KR20110010833A - Liquid crystal aligning agent and liquid crystal display device - Google Patents

Abstract

PURPOSE: A liquid crystal alignment agent is provided to form a liquid crystal alignment agent with excellent vertical aligning property and to enable use for a vertically aligned liquid crystal display device. CONSTITUTION: A liquid crystal alignment agent includes a polymer having one or more structures selected from the group consisting of a structure of chemical formula 1 and a structure of chemical formula 2. In chemical formula 1, A^1 and B^1 are fluorine atoms. The polymer has a group represented by chemical formula 3: -P-Q-R^1-R^2, wherein P is a single bond, -O-, -COO- or -CONH-; Q is structures of chemical formula 1 or 2; R^1 is a divalent cycloaliphatic group; and R^2 is C1-22 linear alkyl group.

Description

Liquid crystal aligning agent and a liquid crystal display device {Liquid Crystal Aligning Agent and Liquid Crystal Display Device}

The present invention relates to a liquid crystal aligning agent and a liquid crystal display element. More specifically, it relates to the liquid crystal aligning agent which has the perpendicular alignment property suitable for a vertical alignment type liquid crystal display element use, and the liquid crystal display element provided with the liquid crystal aligning film obtained from it.

Currently, as a liquid crystal display element, a liquid crystal aligning film containing polyamic acid, polyimide, or the like is formed on the surface of a substrate on which a transparent conductive film is provided to form a substrate for a liquid crystal display element, and the two sheets thereof are disposed opposite to each other in the gap thereof. A so-called twisted nematic liquid crystal cell was formed by forming a nematic liquid crystal layer having dielectric anisotropy of ie, forming a sandwich cell, and causing the long axis of the liquid crystal molecules to be twisted 90 degrees continuously from one substrate to the other. The TN type liquid crystal display element which has is well known.

On the other hand, the vertically oriented liquid crystal display element vertically aligns liquid crystals having a negative dielectric anisotropy and breaks down the liquid crystal molecules by application of a voltage, and is excellent in terms of viewing angle, contrast, etc. .

Here, in order to vertically align a liquid crystal, it is necessary to make a liquid crystal aligning film hydrophobic, and for this reason, it is necessary to contain a large amount of hydrophobic components (henceforth a vertical alignment component) in an aligning agent. As such a vertical orientation component, the thing which has an aliphatic, alicyclic, and fluorine-type functional group is normally used. However, when such a vertical alignment component is used, there is a problem that the stability of the vertical alignment is not necessarily sufficient.

Therefore, the development of the liquid crystal aligning agent excellent in the stability of a vertical alignment is desired.

An object of the present invention is to provide a vertical alignment liquid crystal aligning agent having excellent stability of vertical alignment.

Another object of the present invention is to provide a liquid crystal display device provided with a liquid crystal aligning film obtained from the liquid crystal aligning agent of the present invention.

Still other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the above objects and advantages of the present invention include a polymer having, in a side chain, at least one structure selected from the group consisting of a structure represented by the following general formula (1), and a structure represented by the following general formula (2). It is achieved by the liquid crystal aligning agent characterized by the above-mentioned.

In the formula, A ¹ and B ¹ are each independently a hydrogen atom, a halogen atom or a cyano group. Provided that at least ^one of A ¹ and B ¹ is a halogen atom or a cyano group.

Moreover, the said objective and advantage of this invention are achieved by the liquid crystal display element characterized by including the liquid crystal aligning film formed from the liquid crystal aligning agent of this invention second.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The liquid crystal aligning agent of this invention contains the polymer which has the structure represented by the said General formula (1), or the structure represented by the said General formula (2) in a side chain (henceforth "a specific side chain"). In Formula 1, A ¹ and B ¹ are each independently a hydrogen atom, a halogen atom or a cyano group. Provided that at least ^one of A ¹ and B ¹ is a halogen atom or a cyano group. As such a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned specifically ,. Among these, a fluorine atom is preferable.

Specific examples of the specific side chain include groups having a structure represented by the following general formula (3).

P in the formula (3) is a single bond, -O-, -COO- or -CONH-, Q is a structure represented by the formula (1) or a structure represented by the formula (2). In addition, R ¹ in the general formula (3) is a divalent alicyclic group. As an alicyclic which is a bivalent alicyclic group, For example, it is contained in a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a bicyclohexyl ring, a multicyclohexyl ring, and these rings more specifically. One or two or more hydrogen atoms to be mentioned are monovalent organic groups, such as an alkyl group, an aryl group, an alkoxyl group, an aryloxy group, or the ring substituted by the halogen atom. In addition, R <^2> in the said General formula (3) is a C1-C22 linear alkyl group, Preferably it is a C2-C18 linear alkyl group, Especially preferably, it is a C3-C10 linear alkyl group.

The skeleton structure of the polymer having such a specific side chain is not particularly limited, but is preferably an imidized polymer obtained by dehydrating and closing the polyamic acid and the polyamic acid from the viewpoint of excellent heat resistance and electrical properties.

The polyamic acid is obtained by polycondensing the diamine (A) represented by the following formula (4) and the acid anhydride (B) represented by the following formula (5). In addition, the said imidized polymer is obtained by dehydrating and ring-closing the said polyamic acid. The compound which has a specific side chain in at least one of diamine (A) and an acid anhydride (B) is used for the synthesis | combination of the polyamic acid and imidation polymer which have a specific side chain used for the liquid crystal aligning agent of this invention.

In the formula, Z ¹ represents a divalent organic group.

In the formula, Z ² represents a tetravalent organic group.

It is preferable that it is 1-100 mol% with respect to the sum total of the diamine or acid anhydride which has a specific side chain mentioned above with respect to the total diamine (a) and all the acid anhydride (b) used, and it is more preferable that it is 5-50%. desirable.

<Diamine>

Specific examples of the diamine having a specific side chain include 1- (2,3-difluoro-4- (4-n-propylcyclohexyl) phenoxy) -2,4-diaminobenzene, 1- (2,3- Difluoro-4- (4-n-butylcyclohexyl) phenoxy) -2,4-diaminobenzene, 1- (2,3-difluoro-4- (4-n-pentylcyclohexyl) phenoxy C) -2,4-diaminobenzene, 1- (2,3-difluoro-4- (4-n-hexylcyclohexyl) phenoxy) -2,4-diaminobenzene, 1- (2 , 3-difluoro-4- (4-n-heptylcyclohexyl) phenoxy) -2,4-diaminobenzene;

1- (2,3-dicyano-4- (4-n-propylcyclohexyl) phenoxy) -2,4-diaminobenzene, 1- (2,3-dicyano-4- (4-n- Butylcyclohexyl) phenoxy) -2,4-diaminobenzene, 1- (2,3-dicyano-4- (4-n-pentylcyclohexyl) phenoxy) -2,4-diaminobenzene, 1 -(2,3-dicyano-4- (4-n-hexylcyclohexyl) phenoxy) -2,4-diaminobenzene, 1- (2,3-dicyano-4- (4-n- Heptylcyclohexyl) phenoxy) -2,4-diaminobenzene;

(2,3-difluoro-4- (4-n-propylcyclohexyl) phenyl) -3,5-diaminobenzoate, (2,3-difluoro-4- (4-n-butylcyclo Hexyl) phenyl) -3,5-diaminobenzoate, (2,3-difluoro-4- (4-n-pentylcyclohexyl) phenyl) -3,5-diaminobenzoate, (2,3 -Difluoro-4- (4-n-hexylcyclohexyl) phenyl) -3,5-diaminobenzoate, (2,3-difluoro-4- (4-n-heptylcyclohexyl) phenyl ) -3,5-diaminobenzoate;

(2,3-dicyano-4- (4-n-propylcyclohexyl) phenyl) -3,5-diaminobenzoate, (2,3-dicyano-4- (4-n-butylcyclohexyl) Phenyl) -3,5-diaminobenzoate, (2,3-dicyano-4- (4-n-pentylcyclohexyl) phenyl) -3,5-diaminobenzoate, (2,3-dicyano -4- (4-n-hexylcyclohexyl) phenyl) -3,5-diaminobenzoate, (2,3-dicyano-4- (4-n-heptylcyclohexyl) phenyl) -3,5 -Diaminobenzoate;

1- (6- (4-n-propylcyclohexyl) -3-pyridazinyloxy) -2,4-diaminobenzene, 1- (6- (4-n-butylcyclohexyl) -3-pyrida Genyloxy) -2,4-diaminobenzene, 1- (6- (4-n-pentylcyclohexyl) -3-pyridazinyloxy) -2,4-diaminobenzene, 1- (6- (4 -n-hexylcyclohexyl) -3-pyridazinyloxy) -2,4-diaminobenzene, 1- (6- (4-n-heptylcyclohexyl) -3-pyridazinyloxy) -2, 4-diaminobenzene;

(6- (4-n-propylcyclohexyl) -3-pyridazinyl) -3,5-diaminobenzoate, (6- (4-n-butylcyclohexyl) -3-pyridazinyl) -3 , 5-diaminobenzoate, (6- (4-n-pentylcyclohexyl) -3-pyridazinyl) -3,5-diaminobenzoate, (6- (4-n-hexylcyclohexyl) -3-pyridazinyl) -3,5-diaminobenzoate, (6- (4-n-heptylcyclohexyl) -3-pyridazinyl) -3,5-diaminobenzoate;

1- (2-fluoro-4- (4-n-propylcyclohexyl) phenoxy) -2,4-diaminobenzene, 1- (2-fluoro-4- (4-n-butylcyclohexyl) Phenoxy) -2,4-diaminobenzene, 1- (2-fluoro-4- (4-n-pentylcyclohexyl) phenoxy) -2,4-diaminobenzene, 1- (2-fluoro -4- (4-n-hexylcyclohexyl) phenoxy) -2,4-diaminobenzene, 1- (2-fluoro-4- (4-n-heptylcyclohexyl) phenoxy) -2, 4-diaminobenzene;

1- (3-fluoro-4- (4-n-propylcyclohexyl) phenoxy) -2,4-diaminobenzene, 1- (3-fluoro-4- (4-n-butylcyclohexyl) Phenoxy) -2,4-diaminobenzene, 1- (3-fluoro-4- (4-n-pentylcyclohexyl) phenoxy) -2,4-diaminobenzene, 1- (3-fluoro -4- (4-n-hexylcyclohexyl) phenoxy) -2,4-diaminobenzene, 1- (3-fluoro-4- (4-n-heptylcyclohexyl) phenoxy) -2, 4-diaminobenzene;

1- (2-cyano-4- (4-n-propylcyclohexyl) phenoxy) -2,4-diaminobenzene, 1- (2-cyano-4- (4-n-butylcyclohexyl) Phenoxy) -2,4-diaminobenzene, 1- (2-cyano-4- (4-n-pentylcyclohexyl) phenoxy) -2,4-diaminobenzene, 1- (2-cyano -4- (4-n-hexylcyclohexyl) phenoxy) -2,4-diaminobenzene, 1- (2-cyano-4- (4-n-heptylcyclohexyl) phenoxy) -2, 4-diaminobenzene;

1- (3-cyano-4- (4-n-propylcyclohexyl) phenoxy) -2,4-diaminobenzene, 1- (3-cyano-4- (4-n-butylcyclohexyl) Phenoxy) -2,4-diaminobenzene, 1- (3-cyano-4- (4-n-pentylcyclohexyl) phenoxy) -2,4-diaminobenzene, 1- (3-cyano -4- (4-n-hexylcyclohexyl) phenoxy) -2,4-diaminobenzene, 1- (3-cyano-4- (4-n-heptylcyclohexyl) phenoxy) -2, 4-diaminobenzene;

(2-fluoro-4- (4-n-propylcyclohexyl) phenyl) -3,5-diaminobenzoate, (2-fluoro-4- (4-n-butylcyclohexyl) phenyl) -3 , 5-diaminobenzoate, (2-fluoro-4- (4-n-pentylcyclohexyl) phenyl) -3,5-diaminobenzoate, (2-fluoro-4- (4-n- Hexylcyclohexyl) phenyl) -3,5-diaminobenzoate, (2-fluoro-4- (4-n-heptylcyclohexyl) phenyl) -3,5-diaminobenzoate;

(3-fluoro-4- (4-n-propylcyclohexyl) phenyl) -3,5-diaminobenzoate, (3-fluoro-4- (4-n-butylcyclohexyl) phenyl) -3 , 5-diaminobenzoate, (3-fluoro-4- (4-n-pentylcyclohexyl) phenyl) -3,5-diaminobenzoate, (3-fluoro-4- (4-n- Hexylcyclohexyl) phenyl) -3,5-diaminobenzoate, (3-fluoro-4- (4-n-heptylcyclohexyl) phenyl) -3,5-diaminobenzoate;

(2-cyano-4- (4-n-propylcyclohexyl) phenyl) -3,5-diaminobenzoate, (2-cyano-4- (4-n-butylcyclohexyl) phenyl) -3 , 5-diaminobenzoate, (2-cyano-4- (4-n-pentylcyclohexyl) phenyl) -3,5-diaminobenzoate, (2-cyano-4- (4-n- Hexylcyclohexyl) phenyl) -3,5-diaminobenzoate, (2-cyano-4- (4-n-heptylcyclohexyl) phenyl) -3,5-diaminobenzoate;

(3-cyano-4- (4-n-propylcyclohexyl) phenyl) -3,5-diaminobenzoate, (3-cyano-4- (4-n-butylcyclohexyl) phenyl) -3 , 5-diaminobenzoate, (3-cyano-4- (4-n-pentylcyclohexyl) phenyl) -3,5-diaminobenzoate, (3-cyano-4- (4-n- Hexylcyclohexyl) phenyl) -3,5-diaminobenzoate and (3-cyano-4- (4-n-heptylcyclohexyl) phenyl) -3,5-diaminobenzoate. Among them, 1- (2,3-difluoro-4- (4-n-propylcyclohexyl) phenoxy) -2,4-diaminobenzene, 1- (2,3-difluoro-4- (4-n-butylcyclohexyl) phenoxy) -2,4-diaminobenzene, 1- (2,3-difluoro-4- (4-n-pentylcyclohexyl) phenoxy) -2,4 -Diaminobenzene, 1- (2,3-difluoro-4- (4-n-hexylcyclohexyl) phenoxy) -2,4-diaminobenzene, 1- (2,3-difluoro -4- (4-n-heptylcyclohexyl) phenoxy) -2,4-diaminobenzene;

1- (2,3-dicyano-4- (4-n-propylcyclohexyl) phenoxy) -2,4-diaminobenzene, 1- (2,3-dicyano-4- (4-n- Butylcyclohexyl) phenoxy) -2,4-diaminobenzene, 1- (2,3-dicyano-4- (4-n-pentylcyclohexyl) phenoxy) -2,4-diaminobenzene, 1 -(2,3-dicyano-4- (4-n-hexylcyclohexyl) phenoxy) -2,4-diaminobenzene, 1- (2,3-dicyano-4- (4-n- Heptylcyclohexyl) phenoxy) -2,4-diaminobenzene;

(2,3-difluoro-4- (4-n-propylcyclohexyl) phenyl) -3,5-diaminobenzoate, (2,3-difluoro-4- (4-n-butylcyclo Hexyl) phenyl) -3,5-diaminobenzoate, (2,3-difluoro-4- (4-n-pentylcyclohexyl) phenyl) -3,5-diaminobenzoate, (2,3 -Difluoro-4- (4-n-hexylcyclohexyl) phenyl) -3,5-diaminobenzoate, (2,3-difluoro-4- (4-n-heptylcyclohexyl) phenyl ) -3,5-diaminobenzoate;

(2,3-dicyano-4- (4-n-propylcyclohexyl) phenyl) -3,5-diaminobenzoate, (2,3-dicyano-4- (4-n-butylcyclohexyl) Phenyl) -3,5-diaminobenzoate, (2,3-dicyano-4- (4-n-pentylcyclohexyl) phenyl) -3,5-diaminobenzoate, (2,3-dicyano -4- (4-n-hexylcyclohexyl) phenyl) -3,5-diaminobenzoate, (2,3-dicyano-4- (4-n-heptylcyclohexyl) phenyl) -3,5 -Diaminobenzoate;

1- (6- (4-n-propylcyclohexyl) -3-pyridazinyloxy) -2,4-diaminobenzene, 1- (6- (4-n-butylcyclohexyl) -3-pyrida Genyloxy) -2,4-diaminobenzene, 1- (6- (4-n-pentylcyclohexyl) -3-pyridazinyloxy) -2,4-diaminobenzene, 1- (6- (4 -n-hexylcyclohexyl) -3-pyridazinyloxy) -2,4-diaminobenzene, 1- (6- (4-n-heptylcyclohexyl) -3-pyridazinyloxy) -2, 4-diaminobenzene;

(6- (4-n-propylcyclohexyl) -3-pyridazinyl) -3,5-diaminobenzoate, (6- (4-n-butylcyclohexyl) -3-pyridazinyl) -3 , 5-diaminobenzoate, (6- (4-n-pentylcyclohexyl) -3-pyridazinyl) -3,5-diaminobenzoate, (6- (4-n-hexylcyclohexyl) 3-pyridazinyl) -3,5-diaminobenzoate and (6- (4-n-heptylcyclohexyl) -3-pyridazinyl) -3,5-diaminobenzoate are preferred.

As another diamine used for the synthesis | combination of the polymer contained in the liquid crystal aligning agent of this invention, p-phenylenediamine, m-phenylenediamine, 4,4'- diamino diphenylmethane, 4,4, for example. '-Diaminodiphenylethane, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4, 4'-diaminobenzanilide, 4,4'-diaminodiphenylether, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 5-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 3,4'-diaminodiphenylether , 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-amino Phenoxy) phenyl] sulfone, 1,4-bis (4- Minophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene , 2,7-diaminofluorene, 9,9-bis (4-aminophenyl) fluorene, 4,4'-methylene-bis (2-chloroaniline), 2,2 ', 5,5'-tetra Chloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'- Diaminobiphenyl, 1,4,4 '-(p-phenyleneisopropylidene) bisaniline, 4,4'-(m-phenyleneisopropylidene) bisaniline, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-bis Aromatic diamines such as [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl;

Methaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1,4 -Diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindenylenedimethylenediamine, tricyclo [6.2.1.0 ^2,7 ] -undecylenedimethyldiamine, 4 Aliphatic and alicyclic diamines such as 4'-methylenebis (cyclohexylamine);

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, 1,4-bis (3-aminopropyl) piperazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1, 3,5-triazine, 2,4-diamino- 6-phenyl-1,3,5-triazine, 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazine, 4,6-dia Mino-2-vinyl-s-triazine, 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-phenylphenanthtridine, 1,4-diaminopiperazine, 2, in the molecule, such as 3,6-diaminoacridine, bis (4-aminophenyl) phenylamine and the compound represented by the following formula (6) Diamine having nitrogen atoms other than the primary amino group and the primary amino group;

(Wherein R ³ represents a monovalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, and X ¹ represents a divalent organic group)

(Wherein, R ⁴ represents a divalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine, and piperazine, X ² represents a divalent organic group, and a plurality of groups are present X ² may be the same or different)

Mono-substituted phenylenediamines represented by the following formula (8); Diaminoorganosiloxane represented by the following formula (9);

In the formula, R ⁵ represents a divalent organic group selected from -O-, -COO-, -OCO-, -NHCO-, -CONH-, and -CO-, and R ⁶ represents a steroid skeleton, a trifluoromethyl group and a fluorine group. Monovalent organic group or group having 6 to 30 carbon atoms having a group selected from a furnace group.

In formula, R <^7> represents a C1-C12 hydrocarbon group, two or more R <^7> may be same or different, p is an integer of 1-3 and q is an integer of 1-20.

The compound etc. which are represented by following General formula (1)-(5) are mentioned. These diamine compounds can be used individually or in combination of 2 or more types.

In formula, y is an integer of 2-12 and z is an integer of 1-5.

Among them, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,7-diaminofluorene, 4 , 4'-diaminodiphenylether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4 -(4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-(p-phenylenediisopropylidene) bisaniline, 4, 4 '-(m-phenylenediisopropylidene) bisaniline, 1,4-cyclohexanediamine, 4,4'-methylenebis (cyclohexylamine), 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, the compound represented by the formulas (1) to (5), 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4- Diaminopyrimidine, 3,6-diaminoacridine, the compound represented by the following formula (6) among the compounds represented by the formula (6), the above Among the compounds represented by the following formula (7) of the compound represented by the formula (7) and the compound represented by the formula (8), the compound represented by the following formula (8) to (17), and the compound represented by the formula (9), Preference is given to 3-bis (3-aminopropyl) hexamethyldisiloxane.

Tetracarboxylic dianhydride

Specific examples of the tetracarboxylic dianhydride having a specific side chain include 1,3,3a, 4,5,9b-hexahydro-4- (2,3-difluoro-4- (4-n-propylcyclo). Hexyl) phenoxy) -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4 , 5,9b-hexahydro-4- (2,3-difluoro-4- (4-n-butylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dioxo-3-fura Nil) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4- (2,3-difluoro-4- ( 4-n-pentylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1 , 3,3a, 4,5,9b-hexahydro-4- (2,3-difluoro-4- (4-n-hexylcyclohexyl) phenoxy) -5- (tetrahydro-2,5 -Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4- (2,3- Difluoro-4- (4-n-hexylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan -1,3-dione, 1,3,3a, 4,5,9b-hex Hydro-4- (2,3-difluoro-4- (4-n-heptylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ 1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4- (2,3-dicyano-4- (4-n-propylcyclohexyl) phenoxy) -5- (tetrahydro-2,5- Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4- (2,3-dicy Ano-4- (4-n-butylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1, 3-dione, 1,3,3a, 4,5,9b-hexahydro-4- (2,3-dicyano-4- (4-n-pentylcyclohexyl) phenoxy) -5- (tetrahydro- 2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4- (2 , 3-dicyano-4- (4-n-hexylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] Furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4- (2,3-dicyano-4- (4-n-heptylcyclohexyl) phenoxy) -5 -(Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4- (6- (4-n-propylcyclohexyl) -3-pyridazinyloxy) -5- (tetrahydro-2,5-dioxo 3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4- (6- (4-n- Butylcyclohexyl) -3-pyridazinyloxy) -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4- (6- (4-n-pentylcyclohexyl) -3-pyridazinyloxy) -5- (tetrahydro-2,5-dioxo 3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4- (6- (4-n- Hexylcyclohexyl) -3-pyridazinyloxy) -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione , 1,3,3a, 4,5,9b-hexahydro-4- (6- (4-n-heptylcyclohexyl) -3-pyridazinyloxy) -5- (tetrahydro-2,5-di Oxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4- (2-fluoro-4- (4-n-propylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dioxo 3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4- (2-fluoro-4- (4-n-butylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4- (2-fluoro-4- (4-n-pentylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dioxo 3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4- (2-fluoro-4- (4-n-hexylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione , 1,3,3a, 4,5,9b-hexahydro-4- (2-fluoro-4- (4-n-heptylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-di Oxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4- (3-fluoro-4- (4-n-propylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dioxo -3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4- (3-fluoro-4- (4-n-butylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4- (3-fluoro-4- (4-n-pentylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dioxo -3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4- (3-fluoro-4- (4-n-hexylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione , 1,3,3a, 4,5,9b-hexahydro-4- (3-fluoro-4- (4-n-heptylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-di Oxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4- (2-cyano-4- (4-n-propylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dioxo 3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4- (2-cyano-4- (4-n-butylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4- (2-cyano-4- (4-n-pentylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dioxo 3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4- (2-cyano-4- (4-n-hexylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione , 1,3,3a, 4,5,9b-hexahydro-4- (2-cyano-4- (4-n-heptylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-di Oxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4- (3-cyano-4- (4-n-propylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dioxo 3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4- (3-cyano-4- (4-n-butylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4- (3-cyano-4- (4-n-pentylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dioxo 3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4- (3-cyano-4- (4-n-hexylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione And 1,3,3a, 4,5,9b-hexahydro-4- (3-cyano-4- (4-n-heptylcyclohexyl) phenoxy) -5- (tetrahydro-2,5- Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione.

Among these, 1,3,3a, 4,5,9b-hexahydro-4- (2,3-difluoro-4- (4-n-propylcyclohexyl) phenoxy) -5- (tetrahydro- 2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4- (2 , 3-difluoro-4- (4-n-butylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] Furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4- (2,3-difluoro-4- (4-n-pentylcyclohexyl) phenoxy)- 5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexa Hydro-4- (2,3-difluoro-4- (4-n-hexylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4- (2,3-difluoro-4- (4-n-hex Silcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a , 4,5,9b-hexahydro-4- (2,3-difluoro-4- (4-n-heptylcyclohexyl) phenoxy) -5- (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4- (2,3-dicyano-4- (4-n-propylcyclohexyl) phenoxy) -5- (tetrahydro-2,5- Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4- (2,3-dicy Ano-4- (4-n-butylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1, 3-dione, 1,3,3a, 4,5,9b-hexahydro-4- (2,3-dicyano-4- (4-n-pentylcyclohexyl) phenoxy) -5- (tetrahydro- 2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4- (2 , 3-dicyano-4- (4-n-hexylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] Furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4- (2,3-dicyano-4- (4-n-heptylcyclohexyl) phenoxy) -5 -(Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione;

1,3,3a, 4,5,9b-hexahydro-4- (6- (4-n-propylcyclohexyl) -3-pyridazinyloxy) -5- (tetrahydro-2,5-dioxo 3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4- (6- (4-n- Butylcyclohexyl) -3-pyridazinyloxy) -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4- (6- (4-n-pentylcyclohexyl-3-pyridazinyloxy) -5- (tetrahydro-2,5-dioxo- 3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4- (6- (4-n-hex Silcyclohexyl) -3-pyridazinyloxy) -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, And 1,3,3a, 4,5,9b-hexahydro-4- (6- (4-n-heptylcyclohexyl) -3-pyridazinyloxy) -5- (tetrahydro-2,5-di Preference is given to oxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione.

 As another tetracarboxylic dianhydride used for the synthesis | combination of the polymer contained in the liquid crystal aligning agent of this invention, butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic, for example. Acid dianhydrides, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride , 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarb Acid dianhydrides, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,5,6-tricarboxynorbornane-2-acetic dianhydride, 2,3,4,5-tetrahydrofuranthtetracar Acid dianhydrides, 1,3,3a, 4,5,9b-hexahydrate Rho-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b -Hexahydro-5-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a , 4,5,9b-hexahydro-5-ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione , 1,3,3a, 4,5,9b-hexahydro-7-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan -1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1, 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) Naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-ethyl-5- (tetrahydro-2,5-dioxo 3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5- (tetra Hydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 5- (2,5-dioxotetrahydrofu Yl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2.2.2] -octo-7-ene-2,3,5,6-tetracarboxylic dianhydride Water, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), a compound represented by the following formulas (10) and (11) Aliphatic and alicyclic tetracarboxylic dianhydrides such as;

(Wherein R ⁸ and R ¹⁰ represent a divalent organic group having an aromatic ring, R ⁹ and R ¹¹ represent a hydrogen atom or an alkyl group, and a plurality of R ⁹ and R ¹¹ may be the same or different, respectively)

Pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenylsulfontetracarboxylic dianhydride, 1,4,5 , 8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylethertetracarboxylic dianhydride, 3,3 ', 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3', 4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic Acid dianhydrides, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydrides, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydrides, 4 , 4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3', 4,4 '-Biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphineoxide dianhydride, p-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 (anhydrotrimelitate), propylene glycol bis (anhydro trimellitate), 1,4-butanediol-bis (anhydro trimellitate), 1,6-hexanediol-bis (anhydro Trimellitate), 1,8-octanediol-bis (anhydro trimellitate), 2,2-bis (4-hydroxyphenyl) propane-bis (anhydro trimellitate), formulas (18) to Aromatic tetracarboxylic dianhydrides, such as a compound represented by (21), are mentioned. These are used individually by 1 type or in combination of 2 or more types.

Among these, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanedetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5 -(2,5-dioxotetrahydrofuranyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5 -(Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro- 8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5, 9b-hexahydro-5,8-dimethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, bicyclo [ 2.2.2] -octo-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro -3 '-(tetrahydrofuran-2', 5'-dione), pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4, 4'-biphenylsulfontetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, the compound represented by the following formulas (22) to (24) Among the compounds represented by the above formula (11), the compound represented by the following formula (25) is preferable from the viewpoint of being able to express good liquid crystal alignment, and particularly preferably 1,2,3,4-cyclobutanetetracarboxylic acid Dianhydrides, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 2,3,5-tri Carboxycyclopentylacetic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] Furan-1,3-dione, 1,3,3a, 4,5,9b- Sahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2 .1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), pyromellitic dianhydride and the compound represented by the following general formula (22) are mentioned. have.

Synthesis of Polyamic Acid

The use ratio of the tetracarboxylic dianhydride and the diamine compound provided in the synthesis reaction of the polyamic acid is preferably a ratio such that the acid anhydride group of the tetracarboxylic dianhydride is 0.2 to 2 equivalents to 1 equivalent of the amino group of the diamine, More preferably, it is the ratio used as 0.3-1.2 equivalent.

Synthesis reaction of polyamic acid is performed in organic solvent, Preferably it is -20-150 degreeC, More preferably, it is carried out under the temperature conditions of 0-100 degreeC. The organic solvent is not particularly limited as long as it can dissolve the polyamic acid synthesized. For example, 1-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide Aprotic polar solvents such as dimethyl sulfoxide, γ-butyrolactone, tetramethylurea and hexamethylphosphortriamide; and phenol solvents such as m-cresol, xylenol, phenol, and halogenated phenol. The amount of the organic solvent (α) is preferably such that the total amount (β) of the tetracarboxylic dianhydride and the diamine compound is 0.1 to 30% by weight relative to the total amount (α + β) of the reaction solution. desirable.

In the organic solvent, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like, which are poor solvents of polyamic acid, can be used together in a range in which the resulting polyamic acid is not precipitated. Specific examples of such poor solvents include methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, 4-hydroxy-4-methyl-2-pentanol, ethylene glycol, propylene glycol, 1,4-butanediol, for example. , Triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxy propionate, ethyl Oxypropionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether , Ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, 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 obtained by dissolving polyamic acid can be obtained. The reaction solution is poured into a large amount of poor solvent to obtain a precipitate, and the polyamic acid can be obtained by drying the precipitate under reduced pressure. In addition, the polyamic acid can be purified by dissolving the polyamic acid again in an organic solvent and then precipitating with a poor solvent once or plural times.

 <Synthesis of imidized polymer>

The imidation polymer which comprises the liquid crystal aligning agent of this invention can be synthesize | combined by dehydrating and ring-closing the said polyamic acid. Dehydration ring closure of polyamic acid is carried out by the method of heating (I) polyamic acid, or (II) polyamic acid is dissolved in an organic solvent, and a dehydrating agent and a dehydration ring closure catalyst are added to this solution, and it heats as needed. It is done by the method. In addition, the imidized polymer used in the present invention is an imidized polymer having a degree of imidization (expressed as a percentage of the repeating units formed by forming an imide ring in all the repeating units in the polymer in%) partially dehydrated and closed. It may also include.

Preferably the reaction temperature in the method of heating the polyamic acid of said (I) is 50-200 degreeC, More preferably, it is 60-170 degreeC. When reaction temperature is less than 50 degreeC, dehydration ring-closure reaction does not fully advance, and when reaction temperature exceeds 200 degreeC, the molecular weight of the imidation polymer (B) obtained may fall.

On the other hand, in the method of adding a dehydrating agent and a dehydrating ring-closure catalyst to the solution of the polyamic acid of said (II), acid anhydrides, such as an acetic anhydride, a propionic anhydride, a trifluoroacetic anhydride, can be used as a dehydrating agent, for example. . The amount of dehydrating agent used depends on the desired imidation ratio, but is preferably 0.01 to 20 moles with respect to 1 mole of the repeating unit of the polyamic acid. As the dehydration ring closure catalyst, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used, for example. However, it is not limited to these. It is preferable that the usage-amount of a dehydration ring-closure catalyst shall be 0.01-10 mol with respect to 1 mol of dehydrating agents used. The imidation ratio can be raised so that there are many said dehydrating agents and dehydrating ring closure agents. As the organic solvent used in the dehydration ring closure reaction, an organic solvent exemplified as being used for the synthesis of polyamic acid may be mentioned. And the reaction temperature of dehydration ring-closure reaction becomes like this. Preferably it is 0-180 degreeC, More preferably, it is 10-150 degreeC. Moreover, the imidation polymer can be refine | purified by performing the same operation as the purification method of polyamic acid with respect to the reaction solution obtained in this way.

<Terminal modified polymer>

The polyamic acid and the imidized polymer may be terminally modified with molecular weight. By using this terminal modified polymer, the coating characteristic of a liquid crystal aligning agent, etc. can be improved, without degrading the effect of this invention. Such a terminally modified polymer can be synthesized by adding an acid anhydride, a monoamine compound, a monoisocyanate compound and the like to the reaction system when synthesizing the polyamic acid. Here, examples of the acid anhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, n-hexadecylsuccinic anhydride, and the like. Can be mentioned. As the monoamine compound, for example, aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decyl Amines, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-eicosylamine etc. are mentioned. Moreover, as a monoisocyanate compound, phenyl isocyanate, naphthyl isocyanate, etc. are mentioned, for example.

<Liquid crystal aligning agent>

The liquid crystal aligning agent of this invention is comprised by melt | dissolving and containing the polymer which has a specific side chain, usually a polyamic acid and / or an imidation polymer in an organic solvent.

The temperature at the time of manufacturing the liquid crystal aligning agent of this invention becomes like this. Preferably it is 0 degreeC-200 degreeC, More preferably, it is 20 degreeC-60 degreeC.

As an organic solvent which comprises the liquid crystal aligning agent of this invention, the solvent illustrated to be used for the synthesis reaction of polyamic acid is mentioned. Moreover, the poor solvent illustrated as being usable together at the time of the synthesis reaction of polyamic acid can also be selected suitably, and can be used together. Among these, it is preferable to use 1-methyl-2-pyrrolidone and the solvent whose surface tension is 32 dyn / cm or less. Examples of the solvent having a surface tension of 32 dyn / cm or less include 4-hydroxy-4-methyl-2-pentanol, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methylmethoxypropionate, and ethyl. Oxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate and the like.

The ratio of 1-methyl-2-pyrrolidone and a solvent having a surface tension of 32 dyn / cm or less is 20 to 60 wt% of 1-methyl-2-pyrrolidone and a solvent having a surface tension of 32 dyn / cm or less is 80 to It is preferable that it is 40 weight%. Outside the range of this ratio, sufficient printability cannot be obtained because precipitation of the polymer occurs or leveling is insufficient.

In the liquid crystal aligning agent of this invention, although solid content concentration is selected in consideration of viscosity, volatility, etc., Preferably it is the range of 1 to 10 weight%. That is, although the liquid crystal aligning agent of this invention is apply | coated to the surface of a board | substrate, and the coating film used as a liquid crystal aligning film is formed, when solid content concentration is less than 1 weight%, since the film thickness of this coating film becomes too thin, a favorable liquid crystal aligning film cannot be obtained and solid content concentration is carried out. When the content exceeds 10% by weight, the film thickness of the coating film becomes too thick, so that a good liquid crystal aligning film cannot be obtained, and the viscosity of the liquid crystal aligning agent is increased, resulting in poor coating properties.

The functional silane containing compound and the epoxy compound may be contained in the liquid crystal aligning agent of this invention from a viewpoint of improving the adhesiveness to the board | substrate surface in the range which does not impair the target physical property. Examples of such functional silane-containing compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, and N-. (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltree Ethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N- Trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecan, 10-triethoxysilyl-1,4,7-triazadecan, 9-trimethoxysilyl -3,6-diazanyl acetate, 9-triethoxysilyl-3,6-diazanyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl -3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimeth Oxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, etc. are mentioned. Examples of such epoxy group-containing compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol diglycidyl. Ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3, 5,6-tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidyl Aminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 3- (N-allyl-N-glycidyl) aminopropyltrimethoxy Silane, 3- (N, N- diglycidyl) aminopropyltrimethoxysilane, etc. are mentioned.

<Liquid crystal display element>

The liquid crystal display element obtained using the liquid crystal aligning agent of this invention can be manufactured, for example by the following method.

(1) The liquid crystal aligning agent of this invention is apply | coated to the one surface of the board | substrate with which the patterned transparent conductive film is provided by methods, such as a roll coater method, a spinner method, and a printing method, and then a coating film is formed by heating a coating surface. do. Here, as a board | substrate, For example, glass, such as float glass and a soda glass; A transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone and polycarbonate can be used. As a transparent conductive film provided on one side of the substrate, an NESA film containing tin oxide (SnO ₂ ) (registered trademark of PPG Co., Ltd.) and an ITO film containing indium tin oxide (In ₂ O ₃ -SnO ₂ ) Etc. can be used, and a photo-etching method or a method of using a mask in advance is used for patterning such a transparent conductive film. When apply | coating a liquid crystal aligning agent, in order to make adhesiveness of a board | substrate surface, a transparent conductive film, and a coating film more favorable, you may apply | coat a functional silane containing compound, a functional titanium containing compound, etc. previously on the said surface of a board | substrate. The heating temperature after liquid crystal aligning agent application becomes like this. Preferably it is 80-300 degreeC, More preferably, it is 120-250 degreeC. In addition, although the liquid crystal aligning agent of this invention containing a polyamic acid forms the coating film which becomes an oriented film by removing an organic solvent after application | coating, further heating can advance dehydration ring closure, and can also form more imidized coating film. The film thickness of the coating film formed becomes like this. Preferably it is 0.001-1 micrometer, More preferably, it is 0.005-0.5 micrometer.

(2) The rubbing process of rubbing in a fixed direction is performed with the roll which rolled the cloth which consists of fibers, such as nylon, rayon, and cotton, for example as needed. Thereby, the pretilt angle can be provided to the liquid crystal molecules on the coating film, and the direction in which the liquid crystal molecules collapse upon application of voltage can be controlled. In some cases, the pretilt angle may be provided by irradiating the coating film with ultraviolet light or an ion beam of polarized light or polarized light without using the rubbing method.

Moreover, in the vertically-aligned liquid crystal display element of this invention, when controlling the direction in which a liquid crystal molecule collapses at the time of voltage application by a transverse electric field, the processus | protrusion on a board | substrate, etc., the said coating film is not necessarily performed. It can also be used as a liquid crystal aligning film as it is.

(3) Two board | substrates with a liquid crystal aligning film were produced as mentioned above, and two board | substrates were separated so that the rubbing direction (or the collapsed direction of the liquid crystal molecule at the time of voltage application) may become antiparallel in each liquid crystal aligning film ( The cell gaps are disposed to face each other, two peripheral portions of the substrate are bonded together with a sealant, a liquid crystal is injected and filled into the cell surface partitioned by the substrate surface and the sealant, and the injection hole is sealed to form a liquid crystal cell. On the outer surface of the liquid crystal cell, that is, the other surface side of each substrate constituting the liquid crystal cell, a polarizing plate is placed in a rubbing direction (or liquid crystal molecules at the time of voltage application) of the liquid crystal alignment film whose polarization direction is formed on one side of the substrate. The liquid crystal display element can be obtained by bonding so that it may form an angle of 45 degrees with the collapsed direction).

Here, as the sealant, for example, an epoxy resin or the like containing an aluminum oxide sphere as a curing agent and a spacer can be used.

Examples of the liquid crystal include nematic liquid crystals and smectic liquid crystals, and among them, nematic liquid crystals are preferable, and for example, a sieve base liquid crystal, a subfamily clock liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal and an ester type A liquid crystal, a terphenyl type liquid crystal, a biphenyl cyclohexane type liquid crystal, a pyrimidine type liquid crystal, a dioxane type liquid crystal, a bicyclooctane type liquid crystal, a cuban type liquid crystal, etc. can be used. In addition, such liquid crystals are, for example, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonaate, cholesteryl carbonate, and trade names "C-15" and "CB-15" (manufactured by Merck Co., Ltd.). The chiral agent etc. which are sold can also be added and used. Ferroelectric liquid crystals such as p-disiloxybenzylidene-p-amino-2-methylbutyl cinnamate can also be used.

Moreover, as a polarizing plate bonded to the outer surface of a liquid crystal cell, the polarizing plate which consists of a polarizing plate called H film which absorbed iodine, and extended | stretched polyvinyl alcohol between the cellulose acetate protective film, or the polarizing plate which consists of H film itself is mentioned. .

<Examples>

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not restrict | limited to these Examples. In addition, the evaluation method of the liquid crystal display element in the following Example and a comparative example is as follows.

[Pretilt Angle of Liquid Crystal Display Element]

Based on the method described in TJ Scheffer, et. Al., J. Appl. Phys., Vol. 19, 2013 (1980), it was measured by a crystal rotation method using a He-Ne laser beam (here Pretilt angle is defined as the angle at which the orientation direction of the liquid crystal molecules is tilted at the substrate surface).

Synthesis Example 1

Of polyamic acid  polymerization

0.1 mole (22.4 g) of 2,3,5-tricarboxycyclopentylacetic dianhydride and 1- (2,3-difluoro-4- (4-n-hexylcyclohexyl) phenoxy) -2,4 0.1 mol (40.3 g) of diaminobenzene was dissolved in 300 g of N-methyl-2-pyrrolidone and reacted at 60 ° C for 6 hours. The reaction mixture was then poured into very excess methanol to precipitate the reaction product. Then, the mixture was washed with methanol and dried at 40 ° C. under reduced pressure for 15 hours to obtain 62 g of polyamic acid (hereinafter referred to as “polymer 1a”).

Imidization  reaction

380 g of N-methyl-2-pyrrolidone, 7.9 g of pyridine, and 10.2 g of acetic anhydride were added to 31.2 g of polymer 1a, and an imidization reaction was performed at 120 ° C for 4 hours. Subsequently, the reaction mixture was poured into an excessive amount of methanol to precipitate the reaction product. Thereafter, the mixture was washed with methanol and dried under reduced pressure for 15 hours to obtain 29 g of an imidized polymer (hereinafter referred to as "polymer 1b").

Synthesis Example 2

Of polyamic acid  polymerization

1- (2,3-difluoro-4- (4-n-hexylcyclohexyl) phenoxy) -2,4-diaminobenzene instead of 0.1 mole (40.1 g) of (2,3-dicyano- Polyamic acid (hereinafter referred to as "polymer 2a") in the same manner as in Synthesis Example 1 except that 0.1 mol (43.1 g) of 4- (4-n-pentylcyclohexyl) phenyl) -3,5-diaminobenzoate was used. 64 g was obtained.

Imidization  reaction

30 g of an imidized polymer (hereinafter, referred to as "polymer 2b") was obtained in the same manner as in Synthesis example 1 except that 32.8 g of polymer 2a was used instead of 31.2 g of polymer 1a.

Synthesis Example 3

Of polyamic acid  polymerization

1- (2- (6- (4-) instead of 0.1 mol (40.3 g) of 1, (2,3-difluoro-4- (4-n-hexylcyclohexyl) phenoxy) -2,4-diaminobenzene Polyamic acid (hereinafter referred to as "polymer 3a") in the same manner as in Synthesis example 1 except that 0.1 mol (36.8 g) of n-hexylcyclohexyl) -3-pyridazinyloxy) -2,4-diaminobenzene was used. 57 g was obtained.

Imidization  reaction

26 g of imidized polymer (hereinafter, referred to as "polymer 3b") was obtained in the same manner as in Synthesis example 1 except that 29.6 g of polymer 3a was used instead of 31.2 g of polymer 1a.

Synthesis Example 4

Of polyamic acid  polymerization

1,3,3a, 4,5,9b-hexahydro-4- (6- (4-n-pentylcyclohexyl) -3-pyridazinyloxy) -5- (tetrahydro-2,5-dioxo 0.1 mol (54.6 g) of -3-furanyl) -naphtho [1,2-c] -furan-1,3-dione and 0.1 mol (10.8 g) of p-phenylenediamine were N-methyl-2-pi It melt | dissolved in 300 g of rollidone, and made it react at 60 degreeC for 6 hours. The reaction mixture was then poured into very excess methanol to precipitate the reaction product. Thereafter, the mixture was washed with methanol and dried at 40 DEG C for 15 hours under reduced pressure to obtain 64 g of polyamic acid (hereinafter referred to as "polymer 4a").

Imidization  reaction

26 g of imidized polymer (hereinafter, referred to as "polymer 4b") was obtained in the same manner as in Synthesis example 1 except that 32.7 g of polymer 4a was used instead of 31.2 g of polymer 1a.

Comparative Synthesis Example 1

Of polyamic acid  polymerization

0.1 mole (22.4 g) of 2,3,5-tricarboxycyclopentylacetic dianhydride and 0.1 mole (10.8 g) of p-phenylenediamine were dissolved in 300 g of N-methyl-2-pyrrolidone and 6 at 60 ° C. The reaction was time. The reaction mixture was then poured into very excess methanol to precipitate the reaction product. Then, the mixture was washed with methanol and dried at 40 ° C. under reduced pressure for 15 hours to obtain 27 g of polyamic acid (hereinafter referred to as “polymer Aa”).

Imidization  reaction

380 g of N-methyl-2-pyrrolidone, 7.9 g of pyridine and 10.2 g of acetic anhydride were added to 16.6 g of Polymer Aa, and an imidization reaction was performed at 120 ° C. for 4 hours. Subsequently, the reaction mixture was poured into an excessive amount of methanol to precipitate the reaction product. Thereafter, the mixture was washed with methanol and dried under reduced pressure for 15 hours to obtain 13 g of an imidized polymer (hereinafter referred to as "polymer Ab").

Example 1

(1) Preparation of liquid crystal aligning agent:

The polymer (1) obtained in Synthesis Example 1 was dissolved in γ-butyrolactone to make a solution having a solid content of 2.5% by weight, and the solution was filtered through a filter having a pore size of 1 μm to prepare a liquid crystal aligning agent of the present invention.

(2) Preparation of Liquid Crystal Display Device:

1) A liquid crystal aligning agent of the present invention prepared as described above was applied on a transparent conductive film comprising an ITO film provided on one side of a glass substrate having a thickness of 1 mm using a spinner and dried by drying at 180 ° C. for 1 hour. A film of 800 angstroms in thickness was formed.

2) The liquid crystal aligning film was manufactured by performing the rubbing process on the formed coating film surface using the rubbing machine which has the roll which rolled the cloth made from nylon. The rubbing treatment conditions were made into roll rotation speed 500 rpm and stage movement speed of 1 cm / sec.

3) Two board | substrates with a liquid crystal aligning film were manufactured as mentioned above, and after apply | coating the epoxy resin adhesive containing the aluminum oxide sphere of diameter 17micrometer by the screen printing method to the outer edge part of each board | substrate, Two board | substrates were opposingly arranged through the space | interval so that the rubbing direction in a liquid crystal aligning film might mutually parallel, and the outer edge part contacted and crimped | cured and hardened the adhesive agent.

4) A nematic liquid crystal "MLC-6608" (manufactured by Merck Co., Ltd.) was filled and filled into the cell gap partitioned by the adhesive on the surface of the substrate and the outer edge portion, and then the injection hole was sealed with an epoxy adhesive to constitute a liquid crystal cell. Then, the liquid crystal display element was manufactured by bonding a polarizing plate to the outer surface of a liquid crystal cell so that a polarization direction may make an angle of 45 degree with the rubbing direction of a liquid crystal aligning film, and may orthogonally cross.

5) The pretilt angle of the liquid crystal was 89 degrees in the liquid crystal display element manufactured as mentioned above. Moreover, when a voltage was applied and released to the liquid crystal cell, the abnormal domain was not recognized and the liquid crystal alignment property was good.

Examples 2-4

A liquid crystal display device was produced in the same manner as in Example 1 except that the polymers (2b) to (4b) obtained in Synthesis Examples 2 to 4 were used instead of the polymer (1b). The liquid crystal orientation and the pretilt angle of the produced liquid crystal cell were evaluated. The results are shown in Table 1 below.

Example 5

A liquid crystal display device was produced in the same manner as in Example 1 except that the polymer (4a) obtained in Synthesis Example 4 was used instead of the polymer (1b). The liquid crystal orientation and the pretilt angle of the produced liquid crystal cell were evaluated. The results are shown in Table 1.

Comparative example

A liquid crystal display device was produced in the same manner as in Example 1 except that the polymer (Ab) obtained in Comparative Synthesis Example 1 was used instead of the polymer (1b). The pretilt angle of the liquid crystal of the manufactured liquid crystal display element was 1 degree or less, and was not vertically oriented.

[Effects of the Invention]

According to this invention, when it is set as a liquid crystal aligning film, the liquid crystal aligning agent suitable for the vertically-aligned liquid crystal display element which can form the liquid crystal aligning film with favorable vertical alignment property of a liquid crystal can be provided.

Claims (3)

A liquid crystal aligning agent containing a polymer having at least one structure selected from the group consisting of a structure represented by the following formula (1) and a structure represented by the following formula (2) in the side chain.
<Formula 1>

In the formula, A ¹ and B ¹ are fluorine atoms.
<Formula 2>

The liquid crystal aligning agent according to claim 1, wherein the polymer is a polymer having a group represented by the following formula (3) in a side chain.
<Formula 3>

In the formula, P is a single bond, -O-, -COO- or -CONH-, Q is a structure represented by the formula (1) or a structure represented by the formula (2), R ¹ is a divalent alicyclic group, R ² is a linear alkyl group having 1 to 22 carbon atoms. The liquid crystal aligning film formed from the liquid crystal aligning agent of Claim 1 or 2 is provided, The liquid crystal display element characterized by the above-mentioned.