20 hours, and the DC voltage was cut off. After standing at room temperature for 15 minutes, the residual DC remaining in each liquid crystal display element was determined by a scintillation elimination method. Voltage. At this time, the difference between the residual DC voltage of the liquid crystal display element which was left to stand at 100 ° C for 48 hours and the residual DC voltage of the liquid crystal display element which was allowed to stand at room temperature for 48 hours (Δ residual DC voltage) was examined, and when the value was less than 500 mV When the long-term afterimage was evaluated as "good", when it was 500 mV or more, the long-term afterimage was evaluated as "poor".

Examples 2 to 45 and Comparative Examples 1 to 8

In Example 1, as the solution containing the polymer, the polymer-containing solution shown in Table 1 was used in an amount such that the weight ratio of each polymer was the value shown in Table 1, respectively, and the solvent The liquid crystal alignment agent was prepared and evaluated in the same manner as in Example 1 except that the ratio was the value shown in Table 1. The evaluation results are shown in Table 2.

Further, in Table 1, each polymer was supplied to a liquid crystal alignment agent in the form of a polymer solution prepared in the above Synthesis Example, and the amount of the polymer in Table 1 was converted into a polymer contained in each polymer solution. the amount. The value in the column "Polymer Ratio" is the weight ratio of polymer (A) / polymer (B).

The abbreviation of the solvent in the column of "solvent ratio" in Table 1 has the following meanings.

BL: γ-butyrolactone

BC: butyl cellosolve

NMP: N-methyl-2-pyrrolidone

Claims (6)

A vertical alignment type liquid crystal alignment agent comprising: (A) a polyamic acid and a hydrazine obtained by reacting a tetracarboxylic dianhydride with a diamine containing a compound represented by the following formula (1); At least one polymer of the group consisting of imidized polymers, In the formula (1), A is a monovalent organic group having a steroid skeleton, and (B) a polyfluorene obtained by reacting a tetracarboxylic dianhydride with a diamine containing a compound represented by the following formula (2) a quinone imidized polymer of aminic acid, In the formula (2), B is a steroid skeleton, a trifluoromethylphenyl group, a trifluoromethoxyphenyl group, a fluorophenyl group, an alkyl group having 6 to 10 carbon atoms or a carbon number of 6~ a monovalent organic group of 10 fluoroalkyl groups, wherein the (B) polymer has a ruthenium azide ratio of 25 to 75%, and (A) a polymer content ratio relative to (A) a polymer and B) The total amount of the polymer is 10 to 90% by weight. For example, a vertical alignment type liquid crystal alignment agent of the first application patent scope, wherein The use ratio of the compound represented by the above formula (1) used in the synthesis of the polymer (A) is 1 to 30 mol% based on the total amount of the diamine used in the (A) polymer synthesis. The vertical alignment type liquid crystal alignment agent of claim 1 or 2, wherein the use ratio of the compound represented by the above formula (2) used in the synthesis of the (B) polymer is relative to (B) used in the synthesis of the polymer All diamines are from 1 to 50 mol%. The vertical alignment type liquid crystal alignment agent of claim 1, wherein the (A) polymer is a ruthenium iodide polymer, and the oxime imidization ratio is 25 to 95%. The vertical alignment type liquid crystal alignment agent of claim 1, wherein the tetracarboxylic dianhydride used in the synthesis of at least one of the (A) polymer and the (B) polymer contains 2,3,5-tricarboxyl group. Cyclopentyl acetic acid dianhydride. A vertical alignment type liquid crystal display element comprising a vertical alignment type liquid crystal alignment film formed of a vertical alignment type liquid crystal alignment agent according to any one of claims 1 to 5.