JP5105092B2 - Liquid crystal alignment film, method for forming the same, and liquid crystal display element - Google Patents

Description

The present invention relates to a method of forming the same and a liquid crystal display element and the liquid crystal alignment film. More specifically, a liquid crystal alignment film produced using a liquid crystal aligning agent capable of imparting a suitable liquid crystal alignment ability by irradiation with polarized or non-polarized radiation without rubbing, a method for forming the same, and a liquid crystal display element About.

Conventionally, a nematic liquid crystal having positive dielectric anisotropy is sandwiched with a substrate with a transparent electrode having a liquid crystal alignment film, and the major axis of the liquid crystal molecules is continuously twisted between 0 and 360 ° between the substrates as necessary. Liquid crystal display elements having liquid crystal cells such as TN (twisted nematic), STN (super twisted nematic), and IPS (in-plane switching) are known (see Patent Documents 1 and 2). .
In such a liquid crystal cell, it is necessary to provide a liquid crystal alignment film on the substrate surface in order to align liquid crystal molecules in a predetermined direction with respect to the substrate surface. This liquid crystal alignment film is usually formed by a method (rubbing method) in which the organic film surface formed on the substrate surface is rubbed in one direction with a cloth material such as rayon. However, when the liquid crystal alignment film is formed by a rubbing process, dust and static electricity are likely to be generated in the process, so that there is a problem that dust adheres to the alignment film surface and causes display defects. In particular, in the case of a substrate having a TFT (Thin Film Transistor) element, there has been a problem that the circuit damage of the TFT element occurs due to the generated static electricity, resulting in a decrease in yield. Furthermore, in liquid crystal display elements that will be further refined in the future, unevenness is generated on the substrate surface as the density of pixels increases, and it is becoming difficult to perform rubbing treatment uniformly.
As another means of aligning liquid crystals in a liquid crystal cell, light that imparts liquid crystal alignment ability by irradiating a photosensitive thin film such as polyvinyl cinnamate, polyimide, or azobenzene derivative formed on the substrate surface with polarized or non-polarized radiation. Orientation methods are known. According to this method, uniform liquid crystal alignment can be realized without generating static electricity or dust (see Patent Documents 3 to 13).
By the way, in a liquid crystal cell of TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, etc., the liquid crystal alignment film needs to have a pretilt angle characteristic in which liquid crystal molecules are inclined and aligned at a predetermined angle with respect to the substrate surface. There is. In the case of forming a liquid crystal alignment film by a photo-alignment method, the pretilt angle characteristic is usually imparted by irradiation with radiation whose incident direction to the substrate surface is inclined from the substrate normal.

On the other hand, a vertical (homeotropic) alignment mode in which liquid crystal molecules having negative dielectric anisotropy are aligned perpendicularly to a substrate is also known as an operation mode of a liquid crystal display element different from the above. 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 must be tilted from the substrate normal direction to one direction in the substrate surface. There is. 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 method of tilting (pretilting) has been proposed.
The photo-alignment method is known to be useful as a method for controlling the tilt direction of liquid crystal molecules in a vertical alignment mode liquid crystal cell. That is, it is known that the tilt direction of liquid crystal molecules at the time of voltage application can be uniformly controlled by using a vertical alignment film imparted with alignment regulating ability and pretilt angle expression by a photo-alignment method (Patent Documents 11 to 14). reference).
Thus, the liquid crystal alignment film manufactured by the photo-alignment method can be effectively applied to various liquid crystal display elements. However, the conventional photo-alignment film has a problem that it is difficult to develop an appropriate pretilt angle imparting property.
JP 56-91277 A JP-A-1-120528 JP-A-6-287453 JP-A-10-251646 Japanese Patent Laid-Open No. 11-2815 JP-A-11-152475 JP 2000-144136 A JP 2000-319510 A JP 2000-281724 A JP-A-9-297313 JP 2003-307736 A JP 2004-163646 A Japanese Patent Laid-Open No. 9-21468 JP 2003-114437 A JP-A-9-278724 JP 2007-300250 A JP 2008-250302 A T.A. J. et al. Scheffer et. al. J. et al. Appl. Phys. vo. 19, p2013 (1980)

An object of the present invention is to provide a method for forming a liquid crystal alignment film using a liquid crystal aligning agent capable of imparting suitable liquid crystal alignment ability and pretilt angle expression by irradiation with polarized or non-polarized radiation without rubbing treatment Another object of the present invention is to provide a liquid crystal alignment film exhibiting suitable liquid crystal alignment properties and pretilt angle development properties, and a liquid crystal display device excellent in display characteristics.
Still other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the above objects and advantages of the present invention are as follows.
A method for forming a liquid crystal alignment film, wherein a liquid crystal aligning agent is applied on a substrate to form a coating film, and the coating film is irradiated with radiation.
Tetracarboxylic dianhydride;
Following formula (1)

(In formula (1), Z ¹ represents the following formulas (Z ¹ -1) to (Z ¹ -3).

(In the formulas (Z ¹ -1) and (Z ¹ -2), R is a hydrogen atom or a methyl group, respectively, and a bond marked with “*” is bonded to a benzene ring.)
Z ² is a single bond or a methylene group, and when Z ² is a single bond, Z ³ is an alkyl group having 6 to 30 carbon atoms or 6 to 30 carbon atoms. And when Z ² is a methylene group, Z ³ is an alkoxyl group having 6 to 30 carbon atoms. )
The method comprising at least one polymer selected from the group consisting of a polyamic acid obtained by reacting a diamine containing a compound represented by the formula (I) and an imidized polymer thereof, wherein the formula (1) represents it is when the compound is 1- (3,5-aminophenyl) -3-octadecyl succinimide that is, the diamine except when including the diaminobenzoic acid 4- (2-ethoxycarbonyl-vinyl) phenyl ester, and the formula When the compound represented by (1) is 1- (3,5-diaminophenyl) -3-decylsuccinimide, the liquid crystal aligning agent is
Contains an imidized polymer of polyamic acid obtained by reacting 1,2,3,4-cyclobutanetetracarboxylic dianhydride, phenylenediamine and 4- (2-ethoxycarbonylvinyl) phenyl ester of diaminobenzoic acid And an imidized polymer of polyamic acid obtained by reacting 1,2,3,4-cyclobutanetetracarboxylic dianhydride with 4- (2-ethoxycarbonylvinyl) phenyl ester of diaminobenzoic acid Except the case,
Achieved by:
The above objects and advantages of the present invention are achieved secondly by the liquid crystal alignment film formed by the above method, and thirdly by a liquid crystal display element having the liquid crystal alignment film.

According to the method of the present invention, by irradiating polarized or non-polarized radiation without rubbing treatment, it has suitable liquid crystal alignment ability and pretilt angle expression in a manufacturing process that does not generate static electricity or dust. A liquid crystal alignment film can be formed. The liquid crystal display element of the present invention comprising this liquid crystal alignment film has excellent display characteristics and can be effectively applied to various devices. The liquid crystal display element of the present invention is suitably used for devices such as a desk calculator, wristwatch, table clock, counting display board, word processor, personal computer, or liquid crystal television.

The liquid crystal aligning agent used in the method of the present invention comprises a polyamic acid obtained by reacting a tetracarboxylic dianhydride with a diamine containing a compound represented by the above formula (1) and an imidized polymer thereof. Contains at least one selected from the group.
<Polyamic acid>
The polyamic acid used in the present invention can be synthesized by reacting a tetracarboxylic dianhydride with a diamine containing a compound represented by the above formula (1).
[Tetracarboxylic dianhydride]
Examples of the tetracarboxylic dianhydride used for synthesizing the polyamic acid used in the present invention 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 Tricarboxycyclopentylacetic 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-c] -furan-1,3-dione, 5- ( , 5-dioxotetrahydrofuranyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetra Carboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5 -Dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6- Dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, the following formulas (TI) and (T-II)

(Wherein R ¹ and R ³ each represents a divalent organic group having an aromatic ring, R ² and R ⁴ each represent a hydrogen atom or an alkyl group, and a plurality of R ² and R ^{4 are present.} 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. In addition, the benzene ring of the aromatic tetracarboxylic dianhydride may be substituted with one or two or more alkyl groups having 1 to 4 carbon atoms (preferably a methyl group). These may be used alone or in combination of two or more.
As tetracarboxylic dianhydride used for synthesizing the polyamic acid used in the present invention, among the above, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride 1,3-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 3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, Bicyclo [2.2.2] -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-carboxymethylnorbornane-2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane- 3,5,8,10-tetraone, pyromellitic acid Water, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride, 2,2 ′, 3,3′- Among the compounds represented by biphenyltetracarboxylic 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)

A liquid crystal alignment film formed by using a tetracarboxylic dianhydride containing at least one selected from the group consisting of compounds represented by the following (hereinafter referred to as “specific tetracarboxylic dianhydride”): It is preferable from the viewpoint of exhibiting good liquid crystal orientation. Specific tetracarboxylic dianhydrides include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2, 3,5-tricarboxycyclopentyl acetic 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- Ranyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-dianhydride, 4,9 -Dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, pyromellitic dianhydride and a compound represented by the above formula (T-5) More preferably, at least one selected from the group is selected from 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride At least one selected from the group is particularly preferred because it requires less radiation for forming the liquid crystal alignment film.
The tetracarboxylic dianhydride used for synthesizing the polyamic acid used in the present invention is 10 moles of the specific tetracarboxylic dianhydride as described above with respect to the total amount of tetracarboxylic dianhydride used. %, Preferably 20 mol% or more, more preferably 50 mol% or more.

[Diamine]
The diamine used for synthesizing the polyamic acid used in the present invention includes the compound represented by the above formula (1).
The alkyl group having 6 to 30 carbon atoms of Z ³ in the above formula (1) is preferably an alkyl group having 10 to 20 carbon atoms, and specifically, for example, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, a heptadecyl group. , Octadecyl group, icosyl group, etc .;
The alkoxy group having 6 to 30 carbon atoms of Z ³ is preferably an alkoxy group having 10 to 20 carbon atoms, specifically, for example, a decyloxy group, a dodecyloxy group, a tetradecyloxy group, a hexadecyloxy group, or a heptadecyloxy group. Group, octadecyloxy group, icosyloxy group and the like.
Specific examples of the compound represented by the above formula (1) include those in which Z ¹ is a divalent group represented by the above formula (Z ¹ -1), such as 1- (3,5-diaminophenyl). ) -3-dodecylsuccinimide, 1- (3,5-diaminophenyl) -3-hexadecylsuccinimide, 1- (3,5-diaminophenyl) -3-heptadecylsuccinimide, 1- (3,5-diaminophenyl) ) -3-octadecylsuccinimide, 1- (3,5-diaminophenyl) -3-dodecyloxysuccinimide, 1- (3,5-diaminophenyl) -3-hexadecyloxysuccinimide, 1- (3,5-diamino) Phenyl) -3-heptadecyloxysuccinimide, 1- (3,5-diaminophenyl) -3-octadecyloxysuccinimide, 1- (3 5-Diaminophenyl) -3-dodecyl-4-methylsuccinimide, 1- (3,5-diaminophenyl) -3-hexadecyl-4-methylsuccinimide, 1- (3,5-diaminophenyl) -3-heptadecyl- 4-methylsuccinimide, 1- (3,5-diaminophenyl) -3-octadecyl-4-methylsuccinimide, 1- (3,5-diaminophenyl) -3-dodecyloxy-4-methylsuccinimide, 1- (3 , 5-Diaminophenyl) -3-hexadecyloxy-4-methylsuccinimide, 1- (3,5-diaminophenyl) -3-heptadecyloxy-4-methylsuccinimide, 1- (3,5-diaminophenyl) -3-octadecyloxy-4-methylsuccinimide and the like;

As Z ¹ being a divalent group represented by the above formula (Z ¹ -2), for example, 1- (3,5-diaminophenyl) -3-dodecylmaleimide, 1- (3,5-diaminophenyl) ) -3-hexadecylmaleimide, 1- (3,5-diaminophenyl) -3-heptadecylmaleimide, 1- (3,5-diaminophenyl) -3-octadecylmaleimide, 1- (3,5-diaminophenyl) ) -3-dodecyloxymethylmaleimide, 1- (3,5-diaminophenyl) -3-hexadecyloxymethylmaleimide, 1- (3,5-diaminophenyl) -3-heptadecyloxymethylmaleimide, 1- ( 3,5-diaminophenyl) -3-octadecyloxymethylmaleimide, 1- (3,5-diaminophenyl) -3-dodecyl-4-methylmale 1- (3,5-diaminophenyl) -3-hexadecyl-4-methylmaleimide, 1- (3,5-diaminophenyl) -3-heptadecyl-4-methylmaleimide, 1- (3,5-diamino Phenyl) -3-octadecyl-4-methylmaleimide, 1- (3,5-diaminophenyl) -3-dodecyloxymethyl-4-methylmaleimide, 1- (3,5-diaminophenyl) -3-hexadecyloxy Methyl-4-methylmaleimide, 1- (3,5-diaminophenyl) -3-heptadecyloxymethyl-4-methylmaleimide, 1- (3,5-diaminophenyl) -3-octadecyloxymethyl-4-methyl Maleimide, etc .;
Z ¹ is a divalent group represented by the above formula (Z ¹ -3). For example, 1- (3,5-diaminophenyl) -4-dodecyloxyglutarimide, 1- (3,5- Diaminophenyl) -4-hexadecyloxyglutarimide, 1- (3,5-diaminophenyl) -4-heptadecyloxyglutarimide, 1- (3,5-diaminophenyl) -4-octadecyloxyglutarimide, etc. , Can be mentioned respectively.

  Of these, 1- (3,5-diaminophenyl) -3-dodecylsuccinimide, 1- (3,5-diaminophenyl) -3-hexadecylsuccinimide, 1- (3,5-diaminophenyl) -3- Octadecylsuccinimide, 1- (3,5-diaminophenyl) -3-dodecylmaleimide, 1- (3,5-diaminophenyl) -3-hexadecylmaleimide, 1- (3,5-diaminophenyl) -3-octadecyl Maleimide, 1- (3,5-diaminophenyl) -3-dodecyloxymethylmaleimide, 1- (3,5-diaminophenyl) -3-hexadecyloxymethylmaleimide, 1- (3,5-diaminophenyl)- 3-octadecyloxymethylmaleimide, 1- (3,5-diaminophenyl) -3-heptadecyl-4-me Rumaleimide, 1- (3,5-diaminophenyl) -3-dodecyloxymethyl-4-methylmaleimide, 1- (3,5-diaminophenyl) -3-hexadecyloxymethyl-4-methylmaleimide and 1- ( 3,5-diaminophenyl) -3-octadecyloxymethyl-4-methylmaleimide is preferred, 1- (3,5-diaminophenyl) -3-dodecylsuccinimide, 1- (3,5-diaminophenyl) -3- Hexadecyl succinimide, 1- (3,5-diaminophenyl) -3-octadecyl succinimide, 1- (3,5-diaminophenyl) -3-heptadecyl-4-methylmaleimide, 1- (3,5-diaminophenyl) -3-Dodecyloxymethyl-4-methylmaleimide, 1- (3,5-diaminophenyl) 3-hexadecyloxy-4-methyl-maleimide and 1- (3,5-aminophenyl) -3-octadecyl-oxy-4-methyl-maleimide is particularly preferred.

As the diamine used for synthesizing the polyamic acid used in the present invention, only the compound represented by the above formula (1) may be used, and the compound represented by the above formula (1) and other diamines may be used. May be used in combination.
Examples of other diamines that can be used in the present invention include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, and 4,4′-diaminodiphenyl sulfide. 4,4'-diaminodiphenyl sulfone, 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′-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4′-amino) Phenyl) -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, bis [4 -(4-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 4,4-bis (4-aminophenoxy) biphenyl, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroan Tracene, 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, 4,4 ′-(p-phenylenediisopropylidene) bisaniline, 4,4 ′-(m-phenylenediisopropylidene) bisaniline, 2,2′-bis [4- (4- Amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 4,4′-bis [(4-amino-2 Aromatic diamines such as -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 ] -undecylenediethylenediamine, 4,4′-methylenebis (cyclohexylamine) ), 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane and other aliphatic and alicyclic diamines;
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'-bis (4-aminophenyl) -benzidine, and the following formula (DI)

(In the formula (DI), R ⁵ represents 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 represents a divalent organic group. Group.)
A compound represented by formula (D-II):

(Wherein R ⁶ represents 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 represents a divalent organic group, respectively. And a plurality of X ² may be the same or different.)
A diamine having two primary amino groups and a nitrogen atom other than the primary amino group in a molecule such as a compound represented by:
The following formula (D-III)

(In the formula (D-III), R ⁷ is —O— ^* , —COO— ^* , —OCO— ^* , —NHCO— ^* , —CONH— ^* or —CO— ^* (provided with “*”). bond binds to R ^8.), wherein 1 monovalent organic R ⁸ are having a steroid skeleton, a trifluoromethyl phenyl group, skeleton or a group selected from the group consisting of a trifluoromethoxyphenyl group, and a fluorophenyl group Or a C 6-30 alkyl group or a fluorinated alkyl group.)
Monosubstituted phenylenediamines such as compounds represented by each of
The following formula (D-IV)

(In the formula (D-IV), R ⁹ represents a hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R ⁹ may be the same or different, and p represents 1 to 3 respectively. 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. In addition, the benzene ring of the above aromatic diamine and mono-substituted phenylenediamine may be substituted with one or two or more alkyl groups having 1 to 4 carbon atoms (preferably a methyl group). These diamines can be used alone or in combination of two or more.
Other diamines that can be used to synthesize the polyamic acid used in the present invention include p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 1,5 among the above. -Diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 2,7-diaminofluorene, 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] hexafluoro Propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-(p-phenylene dii Propylidene) bisaniline, 4,4 ′-(m-phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 1,4- Diaminocyclohexane, 4,4′-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane, 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′-bis (4-aminophenyl) -benzene Player's side, the following equation of the above formula (D-I) compound represented by the compound represented by (D-6)

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

Of the compounds represented by formula (D-III), the following formulas (D-8) to (D-16)

And at least one selected from the group consisting of 1,3-bis (3-aminopropyl) -tetramethyldisiloxane among the compounds represented by the formula (D-IV) Hereinafter, it is preferably referred to as “specific diamine”. As the specific diamine, 9,9-bis (4-aminophenyl) fluorene is particularly preferable because it facilitates imparting suitable pretilt angle expression.
The diamine used for synthesizing the polyamic acid used in the present invention preferably contains 1 mol% or more of the compound represented by the above formula (1) with respect to the total amount of the diamine used. More preferably, it is contained in an amount of 50 mol%, more preferably 2-20 mol%.
The diamine used for synthesizing the polyamic acid used in the present invention is a specific diamine as described above, in particular, 9,9-bis (4-aminophenyl) fluorene, with respect to the total amount of diamine used. It is preferable that the content is less than or equal to mol%, more preferably 50 to 95 mol%, and even more preferably 75 to 95 mol%.

[Polyamic acid]
The polyamic acid used in the present invention can be synthesized by reacting the tetracarboxylic dianhydride as described above with a diamine.
The proportion of tetracarboxylic dianhydride and diamine used in the polyamic acid synthesis reaction is such that the acid anhydride group of the tetracarboxylic dianhydride is 0.2 to 1 equivalent to 1 equivalent of an amino group contained in the diamine. A ratio of 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 at a temperature of −20 to 150 ° C., more preferably 0 to 100 ° C. in an organic solvent, preferably 0.5 to 120 hours, more preferably 2 to 10 hours. Performed in reaction time. 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 organic solvent used (a) is such that the total amount (b) of tetracarboxylic dianhydride and diamine is 0.1 to 30% by weight based on the total amount (a + b) of the reaction solution. Preferably there is.

For the organic solvent, alcohol, ketone, ester, ether, halogenated hydrocarbon, hydrocarbon and the like, which are poor solvents for polyamic acid, can be used in combination as long as the polyamic acid to be produced does not precipitate. 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. In That.
When the organic solvent and the poor solvent are used in combination, the use ratio of the poor solvent is preferably 50% by weight or less, more preferably 20% by weight or less, and further 10% by weight with respect to the total amount of the organic solvent and the poor solvent. % Or less is preferable.

  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. Polyamic acid can be 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 the reaction solution under reduced pressure using an evaporator. it can. 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.

<Imidized polymer>
The imidized polymer contained in the liquid crystal aligning agent of the present invention is a polyamic acid synthesized as described above using a diamine containing a tetracarboxylic dianhydride and a compound represented by the above formula (1). It can be obtained by dehydration ring closure.
[Tetracarboxylic dianhydride]
The tetracarboxylic dianhydride used for the synthesis of the imidized polymer used in the present invention is the same as the tetracarboxylic dianhydride used for the synthesis of the polyamic acid described above. The point that the tetracarboxylic dianhydride preferably contains the specific tetracarboxylic dianhydride is also the same as in the case of polyamic acid. However, preferred specific tetracarboxylic dianhydrides used for the synthesis of imidized polymers are 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 acid Anhydride, 3,5,6- Rikarubokishi 2-carboxymethyl norbornane -2: 3,5: 6-dianhydride and 4,9-dioxatricyclo [5.3.1.0 ^{2, 6]} undecane -3,5,8,10 -At least one selected from the group consisting of tetraone, particularly preferably 2,3,5-tricarboxycyclopentylacetic acid dianhydride.
The tetracarboxylic dianhydride used in the synthesis of the imidized polymer used in the present invention is a specific tetracarboxylic dianhydride as described above with respect to the total amount of tetracarboxylic dianhydride used. It is preferably contained in an amount of not less than mol%, more preferably not less than 20 mol%, further preferably not less than 50 mol%.

[Diamine]
The diamine used for the synthesis of the imidized polymer used in the present invention is the same as the diamine used for the synthesis of the polyamic acid described above. In the case of polyamic acid, the diamine used for the synthesis of the imidized polymer includes the compound represented by the above formula (1), and other diamine, preferably the above-mentioned specific diamine can be used together with this. It is the same. However, among diamines used for the synthesis of imidized polymers, p-phenylenediamine is particularly preferable.
The diamine used for synthesizing the imidized polymer used in the present invention preferably contains 1 mol% or more of the compound represented by the above formula (1) based on the total amount of the diamine used, It is more preferable to contain 1-50 mol%, and it is further preferable to contain 2-20 mol%.
The diamine used for synthesizing the imidized polymer used in the present invention preferably contains 98 mol% or less of the specific diamine as described above, particularly p-phenylenediamine, based on the total amount of diamine used. 50 to 98 mol%, more preferably 75 to 95 mol%.

[Synthesis of imidized polymer]
The imidized polymer contained in the liquid crystal aligning agent of the present invention may be a completely imidized product in which all of the amic acid units of the polyamic acid as a precursor are dehydrated and closed, or the amic acid unit and the dehydrated polymer. A partially imidized product in which a ring-closed imide ring coexists may be used. The imidization rate of the imidized polymer is preferably 80% or more, and more preferably 85% or more. Here, the “imidization rate” is a percentage of the number of imide rings to the total number of amic acid structures and the number of imide rings in the polymer. At this time, a part of the imide ring may be an isoimide ring. The imidation rate was determined by dissolving the imidized polymer in a suitable deuterated solvent (for example, deuterated dimethyl sulfoxide), and measuring ¹ H-NMR at room temperature using tetramethylsilane as a reference substance. ).

Imidation 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 precursor of an imidized polymer ( It is the number ratio of other protons to one NH group proton in the polyamic acid).

The imidized polymer constituting the liquid crystal aligning agent of the present invention can be obtained by dehydrating and ring-closing polyamic acid. The polyamic acid is dehydrated and closed by (i) a method of heating the polyamic acid, or (ii) dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring-closing catalyst to this solution, and heating as necessary. By the method.
The reaction temperature in the method of heating the polyamic acid (i) is preferably 50 to 200 ° C, more preferably 60 to 170 ° C. When the reaction temperature is less than 50 ° C., the dehydration ring-closing reaction does not proceed sufficiently, and when the reaction temperature exceeds 200 ° C., the molecular weight of the imidized polymer obtained may decrease. The reaction time is preferably 1 to 120 hours, more preferably 2 to 30 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. The amount of the dehydrating agent used is preferably 0.01 to 20 mol relative to 1 mol of the polyamic acid repeating unit. 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. The amount of the dehydration ring-closing catalyst used is preferably 0.01 to 10 mol with respect to 1 mol of the dehydrating agent used. In addition, as an organic solvent used for dehydration ring closure reaction, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid can be mentioned. And the reaction temperature of dehydration ring closure reaction becomes like this. Preferably it is 0-180 degreeC, More preferably, it is 10-150 degreeC, Reaction time becomes like this. Preferably it is 0.5-30 hours, More preferably, it is 2-10 hours .
The imidized polymer obtained in the above method (i) may be used for the preparation of a liquid crystal aligning agent as it is, or may be used for the preparation of a liquid crystal aligning agent after purifying the obtained imidized polymer. . On the other hand, in the method (ii), a reaction solution is obtained as described above. When preparing the liquid crystal aligning agent of the present invention, this reaction solution may be used as it is for preparing the liquid crystal aligning agent, and after removing the dehydrating agent and the dehydrating ring-closing catalyst from the reaction solution, it is used for preparing the liquid crystal aligning agent. Alternatively, the imidized polymer may be isolated and used for preparation of a liquid crystal aligning agent, or the isolated imidized polymer may be purified and then used for preparation of a liquid crystal aligning agent. 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. Isolation and purification of the imidized polymer can be performed by performing the same operations as in the isolation and purification method of polyamic acid.

-End-modified polymer-
The polyamic acid and the imidized polymer may be of a terminal modified type with a controlled molecular weight. Such a terminal-modified type can be synthesized by adding a molecular weight regulator to the reaction system when synthesizing the polyamic acid. As said molecular weight regulator, an acid monoanhydride, a monoamine compound, a monoisocyanate compound etc. can be mentioned, for example.
Here, examples of the acid monoanhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl. A succinic anhydride etc. can be mentioned. Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, and n-undecyl. Amine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-eicosylamine, etc. be able to. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.
The molecular weight modifier is preferably used in an amount of 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the total of tetracarboxylic dianhydride and diamine used when synthesizing the polyamic acid.
-Solution viscosity-
The polyamic acid or imidized polymer obtained as described above preferably has a solution viscosity of 20 to 800 mPa · s, when it is made into a solution having a concentration of 10% by weight, and preferably has a solution viscosity of 30 to 500 mPa · s. More preferably, it has a solution viscosity.
The solution viscosity (mPa · s) of the above polymer was a value measured at 25 ° C. using an E-type viscometer for a polymer solution having a concentration of 10% by weight using N-methyl-2-pyrrolidone as a solvent. It is.

<Other ingredients>
The liquid crystal aligning agent in this invention contains the at least 1 sort (s) of polymer selected from the group which consists of the above polyamic acids and its imidation polymer. However, when the compound represented by the above formula (1) is 1- (3,5-diaminophenyl) -3-octadecylsuccinimide, the diamine is diaminobenzoic acid 4- (2-ethoxycarbonylvinyl) phenyl ester. If including are excluded.
The liquid crystal aligning agent in the present invention contains other components in addition to at least one selected from the group consisting of the polyamic acid and the imidized polymer thereof as described above, as long as the effects of the present invention are not impaired. May be. However, when the compound represented by the formula (1) is 1- (3,5-diaminophenyl) -3-decylsuccinimide, the liquid crystal aligning agent is
Contains an imidized polymer of polyamic acid obtained by reacting 1,2,3,4-cyclobutanetetracarboxylic dianhydride, phenylenediamine and 4- (2-ethoxycarbonylvinyl) phenyl ester of diaminobenzoic acid And an imidized polymer of polyamic acid obtained by reacting 1,2,3,4-cyclobutanetetracarboxylic dianhydride with 4- (2-ethoxycarbonylvinyl) phenyl ester of diaminobenzoic acid The case is excluded. Examples of other components that can be contained in the liquid crystal aligning agent include a compound having at least one epoxy group in the molecule (hereinafter referred to as “epoxy compound”), a functional silane compound, and the like.
The liquid crystal aligning agent in this invention can contain an epoxy compound from a viewpoint of improving the adhesiveness with respect to the substrate surface. Examples of such epoxy compounds 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, trimethylolpropane triglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3 -Bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenyl Tan, N, N-diglycidyl - benzylamine, N, N-diglycidyl - such as aminomethyl cyclohexane may be mentioned as preferred. The compounding ratio of these epoxy compounds is preferably 40 parts by weight or less, more preferably 100 parts by weight or less, more preferably 100 parts by weight of the total of the polymers (the total of the above polyamic acid and its imidized polymer). 0.1 to 30 parts by weight.

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, 9- Methyl trimethoxysilyl-3,6-diazananoate, methyl 9-triethoxysilyl-3,6-diazananoate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, 3 Glycidoxypropyltrimethoxysilane, and 3-glycidoxypropyl triethoxy silane and the like.
The compounding ratio of the functional silane compound is preferably 1 part by weight or less, more preferably 0.1 part by weight or less, with respect to 100 parts by weight of the total amount of the polymer.

<Liquid crystal aligning agent>
The liquid crystal aligning agent in the present invention preferably contains at least one selected from the group consisting of the polyamic acid and the imidized polymer as described above and other components optionally blended as necessary, preferably in an organic solvent. Dissolved and contained.
Examples of the organic solvent that can be used for the liquid crystal aligning agent in the present invention include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, and 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 di Methyl ether, diethylene 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, diisopentyl ether, ethylene carbonate, propylene carbonate And so on. These can be used alone or in admixture of two or more.

The solid content of the liquid crystal aligning agent of the present invention (proportion of the total weight of the components other than the solvent in the liquid crystal alignment agent to the total weight of the liquid crystal aligning agent), the viscosity may be selected appropriately in consideration of the volatile The range is preferably 1 to 10% by weight. That is, the liquid crystal aligning agent in the present invention is applied to the substrate surface as will be described later, and preferably, a coating film that becomes a liquid crystal aligning film is formed by heating, but the solid content concentration is less than 1% by weight. In this case, the film thickness of the coating film becomes too small to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film becomes excessive. Thus, a good liquid crystal alignment film cannot be obtained, and the viscosity of the liquid crystal aligning agent increases, resulting in poor coating properties.
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 solid content concentration is particularly preferably in the range of 1.5 to 4.5% by weight. 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.

<Liquid crystal display element>
The liquid crystal display device of the present invention are those having a liquid crystal alignment film formed from 如-out liquid crystal aligning agent of the above.
The liquid crystal display element of the present invention can be produced, for example, by the following steps (1) to (3). That is, (1) a liquid crystal aligning agent as described above is applied on a substrate to form a coating film, and (2) a liquid crystal alignment film is formed on the substrate by irradiating the coating film with radiation. 3) A liquid crystal display element can be manufactured using this. Hereafter, the manufacturing method of the liquid crystal display element of this invention is demonstrated in detail.

(1) A liquid crystal aligning agent as described above is applied to one surface of a substrate provided with a patterned transparent conductive film by an appropriate application method such as a roll coater method, a spinner method, a printing method, or an inkjet method, Next, the coated surface is formed by heating the coated surface. Here, as the substrate, for example, glass such as float glass or soda glass; a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, alicyclic polyolefin, or the like can be used. As a transparent conductive film provided on one surface of the substrate, an NESA film (registered trademark of PPG, USA) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ —SnO ₂ ), etc. 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 surface and the transparent conductive film and the coating film, a functional silane compound, a functional titanium compound or the like is applied in advance to the surface of the substrate. It may be left. After applying the liquid crystal aligning agent, preheating (pre-baking) is preferably performed for the purpose of preventing dripping of the applied aligning agent. The pre-baking temperature is preferably 30 to 200 ° C, more preferably 40 to 150 ° C, and particularly preferably 40 to 100 ° C. The prebake time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes, and particularly preferably 1 to 3 minutes. And after removing a solvent completely, it is preferable that a heating (post-baking) process is further implemented. This post-bake temperature is preferably 80 to 300 ° C, more preferably 120 to 250 ° C. The post-bake time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. The liquid crystal aligning agent of the present invention forms a coating film that becomes an alignment film by removing the organic solvent after coating as described above. Is the polymer contained in the liquid crystal aligning agent of the present invention a polyamic acid? Alternatively, in the case of an imidized polymer having both an imide ring structure and an amic acid structure, the film may be further heated after the formation of the coating film so that the dehydration ring-closing reaction proceeds to form a more imidized coating film.
The film thickness of the formed coating film is preferably 0.001-1 μm, more preferably 0.005-0.5 μm.

(2) Next, the coating film is irradiated with linearly polarized light, partially polarized radiation or non-polarized radiation, and optionally further subjected to heat treatment at a temperature of 150 to 250 ° C., preferably for 30 to 150 minutes. A liquid crystal alignment film can be formed by imparting alignment ability. Here, as the radiation, for example, ultraviolet light and visible light including light having a wavelength of 150 to 800 nm can be used, but ultraviolet light including light having a wavelength of 200 to 450 nm is preferable. As the radiation, linearly polarized light is preferable because it has higher alignment regulating power than non-polarized light or partially polarized light. Moreover, in order to improve liquid crystal aligning ability more, you may irradiate, heating a board | substrate at 50-250 degreeC.
The irradiation dose of radiation, preferably 10~100,000J / ^{m 2,} more preferably 100~10,000J / ^{m 2,} and particularly preferably a 200~5,000J / ^{m 2.}
Upon irradiation with radiation, for the purpose of forming a liquid crystal alignment film having a different orientation orientation for each different region in the coating film surface, for each region in the coating film surface, from the group consisting of polarization state, optical axis direction and energy You may irradiate the radiation from which at least one selected condition differs. As a method for changing the polarization state of the radiation to be irradiated, the direction of the optical axis and the energy, a method of irradiating through a photomask, and changing the light intensity, the incident angle, etc. as necessary, the surface of the coating film is irradiated with radiation. The method of sweeping can be mentioned. These methods can be used alone or in combination. Furthermore, one or more of these methods may be combined with batch irradiation on the entire surface of the substrate.
As a radiation light source, 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 preferred wavelength region can be obtained, for example, by means of using these light sources in combination with a filter or a diffraction grating.

(3) Two substrates (a pair) are formed on which the liquid crystal alignment film is formed as described above, and the polarization direction or the incident direction of the irradiated radiation is orthogonal or antiparallel in each liquid crystal alignment film. In addition, the two substrates are arranged opposite to each other with a gap (cell gap), and the peripheral portions of the two substrates are bonded together using a sealant, and the liquid crystal is placed in the cell gap partitioned by the substrate surface and the sealant. The liquid crystal cell is formed by filling and filling and sealing the injection hole. And a liquid crystal display element can be manufactured by arrange | positioning a polarizing plate to the outer surface of a liquid crystal cell, ie, the transparent substrate side which comprises a liquid crystal cell.
Here, as the sealing agent, for example, an epoxy resin containing a curing agent and aluminum oxide spheres as a spacer can be used.
As the liquid crystal, for example, a nematic liquid crystal, a smectic liquid crystal, or the like can be used. Among these, nematic liquid crystal is preferable, for example, Schiff base liquid crystal, azoxy liquid crystal, biphenyl liquid crystal, phenyl cyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, 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 Ferroelectric liquid crystals such as -decyloxybenzylidene-p-amino-2-methylbutylcinnamate may be further added and 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 is excellent in various performances such as display characteristics and long-term reliability.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
The imidization rate of the imidized polymer was determined by measuring ¹ H measured at room temperature using tetramethylsilane as a reference substance after the imidized polymer was sufficiently dried at room temperature under reduced pressure and then dissolved in deuterated dimethyl sulfoxide. -Calculated from NMR spectrum according to the above formula (i).
The solution viscosity of the polymer solution was measured at 25 ° C. using an E-type rotational viscometer.
Synthesis Examples 1 to 6 and Comparative Synthesis Example 1 (Synthesis of polyamic acid)
In 135 g of N-methyl-2-pyrrolidone, diamine and tetracarboxylic dianhydride of the type and amount shown in Table 1 were added in this order and dissolved, and the total amount (b) of diamine and tetracarboxylic dianhydride was A polyamic acid (A-1) to (A-6) and (R-1) was obtained by reacting at 60 ° C. for 6 hours with a solution of 10% by weight based on the total amount of the reaction solution (a + b). 150 g of each solution containing 10% by weight was obtained. The solution viscosity of this solution is shown in Table 1.
Comparative Synthesis Example 2 (Synthesis of polyamic acid)
To 149 g of N-methyl-2-pyrrolidone, 4.9 g (0.045 mol) of p-phenylenediamine and the following scheme 1

2.2 g (0.005 mol) of diamine A synthesized according to the above was dissolved, and further 9.5 g (0.05 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was added, By reacting at room temperature for 6 hours, a solution containing 10% by weight of polyamic acid (R-2) was obtained. The solution viscosity of the obtained polyamic acid solution was 74 mPa · s.
Comparative Synthesis Example 3 (Synthesis of polyamic acid)
To 150 g of N-methyl-2-pyrrolidone, 4.9 g (0.045 mol) of p-phenylenediamine and the following scheme 2

Dissolve 2.3 g (0.005 mol) of diamine B synthesized according to the above, and add 9.5 g (0.05 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, By reacting at room temperature for 6 hours, a solution containing 10% by weight of polyamic acid (R-3) was obtained. The solution viscosity of the obtained polyamic acid solution was 58 mPa · s.
Comparative Synthesis Example 4 (Synthesis of polyamic acid)
The following formula (C) synthesized according to the method described in 149 g of N-methyl-2-pyrrolidone and 4.9 g (0.045 mol) of p-phenylenediamine and JP-A 09-278724

In addition, 1.8 g (0.005 mol) of the compound represented by formula (1) was dissolved, and 9.5 g (0.05 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was further added, Was carried out for 6 hours to obtain a solution containing 10% by weight of polyamic acid (R-4). The solution viscosity of the obtained polyamic acid solution was 67 mPa · s.
Comparative Synthesis Example 5 (Synthesis of polyamic acid)
To 247 g of N-methyl-2-pyrrolidone, 16.6 g (0.0475 mol) of 9,9-bis (4-aminophenyl) fluorene and 1.3 g of the compound represented by the above formula (D-10) (0. 0025 mol), and further 9.5 g (0.05 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was added and reacted at room temperature for 6 hours to obtain a polyamic acid. A solution containing 10% by weight of (R-5) was obtained. The solution viscosity of the obtained polyamic acid solution was 55 mPa · s.

Synthesis Examples 7 to 10 (Synthesis of imidized polymer)
In 135 g of N-methyl-2-pyrrolidone, the diamine and tetracarboxylic dianhydride of the type and amount shown in Table 2 were added in this order and dissolved, and the total amount (b) of diamine and tetracarboxylic dianhydride was The solution is 10% by weight with respect to the total amount (a + b) of the reaction solution, and this is reacted at 60 ° C. for 6 hours to contain 10% by weight of each of polyamic acids (A-7) to (A-10). 150 g of each solution was obtained. The solution viscosities of these solutions are shown in Table 2.
Next, pyridine and acetic anhydride in the amounts shown in Table 2 were added to the solution containing these polyamic acids, respectively, and a dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration cyclization reaction, the solvent in the system was replaced with new N-methyl-2-pyrrolidone (pyridine and acetic anhydride used for the dehydration cyclization reaction were removed from the system in this operation), thereby imido. A solution containing each of the polymerized polymers (B-7) to (B-10) was obtained. The yield of each solution and the imidation ratio of each imidized polymer are shown in Table 2. In addition, Table 2 shows the solution viscosities measured by separating a small amount of each solution and adding N-methyl-2-pyrrolidone as a solution having an imidized polymer concentration of 10% by weight.

In Table 1 and Table 2, the abbreviations of diamine and tetracarboxylic acid have the following meanings, respectively.
[Diamine]
d-1: 9,9-bis (4-aminophenyl) fluorene d-2: p-phenylenediamine d-3: 1- (3,5-diaminophenyl) -3-dodecylsuccinimide d-4: 1- ( 3,5-diaminophenyl) -3-octadecylsuccinimide d-5: 1- (3,5-diaminophenyl) -3-heptadecyl-4-methylmaleimide d-6: 1- (3,5-diaminophenyl)- 3-hexadecyloxymethyl-4-methylmaleimide dA: diamine A synthesized according to Scheme 1 above
d-B: Diamine B synthesized according to Scheme 2 above
dC: Compound represented by the above formula (C) synthesized according to the method described in Patent Document 15 (Japanese Patent Laid-Open No. 09-278724) D-10: Compound represented by the above formula (D-10) [ Tetracarboxylic dianhydride]
t-1: 1,2,3,4-cyclobutanetetracarboxylic dianhydride t-2: 2,3,5-tricarboxycyclopentyl acetic acid dianhydride In addition, diamine (d-3)-(d-6) Each of these was synthesized according to the method described in Patent Document 16 (Japanese Patent Laid-Open No. 2007-300250) or Patent Document 17 (Japanese Patent Laid-Open No. 2008-250302).

Examples 1-6 and Comparative Examples 1-5
N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) were added to the solutions containing the polyamic acids listed in Table 3 for dilution, and the solvent composition was NMP: BC = 40: 60 (weight ratio), solid A liquid crystal aligning agent was prepared by preparing a solution having a partial concentration of 2.5% by weight and filtering the solution using a filter having a pore diameter of 1 μm.
These liquid crystal aligning agents are respectively applied to the transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film by spin coating, heated on a hot plate at 80 ° C. for 1 minute (pre-baked), and then on a hot plate at 200 ° C. By heating (post-baking) for 10 minutes, a coating film having an average film thickness of 600 mm was formed.
On each surface of these coating films, a linearly polarized ultraviolet ray of 1,000 J / m ² including an emission line of 254 nm using a Hg-Xe lamp was tilted 45 ° from the substrate normal, and the polarization plane was the substrate normal. Irradiation was performed so as to be included in a plane formed by the optical axis to obtain a liquid crystal alignment film. This operation was repeated to obtain a pair (two) of substrates having a liquid crystal alignment film on one side.
Next, after applying an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm to the outer edges of the pair of substrates having the liquid crystal alignment films, the liquid crystal alignment film surfaces face each other and the irradiated ultraviolet rays are irradiated. The adhesive was cured by overlapping and pressing so that the projection direction of the optical axis onto the substrate surface was antiparallel. Next, after filling nematic liquid crystal (MLC-6221 manufactured by Merck & Co., Inc.) between a pair of substrates from the liquid crystal injection port, the liquid crystal injection port is sealed with an acrylic photo-curing adhesive to produce a liquid crystal cell. did. For these liquid crystal cells, the pretilt angle and the liquid crystal alignment were evaluated as follows. The results are shown in Table 3.
(1) Evaluation of pretilt angle The method described in Non-Patent Document 1 (TJ Scheffer et. Al. J. Appl. Phys. Vo. 19, p. 2013 (1980)) for the liquid crystal cell produced above. The tilt angle value of the liquid crystal molecules from the substrate surface measured by the crystal rotation method using He—Ne laser light in accordance with the above was defined as the pretilt angle.
(2) Liquid crystal alignment The liquid crystal cell produced above was observed with a polarizing microscope for the presence or absence of abnormal domains when a voltage of 5 V was turned on / off (applied / released) at room temperature. The quality was judged as “good”.

Examples 7-10
N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) were added to the solutions containing the imidized polymers described in Table 3 for dilution, and the solvent composition was NMP: BC = 40: 60 (weight ratio). A liquid crystal aligning agent was prepared by preparing a solution having a solid content concentration of 2.5% by weight and filtering the solution using a filter having a pore size of 1 μm.
Each of the above liquid crystal aligning agents is used, and a non-polarized ultraviolet ray 2,000 J / m ² containing a 254 nm emission line is used instead of a linearly polarized ultraviolet ray 1,000 J / m ² containing a 254 nm emission line. As in Examples 1 to 6 and Comparative Example 1, a liquid crystal cell was produced and evaluated except that MLC-6221 manufactured by Merck was used instead of MLC-6221 manufactured by Merck. The results are shown in Table 3.

Claims (4)

A method for forming a liquid crystal alignment film, wherein a liquid crystal aligning agent is applied on a substrate to form a coating film, and the coating film is irradiated with radiation.
Tetracarboxylic dianhydride;
Following formula (1)

(In formula (1), Z ¹ represents the following formulas (Z ¹ -1) to (Z ¹ -3).

(In the formulas (Z ¹ -1) and (Z ¹ -2), R is a hydrogen atom or a methyl group, respectively, and a bond marked with “*” is bonded to a benzene ring.)
Z ² is a single bond or a methylene group, and when Z ² is a single bond, Z ³ is an alkyl group having 6 to 30 carbon atoms or 6 to 30 carbon atoms. And when Z ² is a methylene group, Z ³ is an alkoxyl group having 6 to 30 carbon atoms. )
The process comprising at least one polymer selected from the group consisting of a polyamic acid obtained by reacting with a diamine containing a compound represented by formula (I) and an imidized polymer thereof; (1) is a compound represented by 1- when (3,5-aminophenyl) -3-octadecyl succinimide, when including a said diamine is diaminobenzoic acid 4- (2-ethoxycarbonyl-vinyl) phenyl ester And when the compound represented by the formula (1) is 1- (3,5-diaminophenyl) -3-decylsuccinimide, the liquid crystal aligning agent is
Contains an imidized polymer of polyamic acid obtained by reacting 1,2,3,4-cyclobutanetetracarboxylic dianhydride, phenylenediamine and 4- (2-ethoxycarbonylvinyl) phenyl ester of diaminobenzoic acid And an imidized polymer of polyamic acid obtained by reacting 1,2,3,4-cyclobutanetetracarboxylic dianhydride with 4- (2-ethoxycarbonylvinyl) phenyl ester of diaminobenzoic acid Except cases.
  The radiation dose is 200 to 5,000 J / m. ² The method of claim 1, wherein A liquid crystal alignment film formed by the method according to claim 1 . Characterized by comprising a liquid crystal alignment film formed by the method according to claim 1 or 2, the liquid crystal display device.