JP5527538B2 - Liquid crystal aligning agent, method for producing liquid crystal aligning film, and liquid crystal display element - Google Patents

Description

  The present invention relates to a liquid crystal alignment agent, a method for manufacturing a liquid crystal alignment film, and a liquid crystal display element.

As one of operation modes of a liquid crystal display element, a vertical (homeotropic) alignment mode in which liquid crystal molecules having negative dielectric anisotropy are aligned perpendicularly to a substrate is also known. In this operation mode, when a voltage is applied between the substrates and the liquid crystal molecules are tilted in the direction parallel to the substrate, the liquid crystal molecules are tilted from the substrate normal direction toward one direction in the substrate surface ( Need to pretilt). As a means for this, for example, a method of providing protrusions on the substrate surface, a method of providing stripes on the transparent electrode, or using a rubbing alignment film, liquid crystal molecules are slightly directed from the substrate normal direction to one direction in the substrate surface. A tilting method, a photo-alignment method, and the like have been proposed (Patent Documents 1 to 5).
Among the above, the liquid crystal alignment film imparted with the pretilt property by the photo-alignment method has a problem that the liquid crystal alignment performance gradually deteriorates due to long-term use even if the liquid crystal alignment property at the beginning of manufacture is excellent. It has been pointed out that this tendency is remarkable in liquid crystal display elements used under conditions.
In addition to this, with the progress of digitalization of television broadcasts and advanced moving image fixing technology, in recent years, the accuracy and quality of image data has been rapidly increasing. In order to accurately reproduce such image data and display a beautiful screen, the requirements for the electrical characteristics of the liquid crystal cell, particularly the voltage holding ratio, are extremely stricter than ever. Furthermore, in order to increase the product yield as much as possible and contribute to the reduction of the product cost, the liquid crystal aligning agent is required to have extremely high printing performance.

JP 2003-307736 A JP 2004-163646 A JP 2004-83810 A Japanese Patent Laid-Open No. 9-21468 JP 2003-114437 A

T.A. J. et al. Scheffer et. al. J. et al. Appl. Phys. , Vol. 48, p1789 (1977)) F. Nakano et. al. JPN. J. et al. Appl. Phys. , Vol. 19, p2013 (1980))

The present invention has been made to solve the above-described problems, and its object is to provide a liquid crystal alignment film that has excellent electrical characteristics and does not deteriorate liquid crystal alignment performance even when used for a long time under high temperature conditions. And providing a liquid crystal aligning agent having excellent printability.
Another object of the present invention is to provide a method for producing a liquid crystal alignment film that has excellent electrical characteristics and does not deteriorate the liquid crystal alignment performance even when used for a long time under high temperature conditions.
Still another object of the present invention is to provide a liquid crystal display device that has excellent display performance and does not deteriorate even when used for a long time under high temperature conditions.

In accordance with the present invention, the above objects and advantages of the present invention are primarily as follows:
At least one polymer selected from the group consisting of polyamic acid and polyimide, provided that at least a part of the polymer has the following formula (0)

(In Formula (0), R ^I is an alkyl group having 3 to 12 carbon atoms or a fluoroalkyl group having 3 to 12 carbon atoms, X ^I is a single bond or an oxygen atom, and R ^II is 1,4-cyclohexane. It is a silene group or a 1,4-phenylene group, X ^II is a single bond, an oxygen atom or ^* —COO— (where a bond marked with “*” is bonded to R ^II ), and n is 0 Or X ^III is represented by the following formula (X ^III -1) or (X ^III -2)

It is group represented by these. )
It is achieved by a liquid crystal aligning agent containing a group represented by:
The above objects and advantages of the present invention are secondly,
This is achieved by a liquid crystal display element comprising a liquid crystal alignment film formed from the above liquid crystal aligning agent.

  According to the present invention, there is provided a liquid crystal aligning agent that is excellent in electrical characteristics, can provide a liquid crystal alignment film that does not deteriorate liquid crystal alignment performance even when used for a long time under high temperature conditions, and is excellent in printability. A liquid crystal display element comprising a liquid crystal alignment film formed from this liquid crystal aligning agent is excellent in display performance, and does not deteriorate even when used for a long time under high temperature conditions.

Hereinafter, the present invention will be described in detail.
The liquid crystal aligning agent of the present invention is at least one polymer selected from the group consisting of polyamic acid and polyimide, provided that the polymer has a group represented by the above formula (0) in at least a part of its molecule. It has. Hereinafter, such a polymer is referred to as a “specific polymer” in the present specification. In the specific polymer, the group represented by the formula (0) may be present in the main chain of the polymer, may be present in the side chain of the polymer, or may be present in the polymer. It may be present in both the main chain and the side chain.
R ^I in the above formula (0) is preferably an alkyl group having 3 to 7 carbon atoms, or a fluoroalkyl group having 3 to 7 carbon atoms and 3 to 5 fluorine atoms. Specific examples of preferred ^{R I,} for example, n- propyl group, n- butyl group, n- pentyl group, n- hexyl, n- heptyl, 4,4,4-trifluoro butyl group, 4,4, 5,5,5-pentafluoropentyl group and the like can be mentioned, and among these, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group or n-heptyl group is particularly preferable.
X ^I in the above formula (0) is a single bond;
R ^II is a 1,4-cyclohexylene group;
X ^II is a single bond;
n is preferably 0, respectively. X ^III is preferably a group represented by the above formula (X ^III -1), and particularly preferably a C—C double bond in the above formula (X ^III -1) is a trans type. The 1,4-cyclohexylene group in the above formula (0) preferably has a chair type structure.
The liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention containing the specific polymer having the group represented by the above formula (0) having such a rigid mesogen structure is excellent in electrical characteristics and at high temperature conditions. Even when used for a long time below, the liquid crystal alignment performance is excellent in stability.

The polyamic acid having a group represented by the above formula (0) as described above in at least a part of the molecule includes, for example, a compound having a group represented by the above formula (0) and two carboxylic anhydride groups. Reacting a tetracarboxylic dianhydride with a diamine, or reacting a tetracarboxylic dianhydride with a diamine containing a group represented by the above formula (0) and a compound having two amino groups. Can be obtained by
A polyimide having a group represented by the above formula (0) in at least a part of the molecule can be obtained, for example, by dehydrating and ring-closing the polyamic acid obtained as described above.
As the specific polymer contained in the liquid crystal aligning agent of the present invention, tetracarboxylic dianhydride is reacted with a diamine containing a group represented by the above formula (0) and a compound having two amino groups. The polyamic acid obtained in this manner and at least one polymer selected from the group consisting of polyimides obtained by dehydrating and ring-closing the polyamic acid are preferred.
<Polyamic acid>
As described above, a preferred polyamic acid in the present invention is obtained by reacting a tetracarboxylic dianhydride with a diamine containing a group represented by the above formula (0) and a compound having two amino groups. is there.
[Tetracarboxylic dianhydride]
Examples of the tetracarboxylic dianhydride used for the synthesis of the polyamic acid include butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 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′-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclo Ntylacetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic 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- 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 (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- ] -Furan-1,3-dione, 5- (2,5-dioxotetrahydrofuranyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2.2.2]- Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran- 2 ', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy 2-carboxynorbornane-2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, The following formulas (TI) and (T-II)

(In the above formula, R ¹ and R ³ are each a divalent organic group having an aromatic ring, R ² and R ⁴ are each a hydrogen atom or an alkyl group, and a plurality of R ² and R ² are present. ⁴ may be the same or different.
An aliphatic tetracarboxylic dianhydride and an alicyclic tetracarboxylic dianhydride such as a compound represented by each of the following:
Pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride, 1,4,5, 8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis ( 3,4-dicar Boxyphenoxy) diphenylpropane dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidene diphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2 , 2 ′, 3,3′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide 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 ( Anhydrotrimellitate), propylene glycol-bis (anhydrotrimellitate), 1,4-butanediol-bis (anhydrotrimellitate) Retate), 1,6-hexanediol-bis (anhydrotrimellitate), 1,8-octanediol-bis (anhydrotrimellitate), 2,2-bis (4-hydroxyphenyl) propane-bis ( Anhydrotrimellitate), the following formulas (T-1) to (T-4)

An aromatic tetracarboxylic dianhydride such as a compound represented by each of the above can be exemplified. These can be used alone or in combination of two or more.
The tetracarboxylic dianhydride used for synthesizing the preferred polyamic acid in the present invention is butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, , 3-Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid 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, , 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] -Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-dione-6 Spiro-3 ′-(tetrahydrofuran-2 ′, 5′-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3, 5,8,10-tetraone, pyromellitic dianhydride, 3 , 3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride, 2,3 ′, 2,3′-biphenyltetracarboxylic acid Among the compounds represented by dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, and the above formula (TI), the following formulas (T-5) to (T-7)

Of the compounds represented by each of the above and the compounds represented by the above formula (T-II), the following formula (T-8)

It is preferable that the liquid crystal layer formed has at least one liquid crystal alignment property including at least one selected from the group consisting of the compounds represented by (hereinafter referred to as “specific tetracarboxylic dianhydride”). It is preferable from the viewpoint of expression.
Specific tetracarboxylic dianhydrides include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid 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, 3-oxabicyclo [3.2.1] octane- 2,4-dione-6-spiro-3 ′-(tetrahydrofuran-2 ′, 5′-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1 , 2-Dicarboxylic anhydride , 3,5,6-tricarboxy-2-carboxymethyl norbornane -2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^{2, 6]} undecane -3 , 5,8,10-tetraone, pyromellitic dianhydride and at least one selected from the group consisting of compounds represented by the above formula (T-5) are preferred, and in particular 2,3,5-tricarboxyl Cyclopentyl acetic acid dianhydride is preferred.
The tetracarboxylic dianhydride used for synthesizing a preferable polyamic acid in the present invention contains 20 mol% or more of the specific tetracarboxylic dianhydride as described above with respect to the total tetracarboxylic dianhydride. It is preferable that 50 mol% or more is included, and 80 mol% or more is particularly preferable.
As the tetracarboxylic dianhydride used for the synthesis of a preferable polyamic acid in the present invention, it is most preferable to use only the specific tetracarboxylic dianhydride as described above.

[Diamine]
The diamine used for synthesizing a preferred polyamic acid in the present invention includes a compound represented by the above formula (0) and a compound having two amino groups. Preferred examples of such compounds include, for example, the following formula (1)

(In the formula (1), R ^I , X ^I , R ^II , X ^II , X ^III and n are as defined in the above formula (0), and R ^III is a single bond, a methylene group or a carbon number. 2 to 6 alkylene group, provided that the alkylene group may be substituted by a hydroxyl group, X ^IV is a single bond, an oxygen atom or ^* -OCO- (provided that a bond marked with "*" R ^III )), but when R ^III is a single bond, X ^IV is a single bond.)
The compound etc. which are represented by these can be mentioned.
The ^{X IV} in the above formula (1) single bond. The two amino groups in the diaminophenyl group of the above formula (1) are preferably in the 2,4-position, 2,5-position or 3,5-position with respect to other groups.
Preferable examples of the compound represented by the above formula (1) include, for example, the following formulas (1-1) to (1-41)

(In the formulas (1-1) to (1-41), R ^I has the same meaning as in the above formula (1), m is an integer of 1 to 6, and R ^III-1 is 1,2-propylene. Group.)
And the like, and the like. In the above formulas (1-1) to (1-41), the C—C double bond is preferably a trans type.
Among these, the above formulas (1-1), (1-4) to (1-7), (1-10) to (1-13), (1-16) to (1-18), (1 -29) and (1-30) are more preferable, and the above formulas (1-4) to (1-6), (1-12), (1-18), (1-29) ) And (1-30) are more preferred, and compounds represented by the above formula (1-6) are particularly preferred.
The compound represented by the above formula (1) can be synthesized by appropriately combining organic chemistry methods.
For example, in the above formula (1), R ^III is a methylene group, X ^III is a group represented by the above formula (X ^III -1), and X ^IV is a single bond. A)

(In the formula (1-A), R ^I , X ^I , R ^II , X ^II and n have the same meanings as in the above formula (1).)
The compound represented by the above and dinitrobenzyl chloride are preferably reacted in the presence of potassium carbonate to obtain a dinitro compound, and then the nitro group of the dinitro compound is reduced (hydrogenated) using an appropriate reduction system. To obtain an amino group.
In the above formula (1), R ^III is a 1,2-ethylene group, X ^III is a group represented by the above formula (X ^III -1), and X ^IV is a single bond. After the compound represented by (1-A) is reacted with thionyl chloride to form an acid chloride, the following formula (1-B)

To obtain a dinitro compound by reacting with a compound in which R ^III is a 1,2-ethylene group and X is a hydroxyl group, and then reducing (hydrogenating) the nitro group of the dinitro compound using an appropriate reduction system. To obtain an amino group.
In the above formula (1), R ^III is a single bond, X ^III is a group represented by the above formula (X ^III -1), and X ^IV is a single bond, for example, the above formula (1-A ) Is reacted with thionyl chloride to give an acid chloride, then reacted with dinitrophenol to obtain a dinitro compound, and then the nitro group of the dinitro compound is reduced (hydrogen) using an appropriate reduction system. To obtain an amino group.
In the above formula (1), R ^III is a 1,2-ethylene group, X ^III is a group represented by the above formula (X ^III -1), and X ^IV is ^* -OCO- (where "*" A bond having a bond with R ^III is a compound represented by the following formula (1-C):

(In formula (1-C), R ^I , X ^I , R ^II , X ^II and n have the same meanings as in formula (1)).
To obtain an amino group by reducing (hydrogenating) the nitro group of the dinitro compound using an appropriate reduction system. Can do. In addition, in the above formula (1-C), by using a compound in which a methylene group is substituted with a group — (CH ₂ ) _m — having a desired m value, the corresponding desired compound can be obtained.
In the above formula (1), R ^III is a methylene group or an alkylene group, X ^III is a group represented by the above formula (X ^III -1), and X ^IV is an oxygen atom. The compound represented by 1-A) is reacted with thionyl chloride to form an acid chloride, and then R ^III is reacted with a compound having a hydroxyl group at both ends of a desired methylene group or alkylene group to form a monoalcohol. Further, the monoalcohol is reacted with fluorodinitrophenol to obtain a dinitro compound by deHF, and then the nitro group of the dinitro compound is reduced (hydrogenated) to form an amino group using an appropriate reduction system. be able to.

The compound represented by each of the above formulas (1-33) to (1-36) is obtained by reacting, for example, 3,5-bis (N, N-diallylamino) hydroxybenzene with glycidyl chloride. Bis (N, N-diallylamino) glycidyloxybenzene is obtained, then the compound and the desired group R ^I , X ^I , R ^II and X ^II and the following formula (1-D) having the number n

After obtaining a diallyl compound by reacting with the compound represented by the formula, it can be preferably obtained by converting an N, N-diallyl group into an amino group in the presence of tetraphenylpalladium.
The compound represented by each of the above formulas (1-37) to (1-40) is, for example, the above formula (1-D) having the desired groups R ^I , X ^I , R ^II and X ^II and the number n. An intermediate compound was obtained by reacting the compound represented with glycidyl chloride, and then the intermediate compound was reacted with 3,5-bis (N, N-diallylamino) hydroxybenzene to obtain a diallyl compound. Thereafter, it can be obtained by converting the N, N-diallyl group into an amino group, preferably in the presence of tetraphenylpalladium.
As a diamine for synthesizing a preferred polyamic acid in the present invention, only the compound represented by the above formula (1) may be used alone, and the compound represented by the above formula (1) and other diamines may be used. You may use it in combination.

  Examples of other diamines that can be used here include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 4,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfone, 3,3′-dimethyl-4,4′-diaminobiphenyl, 4,4′-diaminobenzanilide, 4,4′-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2, 2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 3,3'- Ditrifluoromethyl-4,4′-diaminobiphenyl, 5-amino-1- (4′-aminopheny ) -1,3,3-trimethylindane, 6-amino-1- (4′-aminophenyl) -1,3,3-trimethylindane, 3,4′-diaminodiphenyl ether, 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-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4- Minophenyl) -10-hydroanthracene, 2,7-diaminofluorene, 9,9-dimethyl-2,7-diaminofluorene, 9,9-bis (4-aminophenyl) fluorene, 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, 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 (trifluoro) (Romethyl) biphenyl, aromatic diamines such as 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl;

1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, Tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindanylene methylenediamine, tricyclo [6.2.1.0 ^2,7 ] -undecylenedimethyldiamine, 4,4'-methylenebis (cyclohexylamine) Aliphatic diamines and alicyclic diamines such as;
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-diamino-2-vinyl-s-triazine, 2,4-diamino-5-phenylthiazole, 2,6- Aminopurine, 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-diaminopiperazine, 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'-di (4-aminophenyl) -benzidine, the following formulas (DI) and (D-II)

(In the formula (DI), R ⁵ is a monovalent organic group having a ring structure containing a nitrogen atom selected from the group consisting of pyridine, pyrimidine, triazine, piperidine and piperazine, and X ¹ is a divalent group. An organic group;
In the formula (D-II), R ⁶ is a divalent organic group having a ring structure containing a nitrogen atom selected from the group consisting of pyridine, pyrimidine, triazine, piperidine and piperazine, and X ² is 2 And a plurality of X ² may be the same or different. )
A diamine having two primary amino groups in the molecule and a nitrogen atom other than the primary amino group, such as a compound represented by each of:
The following formula (D-III)

(In the formula (D-III), R ⁷ is —O—, —COO—, —OCO—, —NHCO—, —CONH— or —CO—, and R ⁸ is a steroid skeleton, a trifluoromethylphenyl group, It is a monovalent organic group having a skeleton or group selected from the group consisting of a fluoromethoxyphenyl group and a fluorophenyl group, or an alkyl group having 6 to 30 carbon atoms.)
Monosubstituted phenylenediamines such as compounds represented by:
The following formula (D-IV)

(In the formula (D-IV), R ⁹ is a hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R ⁹ may be the same or different, and p is each 1 is an integer of 1 to 3, and q is an integer of 1 to 20.)
Diaminoorganosiloxanes such as compounds represented by:
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.)
And the like, and the like.
Other diamines used in combination with the compound represented by the above formula (1) when synthesizing a preferred polyamic acid in the present invention include p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4 '-Diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 2,7-diamino Fluorene, 4,4′-diaminodiphenyl ether, 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) hexafluoropro Bread, 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, compounds represented by the above formulas (D-1) to (D-5), 2, 6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3, 6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N′-di (4-aminophenyl) -benzidine, The following formula among the compounds represented by the serial formula (D-I) (D-6)

Of the compounds represented by formula (D-II), the following formula (D-7)

Of the compounds represented by formula (D-III) and dodecanoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2,4-diaminobenzene, octadecanoxy- 2,5-diaminobenzene, dodecanoxy-2,5-diaminobenzene, pentadecanoxy-2,5-diaminobenzene, hexadecanoxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene and the following formula (D-8) ~ (D-16)

It is preferable that it contains at least one selected from the group consisting of the compounds represented by each (hereinafter referred to as “other specific diamine”).
The diamine used for synthesizing the preferred polyamic acid in the present invention preferably contains 1 mol% or more, and 20 mol% or more of the compound represented by the above formula (1) with respect to the total diamine. Is more preferable, and it is particularly preferable to include 50 mol% or more.
The diamine used for synthesizing a preferred polyamic acid in the present invention can further contain other specific diamines as described above, and the content ratio of the other specific diamines is 90 mol% with respect to the total diamines. Or less, more preferably 80 mol% or less, and even more preferably 50 mol% or less.
The preferred diamine used in the synthesis of the polyamic acid in the present invention consists only of the compound represented by the above formula (1), or only from the compound represented by the above formula (1) and other specific diamines. It is preferable that

[Synthesis of polyamic acid]
A preferred polyamic acid in the present invention can be obtained by reacting a tetracarboxylic dianhydride with a diamine containing a compound represented by the above formula (1).
The ratio of the tetracarboxylic dianhydride and the diamine compound used for the polyamic acid synthesis reaction is such that the acid anhydride group of the tetracarboxylic dianhydride is 0.1 relative to 1 equivalent of the amino group contained in the diamine compound. A ratio of 2 to 2 equivalents is preferable, and a ratio of 0.3 to 1.2 equivalents is more preferable.
The polyamic acid synthesis reaction is preferably performed in an organic solvent under a temperature condition of preferably -20 to 150 ° C, more preferably 0 to 100 ° C. The reaction time is preferably 1 to 240 hours, more preferably 2 to 12 hours. Here, the organic solvent is not particularly limited as long as it can dissolve the synthesized polyamic acid. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide And aprotic polar solvents such as γ-butyrolactone, tetramethylurea and hexamethylphosphortriamide; and phenolic solvents such as m-cresol, xylenol, phenol and halogenated phenol. The amount of the organic solvent used (a: when the organic solvent and the poor solvent described later are used in combination) refers to the total amount of the tetracarboxylic dianhydride and the diamine compound (b). The amount is preferably 0.1 to 30% by weight based on the total amount (a + b) of the reaction solution.

For the organic solvent, alcohol, ketone, ester, ether, halogenated hydrocarbon, hydrocarbon, etc., which are generally believed to be poor solvents for polyamic acid, may be used in combination as long as the resulting polyamic acid does not precipitate. it can. Specific examples of the poor solvent include, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, 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 methoxypropionate, ethyl ethoxypropionate, 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- Chill 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, diisobutyl ketone, isoamylpropionate, isoamylisobutyrate, diisopentyl ether, etc. That.
When the organic solvent and the poor solvent as described above are used in combination when synthesizing the polyamic acid, the use ratio of the poor solvent is preferably 50% by weight or less, more preferably, based on the total of the organic solvent and the poor solvent. Is 10% by weight or less.

As described above, a reaction solution obtained by dissolving polyamic acid is obtained.
This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, may be used for the preparation of the liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution, or the isolated polyamic acid was purified. You may use for preparation of a liquid crystal aligning agent.
When polyamic acid is dehydrated and cyclized into a polyimide, the above reaction solution may be directly subjected to dehydration and cyclization reaction, or may be subjected to dehydration and cyclization reaction after isolating the polyamic acid contained in the reaction solution. Alternatively, the isolated polyamic acid may be purified and then subjected to a dehydration ring closure reaction.
The polyamic acid is isolated by pouring the reaction solution into a large amount of poor solvent to obtain a precipitate, and drying the precipitate under reduced pressure, or by distilling off the solvent in the reaction solution under reduced pressure using an evaporator. It can be carried out. Further, the polyamic acid can be purified by a method of dissolving the polyamic acid again in an organic solvent and then precipitating with a poor solvent, or a method of performing the step of distilling under reduced pressure with an evaporator once or several times.

<Polyimide>
A preferred polyimide in the present invention can be obtained by dehydrating and ring-closing the polyamic acid as described above to imidize.
Examples of the tetracarboxylic dianhydride used for the synthesis of the polyimide include the same compounds as the tetracarboxylic dianhydride used for the synthesis of the polyamic acid described above. The kind of preferable tetracarboxylic dianhydride and its preferable usage rate are the same as in the case of polyamic acid.
Examples of the diamine used for synthesizing a preferable polyimide in the present invention include the same diamines as those used for the synthesis of the polyamic acid. That is, the diamine used for the synthesis | combination of the polyimide contained in the liquid crystal aligning agent of this invention contains the compound represented by the said Formula (1), and uses only the compound represented by the said Formula (1). Alternatively, the compound represented by the formula (1) and the other diamine may be used in combination. The types of other preferred diamines and the preferred use ratio of each diamine are the same as in the case of polyamic acid.
The preferred polyimide in the present invention may be a completely imidized product obtained by dehydrating and cyclizing all of the amic acid structure that the polyamic acid as a raw material had, or by dehydrating and cyclizing only a part of the amic acid structure. And a partially imidized product in which the imide ring structure coexists. The polyimide in the present invention preferably has an imidization rate of 20% or more, more preferably 40 to 80%. This imidation ratio represents the ratio of the number of imide ring structures to the total of the number of polyimide amic acid structures and the number of imide ring structures in percentage. At this time, a part of the imide ring may be an isoimide ring. The imidation rate is calculated by the following formula (I) based on the result of measuring ¹ H-NMR at room temperature using tetramethylsilane as a reference substance by dissolving polyimide in a suitable deuterated solvent (for example, deuterated dimethyl sulfoxide). Can be sought.
Imidization rate (%) = (1-A ¹ / A ² × α) × 100 (I)
(In Formula (I), A ¹ is a peak area derived from protons of NH groups appearing near a chemical shift of 10 ppm, A ² is a peak area derived from other protons, and α is a polyimide precursor (polyamic acid). The number ratio of other protons to one proton of NH group in

The dehydration ring closure of the polyamic acid is preferably performed by (i) a method of heating the polyamic acid, or (ii) dissolving the polyamic acid in an organic solvent, and adding a dehydrating agent and a dehydration ring closure catalyst to this solution as necessary. This is done by heating.
The reaction temperature in the method (i) of heating the polyamic acid is preferably 50 to 200 ° C, more preferably 60 to 170 ° C. When the reaction temperature is less than 50 ° C., the dehydration ring-closing reaction does not proceed sufficiently, and when the reaction temperature exceeds 200 ° C., the molecular weight of the resulting polyimide may decrease. The reaction time is preferably 1.0 to 24 hours, more preferably 1.0 to 12 hours.
On the other hand, in the method (ii) of adding a dehydrating agent and a dehydrating ring-closing catalyst to the polyamic acid solution, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride is used as the dehydrating agent. Can do. Although the usage-amount of a dehydrating agent is based on the imidation ratio desired, it is preferable to set it as 0.01-20 mol with respect to 1 mol of the amic acid structure of a polyamic acid. Moreover, as a dehydration ring closure catalyst, tertiary amines, such as a pyridine, a collidine, a lutidine, a triethylamine, can be used, for example. However, it is not limited to these. It is preferable that the usage-amount of a dehydration ring-closing catalyst shall be 0.01-10 mol with respect to 1 mol of dehydrating agents to be used. The imidation rate can be increased as the amount of the above dehydrating agent and dehydrating ring-closing agent increases. Examples of the organic solvent used in the dehydration ring-closing reaction include the organic solvents exemplified as those used for the synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

  The polyimide obtained in the above method (i) may be used for the preparation of the liquid crystal aligning agent as it is, or may be used for the preparation of the liquid crystal aligning agent after purifying the obtained polyimide. On the other hand, in the above method (ii), a reaction solution containing polyimide is obtained. This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, or may be used for the preparation of the liquid crystal aligning agent after removing the dehydrating agent and the dehydrating ring-closing catalyst from the reaction solution. It may be used for the preparation of a liquid crystal aligning agent or may be used for the preparation of a liquid crystal aligning agent after purifying the isolated polyimide. In order to remove the dehydrating agent and the dehydrating ring-closing catalyst from the reaction solution, for example, a method such as solvent replacement can be applied. The isolation and purification of the polyimide can be performed by performing the same operation as described above as the isolation and purification method of the polyamic acid.

-End-modified polymer-
In the present invention, the polyamic acid and the polyimide may each be a terminal-modified polymer having a controlled molecular weight. By using the terminal-modified polymer, the coating properties of the liquid crystal aligning agent can be further improved without impairing the effects of the present invention. Such a terminal-modified polymer can be obtained by adding a molecular weight modifier to a polymerization reaction system when synthesizing a polyamic acid. Examples of molecular weight regulators include acid monoanhydrides, monoamine compounds, monoisocyanate compounds, and the like.
Examples of the acid monoanhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, n -Hexadecyl succinic anhydride etc .;
Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-eicosylamine and the like;
Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.
The use ratio of the molecular weight regulator is preferably 20 parts by weight or less, more preferably 5 parts by weight or less, with respect to 100 parts by weight of the total of tetracarboxylic dianhydride and diamine used when synthesizing the polyamic acid. is there.
-Solution viscosity-
The polyamic acid or polyimide obtained as described above preferably has a solution viscosity of 20 to 800 mPa · s, and a solution viscosity of 30 to 500 mPa · s when a 10% by weight solution is obtained. It is more preferable to have it.
The solution viscosity (mPa · s) of the above polymer is E for a polymer solution having a concentration of 10% by weight prepared using a good solvent for the polymer (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.). It is a value measured at 25 ° C. using a mold rotational viscometer.

<Other ingredients>
The liquid crystal alignment film of the present invention contains the specific polymer as described above as an essential component, but may contain other components as necessary. Examples of such other components include polymers other than the specific polymer (hereinafter referred to as “other polymer”), compounds having at least one epoxy group in the molecule (hereinafter referred to as “epoxy compound”), and the like. Examples thereof include functional silane compounds.
[Other polymers]
These other polymers can be used to improve solution and electrical properties. Such other polymer is a polymer other than the specific polymer as described above. For example, a polyamic obtained by reacting tetracarboxylic dianhydride with a diamine not containing the compound represented by the above formula (1). Acid (hereinafter referred to as “other polyamic acid”), polyimide obtained by dehydrating and ring-closing the polyamic acid (hereinafter referred to as “other polyimide”), polyamic acid ester, polyester, polyamide, polysiloxane, cellulose derivative, Examples include polyacetal, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylates, and the like. Of these, other polyamic acids or other polyimides are preferred, and other polyamic acids are more preferred.
The use ratio of the other polymer is preferably 95% by weight or less, more preferably 50 to 50% with respect to the total of the polymers (referring to the total of the specific polymer and other polymers; the same shall apply hereinafter). 90% by weight.

[Epoxy compound]
Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexane. Diol 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-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diame Diphenylmethane, N, N-diglycidyl - benzylamine, N, N-diglycidyl - such as aminomethyl cyclohexane may be mentioned as preferred. The compounding ratio of these epoxy group-containing compounds is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the total amount of the polymer.

[Functional silane compounds]
Examples of the functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl)- 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyl Trimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4 7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N- Benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis ( Examples thereof include oxyethylene) -3-aminopropyltrimethoxysilane and N-bis (oxyethylene) -3-aminopropyltriethoxysilane.
The blending ratio of these functional silane compounds is preferably 40 parts by weight or less with respect to 100 parts by weight of the total polymer.

<Liquid crystal aligning agent>
The liquid crystal aligning agent of the present invention is constituted by dissolving the specific polymer as described above and other additives optionally blended as required, preferably dissolved in an organic solvent.
As an organic solvent which can be used for the liquid crystal aligning agent of this invention, the solvent illustrated as what is used for the synthesis reaction of a polyamic acid can be mentioned. Moreover, the poor solvent illustrated as what can be used together in the case of the synthesis reaction of a polyamic acid can also be selected suitably, and can be used together. Preferred examples of such organic solvents include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, 4-hydroxy-4-methyl-2- Pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i- Propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, di Examples include ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, and diisopentyl ether. These can be used alone or in admixture of two or more.

The solid content concentration of the liquid crystal aligning agent of the present invention (the ratio of the total weight of components excluding the organic solvent in the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc. However, it is preferably in the range of 1 to 10% by weight. That is, when the liquid crystal aligning agent of the present invention is applied to the substrate surface and the organic solvent is removed to form a coating film that becomes a liquid crystal aligning film, the solid content concentration is less than 1% by weight. The film thickness of this coating film may be too small to obtain a good liquid crystal alignment film. On the other hand, if the solid content concentration exceeds 10% by weight, the film thickness of the coating film will be excessive. Similarly, it may be difficult to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal aligning agent may increase, resulting in poor coating characteristics.
The particularly preferable range of the solid content concentration varies depending on the method used when the liquid crystal aligning agent is applied to the substrate. For example, when the spinner method is used, the range of 1.5 to 4.5% by weight is particularly preferable. In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by weight and thereby the solution viscosity is in the range of 12 to 50 mPa · s. In the case of the inkjet method, it is particularly preferable that the solid content concentration is in the range of 1 to 5% by weight, and thereby the solution viscosity is in the range of 3 to 15 mPa · s.

<Method for forming liquid crystal alignment film>
The liquid crystal aligning agent of this invention can be used conveniently in order to form a liquid crystal aligning film by the photo-alignment method.
As a method for forming a liquid crystal alignment film, for example, a liquid crystal aligning agent is applied onto a substrate to form a coating film, and the coating film is irradiated with polarized or non-polarized ultraviolet rays obliquely with respect to the coating film surface. Or a method of imparting liquid crystal alignment ability to the coating film by irradiating polarized ultraviolet rays from a direction perpendicular to the coating film surface.
First, the liquid crystal aligning agent of this invention is apply | coated to the transparent conductive film side of the board | substrate with which the pattern-shaped transparent conductive film was provided, for example by appropriate coating methods, such as a roll coater method, a spinner method, a printing method, an inkjet method. . Since the liquid crystal aligning agent of this invention is excellent in printability, when the printing method, especially the offset printing method is employ | adopted, the advantageous effect of this invention will be exhibited to the maximum, and it is preferable. After coating, the coated surface is preheated (prebaked) and then baked (postbaked) to form a coating film. The pre-bake conditions are, for example, 0.1 to 5 minutes at 40 to 120 ° C., and the post-bake conditions are preferably 120 to 300 ° C., more preferably 150 to 250 ° C., preferably 5 to 200 minutes, more preferably 10 to 100 minutes. The film thickness of the coating film after post-baking is preferably 0.001-1 μm, more preferably 0.005-0.5 μm.
Examples of the substrate include glass such as float glass and soda glass; and a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, and polycarbonate.
As the transparent conductive film, a NESA film made of SnO _{2 or} an ITO film made of In ₂ O ₃ —SnO ₂ can be used. For patterning these transparent conductive films, a photo-etching method or a method using a mask when forming the transparent conductive film is used.

When applying the liquid crystal aligning agent, in order to further improve the adhesion between the substrate or the transparent conductive film and the coating film, a functional silane compound, titanate compound or the like is previously applied on the substrate and the transparent conductive film. May be.
Next, the coating film becomes a liquid crystal alignment film by imparting liquid crystal alignment ability by irradiating the coating film with polarized or non-polarized ultraviolet rays. Here, as the radiation, for example, ultraviolet rays including light having a wavelength of 150 nm to 800 nm and visible light can be used, but ultraviolet rays including light having a wavelength of 300 nm to 400 nm are preferable. When the radiation to be used is polarized (linearly polarized light or partially polarized light), it may be irradiated from a direction perpendicular to the coating film surface or from an oblique direction for providing a pretilt angle. On the other hand, when irradiating non-polarized radiation, it is necessary to perform irradiation from an oblique direction with respect to the coating surface.
As a light source for irradiation radiation, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used. The ultraviolet rays in the preferable wavelength region can be obtained by means of using the light source in combination with, for example, a filter or a diffraction grating.
The irradiation dose of radiation, preferably less than 1 J / ^{m 2} or more 10,000 J / ^{m 2,} more preferably from 10~3,000J / ^{m 2.} In addition, when providing the liquid crystal aligning ability by the photo-alignment method to the coating film formed from the conventionally known liquid crystal aligning agent, the irradiation dose of 10,000 J / m < ² > or more was required. However, using the liquid crystal aligning agent of the present invention, the radiation dose at the time of photo-alignment method is 3,000 J / ^{m 2} or less, further 1,000 J / ^{m 2} or less, even more was at 300 J / ^{m 2} or less good Liquid crystal alignment ability can be imparted, which contributes to the reduction of the manufacturing cost of the liquid crystal display element.
The “pretilt angle” in the present invention represents an angle of inclination of liquid crystal molecules from a direction parallel to the substrate surface.

<Method for manufacturing liquid crystal display element>
The liquid crystal display element of this invention comprises the liquid crystal aligning film formed from the liquid crystal aligning agent of this invention. The liquid crystal display element of this invention can be manufactured as follows, for example.
A liquid crystal cell is manufactured by preparing two substrates on which a liquid crystal alignment film is formed as described above, and disposing a liquid crystal between the two substrates. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example.
The first method is a conventionally known method. First, two substrates are arranged to face each other through a gap (cell gap) so that the respective liquid crystal alignment films are opposed to each other, and the peripheral portions of the two substrates are bonded using a sealant, and the substrate surface and the sealant are bonded. A liquid crystal cell can be manufactured by injecting and filling liquid crystal into the cell gap partitioned by the step, and then sealing the injection hole.
The second method is a method called an ODF (One Drop Fill) method. For example, an ultraviolet light curable sealant is applied to a predetermined location on one of the two substrates on which the liquid crystal alignment film is formed, and liquid crystal is dropped on the liquid crystal alignment film surface. The other substrate is bonded so as to face each other, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant, whereby a liquid crystal cell can be manufactured.
In any case, it is desirable to remove the flow alignment at the time of filling the liquid crystal by heating the liquid crystal cell to a temperature at which the liquid crystal used has an isotropic phase and then gradually cooling it to room temperature.
And the liquid crystal display element of this invention can be obtained by bonding a polarizing plate on the outer surface of a liquid crystal cell. Here, when the liquid crystal alignment film is horizontally aligned, the angle formed by the polarization direction of the irradiated linearly polarized radiation and the angle between each substrate and the polarizing plate are adjusted on the two substrates on which the liquid crystal alignment film is formed. By doing so, a liquid crystal display element having a TN type or STN type liquid crystal cell can be obtained. On the other hand, in the case where the liquid crystal alignment film is vertically aligned, the cell is configured so that the directions of easy alignment axes of the two substrates on which the liquid crystal alignment film is formed are parallel, A liquid crystal display element having a vertical alignment type liquid crystal cell can be obtained by bonding so that the polarization direction forms an angle of 45 ° with the easy alignment axis.

As the sealing agent, for example, an aluminum oxide sphere as a spacer and an epoxy resin containing a curing agent can be used.
As the liquid crystal, for example, nematic liquid crystal or smectic liquid crystal can be preferably used.
In the case of a TN type liquid crystal cell or an STN type liquid crystal cell, a nematic type liquid crystal having positive dielectric anisotropy is preferable. For example, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, a biphenylcyclohexane liquid crystal, Pyrimidine liquid crystals, dioxane liquid crystals, bicyclooctane liquid crystals, cubane liquid crystals and the like are used. In addition, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonate, cholesteryl carbonate; chiral agents such as those sold under the trade names “C-15” and “CB-15” (manufactured by Merck); p- A ferroelectric liquid crystal such as decyloxybenzylidene-p-amino-2-methylbutylcinnamate may be further added and used.
On the other hand, in the case of a vertical alignment type liquid crystal cell, a nematic liquid crystal having negative dielectric anisotropy is preferable. For example, dicyanobenzene liquid crystal, pyridazine liquid crystal, Schiff base liquid crystal, azoxy liquid crystal, biphenyl liquid crystal, phenyl cyclohexane. System liquid crystal or the like is used.
The polarizing plate used outside the liquid crystal cell is composed of a polarizing film called “H film” in which polyvinyl alcohol is stretched and oriented while absorbing iodine and sandwiched between cellulose acetate protective films, or the H film itself. A polarizing plate etc. can be mentioned.
The liquid crystal display element of the present invention thus produced has excellent display performance, and the display performance does not deteriorate even when used for a long time under high temperature conditions.

<Synthesis of Compound Represented by Formula (1)>
The following synthesis examples were repeatedly carried out at the following synthesis scale as necessary, thereby securing the necessary amount in the following synthesis examples and polymer synthesis.
Synthesis Example 1-1 (Synthesis of Compound (1-4-1))
Compound (1-4-1) is converted into the following scheme 1.

Was synthesized according to
(1) Synthesis of Compound (1-4-1A) In a 5 L three-necked flask equipped with a reflux tube, a thermometer and a nitrogen introduction tube, 310 g of 4- (4-pentylcyclohexyl) bromobenzene, 2.3 g of palladium acetate, 12 g of (o-tolyl) phosphine, 560 mL of triethylamine, 82 mL of acrylic acid, and 2,000 mL of N, N-dimethylacetamide were charged, and the reaction was carried out at 120 ° C. with stirring for 3 hours. After completion of the reaction, the reaction mixture was filtered. The organic layer obtained by adding 10 L of ethyl acetate to the filtrate was washed successively with dilute hydrochloric acid twice and water three times, dried over magnesium sulfate, and the solid obtained by removing the solvent under reduced pressure. Was recrystallized from a mixed solvent consisting of ethyl acetate and tetrahydrofuran to obtain 150 g of crystals of the compound (1-4-1A).
(2) Synthesis of Compound (1-4-1B) In a 500 mL three-necked flask equipped with a stirrer, a thermometer and a nitrogen introduction tube, 30 g of Compound (1-4-1A) synthesized above and 3,5-dinitro 22 g of benzyl chloride, 42 g of potassium carbonate, 30 g of sodium iodide and 150 mL of N, N-dimethylformamide were charged and reacted at 60 ° C. for 8 hours. After completion of the reaction, 300 mL of chloroform was added to the reaction mixture, and the resulting organic layer was washed three times with water and then dried over magnesium sulfate. The organic layer was concentrated and the precipitated solid was collected and washed with ethanol to obtain 41 g of a pale yellow powder of the compound (1-4-1B).
(3) Synthesis of Compound (1-4-1) In a 1 L three-necked flask equipped with a stirrer, a thermometer and a nitrogen introduction tube, 41 g of the compound (1-4-B) synthesized above and tin chloride dihydrate 192 g of the product and 400 mL of ethyl acetate were charged, and the reaction was performed under reflux for 4 hours. After completion of the reaction, the reaction mixture was washed successively with an aqueous potassium fluoride solution and water. The organic layer was dried over magnesium sulfate, and then the solvent was removed under reduced pressure. The solid obtained was recrystallized from ethanol to obtain 21 g of pale yellow crystals of compound (1-4-1).

Synthesis Example 1-2 (Synthesis of Compound (1-22-1))
Compound (1-22-1) is converted into the following scheme 2.

Was synthesized according to
(1) Synthesis of Compound (1-22-1A) In a 500 mL three-necked flask equipped with a reflux tube, a thermometer, and a nitrogen introduction tube, 4- (4- (4,4,4-trifluorobutoxy) cyclohexyl) bromo Charge 37 g of benzene, 0.23 g of palladium acetate, 1.2 g of tri (o-tolyl) phosphine, 56 mL of triethylamine, 8.2 mL of acrylic acid and 200 mL of N, N-dimethylacetamide, and perform the reaction at 120 ° C. with stirring for 3 hours. It was. After completion of the reaction, the reaction mixture was filtered. The organic layer obtained by adding 1 L of ethyl acetate to the filtrate was washed twice with dilute hydrochloric acid and three times with water, dried over magnesium sulfate, and then the solvent was removed under reduced pressure to obtain a solid obtained as ethyl acetate. By recrystallizing from a mixed solvent consisting of and tetrahydrofuran, 18 g of crystals of the compound (1-22-1A) were obtained.
(2) Synthesis of Compound (1-22-1B) In a 300 mL three-necked flask equipped with a stirrer, a thermometer and a nitrogen introduction tube, 18 g of Compound (1-22-1A) synthesized above and 3,5-dinitro 11 g of benzyl chloride, 21 g of potassium carbonate, 15 g of sodium iodide and 75 mL of N, N-dimethylformamide were charged and reacted at 60 ° C. for 8 hours. After completion of the reaction, 150 mL of chloroform was added to the reaction mixture, and the resulting organic layer was washed 3 times with water and then dried over magnesium sulfate. The organic layer was concentrated and the precipitated solid was collected and washed with ethanol to obtain 23 g of a pale yellow powder of the compound (1-22-1B).
(3) Synthesis of Compound (1-22-1) In a 500 mL three-necked flask equipped with a stirrer, a thermometer and a nitrogen introduction tube, 23 g of the compound (1-22B) synthesized above and tin chloride dihydrate 96 g of the product and 200 mL of ethyl acetate were charged, and the reaction was performed under reflux for 4 hours. After completion of the reaction, the reaction mixture was washed successively with an aqueous potassium fluoride solution and water. After drying the organic layer with magnesium sulfate, the solid obtained by removing the solvent was recrystallized from ethanol to obtain 10 g of pale yellow crystals of the compound (1-22-1).

Synthesis Example 1-3 (Synthesis of Compound (1-10-1))
Compound (1-10-1) was converted into the following scheme 3

Was synthesized according to
(1) Synthesis of Compound (1-10-1A) In a 500 mL three-necked flask equipped with a reflux tube, a thermometer and a nitrogen introduction tube, 39 g of Compound (1-10-1G), 0.23 g of palladium acetate, tri (o -Tolyl) phosphine 1.2 g, triethylamine 56 mL, acrylic acid 8.2 mL and N, N-dimethylacetamide 200 mL were charged, and the reaction was performed at 120 ° C. with stirring for 3 hours. After completion of the reaction, the reaction mixture was filtered. The organic layer obtained by adding 1 L of ethyl acetate to the filtrate was washed successively with dilute hydrochloric acid twice and with water three times, then dried over magnesium sulfate, and the solid obtained by removing the solvent under reduced pressure was obtained. By recrystallization from a mixed solvent consisting of ethyl acetate and tetrahydrofuran, 19 g of crystals of the compound (1-10-1A) were obtained.
(2) Synthesis of Compound (1-10-1B) In a 300 mL three-necked flask equipped with a stirrer, a thermometer and a nitrogen introduction tube, 19 g of Compound (1-10-1A) synthesized above and 3,5-dinitro 11 g of benzyl chloride, 21 g of potassium carbonate, 15 g of sodium iodide and 75 mL of N, N-dimethylformamide were charged and reacted at 60 ° C. for 8 hours. After completion of the reaction, 150 mL of chloroform was added to the reaction mixture, and the resulting organic layer was washed 3 times with water and then dried over magnesium sulfate. The organic layer was concentrated and the precipitated solid was collected and washed with ethanol to obtain 24 g of a pale yellow powder of the compound (1-10-1B).
(3) Synthesis of compound (1-10-1) In a 500 mL three-necked flask equipped with a stirrer, a thermometer and a nitrogen introduction tube, 24 g of compound (1-10-B) synthesized above and tin chloride dihydrate 96 g of the product and 200 mL of ethyl acetate were charged, and the reaction was performed under reflux for 4 hours. After completion of the reaction, the reaction mixture was washed successively with an aqueous potassium fluoride solution and water. The organic layer was dried over magnesium sulfate, concentrated, and recrystallized from ethanol to obtain 12 g of pale yellow crystals of the compound (1-10-1).

Synthesis Example 1-4 (Synthesis of Compound (1-16-1))
The compound (1-16-1) is converted into the following scheme 4

Was synthesized according to
(1) Synthesis of Compound (1-16-1A) In a 300 mL eggplant flask equipped with a reflux tube and a nitrogen introduction tube, 21 g of Compound (1-16-1G), 80 mL of thionyl chloride and 0.1 mL of N, N-dimethylformamide Was reacted at 80 ° C. for 1 hour with stirring. After completion of the reaction, unreacted thionyl chloride was distilled off from the reaction mixture under reduced pressure, and then 150 mL of methylene chloride was added to wash the organic layer with water three times. After drying this organic layer with magnesium sulfate, the solvent was removed under reduced pressure to dry it once, and then 400 mL of tetrahydrofuran was added to obtain a solution containing the compound (1-16-1A).
(2) Synthesis of Compound (1-16-1B) In a 1 L three-necked flask equipped with a dropping funnel and a thermometer, 16 g of p-hydroxycinnamic acid, 24 g of potassium carbonate, 0.87 g of tetrabutylammonium bromide, 200 mL of water and tetrahydrofuran 100 mL was charged and this was ice-cooled to 5 ° C. or lower. The whole amount of the solution containing the compound (1-16-1A) prepared above was added dropwise over 3 hours, and the reaction was further performed with stirring for 1 hour. After completion of the reaction, diluted hydrochloric acid was added to the reaction mixture to adjust the pH to 4 or less, and the organic layer obtained by adding 3 L of toluene and 1 L of tetrahydrofuran was washed 3 times with water. The organic layer was dried over magnesium sulfate, the solvent was removed under reduced pressure, and the obtained solid was recrystallized from a mixed solvent consisting of ethanol and tetrahydrofuran to obtain 21 g of compound (1-16-1B). .
(3) Synthesis of Compound (1-16-1C) In a 300 mL three-necked flask equipped with a stirrer, a thermometer and a nitrogen introduction tube, 21 g of Compound (1-16-1B) synthesized above and 3,5-dinitro 11 g of benzyl chloride, 21 g of potassium carbonate, 15 g of sodium iodide and 75 mL of N, N-dimethylformamide were charged and reacted at 60 ° C. for 8 hours. After completion of the reaction, 300 mL of chloroform was added to the reaction mixture, and the resulting organic layer was washed three times with water and then dried over magnesium sulfate. The organic layer was concentrated and the precipitated solid was collected and washed with ethanol to obtain 28 g of a pale yellow powder of the compound (1-16-1C).
(4) Synthesis of Compound (1-16-1) In a 1 L three-necked flask equipped with a stirrer, thermometer and nitrogen introduction tube, 26 g of Compound (1-16-1C) synthesized above and tin chloride dihydrate 96 g of the product and 200 mL of ethyl acetate were charged, and the reaction was performed under reflux for 4 hours. After completion of the reaction, the reaction mixture was washed successively with an aqueous potassium fluoride solution and water. The organic layer was dried over magnesium sulfate, concentrated, and recrystallized from ethanol to obtain 12 g of pale yellow crystals of the compound (1-16-1).

Synthesis Example 1-5
In Synthesis Example 1-4, the following formula (1-16-2G) was used instead of compound (1-16-1G).

The following formula (1-16-2) was carried out in the same manner as in Synthesis Example 1-4 except that 17 g of the compound represented by formula (1) was used.

11 g of the compound represented by (Compound (1-16-2)) was obtained.

Synthesis Example 1-6
The compound (1-6-1) is converted into the following scheme 5

Was synthesized according to
(1) Synthesis of Compound (1-6-1A) Into a 2 L three-necked flask equipped with a dropping funnel, a nitrogen introduction tube and a thermometer, 45.2 g (0.2 mol) of 2,4-dinitrophenylacetic acid and 300 mL of dehydrated tetrahydrofuran were added. Using a dropping funnel, 600 mL of a tetrahydrofuran solution of borane / tetrahydrofuran complex having a concentration of 1 mol / L was added dropwise over 2 hours, and then the reaction was performed at room temperature with stirring for 3 hours. After completion of the reaction, 400 mL of water was slowly added to the reaction mixture, and the organic layer obtained by further adding ethyl acetate was washed with water, dried over magnesium sulfate, and the solvent was removed under reduced pressure to dryness. After purification with a silica column using ethyl acetate: toluene = 1: 1 as a developing solvent, 38 g of compound (1-6-1A) was obtained by recrystallization from a mixed solvent consisting of ethyl acetate and hexane. Obtained.
(2) Synthesis of Compound (1-6-1B) In a 500 mL eggplant-shaped flask equipped with a nitrogen inlet tube, 30 g of Compound (1-4-1A) obtained above, 21 g of Compound (1-6-1A), N, N-dimethylaminopyridine (1.2 g), dichloromethane (200 mL) and N- (3-dimethylaminopropyl) -N′-ethylcarbodiimide hydrochloride were charged, stirred under ice-cooling for 1 hour, and further at room temperature overnight. Reaction was performed. After completion of the reaction, the reaction mixture was washed with water, dried over magnesium sulfate, then the solvent was removed under reduced pressure to dryness, and the solid obtained was recrystallized from a mixed solvent consisting of ethyl acetate and hexane. 45 g of compound (1-6-1B) was obtained.
(3) Synthesis of Compound (1-6-1) In a 1 L three-necked flask equipped with a reflux tube, a thermometer and a nitrogen introduction tube, 45 g of Compound (1-6-1B) synthesized above and tin chloride dihydrate The product 203g and ethyl acetate 500mL were prepared, and it reacted under recirculation | reflux for 4 hours. After completion of the reaction, the reaction mixture was washed successively with an aqueous potassium fluoride solution and water. The organic layer was dried over magnesium sulfate, concentrated, and recrystallized from a mixed solvent consisting of ethanol and tetrahydrofuran to obtain 18 g of pale yellow crystals of the compound (1-6-1).

Synthesis Example 1-7
Compound (1-6-2) was converted into the following scheme 6

Was synthesized according to
(1) Synthesis of Compound (1-6-2B) In a 500 mL eggplant-shaped flask equipped with a nitrogen inlet tube, 34 g of Compound (1-6-2A) was synthesized in the same manner as in Synthesis Example 1-6. The compound (1-6-1A) 21 g, N, N-dimethylaminopyridine 1.2 g, dichloromethane 200 mL and N- (3-dimethylaminopropyl) -N′-ethylcarbodiimide hydrochloride were charged, and cooled with ice The mixture was stirred for 1 hour and further reacted at room temperature for a whole day and night. After completion of the reaction, water was added to the reaction mixture for liquid separation, and the organic layer obtained was dried over magnesium sulfate, and then the solvent was removed under reduced pressure to obtain 49 g of compound (1-6-2B).
(3) Synthesis of Compound (1-6-2) In a 1 L three-necked flask equipped with a reflux tube, a thermometer and a nitrogen introduction tube, 49 g of Compound (1-6-2B) synthesized above and tin chloride dihydrate The product 203g and ethyl acetate 500mL were prepared, and it reacted under recirculation | reflux for 4 hours. After completion of the reaction, the reaction mixture was washed successively with an aqueous potassium fluoride solution and water. The obtained organic layer was dried over magnesium sulfate, and then the solvent was removed under reduced pressure. The solid obtained was recrystallized from a mixed solvent consisting of ethanol and tetrahydrofuran to give a pale compound (1-6-2). 20 g of yellow crystals were obtained.

Synthesis Example 1-8
Compound (1-41-1) is converted into the following scheme 7

Was synthesized according to
(1) Synthesis of Compound (1-41-1B) In a 300 mL eggplant flask equipped with a reflux tube and a nitrogen introduction tube, 30 g of Compound (1-4-1A), 100 mL of thionyl chloride and 0.1 mL of N, N-dimethylformamide And reacted at 80 ° C. for 1 hour. After completion of the reaction, unreacted thionyl chloride was distilled off from the reaction mixture under reduced pressure, and then 150 mL of methylene chloride was added to wash the organic layer with water three times. After drying this organic layer with magnesium sulfate, the solvent was removed under reduced pressure to dryness once, and then 200 mL of tetrahydrofuran was added to contain the reaction product of compound (1-4-1A) and thionyl chloride. A solution was obtained.
On the other hand, in a 500 mL three-necked flask different from the above, 38 g of propylene glycol, 11 g of triethylamine and 50 mL of tetrahydrofuran were charged and cooled on ice at 5 ° C. or lower. Next, a solution containing the reaction product of the above compound (1-4-1A) and thionyl chloride was slowly added dropwise while maintaining the temperature at 5 ° C. or lower, and the reaction was further performed by stirring at room temperature for 1 hour. . After completion of the reaction, the organic layer obtained by adding ethyl acetate to the reaction mixture was washed successively with 1 mol / L hydrochloric acid and water, further dried with manesium sulfate, and then the solvent was removed under reduced pressure. The dried product was purified by a silica column using a mixed solvent consisting of ethyl acetate and hexane as a developing medium, and the solvent was removed from the corresponding fraction to obtain 29 g of compound (14-11-1B).

(3) Synthesis of (1-41-1C) In a 300 mL three-necked flask equipped with a thermometer and a nitrogen inlet tube, 29 g of (1-41-1B) obtained above, 16 g of 2,4-dinitrofluorobenzene and triethylamine were obtained. 16 g was charged and the reaction was carried out at room temperature with stirring all day and night. After completion of the reaction, the organic layer obtained by adding 1 L of ethyl acetate to the reaction mixture was washed with diluted hydrochloric acid once and with water three times in order, dried over magnesium sulfate, and then the solvent was removed under reduced pressure. The obtained dried product was recrystallized from ethanol to obtain 37 g of compound (1-41-1C).
(4) Synthesis of Compound (1-41-1) In a 1 L three-necked flask equipped with a reflux tube, a thermometer and a nitrogen introduction tube, 37 g of the compound (1-41-1C) synthesized above and tin chloride dihydrate 160 g of the product and 400 mL of ethyl acetate were added, and the reaction was performed under reflux for 4 hours. After completion of the reaction, the reaction mixture was washed successively with an aqueous potassium fluoride solution and water. The obtained organic layer was dried over magnesium sulfate, and then the solvent was removed under reduced pressure, and the solid obtained was recrystallized from ethanol to obtain 18 g of pale yellow crystals of the compound (1-41-1). .

Synthesis Examples 1-9, 1-10, and 1-11
Compounds (1-29-1), (1-29-2) and (1-30-1) were converted into the following scheme 8

Was synthesized according to
Synthesis Example 1-9
(1) Synthesis of Compound (1-29-1B) 30 g of Compound (1-4-1A) obtained in the same manner as in Synthesis Example 1-1 above was added to a 200 mL eggplant flask equipped with a reflux tube and a nitrogen introduction tube. Then, 40 mL of thionyl chloride and 0.1 mL of N, N-dimethylformamide were added, and the reaction was performed under reflux for 1 hour. After completion of the reaction, the reaction mixture was reduced in pressure to remove low boiling substances to obtain a white powder. This white powder was dissolved in 100 mL of tetrahydrofuran, and this was designated as solution A.
On the other hand, 73 mL of 1,3-propanediol, 100 mL of tetrahydrofuran and 21 mL of triethylamine were charged into a 500 mL three-necked flask equipped with a dropping funnel, a nitrogen introduction tube and a thermometer, and this was ice-cooled. Subsequently, the above solution A was added dropwise over 2 hours using a dropping funnel, and then returned to room temperature and reacted for another 2 hours. After completion of the reaction, the organic layer obtained by adding 600 mL of ethyl acetate to the reaction mixture was subjected to liquid separation washing once with dilute hydrochloric acid and three times with water, then dried over magnesium sulfate, and the solvent was removed under reduced pressure. As a result, 34 g of a white solid of the compound (1-29-1B) was obtained.

(2) Synthesis of compound (1-29-1C) In a 500 mL three-necked flask equipped with a thermometer and a nitrogen introduction tube, 27 g of the above compound (1-29-1B), 15 g of 2,4-dinitrofluorobenzene, tetrahydrofuran 100 mL and 21 mL of triethylamine were charged and reacted at 40 ° C. for 9 hours. After completion of the reaction, the organic layer obtained by adding 300 mL of ethyl acetate to the reaction mixture was subjected to liquid separation washing once with dilute hydrochloric acid and three times with water, and then obtained by removing the solvent under reduced pressure. The solid was washed with ethanol to obtain 33 g of a white powder of the compound (1-29-1C).
(3) Synthesis of compound (1-29-1) In a 1 L three-necked flask equipped with a thermometer and a nitrogen introduction tube, 32 g of the compound (1-29-1C), 76 g of zinc powder, 12.4 g of ammonium chloride, ethanol After 200 mL of tetrahydrofuran and 200 mL of tetrahydrofuran were charged, 35 mL of water was slowly added thereto over 1 hour, and the reaction was allowed to proceed at room temperature for 5 hours. After completion of the reaction, the organic layer obtained by adding 750 mL of ethyl acetate to the filtrate obtained by filtering the reaction mixture was separated and washed three times with water, and then ethanol was added to obtain a mixed solution. The mixed solution was concentrated under reduced pressure, and the precipitated white crystals were collected and washed with ethanol to obtain 25 g of white crystals of the compound (1-29-1).

Synthesis Example 1-10
(1) Synthesis of Compound (1-29-2B) In the synthesis example 1-1 (1), 337 g of 4- (4-heptylcyclohexyl) bromobenzene was used instead of 4- (4-pentylcyclohexyl) bromobenzene. 163 g of compound (1-4-3A) was obtained in the same manner as in Synthesis Example 1-1 (1) except that it was used.
Furthermore, in (1) of Synthesis Example 1-9, by using 29 g of the compound (1-3-3A) obtained above instead of the compound (1-4-1A), the compound (1-29-2B) ) Was obtained.
(2) Synthesis of Compound (1-29-2C) In Synthesis Example 1-9 (2), 29 g of Compound (1-29-2B) obtained above was used instead of Compound (1-29-1B). By using, 36g of compounds (1-29-2C) were obtained.
(3) Synthesis of Compound (1-29-2) In the above Synthesis Example 1-9 (3), 32 g of the compound (1-29-2C) obtained above was used instead of the compound (1-29-1C). By using, 26g of compounds (1-29-2) were obtained.

Synthesis Example 1-11
(1) Synthesis of Compound (1-30-1B) In Synthesis Example 1-9 (1), by using 38 g of Compound (1-10-1A) instead of Compound (1-4-1A), 42 g of compound (1-30-1B) was obtained.
(2) Synthesis of Compound (1-30-1C) In Synthetic Example 1-9 (2), 33 g of Compound (1-30-1B) obtained above was used instead of Compound (1-29-1B). By using 39 g of compound (1-30-1C) was obtained.
(3) Synthesis of Compound (1-30-1) In Synthetic Example 1-9 (3), 37 g of Compound (1-30-1C) obtained above was used instead of Compound (1-29-1C). By using 28g of compound (1-30-1) was obtained.

Comparative Synthesis Example 1
Compound (R-1) is converted into the following scheme R1.

Was synthesized according to
(1) Synthesis of Compound (R-1A) A 1 L eggplant-shaped flask was charged with 91.3 g of methyl 4-hydroxybenzoate, 182.4 g of potassium carbonate and 320 mL of N-methyl-2-pyrrolidone and stirred at room temperature for 1 hour. Then, 99.7 g of 1-bromopentane was added and the reaction was carried out at 100 ° C. with stirring for 5 hours. After completion of the reaction, water was added to the reaction mixture for reprecipitation. This precipitate was collected, and 48 g of sodium hydroxide and 400 mL of water were added and refluxed for 3 hours to conduct a hydrolysis reaction. After completion of the reaction, the reaction mixture was neutralized by adding hydrochloric acid, and the resulting precipitate was recovered and recrystallized from ethanol to obtain 102 g of white crystals of the compound (R-1A).
(2) Synthesis of Compound (R-1B) 52 g of the compound (R-1A) synthesized above was placed in a reaction vessel, and 100 mL of thionyl chloride and 0.2 mL of N, N-dimethylformamide were added thereto at 80 ° C. The reaction was conducted with stirring for 1 hour. Next, after removing unreacted thionyl chloride from the reaction mixture under reduced pressure, methylene chloride was added, and the organic layer obtained was washed with a saturated aqueous sodium hydrogen carbonate solution, dried over magnesium sulfate, concentrated, and further tetrahydrofuran. To make a solution.
Next, 37 g of 4-hydroxycinnamic acid, 69 g of potassium carbonate, 2.4 g of tetrabutylammonium, 250 mL of tetrahydrofuran and 500 mL of water were charged into a 2 L three-necked flask different from the above. While the aqueous solution was ice-cooled, the above tetrahydrofuran solution was slowly added dropwise thereto, and the reaction was further performed with stirring for 2 hours. After completion of the reaction, the reaction mixture was neutralized by adding hydrochloric acid, extracted with ethyl acetate, the organic layer obtained was dried over magnesium sulfate, the solvent was removed under reduced pressure, and the solid obtained was recrystallized from ethanol. As a result, 45 g of white crystals of the compound (R-1B) were obtained.
(3) Synthesis of Compound (R-1C) In a 500 mL three-necked flask equipped with a stirrer, a thermometer and a nitrogen introduction tube, 35 g of Compound (R-1C) synthesized above, 22 g of 3,5-dinitrobenzyl chloride, 42 g of potassium carbonate, 30 g of sodium iodide and 150 mL of N, N-dimethylformamide were charged, and the reaction was performed at 60 ° C. for 8 hours. After completion of the reaction, 300 mL of chloroform was added to the reaction mixture, and the resulting organic layer was washed three times with water and then dried over magnesium sulfate. The organic layer was concentrated and the precipitated solid was collected and washed with ethanol to obtain 45 g of a pale yellow powder of the compound (R-1C).
(4) Synthesis of Compound (R-1) In a 1 L three-necked flask equipped with a stirrer, a thermometer and a nitrogen introduction tube, 45 g of Compound (R-1C) synthesized above, 192 g of tin chloride dihydrate and acetic acid 400 mL of ethyl was charged, and the reaction was performed under reflux for 4 hours. After completion of the reaction, the reaction mixture was washed successively with an aqueous potassium fluoride solution and water. After drying the organic layer with magnesium sulfate, the solid obtained by removing the solvent under reduced pressure was recrystallized from ethanol to obtain 22 g of pale yellow crystals of the compound (R-1).

Comparative Synthesis Example 2 (Synthesis of Compound (R-2))
Compound (R-2) is converted into the following scheme R2

Was synthesized according to
To a 300 mL eggplant flask equipped with a reflux tube and a nitrogen introduction tube, 30 g of compound (1-4-1A), 100 mL of thionyl chloride and 0.1 mL of N, N-dimethylformamide were added and reacted at 80 ° C. for 1 hour. . After completion of the reaction, unreacted thionyl chloride was distilled off from the reaction mixture under reduced pressure, and then 150 mL of methylene chloride was added to wash the organic layer with water three times. After drying this organic layer with magnesium sulfate, the solvent was removed under reduced pressure to dryness once, and then 200 mL of tetrahydrofuran was added to contain the reaction product of compound (1-4-1A) and thionyl chloride. A solution was obtained.
Next, 13 g of hydroxyethyl methacrylate, 11 g of triethylamine and 50 mL of tetrahydrofuran were added to a 500 mL three-necked flask different from the above, and the mixture was ice-cooled to 5 ° C. or lower. Next, a solution containing a reaction product of the compound (1-4-1A) and thionyl chloride was slowly added dropwise while keeping the temperature at 5 ° C. or lower, and the reaction was performed at room temperature for 1 hour. After completion of the reaction, the organic layer obtained by adding ethyl acetate to the reaction mixture was washed successively with 1M aqueous hydrochloric acid and water, dried over magnesium sulfate, the solvent was removed under reduced pressure, and then ethyl acetate and cyclohexane were used. 40 g of compound (R-2) was obtained as a transparent viscous liquid by purifying with a silica column using the mixed solvent as a developing medium and further removing the solvent from the corresponding fraction under reduced pressure.

<Synthesis of specific polymer>
[Synthesis of polyamic acid]
Synthesis example CPA-1
As a tetracarboxylic acid anhydride, 7.0 g of 2,3,5-tricarboxycyclopentylacetic acid dianhydride (TCA) and 13 g of the compound (1-4-1) synthesized in Synthesis Example 1-1 (based on 1 mol of TCA) Is dissolved in 80 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 4 hours to obtain a solution containing 20% by weight of polyamic acid (CPA-1). . The solution viscosity of this polyamic acid solution was 2,000 mPa · s.
Synthesis example CPA-2
As a tetracarboxylic acid anhydride, 6.9 g of 2,3,5-tricarboxycyclopentylacetic acid dianhydride (TCA) and 13.1 g of the compound (1-6-1) synthesized in Synthesis Example 1-6 (in 1 mol of TCA) Is dissolved in 80 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 4 hours to obtain a solution containing 20% by weight of polyamic acid (CPA-2). Obtained. The solution viscosity of this polyamic acid solution was 1,800 mPa · s.

Synthesis Example CPA-3
As tetracarboxylic acid anhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride (TCA) 6.2 g and 13.8 g of compound (1-10-1) synthesized in Synthesis Example 1-3 above (in 1 mol of TCA) Is dissolved in 80 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 4 hours to obtain a solution containing 20% by weight of polyamic acid (CPA-3). Obtained. The solution viscosity of this polyamic acid solution was 2,100 mPa · s.
Synthesis example CPA-4
As a tetracarboxylic anhydride, 5.9 g of 2,3,5-tricarboxycyclopentylacetic acid dianhydride (TCA) and 14.1 g of the compound (1-16-1) synthesized in Synthesis Example 1-4 above (to 1 mol of TCA) Is dissolved in 80 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 4 hours to obtain a solution containing 20% by weight of polyamic acid (CPA-4). Obtained. The solution viscosity of this polyamic acid solution was 2,200 mPa · s.

Synthesis Example CPA-5
As tetracarboxylic anhydride, 6.1 g of 2,3,5-tricarboxycyclopentylacetic acid dianhydride (TCA) and 13.9 g of compound (1-16-2) synthesized in Synthesis Example 1-5 (in 1 mol of TCA) Is dissolved in 80 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 4 hours to obtain a solution containing 20% by weight of polyamic acid (CPA-5). Obtained. The solution viscosity of this polyamic acid solution was 2,200 mPa · s.
Synthesis Example CPA-6
As a tetracarboxylic anhydride, 6.4 g of 2,3,5-tricarboxycyclopentylacetic acid dianhydride (TCA) and 13.6 g of the compound (1-22-1) synthesized in Synthesis Example 1-2 above (to 1 mol of TCA) Is dissolved in 80 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 4 hours to obtain a solution containing 20% by weight of polyamic acid (CPA-6). Obtained. The solution viscosity of this polyamic acid solution was 2,100 mPa · s.

Synthesis example CPA-7
As a tetracarboxylic acid anhydride, 6.8 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride (TCA), 12.4 g of the compound (1-6-1) synthesized in Synthesis Example 1-6 (in 1 mol of TCA) And 0.8 g of the compound represented by the above formula (D-10) is dissolved in 80 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 4 hours. A solution containing 20% by weight of polyamic acid (CPA-7) was obtained. The solution viscosity of this polyamic acid solution was 1,900 mPa · s.
Synthesis Example CPA-8
As a tetracarboxylic anhydride, 6.4 g of 2,3,5-tricarboxycyclopentylacetic acid dianhydride (TCA) and 13.6 g of the compound (1-6-2) synthesized in Synthesis Example 1-7 (to 1 mol of TCA) Is dissolved in 80 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 4 hours to obtain a solution containing 20% by weight of polyamic acid (CPA-8). Obtained. The solution viscosity of this polyamic acid solution was 1,700 mPa · s.

Synthesis Example CPA-9
As a tetracarboxylic anhydride, 6.5 g of 2,3,5-tricarboxycyclopentylacetic acid dianhydride (TCA) and 13.5 g of the compound (1-41-1) synthesized in Synthesis Example 1-8 (into 1 mol of TCA) Is dissolved in 80 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 4 hours to obtain a solution containing 20% by weight of polyamic acid (CPA-9). Obtained. The solution viscosity of this polyamic acid solution was 2,300 mPa · s.
Synthesis Example CPA-10
6.5 g of 2,3,5-tricarboxycyclopentylacetic acid dianhydride (TCA) as tetracarboxylic anhydride and 14 g of compound (1-29-1) synthesized in Synthesis Example 1-9 (based on 1 mol of TCA) Is dissolved in 80 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 4 hours to obtain a solution containing 20% by weight of polyamic acid (CPA-10). . The solution viscosity of this polyamic acid solution was 2,200 mPa · s.

Synthesis Example CPA-11
6.3 g of 2,3,5-tricarboxycyclopentylacetic acid dianhydride (TCA) as tetracarboxylic anhydride and 14 g of compound (1-29-2) synthesized in Synthesis Example 1-10 (based on 1 mol of TCA) Is dissolved in 80 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 4 hours to obtain a solution containing 20% by weight of polyamic acid (CPA-11). . The solution viscosity of this polyamic acid solution was 2,100 mPa · s.
Synthesis Example CPA-12
As a tetracarboxylic anhydride, 5.8 g of 2,3,5-tricarboxycyclopentylacetic acid dianhydride (TCA) and 14 g of the compound (1-30-1) synthesized in Synthesis Example 1-11 (based on 1 mol of TCA) Is dissolved in 80 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 4 hours to obtain a solution containing 20% by weight of polyamic acid (CPA-12). . The solution viscosity of this polyamic acid solution was 2,000 mPa · s.

[Synthesis of polyimide]
Synthesis Example CPI-1
2.4 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride (TCA) as a tetracarboxylic acid anhydride and 4.6 g of the compound (1-4-1) synthesized in Synthesis Example 1-1 (in 1 mol of TCA) Is dissolved in 28 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 4 hours to obtain a solution containing 20% by weight of polyamic acid. The solution viscosity of this polyamic acid solution was 2,000 mPa · s.
Next, 65 g of N-methyl-2-pyrrolidone, 0.9 g of pyridine and 1.0 g of acetic anhydride were added to the polyamic acid solution, and a dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with new N-methyl-2-pyrrolidone (by this solvent replacement operation, pyridine and acetic anhydride used in the dehydration ring closure reaction were removed from the system). About 45 g of a solution containing 15% by weight of polyimide (CPI-1) having an imidation ratio of about 47% was obtained.
A small amount of this polyimide solution was collected, the solvent was removed under reduced pressure, and the solution viscosity measured at 25 ° C. was 24 mPa · s for a solution having a polymer concentration of 8.0 wt% dissolved in γ-butyrolactone.

<Synthesis of other polymers>
[Synthesis of other polyamic acids]
Synthesis example PA-1
Pyromellitic dianhydride 109 g (0.50 mol) and 1,2,3,4-cyclobutanetetracarboxylic dianhydride 98 g (0.50 mol) as tetracarboxylic dianhydride and 4,4- as diamine By dissolving 200 g (1.0 mol) of diaminodiphenyl ether in 2,290 g of N-methyl-2-pyrrolidone and reacting at 40 ° C. for 3 hours, 1,350 g of N-methyl-2-pyrrolidone was added. About 3,590 g of a solution containing 10% by weight of polyamic acid (PA-1) was obtained. The solution viscosity of this polyamic acid solution was 210 mPa · s.
Synthesis example PA-2
1,2,3,4-cyclobutanetetracarboxylic dianhydride 98 g (0.50 mol) and pyromellitic dianhydride 109 g (0.50 mol) as tetracarboxylic dianhydride and 4,4 ′ as diamine -Dissolve 198 g (1.0 mol) of diaminodiphenylmethane in 2,290 g of N-methyl-2-pyrrolidone, react at 40 ° C. for 3 hours, and then add 1,350 g of N-methyl-2-pyrrolidone. Thus, a solution containing 10% by weight of polyamic acid (PA-2) was obtained. The solution viscosity of this polyamic acid solution was 135 mPa · s.

Synthesis example PA-3
196 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 200 g (1.0 mol) of 4,4′-diaminodiphenyl ether as diamine were added to N-methyl. After dissolving in 2,246 g of 2-pyrrolidone and reacting at 40 ° C. for 4 hours, by adding 1,321 g of N-methyl-2-pyrrolidone, 10% by weight of polyamic acid (PA-3) is contained. A solution was obtained. The solution viscosity of this polyamic acid solution was 220 mPa · s.
Synthesis example PA-4
196 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 212 g (1, .2) of 2,2′-dimethyl-4,4′-diaminobiphenyl as diamine. 0 mol) was dissolved in 3,670 g of N-methyl-2-pyrrolidone and reacted at 40 ° C. for 3 hours to obtain a solution containing 10% by weight of polyamic acid (PA-4). The solution viscosity of this polyamic acid solution was 170 mPa · s.

Synthesis example PA-5
224 g (1.0 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride and 200 g (1.0 mol) of 4,4′-diaminodiphenyl ether as diamine were added to N-methyl-2 -A solution containing polyamic acid (PA-5) was obtained by dissolving in 2,404 g of pyrrolidone and reacting at 40 ° C for 4 hours. A small amount of this polyamic acid solution was taken and N-methyl-2-pyrrolidone was added to measure the solution viscosity as a solution having a concentration of 10% by weight. The solution viscosity was 190 mPa · s.
Synthesis example PA-6
6.5 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride (TCA) as tetracarboxylic anhydride and 13.5 g of compound (R-1) synthesized in Comparative Synthesis Example 1 (1 per 1 mol of TCA) Was dissolved in 80 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 4 hours to obtain a solution containing 20% by weight of polyamic acid (PA-6). The solution viscosity of this polyamic acid solution was 2,000 mPa · s.

[Synthesis of polymethacrylate]
Synthesis example PMA-1
Into a four-necked flask equipped with a stirrer, a three-way cock and a thermometer, 10 g of the compound (R-2) obtained in Comparative Synthesis Example 2 as a monomer was charged, 20 g of diethylene glycol ethyl methyl ether as a solvent, and a polymerization initiator. 0.5 g of 2,2′-azobis (2,4-dimethylvaleronitrile) and 0.2 g of α-methylstyrene dimer as a molecular weight modifier were added. A solution containing 32% by weight of the polymer (PMA-1) was obtained by bubbling this with a nitrogen stream for about 10 minutes to perform nitrogen substitution in the system and then reacting at 70 ° C. for 5 hours in a nitrogen atmosphere. Got. For the polymer (PMA-1), the polystyrene equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) were measured by gel permeation chromatography (GPC) under the following conditions, and the molecular weight distribution (Mw / Mn) was determined. As a result, Mw = 24,000 and Mw / Mn = 2.4, and no peak attributable to the residual monomer was observed.
GPC measuring device: “HLC-8020” manufactured by Tosoh Corporation
Column: Columns TSK guardcolumn α, TSK gel α-M and TSK gel α-2500 manufactured by Tosoh Corporation are used in series. Solvent: 9.4 g of lithium bromide monohydrate with respect to 3 L of dimethylformamide Solution in which 1.7 g of phosphoric acid is dissolved Measurement temperature: 35 ° C.
Standard material: monodisperse polystyrene

<Preparation and evaluation of liquid crystal aligning agent>
Example 1
[Preparation of liquid crystal aligning agent]
(1) Preparation of liquid crystal alignment agent for evaluation of printability Obtained in Synthesis Example PA-1 as a solution containing the polyamic acid (CPA-1) obtained in Synthesis Example CPA-1 as a specific polymer and other polymers The solution containing polyamic acid (PA-1) was mixed so that the ratio of the amount of the polymer contained in the solution was CPA-1: PA-1 = 20: 80 (weight ratio). -Methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) were added to obtain a solution having a solvent composition of NMP: BC = 50: 50 (weight ratio) and a solid content concentration of 7% by weight. A liquid crystal aligning agent (P-1) for printability evaluation was prepared by filtering this solution using a filter having a pore size of 1 μm.
(2) Preparation of Liquid Crystal Alignment Agent for Manufacturing Liquid Crystal Display Element The preparation of the liquid crystal alignment agent for evaluation of printability is the same as the preparation of liquid crystal alignment agent for evaluation of printability except that the solid content concentration is 4% by weight. The liquid crystal aligning agent (A-1) for manufacturing a liquid crystal display element was prepared.
[Evaluation of liquid crystal aligning agent]
Using the two types of liquid crystal aligning agents prepared above, evaluation was performed as follows. The evaluation results are shown in Table 2.
I. Evaluation of printability The liquid crystal aligning agent for printability evaluation (P-1) prepared above is transparent on a glass substrate with a transparent electrode made of an ITO film using a liquid crystal alignment film printer (manufactured by Nippon Photographic Co., Ltd.) After coating on the electrode surface and heating (pre-baking) at 80 ° C. for 1 minute to remove the solvent, heating (post-baking) was performed at 200 ° C. for 60 minutes to form a coating film having a thickness of 60 nm. About this coating film, the presence or absence of a printing nonuniformity and a pinhole was investigated by visual observation and observation with the microscope of 2.5 time magnification. here,
If neither printing unevenness nor pinhole is observed in both visual observation and microscopic observation, the printability is “excellent”
Neither printing unevenness nor pinholes were observed by visual observation, but if at least one of printing unevenness and pinholes was observed by microscopic observation, the printability was “good”,
If at least one of printing unevenness and pinholes is observed by visual observation, the printability is “bad”.
As evaluated.

II. Manufacture and evaluation of liquid crystal display element (1) Manufacture of liquid crystal display element On the transparent electrode surface of the glass substrate with a transparent electrode made of ITO film, the liquid crystal aligning agent (A-1) for liquid crystal display element manufacture prepared above is spinner. And then prebaked for 1 minute on a hot plate at 80 ° C., and then heated at 200 ° C. for 1 hour in an oven in which the inside of the chamber was replaced with nitrogen to form a coating film having a thickness of 0.1 μm. Next, the surface of the coating film was irradiated with polarized ultraviolet rays 200 J / m ² containing a 313 nm emission line from a direction inclined by 40 ° from the normal to the liquid crystal alignment film using a Hg—Xe lamp and a Grand Taylor prism. The same operation was repeated to produce a pair (two) of substrates having a liquid crystal alignment film.
An epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm is applied to the outer periphery of the surface of the substrate having the liquid crystal alignment film by screen printing, and the liquid crystal alignment film surfaces of the pair of substrates are made to face each other. The adhesive was pressure-bonded so that the projection direction of the ultraviolet optical axis of each substrate onto the substrate surface was antiparallel, and the adhesive was thermally cured at 150 ° C. for 1 hour. Next, after filling the gap between the substrates from the liquid crystal injection port with negative type liquid crystal (MLC-6608, manufactured by Merck), the liquid crystal injection port was sealed with an epoxy adhesive. Furthermore, in order to remove the flow alignment at the time of liquid crystal injection, this was heated to 150 ° C. and then gradually cooled to room temperature.
Next, a polarizing plate is bonded to each outer side surface of both substrates so that the polarization directions thereof are orthogonal to each other and form an angle of 45 ° with the irradiation direction of the optical axis of the liquid crystal alignment film to the substrate surface. Thus, a liquid crystal display element was manufactured.

(2) Evaluation of liquid crystal display element (2-1) Evaluation of liquid crystal orientation In the liquid crystal display element manufactured as described above, abnormalities in changes in brightness when a voltage of 5 V is turned ON / OFF (applied / released) at room temperature. The presence or absence of the domain was observed with an optical microscope. When no abnormal domain was observed, the liquid crystal alignment (vertical alignment) was evaluated as “good”.
(2-2) Evaluation of pretilt angle Non-Patent Document 1 (TJ Scheffer et. Al. J. Appl. Phys., Vol. 48, p1789 (1977)) and non-patent documents show the liquid crystal display element manufactured above. In accordance with the method described in Patent Document 2 (F. Nakano et.al.JPN.J.Appl.Phys., Vol.19, p2013 (1980)), a pretilt angle is obtained by a crystal rotation method using a He—Ne laser beam. Was measured.
(2-3) Evaluation of voltage holding ratio For the liquid crystal display device manufactured above, a voltage of 5 V was applied at an environmental temperature of 60 ° C. for 60 microseconds with a span of 167 milliseconds, and then 167 from the release of application. The voltage holding ratio after milliseconds was measured. As a measuring device, model “VHR-1” manufactured by Toyo Corporation was used.
(2-4) Evaluation of high-temperature pretilt angle stability The liquid crystal display device produced above was stored at 70 ° C for 30 days, and then the pretilt angle was measured again in the same manner as in (2-2) above. For this measured value, the high temperature pretilt angle stability is “good” when the change from the initial value is less than 1 °, and the high temperature pretilt angle stability is “poor” when the change is 1 ° or more. It was evaluated as being.

Examples 2-16 and 18-21
In Example 1 above, the liquid crystal aligning agent for printability evaluation (in the same manner as in Example 1 except that the types and amounts of the specific polymer and other polymers are as shown in Table 1, respectively) (P-2) to (P-16) and (P-18) to (P-21) and liquid crystal aligning agents (A-2) to (A-16) and (A-18) to (A-18) A-21) was prepared and evaluated. In Example 13, only the specific polymer was used without using another polymer.
The evaluation results are shown in Table 2.

Example 17
In the above Example 1, after adding N-methyl-2-pyrrolidone and butyl cellosolve, the following formula (E-1) is further used as an epoxy compound:

A liquid crystal aligning agent for printability evaluation (P-17) and a liquid crystal aligning agent for manufacturing a liquid crystal display element (A-17) were prepared in the same manner as in Example 1 except that 20 parts by weight of the compound represented by formula (1) was added. And evaluated.
The evaluation results are shown in Table 2.

Comparative Example 1
In the above Example 1, a liquid crystal aligning agent for evaluating printability (RP) was used in the same manner as in Example 1 except that the specific polymer was not used and two types of other polymers were used as shown in Table 1. -1) and a liquid crystal aligning agent (RA-1) for manufacturing a liquid crystal display element were prepared and evaluated.
The evaluation results are shown in Table 2.
Comparative Example 2
N-methyl-1-pyrrolidone (NMP) and butyl cellosolve are added to the solution containing polymethacrylate (PMA-1) obtained in the above comparative synthesis example PMA-1, and the solvent composition is NMP / butyl cellosolve / γ-butyrolactone. / Diethylene glycol ethyl methyl ether = 23/50/25/2 (weight ratio), liquid crystal aligning agent for printability evaluation (RP-2) having a solid content concentration of 7.0% by weight, and a solid content concentration of 3.5% A liquid crystal aligning agent (RA-2) for producing a liquid crystal display element was prepared and evaluated. The evaluation results are shown in Table 2.

Claims (6)

At least one polymer selected from the group consisting of polyamic acid and polyimide, provided that at least a part of the polymer has the following formula (0)

(In Formula (0), R ^I is an alkyl group having 3 to 12 carbon atoms or a fluoroalkyl group having 3 to 12 carbon atoms, X ^I is a single bond or an oxygen atom, and R ^II is 1,4-cyclohexane. It is a silene group or a 1,4-phenylene group, X ^II is a single bond, an oxygen atom or ^* —COO— (where a bond marked with “*” is bonded to R ^II ), and n is 0 Or X ^III is represented by the following formula (X ^III -1) or (X ^III -2)

It is group represented by these. )
The liquid crystal aligning agent characterized by containing the group represented by these. The polymer is tetracarboxylic dianhydride and the following formula (1)

(In the formula (1), R ^I , X ^I , R ^II , X ^II , X ^III and n are as defined in the above formula (0), and R ^III is a single bond, a methylene group or a carbon number. is 1-6 alkylene group, provided that the alkylene group may be substituted by a hydroxyl group, X ^IV is a single bond, an oxygen atom or ^* -OCO- (provided that a bond marked with "*" R ^III )), but when R ^III is a single bond, X ^IV is a single bond.)
The liquid crystal aligning agent of Claim 1 which is at least 1 sort (s) selected from the group which consists of the polyamic acid obtained by making it react with the diamine containing the compound represented by this, and the polyamic acid which spin-dry | dehydrates and cyclizes this polyamic acid. .   A liquid crystal display element comprising a liquid crystal alignment film formed from the liquid crystal aligning agent according to claim 1.   A polyamic acid obtained by reacting tetracarboxylic dianhydride with a diamine containing a compound represented by the above formula (1).   A polyimide obtained by dehydrating and ring-closing a polyamic acid obtained by reacting a tetracarboxylic dianhydride and a diamine containing a compound represented by the above formula (1).   A compound represented by the above formula (1).