KR20110085891A - Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display device - Google Patents

Abstract

PURPOSE: A liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display device are provided to secure the excellent preserving stability of the liquid crystal alignment agent. CONSTITUTION: A liquid crystal alignment agent contains at least one polymer selected from the group consisting of polyamic acid obtained by reacting tetracarboxylic dianhydride and diamine, and a polyimide obtained by dehydrate-cyclizing the polyamic acid. The tetracarboxylic dianhydride contains 5~80mol% of one compound selected from 1S,2S,4R,5R-cyclohexanetetracarboxylic dianhydride and 1S,2S,4S,5R-cyclohexanetetracarboxylic dianhydride.

Description

Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element {LIQUID CRYSTAL ALIGNING AGENT, LIQUID CRYSTAL ALIGNMENT FILM AND LIQUID CRYSTAL DISPLAY DEVICE}

This invention relates to a liquid crystal aligning agent and a liquid crystal display element. In more detail, it is related with the liquid crystal aligning agent which is excellent in storage stability, especially the heat resistance, and high quality display is possible, the display deterioration by heat stress is suppressed, and can drive for a long time. .

As a material of the liquid crystal aligning film used for a liquid crystal display element, resin materials, such as a polyimide, a polyamide, a polyamic acid, and polyester, are known. Especially, the liquid crystal aligning film which consists of polyamic acid or polyimide is excellent in heat resistance, mechanical strength, affinity with a liquid crystal, etc., and is used for many liquid crystal display elements (patent documents 1-6).

Among these, since polyamic acid has high solubility in a general organic solvent, there exists an advantage that the liquid crystal aligning agent which is easy in the printing process in the manufacturing process of a liquid crystal display element can be obtained, and resin price is low. However, the liquid crystal display element which has the liquid crystal aligning film which consists of polyamic acid is vulnerable to heat stress, and when the liquid crystal display element is driven for a long time, the fall of the voltage holding ratio by deterioration of a liquid crystal aligning film becomes a problem. In recent years, it is designed on the premise that the lifetime of a liquid crystal display element exceeds 10 years, as represented by a liquid crystal television. Therefore, even when the liquid crystal display element is driven for a long time, in order to maintain high quality display, it is important to exhibit a stable voltage holding ratio for a long time, and the improvement of the heat resistance reliability of the alignment film is suddenly increasing. As a method of improving the heat resistance reliability (heat stress resistance) of the alignment film known so far, the method of increasing the chemical stability of a liquid crystal aligning film by mix | blending an epoxy compound with a liquid crystal aligning agent (patent document 7), the monomer which has carbonic acid By applying the introduced polyamic acid, a method (patent document 8) or the like has been proposed to form an intermolecular crosslink during firing of the liquid crystal alignment film, thereby increasing the stability of the film. However, according to these techniques, in order to exhibit a desired performance, it is necessary to use a large amount of an epoxy compound or a carboxylic acid, and the rework property of the liquid crystal aligning film (easiness of coating film peeling at the time of poor printing of a liquid crystal aligning agent), rubbing Resistance or the like may be damaged, requiring further improvement.

On the other hand, the liquid crystal aligning film containing a polyimide has relatively high heat stress resistance of the obtained liquid crystal aligning film, but since the conventionally known polyimide does not have sufficient solubility in a general purpose organic solvent, it is a problem in the storage stability of a liquid crystal aligning agent. May be generated.

Under such circumstances, there is a demand for a polyamic acid / polyimide-based liquid crystal aligning agent capable of forming a liquid crystal aligning film having sufficient solubility in a general purpose organic solvent and excellent in thermal stress resistance.

Recently, however, a method for stereoselectively preparing cyclohexanetetracarboxylic acid anhydride has been developed, and 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic acid dianhydride and 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic acid 2 It became possible to selectively manufacture anhydride, respectively (patent document 9, patent document 10, and nonpatent literature 1). Patent Documents 9 and 10 describe polyamic acids synthesized using 100% of the diastereomers as tetracarboxylic dianhydride, respectively, and are described as polymers having sufficiently high molecular weights. And although it is described that the said polyamic acid can be used for the liquid crystal aligning film use of a liquid crystal display element, in these documents, the characteristic of a liquid crystal aligning film is not measured at all, The structure of the tetracarboxylic dianhydride which is a raw material, and the liquid crystal obtained Consideration has not been given to the relationship between the storage stability of the alignment agent and the thermal stress resistance of the formed liquid crystal alignment film.

Japanese Patent Application Laid-open No. Hei 4-153622 Japanese Laid-Open Patent Publication No. 60-107020 Japanese Patent Application Laid-Open No. 11-258605 Japanese Laid-Open Patent Publication No. 56-91277 US Patent No. 5,928,733 Japanese Laid-open Patent Publication No. 62-165628 Japanese Laid-Open Patent Publication No. 2008-299318 Japanese Laid-Open Patent Publication No. 2009-157351 Japanese Laid-Open Patent Publication No. 2009-191253 Japanese Laid-Open Patent Publication No. 2009-286706 Japanese Patent Laid-Open No. 6-222366 Japanese Patent Application Laid-open No. Hei 6-281937 Japanese Patent Application Laid-Open No. 5-107544 Japanese Laid-Open Patent Publication No. 2010-97188

 Japanese Polymer Society Preliminary Collection, Vol. 57, No. 2 (2002)

This invention is made | formed in view of the said situation, The objective is providing the liquid crystal aligning agent which provides the liquid crystal aligning film which is excellent in storage stability and can maintain high quality display, even when using a liquid crystal display element for a long time. will be.

Another object of the present invention is to provide a liquid crystal display device capable of sustaining high quality display even when used for a long time.

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, firstly,

As a liquid crystal aligning agent containing at least 1 sort (s) of polymer chosen from the group which consists of polyamic acid obtained by making tetracarboxylic dianhydride and diamine react, and the polyimide formed by dehydrating and closing the said polyamic acid,

The tetracarboxylic dianhydride,

To at least one kind selected from the group consisting of 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic acid dianhydride and 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic acid dianhydride, with respect to the total tetracarboxylic dianhydride It is achieved by the said liquid crystal aligning agent containing 5-80 mol%.

The above object and advantages of the present invention, secondly,

It is achieved by the liquid crystal display element provided with the liquid crystal aligning film formed from said liquid crystal aligning agent.

While the liquid crystal aligning agent of this invention is excellent in storage stability, when used for a liquid crystal display element, even if it operates for a long time, it provides the liquid crystal aligning film which can sustain the display of high quality. Therefore, the liquid crystal display element of this invention provided with the liquid crystal aligning film formed from such a liquid crystal aligning agent can maintain high quality display, even when it uses for a long time.

The liquid crystal display device of the present invention can be effectively applied to various apparatuses, for example, a clock, a portable game, a word processor, a notebook personal computer, a car navigation system, a camcorder, a portable information terminal, a digital camera, a mobile phone, It can use suitably for display apparatuses, such as various monitors and a liquid crystal television.

(Form to carry out invention)

The liquid crystal aligning agent of this invention,

As a liquid crystal aligning agent containing at least 1 sort (s) of polymer chosen from the group which consists of polyamic acid obtained by making tetracarboxylic dianhydride and diamine react, and the polyimide formed by dehydrating and closing the said polyamic acid,

The tetracarboxylic dianhydride,

To at least one kind selected from the group consisting of 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic acid dianhydride and 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic acid dianhydride, with respect to the total tetracarboxylic dianhydride 5 to 80 mol% is included.

At least one polymer selected from the group consisting of polyamic acid obtained by reacting such specific tetracarboxylic dianhydride and diamine and polyimide formed by dehydrating and ring-closing the polyamic acid is hereinafter referred to as "specific polymer" in the present specification. There is a case.

<Tetracarboxylic dianhydride>

As tetracarboxylic dianhydride for synthesizing polyamic acid in the present invention, 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic dianhydride and 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic acid dianhydride At least 1 sort (s) chosen from the group which consists of, and other tetracarboxylic dianhydride are used together.

Herein, at least one total tetracarboxylic anhydride selected from the group consisting of 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic dianhydride and 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic dianhydride. Although the use ratio with respect to is 5-80 mol%, it is preferable to contain this 10-60 mol%, and it is more preferable to contain 15-50 mol%. When this ratio is less than 5 mol%, the heat resistance reliability of the liquid crystal aligning film formed may be inferior, and when it exceeds 80 mol%, the storage stability of the liquid crystal aligning film obtained may be inferior.

As for the said tetracarboxylic dianhydride, it is more preferable that 1S, 2S, 4R, 5R-cyclohexane tetracarboxylic dianhydride is included in said range.

As said other tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, etc. are mentioned, for example. As these specific examples, As an aliphatic tetracarboxylic dianhydride, For example, butanetetracarboxylic dianhydride etc .;

As alicyclic tetracarboxylic dianhydride, For example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5- tricarboxy cyclopentyl acetic 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-tricarboxy-2-carboxymethylnorbornan-2: 3,5: 6-2 anhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-2 anhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3 , 5,8,10-tetraon and the like;

As aromatic tetracarboxylic dianhydride, a pyromellitic dianhydride etc. are mentioned, respectively, for example,

The tetracarboxylic dianhydride described in patent document 14 (Unexamined-Japanese-Patent No. 2010-97188) can be used.

As said other tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 2,3,5- tricarboxy cyclopentyl acetic 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-oxabi Cyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3-fura Yl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-2 anhydride, 2, 4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-2 anhydride and 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5 At least one selected from the group consisting of, 8,10-tetraone (hereinafter, "specific tetracarboxylic dianhydride" To include yelling) is preferred.

It is preferable that it is 50 mol% or more with respect to the whole said other tetracarboxylic dianhydride, it is more preferable that it is 80 mol% or more, and, as for the use ratio of the said specific tetracarboxylic dianhydride, it is especially preferable that it is 100 mol%.

<Diamine>

As a diamine used for synthesize | combining the polyamic acid in this invention, aliphatic diamine, alicyclic diamine, aromatic diamine, diamino organosiloxane, etc. are mentioned, for example. As these specific examples, As an aliphatic diamine, For example, 1, 1- metha xylylenediamine, 1, 3- propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, etc .;

As alicyclic diamine, For example, 1, 4- diamino cyclohexane, 4, 4'- methylenebis (cyclohexylamine), 1, 3-bis (aminomethyl) cyclohexane, etc .;

As aromatic diamine, for example, p-phenylenediamine, 4,4'- diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 4,4'- diaminodiphenylamine, 1,5 -Diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,7-dia Minofluorene, 4,4'-diaminodiphenylether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2, 2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-(p-phenylenediisopropylidene) Bisaniline, 4,4 '-(m-phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 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) -benzidine, N, N'-bis (4-aminophenyl) -N, N'-dimethylbenzidine, 1,4-bis- (4-aminophenyl) -piperazine, 3,5-diaminobenzoic acid, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3, 5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestanyl, 3,5-diaminobenzoic acid Cholestenyl, 3,5-diaminobenzoic acid ranostanyl, 3,6-bis (4-aminobenzoyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, 4- (4 ' -Trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (4'-trifluoromethylbenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-heptylcyclohexane, 1,1- S (4-((aminophenoxy) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4- (4-heptylcyclohexyl) cyclohexane And the following formula (A-1):

(In formula (A-1), X <^I> is a C1-C3 alkylene group, ^* -O-, ^* -COO-, or ^* -OCO- (However, the bond which attached "*" couples with a diaminophenyl group.) A is 0 or 1, b is an integer of 0 to 2, c is an integer of 1 to 20)

Compounds represented by these;

Examples of the diaminoorganosiloxanes include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and the like.

The diamine described in patent document 14 (Unexamined-Japanese-Patent No. 2010-97188) can be used.

X ^I in the formula (A-1) is an alkylene group having 1 to 3 carbon atoms, ^* -O- or ^* -COO-, provided that the bond to which "*" is attached is combined with a diaminophenyl group. desirable. Group _{C c} H _{2c + 1} - Specific examples of, for example, methyl, ethyl, n- propyl, n- butyl, n- pentyl, n- hexyl, n- heptyl, n- octyl, n -Nonyl group, n-decyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, etc. are mentioned. It is preferable that two amino groups in a diaminophenyl group exist in 2, 4-position or 3, 5-position with respect to another group.

As a specific example of a compound represented by said formula (A-1), For example, dodecaneoxy-2,4-diaminobenzene, tetradecaneoxy-2,4-diaminobenzene, pentadecaneoxy-2,4-dia Minobenzene, hexadecaneoxy-2,4-diaminobenzene, octadecaneoxy-2,4-diaminobenzene, dodecaneoxy-2,5-diaminobenzene, tetradecaneoxy-2,5-diaminobenzene Pentadecaneoxy-2,5-diaminobenzene, hexadecaneoxy-2,5-diaminobenzene, octadecaneoxy-2,5-diaminobenzene, the following formulas (A-1-1) to (A- 1-3):

The compound etc. which are represented by each of these are mentioned.

In Formula (A-1), a and b are preferably not 0 at the same time.

The diamine is p-phenylenediamine, 3,5-diaminobenzoic acid, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4 '-Diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-diaminodiphenylamine and 4,4'-(m-phenyl It is preferable to contain at least 1 sort (s) hereafter called "specific diamine 1" chosen from the group which consists of a lendiisopropylidene) dianiline.

In addition, when the liquid crystal aligning agent of this invention is used for formation of the liquid crystal aligning film in the liquid crystal display element of a vertical alignment type (VA type), in addition to the above-mentioned specific diamine, cholestanyloxy-3,5- Diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid Cholestanyl, 3,5-diaminobenzoic acid cholestenyl, 3,5-diaminobenzoic acid ranostanyl, 3,6-bis (4-aminobenzoyloxy) cholestane, 3,6-bis (4-amino It is preferable to further contain at least 1 type (henceforth "specific diamine 2") chosen from the group which consists of a phenoxy) cholestan and the compound represented by said formula (A-1).

When the liquid crystal aligning agent of this invention is used for formation of the liquid crystal aligning film in VA type | mold vertical alignment type liquid crystal display element, the preferable use ratio with respect to all the diamine of the said specific diamine 1 and the specific diamine 2 is as follows. same.

Specific diamine 1: Preferably it is 20 to 97%, More preferably, it is 50 to 95%, Especially preferably, it is 60 to 90%

Specific diamine 2: Preferably it is 3 to 80 mol%, More preferably, it is 5 to 50%, Especially preferably, it is 10 to 40%

In this case, it is preferable to make the use ratio of the sum total of the said specific diamine 1 and the specific diamine 2 into 100 mol% with respect to all diamine.

On the other hand, the liquid crystal aligning agent of this invention is liquid crystal display elements (for example, TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, transverse electric field system (for example, IPS (In-Plane Switching), FFS) other than VA type). (Fringe Field Switching, etc.), etc.), when used for formation of the liquid crystal aligning film, the preferable use ratio with respect to all the diamine of the said specific diamine 1 and the specific diamine 2 is as having described below.

Specific diamine 1: Preferably it is 50 mol% or more, More preferably, it is 80 mol% or more, Especially preferably, it is 100 mol%

Specific diamine 2: Preferably it is 30 mol% or less, More preferably, it is 10% or less, Especially preferably, 0 mol%

In this case, as a diamine, it is preferable to make the sum total of the said specific diamine 1 and the specific diamine 2 into 100 mol%, and it is more preferable to use only the specific diamine 1 only.

<Molecular weight regulator>

When synthesize | combining the said polyamic acid, you may synthesize | combine the terminal-modified polymer with the said tetracarboxylic dianhydride and diamine using a suitable molecular weight modifier. By making polyamic acid into such a terminal-modified polymer, the liquid crystal aligning agent containing at least 1 sort (s) of polymer chosen from the group which consists of the said polyamic acid and polyimide formed by dehydrating and ring-closing this impairs the effect of this invention. The coating property (printability) is further improved without.

As said molecular weight modifier, an acid monoanhydride, a monoamine compound, a monoisocyanate compound, etc. are mentioned, for example. As these specific examples, as acid monoanhydride, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, n-hexadecylsuccinic anhydride My back;

As a monoamine compound, For example, aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, etc .;

As a monoisocyanate compound, phenyl isocyanate, naphthyl isocyanate, etc. are mentioned, respectively.

It is preferable to set it as 20 weight part or less with respect to a total of 100 weight part of tetracarboxylic dianhydride and diamine to be used, and, as for the usage ratio of a molecular weight modifier, it is more preferable to set it as 10 weight part or less.

Synthesis of Polyamic Acid

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

Synthesis reaction of polyamic acid, Preferably in an organic solvent, Preferably it is -20 degreeC-150 degreeC, More preferably, it is 0-100 degreeC, Preferably it is 0.1-24 hours, More preferably, it is 0.5-12 Time is done.

Here, as an organic solvent, a non-protic polar solvent, a phenol, its derivatives, alcohol, a ketone, ester, an ether, halogenated hydrocarbon, hydrocarbon, etc. are mentioned, for example.

As specific examples of these organic solvents, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ- as the aprotic polar solvent. Butyrolactone, tetramethylurea, hexamethylphosphortriamide and the like;

As said phenol derivative, For example, m-cresol, xylenol, a halogenated phenol etc .;

As said alcohol, For example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1, 4- butanediol, triethylene glycol, ethylene glycol monomethyl ether, etc .;

As said ketone, For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc .;

As said ester, For example, ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, diethyl oxalate, diethyl malonate, etc .;

Examples of the ether include diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, Ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetra Hydrofuran and the like;

Examples of the halogenated hydrocarbons include dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, and the like;

Examples of the hydrocarbons include hexane, heptane, octane, benzene, toluene, xylene, isoamylpropionate, isoamyl isobutylate, diisopentyl ether, and the like.

Among these organic solvents, at least one selected from the group consisting of aprotic polar solvents and phenols and derivatives thereof (first group of organic solvents), or at least one type and alcohols selected from the first group of organic solvents, Preference is given to using mixtures with at least one member selected from the group consisting of ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons (organic solvents of the second group). In the latter case, the use ratio of the second group of organic solvents is preferably 50% by weight or less, and more preferably 40% by weight or less with respect to the sum of the organic solvents of the first group and the organic solvents of the second group. Furthermore, it is preferable that it is 30 weight% or less.

The amount (a) of the organic solvent is preferably set to an amount such that the total amount (b) of the tetracarboxylic dianhydride and the diamine is 0.1 to 50% by weight relative to the total amount (a + b) of the reaction solution.

As described above, a reaction solution obtained by dissolving polyamic acid is obtained.

This reaction solution may be used as it is for preparation of a liquid crystal aligning agent, may be provided to preparation of a liquid crystal aligning agent after isolating the polyamic acid contained in a reaction solution, or after refine | purifying the isolated polyamic acid, preparation of a liquid crystal aligning agent You may provide to. When polyamic acid is dehydrated and closed, and it is set as polyimide, the said reaction solution may be used for a dehydration ring-closure reaction as it is, may be used for dehydration ring-closure reaction after isolating the polyamic acid contained in the reaction solution, or the isolated polyamic acid After purification, the dehydration ring-closure reaction may be used. Isolation and purification of polyamic acid can be performed according to a well-known method.

Synthesis of Polyimide

The said polyimide can be obtained by dehydrating and ring-closing the polyamic acid synthesize | combined as mentioned above and imidating.

The polyimide in the present invention may be a complete imide obtained by dehydrating and ring-closing all the dark acid structures possessed by the polyamic acid as a precursor thereof, or by dehydrating and ring-closing only a part of the dark acid structure to coexist with the dark acid structure and the imide ring structure. Imide may be sufficient. It is preferable that the imidation ratio of the polyimide in this invention is 30% or more, It is more preferable that it is 50% or more, It is preferable that it is especially 55% or more. This imidation ratio shows the ratio which the number of the imide ring structure to the sum of the number of the dark acid structures of a polyimide, and the number of imide ring structures occupies as a percentage. Here, part of the imide ring may be an isoimide ring.

The dehydration ring closure of the polyamic acid is preferably carried out by a method of heating the polyamic acid, or by dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to the solution and heating it as necessary. . Among these, it is preferable by the latter method.

In the method of adding a dehydrating agent and a dehydrating ring-closure catalyst in the solution of the polyamic acid, for example, 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 shall be 0.01-20 mol with respect to 1 mol of dark acid structures of polyamic acid. As the dehydration ring closure catalyst, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used, for example. It is preferable that the usage-amount of a dehydration ring-closure catalyst shall be 0.01-10 mol with respect to 1 mol of dehydrating agents used. As an organic solvent used for a dehydration ring-closure reaction, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid is mentioned. The reaction temperature of the dehydration ring-closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

In this way, a reaction solution containing a polyimide is obtained. This reaction solution may be provided as it is to preparation of a liquid crystal aligning agent as it is, may be provided to preparation of a liquid crystal aligning agent after removing a dehydrating agent and a dehydration ring-closure catalyst from a reaction solution, and after isolation of a polyimide to preparation of a liquid crystal aligning agent You may provide, or after refine | purifying an isolated polyimide, you may provide for preparation of a liquid crystal aligning agent. These purification operations can be performed according to a well-known method.

<Solution Viscosity of Polymer>

When the specific polymer obtained as mentioned above is made into the solution of 10 weight% of concentration, it is preferable to have a solution viscosity of 20-800 mPa * s, and it is more preferable to have a solution viscosity of 30-500 mPa * s.

The solution viscosity (mPa * s) of the said polymer is 10 weight% of the density | concentration prepared using the quantity solvent of the said polymer (for example, (gamma) -butyrolactone, N-methyl- 2-pyrrolidone, etc.). About a polymer solution, it is the value measured at 25 degreeC using the E-type rotational viscometer.

<Other additives>

Although the liquid crystal aligning film of this invention contains the above-mentioned specific polymer as an essential component, you may contain other components as needed. As such other components, polymers other than the said specific polymer (henceforth "other polymer"), the compound which has at least 1 epoxy group in a molecule (henceforth "epoxy compound"), a functional silane compound Etc. can be mentioned.

[Other polymers]

The other polymer can be used for improving solution properties and electrical properties. Such other polymers are polymers other than the specific polymer, and are, for example, polyamic acid obtained by reacting tetracarboxylic dianhydride and diamine, and are 1S, 2S, 4R, 5R-cyclohexanetetracarbonate with respect to all tetracarboxylic dianhydrides. The polyamic acid having a content ratio of at least one selected from the group consisting of acid dianhydride and 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic dianhydride is less than 5 mol% or more than 80 mol% ( Hereinafter, "other polyamic acid"), polyimide formed by dehydrating and closing the polyamic acid (hereinafter referred to as "other polyimide"), polyamic acid ester, polyester, polyamide, polysiloxane, cellulose derivative, polyacetal , Polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylates and the like. Among these, other polyamic acid or other polyimide is preferable, and other polyamic acid is more preferable.

As tetracarboxylic dianhydride used for synthesizing the said other polyamic acid or other polyimide, although the thing similar to what was mentioned above as other tetracarboxylic dianhydride preferably used for synthesize | combining a specific polymer is mentioned preferably, Is 1,2,3,4-cyclobutanetetracarboxylic dianhydride, pyromellitic dianhydride, 2,3,5-tricarboxycyclopentyl acetic dianhydride and 1,3,3a, 4,5,9b-hexa It is preferable to use at least one member selected from the group consisting of hydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione. desirable.

As the diamine used to synthesize the other polyamic acid or other polyimide, it is preferable to use at least one selected from those exemplified above as the diamine used when synthesizing the specific polymer. Examples of the diamine used to synthesize other polyamic acid or other polyimide include 4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminobiphenyl and cholestanyloxy-2. Preference is given to using at least one member selected from the group consisting of, 4-diaminobenzene, 3,5-diaminobenzoic acid and 1,4-bis- (4-aminophenyl) -piperazine.

As a usage ratio of other polymer, it is 50 weight% or less, More preferably, it is 40 weight% or less with respect to the sum total of a polymer (it says the sum total of said specific polymer and other polymers, the same hereafter), and further 30 weights It is preferable that it is% or less. When using other polymer, when the use ratio is 0.1 weight% or more with respect to the sum total of a polymer, the effect of the addition will express significantly.

[Epoxy Compound]

An epoxy compound can be contained in the liquid crystal aligning agent of this invention for the purpose of further improving adhesiveness, heat resistance, etc. with respect to the board | substrate of the liquid crystal aligning film obtained.

As said epoxy compound, the epoxy compound which has two or more epoxy groups in a molecule | numerator is preferable, For example, ethylene glycol diglycidyl ether, polyethyleneglycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol di Glycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylol propane triglycidyl ether, 2,2-dibromoneopentylglycol diglycidyl ether, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycid) Dilaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl-benzylamine, N, N-di Glycidyl-aminomethylcyclohexane, N, N- diglycidyl cyclohexylamine, etc. are mentioned as a preferable thing. .

When the use ratio is too small, the desired effect as described above is not sufficiently exhibited. On the other hand, when the use ratio is excessive, the reworkability and rubbing resistance of the liquid crystal alignment film are impaired. From such a viewpoint, the compounding ratio of the epoxy compound is preferably 30 parts by weight or less, more preferably 0.1 to 15 parts by weight, and more preferably 0.5 to 8 parts by weight with respect to 100 parts by weight of the total polymer. More preferably, it is especially preferable to set it as 1-3 weight part.

[Functional silane compound]

As said functional silane compound, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 2-aminopropyl trimethoxysilane, 2-aminopropyl triethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxy Silane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimeth Methoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecan, 10-triethoxysilyl-1,4,7-triazadecan, 9-trimethoxysilyl-3 , 6-Diazonayl acetate, 9-triethoxysilyl-3,6-diazanyl acetate, 9-trimethoxysilyl-3,6-methyl diazanoanoate, 9-triethoxy Methyl 3,6-diazananoic acid, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltrie A methoxysilane, 3-glycidoxy propyl trimethoxysilane, 3-glycidoxy propyl triethoxysilane, etc. are mentioned.

The blending ratio of these functional silane compounds is preferably 2 parts by weight or less, more preferably 0.02 to 0.2 parts by weight based on 100 parts by weight of the polymer in total.

<Liquid crystal aligning agent>

The liquid crystal aligning agent of this invention is melt | dissolved and contained in the organic solvent, Preferably the specific polymer mentioned above and other additives mix | blended arbitrarily as needed are comprised.

As an organic solvent used for the liquid crystal aligning agent of this invention, N-methyl- 2-pyrrolidone, (gamma) -butyrolactone, (gamma) -butyrolactam, N, N- dimethylformamide, N, N- Dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, ethylene glycol methyl ether, ethylene Glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether , Diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, di Isobutyl ketone, isoamyl propionate, isoamyl isobutyrate, di-isopentyl ether, ethylene carbonate, propylene carbonate, and the like. These can be used independently, or can mix and use 2 or more types.

Although solid content concentration (the ratio which the total weight of components other than the solvent of a liquid crystal aligning agent occupies in the total weight of a liquid crystal aligning agent) in the liquid crystal aligning agent of this invention is selected suitably in consideration of viscosity, volatility, etc., Preferably It is the range of 1-10 weight%. That is, the liquid crystal aligning agent of this invention is apply | coated to the surface of a board | substrate as mentioned later, Preferably, the coating film which becomes a coating film which is a liquid crystal aligning film, or a liquid crystal aligning film is formed by heating, However, when solid content concentration is less than 1 weight%, this coating film When the film thickness of the film becomes too small to obtain a good liquid crystal alignment film, and on the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film becomes excessive and a good liquid crystal alignment film cannot be obtained. Viscosity increases and application characteristics are inferior.

The range of especially preferable solid content concentration changes with the method used when apply | coating a liquid crystal aligning agent to a board | substrate. For example, in the case of a spinner method, the range of 1.5 to 4.5 weight% of solid content concentration is especially preferable. In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by weight, and the solution viscosity is in the range of 12 to 50 mPa · s. When using the inkjet method, it is especially preferable to make solid content concentration into the range of 1 to 5 weight%, and to make solution viscosity into the range of 3-15 mPa * s.

The temperature at the time of preparing the liquid crystal aligning agent of this invention becomes like this. Preferably it is 10-50 degreeC, More preferably, it is 20-30 degreeC.

<Liquid crystal display element>

The liquid crystal display element of this invention is equipped with the liquid crystal aligning film formed from the above-mentioned liquid crystal aligning agent of this invention. In more detail, the liquid crystal display element of this invention consists of arrange | positioning a polarizing plate in the both outer surface of a liquid crystal cell, and the said liquid crystal cell is made so that each liquid crystal aligning film surface may face two sheets of the board | substrate which has a liquid crystal aligning film. It has a structure which clamped the liquid crystal layer in the clearance gap which opposes, and the said liquid crystal aligning film is formed from the liquid crystal aligning agent of this invention, It is characterized by the above-mentioned.

Such a liquid crystal display element of this invention can be manufactured by the process of the following (1)-(3), for example. In the step (1), the substrate used differs depending on the desired operation mode. Steps (2) and (3) are common to each operation mode.

(1) First, the liquid crystal aligning agent of this invention is apply | coated on a board | substrate, and then a coating film is formed on a board | substrate by heating a coating surface.

(1-1) When manufacturing a TN type, STN type, or VA type liquid crystal display element, two board | substrates with which the patterned transparent conductive film is formed in one side are made into a pair, and on each transparent conductive film formation surface, The liquid crystal aligning agent of this invention is apply | coated preferably by the offset printing method, the spin coating method, or the inkjet printing method, respectively, and then a coating film is formed by heating each application surface. Here, as a board | substrate, For example, glass, such as float glass and a soda glass; A transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and poly (alicyclic olefin) can be used. As the transparent conductive film formed on one side of the substrate, an NESA film (registered trademark of PPG Co., Ltd.) made of tin oxide (SnO ₂ ), an ITO film made of indium tin oxide (In ₂ O ₃ -SnO ₂ ), or the like can be used. In order to obtain a patterned transparent conductive film, for example, by forming a patternless transparent conductive film and then forming a pattern by photo-etching, using a mask having a desired pattern when forming the transparent conductive film, or the like can do. At the time of coating of 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, and the like are previously added to the surface on which the coating film should be formed on the substrate surface. The pretreatment to apply may be performed.

After application of the liquid crystal aligning agent, preliminary heating (prebaking) is preferably performed for the purpose of preventing liquid flow of the applied alignment agent. Prebaking temperature becomes like this. Preferably it is 30-200 degreeC, More preferably, it is 40-150 degreeC, Especially preferably, it is 40-100 degreeC. Prebaking time becomes like this. Preferably it is 0.25-10 minutes, More preferably, it is 0.5-5 minutes. Thereafter, the solvent is completely removed, and a firing (postbaking) step is performed for the purpose of thermally imidating the polyamic acid as necessary. This baking (post-baking) temperature becomes like this. Preferably it is 80-300 degreeC, More preferably, it is 120-250 degreeC. Post-baking time becomes like this. Preferably it is 5-200 minutes, More preferably, it is 10-100 minutes. Thus, the film thickness of the film formed becomes like this. Preferably it is 0.001-1 micrometer, More preferably, it is 0.005-0.5 micrometer.

(1-2) On the other hand, when manufacturing a transverse electric field type liquid crystal display element, the conductive film formation surface of the board | substrate with which the comb-shaped patterned transparent conductive film was formed in the single side | surface, and the single side | surface of the opposing board | substrate in which the conductive film is not formed is provided. The liquid crystal aligning agent of this invention is apply | coated to each, and then a coating film is formed by heating each application surface.

In this case, the material of the substrate and the transparent conductive film, the patterning method of the transparent conductive film, the pretreatment of the substrate, the coating method of the liquid crystal aligning agent, the heating method after applying the liquid crystal aligning agent, and the film thickness of the formed coating film are described in (1-1). Same as).

(2) When the liquid crystal display element manufactured by the method of this invention is a VA type liquid crystal display element, although the coating film formed as mentioned above can be used as a liquid crystal aligning film as it is, the rubbing process mentioned next as needed as needed. You may provide for use after performing this.

On the other hand, when manufacturing liquid crystal display elements other than VA type, a rubbing process is given to the coating film formed as mentioned above, and it is set as a liquid crystal aligning film.

The rubbing treatment can be performed by rubbing in a predetermined direction with a roll wound with a cloth made of fibers such as nylon, rayon, cotton and the like on the coating film surface formed as described above. Thereby, the orientation ability of a liquid crystal molecule is provided to a coating film, and it becomes a liquid crystal aligning film.

Moreover, the process which changes the pretilt angle of a some area | region of a liquid crystal aligning film by irradiating an ultraviolet-ray to a part of liquid crystal aligning film, for example with respect to the liquid crystal aligning film formed as mentioned above (patent document 11 (Japanese Patent Laid-Open No. 6-222366). No.) and Patent Document 12 (Japanese Patent Laid-Open No. Hei 6-281937)), after forming a resist film on a part of the surface of the liquid crystal alignment film, a rubbing treatment is performed in a direction different from the preceding rubbing treatment, and then a resist film is removed. It is possible to improve the field of view characteristics of the liquid crystal display device obtained by making the liquid crystal alignment film have different liquid crystal alignment ability for each region (see Patent Document 13 (Japanese Patent Laid-Open No. 5-107544)).

(3) The liquid crystal cell is manufactured by preparing two board | substrates with a liquid crystal aligning film as mentioned above, and arrange | positioning a liquid crystal between two board | substrates which oppose. Here, when the rubbing process is performed with respect to a coating film, two board | substrates are mutually arrange | positioned so that the rubbing direction in each coating film may mutually become a predetermined angle, for example, orthogonal or antiparallel.

In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example.

The first method is a conventionally known method. First, two substrates are disposed to face each other through a gap (cell gap) so that the respective liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded together using a sealing agent, and the cells partitioned by the substrate surface and the sealing agent. After the liquid crystal is injected and filled into the gap, the liquid crystal cell can be manufactured by sealing the injection hole.

The second method is a method called an ODF (One Drop Fill) method. After apply | coating an ultraviolet-ray curable sealing compound, for example to the predetermined place on one board | substrate among two board | substrates which formed the liquid crystal aligning film, and further dropping a liquid crystal in several places on the liquid crystal aligning film surface, a liquid crystal aligning film A liquid crystal cell can be manufactured by bonding another board | substrate so that this may oppose, spreading a liquid crystal on the whole surface of a board | substrate, then irradiating an ultraviolet light to the whole surface of a board | substrate, and hardening a sealing compound.

Even in the case of any of the methods, the liquid crystal cell produced as described above is subsequently heated to a temperature at which the used liquid crystal takes an isotropic phase, and then gradually cooled to room temperature, thereby allowing flow orientation during liquid crystal injection. It is desirable to remove.

And the liquid crystal display element of this invention can be obtained by bonding a polarizing plate to the outer surface of a liquid crystal cell.

Here, as a sealing agent, the epoxy resin etc. which contain the hardening agent and the aluminum oxide sphere as a spacer can be used, for example.

As said liquid crystal, a nematic liquid crystal, a smectic liquid crystal, etc. can be used, for example, a nematic liquid crystal is preferable among these, For example, a siphon base liquid crystal, a subfamily clock liquid crystal, a biphenyl liquid crystal, a phenyl cyclohexane type A liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, a biphenyl cyclohexane type liquid crystal, a pyrimidine type liquid crystal, a dioxane type liquid crystal, a bicyclooctane type liquid crystal, a cuban type liquid crystal, etc. can be used. Moreover, for these liquid crystals, For example, cholesteric liquid crystals, such as cholesteryl chloride, cholesteryl nonaate, cholesteryl carbonate; Chiral agents such as those sold under the trade names C-15 and CB-15 (manufactured by Merck); Strong dielectric liquid crystals such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate may be further added and used.

As a polarizing plate bonded to the outer surface of a liquid crystal cell, the polarizing plate which consists of a polarizing plate called "H film" which absorbed iodine while extending | stretching polyvinyl alcohol, and sandwiched between the cellulose acetate protective films, or the H film itself is mentioned. .

(Example)

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not restrict | limited to these Examples. The solution viscosity of each polymer solution in a polymerization example, and the imidation ratio of polyimide were measured by the following method.

[Solution Viscosity of Polymer Solution]

The solution viscosity (mPa * s) of the polymer solution was measured at 25 degreeC using the E-type rotational viscometer in the solvent and concentration described in each synthesis example.

[Imidation Rate of Polyimide]

A small amount of the polyimide solution was collected and poured into pure water. The precipitate obtained was dried under reduced pressure at room temperature, and then dissolved in deuterated dimethyl sulfoxide. The tetramethylsilane was used as reference material at room temperature for ¹ H-NMR. Was measured. H-NMR spectrum obtained from the ^first, to the imidization ratio was calculated according to the equation represented by the formula (1).

Imidation ratio (%) = (1-A ¹ / A ² × α) × 100 (1)

(In Formula (1), A ¹ is the peak area derived from the proton of the NH group which appears in the vicinity of 10 ppm of chemical shift,

A ² is the peak area derived from other protons,

α is the number ratio of the other protons to one proton of the NH group in the precursor (polyamic acid) of the polymer)

<Synthesis and stability evaluation of the polymer for TN type liquid crystal aligning agent>

[Synthesis example of polyamic acid as a specific polymer]

Synthesis Example A-TN1

112 g (0.50 mol) of 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic acid dianhydride as tetracarboxylic dianhydride and 109 g (0.50 mol) of pyromellitic dianhydride and 4,4'-diaminodiphenylmethane as diamine Polyamic acid (A-TN1) by dissolving 198 g (1.0 mol) in a mixed solvent consisting of 246 g of N-methyl-2-pyrrolidone and 2,213 g of γ-butyrolactone and reacting at 40 ° C for 3 hours. The solution containing 15 weight% of was obtained. The solution viscosity of this solution was 179 mPa · s.

When this polymer solution was left to stand at 20 degreeC for 3 days, storage stability was favorable, without gelatinizing.

Synthesis Example A-TN2

67 g (0.30 mol) of 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 153 g (0.70 mol) of pyromellitic dianhydride and 4,4'-diaminodiphenylmethane as diamine Polyamic acid (A-TN2) by dissolving 198 g (1.0 mol) in a mixed solvent consisting of 246 g of N-methyl-2-pyrrolidone and 2,213 g of γ-butyrolactone, and reacting at 40 ° C for 3 hours. The solution containing 15 weight% of was obtained. The solution viscosity of this solution was 153 mPa · s.

When this polymer solution was left to stand at 20 degreeC for 3 days, storage stability was favorable, without gelatinizing.

[Synthesis example of other polyamic acid]

Synthesis Example a-TN3

109 g (0.50 mol) of pyromellitic dianhydride as tetracarboxylic dianhydride and 98 g (0.50 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 4,4'-diaminodiphenylmethane as diamine Polyamic acid (a-TN3) by dissolving 198 g (1.0 mol) in a mixed solvent consisting of 230 g of N-methyl-2-pyrrolidone and 2,068 g of γ-butyrolactone and reacting at 40 ° C for 3 hours. The solution containing 15 weight% of was obtained. The solution viscosity of this solution was 193 mPa · s.

When this polymer solution was left to stand at 20 degreeC for 3 days, storage stability was favorable, without gelatinizing.

[Synthesis example of polyimide as a specific polymer]

Synthesis Example B-TN1

112 g (0.50 mol) of 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 112 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic dianhydride and p- as diamine 106 g (0.985 mole) of phenylenediamine and 7.8 g (0.015 mole) of 3- (3,5-diaminobenzoyloxy) cholestan are dissolved in 3,042 g of N-methyl-2-pyrrolidone, and 6 hours at 60 ° C. By reacting, the solution containing polyamic acid was obtained. The solution viscosity of the polyamic acid solution obtained here was 160 mPa · s.

3,380 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 395 g of pyridine and 306 g of acetic anhydride were added, and the dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring closure reaction, the solvent in the system is solvent-substituted with fresh γ-butyrolactone (the pyridine and acetic anhydride used in the imidation reaction in this operation are removed to the outside of the system, hereinafter the same), and further concentrated. A solution containing 10% by weight of polyimide (B-TN1) having a dehydration rate of about 94% was obtained.

The solution viscosity was fractionated and the solution viscosity measured as a solution of 6 weight% of the addition of (gamma) -butyrolactone was 28 mPa * s.

When this polymer solution was left to stand at 20 degreeC for 3 days, storage stability was favorable, without gelatinizing.

[Synthesis example of other polyimide]

Synthesis Example b-TN2

110 g (0.50 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-) as tetracarboxylic dianhydride 155 g (0.50 mol) of 2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione, 92 g (0.87 mol) of p-phenylenediamine as diamine, bisaminopropyl 25 g (0.10 mol) of tetramethyldisiloxane and 13 g (0.02 mol) of 3,6-bis (4-aminobenzoyloxy) cholestane and 2.7 g (0.030 mol) of aniline as monoamine were added to N-methyl-2-pyrrolidone. It melt | dissolved in 960g and reacted at 60 degreeC for 6 hours, and obtained the solution containing polyamic acid. The solution viscosity measured as a small amount of the obtained polyamic acid solution, the addition of N-methyl- 2-pyrrolidone and making it the solution of 10 weight% of polyamic acid concentration was 59 mPa * s.

Subsequently, 2,700 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 396 g of pyridine and 409 g of acetic anhydride were added, and dehydration ring closing was performed at 110 degreeC for 4 hours. After the dehydration ring closure reaction, the solvent in the system was solvent-substituted with fresh γ-butyrolactone, and further concentrated, whereby about 2,520 g of a solution containing 15 wt% of polyimide (b-TN2) having an imidization ratio of about 95% was obtained. Got it. A small amount of this polyimide solution was collected, and the solution viscosity measured as a solution having a polyimide concentration of 6.0% by weight by adding γ-butyrolactone was 18 mPa · s.

When this polymer solution was left to stand at 20 degreeC for 3 days, storage stability was favorable, without gelatinizing.

Synthesis Example b-TN3

224 g (1.0 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 106 g (0.985 mol) of p-phenylenediamine as diamine and 3- (3,5-diaminobenzoyloxy) 7.8 g (0.015 mol) of cholestan was dissolved in 3,042 g of N-methyl-2-pyrrolidone, and reacted at 60 degreeC for 6 hours, and the solution containing polyamic acid was obtained. The solution viscosity of the polyamic acid solution obtained here was 181 mPa · s.

3,380 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 395 g of pyridine and 306 g of acetic anhydride were added, and the dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was solvent-substituted with fresh γ-butyrolactone and further concentrated to obtain a solution containing 10% by weight of polyimide (b-TN3) having an imidization ratio of about 95%.

A small amount of this solution was collected, and the solution viscosity measured as a solution having a concentration of 6% by weight by adding γ-butyrolactone was 35 mPa · s.

When this polymer solution was left to stand at 20 degreeC for 3 days, storage stability was favorable, without gelatinizing.

<Synthesis and stability evaluation of the polymer for VA type liquid crystal aligning agent>

[Synthesis example of polyimide as a specific polymer]

Synthesis Example B-VA1

112 g (0.50 mol) of 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 112 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic dianhydride and 3, as diamine 52 g (0.1 mole) of 5-diaminobenzoic acid cholestanyl, 49 g (0.1 mole) of cholestanyloxy-2,4-diaminobenzene and 87 g (0.80 mole) of p-phenylenediamine were N-methyl-2-pi It melt | dissolved in 1,652 g of ralidones, and it reacted at 60 degreeC for 6 hours, and obtained the polyamic acid solution. The solution viscosity measured as a small amount of the obtained polyamic-acid solution, the addition of N-methyl- 2-pyrrolidone as a solution of 10 weight% of polymer concentrations, was 79 mPa * s.

Subsequently, 3,835 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 79 g of pyridine and 102 g of acetic anhydride were added, and dehydration ring closing was performed at 110 degreeC for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was solvent-substituted with fresh N-methyl-2-pyrrolidone to obtain a solution containing about 15% by weight of polyimide (B-VA1) having an imidation ratio of about 51%. A small amount of the obtained polyimide solution was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 102 mPa · s.

When this polymer solution was left to stand at 20 degreeC for 3 days, storage stability was favorable, without gelatinizing.

Synthesis Example B-VA2

112 g (0.50 mol) of 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 112 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic dianhydride and 3, as diamine 52 g (0.1 mole) of 5-diaminobenzoic acid cholestanyl, 49 g (0.1 mole) of cholestanyloxy-2,4-diaminobenzene and 87 g (0.80 mole) of p-phenylenediamine were N-methyl-2-pi It melt | dissolved in 1,652 g of ralidones, and it reacted at 60 degreeC for 6 hours, and obtained the polyamic acid solution. A small amount of the obtained polyamic acid solution was aliquoted, and the solution viscosity measured as a solution having a polymer concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 71 mPa · s.

Subsequently, 3,835 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 79 g of pyridine and 102 g of acetic anhydride were added, and dehydration ring closing was performed at 110 degreeC for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was solvent-substituted with fresh N-methyl-2-pyrrolidone to obtain a solution containing about 15% by weight of polyimide (B-VA2) having an imidation ratio of about 48%. A small amount of the obtained polyimide solution was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 99 mPa · s.

When this polymer solution was left to stand at 20 degreeC for 3 days, storage stability was favorable, without gelatinizing.

Synthesis Example B-VA3

45 g (0.20 mol) of 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 180 g (0.80 mol) of 2,3,5-tricarboxycyclopentyl acetic dianhydride and 3, as diamine 105 g (0.20 mol) of 5-diaminobenzoic acid cholestanyl and 87 g (0.80 mol) of p-phenylenediamine were dissolved in 1,663 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours to obtain poly A dark acid solution was obtained. The solution viscosity measured as a small amount of the obtained polyamic-acid solution, the addition of N-methyl- 2-pyrrolidone as a solution of 10 weight% of polymer concentrations, was 59 mPa * s.

Subsequently, 3,861 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 79 g of pyridine and 102 g of acetic anhydride were added, and dehydration ring closure was performed at 110 degreeC for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was solvent-substituted with fresh N-methyl-2-pyrrolidone to obtain a solution containing about 15% by weight of polyimide (B-VA3) having an imidization ratio of about 47%. A small amount of the obtained polyimide solution was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 80 mPa · s.

When this polymer solution was left to stand at 20 degreeC for 3 days, storage stability was favorable, without gelatinizing.

Synthesis Example B-VA4

45 g (0.20 mol) of 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 180 g (0.80 mol) of 2,3,5-tricarboxycyclopentyl acetic dianhydride and 3, as diamine 105 g (0.20 mol) of 5-diaminobenzoic acid cholestanyl and 87 g (0.80 mol) of p-phenylenediamine were dissolved in 1,663 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours to obtain poly A dark acid solution was obtained. The solution viscosity measured as a small amount of the obtained polyamic-acid solution, the addition of N-methyl- 2-pyrrolidone as a solution of 10 weight% of polymer concentrations, was 66 mPa * s.

Subsequently, 3,861 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 79 g of pyridine and 102 g of acetic anhydride were added, and dehydration ring closure was performed at 110 degreeC for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was solvent-substituted with fresh N-methyl-2-pyrrolidone to obtain a solution containing about 15% by weight of polyimide (B-VA4) having an imidization ratio of 50%. A small amount of the obtained polyimide solution was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 89 mPa · s.

When this polymer solution was left to stand at 20 degreeC for 3 days, storage stability was favorable, without gelatinizing.

Synthesis Example B-VA5

135 g (0.60 mol) of 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic acid dianhydride as tetracarboxylic dianhydride and 90 g (0.40 mol) of 2,3,5-tricarboxycyclopentyl acetic dianhydride and 3, as diamine 105 g (0.20 mol) of 5-diaminobenzoic acid cholestanyl, 65 g (0.60 mol) of p-phenylenediamine and 30 g (0.20 mol) of 3,5-diaminobenzoic acid were added to 1,697 g of N-methyl-2-pyrrolidone. It melt | dissolved and reacted at 60 degreeC for 6 hours, and obtained the polyamic acid solution. A small amount of the obtained polyamic acid solution was added, and the solution viscosity measured as a solution having a polymer concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 50 mPa · s.

Subsequently, 3,939 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 119 g of pyridine and 153 g of acetic anhydride were added, and dehydration ring closure was performed at 110 degreeC for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was solvent-substituted with fresh N-methyl-2-pyrrolidone to obtain a solution containing about 15% by weight of polyimide (B-VA5) having an imidization ratio of about 66%. A small amount of the obtained polyimide solution was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 79 mPa · s.

When this polymer solution was left to stand at 20 degreeC for 3 days, storage stability was favorable, without gelatinizing.

Synthesis Example B-VA6

45 g (0.20 mol) of 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 179 g (0.80 mol) of 2,3,5-tricarboxycyclopentyl acetic dianhydride and 3, as diamine 131 g (0.25 mole) of 5-diaminobenzoic acid cholestanyl, 53 g (0.50 mole) of p-phenylenediamine and 38 g (0.25 mole) of 3,5-diaminobenzoic acid were added to 1,697 g of N-methyl-2-pyrrolidone. It melt | dissolved and reacted at 60 degreeC for 6 hours, and obtained the polyamic acid solution. A small amount of the obtained polyamic acid solution was aliquoted, and the solution viscosity measured as a solution having a polymer concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 58 mPa · s.

Subsequently, 3,939 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 119 g of pyridine and 153 g of acetic anhydride were added, and dehydration ring closure was performed at 110 degreeC for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was solvent-substituted with fresh N-methyl-2-pyrrolidone to obtain a solution containing about 15% by weight of polyimide (B-VA6) having an imidization ratio of about 69%. A small amount of the obtained polyimide solution was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 81 mPa · s.

When this polymer solution was left to stand at 20 degreeC for 3 days, storage stability was favorable, without gelatinizing.

[Synthesis example of other polyimide]

Synthesis Example b-VA7

224 g (1.0 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 52 g (0.10 mol) of 3,5-diaminobenzoic acid cholestanyl as diamine, cholestanyloxy-2, 49 g (0.10 mol) of 4-diaminobenzene and 87 g (0.80 mol) of p-phenylenediamine were dissolved in 1,652 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours to give a polyamic acid solution. Got it. The solution viscosity measured as a small amount of the obtained polyamic-acid solution, the addition of N-methyl- 2-pyrrolidone as a solution of 10 weight% of polymer concentrations, was 70 mPa * s.

Subsequently, 3,835 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 79 g of pyridine and 102 g of acetic anhydride were added, and dehydration ring closing was performed at 110 degreeC for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was solvent-substituted with fresh N-methyl-2-pyrrolidone to obtain a solution containing about 15% by weight of polyimide (b-VA7) having an imidation ratio of about 49%. A small amount of the obtained polyimide solution was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 80 mPa · s.

When this polymer solution was left to stand at 20 degreeC for 3 days, storage stability was favorable, without gelatinizing.

Synthesis Example b-VA8

224 g (1.0 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride, 105 g (0.20 mol) of 3,5-diaminobenzoic acid cholestanyl as diamine, 65 g of p-phenylenediamine 0.60 mol) and 30 g (0.20 mol) of 3,5-diaminobenzoic acid were dissolved in 1,697 g of N-methyl-2-pyrrolidone, and reacted at 60 ° C. for 6 hours to obtain a polyamic acid solution. A small amount of the obtained polyamic acid solution was added, and the solution viscosity measured as a solution having a polymer concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 50 mPa · s.

Subsequently, 3,939 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 119 g of pyridine and 153 g of acetic anhydride were added, and dehydration ring closure was performed at 110 degreeC for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was solvent-substituted with fresh N-methyl-2-pyrrolidone to obtain a solution containing about 15% by weight of polyimide (b-VA8) having an imidization ratio of about 67%. A small amount of the obtained polyimide solution was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 73 mPa · s.

When this polymer solution was left to stand at 20 degreeC for 3 days, storage stability was favorable, without gelatinizing.

<Synthesis and stability evaluation of the polymer for IPS type liquid crystal aligning agent>

[Synthesis example of polyamic acid as a specific polymer]

Synthesis Example A-IPS1

45 g (0.20 mol) of 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 174 g (0.80 mol) of pyromellitic dianhydride and 108 g (1.0 mol) of p-phenylenediamine as diamine Was dissolved in 1,900 g of N-methyl-2-pyrrolidone and reacted at 40 ° C. for 3 hours to obtain a solution containing 15% by weight of polyamic acid (A-IPS1).

A small amount of this solution was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 75 mPa · s.

When this polymer solution was left to stand at 20 degreeC for 3 days, storage stability was favorable, without gelatinizing.

[Synthesis example of other polyamic acid]

Synthesis Example a-IPS2

Same as Synthesis Example A-IPS1 except that 190 g (0.85 mol) of 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic dianhydride and 33 g (0.15 mol) of pyromellitic dianhydride were used as tetracarboxylic dianhydride. The solution containing 15 weight% of polyamic acid (a-IPS2) was obtained.

This solution was aliquoted in small amounts, and the solution viscosity measured as the solution of 10 weight% of polyamic acid concentration by adding N-methyl- 2-pyrrolidone was 63 mPa * s.

When this polymer solution was left to stand at 20 degreeC for 3 days, gelation was seen and the storage stability was poor.

Regarding this polyamic acid (a-IPS2), remaining evaluation was not performed.

[Synthesis example of polyamic acid as a specific polymer]

Synthesis Example A-IPS3

180 g (0.80 mol) of 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic dianhydride and 44 g (0.20 mol) of pyromellitic dianhydride as tetracarboxylic dianhydride and 4,4'-diaminodiphenyl ether as diamine Polyamic acid (A-IPS3) was dissolved by dissolving 160 g (0.80 mol) and 110 g (0.20 mol) of p-phenylenediamine in 2,300 g of N-methyl-2-pyrrolidone and reacting at 40 ° C for 3 hours. The solution containing 15 weight% was obtained.

A small amount of the solution was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 74 mPa · s.

When this polymer solution was left to stand at 20 degreeC for 3 days, storage stability was favorable, without gelatinizing.

Synthesis Example A-IPS4

In the same manner as in Synthesis Example A-IPS3, except that 180 g (0.80 mol) of 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic dianhydride and 44 g (0.20 mol) of pyromellitic dianhydride were used as tetracarboxylic dianhydride. To obtain a solution containing 15% by weight of polyamic acid (A-IPS4).

A small amount of this solution was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 60 mPa · s.

When this polymer solution was left to stand at 20 degreeC for 3 days, storage stability was favorable, without gelatinizing.

Synthesis Example A-IPS5

180 g (0.80 mole) of 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic dianhydride and 44 g (0.20 mole) of pyromellitic dianhydride as tetracarboxylic dianhydride and 4,4'-diaminodiphenylamine as diamine 200 g (1.0 mole) was dissolved in 2,400 g of N-methyl-2-pyrrolidone and reacted at 40 ° C for 3 hours to obtain a solution containing 15% by weight of polyamic acid (A-IPS5).

A small amount of this solution was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 65 mPa · s.

When this polymer solution was left to stand at 20 degreeC for 3 days, storage stability was favorable, without gelatinizing.

Synthesis Example A-IPS6

180 g (0.80 mol) of 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic dianhydride and 44 g (0.20 mol) of pyromellitic dianhydride as tetracarboxylic dianhydride and 4,4'-diaminodiphenyl ether as diamine A solution containing 15% by weight of polyamic acid (A-IPS6) in the same manner as in Synthesis Example A-IPS5 except that 100 g (0.50 mol) and 100 g (0.50 mol) of 4,4'-diaminodiphenylamine were used, respectively. Got.

A small amount of this solution was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 70 mPa · s.

When this polymer solution was left to stand at 20 degreeC for 3 days, storage stability was favorable, without gelatinizing.

[Synthesis example of other polyamic acid]

Synthesis Example a-IPS7

224 g (1.0 mole) of 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 108 g (1.0 mole) of p-phenylenediamine as diamine were added to N-methyl-2-pyrrolidone 1,900. It melt | dissolved in g and reacted at 40 degreeC for 3 hours, and obtained the solution containing 15 weight% of polyamic acid (a-IPS7).

A small amount of this solution was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 99 mPa · s.

When this polymer solution was left to stand at 20 degreeC for 3 days, gelation was observed and storage stability was poor.

Regarding this polyamic acid (a-IPS7), the remaining evaluation was not performed.

Synthesis Example a-IPS8

Polyamic acid (a-IPS8) was weighed in the same manner as in Synthesis Example A-IPS5 except that 224 g (1.0 mol) of 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic dianhydride was used as tetracarboxylic dianhydride. The solution containing% was obtained.

Although this solution was in solution form at reaction temperature (40 degreeC), since gelation generate | occur | produced in the process of cooling this to room temperature, the viscosity was not able to be measured.

Regarding this polyamic acid (a-IPS8), remaining evaluation was not performed.

Synthesis Example a-IPS9

220 g (1.0 mole) of pyromellitic dianhydride as tetracarboxylic dianhydride and 110 g (1.0 mole) of p-phenylenediamine as diamine were dissolved in 1,800 g of N-methyl-2-pyrrolidone, and 3 hours at 40 degreeC. By reacting, the solution containing 15 weight% of polyamic acid (a-IPS9) was obtained.

The solution viscosity of this solution was 180 mPa · s.

When this polymer solution was left to stand at 20 degreeC for 3 days, storage stability was favorable, without gelatinizing.

Synthesis Example a-IPS10

220 g (1.0 mole) pyromellitic dianhydride as tetracarboxylic dianhydride and 160 g (0.80 mole) of 4,4'-diaminodiphenyl ether as diamine and 22 g (0.20 mole) of p-phenylenediamine as N-methyl- It dissolved in 2,300 g of 2-pyrrolidone and reacted at 40 degreeC for 3 hours, and the solution containing 15 weight% of polyamic acid (a-IPS10) was obtained.

A small amount of this solution was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 71 mPa · s.

When this polymer solution was left to stand at 20 degreeC for 3 days, storage stability was favorable, without gelatinizing.

Synthesis Example a-IPS11

200 g (0.90 mol) of pyromellitic dianhydride as tetracarboxylic dianhydride and 20 g (0.10 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 4,4'-diaminodiphenyl ether as diamine 160 g (0.80 mole) and 22 g (0.20 mole) of p-phenylenediamine were dissolved in 2,300 g of N-methyl-2-pyrrolidone and reacted at 40 ° C. for 3 hours to produce polyamic acid (a-IPS11). The solution containing 15 weight% was obtained.

A small amount of this solution was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 77 mPa · s.

When this polymer solution was left to stand at 20 degreeC for 3 days, storage stability was favorable, without gelatinizing.

[Synthesis example of polyimide as a specific polymer]

Synthesis Example B-IPS1

112 g (0.50 mol) of 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 112 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic dianhydride and p- as diamine 86 g (0.80 mol) of phenylenediamine, 23 g (0.10 mol) of 4,4'-diaminodiphenylmethane and 32 g (0.10 mol) of 4,4'-bis (trifluoromethyl) biphenyl It melt | dissolved in 2,100 g of pyrrolidone, and reacted at 40 degreeC for 3 hours, and obtained the polyamic acid solution. A small amount of the obtained polyamic acid solution was added, N-methyl-2-pyrrolidone was added, and the solution viscosity measured as a solution of 10 weight% of polymer concentrations was 40 mPa * s.

Next, 2,800 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 400 g of pyridine and 310 g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was solvent-substituted with γ-butyrolactone, and then concentrated to obtain 2,300 g of a solution containing 15% by weight of polyimide (B-IPS1) having an imidization ratio of about 92%. The solution was aliquoted in small amounts, and the viscosity measured as the solution of 10 weight% of polyimide concentrations by adding (gamma) -butyrolactone was 36 mPa * s.

When this polymer solution was left to stand at 20 degreeC for 3 days, storage stability was favorable, without gelatinizing.

Synthesis Example B-IPS2

As the tetracarboxylic dianhydride, 112 g (0.50 mol) of 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic dianhydride and 112 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic dianhydride were used. A polyamic acid solution was obtained in the same manner as in Synthesis example B-IPS1. A small amount of this solution was added, and the solution viscosity measured as a solution having a polymer concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 35 mPa · s.

Subsequently, after performing dehydration ring-closure reaction similarly to the synthesis example B-IPS1, the solvent in a system is substituted by gamma-butyrolactone, and it concentrates then, the polyimide (B-IPS2) of about 94% of imidation ratio is obtained. 2300 g of solutions containing 15 weight% were obtained. The solution was aliquoted in small amounts, and the viscosity measured as a solution of 10 weight% of polyimide concentration by adding (gamma) -butyrolactone was 34 mPa * s.

When this polymer solution was left to stand at 20 degreeC for 3 days, storage stability was favorable, without gelatinizing.

Synthesis Example B-IPS3

112 g (0.50 mol) of 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 112 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic dianhydride and p- as diamine 97 g (0.90 mol) of phenylenediamine and 32 g (0.10 mol) of 4,4'-bis (trifluoromethyl) biphenyl were dissolved in 2,000 g of N-methyl-2-pyrrolidone and reacted at 40 ° C. for 3 hours. Was carried out to obtain a polyamic acid solution. The solution viscosity measured as a small amount of the obtained polyamic-acid solution, the addition of N-methyl- 2-pyrrolidone as a solution of 10 weight% of polymer concentrations, was 46 mPa * s.

Subsequently, 2,700 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 400 g of pyridine and 310 g of acetic anhydride were added, and the dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was solvent-substituted with γ-butyrolactone, and then concentrated to give 2,300 g of a solution containing 15% by weight of polyimide (B-IPS3) having an imidization ratio of about 93%. A small amount of this solution was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by weight by adding γ-butyrolactone was 42 mPa · s.

When this polymer solution was left to stand at 20 degreeC for 3 days, storage stability was favorable, without gelatinizing.

Synthesis Example B-IPS4

As the tetracarboxylic dianhydride, 112 g (0.50 mol) of 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic dianhydride and 112 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic dianhydride were used. Polyamic acid solution was obtained similarly to the synthesis example B-IPS3. A small amount of this solution was added, and the solution viscosity measured as a solution having a polymer concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 35 mPa · s.

Subsequently, after performing dehydration ring-closure reaction similarly to the synthesis example B-IPS3, the solvent in a system was solvent-substituted by (gamma) -butyrolactone, and it concentrated then polyimide (B-IPS4) of about 91% of imidation ratio. 2,300 g of a solution containing 15 wt% of was obtained. A small amount of this solution was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by weight by adding γ-butyrolactone was 33 mPa · s.

When this polymer solution was left to stand at 20 degreeC for 3 days, storage stability was favorable, without gelatinizing.

[Synthesis example of other polyimide]

Synthesis Example b-IPS5

A polyamic acid solution was obtained in the same manner as in Synthesis Example B-IPS1 except that 220 g (1.0 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride was used as tetracarboxylic dianhydride. A small amount of this solution was added, and the solution viscosity measured as a solution having a polymer concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 48 mPa · s.

Subsequently, after performing dehydration ring-closure reaction similarly to the synthesis example B-IPS1, the solvent in a system is substituted by gamma-butyrolactone, and it concentrates, and the polyimide (b-IPS5) of about 93% of imidation ratio is then condensed. 2300 g of solutions containing 15 weight% were obtained. A small fraction of this solution was added, and the viscosity measured as a solution having a polyimide concentration of 10% by weight by adding γ-butyrolactone was 45 mPa · s.

When this polymer solution was left to stand at 20 degreeC for 3 days, storage stability was favorable, without gelatinizing.

Synthesis Example b-IPS6

A polyamic acid solution was obtained in the same manner as in Synthesis Example B-IPS4 except that 220 g (1.0 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride was used as tetracarboxylic dianhydride. A small amount of this solution was added, and the solution viscosity measured as a solution having a polymer concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 45 mPa · s.

Subsequently, after performing dehydration ring-closure reaction similarly to the synthesis example B-IPS4, the solvent in a system was solvent-substituted by (gamma) -butyrolactone, and it concentrated then, the polyimide (b-IPS6) of about 93% of imidation ratio was obtained. 2300 g of solutions containing 15 weight% were obtained. The solution was aliquoted in small portions, and the viscosity measured as a solution having a polyimide concentration of 10% by weight by adding γ-butyrolactone was 41 mPa · s.

When this polymer solution was left to stand at 20 degreeC for 3 days, storage stability was favorable, without gelatinizing.

<Preparation and evaluation of a TN type liquid crystal aligning agent>

Example TN-1

(I) Preparation of liquid crystal aligning agent

An amount equivalent to 80 parts by weight in terms of polyamic acid (A-TN1), which is a solution containing polyamic acid (A-TN1) obtained in Synthesis Example A-TN1, as a specific polymer, and Synthesis Example b-TN2 as another polymer The amount equivalent to 20 parts by weight in terms of polyimide (b-TN2), which is a solution containing polyimide (b-TN2) obtained in the above, was added, and N-methyl-2-pyrrolidone (NMP) and γ were added thereto. Butyrolactone (BL) and butyl cellosolve (BC) were added so that the final solvent composition was NMP: BL: BC = 17: 71: 12 (weight ratio), and further N, N, N 'as an epoxy compound. 2 weight part of and N'- tetraglycidyl-4,4'- diamino diphenylmethane were added, and the solution of 3.5 weight% of solid content concentration was prepared. After fully stirring this solution, the liquid crystal aligning agent was prepared by filtering using the filter of 1 micrometer of pore diameters.

(II) Evaluation of the liquid crystal aligning agent

(1) Preparation of TN type liquid crystal cell

The liquid crystal aligning agent prepared above is apply | coated to the transparent electrode surface of the glass substrate with a transparent electrode which consists of an ITO film using a liquid crystal aligning film printing machine (made by Nippon Shashin Inc.), and it heats on a 80 degreeC hotplate for 1 minute. (Prebaking) After removing a solvent, it heated on 10 degreeC hotplate for 10 minutes (postbaking), and formed the coating film of average film thickness of 600 Pa.

About this coating film, the rubbing process was performed by the rubbing machine which has the roll which wound the rayon cloth at roll rotation speed 500rpm, stage movement speed | rate 3cm / sec, and hairpin indentation length 0.4mm, and provided the liquid-crystal orientation ability. Thereafter, ultrasonic cleaning was performed in ultrapure water for 1 minute, and then dried in a 100 ° C clean oven for 10 minutes to obtain a substrate having a liquid crystal alignment film. This operation was repeated and the pair (2 sheets) of the board | substrate which has a liquid crystal aligning film was obtained.

Next, a 5.5-micrometer-diameter aluminum oxide containing epoxy resin adhesive is apply | coated to the outer edge of the surface which has one liquid crystal aligning film among the said pair of board | substrates, and a pair of board | substrates has a liquid crystal aligning film surface relative. The adhesive was hardened after opposing so that it might be pressed. Subsequently, after filling a nematic liquid crystal (Merck, MLC-6221) between a pair of board | substrates from a liquid crystal injection port, the liquid crystal cell was manufactured by sealing a liquid crystal injection port with an acryl-type photocuring adhesive.

(2) Evaluation of heat stability

The durability against heat stress was evaluated by using the voltage holding ratio as an index. As a measuring device of the voltage holding ratio, Toyo Technica Co., Ltd. make and model "VHR-1" were used.

About the liquid crystal cell manufactured above, after applying the voltage of 5V to 60 microseconds of application time and 167 milliseconds of span to a liquid crystal display element at 60 degreeC, voltage preservation rate was measured 167 milliseconds after voltage application release ( Initial Voltage Integrity VHR0).

Subsequently, about the liquid crystal display element after voltage preservation rate measurement before thermal stress application, after standing still in an oven at 100 degreeC for 1,000 hours, and applying thermal stress, it carried out similarly to the above, and measured voltage preservation rate again (voltage preservation rate after heat stress application). VHR1).

Using the values of VHR0 and VHR1 measured above, the following formula (1):

ΔVHR = VHR0-VHR1 (1)

The difference DELTA VHR of the voltage holding ratios before and after applying the thermal stress was obtained. When this value is within 5%, it can be evaluated that heat resistance is favorable.

The evaluation results are shown in Table 1.

Examples TN-2 and TN-3 and Comparative Examples tn-1 and tn-2

In the above Example TN-1, as a specific polymer and other polymers, solutions containing polymers of the kind and amount shown in Table 1, respectively, were used, and each solvent was added so that the final solvent composition was as shown in Table 1. Others were prepared and evaluated in the same manner as in Example TN-1 to prepare a liquid crystal aligning agent.

The evaluation results are shown in Table 1.

"-" In Table 1 shows that the polymer corresponding to the said column was not used. In Comparative Example tn-1, two kinds of polymers were mixed and used as other polymers.

The abbreviation of the solvent in Table 1 has the following meanings, respectively.

NMP: N-methyl-2-pyrrolidone

BL: γ-butyrolactone

BC: Butyl Cellosolve

<Preparation and evaluation of a VA type liquid crystal aligning agent>

Example VA-1

(I) Preparation of liquid crystal aligning agent

As a polymer, N-methyl-2-pyrrolidone and butyl cellosolve were added to a solution containing the polyimide (B-VA1) obtained in Synthesis Example B-VA1, and further N, N, N as an epoxy compound. 5 weight part of ', N'- tetraglycidyl-m-xylenediamine is added with respect to 100 weight part of used polyimides, and it fully stirs and a solvent composition N-methyl- 2-pyrrolidone: butyl cellosolve It was set as the solution of = 50: 50 (weight ratio) and solid content concentration 3.5 weight%. The liquid crystal aligning agent was prepared by filtering this solution using the filter of 1 micrometer of pore diameters.

(II) Evaluation of the liquid crystal aligning agent

(1) Preparation of VA type liquid crystal cell

On the transparent conductive film which consists of an ITO film formed on the single side | surface of the glass substrate of thickness 1mm, the liquid crystal aligning agent prepared above was apply | coated with a spinner, prebaking was carried out for 1 minute at 80 degreeC on a hotplate, and then hotplate phase By post-baking at 210 degreeC for 30 minutes, the coating film (liquid crystal aligning film) of 80 nm in film thickness was formed. This operation was repeated and two pieces (pair) of board | substrates which have a liquid crystal aligning film were obtained.

Next, an aluminum oxide sphere-containing epoxy resin adhesive having a diameter of 3.5 μm is applied to the outer edge of the surface having one liquid crystal alignment film among the pair of substrates, and the pair of substrates are faced to face each other so that the liquid crystal alignment films face each other. After that, the adhesive was cured. Subsequently, after filling a negative liquid crystal (MLC-6608 by Merck Co., Ltd.) between board | substrates from a liquid crystal injection port, the liquid crystal injection port was sealed with the acryl-type photocuring adhesive agent, and the liquid crystal cell was produced.

(2) Evaluation of heat stability

Using the liquid crystal cell produced above, heat resistance stability was evaluated in the same manner as in Example TN-1. However, in the case of the VA type liquid crystal cell, the heat resistance stability can be evaluated to be good when the value of the difference? VHR of the voltage holding ratio before and after heat stress is within 2%.

The evaluation results are shown in Table 2.

Examples VA-2 to VA-6 and Comparative Examples va-1 and va-2

In the said Example VA-1, the liquid crystal aligning agent was prepared and evaluated similarly to Example VA-1 except having used the solution containing the polymer of Table 2 as a polymer, respectively.

The evaluation results are shown in Table 2.

"-" In Table 2 shows that the polymer corresponding to the said column was not used.

The abbreviation of the solvent in Table 2 is the same as that of Table 1.

<Preparation and evaluation of IPS type liquid crystal aligning agent>

Example IPS-1

(I) Preparation of liquid crystal aligning agent

To the solution containing polyamic acid (A-IPS1) obtained in Synthesis Example A-IPS1 as a polymer, N-methyl-2-pyrrolidone and butyl cellosolve are added as a solvent, and N, N as an epoxy compound is further added. 5 parts by weight of, N ', N'-tetraglycidyl-m-xylenediamine is added to 100 parts by weight of the polyamic acid used, and the mixture is sufficiently stirred. The solvent composition is N-methyl-2-pyrrolidone: butyl cell. Low solution = 80:20 (weight ratio) and solid content concentration were used as the solution of 3.5 weight%. The liquid crystal aligning agent was prepared by filtering this solution using the filter of 1 micrometer of pore diameters.

(II) Evaluation of the liquid crystal aligning agent

(1) Preparation of liquid crystal cell

The liquid crystal cell was produced like the thing in Example TN-1 except having used the liquid crystal aligning agent prepared above, and the heat resistance stability was evaluated.

The evaluation results are shown in Table 3.

In addition, although the liquid crystal cell manufactured here is a TN type liquid crystal cell, the present inventors have empirically confirmed that a TN type liquid crystal cell can be used as a sample for heat stability stability evaluation of an IPS type liquid crystal cell. .

Examples IPS-2 to IPS-5 and Comparative Examples ips-1 to ips-3

In the said Example IPS-1, the liquid crystal aligning agent was prepared and evaluated similarly to Example IPS-1 except having used the solution containing the polymer of Table 3 as a polymer, respectively.

The evaluation results are shown in Table 3.

Examples IPS-6-9 and Comparative Examples ips-4 and ips-5

In Example IPS-1, a solution containing the polymers listed in Table 3 as polymers, respectively, was used as N-methyl-2-pyrrolidone (NMP), γ-butyrolactone (BL), and butylcell as solvents. A liquid crystal aligning agent was prepared in the same manner as in Example IPS-1 except that each of these solvents was added so that the final solvent composition was NMP: BL: BC = 10: 70: 20 (weight ratio) using a solution (BC). It prepared and evaluated.

The evaluation results are shown in Table 3.

"-" In Table 3 shows that the polymer corresponding to the said column was not used.

The abbreviation of the solvent in Table 3 is the same as that of Table 1.

Claims (6)

As a liquid crystal aligning agent containing at least 1 sort (s) of polymer chosen from the group which consists of polyamic acid obtained by making tetracarboxylic dianhydride and diamine react, and the polyimide formed by dehydrating and closing the said polyamic acid,
The tetracarboxylic dianhydride is at least one selected from the group consisting of 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic dianhydride and 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic dianhydride, It contains 5-80 mol% with respect to the total tetracarboxylic dianhydride, The said liquid crystal aligning agent characterized by the above-mentioned. The method of claim 1,
The tetracarboxylic dianhydride is 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic 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-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-2 anhydride, 2,4, 6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-2 anhydride and 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8 The liquid crystal aligning agent which further contains at least 1 sort (s) chosen from the group which consists of a 10- tetraone. The method of claim 1,
P-phenylenediamine, 3, 5- diamino benzoic acid, 4,4'- diamino diphenyl ether, 4,4'- diamino diphenylmethane, 2,2'- dimethyl- 4,4 '-Diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-diaminodiphenylamine and 4,4'-(m-phenyl The liquid crystal aligning agent containing at least 1 sort (s) chosen from the group which consists of a lendiisopropylidene) dianiline. 4. The method according to any one of claims 1 to 3,
The liquid crystal aligning agent which further contains the compound which has at least 1 epoxy group in a molecule | numerator. It formed with the liquid crystal aligning agent in any one of Claims 1-3, The liquid crystal aligning film characterized by the above-mentioned. The liquid crystal aligning film of Claim 5 is provided, The liquid crystal display element characterized by the above-mentioned.