KR20090131259A - Liquid crystal aligning agent and liquid crystal display element - Google Patents

Abstract

The objective of this invention is providing the liquid crystal aligning agent which provides the liquid crystal aligning film excellent in liquid crystal aligning property, rubbing resistance, and heat resistance.

The liquid crystal aligning agent is a polyamic acid obtained by reacting a tetraamine dianhydride with a diamine containing a specific compound represented by a compound represented by the following formula (A-2) and an imidized polymer formed by dehydrating and ring-closing the polyamic acid. It contains at least one polymer selected from the group consisting of.

[Formula A-2]

Description

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

This invention relates to a liquid crystal aligning agent and a liquid crystal display element. In more detail, it is related with the liquid crystal aligning agent which provides the liquid crystal aligning film excellent in liquid crystal orientation, rubbing resistance, and heat resistance, and a liquid crystal display element excellent in display quality and long-term reliability.

At present, as a liquid crystal display element, a liquid crystal aligning film is formed on the surface of the board | substrate with which the transparent conductive film was provided, it is set as a board | substrate for liquid crystal display elements, the two sheets are opposed, and the layer of the nematic liquid crystal which has positive dielectric anisotropy in the clearance gap is formed, A so-called TN type liquid crystal display device having a so-called TN type (Twisted Nematic) liquid crystal cell in which the long axis of the liquid crystal molecules is continuously twisted 90 ° from one substrate to the other substrate is known (the following patent document). One). In addition, an STN (Super Twisted Nematic) type liquid crystal display element (Patent Document 2) which can realize a high contrast ratio compared to a TN type liquid crystal display element, or an IPS (In-Plane Switching) type liquid crystal display element having less visual dependence Patent Literatures 3 and 4, Non-Patent Literature 1), an optically compensated bend (Optically Compensated Birefringence = OCB) type liquid crystal display device (Non-Patent Literature 2 below), which has a low visual dependence and excellent high-speed response of an image screen, is negative. VA (Vertical Alignment) type liquid crystal display elements using the nematic liquid crystal having dielectric anisotropy (Patent Document 4, Non-Patent Documents 3 to 5) and the like have been developed.

As a material of the liquid crystal aligning film in these liquid crystal display elements, the film | membrane containing organic polymer resins, such as a polyimide, polyamide, and polyester, is known conventionally, but especially polyimide is excellent in heat resistance, affinity with a liquid crystal, mechanical strength, etc. Therefore, it is used for many liquid crystal display elements (patent document 5 below).

In the liquid crystal aligning film currently used for the TN type, STN type, and IPS type liquid crystal display element, in most cases, a rubbing process is given to an organic resin film, and the liquid crystal aligning capability is provided by this. In recent years, in order to further improve the ability of the liquid crystal molecules to be aligned by the alignment film, the indentation depth of the rubbing cloth and the number of rotations of the rubbing rolls used in the rubbing treatment are increased, or the moving speed of the stage is reduced, so that the conditions of the rubbing treatment become more severe. have. As a result, in the rubbing treatment process, the liquid crystal aligning film was peeled off by the rubbing treatment, resulting in a problem that the liquid crystal alignment ability was lowered.

In addition, in recent years, with the spread of liquid crystal televisions, high definition of contents, and improvement of moving picture fixing technologies, liquid crystals of high-speed response have been used in any liquid crystal display devices of TN type, STN type, IPS type and VA type. have. It is pointed out that the liquid crystal display element using such a high-speed responsive liquid crystal deteriorates heat stability, that is, the performance which can maintain a high voltage retention even after applying thermal stress for a long time. This is considered to be an inevitable problem of using a high-speed responsive liquid crystal, and it is desired to solve this problem by improving the liquid crystal alignment film.

[Patent Document 1] Japanese Patent Application Laid-Open No. 4-153622

[Patent Document 2] Japanese Unexamined Patent Publication No. 60-107020

[Patent Document 3] Japanese Unexamined Patent Application Publication No. 56-91277

[Patent Document 4] US Patent No. 5928733

[Patent Document 5] Japanese Patent Application Laid-Open No. 11-258605

[Patent Document 6] Japanese Patent Application Laid-Open No. 62-165628

[Non-Patent Document 1] Liq. Cryst., Vol. 22, 379 (1996)

[Non-Patent Document 2] Liquid Crystal, vol. 3, No. 2, 117 (1999)

[Non-Patent Document 3] Liquid Crystal, vol. 3, No. 4, 272 (1999)

[Non-Patent Document 4] Jpn Appl. phys., vol. 36, 428 (1997)

[Non-Patent Document 5] SID '94 Digest, p. 927 (1997)

This invention is made | formed in view of the said situation, The objective is to provide the liquid crystal aligning agent which provides the liquid crystal aligning film excellent in liquid crystal orientation, rubbing resistance, and heat resistance, and the liquid crystal display element excellent in display quality and long-term reliability.

Still other objects and advantages of the present invention are apparent from the following description.

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

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

It is achieved by the liquid crystal aligning agent in which the said diamine contains the compound represented by following formula (A).

[Formula A]

In Formula A, R ^I represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a fluoroalkyl group having 1 to 30 carbon atoms, a phenyl group, a fluorophenyl group, an alkylphenyl group having 1 to 30 carbon atoms or a fluorine having 1 to 30 carbon atoms. Is a fluoroalkylphenyl group having a roalkyl group, R ^II is a single bond, an oxygen atom, -COO- ^* (wherein the bond to which "*" is attached is-(CH ₂ ) _{n 2} -C≡R ^I side) or -NR (Wherein R is an alkyl group having 1 to 8 carbon atoms or an alkenyl group or alkynyl group having 2 to 8 carbon atoms), R ^III is an alkyl group having 1 to 4 carbon atoms, n1 is 0 or 1, n2 is 0 to 8 Integer, n3 is an integer from 0 to 3, provided that when R ^II is a single bond, n1 is 0.

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

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

According to this invention, the liquid crystal aligning agent which provides the liquid crystal aligning film excellent in liquid crystal aligning property, rubbing resistance, and heat resistance, the display quality, and the liquid crystal display element excellent in long-term reliability can be provided.

The liquid crystal aligning agent of this invention is chosen from the group which consists of the polyamic acid obtained by making tetracarboxylic dianhydride and the diamine containing the compound represented by the said Formula A, and the imidation polymer formed by dehydrating and ring-closing the said polyamic acid. It contains at least one polymer.

Tetracarboxylic dianhydride

As tetracarboxylic dianhydride used for synthesize | combining the polyamic acid which the liquid crystal aligning agent of this invention can contain, For example, aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic Acid dianhydrides; and the like.

As said aliphatic tetracarboxylic dianhydride, For example, butane tetracarboxylic dianhydride etc .;

As said alicyclic tetracarboxylic dianhydride, it is 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic, for example. Acid dianhydrides, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4 , 5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,5, 6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride,

1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3- Dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan -1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1, 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) Naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-ethyl-5- (tetrahydro-2,5-dioxo 3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro- 2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-ethyl- 5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexa Hydro-5,8-dimethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 5- (2, 5-D Sotetrahydrofuranyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetra Carboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2, 5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2: 3,5: 6-anhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, represented by the following formulas TI and T-II, respectively Compound or the like;

[Formula T-I]

[Formula T-II]

(In the above formula, R ¹ and R ³ each represent a divalent organic group having an aromatic ring, R ² and R ⁴ each represent a hydrogen atom or an alkyl group, and a plurality of R ² and R ⁴ are the same or different, respectively. Can be)

As said aromatic tetracarboxylic dianhydride, a pyromellitic dianhydride, 3,3 ', 4,4'- benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-biphenyl Sulfontetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'- Biphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3', 4,4'- tetraphenylsilane tetracarboxylic dianhydride , 1,2,3,4-furtetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4'-bis (3,4 -Dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropyl Dendiphthalic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetraca Acid dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'- diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4'- diphenylmethane dianhydride, ethylene glycol-bis (anhydrotrimelitate), propylene glycol-bis (anhydrotri Mellitate), 1,4-butanediol-bis (anhydrotrimellitate), 1,6-hexanediol-bis (anhydrotrimellitate), 1,8-octanediol-bis (anhydrotrimellitate) And 2,2-bis (4-hydroxyphenyl) propane-bis (anhydrotrimellitate), the compounds represented by the following general formulas T-1 to T-4, and the like. These tetracarboxylic dianhydrides can be used individually by 1 type or in combination of 2 or more types.

[Formula T-1]

[Formula T-2]

[Formula T-3]

[Formula T-4]

As a specific example of the compound represented by the said General formula T-I, For example, the compound etc. which are represented by each of following formula T-5-T-7;

[Formula T-5]

[Formula T-6]

[Formula T-7]

As a specific example of the compound represented by the said general formula T-II, the compound etc. which are represented, for example by following Chemical formula T-8 are mentioned, respectively.

[Formula T-8]

The tetracarboxylic dianhydride used for synthesizing the polyamic acid which the liquid crystal aligning agent of the present invention may contain is the butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracar among the above. Acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5 Tricarboxycyclopentylacetic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5- (tetrahydro-2,5-dioxo-3 -Furanyl) -naphtho [1,2-c] furan-1,3-dione, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride , 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetra Drofuran-2 ', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 3 , 5,6-tricarboxy-2-carboxynorbornane-2: 3,5: 6-anhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8 , 10-tetraone, pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenylsulfontetracarboxylic dianhydride , 2,3 ', 2,3'-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, each of the formulas T-5 to T-7 It is preferable to include one or more selected from the group consisting of the compound represented by the compound represented by the above formula (T-8) (hereinafter referred to as "specific tetracarboxylic dianhydride (1)") to express good liquid crystal orientation. It is preferable from the viewpoint that it can.

The tetracarboxylic dianhydride used for synthesizing the polyamic acid which the liquid crystal aligning agent of the present invention may contain, the specific tetracarboxylic dianhydride (1) as described above with respect to the total tetracarboxylic dianhydride. It is preferable to contain 20 mol% or more, It is more preferable to contain 50 mol% or more, It is preferable to contain especially 80 mol% or more.

<Diamine>

The diamine used for synthesize | combining the polyamic acid which the liquid crystal aligning agent of this invention can contain is the diamine containing the compound represented by the said General formula (A).

As R ^I in the formula (A), an alkylphenyl group having 1 to 12 carbon atoms or a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, a phenyl group, a fluorophenyl group, or an alkyl group having 1 to 12 carbon atoms. It is preferable that it is a fluoroalkylphenyl group which has a fluoroalkyl group, and is a hydrogen atom, a methyl group, a C12-C20 linear alkyl group, a C12-C20 linear fluoroalkyl group, a phenyl group, a C6-C12 linear alkyl group It is more preferable that it is an alkylphenyl group which has, or a fluoroalkylphenyl group which has a C6-C12 linear fluoroalkyl group. It is preferable that the alkyl group or fluoroalkyl group which these alkylphenyl group and fluoroalkylphenyl group have is located in the 4 position of a phenyl group, respectively. R ¹ is a straight alkyl group having 12 to 20 carbon atoms, a fluoroalkyl group having 12 to 20 carbon atoms, a phenyl group, an alkylphenyl group having a straight chain alkyl group having 6 to 12 carbon atoms at the 4 position, or a straight chain having 6 to 12 carbon atoms at the 4 position; In the case of a fluoroalkylphenyl group having a fluoroalkyl group, the compound represented by the formula (A) has a good pretilt angle expression function.

As n1 in the said Formula A, it is preferable that it is 0, and as n2, it is preferable that it is 1.

As R ^III in the general formula (A), a methyl group is preferable, n3 is preferably 0 or 1, and more preferably 0.

As a compound represented by the said Formula (A), the compound represented by each of following formula (A-1)-A-9 is mentioned. The group -C _b H _{2b + 1} in the formula A-8 is preferably linear.

[Formula A-1]

[Formula A-2]

[Formula A-3]

[Formula A-4]

[Formula A-5]

[Formula A-6]

[Formula A-7]

[Formula A-8]

[Formula A-9]

(A in Chemical Formula A-4 is an integer of 1 to 30, and b in Chemical Formula A-8 is an integer of 12 to 20).

The compound represented by the said Formula (A) can be synthesize | combined by combining suitably the method in organic chemistry, respectively.

For example, the compound represented by the formula (A-1), for example, by reacting 3,5-dinitrobenzoic acid with propargyl bromide in the presence of a suitable base such as diazabicyclo undecene to form an ester bond It can obtain by reducing a nitro group using suitable reducing agents, such as and tin chloride.

The compound represented by the formula (A-2), for example, by reacting 2,4-dinitrochlorobenzene with propargyl alcohol in the presence of a suitable alkali such as t-butoxy potassium to form an ether bond, A method of reducing the nitro group using a suitable reducing agent such as tin chloride or acetic anhydride and sodium acetate in water to act on amidol to protect the amino group by acetylating and then protecting this and propargyl bromide with an aqueous solution of sodium hydroxide It can be obtained by a method of reacting by heating and stirring in an ether to form an ether bond and deprotection under reflux in hydrochloric acid.

The compound represented by the above formula (A-3) may be reacted with propargyl bromide by reacting 2,5-dinitrophenol with propargyl bromide in the presence of a suitable base such as potassium carbonate, for example. It can obtain by reducing a nitro group using a reducing agent.

For example, the compound represented by the above formula (A-4) reacts with an excess amount of an alkylamine having _a C _a H _{2a + 1} -group and propargyl bromide to synthesize a secondary amine, which is then used as a 2,4-di It can be obtained by tertiary amine using a suitable base such as nitrofluorobenzene and cesium fluoride and then reducing the nitro group using a suitable reducing agent such as tin chloride.

The compound represented by the formula (A-5) can be obtained in the same manner as in the case of the compound represented by the formula (A-4) except that allylamine is used instead of the alkylamine.

The compound represented by the formula (A-6) can be obtained in the same manner as in the case of the compound represented by the formula (A-4) except that dipropargylamine is used instead of the alkylamine.

The compound represented by the formula (A-7), for example, coupling trimethylsilylacetylene and 2,4-dinitrobromobenzene in the presence of a palladium complex, a copper salt and an amine (generally, "sonogashira coupling" It is obtained by removing a trimethylsilyl group in aqueous alkali solution after being called.

The compound represented by the above formula (A-8) can be obtained in the same manner as in the case of the compound represented by the above formula (A-7) except for using alkylacetylene having a C _b H _{2b + 1-} group instead of trimethylsilylacetylene. .

The compound represented by the above formula (A-9) reacts N, N, N ', N'-tetraallyl-3,5-diaminophenol and propargyl bromide in the presence of a suitable base such as sodium hydride, for example. After forming an ether bond, it can obtain by deprotection with a palladium catalyst etc.

As a diamine used for synthesizing the polyamic acid which the liquid crystal aligning agent of the present invention may contain, only the compound represented by the above formula (A) may be used, or other diamine may be used together with the compound represented by the above formula (A). . Here, as another diamine which can be used together with the compound represented by the said Formula (A), For example, aromatic diamines other than the compound represented by the said Formula (A), aliphatic diamine, alicyclic diamine, two primary amino groups in a molecule | numerator, and said 1 And diamines having nitrogen atoms other than the class amino groups, mono-substituted phenylenediamines other than the compound represented by the formula (A), diamino organosiloxane, and the like.

As aromatic diamines other than the compound represented by the said Formula (A), For example, p-phenylenediamine, m-phenylenediamine, 4,4'- diamino diphenylmethane, 4,4'- diamino diphenylethane, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 4,4'-diaminodiphenylether, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diamino Biphenyl, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 3,3'-ditrifluoromethyl-4,4'-diaminobiphenyl, 5-amino-1 -(4'-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 3,4'-diaminodiphenyl Ether, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane , 2,2-bis [4- (4-aminophenoxy) phenyl] hexaflu Ropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy ) Benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2, 7-diaminofluorene, 9,9-dimethyl-2,7-diaminofluorene, 9,9-bis (4-aminophenyl) fluorene, 4,4'-methylene-bis (2-chloroaniline) , 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3 , 3'-dimethoxy-4,4'-diaminobiphenyl, 1,4,4 '-(p-phenyleneisopropylidene) bisaniline, 4,4'-(m-phenyleneisopropylidene) Bisaniline, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-diamino-2,2'-bis (trifluoro Rhomethyl) biphenyl, 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl, Compounds represented by the following formulas D-1 to D-5, and the like;

[Formula D-1]

[Formula D-2]

[Formula D-3]

[Formula D-4]

[Formula D-5]

(Y in Formula D-4 is an integer of 2-12, z in Formula D-5 is an integer of 1-5)

As aliphatic diamine, For example, 1, 1- methacrylylenediamine, 1, 3- propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, etc .;

Examples of the alicyclic diamines include 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindenylenedimethylenediamine and tricyclo [6.2.1.0. ^2,7 ] ^{-undecylenedimethyldiamine} , 4,4'-methylenebis (cyclohexylamine), etc .;

As a diamine which has two primary amino groups and nitrogen atoms other than the said primary amino group in a molecule | numerator, it is 2, 3- diamino pyridine, 2, 6- diamino pyridine, 3, 4- diamino pyridine, 2, 4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrazine, 5,6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino -1,3,5-triazine, 1,4-bis (3-aminopropyl) piperazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2,4 -Diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-phenyl-1,3,5-triazine, 2,4-diamino-6-methyl-s -Triazine, 2,4-diamino-1, 3,5-triazine, 4,6-diamino-2-vinyl-s-triazine, 2,4-diamino-5-phenylthiazole, 2 , 6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5-diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridinlac Tate, 3,8-diamino-6-phenylphenanthridine, 1,4-diaminopiperazine, 3,6-dia Noacridin, bis (4-aminophenyl) phenylamine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N -Phenyl-3,6-diaminocarbazole, N, N'-di (4-aminophenyl) -benzidine, a compound represented by the following formula (DI), a compound represented by the following formula (D-II), and the like;

[Formula D-I]

In formula DI, R ⁵ is a monovalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine, and piperazine, X ¹ is a divalent organic group, and R is ⁶ is an alkyl group having 1 to 4 carbon atoms, a1 is an integer of 0 to 3)

[Formula D-II]

(Formula D-II, R ⁷ is a divalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, each of X ² is a divalent organic group) And a plurality of X ^{2 's} may be the same or different, and each R ⁸ is an alkyl group having 1 to 4 carbon atoms, and a2 is an integer of 0 to 3, respectively.

As mono-substituted phenylenediamines other than the compound represented by the said Formula (A), For example, the compound etc. which are represented by following formula (D-III);

[Formula D-III]

(In Formula D-III, R ⁹ is -O-, -COO- ^* , -OCO- ^* , -NHCO- ^* , -CONH- ^* , provided that a bond with "*" is bonded to R ^10. ) Or -CO-, R ¹⁰ is a monovalent organic group having 6 to 30 carbon atoms or an alkyl group having a skeleton or group selected from a steroid skeleton, a trifluoromethylphenyl group, a trifluoromethoxyphenyl group, and a fluorophenyl group, and R ¹¹ is An alkyl group having 1 to 4 carbon atoms, a3 is an integer of 0 to 3)

As diamino organosiloxane, the compound etc. which are represented by following General formula (D-IV) are mentioned, for example. These diamine can be used individually or in combination of 2 or more types.

[Formula D-IV]

(In formula (D-IV), R <^12> is a C1-C12 hydrocarbon group, respectively, two or more R <^12> may be same or different, respectively, p is an integer of 1-3, q is 1-20 Integer)

Aromatic diamines other than the compound represented by the formula (A), diamines having two primary amino groups and nitrogen atoms other than the primary amino group in the molecule, and benzene rings of mono-substituted phenylenediamines other than the compound represented by the formula (A), It may also be substituted with one or two or more alkyl groups (preferably methyl groups) having 1 to 4 carbon atoms. It is preferable that R <^6> , R <^8> and R <^11> in the said Formula (DI), D-II and D-III are respectively methyl groups, It is preferable that a1, a2 and a3 are each 0 or 1, and it is more preferable that it is 0. .

The steroid skeleton in R ¹⁰ of Formula (D-III) refers to a skeleton comprising a cyclopentano-perhydrophenanthrene nucleus or a skeleton in which one or two or more of its carbon-carbon bonds are double bonds. As a monovalent organic group of R <^10> which has such a steroid skeleton, it is preferable that it is C1-C51, and it is more preferable that it is C1-C29.

As a specific example of R <^10> which has such a steroid skeleton, it is a cholestan-3-yl group, a cholesta-5-en-3-yl group, a cholesta-24-en-3-yl group, cholesta-5,24-, for example. And a diene-3-yl group.

As a specific example of the compound represented by the said General formula (D-I), For example, the compound etc. which are represented by following General formula (D-6);

[Formula D-6]

As a specific example of a compound represented by the said General formula (D-II), For example, the compound etc. which are represented by following General formula (D-7);

[Formula D-7]

As a specific example of the compound represented by the said General formula (D-III), For example, dodecaneoxy-2,4-diaminobenzene, pentadecaneoxy-2,4-diaminobenzene, hexadecaneoxy-2,4- diami Nobenzene, octadecaneoxy-2,5-diaminobenzene, dodecaneoxy-2,5-diaminobenzene, pentadecaneoxy-2,5-diaminobenzene, hexadecaneoxy-2,5-diaminobenzene , Octadecaneoxy-2,5-diaminobenzene, and the compounds represented by the following formulas D-8 to D-16, etc. may be mentioned, respectively.

[Formula D-8]

[Formula D-9]

[Formula D-10]

[Formula D-11]

[Formula D-12]

[Formula D-13]

[Formula D-14]

[Formula D-15]

[Formula D-16]

Another diamine used in combination with the compound represented by the formula (A) when synthesizing the polyamic acid which may be contained in the liquid crystal aligning agent of the present invention is p-phenylenediamine, 4,4'-diaminodi Phenylmethane, 4,4'-diaminodiphenylsulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-ditrifluoromethyl -4,4'-diaminobiphenyl, 2,7-diaminofluorene, 4,4'-diaminodiphenylether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoro Propane, 4,4 '-(p-phenylenediisopropylidene) bisaniline, 4,4'-(m-phenylenediisopropylidene) bisaniline, 1,4-cyclohexanediamine, 4,4'-methylene Bis (cyclohexylamine), 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, phase Compounds represented by each of the formulas D-1 to D-5, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine , 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N , N'-di (4-aminophenyl) -benzidine, the compound represented by the formula (D-6), the compound represented by the formula (D-7), dodecaneoxy-2,4-diaminobenzene, pentadecaneoxy- 2,4-diaminobenzene, hexadecaneoxy-2,4-diaminobenzene, octadecaneoxy-2,5-diaminobenzene, dodecaneoxy-2,5-diaminobenzene, pentadecaneoxy-2, Selected from the group consisting of 5-diaminobenzene, hexadecaneoxy-2,5-diaminobenzene, octadecaneoxy-2,5-diaminobenzene and the compounds represented by the above formulas D-8 to D-16 Containing one or more (hereinafter referred to as "other specific diamines") It is preferable.

The diamine used for synthesizing the polyamic acid that the liquid crystal aligning agent of the present invention may contain preferably contains 1 to 80 mol% of the compound represented by the above formula (A) with respect to all diamines. It is more preferable, and it is especially preferable to contain 10-60 mol%.

The diamine used to synthesize the polyamic acid that the liquid crystal aligning agent of the present invention may contain preferably contains 20 to 99 mol% of other specific diamines as described above with respect to all diamines, and contains 50 to 99 mol%. It is more preferable to carry out, and it is especially preferable to contain 80-99 mol%.

Synthesis of Polyamic Acid

The polyamic acid which the liquid crystal aligning agent of this invention can contain can be obtained by making tetracarboxylic dianhydride and diamine as mentioned above react.

The use ratio of the tetracarboxylic dianhydride and the diamine compound used for the polyamic acid synthesis reaction is preferably such that the acid anhydride group of the tetracarboxylic dianhydride is 0.2 to 2 equivalents to 1 equivalent of the amino group contained in the diamine compound. More preferably, it is the ratio which becomes 0.3 to 1.2 equivalent.

The synthesis reaction of the polyamic acid is preferably carried out in an organic solvent under temperature conditions of -20 to 150 ° C, more preferably 0 to 100 ° C. The reaction time is preferably 1 to 240 hours, more preferably 2 to 12 hours. The organic solvent is not particularly limited as long as it can dissolve the polyamic acid synthesized. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, Aprotic polar solvents such as dimethyl sulfoxide, γ-butyrolactone, tetramethylurea and hexamethylphosphortriamide; and phenol solvents such as m-cresol, xylenol, phenol, and halogenated phenol. In addition, as for the usage-amount of organic solvent (a; when using together an organic solvent and the poor solvent mentioned later, the total amount thereof), the total amount (b) of tetracarboxylic dianhydride and a diamine compound is the whole quantity of a reaction solution. The amount is preferably 0.1 to 30% by weight based on (a + b).

In the organic solvent, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like, which are poor solvents of polyamic acids, can be used in combination without causing precipitation of the resulting polyamic acid. As a specific example of such a poor solvent, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, lactate Butyl acid, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, diethyl oxalate, diethyl malonic acid, Diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, di Ethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene Recol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o -Dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether and the like.

When using an organic solvent and a poor solvent together when synthesize | combining a polyamic acid, the use ratio of the poor solvent becomes like this. Preferably it is 50 weight% or less with respect to the sum total of an organic solvent and a poor solvent, More preferably, it is 10 weight% or less.

As described above, a reaction solution obtained by dissolving the polyamic acid is obtained. This reaction solution may be used as it is for the production of a liquid crystal aligning agent, may be used for the production of a liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution, or after the isolated polyamic acid is purified to prepare a liquid crystal aligning agent. Can also be used for Isolation of a polyamic acid can be performed by pouring the said reaction solution in a large quantity of poor solvents, obtaining a precipitate, and drying this precipitate under reduced pressure, or the method of distilling a reaction solution under reduced pressure with an evaporator. Moreover, polyamic acid can be refine | purified by the method which melt | dissolves this polyamic acid again in an organic solvent, and then precipitates with a poor solvent, or performs the process of distilling off under reduced pressure with an evaporator once or several times.

<Imidated Polymer>

The imidation polymer which can be contained in the liquid crystal aligning agent of this invention can be obtained by imidating by dehydrating and ring-closing the polyamic acid as mentioned above.

As tetracarboxylic dianhydride used for the synthesis | combination of an imidation polymer, 1 or more types (it is called "a specific tetracarboxylic dianhydride (2)" hereafter) chosen from alicyclic tetracarboxylic dianhydride are included. It is preferable to use tetracarboxylic dianhydride. As specific tetracarboxylic dianhydride (2), 2,3,5- tricarboxycyclopentyl acetic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2, 5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- ( Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane-2,4-dione -6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1 , 2-dicarboxylic acid anhydride, 3,5,6-tricarboxy- ^2- carboxynorbornane-2: 3,5: 6-dianhydride and 4,9-dioxatricyclo [5.3.1.0 ^{2, 6} ] at least one selected from the group consisting of undecane-3,5,8,10-tetraone is preferred.

The tetracarboxylic dianhydride used for synthesizing the imidized polymer which the liquid crystal aligning agent of this invention can contain, the specific tetracarboxylic dianhydride (2) as mentioned above to all tetracarboxylic dianhydrides. It is preferable to contain 20 mol% or more with respect to it, It is more preferable to contain 50 mol% or more, It is preferable to contain especially 80 mol% or more.

As diamine used for the synthesis | combination of the said imidation polymer, the diamine same as the diamine used for the synthesis | combination of the polyamic acid mentioned above is mentioned.

The imidized polymer may be a complete imide compound in which all of the amic acid structure possessed by the polyamic acid as a raw material is dehydrated and closed, and only a part of the amic acid structure is dehydrated and closed, so that the amic acid structure and the imide ring structure coexist. It may be an imide.

It is preferable that the imidation ratio of the imidation polymer contained in the liquid crystal aligning agent of this invention is 20% or more, and it is especially preferable that it is 40 to 80%.

The said imidation ratio shows the ratio which the number of the imide ring structures to the sum total of the number of the amic acid structures and the number of imide ring structures of an imidation polymer occupies as a percentage. At this time, a part of the imide ring may be an isoimide ring. The imidation ratio is obtained by dissolving the imidized polymer in a suitable deuterated solvent (for example, deuterated dimethyl sulfoxide) and measuring ¹ H-NMR at room temperature using tetramethylsilane as a reference substance. Can be obtained by

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

(In Formula 1, A ¹ is the peak area derived from the proton of the NH group which appears near 10 ppm of chemical shift, A ² is the peak area derived from the other proton, and α is a precursor of the imidized polymer (polyamic acid Is ratio of number of other protons to one proton of NH group in

The dehydration ring closure of the polyamic acid for synthesizing the imidized polymer may be carried out by (i) heating the polyamic acid or (ii) dissolving the polyamic acid in an organic solvent and adding a dehydrating agent and a dehydration ring closure catalyst to the solution. It is performed by the method of heating as needed.

Preferably the reaction temperature in the method of heating the polyamic acid of said (i) is 50-200 degreeC, More preferably, it is 60-170 degreeC. When reaction temperature is less than 50 degreeC, dehydration ring-closure reaction does not fully advance, and when reaction temperature exceeds 200 degreeC, the molecular weight of the imidation polymer obtained may fall. The reaction time is preferably 1 to 24 hours, more preferably 2 to 8 hours.

As a dehydrating agent, acid anhydrides, such as an acetic anhydride, a propionic anhydride, and a trifluoroacetic anhydride, can be used as a dehydrating agent in the method of adding a dehydrating agent and a dehydration ring-closure catalyst in the solution of said polyamic acid of said (ii). It is preferable that the usage-amount of a dehydrating agent shall be 0.01-20 mol with respect to 1 mol of repeating units of a polyamic acid. As the dehydration ring closure catalyst, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used, for example. However, it is not limited to this. It is preferable that the usage-amount of a dehydration ring-closure catalyst shall be 0.01-10 mol with respect to 1 mol of dehydrating agents used. Moreover, as an organic solvent used for dehydration ring-closure reaction, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid is mentioned. The reaction temperature of the dehydration ring-closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. The reaction time is preferably 1 to 24 hours, more preferably 2 to 8 hours.

The imidation polymer obtained by the said method (i) may be used for manufacture of a liquid crystal aligning agent as it is, or may be used for manufacture of a liquid crystal aligning agent after refine | purifying the imidation polymer obtained. On the other hand, in the said method (ii), the reaction solution containing an imidation polymer is obtained. This reaction solution may be used as it is for the production of a liquid crystal aligning agent, or may be used for the production of a liquid crystal aligning agent after removing the dehydrating agent and the dehydration ring-closure catalyst from the reaction solution. It may be used, or may be used for the production of a liquid crystal aligning agent after purifying the isolated imidized polymer. In order to remove a dehydrating agent and a dehydration ring-closure catalyst from a reaction solution, methods, such as solvent substitution, can be applied, for example. Isolation and purification of the imidized polymer can be performed by performing the same operation as described above as the isolation and purification method of the polyamic acid.

Terminal Modified Polymer

The polyamic acid or imidation polymer thereof which the liquid crystal aligning agent of the present invention may contain may be a terminal modified form in which molecular weight is controlled. By using the polymer of terminal modification type, the coating characteristic of a liquid crystal aligning agent, etc. can be further improved, without impairing the effect of this invention. Such a terminal-modified polymer can be performed by adding a molecular weight modifier to the polymerization reaction system when synthesizing the polyamic acid. As a molecular weight modifier, an acid anhydride, a monoamine compound, a monoisocyanate compound, etc. are mentioned, for example.

Examples of the acid anhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, n-hexadecylsuccinic anhydride, and the like. have. Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n- Eicosylamine, etc. are mentioned. As said monoisocyanate compound, phenyl isocyanate, naphthyl isocyanate, etc. are mentioned, for example.

The use ratio of the molecular weight modifier is preferably 20 parts by weight or less, more preferably 5 parts by weight or less based on 100 parts by weight of the total of tetracarboxylic dianhydride and diamine used when synthesizing the polyamic acid.

Solution viscosity

The polyamic acid or the imidized polymer obtained as described above 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 has a concentration of 10% by weight. desirable.

The solution viscosity (mPa · s) of the polymer is a polymer solution having a concentration of 10% by weight using a good solvent of the polymer (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.). It is a value measured at 25 ° C. using an E-type rotational viscometer.

<Other additives>

Although the liquid crystal aligning film of this invention contains as an essential component 1 or more types of polymers chosen from the group which consists of the polyamic acid mentioned above and the imidation polymer formed by dehydrating and ring-closing this as an essential component, you may contain other components as needed. Examples of such other components include compounds having one or more epoxy groups in the molecule (hereinafter referred to as "epoxy compound"), functional silane compounds, and the like.

Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, Neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, N, N, N ' , N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4 , 4'-diaminodiphenylmethane, N, N- diglycidyl-benzylamine, N, N- diglycidyl-aminomethylcyclohexane, etc. are mentioned as a preferable thing. The blending ratio of these epoxy group-containing compounds is preferably 40 parts by weight or less, more preferably 100 parts by weight with respect to 100 parts by weight of the total amount of the polymer (the total amount of the polyamic acid and its imidized polymer contained in the liquid crystal aligning agent, which is the same below). Preferably from 0.1 to 30 parts by weight.

As said functional silane compound, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 2-aminopropyl trimethoxysilane, 2-aminopropyl triethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxy Silane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimeth Methoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecan, 10-triethoxysilyl-1,4,7-triazadecan, 9-trimethoxysilyl-3 , 6-diazanyl acetate, 9-triethoxysilyl-3,6-diazanyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-acea Minopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyl triethoxysilane etc. are mentioned.

The compounding ratio of these functional silane compounds becomes like this. Preferably it is 40 weight part or less with respect to 100 weight part of total amounts of a polymer.

The liquid crystal aligning agent of the present invention preferably comprises one or more polymers selected from the group consisting of polyamic acid and imidized polymers thereof as described above, and other additives optionally blended as needed, preferably dissolved in an organic solvent. do.

As an organic solvent which can be used for the liquid crystal aligning agent of this invention, the solvent illustrated as what is used for the synthesis reaction of polyamic acid is mentioned. Moreover, the poor solvent illustrated as what can be used together at the time of the synthesis reaction of polyamic acid can also be selected suitably, and can be used together. Preferred examples of such organic solvents include, for example, N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, 4- Hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol -n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl Ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, And the like can be mentioned isoamyl propionate, isoamyl isobutyrate, di-isopentyl ether. These may be used independently, or may mix and use 2 or more types.

The solid content concentration (the ratio of the total weight of the components except the organic solvent in the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) of the liquid crystal aligning agent of the present invention is appropriately selected in consideration of viscosity, volatility, and the like, but preferably 1 To 10% by weight. That is, although the coating film which becomes a liquid crystal aligning film is formed by apply | coating this to the surface of a board | substrate and removing an organic solvent, when the solid content concentration is less than 1 weight%, the film thickness of this coating film becomes too small and a favorable liquid crystal In some cases, it may be difficult to obtain an alignment film, and on the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film may be too large to obtain a good liquid crystal alignment film in the same manner, and the viscosity of the liquid crystal aligning agent may be increased to apply the coating. A characteristic may fall.

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

<Liquid crystal display element>

The liquid crystal display element of this invention is equipped with the liquid crystal aligning film formed from the above-mentioned liquid crystal aligning agent of this invention.

As a preferable operation mode in the liquid crystal display element of this invention, TN type, STN type, VA type, or IPS type is mentioned.

The liquid crystal display element of this invention can be manufactured by the process of the following (1)-(3), for example. The process (1) differs in the heating substrate after apply | coating a use board | substrate, the preferable coating method of a liquid crystal aligning agent, and a liquid crystal aligning agent depending on a desired operation mode. Steps (2) and (3) are common to each operation mode.

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

(1-1) When manufacturing a TN type, STN type, or VA type liquid crystal display element, two board | substrates with which the patterned transparent conductive film is provided are a pair, and the liquid crystal orientation of this invention on each transparent conductive film formation surface. The agent is preferably applied by an offset printing method, a spin coating method or an inkjet printing method, respectively, and then a coating film is formed by heating each application surface. Here, as a board | substrate, For example, glass, such as float glass and a soda glass; Transparent substrates containing plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, poly (alicyclic olefin) and the like can be used. Examples of the transparent conductive film provided on one side of the substrate include an NESA film containing tin oxide (SnO ₂ ) (registered trademark of PPG Co., Ltd.) and an ITO film containing indium tin oxide (In ₂ O ₃ -SnO ₂ ). In order to obtain a patterned transparent conductive film, for example, a method of forming a pattern by photoetching after forming a transparent conductive film without a pattern and a method of using a mask having a desired pattern when forming a transparent conductive film Or the like. At the time of coating of the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a pretreatment for applying a functional silane compound, a functional titanium compound, or the like to the surface on which the coating film should be formed on the substrate surface in advance. May be performed.

The heating temperature after liquid crystal aligning agent application becomes like this. Preferably it is 30-300 degreeC, More preferably, it is 40-250 degreeC, Heating time becomes like this. Preferably it is 1 to 60 minutes, More preferably, it is 10 to 30 minutes. The film thickness of the coating film formed becomes like this. Preferably it is 0.001-1 micrometer, More preferably, it is 0.005-0.5 micrometer.

(1-2) On the other hand, when manufacturing an IPS type liquid crystal display element, the conductive film formation surface of the board | substrate with which the transparent conductive film patterned by the comb-tooth shape is provided, and the one side of the opposing board | substrate with which the conductive film is not provided, The liquid crystal aligning agent of this invention is apply | coated preferably by the roll coater method, the spinner method, or the inkjet printing method, respectively, and then each coating surface is heated, and a coating film is formed.

The material of the substrate and the transparent conductive film used at this time, the patterning method of the transparent conductive film, and the pretreatment of the substrate are the same as in the above (1-1).

The heating temperature after apply | coating a liquid crystal aligning agent becomes like this. Preferably it is 80-300 degreeC, More preferably, it is 120-250 degreeC, Heating time becomes like this. Preferably it is 1 to 60 minutes, More preferably, it is 10 to 30 minutes.

The preferable film thickness of the coating film formed is the same as that of said (1-1).

In any case of (1-1) and (1-2), although the liquid crystal aligning agent of this invention forms the coating film used as an alignment film by removing an organic solvent after application | coating, the polymer contained in the liquid crystal aligning agent of this invention is In the case of the imidized polymer which has a polyamic acid or an imide ring structure, and an amic acid structure, dehydration ring-closure reaction is advanced by further heating after coating film formation, and it can also be set as the imidized coating film.

(2) Although the coating film formed as mentioned above can be used as a liquid crystal aligning film for VA type liquid crystal display elements as it is, the rubbing process mentioned later can also be performed to this coating film surface arbitrarily.

When using the coating film formed as mentioned above as a liquid crystal aligning film for liquid crystal display elements of a TN type, STN type, or IPS type, by carrying out a rubbing process with respect to a coating film surface, liquid crystal molecular orientation capability is provided to a coating film, and it becomes a liquid crystal aligning film. .

A rubbing process can be performed by the method of rubbing a coating film surface in the fixed direction with the roll which wound the cloth containing fibers, such as nylon, a rayon, a cotton, for example.

Since the coating film formed of the liquid crystal aligning agent of this invention is excellent in rubbing tolerance, even if the rubbing depth of the rubbing cloth increases or the rotation speed of a rubbing roll increases in the said rubbing process, and the harsher rubbing conditions are used than before, the liquid crystal aligning film is used. No peeling or defect occurs.

(3) The liquid crystal cell is manufactured by preparing two board | substrates with a liquid crystal aligning film as above-mentioned, and arrange | positioning a liquid crystal between these two board | substrates. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example.

The first method is a conventionally known method. First, two substrates are disposed to face each other with a gap (cell spacing) so that the respective liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded together using a sealant, and the cells partitioned by the substrate surface and the sealant. After the injection filling of the liquid crystal within the interval, the liquid crystal cell can be produced by sealing the injection hole.

The second method is a method called an ODF (One Drop Fill) method. An ultraviolet-ray curable sealing material is apply | coated to the predetermined place on one board | substrate among two board | substrates with which the liquid crystal aligning film was formed, for example, after dropping a liquid crystal on the liquid crystal aligning film surface, the other board | substrate is bonded so that a liquid crystal aligning film may oppose. Then, a liquid crystal cell can be manufactured by irradiating ultraviolet-ray to the whole surface of a board | substrate, and hardening a sealing agent. Since the liquid crystal aligning agent of this invention can form the liquid crystal aligning film excellent in the vertical orientation, it has the advantage that the liquid crystal display element which ODF nonuniformity does not generate | occur | produce even when a VA type liquid crystal display element is manufactured by ODF method is obtained. .

Also by any method, it is preferable to remove the liquid orientation at the time of injection | pouring then, after heating a liquid crystal cell to the temperature which the used liquid crystal takes an isotropic phase, and then gradually cooling to room temperature.

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

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

Examples of the liquid crystal include nematic liquid crystals and smectic liquid crystals. Especially, a nematic type liquid crystal is preferable, for example, a Schiff base type liquid crystal, a subfamily clock liquid crystal, a biphenyl type liquid crystal, a phenyl cyclohexane type liquid crystal, an ester type liquid crystal, a terphenyl type liquid crystal, a biphenyl cyclohexane type liquid crystal, a pyrimi Din type liquid crystal, a dioxane type liquid crystal, a bicyclooctane type liquid crystal, a cuban type liquid crystal, etc. can be used. Furthermore, for these liquid crystals, for example, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonaate, cholesteryl carbonate; Chiral agents such as those sold under the brand names "C-15" and "CB-15" (manufactured by Merck); Ferroelectric liquid crystals, such as p-disiloxybenzylidene-p-amino-2-methylbutyl cinnamate, can also be added and used.

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

<Example>

<Synthesis of Compound Represented by Formula A>

Example 1 (Synthesis of Compound Represented by Formula A-1)

The compound represented by Chemical Formula A-1 (hereinafter referred to as "Compound (A-1)") was synthesized according to the following Scheme 1.

(1) Synthesis of Compound (A-1a)

To a 500 mL three-necked flask equipped with a stirrer, a nitrogen inlet tube and a thermometer, 32 g of 3,5-dinitrobenzoic acid, 18 g of propargyl bromide, 23 g of diazabicycloundecene and 300 mL of dimethyl sulfoxide were added. The reaction was carried out at 占 폚 for 3 hours. After the completion of the reaction, 2 L of ethyl acetate was added to the reaction mixture, and the organic layer was washed once sequentially with 1 M hydrochloric acid and saturated aqueous sodium hydrogen carbonate solution, further washed three times with water, and then dried over magnesium sulfate. Subsequently, after removing a solvent from an organic layer, 29g of yellow crystals of a compound (A-1a) were obtained by recrystallization with methanol.

(2) Synthesis of Compound (A-1)

Into a 1 L three-necked flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 29 g of the compound (A-1a) synthesized above, 280 g of tin chloride dihydrate, and 400 mL of ethanol were added thereto, and reacted at 70 ° C. for 1 hour. Was performed. After the reaction was completed, the reaction mixture was washed sequentially with an aqueous potassium fluoride solution and water. The organic layer was dried over magnesium sulfate, and then the solvent was removed, followed by recrystallization with methanol to obtain 15 g of brown crystals of compound (A-1).

Example 2-1 (Synthesis of Compounds Represented by Chemical Formula A-2 (1))

The compound represented by Chemical Formula A-2 (hereinafter, referred to as "compound (A-2)") was synthesized according to the following Scheme 2-1.

(1) Synthesis of Compound (A-2a)

In a 500 mL three-necked flask equipped with a stirrer, a nitrogen introduction tube and a thermometer, 19 mL of propargyl alcohol, 10 g of tetrabutylammonium bromide, 300 mL of tetrahydrofuran, and 36 g of t-butoxy potassium were added thereto, and 3 at 0 ° C. The reaction was carried out for a time (this is referred to as "reaction liquid A").

Meanwhile, 61 g of 2,4-dinitrochlorobenzene and 300 mL of tetrahydrofuran were added to a separate 500 mL three-necked flask equipped with a dropping funnel, a nitrogen introduction tube, and a thermometer, and the reaction solution A was cooled to 0 ° C. Was added dropwise over 2 hours, and the reaction was carried out at 0 ° C for 2 hours. After the reaction was completed, 500 mL of ethyl acetate was added to the reaction mixture, the organic layer was washed three times with water, then dried over magnesium sulfate, and then the solvent was removed, followed by recrystallization with methanol, to obtain 39 g of brown crystals of the compound (A-2a). Got it.

(2) Synthesis of Compound (A-2)

Into a 1 L three-necked flask equipped with a reflux tube, a nitrogen introduction tube, and a thermometer, 22 g of the compound (A-2a) synthesized above, 226 g of tin chloride dihydrate, and 500 mL of ethyl acetate were added thereto, and the mixture was heated at 80 ° C for 1 hour. Reaction was carried out. After completion | finish of reaction, the precipitate produced by adding and neutralizing 2M sodium hydroxide aqueous solution to the reaction mixture was filter-separated, and filtrate was obtained. The filtrate was washed once with saturated aqueous sodium hydrogen carbonate solution and then three times with water, and then 15 g of a dark brown individual of compound (A-2) was obtained by removing the solvent.

Example 2-2 (Synthesis of Compound (2) Represented by Formula A-2)

Compound (A-2) was synthesized according to the following Scheme 2-2.

(1) Synthesis of Compound (A-2b)

To a 3 L beaker 144 g of amidol, 650 mL of water and 150 mL of acetic anhydride were weighed, followed by 150 g of sodium acetate dissolved in 400 mL of water. The precipitated precipitate was collected by filtration, washed with water and dried to obtain a powder of compound (A-2b).

(2) Synthesis of Compound (A-2c)

Into a 1 L three-necked flask equipped with a dropping funnel, a thermometer, and a nitrogen introduction tube, 104 g of Compound (A-2b), 20 g of sodium hydroxide, 16.1 g of tetrabutylammonium bromide, and 650 mL of water were added thereto and heated to 50 ° C. . Subsequently, 15.45 g of propargyl bromide was dripped over 30 minutes using the dropping funnel, and reaction was performed at 50 degreeC for 4 hours. The precipitate was collected by filtration after completion of the reaction, washed with water and dried to obtain 105 g of a powder of the compound (A-2c).

(3) Synthesis of Compound (A-2)

Into a 1 L flask equipped with a nitrogen introduction tube and a reflux tube, 25 g of a compound (A-2c) and 500 mL of a 3N hydrochloric acid aqueous solution were added, and the reaction was carried out at reflux for 1 hour. After completion of the reaction, the reaction mixture was poured into saturated aqueous sodium hydrogen carbonate solution and then extracted with 3 L of methylene chloride, the methylene chloride layer was washed three times with water, and then the solvent was removed and dried to give a dark brown color of the compound (A-2). 12 g of the subject was obtained.

Example 3 (Synthesis of Compound Represented by Formula (A-4-1))

The compound represented by the following formula (A-4-1) (hereinafter referred to as "compound (A-4-1)") was synthesized according to Scheme 3 below.

(1) Synthesis of Compound (A-4-1a)

Into a 200 mL three-necked flask equipped with a stirrer, a nitrogen inlet tube and a thermometer, 74 g of 2,4-dinitrofluorobenzene was added, which was cooled in a water bath and 28 g of N-methyl-N-propargylamine was added thereto. Was slowly added dropwise. Subsequently, 40 g of triethylamine was slowly added dropwise, and then the reaction was carried out at 50 ° C. for 2 hours. After completion of the reaction, the reaction mixture was washed with a saturated aqueous solution of sodium bicarbonate, further washed three times with water, and then the organic layer was dried over magnesium sulfate and the solvent was removed to give 84 g of an oily compound (A-4-1a). Got.

(2) Synthesis of Compound (A-4-1)

79 g of the compound (A-4-1a) synthesized above, 677 g of tin chloride dihydrate, and 1.5 L of ethyl acetate were added to a 3 L three-necked flask equipped with a reflux tube, a nitrogen introduction tube, and a thermometer, and the mixture was heated at 80 ° C. The reaction was carried out for 1 hour. After completion | finish of reaction, the precipitate produced by adding and neutralizing 2M sodium hydroxide aqueous solution to the reaction mixture was filter-separated, and filtrate was obtained. The filtrate was washed once with saturated aqueous sodium hydrogen carbonate solution and then with water three times, concentrated and silica column purification was carried out using a mixed solvent containing hexane and ethyl acetate as a developing medium, and then the solvent was removed. 54 g of dark brown individuals of (A-4-1) were obtained.

Synthesis Example 4 (Synthesis of Compound Represented by Formula A-5)

The compound represented by Chemical Formula A-5 (hereinafter referred to as "Compound (A-5)") was synthesized according to Scheme 4 below.

(1) Synthesis of Compound (A-5a)

613 mL of allylamine, 95 mL of propargyl bromide, 60 mL of tetrahydrofuran, and 375 mL of water were added to a 2 L three-necked flask equipped with a stirrer and a nitrogen introduction tube, and the reaction was performed at room temperature for 12 hours. After completion of the reaction, 1 L of methylene chloride was added to the reaction mixture, which was then washed three times with water, and the organic layer was dried over magnesium sulfate, and then distilled to obtain 80 g of a clear liquid of compound (A-5a).

(2) Synthesis of Compound (A-5b)

74 g of 2,4-dinitrofluorobenzene was added to a 200 mL three-necked flask equipped with a stirrer, a nitrogen inlet tube and a thermometer, and 38 g of the compound (A-5a) synthesized above was slowly cooled while cooling in a water bath. It dripped. Subsequently, 40 g of triethylamines were slowly added dropwise, followed by reaction at 50 ° C. for 2 hours. After completion of the reaction, the reaction mixture was washed with saturated aqueous sodium hydrogen carbonate solution, further washed three times with water, and then the organic layer was dried over magnesium sulfate and the solvent was removed to obtain 82 g of an oily compound (A-5b).

(3) Synthesis of Compound (A-5)

78 g of the compound (A-5b) synthesized above, 677 g of tin chloride dihydrate, and 1.5 L of ethyl acetate were added to a 3 L three-necked flask equipped with a reflux tube, a nitrogen introduction tube, and a thermometer, and the mixture was heated at 80 ° C for 1 hour. Reaction was carried out. After completion | finish of reaction, the precipitate produced by adding and neutralizing 2M sodium hydroxide aqueous solution to the reaction mixture was filter-separated, and filtrate was obtained. The filtrate was washed once with saturated aqueous sodium hydrogen carbonate solution and then with water three times, concentrated and silica column purification was carried out using a mixed solvent containing hexane and ethyl acetate as a developing medium, and then the solvent was removed. 50g of dark brown individuals of (A-5) were obtained.

Synthesis Example 5 (Synthesis of Compound Represented by Formula A-6)

The compound represented by Chemical Formula A-6 (hereinafter referred to as “Compound (A-6)”) was synthesized according to Scheme 5 below.

(1) Synthesis of Compound (A-6a)

74 g of 2,4-dinitrofluorobenzene was added to a 200 mL three-necked flask equipped with a stirrer, a nitrogen inlet tube and a thermometer, and 37 g of N, N-dipropargylamine was added thereto while cooling in a water bath. It was dripped slowly. Subsequently, 40 g of triethylamine was slowly added dropwise, followed by reaction at 50 ° C. for 2 hours. After completion of the reaction, the reaction mixture was washed with saturated aqueous sodium hydrogen carbonate solution, further washed three times with water, and then the organic layer was dried over magnesium sulfate and the solvent was removed to obtain 79 g of an oily compound (A-6a).

(2) Synthesis of Compound (A-6)

78 g of the compound (A-6a) synthesized above, 677 g of tin chloride dihydrate, and 1.5 L of ethyl acetate were added to a 3 L three-neck flask equipped with a reflux tube, a nitrogen introduction tube, and a thermometer, and the mixture was heated at 80 ° C for 1 hour. Reaction was carried out. After completion | finish of reaction, the 2 M aqueous sodium hydroxide aqueous solution was added to the reaction mixture, and the precipitation produced by neutralization was separated by filtration, and the filtrate was obtained. The filtrate was washed once with saturated aqueous sodium hydrogen carbonate solution and then with water three times, concentrated and silica column purification was carried out using a mixed solvent containing hexane and ethyl acetate as a developing medium, and then the solvent was removed. 50 g of dark brown individuals of (A-6) were obtained.

Synthesis of Polyimide

Example 6-1

11 g (0.05 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride, 2.7 g (0.025 mol) of p-phenylenediamine as diamine and the compound obtained in Example 2-1 4.1 g (0.025 mol) of (A-2) was dissolved in 100 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours to obtain a solution containing polyamic acid. The solution viscosity measured as a small amount of the obtained polyamic-acid solution, the addition of N-methyl- 2-pyrrolidone, and the solution of 10 weight% of polyamic-acid concentration was 65 mPa * s.

Subsequently, 180 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 20 g of pyridine and 15 g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring reaction, the solvent in the system was solvent-substituted with fresh γ-butyrolactone (by this solvent substitution operation, the pyridine and acetic anhydride used for the dehydration ring-closure reaction were removed to the outside of the system), and then concentrated. About 105 g of a solution containing 15% by weight of 85% of the imidized polymer (PI-1 (1)) was obtained. The solution viscosity measured as a small amount of this imidated polymer solution, the addition of (gamma) -butyrolactone, and measuring as a solution of the imidation polymer concentration of 10 weight% was 60 mPa * s.

Examples 6-2, 7 to 11, Comparative Examples 1 and 2

As the tetracarboxylic dianhydride, 11 g (0.05 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride was used in the same manner as in Example 6-1, and as the diamine, the kind and amount shown in Table 1 below A solution containing 15 wt% of the imidized polymer PI-1 (2), PI-2 to PI-6, R-1 and R-2 in the same manner as in Example 6-1 except that each of Got.

Each imidized polymer solution was aliquoted in small amounts, and the solution viscosity measured as a solution of 10 weight% of imidation polymer concentration by adding (gamma) -butyrolactone, and the imidation ratio of each imidation polymer are shown in Table 1, respectively.

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

(A-2 (1)): Compound (A-2) synthesized in Example 2-1

(A-2 (2)): Compound (A-2) synthesized in Example 2-2

(A-4-1): Compound (A-4-1) synthesized in Synthesis Example 3

(A-1): Compound (A-1) synthesized in Example 1

(A-5): Compound (A-5) synthesized in Synthesis Example 4

(A-6): Compound (A-6) synthesized in Synthesis Example 5

PDA: p-phenylenediamine

Compound (D-10): a compound represented by Chemical Formula D-10

The solution viscosity of the 10 weight% imidation polymer solution was measured at 25 degreeC using the E-type viscosity meter.

Example 12-1

<Production of Liquid Crystal Alignment Agent>

(Gamma) -butyrolactone and butyl cellosolve in the solution containing the imidation polymer (PI-1 (1)) obtained by the said Example 6-1 in ratio of (gamma) -butyrolactone: butyl cellosolve by weight ratio 88 It added so that it might be: 12, and the solution of 3.5 weight% of solid content concentration was prepared. After fully stirring this solution, the liquid crystal aligning agent was manufactured by filtering using the filter of 1 micrometer of pore diameters.

It evaluated as follows using this liquid crystal aligning agent.

<Evaluation of Rubbing Resistance>

(1) Coating of liquid crystal aligning agent

The above-mentioned liquid crystal aligning agent was apply | coated on the transparent conductive film containing the ITO film | membrane provided in one side of the glass substrate of thickness 1mm using the spinner on condition of rotation speed 2,000rpm and rotation time 20 second, and 60 minutes at 200 degreeC. By heating to remove the solvent, a coating film having a film thickness of 0.08 mu m was formed.

(2) acceleration test of rubbing

By the rubbing machine which has the roll which wound the cloth made from rayon to this film, the rubbing process was performed on conditions of 1,000 rpm of rotation of a roll, 2.5 cm / sec of moving speed of a stage, and 0.4 mm of bristle indentation lengths. These rubbing conditions were harsher conditions than usual, as can be understood from the conditions in "(2) rubbing treatment" of "Manufacture of a TN type liquid crystal display element" described later.

When this rubbing process was repeated 10 times with respect to the same coating film, the case where the peeling of the liquid crystal aligning film was not visually observed was evaluated as rubbing resistance "good" and the case where it was observed as rubbing resistance "poor". As a result, the rubbing resistance of the coating film formed from the said liquid crystal aligning agent was favorable.

 <Manufacture and Evaluation of TN-type Liquid Crystal Display Device>

[Manufacture of TN type liquid crystal display element]

(1) Coating of liquid crystal aligning agent

A coating film having a film thickness of 0.08 μm was formed on the transparent conductive film of the glass substrate in the same manner as in “coating of the (1) liquid crystal aligning agent” in the “evaluation resistance”.

(2) rubbing treatment

The rubbing process is performed by the rubbing machine which has the roll which wound the cloth made from rayon to this film on the conditions of 400 rpm of rotation of a roll, the movement speed of 3 cm / sec of a stage, and 0.4 mm of a seedling indentation length, and liquid-crystal orientation ability is carried out to a coating film. Was added to obtain a liquid crystal alignment film.

(3) cleaning and drying of the substrate after rubbing

After ultrasonically cleaning the board | substrate which has this liquid crystal aligning film in ultrapure water for 1 minute, it dried in the clean oven of 100 degreeC for 10 minutes, and obtained the board | substrate which has a liquid crystal aligning film on a transparent conductive film.

By repeating the operation of (1) to (3), a pair (two sheets) of substrates having a liquid crystal alignment film on a transparent conductive film were produced.

(4) bonding of substrate, liquid crystal injection process and adhesion of polarizing plate

Subsequently, after apply | coating the 5.5-micrometer diameter aluminum oxide sphere containing epoxy resin adhesive agent on each outer edge part which has a liquid crystal aligning film of the board | substrate which has this pair of liquid crystal aligning films, it overlaps and compresses so that a liquid crystal aligning film surface may face, and an adhesive agent is Cured. Subsequently, after filling the nematic liquid crystal (MLC-2019 by Merck Co., Ltd.) which shows a positive value of dielectric anisotropy between a liquid crystal injection hole and a board | substrate, the liquid crystal injection hole is sealed with acrylic photocuring adhesive, and both surfaces of the outer side of a board | substrate are The liquid crystal display element was manufactured by bonding a polarizing plate to the.

[Evaluation of TN type liquid crystal display element]

(1) Evaluation of liquid crystal alignment

About the liquid crystal display element manufactured above, it observed using the optical microscope. At this time, when the liquid crystal aligning property "good" and the thing which light leakage was observed were evaluated by the liquid crystal aligning property "poor" that there was no light leakage, the liquid crystal alignability of this liquid crystal display element was favorable.

(2) evaluation of heat resistance

About the liquid crystal display element manufactured above, first, the voltage of 5V was applied in 60 microseconds application time and 167 milliseconds span, and the voltage retention after 167 milliseconds after application | release cancellation was measured. The numerical value at this time was made into initial stage voltage retention (VHR _BF ).

After the VHR _BF measurement, the liquid crystal display device was placed in an oven at 100 ° C. and thermal stress was applied for 1,000 hours. Subsequently, after standing the liquid crystal display element at room temperature and cooling to room temperature, the voltage retention VHR _AF after heat stress application was measured.

The change (ΔVHR) of the voltage retention before and after heat stress application was calculated by the following equation (2), and the value of less than 5% was evaluated as heat resistance "good" and 5% or more as heat resistance "poor". (Triangle | delta) VHR of the said liquid crystal display element was 2%, and heat resistance was "good."

Examples 12-2, 13 to 16 and Comparative Example 3

A liquid crystal aligning agent was produced and evaluated in the same manner as in Example 12-1 except that each containing the imidized polymer shown in Table 2 was used as the solution containing the imidized polymer. The results are shown in Table 2.

Example 17

<Production of Liquid Crystal Alignment Agent>

(Gamma) -butyrolactone, N-methyl-2-pyrrolidone, and butyl cellosolve were added to the solution containing the imidation polymer (PI-6) obtained in Example 11, (gamma) -butyrolactone: N-methyl- A solution having a solid content concentration of 3.5% by weight was added so that the ratio of 2-pyrrolidone: butyl cellosolve was 40:30:30 in weight ratio. After fully stirring this solution, the liquid crystal aligning agent was manufactured by filtering using the filter of 1 micrometer of pore diameters.

It evaluated as follows using this liquid crystal aligning agent.

<Production and Evaluation of VA Type Liquid Crystal Cell>

[Manufacture of VA type liquid crystal cell]

(1) Coating of liquid crystal aligning agent

On the transparent conductive film containing the ITO film provided on one side of the glass substrate of thickness 1mm, the liquid crystal aligning agent for liquid crystal display element manufacture manufactured above was apply | coated with a spinner, and it heats at 200 degreeC for 60 minutes, and is 0.08 micrometers in film thickness. A coating film (liquid crystal aligning film) was formed.

By repeating this operation, a pair (two sheets) of substrates having a liquid crystal alignment film were prepared on the transparent conductive film.

(2) Bonding of substrate and liquid crystal injection process

After apply | coating the aluminum oxide sphere containing epoxy resin adhesive of diameter 5.5micrometer to each outer edge part which has a liquid crystal aligning film of the said pair of board | substrates, it overlapped and crimped | bonded so that the liquid crystal aligning film surface might become antiparallel, and hardened the adhesive agent. Subsequently, after filling a nematic liquid crystal (MLC-6608, manufactured by Merck Co., Ltd.) showing a negative value of dielectric anisotropy between a pair of substrates from a liquid crystal injection hole, the liquid crystal injection hole is sealed with an acrylic photocuring adhesive. The cell was prepared.

[Evaluation of VA Type Liquid Crystal Cell]

(1) Evaluation of liquid crystal alignment

About the liquid crystal cell produced above, it observed under cross nicol using the polarization microscope. Under the present circumstances, when the liquid-crystal orientation "good" and the thing which light leakage was observed were evaluated that there was no light leakage as liquid-crystal orientation "poor", the liquid crystal orientation of this liquid crystal cell was favorable.

(2) evaluation of heat resistance

About the liquid crystal cell manufactured above, the change ((DELTA) VHR) of voltage retention before and behind heat stress was calculated | required similarly to "(2) heat resistance evaluation" in the said Example 12. When the value which was less than 5% evaluated heat resistance "good" and 5% or more as heat resistance "poor", (DELTA) VHR of the said liquid crystal cell was 2%, and heat resistance was "good".

Comparative Example 4

A liquid crystal aligning agent was produced and evaluated in the same manner as in Example 17 except that the solution containing the imidized polymer (R-2) synthesized in Comparative Example 2 was used as the solution containing the imidized polymer. Although liquid crystal aligning property was "good", (triangle | delta) VHR was 7% and heat resistance was "poor".

Claims (7)

It is a liquid crystal aligning agent containing at least 1 sort (s) of polymer chosen from the group which consists of the polyamic acid obtained by making tetracarboxylic dianhydride and diamine react, and the imidation polymer formed by dehydrating and closing said polyamic acid, The diamine comprises a compound represented by the following formula (A). <Formula A>

In Formula A, R ^I represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a fluoroalkyl group having 1 to 30 carbon atoms, a phenyl group, a fluorophenyl group, an alkylphenyl group having 1 to 30 carbon atoms or a fluorine having 1 to 30 carbon atoms. Is a fluoroalkylphenyl group having a roalkyl group, R ^II is a single bond, an oxygen atom, -COO- ^* (wherein the bond to which "*" is attached is-(CH ₂ ) _{n 2} -C≡R ^I side) or -NR (Wherein R is an alkyl group having 1 to 8 carbon atoms or an alkenyl group or alkynyl group having 2 to 8 carbon atoms), R ^III is an alkyl group having 1 to 4 carbon atoms, n1 is 0 or 1, n2 is 0 to 8 Integer, n3 is an integer from 0 to 3, provided that when R ^II is a single bond, n1 is 0. The alkylphenyl group according to claim 1, wherein R ^I in Formula A is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, a phenyl group, a fluorophenyl group, or an alkyl group having 1 to 12 carbon atoms; The liquid crystal aligning agent which is a fluoroalkylphenyl group which has a fluoroalkyl group having 1 to 12 carbon atoms. The liquid crystal aligning agent of Claim 1 or 2 whose n2 in the said General formula A is 1. The liquid crystal aligning film formed from the liquid crystal aligning agent in any one of Claims 1-3 is provided. The liquid crystal display element characterized by the above-mentioned. Polyamic acid obtained by making tetracarboxylic dianhydride and the diamine containing the compound represented by the said Formula (A) react. The imidation polymer formed by dehydrating and ring-closing the polyamic acid obtained by making tetracarboxylic dianhydride and the diamine containing the compound represented by the said Formula (A) react. Compound represented by the formula (A).