CN1712491A - Vertical liquid crystal alignment agent and vertical liquid crystal display element with reflective electrodes - Google Patents

Abstract

The invention provides a liquid crystal aligning agent which brings about a vertical liquid crystal alignment layer excellent in image persistence characteristics and reliability even when used with a reflection electrode. The vertical liquid crystal aligning agent includes 100 weight parts of a polymer with an amic acid repeating unit and/or an imide repeating unit and at least 5 weight parts of a compound having at least two epoxy groups in a molecule.

Description

Vertical liquid crystal alignment agent and vertical liquid crystal display element with reflective electrodes

technical field

The invention relates to a vertical liquid crystal aligning agent and a vertical liquid crystal display element with reflective electrodes. More specifically, it relates to a vertical liquid crystal aligning agent capable of producing a vertical liquid crystal aligning film excellent in print characteristics regardless of the type of electrodes constituting a liquid crystal display element, and a reflective liquid crystal aligning film equipped with the vertical liquid crystal aligning film. Electrodes of liquid crystal display elements.

Background technique

At present, there is known a TN-type liquid crystal display element having a TN (twisted nematic) type liquid crystal cell, which has a positive dielectric anisotropy formed between two substrates on which a liquid crystal alignment film is formed on the surface through a transparent conductive film. The nematic liquid crystal layer constitutes a cell with a sandwich structure, and the long axis of the above-mentioned liquid crystal molecules is continuously twisted 90 degrees from one substrate to the other.

In addition, there is an STN (Super Twisted Nematic) type liquid crystal display element, which makes the long axis of the liquid crystal molecule into a state of continuously twisting a span of more than 180 degrees between the substrates by adding a chiral reagent, thereby utilizing the resulting birefringence effect. In addition, a guest-host type reflective liquid crystal display element has recently been developed, which forms a nematic liquid crystal layer in a homeotropic orientation state with negative dielectric anisotropy or a helical axis parallel to the normal line of the substrates between opposing substrates. state of cholesteric liquid crystal layers, and add pigments to these liquid crystal layers. The alignment of liquid crystals in these liquid crystal display elements is usually visualized by a liquid crystal alignment film subjected to polishing. Here, polyimide, polyamide, polyester, etc. are conventionally known as a material of the liquid crystal alignment film which comprises a liquid crystal display element. In particular, polyimide is used in many liquid crystal display elements due to its excellent heat resistance, affinity with liquid crystals, mechanical strength, and the like.

Recently, research has been carried out to improve display quality and reduce power consumption, represented by high-precision liquid crystal display elements, and the range of applications of liquid crystal display elements is also expanding. In particular, reflective or transflective liquid crystal display elements that can maintain high display quality when used outdoors are used in mobile terminals, and various metal electrodes (hereinafter referred to as emitter electrodes) are used in order to show the performance of reflecting external light. . However, in a vertical liquid crystal display element having a reflective electrode, when an alignment film conventionally used for an ITO electrode is used, there are problems of poor reliability such as printing and alignment spots during long-time illumination.

Contents of the invention

The object of the present invention is to provide a liquid crystal aligning agent which, when used together with a reflective electrode, can also produce a vertical liquid crystal aligning film excellent in printing characteristics and reliability.

Another object of the present invention is to provide a vertical liquid crystal display element equipped with a reflective electrode provided with a vertical liquid crystal alignment film made of the liquid crystal alignment agent of the present invention.

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

According to the present invention, the above-mentioned object and advantage of the present invention are realized by a kind of liquid crystal aligning agent, it is characterized in that comprising 100 parts by weight of the repeating unit represented by the following formula (1) and/or the polymerization of the repeating unit represented by the following formula (2) substances, and at least 5 parts by weight of compounds with at least 2 epoxy groups in the molecule,

(wherein, P ¹ is a 4-valent organic group, and Q ¹ is a 2-valent organic group),

(wherein, P ² is a 4-valent organic group, and Q ² is a 2-valent organic group).

The vertical liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention is not limited to the situation of being used together with ITO electrodes, but also has excellent printing characteristics and reliability when used with reflective electrodes, and can be suitable for forming liquid crystal display element.

The liquid crystal display device of the present invention can be effectively used in various devices, for example, it is suitable for display devices such as desktop computers, watches, desk clocks, mobile phones, counter displays, word processors, personal computers, and liquid crystal televisions.

Detailed ways

Hereinafter, the present invention will be described in detail.

The liquid crystal aligning agent in this invention contains the polymer (henceforth "specific polymer") which has the repeating unit represented by said (1) and/or the repeating unit represented by said formula (2). Specific polymer can be (1) have the mixture of the polyamic acid of the repeating unit represented by above-mentioned (1) and the polyimide that has the repeating unit represented by above-mentioned formula (2), (2) also can be in the same molecule A polymer having a repeating unit represented by the above (1) and a repeating unit represented by the above formula (2) bonded randomly or in a block form (hereinafter also referred to as a "partial imidization polymer").

The above-mentioned polyamic acid is prepared by ring-opening polyaddition of tetracarboxylic dianhydride and diamine compound. In addition, polyimide is usually prepared by dehydration and ring closure of polyamic acid. Partially imidized polymers can usually be prepared by partially dehydrating and ring-closing polyamic acid, or by bonding an amic acid prepolymer and an imide prepolymer to form a block copolymer.

<Polyamic acid>

[Tetracarboxylic dianhydride]

As the tetracarboxylic dianhydride, for example, butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic 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- Cyclobutane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetra Carboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxylic Amyl acetic dianhydride, 3,5,6-tricarboxynorbornane-2-acetic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3a, 4,5,9b -Hexahydro-5-(tetrahydro-2,5-dioxo-3-furyl)-naphthalene[1,2-c]-furan-1,3-dione, 1,3,3a,4, 5,9b-hexahydro-5-methyl-5-(tetrahydro-2,5-dioxo-3-furyl)-naphthalene[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-Hexahydro-5-ethyl-5-(tetrahydro-2,5-dioxo-3-furyl)-naphthalene[1,2-c]-furan -1,3-diketone, 1,3,3a,4,5,9b-hexahydro-7-methyl-5-(tetrahydro-2,5-dioxo-3-furyl)-naphthalene[ 1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-ethyl-5-(tetrahydro-2,5-dioxo- 3-furyl)-naphthalene[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro- 2,5-dioxo-3-furyl)-naphthalene[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-ethane Base-5-(tetrahydro-2,5-dioxo-3-furyl)-naphthalene[1,2-c]-furan-1,3-dione, 1,3,3a,4,5, 9b-Hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furyl)-naphthalene[1,2-c]-furan-1,3-dione , 5-(2,5-dioxotetrahydrofuryl methylene)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo[2,2,2]-octane-7 -ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2', 5'-diketone), aliphatic and alicyclic tetracarboxylic dianhydrides such as compounds represented by the following formulas (I) and (II),

(In the formula, ^R1 and ^R3 represent a divalent organic group with an aromatic ring, ^R2 and ^R4 represent a hydrogen atom or an alkyl group, and multiple ^R2 and ^R4 that exist can be the same or different);

Pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 1,4, 5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3' , 4,4'-Dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic Acid dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfone Dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-homofluoroisopropylidene diphthalic anhydride, 3 , 3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene Base-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl Methane dianhydride, ethylene glycol-bis(anhydrotrimellitate), propylene glycol-bis(anhydrotrimellitate), 1,4-butanediol-bis(anhydrotrimellitate), 1, 6-hexanediol-bis(dehydrated trimellitate), 1,8-octanediol-bis(dehydrated trimellitate), 2,2-bis(4-hydroxyphenyl)propane-bis( Aromatic tetracarboxylic dianhydrides such as dehydrated trimellitate), compounds represented by the following formulas (1) to (4). These can be used alone or in combination of two or more.

Among them, butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1 , 2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, 2,3,5-Tricarboxycyclopentylacetic dianhydride, 5-(2,5-dioxotetrahydrofuryl methylene)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furyl)-naphthalene[1,2-c]-furan-1, 3-diketone, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furyl)-naphthalene[1,2 -c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo- 3-furyl)-naphthalene[1,2-c]-furan-1,3-dione, bicyclo[2,2,2]-oct-7-ene-2,3,5,6-tetracarboxylic acid Dianhydride, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic Acid dianhydrides, compounds represented by the following formulas (5) to (7) among the compounds represented by the above formula (I), and compounds represented by the following formula (8) among the compounds represented by the above formula (II), are particularly preferred , can include 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,4 , 5-cyclohexanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2, 5-dioxo-3-furyl)-naphthalene[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl- 5-(tetrahydro-2,5-dioxo-3-furyl)-naphthalene[1,2-c]-furan-1,3-dione, 3-oxabicyclo[3.2.1]octane - 2,4-diketone-6-spiro-3'-(tetrahydrofuran-2',5'-dione), pyromellitic dianhydride, and a compound represented by the following formula (5).

In particular, when the repeating unit (amic acid unit) represented by the above-mentioned (1) and the repeating unit (imide unit) represented by the above-mentioned formula (2) exist at the same time, the 4-valent organic group represented by P in ( ¹ ) The 4-valent organic groups represented by P in the repeating unit (imide unit) represented by ( ² ) may be the same or different, and the preferred groups of ^P include the following formulas (i) and Groups represented by each of the formulas (i'). Preferable groups of ^P2 include groups having an alicyclic skeleton, particularly preferably groups represented by the following formulas (ii) and (ii′).

(In the formula, R is a halogen atom, a methyl group or an ethyl group, a is an integer of 0 or 1, b is an integer of 0 to 5, and c and d are each independently an integer of 0 to 4).

As specific examples of preferred tetracarboxylic dianhydrides in each repeating unit, the tetracarboxylic dianhydrides constituting the amic acid unit include, for example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3- Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, pyromellitic dianhydride, and the like. In addition, the tetracarboxylic dianhydride constituting the imide unit is preferably an alicyclic tetracarboxylic dianhydride, and specifically, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,3,3a,4, 5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furyl)-naphthalene[1,2-c]-furan-1,3-dione, 1,3,3a , 4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furyl)-naphthalene[1,2-c]-furan-1,3- Diketone, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), etc.

[Diamine compound]

Examples of the diamine compound used in the synthesis of the polyamic acid include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethylene Alkane, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'- Diaminobenzanilide, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 5-amino-1 -(4'-aminophenyl)-1,3,3-trimethylindane, 6-amino-1-(4'-aminophenyl)1,3,3-trimethylindane, 3, 4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-di[4 -(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-aminophenyl]hexafluoropropane Fluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy Base) benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 2,7-diaminofluorene, 9,9-bis (4-aminophenyl)fluorene, 4,4'-methylene-bis(2-chloroaniline), 2,2',5,5'-tetrachloro-4,4'-diaminobiphenyl, 2 , 2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 1,4 , 4'-(p-phenyleneisopropylidene)bis(aniline), 4,4'-(m-phenyleneisopropylidene)bis(aniline), 2,2'-bis[4- (4-Amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'- Bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl, 4-(4-n-heptylcyclohexyl)-phenoxy-2,4-diaminobenzene and other aromatic Diamine;

1,1-m-xylylenediamine (1,1-metakisililendiamin), 1,3-propylenediamine, butylenediamine, pentamethylenediamine, hexamethylenediamine, heptanediamine, octyldiamine, Nonanediamine, 4,4-diaminoheptanediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienediamine, hexahydro-4,7-methylene ^Aliphatic and Alicyclic diamine;

2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrazine, 5 , 6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 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-diaminopurine, 5,6-diamino-1,3-di Methyluracil, 3,5-diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridine lactate, 3,8-diamino-6-phenyl Phenanthridine, 1,4-diaminopiperazine, 3,6-diaminoacridine, bis(4-aminophenyl)phenylamine, and compounds represented by the following formulas (III) to (IV) have 2 a primary amino group and a diamine of a nitrogen atom other than the primary amino group,

(wherein, R represents a monovalent organic group with a ring structure containing ^a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, and X represents a divalent organic group),

(In the formula, X represents a divalent organic group selected from pyridine, pyrimidine, triazine, piperidine and piperazine with a ring structure containing a nitrogen atom, R represents a divalent organic group, and ^multiple existing X can be same or different);

Monosubstituted phenylenediamines represented by the following formula (V); diaminoorganosiloxanes represented by the following formula (VI);

(In the formula, R ⁷ represents a divalent organic group selected from -O-, -COO-, -OCO-, -NHCO-, -CONH- and -CO-, R ⁸ represents a divalent organic group selected from the group consisting of steroid skeleton, three Monovalent organic groups of fluoromethyl groups and fluorine groups or alkyl groups with 6 to 30 carbon atoms),

(wherein, R ⁹ represents a hydrocarbon group with 1 to 12 carbon atoms, multiple R ⁹ can be the same or different, p is an integer of 1 to 3, and q is an integer of 1 to 20);

Examples thereof include compounds represented by the following formulas (9) to (13). These diamine compounds may be used alone or in combination of two or more.

(In the formula, y is an integer of 2 to 12, and z is an integer of 1 to 5). Among them, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 1,5-diaminonaphthalene, 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]hexafluoropropane, 2,2-bis[4-aminophenyl]hexafluoropropane, 4,4'-(p-phenylene diisopropylidene) Bis(aniline), 4,4'-(m-phenylene diisopropylidene)bis(aniline), 1,4-cyclohexanediamine, 4,4'-methylene bis(cyclohexylamine) ), 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4-(4-n-heptylcyclohexyl)phenoxy-2 , 4-diaminobenzene, compounds represented by the above formulas (9) to (13), 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminopyridine Acridine, the compound represented by the following formula (14) among the compounds represented by the above formula (III), the compound represented by the following formula (15) among the compounds represented by the above formula (IV), and the compound represented by the above formula (V) Compounds represented by the following formulas (16) to (21).

[Synthesis reaction of polyamic acid]

The usage ratio of the tetracarboxylic dianhydride and the diamine compound used in the polyamic acid synthesis reaction is preferably such that the acid anhydride group of the tetracarboxylic dianhydride is 0.2 to 2 equivalents to the amino group contained in 1 equivalent of the diamine compound. , more preferably a ratio of 0.3 to 1.2 equivalents.

The synthesis reaction of polyamic acid is preferably carried out in an organic solvent at a temperature of -20 to 150°C, more preferably at a temperature of 0 to 100°C. 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, γ-butyrolactone, tetramethylurea, hexa Aprotic polar solvents such as methylphosphite triamide; phenolic solvents such as m-cresol, xylenol, phenol, and halogenated phenol. Moreover, it is preferable that the usage-amount (a) of an organic solvent is the quantity which makes the total amount (b) of a tetracarboxylic dianhydride and a diamine compound be 0.1-30 weight% with respect to the total amount (a+b) of a reaction solution.

[Poor solvent]

In addition, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, etc., which are poor solvents for polyamic acid, may be used in combination with the above-mentioned organic solvent within the range where the generated polyamic acid is not precipitated. Specific examples of such poor solvents include methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, lactic acid Ethyl ester, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethoxypropyl Ethyl acetate, diethyl oxalate, diethyl malonate, ethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol Alcohol dimethyl ether, ethylene glycol ethyl ether acetate, diglyme, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, Diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane alkanes, octane, benzene, toluene, xylene, etc.

As mentioned above, the reaction solution which melt|dissolved polyamic acid was obtained. Then, this reaction solution was poured into a large amount of poor solvent to obtain a precipitate. The polyamic acid can be obtained by drying this precipitate under reduced pressure. Then, the polyamic acid can be purified by dissolving the polyamic acid in an organic solvent again, and then precipitating with a poor solvent, and performing this step once or several times.

[Imidated Polymer]

<imidized polymer>

The imidized polymer constituting the liquid crystal aligning agent of the present invention can be prepared by dehydrating and ring-closing the aforementioned polyamic acid. The dehydration ring-closing of polyamic acid is successfully achieved by, for example, (i) heating polyamic acid, or (ii) dissolving polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution, and heating as required. proceed.

In the above (i) method of heating polyamic acid, the reaction temperature 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 is difficult to proceed completely, and when the reaction temperature exceeds 200°C, the molecular weight of the obtained imidized polymer may decrease.

On the other hand, in the above (ii) method of adding a dehydrating agent and a dehydrating ring-closing catalyst to the polyamic acid solution, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used as the dehydrating agent. It is preferable that the usage-amount of a dehydrating agent is 0.01-20 mol with respect to 1 mol of polyamic-acid repeating units. In addition, as the dehydration ring-closing catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used. However, it is not limited to these. The amount of the dehydration ring-closing catalyst used is preferably 0.01 to 10 moles relative to 1 mole of the dehydrating agent used. In addition, examples of the organic solvent used in the dehydration ring-closing reaction include the same organic solvents as those exemplified as the solvent used in polyamic acid synthesis. In addition, the reaction temperature of the dehydration ring-closing reaction is preferably 0 to 180°C, more preferably 10 to 150°C. Moreover, the imidation polymer can be purified by performing the same operation as the polyamic acid purification method with respect to the reaction solution obtained in this way.

[Partial imide]

<Partially imidized polymer>

The partially imidized polymer used in the present invention has a structure obtained by partially imidizing the above-mentioned polyamic acid. The imidization rate of the partially imidized polymer used in the present invention is preferably 10 to 90%, more preferably 30 to 70%. Here, the "imidization ratio" refers to a value expressed in % as a ratio of the number of repeating units forming imide rings to the total number of repeating units in the polymer. In this case, a part of the imide ring may be an isoimide ring.

As a method of synthesizing a partial imide polymer, for example, (i) a method of partially dehydrating and ring-closing the polyamic acid by heating, (ii) dissolving the polyamic acid in an organic solvent and dissolving the polyamic acid in the solution Synthesis by adding a dehydrating agent and a dehydration ring-closing catalyst and heating as necessary to partially dehydrate and ring-close the compound, or (iii) synthesis by mixing a tetracarboxylic dianhydride, a diamine compound, and a diisocyanate compound, heating as necessary, and condensing Methods.

In the method of (i) above, the reaction temperature is preferably 300°C or lower, more preferably 100 to 250°C. When the reaction temperature exceeds 300° C., the molecular weight of the obtained imide group-containing polyamic acid may decrease.

On the other hand, examples of the dehydrating agent used in the method (ii) above include acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride. It is preferable that the usage-amount of a dehydrating agent is 0.2-20 mol with respect to 1 mol of polyamic-acid repeating units. In addition, as the dehydration ring-closing catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used. However, it is not limited to these. Moreover, it is preferable that the usage-amount of an imidation catalyst is 0.1-10 mol with respect to 1 mol of the dehydrating agent used. In addition, examples of the organic solvent used in the dehydration ring-closing reaction include the same organic solvents as those exemplified as the solvent used in polyamic acid synthesis. In addition, the reaction temperature for dehydration and ring closure is preferably 0 to 180°C, more preferably 60 to 150°C. Moreover, the partial imidation polymer can be purified by performing the same operation as the polyamic acid purification method with respect to the reaction solution obtained in this way.

Specific examples of diisocyanate compounds used in the reaction of (iii) above include aliphatic diisocyanates such as hexamethylene diisocyanate; cyclohexane-1,2-diisocyanate, 1-methylcyclohexane- 2,4-diisocyanate, 1,2-dimethylcyclohexane-ω,ω'-diisocyanate, 1,4-dimethylcyclohexane-ω,ω'-diisocyanate, isophorone di Alicyclic diisocyanates such as isocyanate, 1,3,5-trimethyl-2-2-propylcyclohexane-1ω,2ω-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate; diphenyl Methyl methane-4,4'-diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1-methyl-2,4-phenylene diisocyanate, 1-methyl - Aromatic diisocyanates such as 2,6-phenylene diisocyanate and diisocyanates represented by the following formulas (22) to (26).

Among them, dicyclohexylmethane-4,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, 1-methyl-2,4-phenylene diisocyanate, 1- Methyl-2,6-phenylene diisocyanate. These can be used alone or in combination of 2 or more. In addition, the above reaction of (iii) does not particularly require a catalyst, and the reaction temperature is preferably 50 to 200°C, more preferably 100 to 160°C.

[Terminal modification]

<Terminal modified polymer>

The above-mentioned polyamic acid and partially imidized polymer may be an end-modified polymer whose molecular weight has been adjusted. By using this terminal-modified polymer, the application|coating characteristic of a liquid crystal aligning agent, etc. can be improved, without impairing the effect of this invention. Such an end-modified polymer can be synthesized by adding, for example, a monoacid anhydride, a monoamine compound, a monoisocyanate compound, etc. to the reaction system during the synthesis of polyamic acid. Here, examples of monoacid anhydrides include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, n-hexadecylsuccinic anhydride, etc. . In addition, 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, etc. Moreover, as a monoisocyanate compound, phenyl isocyanate, naphthyl isocyanate, etc. are mentioned, for example.

[logarithmic viscosity]

<Logarithmic viscosity of polymer>

The logarithmic viscosity (ηln) of the polyamic acid and partially imidized polymer obtained above is preferably 0.05-10 dl/g, more preferably 0.05-5 dl/g.

The logarithmic viscosity (ηln) value of the present invention is by using N-methyl-2-pyrrolidone as solvent, at 30 ℃, the solution that concentration is 0.5g/100ml carries out viscosity measurement, obtains by following formula (A) value.

[LCD alignment agent]

The liquid crystal aligning agent of the present invention is advantageously constituted by dissolving a specific polymer in an organic solvent.

Examples of the organic solvent constituting the liquid crystal aligning agent of the present invention include the same solvents as those exemplified as the solvent used in the polyamic acid synthesis reaction. Moreover, you may select suitably the same solvent as the poor solvent illustrated as the solvent which can be used together at the time of polyamic-acid synthesis reaction, and you may use it together.

The solid content concentration in the liquid crystal aligning agent of the present invention is selected in consideration of viscosity and volatility, and is preferably 1 to 10% by weight. That is to say, the liquid crystal alignment agent of the present invention is coated on the substrate surface to form a coating film as a liquid crystal alignment film. When the solid content concentration is less than 1% by weight, the thickness of the coating film is too small, and it is difficult to obtain good liquid crystal alignment. membrane. When the solid content concentration exceeds 10% by weight, the thickness of the coating film becomes too thick, making it difficult to obtain a good liquid crystal aligning film, and the viscosity of the liquid crystal aligning agent increases, which tends to deteriorate coating properties. In addition, the temperature when preparing the liquid crystal aligning agent of the present invention is preferably 0°C to 200°C, more preferably 20°C to 60°C.

The liquid crystal aligning agent of the present invention contains at least 5 parts by weight of a compound having at least two epoxy groups in the molecule (hereinafter also referred to as "epoxy group-containing compound") with respect to 100 parts by weight of the specific polymer.

Preferable examples of such epoxy group-containing compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether. ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5, 6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-di(N,N-diglycidyl (aminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, etc. The content of such an epoxy compound may be contained in an amount within a range that does not impair the properties of the aligning agent, and is preferably 5 to 40 parts by weight, more preferably 10 to 30 parts by weight, relative to 100 parts by weight of the specific polymer contained in the aligning agent. parts by weight.

Moreover, the liquid crystal aligning agent of this invention may optionally contain the compound (henceforth "silane coupling agent") which has functional silicon. Examples of such silane coupling agents include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane Silane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyl Trimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane , N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilane-1,4,7-triazadecane , 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilane -3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(hydroxyethyl)-3-aminopropyltrimethoxysilane, N-bis( Hydroxyethyl)-3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, and the like.

The mixing ratio of these silane coupling agents is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the specific polymer.

<Liquid crystal display element>

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

(1) By methods such as roll coater method, spin coater method, printing method, inkjet method, etc., the liquid crystal aligning agent of the present invention is coated on one side of the substrate provided with a patterned transparent conductive film, and then, by The coated surface is heated to form a coating film. Here, as the substrate, glass such as float glass and soda lime glass; transparent substrates made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, and polycarbonate can be used. As the transparent conductive film provided on one side of the substrate, NESA film (registered trademark of PPG Corporation of the United States) made of tin oxide (SnO ₂ ), ITO film made of indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ), etc. can be used. . These transparent conductive film patterns are formed using a photolithography method and a method using a mask in advance. Metals such as Al or Ag, alloys containing these metals, or the like can be used for the reflective electrode. It is not particularly limited as long as it has sufficient reflectance. In the coating of the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film or the reflective electrode and the coating film, it is also possible to pre-coat the compound containing functional silane and the compound containing functional titanium on the surface of the substrate. compounds, etc. The heating temperature after applying the liquid crystal aligning agent is preferably 80 to 300°C, more preferably 120 to 250°C. The liquid crystal aligning agent of the present invention containing polyamic acid can form a coating film as an alignment film by removing the organic solvent after coating, or further dehydrating and ring-closing by heating to form a further imidized coating film. The thickness of the formed coating film is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm.

(2) The surface of the formed coating film is formed on a substrate with a photosensitive resin structure as disclosed in Japanese Patent Laid-Open No. 2002-327058, and a vertical liquid crystal alignment film is formed thereon.

(3) Make 2 substrates on which the vertical liquid crystal alignment film is formed as above, place the 2 substrates relatively through the gap (cell gap), bond the peripheral parts of the 2 substrates with a sealant, and place them on the surface of the substrate and the sealant. Liquid crystal is injected into the cell gap, and the injection hole is closed to form a liquid crystal cell. Then, a polarizing plate is provided on the outer surface of the liquid crystal cell, that is, on the side of the transparent substrate constituting the liquid crystal cell, to obtain a liquid crystal display element.

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

Examples of liquid crystals include nematic liquid crystals and smectic liquid crystals, among which nematic liquid crystals are preferable, and for example, Schiff's base liquid crystals, azoxy-based liquid crystals, biphenyl liquid crystals, and phenylcyclohexane liquid crystals can be used. Liquid crystals, ester liquid crystals, terphenyl liquid crystals, biphenylcyclohexane liquid crystals, pyrimidine liquid crystals, dioxane liquid crystals, bicyclooctane liquid crystals, cubane liquid crystals, etc. In addition, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonanoate, and cholesteryl carbonate may be added to these liquid crystals, and they are sold under the trade names "C-15" and "CB-15" (manufactured by Merck Corporation). Chiral reagents and the like are used. Furthermore, ferroelectric liquid crystals such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamic acid can also be used.

In addition, as the polarizing plate attached to the outer surface of the liquid crystal cell, a polarizing film or an H film made by sandwiching a polarizing film called an H film that stretches and aligns polyvinyl alcohol and absorbs iodine in a protective film of cellulose acetate is mentioned. self-made polarizer.

The present invention will be described more specifically by way of examples below, but the present invention is not limited to these examples. In Examples and Comparative Examples, transparency, voltage residual ratio, and printing were evaluated by the following methods.

[transparency]

As a measurement device, a HITACHI U-2010 spectrophotometer (manufactured by Hitachi, Ltd.) was used. The liquid crystal aligning agent of the present invention prepared above was coated on a quartz substrate with a thickness of 1.5 mm by a spin coater, and dried at 180° C. for 1 hour to form a coating film with a dry film thickness of 800 Å. The transmittance of the produced coating film was measured. The measurement of transmittance obtained the values at the wavelengths of 700nm, 600nm, 500nm, 450nm, 400nm, 350nm and 300nm. When the transmittance was 90% or more at any measurement wavelength, it was evaluated as good, and other cases were evaluated as poor.

[Vertical Directionality]

The liquid crystal display element was observed through a cross Nicol with the voltage off and an AC voltage of 12 V (peak-peak) applied.

[Print]

Apply a 30Hz, 2.0V rectangular wave superimposed on 1.0V DC to the liquid crystal display element at an ambient temperature of 50°C for 1 hour. Immediately after cutting off the voltage, use the flicker-elimination method to obtain the residual voltage in the liquid crystal cell as the residual DC voltage. Regardless of the type of electrode constituting the liquid crystal display element, the residual DC voltage is 2V or less, and the residual DC difference between the electrode types is 0.5V or less. The evaluation is good, and the other cases are evaluated as poor. .

[Reliability test of liquid crystal display elements (presence or absence of display defects)]

In a high-temperature and high-humidity environment (temperature is 70°C, relative humidity is 80%), the liquid crystal display element is driven by a 5V, 60Hz rectangular wave, and after 100 hours, the presence or absence of display defects is observed through a polarizing microscope.

Synthesis Example 1

With 2,3,5-tricarboxycyclopentyl acetic acid dianhydride 224.17g (1.0 mol) as tetracarboxylic dianhydride, p-phenylenediamine 54.07g (0.5 mol) as diamine compound, above-mentioned formula (16 ) The diamine compound 261.41g (0.5 mole) represented was dissolved in 4500g N-methyl-2-pyrrolidone, and reacted at 60°C for 6 hours. Next, the reaction solution was injected into a large excess of methanol to precipitate the reaction product, and then washed with methanol and dried at 40° C. under reduced pressure for 15 hours to obtain 520 g of polyamic acid with a logarithmic viscosity of 0.57 dl/g (It is called "polyamic acid (A-1)").

Synthesis example 2

In Synthesis Example 1, except that 94.62 g (0.8 mol) of p-phenylenediamine and 104.56 g (0.2 mol) of the diamine compound represented by the above-mentioned formula (16) were used as the diamine compound, it was performed in the same manner as in Synthesis Example 1 to obtain 390 g of polyamic acid with a logarithmic viscosity of 0.46 dl/g. Dissolve 30 g of the obtained polyamic acid in 570 g of N-methyl-2-pyrrolidone, add 5.7 g of pyridine and 7.4 g of acetic anhydride, dehydrate and close the ring at 110 ° C for 4 hours, carry out the same precipitation, washing, and decompression as above to obtain 19.5 g of polyimide having a logarithmic viscosity of 0.53 dl/g (this is referred to as "polyimide (A-2)").

Synthesis example 3

In Synthesis Example 2, except that 64.88 g (0.6 mol) of p-phenylenediamine and 209.13 g (0.4 mol) of the diamine compound represented by the above-mentioned formula (16) were used as the diamine compound, it was performed in the same manner as in Synthesis Example 2 to obtain 450 g of polyamic acid with a logarithmic viscosity of 0.33 dl/g. Then, except that 4.8 g of pyridine and 6.1 g of acetic anhydride were used, the same operation was performed as in Synthesis Example 2 to obtain 20.1 g of a polyimide having a logarithmic viscosity of 0.41 dl/g (which is called "polyimide (A -3)").

Synthesis Example 4

In Synthesis Example 2, in addition to using 75.70g (0.7 moles) of p-phenylenediamine, 39.65g (0.2 moles) of 1,1-bis(4-aminophenyl) methane, 52.28g (0.1 moles) of the above formula (16) Except the diamine compound shown being a diamine compound, it carried out similarly to the synthesis example 2, and obtained 363 g of polyamic acids whose logarithmic viscosity was 0.39 dl/g. Then, except that 12.1 g of pyridine and 15.6 g of acetic anhydride were used, the same operation was performed as in Synthesis Example 2 to obtain 24.3 g of a polyimide having a logarithmic viscosity of 0.50 dl/g (which is called "polyimide (A -4)").

Synthesis Example 5

In Synthesis Example 4, except that 37.66 g (0.1 mol) of 2,4-diamino-1-octadecyloxybenzene was used instead of the diamine compound (16), the same procedure as Synthesis Example 4 was performed to obtain 24.3 g of A polyimide having a numerical viscosity of 0.42 d1/g (this is referred to as "polyimide (A-5)").

Synthesis Example 6

In Synthesis Example 4, except that 36.65 g (0.1 mol) of 4-(4-n-heptylcyclohexyl)phenoxy-2,4-diaminobenzene was used instead of diamine compound (16), it was the same as Synthesis Example 4 By operating, 24.0 g of a polyimide having a logarithmic viscosity of 0.49 dl/g (which is referred to as "polyimide (A-6)") was obtained.

Synthesis Example 7

In Synthesis Example 1, in addition to using 109.06 g (0.5 mol) of pyromellitic dianhydride and 98.06 g (0.5 mol) of cyclobutane tetracarboxylic dianhydride as tetracarboxylic dianhydride, 198.27 g (1.0 mol) of 4, 4'-diaminodiphenylmethane was used as the diamine compound, and was operated in the same manner as Synthetic Example 1 to obtain 401 g of polyamic acid (which is called "polyamic acid (B-1 )”).

Synthesis Example 8

In Synthesis Example 7, except that 200.5 g (1.01 mol) of 4,4'-diaminodiphenylmethane was used as the diamine compound, 410 g of diaminodiphenylmethane with a logarithmic viscosity of 0.81 dl/g was obtained in the same manner as in Synthesis Example 7. Polyamic acid (which is referred to as "polyamic acid (B-2)").

Synthesis Example 9

In Synthesis Example 2, except that 85.43 g (0.79 mol) of p-phenylenediamine was used, the imide prepolymer was synthesized in the same manner as in Synthesis Example 2, and dissolved in N-methyl-2-pyrrolidone, A solution having a solid content concentration of 10% by weight was prepared. And, using the polyamic acid (B-2) obtained in the above synthesis example 8 as the amic acid prepolymer, it was dissolved in N-methyl-2-pyrrolidone in the same way, and the solid content concentration was 10% by weight. The solution. Next, 500g of imide prepolymer solution is mixed with 500g of amic acid prepolymer, and after stirring for 2 hours, the reaction solution is injected into a large excess of methanol to precipitate the reaction product, and then, washed with methanol, passed under reduced pressure Drying under pressure at 40° C. for 15 hours gave 99 g of a partially imidized polymer having a logarithmic viscosity of 0.67 dl/g (which is referred to as “polymer (C-1)”).

Synthesis Example 10

In Synthesis Example 3, except that 63.80 g (0.59 moles) of p-phenylenediamine was used, the imide prepolymer was synthesized in the same manner as in Synthesis Example 3, and then, in the same manner as in Synthesis Example 9, 98 g of p-phenylenediamine was obtained. A partially imidized polymer having a viscosity of 0.55 dl/g (which is referred to as "polymer (C-2)").

Synthesis Example 11

In Synthesis Example 4, except that 74.62 g (0.69 moles) of p-phenylenediamine was used, the imide prepolymer was synthesized in the same manner as in Synthesis Example 4, and then, in the same manner as in Synthesis Example 9, 99 g of p-phenylenediamine was obtained. A partially imidized polymer having a viscosity of 0.72 dl/g (which is referred to as "polymer (C-3)").

Example 1

The polyamic acid (A-1) prepared in Synthesis Example 1 is dissolved in a mixed solvent of N-methyl-2-pyrrolidone/γ-butyrolactone (weight ratio 30/70), with respect to 100 parts by weight of polymerization substance, dissolve 10 parts by weight of polyethylene glycol diglycidyl ether (molecular weight is about 400), and make a solution with a solid content concentration of 4% by weight. After fully stirring, the solution is filtered with a filter with a pore size of 1 μm to prepare this product. Invented liquid crystal alignment agent. Apply the above liquid crystal aligning agent on a transparent conductive film made of ITO film and a reflective film made of Al provided on one side of a glass substrate with a thickness of 1mm by a spin coater, and dry at 200°C for 1 hour to form a dry film thickness 0.08μm coating film. Then, on each outer edge of a pair of transparent electrode/transparent electrode substrate and a pair of transparent electrode/reflective electrode substrate with the liquid crystal alignment film of the above-mentioned coated liquid crystal alignment film, apply aluminum oxide balls with a diameter of 5.5 μm The epoxy resin adhesive was used, and then, the surfaces of the liquid crystal aligning film were superimposed and pressed together, and the adhesive was cured. Next, negative-type liquid crystal (MLC-6608, manufactured by Melk Corporation) was filled between the substrates through the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photocurable adhesive, and polarizers were bonded on both sides of the substrate outside. Made of liquid crystal display elements. Printing and reliability of the obtained liquid crystal display element were evaluated. The liquid crystal aligning agent of the present invention prepared as above was coated on a quartz substrate with a thickness of 1.5 mm by a spin coater, and a coating film was formed in the same manner as in the production of a liquid crystal display element. The transparency of the produced coating film was evaluated by the transmittance measurement. The results are listed in Table 2. It was confirmed that the liquid crystal aligning agent obtained in the present invention has good printing and reliability.

Examples 2-30

According to the prescription shown in following table 1 and table 2, polyimide (A-2)～(A-6), polyamic acid (B-1)～(B) obtained in synthesis examples 2～7 were prepared -2), partial imidization polymers (C-1)～(C-3) and epoxy group-containing compound, silane coupling agent are dissolved in the mixed solvent with gamma-butyrolactone as main component, obtain A solution having a solid content concentration of 4.0% was filtered through a filter having a pore diameter of 1 μm to prepare the liquid crystal aligning agent of the present invention. Using the liquid crystal aligning agents prepared in this way, a coating film was formed on the surface of the substrate in the same manner as in Example 1, and a liquid crystal display element was produced using the substrate on which the liquid crystal aligning film was formed. Also, evaluations were performed on transparency, printing characteristics and reliability. The results are listed in Table 2.

Comparative example 1-5

According to the prescription shown in following Table 1 and Table 2, it carried out similarly to an Example and produced the liquid crystal display element. Also, transparency, voltage residual ratio and printing characteristics were evaluated. The results are listed in Table 2.

Table 1 polymer Polymer Mixing Ratio Compounds containing epoxy groups type add heavy Example 1 A-1 Polyethylene glycol diglycidyl ether 10 Example 2 A-1 Polyethylene glycol diglycidyl ether 20 Example 3 A-1 Polyethylene glycol diglycidyl ether 30 Example 4 A-2 Polyethylene glycol diglycidyl ether 10 Example 5 A-3 Polyethylene glycol diglycidyl ether 10 Example 6 A-4 Polyethylene glycol diglycidyl ether 10 Example 7 A-5 Polyethylene glycol diglycidyl ether 10 Example 8 A-6 Polyethylene glycol diglycidyl ether 10 Example 9 A-4 B-1 50/50 Polyethylene glycol diglycidyl ether 20 Example 10 A-4 B-1 40/60 Polyethylene glycol diglycidyl ether 20 Example 11 A-4 B-1 60/40 Polyethylene glycol diglycidyl ether 20 Example 12 A-4 B-1 50/50 Polyethylene glycol diglycidyl ether 20 Example 13 A-4 B-1 50/50 Polyethylene glycol diglycidyl ether 20 Example 14 A-4 B-1 50/50 Polyethylene glycol diglycidyl ether 20 Example 15 A-4 B-1 50/50 Polyethylene glycol diglycidyl ether 20 Example 16 A-4 B-1 50/50 Polyethylene glycol diglycidyl ether 20 Example 17 A-4 B-1 50/50 Polyethylene glycol diglycidyl ether 20 Example 18 A-4 B-1 50/50 Polyethylene glycol diglycidyl ether 20 Example 19 A-4 B-1 50/50 1,3,5,6-tetraglycidyl-2,4-hexanediol 10 Example 20 A-4 B-1 50/50 1,3,5,6-tetraglycidyl-2,4-hexanediol 10 Example 21 A-4 B-1 50/50 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane 10 Example 22 A-4 B-1 50/50 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane 10 Example 23 A-4 B-1 50/50 N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane 20 Example 24 A-4 B-1 50/50 Polyethylene glycol diglycidyl ether 5 Example 25 A-4 B-1 50/50 N,N,N'N'-tetraglycidyl-m-xylylenediamine 5 Example 26 A-4 B-1 50/50 Polyethylene glycol diglycidyl ether 20 Example 27 A-4 B-1 50/50 Ethylene glycol diglycidyl ether 20 Example 28 C-1 Polyethylene glycol diglycidyl ether 20 Example 29 C-2 Ethylene glycol diglycidyl ether 20 Example 30 C-3 N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane 20 Comparative example 1 A-1 - 10 Comparative example 2 A-2 - 10 Comparative example 3 A-2 B-1 50/50 - 10 Comparative example 3 B-3 - 10 Comparative example 4 C-1 - 10 Comparative Example 5 C-3 - 10

The addition amount of the compound containing an epoxy group is the weight amount per 100 weight part of polymers.

Table 2 Silane coupling agent transparency vertical orientation printing reliability type Amount added Through type reflective Through type reflective Through type reflective Example 1 - - good good good good good good good Example 2 - - good good good good good good good Example 3 - - good good good good good good good Example 4 - - good good good good good good good Example 5 - - good good good good good good good Example 6 - - good good good good good good good Example 7 - - good good good good good good good Example 8 - - good good good good good good good Example 9 - - good good good good good good good Example 10 - - good good good good good good good Example 11 - - good good good good good good good Example 12 - - good good good good good good good Example 13 - - good good good good good good good Example 14 - - good good good good good good good Example 15 3-Glycidoxypropyltrimethoxysilane 2 good good good good good good good Example 16 3-Glycidoxypropyltrimethoxysilane 5 good good good good good good good Example 17 3-Glycidoxypropyltrimethoxysilane 15 good good good good good good good Example 18 3-ureidopropyltrimethoxysilane 5 good good good good good good good Example 19 - - good good good good good good good Example 20 - - good good good good good good good Example 21 - - good good good good good good good Example 22 - - good good good good good good good Example 23 - - good good good good good good good Example 24 - - good good good good good good good Example 25 - - good good good good good good good Example 26 - - good good good good good good good Example 27 - - good good good good good good good Example 28 - - good good good good good good good Example 29 - - good good good good good good good Example 30 - - good good good good good good good Comparative example 1 - - good good good good bad good bad Comparative example 2 - - good good good good bad good bad Comparative example 3 - - good good good good bad good bad Comparative example 3 - - good good good good bad good bad Comparative example 4 - - good good good good bad good bad Comparative Example 5 - - good good good good bad good bad

The added amount of the silane coupling agent is per 100 parts by weight of polymer.

Claims (4)

1, a kind of vertical liquid crystal orientating agent is characterized in that comprising that 100 weight parts have the polymkeric substance of the repeating unit of the repeating unit of following formula (1) expression and/or following formula (2) expression, and at least 5 weight part intramolecularly compound that has 2 epoxy group(ing) at least,

In the formula, P ¹Be the organic group of 4 valencys, and Q ¹Organic group for divalent;

In the formula, P ²Be the organic group of 4 valencys, and Q ²Organic group for divalent.

2, vertical liquid crystal orientating agent as claimed in claim 1, wherein the intramolecularly compound that has 2 epoxy group(ing) at least is at least a compound that contains epoxy group(ing) of the compound of the compound that is selected from following formula (3) expression and following formula (4) expression,

In the formula, R ⁰¹The aliphatic group of expression divalent,

In the formula, R ⁰²The organic group of expression divalent.

3, as claim 1 or 2 described vertical liquid crystal orientating agents, wherein the transmitance of polymkeric substance in 300nm～700nm wavelength region be 90% or more than.

4, a kind of vertical liquid crystal display element with reflecting electrode is characterized in that having by any liquid crystal orientating membrane that described vertical liquid crystal orientating agent forms of claim 1～3.