KR101798375B1 - Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display device - Google Patents

Abstract

Disclosed is a liquid crystal aligning agent which is excellent in storage stability and which can maintain a high quality display even when the liquid crystal display element is used for a long time.
(Solution) The liquid crystal aligning agent is a liquid crystal alignment liquid containing at least one polymer selected from the group consisting of a polyamic acid obtained by reacting a tetracarboxylic acid dianhydride with a diamine and a polyimide obtained by dehydrating and ring- Wherein the tetracarboxylic acid dianhydride is at least one selected from the group consisting of 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic dianhydride and 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic dianhydride. And the species is contained in an amount of 5 to 80 mol% based on the total tetracarboxylic dianhydride.

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal alignment material, a liquid crystal alignment film, and a liquid crystal display device,

The present invention relates to a liquid crystal aligning agent and a liquid crystal display element. More particularly, the present invention relates to a liquid crystal aligning agent excellent in storage stability, particularly excellent in heat resistance, and a liquid crystal display element capable of high-quality display, suppressed display deterioration due to thermal stress, and capable of driving for a long time .

As the material of the liquid crystal alignment film used in the liquid crystal display element, a resin material such as polyimide, polyamide, polyamic acid, polyester and the like is known. Among them, a liquid crystal alignment film made of polyamic acid or polyimide has excellent heat resistance, mechanical strength, affinity with liquid crystal, and is used in many liquid crystal display devices (Patent Documents 1 to 6).

Among them, the polyamic acid has a high solubility in a general-purpose organic solvent, so that a liquid crystal aligning agent which facilitates the printing process in the production process of the liquid crystal display element can be obtained, and the resin has an advantage that the cost is low. However, a liquid crystal display element having a liquid crystal alignment film made of polyamic acid is vulnerable to thermal stress, and when the liquid crystal display element is driven for a long time, the voltage holding rate is deteriorated due to deterioration of the liquid crystal alignment film. In recent years, as exemplified by a liquid crystal television, the liquid crystal display device is designed on the premise that the lifetime of the liquid crystal display device exceeds 10 years. Therefore, even when the liquid crystal display element is driven for a long time, it is important to exhibit a stable voltage holding ratio for a long period of time in order to maintain a high-quality display, and improvement of the heat resistance reliability of the orientation film is urgently required. As a method for improving the heat resistance reliability (heat stress resistance) of the alignment film so far known, there are a method of increasing the chemical stability of the liquid crystal alignment film by adding an epoxy compound to the liquid crystal aligning agent (Patent Document 7) A method of forming an intermolecular crosslink at the time of baking a liquid crystal alignment film by applying the introduced polyamic acid, thereby increasing the stability of the film (Patent Document 8), and the like have been proposed. However, according to these techniques, it is necessary to use a large amount of an epoxy compound or a carbonic acid in order to exhibit desired performance, and it is necessary to use a large amount of epoxy compound or carbonic acid in order to improve the reworkability (easiness of peeling of the coating film in printing failure of the liquid crystal aligning agent) Resistance and the like may be damaged, and further improvement is required.

On the other hand, in the liquid crystal alignment film containing polyimide, although the obtained liquid crystal alignment film has a relatively high thermal stress resistance, the conventionally known polyimide has insufficient solubility in a general organic solvent, and therefore, problems in the storage stability of the liquid crystal aligning agent In some cases.

Under these circumstances, a polyamic acid / polyimide-based liquid crystal aligning agent capable of forming a liquid crystal alignment film having sufficient solubility in a general-purpose organic solvent and having excellent heat stress resistance is required.

Recently, however, a process for stereoselectively preparing cyclohexanetetracarboxylic acid anhydride has been developed, and 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic dianhydride and 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic acid 2 (Patent Document 9, Patent Document 10, and Non-Patent Document 1). Patent Documents 9 and 10 describe a polyamic acid synthesized using tetracarboxylic acid dianhydrides each using 100% of the above diastereomers, which is described as a polymer having a sufficiently high molecular weight. Although it is described that the polyamic acid can be used for a liquid crystal alignment film of a liquid crystal display device, in these documents, the properties of the liquid crystal alignment film are not measured at all, and the structure of the tetracarboxylic acid dianhydride, There is no consideration as to the relationship between the storage stability of the alignment agent and the heat stress resistance of the formed liquid crystal alignment film.

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

 Journal of Polymer Society of Japan, Vol. 57, No. 2 (2002)

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid crystal aligning agent which gives a liquid crystal alignment film which is excellent in storage stability and can maintain high quality display even when a liquid crystal display element is used for a long time will be.

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

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

According to the present invention, the above objects and advantages of the present invention are achieved by firstly,

1. A liquid crystal aligning agent comprising at least one polymer selected from the group consisting of a polyamic acid obtained by reacting a tetracarboxylic acid dianhydride with a diamine and a polyimide obtained by dehydrocondylating the polyamic acid,

Wherein the tetracarboxylic acid dianhydride is at least one selected from the group consisting of

At least one selected from the group consisting of 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic acid dianhydride and 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic dianhydride is added to the total tetracarboxylic dianhydride And 5 to 80 mol% of the liquid crystal aligning agent.

The above objects and advantages of the present invention are secondly,

And a liquid crystal alignment film formed of the above liquid crystal aligning agent.

The liquid crystal aligning agent of the present invention is excellent in storage stability and gives a liquid crystal alignment film capable of continuing high quality display even when it is used for a liquid crystal display element for a long time. Therefore, the liquid crystal display element of the present invention including the liquid crystal alignment film formed of such a liquid crystal aligning agent can continue the high-quality display even when used for a long time.

The liquid crystal display device of the present invention can be effectively applied to various devices and can be used for various applications such as a clock, a portable game, a word processor, a notebook type personal computer, a car navigation system, a camcorder, a portable information terminal, It can be suitably used for display devices such as various monitors and liquid crystal televisions.

(Mode for carrying out the invention)

The liquid crystal aligning agent of the present invention,

1. A liquid crystal aligning agent comprising at least one polymer selected from the group consisting of a polyamic acid obtained by reacting a tetracarboxylic acid dianhydride with a diamine and a polyimide obtained by dehydrocondylating the polyamic acid,

Wherein the tetracarboxylic acid dianhydride is at least one selected from the group consisting of

At least one selected from the group consisting of 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic acid dianhydride and 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic dianhydride is added to the total tetracarboxylic dianhydride 5 to 80 mol%.

At least one kind of polymer selected from the group consisting of a polyamic acid obtained by reacting such a specific tetracarboxylic acid dianhydride with a diamine and a polyimide obtained by dehydrocondylating the polyamic acid is referred to as a " .

≪ Tetracarboxylic acid dianhydride >

Examples of the tetracarboxylic acid dianhydride for synthesizing the polyamic acid in the present invention include 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic dianhydride and 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic dianhydride And other tetracarboxylic acid dianhydrides are used in combination.

Here, at least one total tetracarboxylic anhydride selected from the group consisting of 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic acid dianhydride and 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic dianhydride Is preferably 5 to 80 mol%, more preferably 10 to 60 mol%, further preferably 15 to 50 mol%. If the ratio is less than 5 mol%, the liquid crystal alignment film to be formed may have poor heat resistance reliability, while when it exceeds 80 mol%, the storage stability of the obtained liquid crystal alignment film may be poor, which is not preferable.

The tetracarboxylic acid dianhydride preferably contains 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic dianhydride in the above-mentioned range.

Examples of other tetracarboxylic acid dianhydrides include aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, aromatic tetracarboxylic dianhydrides, and the like. Specific examples thereof include aliphatic tetracarboxylic acid dianhydrides such as butanetetracarboxylic dianhydride;

As the alicyclic tetracarboxylic acid dianhydride, for example, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a, 4, 5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] furan-1,3-dione, , 5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ (Tetrahydrofuran-2 ', 5'-dione), 5- (2,5-dioxotetrahydro-3 ' 3-cyclohexene-1,2-dicarboxylic 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, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane- , 5,8,10-tetralone, and the like;

Examples of the aromatic tetracarboxylic acid dianhydride include pyromellitic dianhydride and the like,

Tetracarboxylic acid dianhydride described in Patent Document 14 (Japanese Patent Laid-Open No. 2010-97188) can be used.

Examples of other tetracarboxylic acid dianhydrides include 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a, 4,5, (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 [ (Tetrahydrofuran-2 ', 5 ' -dione), 5- (2,5- dioxotetrahydro-3-fura Carboxymethylnorbornane-2: 3,5: 6-2 anhydride, 2, 3-cyclohexene-1,2-dicarboxylic anhydride, 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- , 8,10-tetraon (hereinafter, referred to as " specific tetracarboxylic acid dianhydride " To include yelling) is preferred.

The use ratio of the specific tetracarboxylic acid dianhydride is preferably 50 mol% or more, more preferably 80 mol% or more, and particularly preferably 100 mol%, based on the total amount of the other tetracarboxylic dianhydrides.

<Diamine>

Examples of the diamine used for synthesizing the polyamic acid in the present invention include aliphatic diamines, alicyclic diamines, aromatic diamines, diaminoorganosiloxanes and the like. Specific examples thereof include aliphatic diamines such as 1,1-meta-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine and the like;

As the alicyclic diamine, for example, 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane and the like;

As the aromatic diamine, for example, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylamine, 1,5 Diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,7- Bis (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2, (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '- (p- phenylenediisopropylidene) Bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, Diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacrylidine, 3,6-diaminocarbazole, - diaminocarbazole, N-ethyl-3, N, N'-bis (4-aminophenyl) -N, N'-diaminocarbazole, N-dimethylbenzidine, 1,4-bis- (4-aminophenyl) -piperazine, 3,5-diaminobenzoic acid, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy- Diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestanyl, 3,5-diaminobenzoic acid (4'-aminophenoxy) cholestane, 3, 6-bis (4-aminobenzoyloxy) cholestane, (Trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (4'-trifluoromethylbenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 1,1-bis (4 - ((aminophenyl) methyl) phenyl) -4-heptylcyclohexane, 1,1- Bis (4 - ((aminophenyl) methyl) phenyl) -4- (4-heptylcyclohexyl) cyclohexane, And the following formula (A-1):

(Wherein (A-1) of, X ^I is an alkylene group, having a carbon number of 1~3 ^* -O-, ^* -COO- or ^* -OCO- (However, the bond attached to "*" hands are engaged with diamino group A is 0 or 1, b is an integer of 0 to 2, and c is an integer of 1 to 20)

And the like;

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

Diamines described in Patent Document 14 (Japanese Patent Application Laid-Open No. 2010-97188) can be used.

X ^I in the above formula (A-1) is an alkylene group having 1 to 3 carbon atoms, ^* -O- or ^* -COO- (provided that the bond with "*" is bonded to a diaminophenyl group) desirable. Specific examples of the group C _c H _{2c + 1} - include a methyl group, an ethyl group, a n-propyl group, an n-butyl group, an n-pentyl group, N-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-hexadecyl group, n-hexadecyl group, an n-nonadecyl group, and an n-eicosyl group. The two amino groups in the diaminophenyl group are preferably in the 2,4-position or the 3,5-position with respect to the other groups.

Specific examples of the compound represented by the formula (A-1) include dodecanoxy-2,4-diaminobenzene, tetradecanoxy-2,4-diaminobenzene, pentadecanoxy- Diaminobenzene, hexadecaneoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, dodecaneoxy-2,5-diaminobenzene, tetradecanoxy-2,5-diaminobenzene Diaminobenzene, hexadecaneoxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene, the following formulas (A-1-1) to (A- 1-3):

And the like.

In the formula (A-1), it is preferable that a and b are not 0 at the same time.

Examples of the diamine include p-phenylenediamine, 3,5-diaminobenzoic acid, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 2,2'- Diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-diaminodiphenylamine and 4,4'- (Hereinafter referred to as &quot; specific diamine 1 &quot;) selected from the group consisting of ethylene diamine, propylene diamine, and diisopropylene dianiline.

When the liquid crystal aligning agent of the present invention is used for forming a liquid crystal alignment film in a vertical alignment type (VA type) liquid crystal display device, in addition to the specific diamine as described above, cholestanyloxy- Diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid Cholestanyl 3,5-diaminobenzoate, lanthanil 3,5-diaminobenzoate, 3,6-bis (4-aminobenzoyloxy) cholestane, 3,6-bis (Hereinafter referred to as &quot; specific diamine 2 &quot;) selected from the group consisting of a compound represented by the above formula (A-1) and a compound represented by the above formula (A-1).

In the case where the liquid crystal aligning agent of the present invention is used for forming a liquid crystal alignment film in a vertical alignment type liquid crystal display element of the VA type, the preferred ratio of the specific diamine 1 and the specific diamine 2 to all diamines is same.

Specific diamine 1: preferably 20 to 97%, more preferably 50 to 95%, particularly preferably 60 to 90%

Specific diamine 2: preferably 3 to 80 mol%, more preferably 5 to 50%, particularly preferably 10 to 40%

In this case, it is preferable that the total use ratio of the specific diamine 1 and the specific diamine 2 is 100 mol% based on the total diamine.

On the other hand, when the liquid crystal aligning agent of the present invention is applied to liquid crystal display devices other than the VA type (for example, TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, (Fringe Field Switching), etc.)), the specific ratio of the specific diamine 1 and the specific diamine 2 to the total diamine is as described below.

Specific diamine 1: preferably 50 mol% or more, more preferably 80 mol% or more, particularly preferably 100 mol%

Specific diamine 2: preferably 30 mol% or less, more preferably 10% or less, particularly preferably 0 mol%

In this case, as the diamine, the total amount of the specific diamine 1 and the specific diamine 2 is preferably 100 mol%, more preferably only the specific diamine 1 is used.

&Lt; Molecular weight regulator &

In the synthesis of the polyamic acid, a terminal modifier type polymer may be synthesized by using a suitable molecular weight modifier together with the tetracarboxylic dianhydride and the diamine as described above. The liquid crystal aligning agent containing at least one polymer selected from the group consisting of the polyamic acid and the polyimide obtained by dehydration ring closure thereof by making the polyamic acid a polymer having such a terminal modification type is not capable of impairing the effect of the present invention (Printing property) is further improved.

Examples of the molecular weight modifier include acid anhydrides, monoamine compounds, and monoisocyanate compounds. Specific examples thereof include acid anhydrides such as maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, n-hexadecylsuccinic anhydride My back;

As the monoamine compound, for example, aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine and the like;

Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

The use ratio of the molecular weight regulator is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the total amount of tetracarboxylic acid dianhydride and diamine to be used.

<Synthesis of polyamic acid>

The ratio of the tetracarboxylic acid dianhydride and the diamine to be used in the synthesis reaction of the polyamic acid is preferably such that the amount of the acid anhydride group of the tetracarboxylic acid dianhydride is from 0.2 to 2 equivalents based on 1 equivalent of the amino group of the diamine, Preferably 0.3 to 1.2 equivalents.

The synthesis reaction of the polyamic acid is preferably carried out in an organic solvent at a temperature of preferably -20 ° C to 150 ° C, more preferably 0 to 100 ° C, preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours Time is done.

Examples of the organic solvent include non-protic polar solvents, phenol and derivatives thereof, alcohols, ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons.

Specific examples of these organic solvents include non-protonic polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, Butyrolactone, tetramethyl urea, hexamethylphosphoric triamide and the like;

As the phenol derivative, for example, m-cresol, xylenol, halogenated phenol and the like;

As the alcohol, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether and the like;

As the ketone, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like;

As the ester, for example, ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate and the like;

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 monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetraethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, Hydrofuran and the like;

As the halogenated hydrocarbon, for example, 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, isoamyl propionate, isoamyl isobutylate, and diisopentyl ether.

Among these organic solvents, at least one selected from the group consisting of an aprotic polar solvent and a group consisting of phenol and a derivative thereof (first group of organic solvents), or at least one selected from organic solvents of the first group and an alcohol, It is preferable to use a mixture of at least one member selected from the group consisting of ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons (organic solvent of the second group). In the latter case, the use ratio of the organic solvent of the second group is preferably 50% by weight or less, more preferably 40% by weight or less based on the total amount of the organic solvent of the first group and the organic solvent of the second group By weight, more preferably not more than 30% by weight.

The amount (a) of the organic solvent used is preferably such that the total amount (b) of the tetracarboxylic acid dianhydride and the diamine is 0.1 to 50 wt% with respect to the total amount (a + b) of the reaction solution.

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

The reaction solution may be directly supplied to the preparation of the liquid crystal aligning agent. Alternatively, the polyamic acid contained in the reaction solution may be isolated and then supplied to the preparation of the liquid crystal aligning agent, or after the isolated polyamic acid is purified, . When the polyamic acid is subjected to dehydration ring closure to form a polyimide, the reaction solution may be directly supplied to the dehydration ring-closing reaction. Alternatively, the polyamic acid contained in the reaction solution may be isolated and then subjected to dehydration ring- May be purified and then subjected to a dehydration ring-closing reaction. The polyamic acid can be isolated and purified by a known method.

<Synthesis of polyimide>

The polyimide can be obtained by dehydrating and ring closure of the polyamic acid synthesized as described above to imidize it.

The polyimide in the present invention may be a completely imidized product in which all of the arboric acid structure of the polyamic acid as a precursor thereof is subjected to dehydration ring closure and only a part of the arboric acid structure is subjected to dehydration ring closure, It may be an imaged cargo. The imide ratio of the polyimide in the present invention is preferably 30% or more, more preferably 50% or more, particularly preferably 55% or more. The imidization rate is a percentage of the ratio of the number of imide ring structures to the sum of the number of amide structure and the number of imide ring structure of polyimide. Here, a 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 a method of dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring-closing catalyst to the solution, and optionally heating . Of these, the latter method is preferable.

In the method of adding the dehydrating agent and the dehydrating ring-closing catalyst to the solution of the polyamic acid, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent to be used is preferably 0.01 to 20 mol based on 1 mol of the acid structure of the polyamic acid. As the dehydration ring-closing catalyst, for example, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used. The amount of the dehydration ring-closing catalyst to be used is preferably 0.01 to 10 mol based on 1 mol of the dehydrating agent to be used. Examples of the organic solvent used in the dehydration ring-closure reaction include the organic solvents exemplified for use in the synthesis of polyamic acid. The reaction temperature of the dehydration ring-closing reaction is preferably 0 to 180 캜, more preferably 10 to 150 캜. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

In this way, a reaction solution containing polyimide is obtained. This reaction solution may be provided as it is in the preparation of a liquid crystal aligning agent or may be provided in the preparation of a liquid crystal aligning agent after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution. Alternatively, after the polyimide is isolated, Or may be provided to the preparation of a liquid crystal aligning agent after purification of the isolated polyimide. These purification operations can be carried out according to a known method.

&Lt; Solution viscosity of polymer >

The specific polymer thus obtained preferably has a solution viscosity of 20 to 800 mPa · s and more preferably a solution viscosity of 30 to 500 mPa · s when the solution is a solution having a concentration of 10% by weight.

The solution viscosity (mPa 占 퐏) of the polymer is preferably 10% by weight or less, more preferably 10% by weight or less, by using a good solvent (e.g.,? -Butyrolactone, N-methyl- Polymer solution was measured at 25 占 폚 using an E-type rotational viscometer.

<Other additives>

The liquid crystal alignment film of the present invention contains the above specific polymer as an essential component, but may contain other components as required. Examples of such other components include a polymer other than the specific polymer (hereinafter referred to as "another polymer"), a compound having at least one epoxy group in the molecule (hereinafter referred to as "epoxy compound"), a functional silane compound And the like.

[Other Polymers]

These other polymers can be used for improving solution properties and electrical properties. Such other polymer is a polymer other than the specific polymer, for example, a polyamic acid obtained by reacting a tetracarboxylic acid dianhydride with a diamine, wherein 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic acid Wherein the content ratio of at least one member selected from the group consisting of acid anhydrides and 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic dianhydrides is less than 5 mol% or more than 80 mol% (Hereinafter referred to as &quot; other polyamic acid &quot;), polyimide obtained by subjecting the polyamic acid to dehydration cyclization (hereinafter referred to as &quot; other polyimide &quot;), polyamic acid ester, polyester, polyamide, polysiloxane, , Polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives, and poly (meth) acrylates. Of these, other polyamic acids or other polyimides are preferable, and other polyamic acids are more preferable.

The tetracarboxylic acid dianhydride used for synthesizing the above other polyamic acid or other polyimide may be the same as the above-mentioned other tetracarboxylic dianhydrides preferably used for synthesizing a specific polymer, Cyclobutanetetracarboxylic acid dianhydride, pyromellitic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 1,3,3a, 4,5,9b-hexa (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione desirable.

As the diamine to be used for synthesizing the above other polyamic acid or other polyimide, it is preferable to use at least one selected from among those exemplified above as a diamine to be used in synthesizing a specific polymer. Examples of diamines used for synthesizing other polyamic acids or other polyimides include 4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminobiphenyl, cholestanyloxy-2 , 4-diaminobenzene, 3,5-diaminobenzoic acid and 1,4-bis- (4-aminophenyl) -piperazine are preferably used.

The proportion of the other polymer to be used is preferably 50% by weight or less, more preferably 40% by weight or less, further preferably 30% by weight or less based on the total amount of the polymers (referred to the total amount of the specific polymer and the other polymers described above, % Or less. When other polymers are used, if the use ratio is 0.1% by weight or more based on the total amount of the polymers, the effect of the addition is significantly expressed.

[Epoxy Compound]

The epoxy compound may be contained in the liquid crystal aligning agent of the present invention for the purpose of further improving the adhesiveness and heat resistance of the obtained liquid crystal alignment film to the substrate.

The epoxy compound is preferably an epoxy compound having two or more epoxy groups in the molecule, and examples thereof include ethylene glycol diglycidyl ether, polyethylene glycol 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-dibromonopentyl glycol diglycidyl ether, N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl-benzylamine, N, Glycidyl-aminomethylcyclohexane, N, N-diglycidyl-cyclohexylamine, and the like are preferably used .

When the use ratio is too low, the above-mentioned desired effects are not sufficiently exhibited. On the other hand, if the use ratio is excessive, the reworkability and rubbing resistance of the liquid crystal alignment film are impaired. From this point of view, the blending ratio of the epoxy compound is preferably 30 parts by weight or less, more preferably 0.1 to 15 parts by weight, and preferably 0.5 to 8 parts by weight, based on 100 parts by weight of the total amount of the polymer More preferably 1 to 3 parts by weight.

[Functional silane compound]

Examples of the functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxy Silane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N- Trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3 , 6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, methyl 9-trimethoxysilyl-3,6-diazononanoate, Benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl- N-phenyl-3-aminopropyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and the like.

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 total of the polymers.

<Liquid Crystal Aligner>

The liquid crystal aligning agent of the present invention is constituted by dissolving and incorporating the above-mentioned specific polymer and optionally other additives optionally added in an organic solvent.

Examples of the organic solvent used in the liquid crystal aligning agent of the present invention include N-methyl-2-pyrrolidone,? -Butyrolactone,? -Butyrolactam, N, N-dimethylformamide, Methylene-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene Diethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether (ethylene glycol diethyl ether), ethylene glycol n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol- , 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 may be used alone or in combination of two or more.

The solid concentration of the liquid crystal aligning agent of the present invention (the ratio of the total weight of components other than the solvent of the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc., 1 to 10% by weight. That is, the liquid crystal aligning agent of the present invention is applied to the surface of the substrate as described later, and is preferably heated to form a coating film which becomes a liquid crystal alignment film or a liquid crystal alignment film. When the solid concentration is less than 1 wt% If the concentration of the solid content exceeds 10% by weight, the film thickness of the coating film becomes excessively large, so that a good liquid crystal alignment film can not be obtained. In addition, the liquid crystal alignment film The viscosity is increased and the coating properties are deteriorated.

A particularly preferable range of the solid concentration is different depending on the method used when the liquid crystal aligning agent is applied to the substrate. For example, in the case of the spinner method, the solid content concentration is particularly preferably in the range of 1.5 to 4.5% by weight. In the case of the printing method, it is particularly preferable to set the solid concentration in the range of 3 to 9% by weight and the solution viscosity in the range of 12 to 50 mPa · s accordingly. In the case of the ink-jet method, it is particularly preferable that the solid concentration is in the range of 1 to 5 wt%, and thus the solution viscosity is in the range of 3 to 15 mPa · s.

The temperature for preparing the liquid crystal aligning agent of the present invention is preferably 10 to 50 占 폚, more preferably 20 to 30 占 폚.

<Liquid crystal display element>

The liquid crystal display element of the present invention comprises the liquid crystal alignment layer formed of the liquid crystal aligning agent of the present invention as described above. More specifically, the liquid crystal display element of the present invention is formed by disposing a polarizing plate on both outer surfaces of a liquid crystal cell. In the liquid crystal cell, two liquid crystal alignment films are aligned so that two liquid crystal alignment film surfaces face each other And the liquid crystal alignment layer is formed of the liquid crystal aligning agent of the present invention.

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

(1) First, a liquid crystal aligning agent of the present invention is applied onto a substrate, and then a coated film is formed on the substrate by heating the coated surface.

(1-1) In the case of producing a TN type, STN type or VA type liquid crystal display device, two pairs of substrates each having a patterned transparent conductive film formed on one side thereof are formed as a pair, The liquid crystal aligning agent of the present invention is preferably applied by an offset printing method, a spin coating method, or an inkjet printing method, respectively, and then each coated surface is heated to form a coated film. Examples of the substrate include glass such as float glass and 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 to be formed on one surface of the substrate, an ITO film made of NESA film (a registered trademark of PPG Corporation of the US) or indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) made of tin oxide (SnO ₂ ) In order to obtain a patterned transparent conductive film, for example, a method of forming a pattern by photoetching after forming a patternless transparent conductive film, a method of using a mask having a desired pattern in forming a transparent conductive film, and the like can do. When the liquid crystal aligning agent is applied, a functional silane compound, a functional titanium compound or the like may be added to the surface of the substrate surface on which the coating film should be formed, in order to improve the adhesion between the substrate surface and the transparent conductive film and the coating film It is also possible to carry out the pre-treatment for applying the coating.

Pre-heating (pre-baking) is preferably performed for the purpose of preventing the liquid flow of the applied aligning agent after application of the liquid crystal aligning agent. The prebaking temperature is preferably 30 to 200 캜, more preferably 40 to 150 캜, particularly preferably 40 to 100 캜. The prebaking time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes. Thereafter, the baking (post-baking) step is carried out for the purpose of completely removing the solvent and, if necessary, thermally modifying the polyamic acid. The firing (post-baking) temperature is preferably 80 to 300 占 폚, and more preferably 120 to 250 占 폚. The post baking time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. The film thickness of the film thus formed is preferably 0.001 to 1 占 퐉, and more preferably 0.005 to 0.5 占 퐉.

(1-2) On the other hand, when a transverse electric field type liquid crystal display element is manufactured, the conductive film formation surface of the substrate on which the transparent conductive film patterned in the comb shape is formed on one side, , The liquid crystal aligning agent of the present invention is respectively applied, and then each coated surface is heated to form a coated film.

The substrate and the transparent conductive film to be used at this time, the method of patterning the transparent conductive film, the pretreatment of the substrate, the application method of the liquid crystal aligning agent, the heating method after application of the liquid crystal aligning agent, ).

(2) When the liquid crystal display element produced by the method of the present invention is a VA type liquid crystal display element, the coating film formed as described above can be used as it is as a liquid crystal alignment film as it is. However, And may be provided for use.

On the other hand, in the case of manufacturing a liquid crystal display device other than VA type, a coating film formed as described above is subjected to rubbing treatment to form a liquid crystal alignment film.

The rubbing treatment can be performed by rubbing the coating film surface formed as described above in a predetermined direction with a roll formed of a fiber such as nylon, rayon, or cotton, for example. Accordingly, the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film.

Further, with respect to the liquid crystal alignment film formed as described above, for example, a treatment for changing a pretilt angle of a part of the liquid crystal alignment film by irradiating a part of the liquid crystal alignment film with ultraviolet rays (Patent Document 11 (Japanese Patent Application Laid- Japanese Patent Application Laid-open No. Hei 6-281937), a process of forming a resist film on a part of the surface of the liquid crystal alignment film and rubbing the film in a direction different from the rubbing process before the process of removing the resist film is performed (See Patent Document 13 (Japanese Patent Application Laid-Open No. 5-107544)), and the like, which improves the visual field characteristics of a liquid crystal display element obtained by causing the liquid crystal alignment film to have a liquid crystal aligning ability different for each region.

(3) A liquid crystal cell is prepared by preparing two substrates on which the liquid crystal alignment film is formed as described above, and arranging the liquid crystal between two substrates opposed to each other. Here, when the coating film is subjected to the rubbing treatment, the two substrates are opposed to each other such that the rubbing directions of the coating films are at a predetermined angle, for example, orthogonal or anti-parallel to each other.

For example, the following two methods can be used to manufacture the liquid crystal cell.

The first method is a conventionally known method. First, two substrates are opposed to each other through a gap (cell gap) so that the respective liquid crystal alignment films are opposed to each other. The peripheral portions of the two substrates are bonded to each other using a sealant, The liquid crystal is injected and filled in the gap, and then the injection hole is sealed, whereby the liquid crystal cell can be manufactured.

The second method is a so-called ODF (One Drop Fill) method. For example, an ultraviolet curable sealant is applied to a predetermined position on one of the two substrates on which the liquid crystal alignment film is formed, and further liquid crystal is dropped to a predetermined position on a predetermined position on the liquid crystal alignment film surface, The liquid crystal cell can be manufactured by spreading the liquid crystal on the entire surface of the substrate and then irradiating the entire surface of the substrate with ultraviolet light to cure the sealant.

Regardless of the method, the liquid crystal cell manufactured as described above is then heated to a temperature at which the liquid crystal used has an isotropic phase, and then slowly cooled to room temperature to obtain a liquid crystal cell having a flow orientation Is preferably removed.

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

As the sealing agent, for example, an epoxy resin containing an aluminum oxide sphere as a curing agent and a spacer can be used.

As the liquid crystal, for example, a nematic liquid crystal, a smectic liquid crystal and the like can be used. Among them, a nematic liquid crystal is preferable, and for example, a cypher base liquid crystal, an agar liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane There can be used a liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, a biphenyl cyclohexane liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a quartz liquid crystal and the like. Further, to these liquid crystals, for example, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonanoate and cholesteryl carbonate; Chiral agents such as those sold under the trade names C-15 and CB-15 (Merck); p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate and the like may be further added and used.

As the polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing plate in which a polarizing film called "H film" in which iodine is absorbed while polyvinyl alcohol is oriented in a stretched polyvinyl alcohol is sandwiched between cellulose acetate protective films or a polarizing plate comprising H film itself .

(Example)

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to these examples. The solution viscosity of each polymer solution in the polymerization example and the imidization rate of the polyimide were measured by the following methods.

[Solution viscosity of polymer solution]

The solution viscosity (mPa 占 퐏) of the polymer solution was measured at 25 占 폚 using the E-type rotational viscometer at the solvent and the concentration described in each Synthesis Example.

[Imidization Rate of Polyimide]

A small amount of the polyimide solution was added to pure water and the resulting precipitate was sufficiently dried under reduced pressure at room temperature and then dissolved in deuterated dimethyl sulfoxide and subjected to ¹ H-NMR at room temperature using tetramethylsilane as a reference . From the obtained ¹ H-NMR spectrum, the imidization rate was determined by the equation shown by the following formula (1).

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

(In the formula (1), A ¹ is the peak area originating from the proton of the NH group near the chemical shift of 10 ppm,

A ² is the peak area derived from other proton,

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

<Synthesis and Stability Evaluation of Polymer for TN Type Liquid Crystal Aligner>

[Example of synthesis of polyamic acid as a specific polymer]

Synthesis Example A-TN1

(0.50 mol) of 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic dianhydride and 109 g (0.50 mol) of pyromellitic dianhydride as a tetracarboxylic acid dianhydride and 4,4'-diaminodiphenylmethane (A-TN1) was obtained by dissolving 198 g (1.0 mole) of the compound (A-TN1) in a mixed solvent consisting of 246 g of N-methyl-2-pyrrolidone and 2,213 g of? -Butyrolactone, Was obtained. The solution viscosity of this solution was 179 mPa s.

The polymer solution was allowed to stand at 20 占 폚 for 3 days. As a result, the polymer solution was not gelated, and storage stability was good.

Synthesis Example A-TN2

67 g (0.30 mol) of 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic dianhydride and 153 g (0.70 mol) of pyromellitic dianhydride as tetracarboxylic dianhydrides and 4,4'-diaminodiphenylmethane (A-TN2) was obtained by dissolving 198g (1.0 mole) in a mixed solvent consisting of 246g of N-methyl-2-pyrrolidone and 2,213g of? -Butyrolactone, Was obtained. The solution viscosity of this solution was 153 mPa..

The polymer solution was allowed to stand at 20 占 폚 for 3 days. As a result, the polymer solution was not gelated, and storage stability was good.

[Synthesis example of other polyamic acid]

Synthesis Example a-TN3

109 g (0.50 mol) of pyromellitic dianhydride as tetracarboxylic dianhydride, 98 g (0.50 mol) of 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride and 4,4'-diaminodiphenylmethane (A-TN3) was obtained by dissolving 198g (1.0 mole) in a mixed solvent consisting of 230 g of N-methyl-2-pyrrolidone and 2,068 g of? -Butyrolactone and conducting the reaction at 40 占 폚 for 3 hours, Was obtained. The solution viscosity of this solution was 193 mPa · s.

The polymer solution was allowed to stand at 20 占 폚 for 3 days. As a result, the polymer solution was not gelated, and storage stability was good.

[Example of synthesis of polyimide as specific polymer]

Synthesis Example B-TN1

(0.50 mol) of 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic dianhydride and 112 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic acid dianhydride, and p- (0.0155 mol) of phenylenediamine and 7.8 g (0.015 mol) of 3- (3,5-diaminobenzoyloxy) cholestane were dissolved in 3,042 g of N-methyl-2-pyrrolidone, The reaction was carried out to obtain a solution containing polyamic acid. The solution viscosity of the obtained polyamic acid solution was 160 mPa · s.

To the resulting polyamic acid solution, 3,380 g of N-methyl-2-pyrrolidone was added, and 395 g of pyridine and 306 g of acetic anhydride were added, followed by dehydration ring-closure reaction at 110 DEG C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a solvent with a new? -Butyrolactone (in this operation, pyridine and anhydrous acetic acid used in the imidization reaction were removed from the system, the same applies hereinafter) To obtain a solution containing 10% by weight of a polyimide (B-TN1) having a durability of about 94%.

A small amount of this solution was fractionated and? -Butyrolactone was added thereto to give a solution having a concentration of 6 wt%, and the solution viscosity was 28 mPa · s.

The polymer solution was allowed to stand at 20 占 폚 for 3 days. As a result, the polymer solution was not gelated, and storage stability was good.

[Synthesis example of other polyimide]

Synthesis Example b-TN2

(0.50 mole) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as the tetracarboxylic acid dianhydride, and 110 g (0.50 mole) of 1,3,3a, 4,5,9b-hexahydro-8- 155 g (0.50 mol) of p-phenylenediamine as diamine, 92 g (0.87 mol) of bis-aminopropyl (0.10 mole) of tetramethyldisiloxane, 13 g (0.02 mole) of 3,6-bis (4-aminobenzoyloxy) cholestane and 2.7 g (0.030 mole) of aniline as a monoamine were dissolved in N-methyl- And the reaction was carried out at 60 DEG C for 6 hours to obtain a solution containing polyamic acid. A small amount of the resulting polyamic acid solution was collected and N-methyl-2-pyrrolidone was added thereto to prepare a solution having a polyamic acid concentration of 10 wt%, and the solution viscosity was 59 mPa · s.

Then, 2,700 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 396 g of pyridine and 409 g of acetic anhydride were added, followed by dehydration cyclization at 110 DEG C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a solvent with fresh? -Butyrolactone and further concentrated to obtain about 2,520 g of a solution containing 15% by weight of polyimide (b-TN2) having an imidization rate of about 95% . A small amount of the polyimide solution was fractionated and? -Butyrolactone was added thereto to obtain a solution having a polyimide concentration of 6.0 wt%, and the solution viscosity was 18 mPa · s.

The polymer solution was allowed to stand at 20 占 폚 for 3 days. As a result, the polymer solution was not gelated, and storage stability was good.

Synthesis Example b-TN3

224 g (1.0 mole) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 106 g (0.985 mole) of p-phenylenediamine as a diamine and 3- (3,5-diaminobenzoyloxy) 7.8 g (0.015 mol) of cholestane was dissolved in 3,042 g of N-methyl-2-pyrrolidone, and the reaction was carried out at 60 DEG C for 6 hours to obtain a solution containing polyamic acid. The solution viscosity of the obtained polyamic acid solution was 181 mPa · s.

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

A small amount of this solution was fractionated and? -Butyrolactone was added thereto to prepare a solution having a concentration of 6% by weight. The viscosity of the solution was 35 mPa · s.

The polymer solution was allowed to stand at 20 占 폚 for 3 days. As a result, the polymer solution was not gelated, and storage stability was good.

&Lt; Synthesis and Stability Evaluation of Polymer for VA Type Liquid Crystal Aligner &

[Example of synthesis of polyimide as specific polymer]

Synthesis Example B-VA1

112 g (0.50 mol) of 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic dianhydride and 112 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydrides, 49 g (0.1 mol) of cholestanyloxy-2,4-diaminobenzene and 87 g (0.80 mol) of p-phenylenediamine were dissolved in N-methyl-2-pyrrolidone And the reaction was carried out at 60 DEG C for 6 hours to obtain a polyamic acid solution. A small amount of the resulting polyamic acid solution was collected and added with N-methyl-2-pyrrolidone to obtain a solution having a polymer concentration of 10 wt%, and the solution viscosity was 79 mPa · s.

Subsequently, 3,835 g of N-methyl-2-pyrrolidone was added to the resulting polyamic acid solution, 79 g of pyridine and 102 g of acetic anhydride were added, and dehydration ring closure was carried out at 110 DEG C for 4 hours. After the dehydration cyclization reaction, the solvent in the system was replaced with fresh N-methyl-2-pyrrolidone to obtain a solution containing about 15% by weight of polyimide (B-VA1) having an imidization rate of about 51%. A small amount of the obtained polyimide solution was collected and N-methyl-2-pyrrolidone was added thereto to give a solution having a polyimide concentration of 10% by weight, and the solution viscosity was 102 mPa · s.

The polymer solution was allowed to stand at 20 占 폚 for 3 days. As a result, the polymer solution was not gelated, and storage stability was good.

Synthesis Example B-VA2

112 g (0.50 mol) of 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic dianhydride and 112 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydrides, 49 g (0.1 mol) of cholestanyloxy-2,4-diaminobenzene and 87 g (0.80 mol) of p-phenylenediamine were dissolved in N-methyl-2-pyrrolidone And the reaction was carried out at 60 DEG C for 6 hours to obtain a polyamic acid solution. A small amount of the obtained polyamic acid solution was collected and N-methyl-2-pyrrolidone was added to obtain a solution having a polymer concentration of 10 wt%, and the solution viscosity was 71 mPa · s.

Subsequently, 3,835 g of N-methyl-2-pyrrolidone was added to the resulting polyamic acid solution, 79 g of pyridine and 102 g of acetic anhydride were added, and dehydration ring closure was carried out at 110 DEG C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with fresh N-methyl-2-pyrrolidone to obtain a solution containing about 15% by weight of polyimide (B-VA2) having an imidization rate of about 48%. A small amount of the obtained polyimide solution was collected and N-methyl-2-pyrrolidone was added to obtain a solution having a polyimide concentration of 10% by weight, and the solution viscosity was 99 mPa · s.

The polymer solution was allowed to stand at 20 占 폚 for 3 days. As a result, the polymer solution was not gelated, and storage stability was good.

Synthesis Example B-VA3

45 g (0.20 mol) of 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic dianhydride and 180 g (0.80 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic acid dianhydride, 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 An acid solution was obtained. A small amount of the obtained polyamic acid solution was added to N-methyl-2-pyrrolidone to prepare a solution having a polymer concentration of 10% by weight, and the solution viscosity was 59 mPa · s.

Then, 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 cyclization was carried out at 110 DEG C for 4 hours. After the dehydration cyclization reaction, the solvent in the system was replaced with fresh N-methyl-2-pyrrolidone to obtain a solution containing about 15% by weight of polyimide (B-VA3) having an imidization rate of about 47%. A small amount of the obtained polyimide solution was collected and N-methyl-2-pyrrolidone was added thereto to give a solution having a polyimide concentration of 10 wt%, and the solution viscosity was 80 mPa · s.

The polymer solution was allowed to stand at 20 占 폚 for 3 days. As a result, the polymer solution was not gelated, and storage stability was good.

Synthesis Example B-VA4

45 g (0.20 mol) of 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic dianhydride and 180 g (0.80 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydrides, 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 An acid solution was obtained. A small amount of the obtained polyamic acid solution was collected and added with N-methyl-2-pyrrolidone to prepare a solution having a polymer concentration of 10% by weight, and the solution viscosity was 66 mPa · s.

Then, 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 cyclization was carried out at 110 DEG C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with fresh N-methyl-2-pyrrolidone to obtain a solution containing about 15% by weight of a polyimide (B-VA4) having an imidation rate of 50%. A small amount of the obtained polyimide solution was collected and N-methyl-2-pyrrolidone was added thereto to obtain a solution having a polyimide concentration of 10% by weight, and the solution viscosity was 89 mPa · s.

The polymer solution was allowed to stand at 20 占 폚 for 3 days. As a result, the polymer solution was not gelated, and storage stability was good.

Synthesis Example B-VA5

135 g (0.60 mol) of 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic dianhydride and 90 g (0.40 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydrides, (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 dissolved in 1,697 g of N-methyl- And the reaction was carried out at 60 DEG C for 6 hours to obtain a polyamic acid solution. A small amount of the resulting polyamic acid solution was collected and added with N-methyl-2-pyrrolidone to prepare a solution having a polymer concentration of 10% by weight, and the solution viscosity was 50 mPa · s.

Next, 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 the dehydration ring closure was carried out at 110 DEG C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with fresh N-methyl-2-pyrrolidone to obtain a solution containing about 15% by weight of polyimide (B-VA5) having an imidization rate of about 66%. A small amount of the polyimide solution thus obtained was added to N-methyl-2-pyrrolidone to prepare a solution having a polyimide concentration of 10% by weight, and the solution viscosity was 79 mPa · s.

The polymer solution was allowed to stand at 20 占 폚 for 3 days. As a result, the polymer solution was not gelated, and storage stability was good.

Synthesis Example B-VA6

45 g (0.20 mol) of 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic dianhydride and 179 g (0.80 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydrides, (0.25 mol) of 5-diaminobenzoic acid cholestanyl, 53 g (0.50 mol) of p-phenylenediamine and 38 g (0.25 mol) of 3,5-diaminobenzoic acid were dissolved in 1,697 g of N-methyl- And the reaction was carried out at 60 DEG C for 6 hours to obtain a polyamic acid solution. A small amount of the obtained polyamic acid solution was added to N-methyl-2-pyrrolidone to prepare a solution having a polymer concentration of 10 wt%, and the solution viscosity was 58 mPa · s.

Next, 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 the dehydration ring closure was carried out at 110 DEG C for 4 hours. After the dehydration cyclization reaction, the solvent in the system was replaced with fresh N-methyl-2-pyrrolidone to obtain a solution containing about 15% by weight of polyimide (B-VA6) having an imidization rate of about 69%. A small amount of the polyimide solution thus obtained was added to N-methyl-2-pyrrolidone to prepare a solution having a polyimide concentration of 10 wt%, and the solution viscosity was 81 mPa · s.

The polymer solution was allowed to stand at 20 占 폚 for 3 days. As a result, the polymer solution was not gelated, and storage stability was good.

[Synthesis example of other polyimide]

Synthesis Example b-VA7

224 g (1.0 mole) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic acid dianhydride, 52 g (0.10 mole) of 3,5-diaminobenzoic acid cholestanil as a diamine, 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 DEG C for 6 hours to give a polyamic acid solution . A small amount of the obtained polyamic acid solution was added to N-methyl-2-pyrrolidone to prepare a solution having a polymer concentration of 10% by weight, and the solution viscosity was 70 mPa · s.

Subsequently, 3,835 g of N-methyl-2-pyrrolidone was added to the resulting polyamic acid solution, 79 g of pyridine and 102 g of acetic anhydride were added, and dehydration ring closure was carried out at 110 DEG C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with fresh N-methyl-2-pyrrolidone to obtain a solution containing about 15% by weight of polyimide (b-VA7) having an imidization rate of about 49%. A small amount of the obtained polyimide solution was collected and N-methyl-2-pyrrolidone was added thereto to give a solution having a polyimide concentration of 10 wt%, and the solution viscosity was 80 mPa · s.

The polymer solution was allowed to stand at 20 占 폚 for 3 days. As a result, the polymer solution was not gelated, and storage stability was good.

Synthesis Example b-VA8

224 g (1.0 mole) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 105 g (0.20 mole) of 3,5-diaminobenzoic acid cholestanil as diamine and 65 g 0.60 mole) and 30 g (0.20 mole) 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 resulting polyamic acid solution was collected and added with N-methyl-2-pyrrolidone to prepare a solution having a polymer concentration of 10% by weight, and the solution viscosity was 50 mPa · s.

Next, 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 the dehydration ring closure was carried out at 110 DEG C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with fresh N-methyl-2-pyrrolidone to obtain a solution containing about 15% by weight of polyimide (b-VA8) having an imidization rate of about 67%. A small amount of the obtained polyimide solution was collected and N-methyl-2-pyrrolidone was added thereto to obtain a solution having a polyimide concentration of 10 wt%, and the solution viscosity was 73 mPa · s.

The polymer solution was allowed to stand at 20 占 폚 for 3 days. As a result, the polymer solution was not gelated, and storage stability was good.

<Synthesis and Stability Evaluation of Polymer for IPS Type Liquid Crystal Aligner>

[Example of synthesis of polyamic acid as a specific polymer]

Synthesis Example A-IPS1

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

A small amount of this solution was fractionated and N-methyl-2-pyrrolidone was added thereto to give a solution having a polyamic acid concentration of 10 wt%, and the solution viscosity was 75 mPa · s.

The polymer solution was allowed to stand at 20 占 폚 for 3 days. As a result, the polymer solution was not gelated, and storage stability was good.

[Synthesis example of other polyamic acid]

Synthesis Example a-IPS2

Was the same as that of 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 the tetracarboxylic acid dianhydride. To obtain a solution containing 15 wt% of polyamic acid (a-IPS2).

A small amount of this solution was collected and N-methyl-2-pyrrolidone was added thereto to give a solution having a polyamic acid concentration of 10 wt%, and the solution viscosity was 63 mPa · s.

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

The evaluation of the polyamic acid (a-IPS2) was not performed.

[Example of synthesis 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 dianhydrides and 4,4'-diaminodiphenyl ether (A-IPS3) was obtained by dissolving 160 g (0.80 mol) of p-phenylenediamine and 110 g (0.20 mol) of p-phenylenediamine in 2,300 g of N-methyl- 15% by weight.

A small amount of this solution was collected and added to N-methyl-2-pyrrolidone to give a solution having a polyamic acid concentration of 10 wt%, and the solution viscosity was 74 mPa · s.

The polymer solution was allowed to stand at 20 占 폚 for 3 days. As a result, the polymer solution was not gelated, and storage stability was good.

Synthesis Example A-IPS4

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 the tetracarboxylic acid dianhydride To obtain a solution containing 15 wt% of polyamic acid (A-IPS4).

A small amount of this solution was collected and N-methyl-2-pyrrolidone was added thereto to prepare a solution having a polyamic acid concentration of 10 wt%, and the solution viscosity was 60 mPa · s.

The polymer solution was allowed to stand at 20 占 폚 for 3 days. As a result, the polymer solution was not gelated, and storage stability was good.

Synthesis Example A-IPS5

180 g (0.80 mol) of 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic dianhydride and 44 g (0.20 mol) of pyromellitic dianhydride as tetracarboxylic dianhydrides and 4,4'-diaminodiphenylamine (1.0 mole) was dissolved in 2,400 g of N-methyl-2-pyrrolidone and the reaction was carried out at 40 占 폚 for 3 hours to obtain a solution containing 15 mass% of polyamic acid (A-IPS5).

A small amount of this solution was collected and N-methyl-2-pyrrolidone was added to obtain a solution having a polyamic acid concentration of 10 wt%, and the solution viscosity was 65 mPa · s.

The polymer solution was allowed to stand at 20 占 폚 for 3 days. As a result, the polymer solution was not gelated, and storage stability was good.

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 dianhydrides and 4,4'-diaminodiphenyl ether Except that 100 g (0.50 mole) of 4,4'-diaminodiphenylamine and 100 g (0.50 mole) of 4,4'-diaminodiphenylamine were respectively used in the same manner as in Synthesis Example A-IPS5 &Lt; / RTI &gt;

A small amount of this solution was collected and added with N-methyl-2-pyrrolidone to give a solution having a polyamic acid concentration of 10 wt%, and the solution viscosity was 70 mPa · s.

The polymer solution was allowed to stand at 20 占 폚 for 3 days. As a result, the polymer solution was not gelated, and storage stability was good.

[Synthesis example of other polyamic acid]

Synthesis Example a-IPS7

224 g (1.0 mol) of 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 108 g (1.0 mol) of p-phenylenediamine as diamine were dissolved in N-methyl-2-pyrrolidone 1,900 g, and the reaction was carried out at 40 占 폚 for 3 hours to obtain a solution containing 15 wt% of polyamic acid (a-IPS7).

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

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

The evaluation of the polyamic acid (a-IPS7) was not performed.

Synthesis Example a-IPS8

(A-IPS8) was polymerized in the same manner as in Synthesis Example A-IPS5 except that 224 g (1.0 mole) of 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic acid dianhydride was used as the tetracarboxylic acid dianhydride. % Solution.

This solution was in the form of a solution at the reaction temperature (40 ° C), but since the gelation occurred during cooling to room temperature, the viscosity could not be measured.

The evaluation of the polyamic acid (a-IPS8) was not performed.

Synthesis Example a-IPS9

220 g (1.0 mole) of pyromellitic dianhydride as tetracarboxylic acid dianhydride and 110 g (1.0 mole) of p-phenylenediamine as a diamine were dissolved in 1,800 g of N-methyl-2-pyrrolidone, The reaction was carried out to obtain a solution containing 15 wt% of polyamic acid (a-IPS9).

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

The polymer solution was allowed to stand at 20 占 폚 for 3 days. As a result, the polymer solution was not gelated, and storage stability was good.

Synthesis Example a-IPS10

220 g (1.0 mol) of pyromellitic dianhydride as tetracarboxylic dianhydride, 160 g (0.80 mol) of 4,4'-diaminodiphenyl ether as diamine and 22 g (0.20 mol) of p- Was dissolved in 2,300 g of 2-pyrrolidone and reacted at 40 占 폚 for 3 hours to obtain a solution containing 15 mass% of polyamic acid (a-IPS10).

A small amount of this solution was collected and N-methyl-2-pyrrolidone was added to obtain a solution having a polyamic acid concentration of 10 wt%, and the solution viscosity was 71 mPa · s.

The polymer solution was allowed to stand at 20 占 폚 for 3 days. As a result, the polymer solution was not gelated, and storage stability was good.

Synthesis Example a-IPS11

200 g (0.90 mol) of pyromellitic dianhydride as tetracarboxylic dianhydride, 20 g (0.10 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 4,4'-diaminodiphenyl ether as a diamine Methyl-2-pyrrolidone was dissolved in 2,300 g of N-methyl-2-pyrrolidone and the reaction was carried out at 40 占 폚 for 3 hours to obtain polyamic acid (a-IPS11) 15% by weight.

A small amount of this solution was collected and N-methyl-2-pyrrolidone was added thereto to give a solution having a concentration of 10% by weight of polyamic acid. The viscosity of the solution was 77 mPa · s.

The polymer solution was allowed to stand at 20 占 폚 for 3 days. As a result, the polymer solution was not gelated, and storage stability was good.

[Example of synthesis of polyimide as specific polymer]

Synthesis Example B-IPS1

(0.50 mol) of 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic dianhydride and 112 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic acid dianhydride, and p- (0.10 mol) of 4,4'-diaminodiphenylmethane and 32 g (0.10 mol) of 4,4'-bis (trifluoromethyl) biphenyl were dissolved in N, N-dimethylformamide -Pyrrolidone, and the reaction was carried out at 40 DEG C for 3 hours to obtain a polyamic acid solution. A small amount of the obtained polyamic acid solution was added to N-methyl-2-pyrrolidone to prepare a solution having a polymer concentration of 10 wt%, and the solution viscosity was 40 mPa · s.

Then, 2,800 g of N-methyl-2-pyrrolidone was added to the resulting polyamic acid solution, and 400 g of pyridine and 310 g of acetic anhydride were added and the dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with γ-butyrolactone by solvent and then concentrated to obtain 2,300 g of a solution containing 15% by weight of polyimide (B-IPS1) having an imidization rate of about 92%. A small amount of this solution was fractionated and? -Butyrolactone was added to obtain a solution having a polyimide concentration of 10 wt%, and the viscosity of the solution was found to be 36 mPa · s.

The polymer solution was allowed to stand at 20 占 폚 for 3 days. As a result, the polymer solution was not gelated, and storage stability was good.

Synthesis Example B-IPS2

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

Subsequently, the dehydration ring closure reaction was carried out in the same manner as in Synthesis Example B-IPS1, the solvent in the system was replaced with γ-butyrolactone by solvent and then concentrated to obtain a polyimide (B-IPS2) having an imidization rate of about 94% 15% by weight. A small amount of this solution was fractionated and? -Butyrolactone was added to obtain a solution having a polyimide concentration of 10 wt%, and the viscosity of the solution was found to be 34 mPa · s.

The polymer solution was allowed to stand at 20 占 폚 for 3 days. As a result, the polymer solution was not gelated, and storage stability was good.

Synthesis Example B-IPS3

(0.50 mol) of 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic dianhydride and 112 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic acid dianhydride, and p- (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 To obtain a polyamic acid solution. A small amount of the obtained polyamic acid solution was collected and N-methyl-2-pyrrolidone was added thereto to obtain a solution having a polymer concentration of 10% by weight, and the solution viscosity was 46 mPa · s.

Next, 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 carried out at 110 DEG C for 4 hours. After the dehydration cyclization reaction, the solvent in the system was replaced with γ-butyrolactone by solvent and then concentrated to obtain 2,300 g of a solution containing 15% by weight of polyimide (B-IPS3) having an imidization rate of about 93%. A small amount of this solution was fractionated and? -Butyrolactone was added thereto to obtain a solution having a polyimide concentration of 10 wt%, and the solution viscosity was 42 mPa · s.

The polymer solution was allowed to stand at 20 占 폚 for 3 days. As a result, the polymer solution was not gelated, and storage stability was good.

Synthesis Example B-IPS4

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

Subsequently, the dehydration ring closure reaction was carried out in the same manner as in Synthesis Example B-IPS3, the solvent in the system was replaced with γ-butyrolactone solvent and then concentrated to obtain a polyimide (B-IPS4) having an imidization rate of about 91% To obtain 2,300 g of a solution containing 15% by weight. A small amount of this solution was collected, and? -Butyrolactone was added thereto to obtain a solution having a polyimide concentration of 10 wt%, and the solution viscosity was 33 mPa · s.

The polymer solution was allowed to stand at 20 占 폚 for 3 days. As a result, the polymer solution was not gelated, and storage stability was good.

[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 the tetracarboxylic acid dianhydride. A small amount of this solution was taken out and N-methyl-2-pyrrolidone was added to obtain a solution having a polymer concentration of 10% by weight, and the solution viscosity was 48 mPa · s.

Subsequently, the dehydration ring closure reaction was carried out in the same manner as in Synthesis Example B-IPS1, the solvent in the system was replaced with gamma -butyrolactone by solvent and then concentrated to obtain a polyimide (b-IPS5) having an imidization rate of about 93% 15% by weight. A small amount of this solution was fractionated and? -Butyrolactone was added to obtain a solution having a polyimide concentration of 10 wt%, and the viscosity of the solution was found to be 45 mPa · s.

The polymer solution was allowed to stand at 20 占 폚 for 3 days. As a result, the polymer solution was not gelated, and storage stability was good.

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 the tetracarboxylic acid dianhydride. A small amount of this solution was collected and added with N-methyl-2-pyrrolidone to obtain a solution having a polymer concentration of 10 wt%, and the solution viscosity was 45 mPa · s.

Subsequently, the dehydration ring closure reaction was carried out in the same manner as in Synthesis Example B-IPS4, the solvent in the system was replaced with γ-butyrolactone solvent and then concentrated to obtain a polyimide (b-IPS6) having an imidization rate of about 93% 15% by weight. A small amount of this solution was fractionated and? -Butyrolactone was added to obtain a solution having a polyimide concentration of 10 wt%, and the viscosity of the solution was found to be 41 mPa · s.

The polymer solution was allowed to stand at 20 占 폚 for 3 days. As a result, the polymer solution was not gelated, and storage stability was good.

<Preparation and Evaluation of TN Type Liquid Crystal Aligning Agent>

Example TN-1

(I) Preparation of liquid crystal aligning agent

(A-TN1) which is a solution containing the polyamic acid (A-TN1) obtained in Synthesis Example A-TN1 as a specific polymer and the amount equivalent to 80 parts by weight in terms of polyamic acid (B-TN2) as a solution containing the polyimide (b-TN2) obtained in Example 1, and adding thereto 20 parts by weight of N-methyl-2-pyrrolidone (NMP) -Butyrolactone (BL) and butyl cellosolve (BC) were added in such a manner that the final solvent composition was NMP: BL: BC = 17: 71: 12 (weight ratio) , And N'-tetraglycidyl-4,4'-diaminodiphenyl methane were added to prepare a solution having a solid concentration of 3.5% by weight. This solution was sufficiently stirred, and then filtered using a filter having a pore diameter of 1 탆 to prepare a liquid crystal aligning agent.

(II) Evaluation of liquid crystal aligning agent

(1) Preparation of TN type liquid crystal cell

The liquid crystal aligning agent prepared above was applied to the transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film using a liquid crystal alignment film printing machine (manufactured by Nihon Shinsengattsu Co., Ltd.) and heated on a hot plate at 80 캜 for 1 minute (Prebaked) to remove the solvent, and then heated (post baking) on a hot plate at 200 ° C for 10 minutes to form a coating film having an average film thickness of 600 Å.

The coating film was rubbed with a rubbing machine having a roll covered with a rayon cloth at a roll rotation speed of 500 rpm, a stage moving speed of 3 cm / sec, and a hair pressing indentation length of 0.4 mm to give a liquid crystal aligning ability. Thereafter, the substrate was ultrasonically cleaned 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 to obtain a pair of substrates (two substrates) each having a liquid crystal alignment film.

Next, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 占 퐉 was applied to the outer edge of the surface having one liquid crystal alignment film among the pair of substrates, and a pair of substrates was laminated on the liquid crystal alignment film surface And then the adhesive was cured. Subsequently, a nematic liquid crystal (Merck, MLC-6221) was filled between a pair of substrates from a liquid crystal injection port, and then a liquid crystal injection hole was sealed with an acrylic photo-curable adhesive to manufacture a liquid crystal cell.

(2) Evaluation of heat resistance stability

The durability against thermal stress was evaluated using the voltage holding ratio as an index. As the device for measuring the voltage holding ratio, a type &quot; VHR-1 &quot; manufactured by Toyo Technica Co., Ltd. was used.

A voltage of 5 V was applied to the liquid crystal cell at a temperature of 60 占 폚 for an application time of 60 microseconds and a span of 167 milliseconds at a temperature of 60 占 폚 and the voltage maintenance ratio was measured 167 milliseconds after the voltage was removed Initial voltage reserve ratio VHR0).

Subsequently, the liquid crystal display element after the measurement of the voltage stress compensation applied voltage was held for 1,000 hours in an oven at 100 deg. C to apply thermal stress, and then the voltage maintenance ratio was measured again in the same manner as described above VHR1).

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

VHR = VHR0 - VHR1 (1)

The difference ΔVHR between the voltages before and after the application of the thermal stress was obtained. When this value is within 5%, it can be evaluated that the heat stability is good.

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 the specific polymer and the other polymer, a solution containing a polymer of the kind and amount described in Table 1 was used, and each solvent was added so that the final solvent composition was as shown in Table 1 A liquid crystal aligning agent was prepared and evaluated in the same manner as in Example TN-1.

The evaluation results are shown in Table 1.

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

The abbreviations of the solvents in Table 1 are as follows.

NMP: N-methyl-2-pyrrolidone

BL:? -Butyrolactone

BC: butyl cellosolve

&Lt; Preparation and evaluation of VA type liquid crystal aligning agent >

Example VA-1

(I) Preparation of liquid crystal aligning agent

N-methyl-2-pyrrolidone and butyl cellosolve were added to a solution containing the polyimide (B-VA1) obtained in Synthesis Example B-VA1 as a polymer, and N, N, N ', N'-tetraglycidyl-m-xylylenediamine was added in an amount of 5 parts by weight based on 100 parts by weight of the polyimide used and sufficiently stirred to obtain a solution having a solvent composition of N-methyl-2-pyrrolidone: butyl cellosolve = 50: 50 (weight ratio), and a solid content concentration of 3.5% by weight. This solution was filtered using a filter having a pore size of 1 탆 to prepare a liquid crystal aligning agent.

(II) Evaluation of liquid crystal aligning agent

(1) Production of VA type liquid crystal cell

The liquid crystal aligning agent prepared above was applied on a transparent conductive film made of an ITO film formed on one side of a glass substrate having a thickness of 1 mm by a spinner and prebaked on a hot plate at 80 DEG C for 1 minute, Followed by post-baking at 210 占 폚 for 30 minutes to form a coating film (liquid crystal alignment film) having a thickness of 80 nm. This operation was repeated to obtain two substrates (one pair) each having a liquid crystal alignment film.

Next, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 3.5 탆 was applied to the outer edge of the surface having one liquid crystal alignment film among the pair of substrates, and the pair of substrates were opposed to each other so that the liquid crystal alignment films opposed to each other, After that, the adhesive was cured. Subsequently, a negative-type liquid crystal (MLC-6608, manufactured by Merck Ltd.) was charged between the substrates from the liquid crystal injection port, and then a liquid crystal injection hole was sealed with an acrylic-based photo-curable adhesive to produce a liquid crystal cell.

(2) Evaluation of heat resistance stability

Using the liquid crystal cell prepared above, thermal stability was evaluated in the same manner as in Example TN-1. However, in the case of the VA type liquid crystal cell, it can be evaluated that the heat stability is good when the value of the difference ΔVHR between before and after the application of 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

A liquid crystal aligning agent was prepared and evaluated in the same manner as in Example VA-1 except that a solution containing the polymer shown in Table 2 was used as the polymer in Example VA-1.

The evaluation results are shown in Table 2.

&Quot; - &quot; in Table 2 indicates that the polymer corresponding to the column was not used.

The abbreviations of the solvents in Table 2 are the same as those in Table 1.

&Lt; Preparation and evaluation of IPS liquid crystal aligning agent >

Example IPS-1

(I) Preparation of liquid crystal aligning agent

N-methyl-2-pyrrolidone and butyl cellosolve were added as a solvent to the solution containing the polyamic acid (A-IPS1) obtained in Synthesis Example A-IPS1 as a polymer, and N, N And N ', N'-tetraglycidyl-m-xylylenediamine were added to 100 parts by weight of the polyamic acid used, and the mixture was thoroughly stirred to prepare a solution having a solvent composition of N-methyl-2-pyrrolidone: butyl cell Rosorb = 80: 20 (weight ratio), and a solid content concentration of 3.5% by weight. This solution was filtered using a filter having a pore size of 1 탆 to prepare a liquid crystal aligning agent.

(II) Evaluation of liquid crystal aligning agent

(1) Production of liquid crystal cell

A liquid crystal cell was produced in the same manner as in Example TN-1 except that the liquid crystal aligning agent prepared above was used, and the heat stability was evaluated.

The evaluation results are shown in Table 3.

Further, the inventors of the present invention have experimentally confirmed that a TN liquid crystal cell produced herein can be used as a TN liquid crystal cell, but a TN liquid crystal cell can be alternatively used as a sample for evaluating the heat stability of an IPS liquid crystal cell .

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

A liquid crystal aligning agent was prepared and evaluated in the same manner as in Example IPS-1 except that a solution containing the polymer shown in Table 3 was used as the polymer in the IPS-1.

The evaluation results are shown in Table 3.

Examples IPS-6 to 9 and comparative examples ips-4 and ips-5

In Example IPS-1, a solution containing the polymer shown in Table 3 as a polymer was dissolved in N-methyl-2-pyrrolidone (NMP),? -Butyrolactone (BL) Except that each of these solvents was added so as to have a final solvent composition of NMP: BL: BC = 10: 70: 20 (weight ratio), to thereby obtain a liquid crystal aligning agent Were prepared and evaluated.

The evaluation results are shown in Table 3.

"-" in Table 3 indicates that the polymer corresponding to the column was not used.

The abbreviations of the solvents in Table 3 are the same as those in Table 1.

Claims (6)

1. A liquid crystal aligning agent comprising at least one polymer selected from the group consisting of a polyamic acid obtained by reacting a tetracarboxylic acid dianhydride with a diamine and a polyimide obtained by dehydrocondylating the polyamic acid,
Wherein the tetracarboxylic acid dianhydride is at least one selected from the group consisting of 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic dianhydride and 1R, 2S, 4S, 5R- cyclohexanetetracarboxylic dianhydride, Is contained in an amount of 5 to 80 mol% based on the total tetracarboxylic dianhydride,
Wherein the diamine is composed of 20 to 97 mol% of the first diamine and 3 to 80 mol% of the second diamine, or 70 to 100 mol% of the first diamine and 0 to 30 mol% of the second diamine, The total ratio of the first diamine and the second diamine is 100 mol% based on the total diamine,
The first diamine may be selected from the group consisting of p-phenylenediamine, 3,5-diaminobenzoic acid, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 2,2'- , 4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-diaminodiphenylamine and 4,4'- -Phenylene diisopropylidene) dianiline, and at least one member selected from the group consisting of
Wherein the second diamine is selected from the group consisting of 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 Benzoyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane and a compound represented by the following formula (A-1)
A liquid crystal aligning agent,

(Wherein (A-1) of, X ^I is an alkylene group, having a carbon number of 1~3 ^* -O-, ^* -COO- or ^* -OCO- (However, the bond attached to "*" hands are engaged with diamino group A is 0 or 1, b is an integer of 0 to 2, and c is an integer of 1 to 20). The method according to claim 1,
Wherein the tetracarboxylic acid dianhydride is selected from the group consisting of 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a, 4,5,9b- (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 [ 3.2.1] octane-2,4-dione-6-spiro-3 '- (tetrahydrofuran-2', 5'- dione), 5- (2,5- dioxotetrahydro- Carboxymethylnorbornane-2: 3,5: 6-2 anhydride, 2,4,6-tricarboxy-2-carboxymethylnorbornane- 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 , And 10-tetraene. The liquid crystal aligning agent according to claim 1, wherein the liquid crystal aligning agent further comprises at least one member selected from the group consisting of: delete 3. The method according to claim 1 or 2,
A liquid crystal aligning agent further comprising a compound having at least one epoxy group in the molecule. A liquid crystal alignment film formed by the liquid crystal aligning agent according to claim 1 or 2. A liquid crystal display element comprising the liquid crystal alignment film according to claim 5.