TW201723023A - Liquid crystal alignment agent and its application - Google Patents

Abstract

The present invention relates to a liquid crystal alignment agent comprising a polymer composition (A) and a solvent (B), wherein the polymer composition (A) consists of a component comprising a tetracarboxylic dianhydride (a) And a mixture of the diamine component (b) is obtained by reacting a mixture. The liquid crystal alignment agent according to the present invention has an advantage of good environmental resistance. Furthermore, the present invention also provides a liquid crystal alignment film formed by the above liquid crystal alignment agent, a method for producing a liquid crystal alignment film, and a liquid crystal display element comprising the alignment film.

Description

Liquid crystal alignment agent and its application

The invention relates to a liquid crystal alignment agent and application thereof, in particular to a liquid crystal alignment agent capable of forming a high environmental resistance liquid crystal alignment film, a liquid crystal alignment film manufacturing method, a liquid crystal alignment film formed thereby, and a liquid crystal having the alignment film Display component.

As consumers' requirements for the wide viewing angle characteristics of liquid crystal displays have been increasing year by year, the requirements for electrical characteristics or display characteristics of liquid crystal display elements with wide viewing angles are more stringent than before, among which vertical alignment type (Vertical Alignment) liquid crystal displays are used. The components are most widely studied. In order to have the above-mentioned characteristics, the liquid crystal alignment film is one of the important research objects for improving the characteristics of the vertical alignment type liquid crystal display element.

The liquid crystal alignment film in the vertical alignment type liquid crystal display element is mainly used for regularly aligning liquid crystal molecules, and can provide liquid crystal molecules with a large inclination angle without providing an electric field, and the liquid crystal alignment film is usually formed by containing A liquid crystal alignment agent of a polymer material such as a polyaminic acid polymer or a polyimide polymer is applied onto the surface of a substrate, and is formed by heat treatment and alignment treatment.

In general, a liquid crystal pretilt component is introduced into the polymer material to obtain a good liquid crystal alignment property. However, the liquid crystal pretilt component lowers the solubility of the polymer, resulting in easy aggregation of the polymer, and the liquid crystal alignment agent. Printing defects (mura) occur when applied to a substrate; in addition, when printing for a long period of time, there is a problem that polymer deposition causes a problem of low printability.

JP-A-2013-101303 discloses a polyimide-based polymer obtained by polymerizing a diamine compound having one or more carboxyl groups in a molecule and a tetracarboxylic dianhydride compound. A solvent such as 1,3-dimethyl-2-imidazolidinone or N-ethyl-2-pyrrolidone can be used to obtain a liquid crystal alignment agent having good printability. However, the liquid crystal alignment film produced by the liquid crystal alignment agent has the disadvantage of poor environmental resistance, for example, the problem that the ion density is too high in an environment of high temperature and high humidity, and cannot be accepted by the industry.

Therefore, how to provide a liquid crystal alignment agent capable of forming an environmentally-friendly liquid crystal alignment film, and the liquid crystal alignment film formed thereon can have better display quality when applied to a liquid crystal display element, which is currently desired by those skilled in the art. solved problem.

The present invention provides a vertical alignment type liquid crystal alignment agent by providing a component of a specific polymer composition, and the liquid crystal alignment film and the liquid crystal display element formed of the above liquid crystal alignment agent have the advantages of good environmental resistance.

Accordingly, the present invention relates to a liquid crystal alignment agent comprising: a polymer composition (A) prepared by reacting a mixture comprising a tetracarboxylic dianhydride component (a) and a diamine component (b) And the solvent (B); wherein the diamine component (b) comprises at least one diamine compound selected from the diamine compound (b-1) represented by the formula (1) and the formula (2) ( a group consisting of b-2) and a carboxylic acid group-containing diamine compound (b-3);

In the formula (1): Y ¹ represents a C ₁ to C ₂ alkylene group; and Y ² represents a nitrogen-containing aromatic heterocyclic group;

In formula (2): R ¹⁵ is selected from -O-, , , , and a group consisting of; and R ¹⁶ represents an organic group represented by the formula (II-1):

Wherein: R ¹⁷ represents hydrogen, fluorine or methyl; R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a single bond, -O-, , C ₁ to C ₃ alkylene; R ²¹ is selected from and a group consisting of: wherein R ²³ and R ²⁴ each independently represent hydrogen, fluorine or methyl; and R ²² is selected from the group consisting of hydrogen, fluorine, C ₁ to C ₁₂ alkyl, C ₁ to C ₁₂ fluoroalkyl a group of C ₁ to C ₁₂ alkoxy groups, -OCH ₂ F, -OCHF ₂ and -OCF ₃ ; k represents an integer of 1 or 2; w, m and t each independently represent an integer of 0 to 4 ; y, p and q each independently represent an integer from 0 to 3, and y+p+q≧3; and u and v each independently represent 1 or 2; when R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , When R ²¹ , R ²³ or R ²⁴ is plural, each may be the same or different.

The invention further provides a method for producing a liquid crystal alignment film, which comprises applying the liquid crystal alignment agent to a substrate.

The present invention also provides a liquid crystal alignment film which is produced by the aforementioned liquid crystal alignment agent.

The present invention further provides a liquid crystal display element comprising the liquid crystal alignment film described above.

11‧‧‧ first unit

12‧‧‧Second unit

13‧‧‧Liquid Crystal Unit

111‧‧‧First substrate

112‧‧‧First conductive film

113‧‧‧First liquid crystal alignment film

121‧‧‧second substrate

122‧‧‧Second conductive film

123‧‧‧Second liquid crystal alignment film

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic view showing the structure of a preferred embodiment of a liquid crystal display device of the present invention.

The present invention provides a liquid crystal alignment agent comprising: a polymer composition (A) obtained by reacting a mixture comprising a tetracarboxylic dianhydride component (a) and a diamine component (b); a solvent (B); wherein the diamine component (b) comprises at least one diamine compound (b-2) selected from the diamine compound (b-1) represented by the formula (1) and the formula (2). And a group consisting of a carboxylic acid group-containing diamine compound (b-3);

In the formula (1): Y ⁷ represents a C ₁ to C ₂ alkylene group; and Y ² represents a nitrogen-containing aromatic heterocyclic group;

In formula (2): R ¹⁵ is selected from -O-, , , , and a group consisting of; and R ¹⁶ represents an organic group represented by the formula (II-1):

Wherein: R ¹⁷ represents hydrogen, fluorine or methyl; R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a single bond, -O-, , C ₁ to C ₃ alkylene; R ²¹ is selected from and a group consisting of: wherein R ²³ and R ²⁴ each independently represent hydrogen, fluorine or methyl; and R ²² is selected from the group consisting of hydrogen, fluorine, C ₁ to C ₁₂ alkyl, C ₁ to C ₁₂ fluoroalkyl a group of C ₁ to C ₁₂ alkoxy groups, -OCH ₂ F, -OCHF ₂ and -OCF ₃ ; k represents an integer of 1 or 2; w, m and t each independently represent an integer of 0 to 4 y, p and q each independently represent an integer from 0 to 3, and y+p+q≧3; and u and v each independently represent 1 or 2; when R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , When R ²¹ , R ²³ or R ²⁴ is plural, each may be the same or different.

The polymer composition (A) is selected from the group consisting of a polyamic acid polymer, a polyimine polymer, a polyamidene block copolymer, or any combination of the above. Wherein, the polyamidene block copolymer is selected from the group consisting of a polyamido block copolymer, a polyamidiene block copolymer, and a polyamidino-polyimine block copolymer. Or any combination of the above polymers.

The poly-proline polymer, the polyimine polymer, and the polyimide block copolymer in the polymer composition (A) may each be composed of a tetracarboxylic dianhydride component (a) and a diamine group. The mixture of parts (b) is obtained by a reaction in which the tetracarboxylic dianhydride component (a), the diamine component (b) and the method for preparing the polymer composition (A) are as follows.

The tetracarboxylic dianhydride component (a) may be selected from an aliphatic tetracarboxylic dianhydride compound, an alicyclic tetracarboxylic dianhydride compound, an aromatic tetracarboxylic dianhydride compound or the following formula (a-1) To the tetracarboxylic dianhydride component represented by the formula (a-6).

Specific examples of the aliphatic tetracarboxylic dianhydride compound may include, but are not limited to, an aliphatic tetracarboxylic dianhydride component such as ethane tetracarboxylic dianhydride or butane tetracarboxylic dianhydride.

Specific examples of the alicyclic tetracarboxylic dianhydride compound may include, but are not limited to, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4. - cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4- Cyclobutane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentane IV Carboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, cis-3,7-dibutyl Cycloheptyl-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride or bicyclo[2.2.2]-octyl- An alicyclic tetracarboxylic dianhydride compound such as 7-ene-2,3,5,6-tetracarboxylic dianhydride.

Specific examples of the aromatic tetracarboxylic dianhydride compound may include, but are not limited to, 3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, benzene tetracarboxylic dianhydride. , 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4' -biphenyl fluorene tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3'-4,4'- Diphenylethane tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylnonanetetracarboxylic dianhydride, 3,3',4,4'-tetraphenylnonane tetracarboxylic acid Acid dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenyl Ether tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 2,3,3',4'-diphenyl sulfide tetracarboxylic dianhydride , 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl phthalic anhydride, 4,4'-double (3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene diphthalic dianhydride, 2,2',3,3'- Diphenyltetracarboxylic dianhydride, 2,3,3',4'-diphenyltetracarboxylic dianhydride, 3,3',4,4'-di Tetracarboxylic acid dianhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylbenzenedioic acid) dianhydride, m-phenylene-bis(triphenylbenzene) Diacid) dianhydride, bis(triphenylbenzenedioic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, Ethylene glycol-bis(dehydrated trimellitate), propylene glycol-bis(hydrogen trimellitate), 1,4-butanediol-bis(hydrogen trimellitate), 1,6-hexane Alcohol-bis(hydrogen trimellitate), 1,8-octanediol-bis(anhydrotrimellitic acid ester), 2,2-bis(4-hydroxyphenyl)propane-bis(dehydrated trimellitate) Acid ester), 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-di-oxy-3 -furyl)-naphtho[1,2-c]-furan-1,3-dione {(1,3,3a,4,5,9b-Hexahydro-5-(tetrahydro-2,5-dioxofuran- 3-yl)naphtho[1,2-c]furan-1,3-dione)}, 1,3,3a,4,5,9b-hexahydro-5-methyl-5-(tetrahydro-2, 5-di-oxo-3-furyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-B 5-(4-hydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4, 5,9b-hexahydro-7-methyl-5-(tetrahydro-2,5- Oxyloxy-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-ethyl-5 -(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b -hexahydro-8-methyl-5-(four Hydrogen-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydrogen -8-ethyl-5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3, 3a,4,5,9b-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]- Furan-1,3-dione, 5-(2,5-di-oxytetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, and the like.

The tetracarboxylic dianhydride component represented by the formula (a-1) to the formula (a-6) is as follows:

In the formula (a-5), A ₁ represents a divalent group containing an aromatic ring; r represents an integer of 1 to 2; and A ₂ and A ₃ may be the same or different and each may represent a hydrogen atom or an alkyl group. Preferably, the tetracarboxylic dianhydride compound represented by the formula (a-5) may be selected from the compounds represented by the following formulas (a-5-1) to (a-5-3).

In the formula (a-6), A ₄ represents a divalent group containing an aromatic ring; A ₅ and A ₆ may be the same or different and each represents a hydrogen atom or an alkyl group. Preferably, the tetracarboxylic dianhydride compound represented by the formula (a-6) may be selected from the compounds represented by the following formula (a-6-1).

Preferably, the tetracarboxylic dianhydride component (a) comprises, but is not limited to, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic acid Dihydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4- Tetrahydronaphthalene-1-succinic dianhydride, benzene tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, and 3,3',4,4'-linked Benzoquinonetetracarboxylic dianhydride. The above tetracarboxylic dianhydride component (a) may be used singly or in combination of plural kinds.

The total amount of the diamine component (b) used is 100 moles, and the tetracarboxylic dianhydride component (a) is used in an amount of 20 moles to 200 moles, preferably 30 moles to 120 moles. More preferably 50 to 100 moles.

The diamine component (b) of the present invention comprises at least one selected from the diamine compound (b-1) represented by the formula (1), the diamine compound (b-2) represented by the formula (2), and a carboxylic acid. a group consisting of a diamine compound (b-3);

In the formula (1): Y ¹ represents a C ₁ to C ₂ alkylene group; and Y ² represents a nitrogen-containing aromatic heterocyclic group; preferably, Y ² represents a pyrrolidinyl group, a piperazinyl group, or a piperidinyl group. Or pyridyl.

Specific examples of the diamine compound (b-1) represented by the formula (1) are as follows: Wait.

The total amount of the diamine component (b) used is 100 moles, and the diamine compound (b-1) is used in an amount of 10 moles to 40 moles, preferably 12 moles to 38 moles, more preferably It is 15 to 35 moles.

The diamine compound (b-2) represented by the formula (2) is as follows:

In formula (2): R ¹⁵ is selected from -O-, , , , and a group consisting of; and R ¹⁶ represents an organic group represented by the formula (II-1):

Wherein: R ¹⁷ represents hydrogen, fluorine or methyl; R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a single bond, -O-, , C ₁ to C ₃ alkylene; R ²¹ is selected from and a group consisting of: wherein R ²³ and R ²⁴ each independently represent hydrogen, fluorine or methyl; and R ²² is selected from the group consisting of hydrogen, fluorine, C ₁ to C ₁₂ alkyl, C ₁ to C ₁₂ fluoroalkyl a group of C ₁ to C ₁₂ alkoxy groups, -OCH ₂ F, -OCHF ₂ and -OCF ₃ ; k represents an integer of 1 or 2; w, m and t each independently represent an integer of 0 to 4 y, p, and q each independently represent an integer of 0 to 3, and y+p+q≧3; and u and v each independently represent 1 or 2.

When R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²³ or R ²⁴ is plural, each may be the same or different.

Specific examples of the diamine compound (b-2) include at least one of the diamine compounds represented by the formula (2-1) to the formula (2-8), or a combination of the above compounds.

In the formula (2-1) to the formula (2-8), B ¹¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

The diamine compound represented by the formula (2-1) to the formula (2-8) is preferably at least one of the diamine compounds represented by the formula (2-9) to the formula (2-13), or a compound of the above combination.

The above diamine compound (b-2) may be used singly or in combination of two or more.

The total amount of the diamine component (b) used is 100 moles, and the diamine compound (b-2) is used in an amount of 10 moles to 40 moles, preferably 12 moles to 38 moles, more preferably It is 15 to 35 moles.

The carboxylic acid group-containing diamine compound (b-3) has a structure represented by the following formula (3):

In the formula (3), X represents an organic group containing a C ₆ to C ₃₀ aromatic ring; and n represents an integer of 1 to 4.

The carboxylic acid group-containing diamine compound (b-3) is not particularly limited as long as it has a carboxylic acid group, and the carboxylic acid group-containing diamine compound (b-3) may include, but is not limited to, fat. A diamine, an alicyclic diamine, an aromatic diamine or a diamine organooxane. The carboxylic acid group-containing diamine compound (b-3) is preferably an alicyclic diamine or an aromatic diamine, more preferably an aromatic diamine.

The carboxylic acid group-containing diamine compound (b-3) preferably has 1 to 4 carboxylic acid groups, more preferably 1 or 2 carboxylic acid groups.

The carboxylic acid group-containing diamine compound (b-3) is at least one selected from the group consisting of the following formulas (3-1) to (3-5);

In the formula, X ₁ and X ₃ independently represent a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, - O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON(CH ₃₎ - or _{-N (CH 3) CO-; X} 2 represents a straight-chain alkyl or C ₁ to C ₅ C ₁ to C ₅ of the branched chain alkyl; N1, and n7 independently represent an integer of from 1 to 4; N2 and n3 independently represent an integer of 0 to 4, and n2+n3 is an integer of 1 to 4; and n4, n5, and n6 independently represent an integer of 1 to 5.

Preferably, in the formula (3-1), n1 may represent 1 or 2; in the formula (3-2), X ₁ represents a single bond, -CH ₂ -, -C ₂ H ₄ -, -C ( CH ₃ ) ₂ -, -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -COO- or -OCO-, and n2 and n3 represent 1 at the same time; In the formula (3-5), X ₃ represents a single bond, -CH ₂ -, -O-, -CO-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ - , -COO- or -OCO-, and n7 represents 1 or 2.

Specific examples of the carboxylic acid group-containing diamine compound (b-3) are diamine compounds represented by the following formulas (3-6) to (3-16):

In the above formula (3-14) and formula (3-15), X ₅ may represent a single bond, -CH ₂ -, -O-, -CO-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO- or -OCO-.

The carboxylic acid group-containing diamine compound (b-3) may be used singly or in combination of plural kinds.

The total amount of the diamine component (b) used is 100 moles, and the carboxylic acid group-containing diamine compound (b-3) is used in an amount of 20 moles to 80 moles, preferably 25 moles to 75 Moor, more preferably 30 to 70 moles.

When the diamine component (b) of the polymer composition (A) of the present invention is used without the diamine compound (b-1), the diamine compound (b-2), and the carboxylic acid group-containing diamine compound (b) When -3), the prepared liquid crystal alignment agent has a defect of poor environmental resistance.

The diamine component (b) of the present invention may further comprise another diamine compound (b-4).

The other diamine compound (b-4) may include, but is not limited to, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diamine Pentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane, 1,10-diamine Baseline, 4,4'-diaminoheptane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7-Diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane 1,9-Diamino-5-methylnonane, 2,11-diaminododecane, 1,12-diaminooctadecane, 1,2-bis(3-aminopropoxyl) Ethylene, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylamine, 1,3-diaminocyclohexane , 1,4-diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentadiene diamine, tricyclo(6.2.1.0 ^2,7 )-undecene Diamine, 4,4'-methylenebis(cyclohexylamine), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4' -diaminodiphenylanthracene, 4,4'-diaminobenzimidamide, 4,4'-diaminodiphenyl ether, 3,4'- Aminodiphenyl ether, 1,5-diaminonaphthalene, 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylhydroquinone, 6-amino group- 1-(4'-Aminophenyl)-1,3,3-trimethylhydroquinone, hexahydro-4,7-methyl bridge hydroquinone dimethylene diamine, 3,3'-di Aminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis[4-(4-aminophenoxy) Phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2- Bis[4-(4-aminophenoxy)phenyl]anthracene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroquinone, 9,10-bis(4-aminophenyl)anthracene [ 9,10-bis(4-aminophenyl)anthracene], 2,7-diaminopurine, 9,9-bis(4-aminophenyl)anthracene, 4,4'-methylene-bis(2- Chloroaniline), 4,4'-(p-phenylene isopropylidene)diphenylamine, 4,4'-(m-phenylene isopropylidene)diphenylamine, 2,2'-bis[4 -(4-Amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-eight Fluorobiphenyl, 5-[4-(4-n-pentylcyclohexyl)cyclohexyl]benzene {5-[4-(4-n-pentylcyclohexyl)cyclohexyl]phenylmethylene-1,3-diaminobenzene}, 1,1-bis[4-(4-aminobenzene) Oxy)phenyl]-4-(4-ethylphenyl)cyclohexane {1,1-bis[4-(4-aminophenoxy)phenyl]-4-(4-ethylphenyl)cyclohexane} or the following formula ( 4-1) to other diamine compounds of formula (4-25):

In the formula (4-1), X ₆ represents -O-, , , , or And X ₇ represents a fluorenyl group, a trifluoromethyl group, a fluoro group, an alkyl group having 2 to 30 carbon atoms or a cyclic structure containing a nitrogen atom derived from pyridine, pyrimidine, triazine, piperidine and piperazine A monovalent group.

The other diamine compound (b-4) represented by the above formula (4-1) is preferably 2,4-diaminophenyl ethyl formate or 3,5-diamine. 3,5-diaminophenyl ethyl formate, 2,4-diaminophenyl propyl formate, propyl 3,5-diaminophenylcarboxylate (3,5-diaminophenyl propyl formate), 1-dodecoxy-2,4-diaminobenzene, 1-hexadecyloxy-2,4- 1-hexadecoxy-2,4-diaminobenzene, 1-octadecoxy-2,4-diaminobenzene or the following formula (4-1) -1) to other diamine compounds of formula (4-1-6):

In the formula (4-2), X ₈ represents -O-, , , , or , X ₉ and X ₁₀ represent an aliphatic ring, an aromatic ring or a heterocyclic group, and X ₁₁ represents an alkyl group having 3 to 18 carbon atoms, an alkoxy group having 3 to 18 carbon atoms, and a carbon number. It is a fluoroalkyl group of 1 to 5, a fluoroalkoxy group having 1 to 5 carbon atoms, a cyano group or a halogen atom.

The other diamine compound (b-4) represented by the above formula (4-2) is preferably a diamine compound represented by the following formula (4-2-1) to formula (4-2-13):

In the formula (4-2-10) to the formula (4-2-13), s may represent an integer of from 3 to 12.

In the formula (4-3), X ₁₂ represents a hydrogen atom, a fluorenyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a halogen, and each X ₁₂ in the repeating units may be the same or different. X ₁₃ is an integer of 1 to 3.

The diamine compound represented by the formula (4-3) is preferably selected from the group consisting of (1) X ₁₃ being 1: p-diamine benzene, m-diamine benzene, o-diamine benzene or 2,5-di Amine toluene, etc.; (2) X ₁₃ is 2:4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl Base-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino Biphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 2,2',5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl or 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl; (3) X ₁₃ is 3: 1,4-bis(4'-aminophenyl)benzene or the like, more preferably selected from p-diamine benzene, 2,5-diamine toluene, 4,4'- Diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl or 1,4-bis(4'-aminophenyl)benzene.

In the formula (4-4), X ₁₄ represents an integer of 2 to 12.

In the formula (4-5), X ₁₅ represents an integer of 1 to 5. The formula (4-5) is preferably selected from 4,4'-diaminodiphenyl sulfide.

In the formula (4-6), X ₁₆ and X ₁₈ may be the same or different and each represent a divalent organic group, and X ₁₇ represents a nitrogen atom derived from a pyridine, a pyrimidine, a triazine, a piperidine or a piperazine. A divalent group of a cyclic structure.

In the formula (4-7), X ₁₉ , X ₂₀ , X ₂₁ and X ₂₂ may be the same or different, respectively, and may represent a hydrocarbon group having a carbon number of 1 to 12. X ₂₃ represents an integer of 1 to 3, and X ₂₄ represents an integer of 1 to 20.

In the formula (4-8), X ₂₅ represents -O- or a cyclohexane group, X ₂₆ represents -CH ₂ -, X ₂₇ represents a phenyl or cyclohexane group, and X ₂₈ represents a hydrogen atom or Heptyl.

The diamine compound represented by the formula (4-8) is preferably selected from the diamine compounds represented by the following formulas (4-8-1) to (4-8-2):

Other diamine compounds of formula (4-9) to formula (4-25) are as follows:

In the formulae (4-17) to (4-25), X ₂₉ is preferably an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and X ₃₀ is hydrogen. The atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms is preferred.

The other diamine compound (b-4) may preferably include, but is not limited to, a 1,2-diamino group. Ethane, 4,4'-diaminodicyclohexylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 5-[4-(4- n-Pentylcyclohexyl)cyclohexyl]phenylmethylene-1,3-diaminobenzene, 1,1-bis[4-(4-aminophenoxy)phenyl]-4-(4) -ethylphenyl)cyclohexane, ethyl 2,4-diaminophenylcarboxylate, formula (4-1-1), formula (4-1-2), formula (4-1-5), Formula (4-1-6), formula (4-2-1), formula (4-2-11), p-diamine benzene, m-diamine benzene, o-diamine benzene, formula (4-8) -1) The compound represented.

The other diamine compound (b-4) described above may be used singly or in combination of plural kinds.

When the polymer composition (A) in the liquid crystal alignment agent contains at least one of the diamine compound (b-4) represented by the formula (4-1) and the formula (4-2), the resistance of the liquid crystal alignment agent can be further improved. Environmental issues.

The total amount used based on the diamine component (b) is 100 moles, and the other diamine compound (b-4) is usually used in an amount of from 0 moles to 60 moles, preferably from 5 moles to 50 moles. More preferably from 10 to 40 moles.

The preparation of the poly-proline polymer according to the present invention may be a general method. Preferably, the preparation method of the poly-proline polymer comprises the steps of: comprising a component comprising a tetracarboxylic dianhydride (a) The mixture of the diamine component (b) is dissolved in a solvent, and a polycondensation reaction is carried out at a temperature of from 0 ° C to 100 ° C for 1 hour to 24 hours, and then the above reaction solution is subjected to distillation under reduced pressure by an evaporator. In a manner, a poly-proline polymer is obtained, or the above reaction solution is poured into a large amount of a poor solvent to obtain a precipitate, and then the precipitate is dried by a vacuum drying method to obtain a polyfluorene. Amino acid polymer.

The solvent used in the polycondensation reaction may be the same as or different from the solvent (B) in the liquid crystal alignment agent described below, and the solvent used in the polycondensation reaction is not particularly limited as long as it is a soluble reactant and The product can be. Preferably, the solvent includes, but is not limited to, (1) an aprotic polar solvent such as N-methyl-2-pyrrolidinone (NMP), N,N-dimethylacetamidine. An aprotic polar solvent such as amine, N,N-dimethylformamide, dimethyl hydrazine, γ -butyrolactone, tetramethyl urea or hexamethylphosphoric acid triamide; (2) phenolic solvent For example, a phenolic solvent such as m-cresol, xylenol, phenol or halogenated phenol. The solvent used in the polycondensation reaction is preferably used in an amount of from 200 parts by weight to 2000 parts by weight, more preferably from 300 parts by weight to 1800 parts by weight, based on the use of the mixture in an amount of 100 parts by weight.

In particular, in the polycondensation reaction, the solvent may be used in combination with an appropriate amount of a poor solvent, wherein the poor solvent does not cause precipitation of the poly-proline polymer. The poor solvent may be used alone or in combination, and includes, but is not limited to, (1) an alcohol such as methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, or 1,4-butylene. An alcohol such as a diol or a triethylene glycol; (2) a ketone such as a ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; or (3) an ester such as an ester. : esters of methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate or ethylene glycol ethyl ether acetate; (4) ethers, for example: diethyl ether , ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether or diethylene glycol An ether such as methyl ether; (5) a halogenated hydrocarbon such as dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene or o-di a halogenated hydrocarbon such as chlorobenzene; (6) a hydrocarbon such as a hydrocarbon such as tetrahydrofuran, hexane, heptane, octane, benzene, toluene or xylene or any combination of the above solvents. The amount of the poor solvent is preferably from 0 part by weight to 60 parts by weight, more preferably from 0 part by weight to 50 parts by weight, based on 100 parts by weight of the diamine component (b).

The preparation of the polyimine polymer according to the present invention may be a general method. Preferably, the polyiminoimine polymer is prepared by first dissolving a mixture in a solution, wherein the mixture comprises tetracarboxylic dianhydride. Component (a) and diamine component (b) are subjected to polymerization to form a poly-proline polymer. Then, in the presence of a dehydrating agent and a catalyst, further heating and performing a dehydration ring-closing reaction, so that the proline functional group in the polyaminic acid polymer is converted into a quinone imine functional group via a dehydration ring-closure reaction (ie, hydrazine Imine To the polyimine polymer.

Preferably, the polymer composition (A) has a oxime imidization ratio of usually 30% to 90%, preferably 35% to 85%, more preferably 40% to 80%. When the polymer composition (A) of the present invention has an imidization ratio of the above range, the prepared liquid crystal alignment agent has an advantage of being excellent in environmental resistance.

The solvent used in the dehydration ring closure reaction may be the same as the solvent in the liquid crystal alignment agent described below, and therefore will not be further described. The solvent used in the dehydration ring closure reaction is preferably used in an amount of from 200 parts by weight to 2000 parts by weight, more preferably from 300 parts by weight to 1800 parts by weight, based on 100 parts by weight of the polyphthalic acid polymer.

In order to obtain a preferred degree of ruthenium iodide polymerization, the operation temperature of the dehydration ring closure reaction is preferably from 40 ° C to 200 ° C, more preferably from 40 ° C to 150 ° C. If the operating temperature of the dehydration ring-closure reaction is lower than 40 ° C, the reaction of hydrazide is incomplete, and the degree of ruthenium iodide of the poly-proline polymer is lowered. However, if the operating temperature of the dehydration ring-closure reaction is higher than 200 ° C, the weight average molecular weight of the obtained polyimine polymer is low.

The dehydrating agent used in the dehydration ring-closure reaction may be selected from acid anhydride compounds, and specific examples thereof include acid anhydride compounds such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride. The dehydrating agent is used in an amount of from 0.01 mol to 20 mol based on the polyamic acid polymer being 1 mol. The catalyst for use in the dehydration ring closure reaction may be selected from the group consisting of (1) a pyridine compound such as a pyridine compound such as pyridine, trimethylpyridine or lutidine; and (2) a tertiary amine compound such as A tertiary amine compound such as triethylamine. The amount of the dehydrating agent used is 1 mol, and the catalyst is used in an amount of 0.01 mol to 20 mol.

Preferred specific examples of the polyfluorene-based block copolymer according to the present invention are a poly-proline block copolymer, a polyamidiene block copolymer, and a polyamidino-polyimine. Segment copolymer, or a combination of these.

The preparation of the polyimide-based block copolymer according to the present invention may be a general method. Preferably, the preparation method of the poly-imide-based block copolymer is first The starting material is dissolved in a solvent and subjected to a polycondensation reaction, wherein the starting material comprises at least one polylysine polymer described above and/or at least one polyimine polymer described above, and may further comprise a tetracarboxylic acid Acid dianhydride component and diamine component.

The tetracarboxylic dianhydride component and the diamine component in the starting material are the tetracarboxylic dianhydride component (a) and the diamine component (b) used in the preparation of the polyamic acid polymer described above. The solvent used in the polycondensation reaction may be the same as the solvent (B) in the liquid crystal alignment agent described below, and will not be further described herein.

The solvent used in the polycondensation reaction is preferably used in an amount of from 200 parts by weight to 2000 parts by weight, more preferably from 300 parts by weight to 1800 parts by weight, based on 100 parts by weight of the starting material. The operation temperature of the polycondensation reaction is preferably from 0 ° C to 200 ° C, more preferably from 0 ° C to 100 ° C.

Preferably, the starting material comprises, but is not limited to, (1) two poly-proline polymers having different terminal groups and different structures; (2) two different kinds of terminal groups having different terminal groups and different structures Amine polymer; (3) poly-proline polymer and heteropolyamine polymer with different terminal groups and different structures; (4) poly-proline polymer, tetracarboxylic dianhydride component and diamine And a composition in which at least one of the tetracarboxylic dianhydride component and the diamine component is different from the structure of the tetracarboxylic dianhydride component and the diamine component used for forming the polyaminic acid polymer (5) a polyimine polymer, a tetracarboxylic dianhydride component, and a diamine component, wherein at least one of the tetracarboxylic dianhydride component and the diamine component is polymerized to form a polyimine The structure of the tetracarboxylic dianhydride component and the diamine component used in the material are different; (6) poly-proline polymer, polyimine polymer, tetracarboxylic dianhydride component and diamine component Wherein at least one of the tetracarboxylic dianhydride component and the diamine component and the tetracarboxylic dianhydride component and the diamine component used to form the polyphthalic acid polymer or the polyimide polymer Different structures; (7) two Polyglycine polymer, tetracarboxylic dianhydride component and diamine component having different structures; (8) two kinds of polyimine polymers having different structures, tetracarboxylic dianhydride component and diamine a component; (9) a poly-proline polymer having an acid anhydride group and a structural difference, and a diamine component; (10) the two terminal groups are an amine group and a structural phase a different poly-proline polymer and a tetracarboxylic dianhydride component; (11) a polyimine polymer having an acid anhydride group and a different structure, and a diamine component; (12) two kinds of ends The base is an amine group and has a structurally different polyimine polymer and a tetracarboxylic dianhydride component.

Preferably, the polyaminic acid polymer, the polyimine polymer, and the polyamidene block copolymer may be the end of molecular weight adjustment first, without affecting the efficacy of the present invention. Modified polymer. The coating property of the liquid crystal alignment agent can be improved by using a terminal-modified polymer. The manner of preparing the terminal modified polymer can be obtained by adding a monofunctional compound while the polyamic acid polymer is subjected to a polycondensation reaction, and the monofunctional compound includes, but is not limited to, (1) one element. An acid anhydride such as maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride or n-hexadecyl succinic anhydride Anhydride; (2) a monoamine compound such as aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-undecylamine, Single dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecaneamine, n-heptadecaneamine, n-octadecylamine or n-icosylamine An amine compound; (3) a monoisocyanate compound, for example, a monoisocyanate compound such as phenyl isocyanate or naphthyl isocyanate.

Preferred specific examples of the solvent (B) according to the present invention are N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, 4-hydroxy-4-methyl-2-pentanone, Ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxy propionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol positive Ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl Ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, N, N-dimethylformamide , N,N-dimethylacetamide. The solvent may be used singly or in combination of plural kinds.

The liquid crystal alignment agent according to the present invention, wherein the solvent (B) is used in an amount of from 500 to 5,000 by weight based on 100 parts by weight of the polymer composition (A). Parts; preferably from 900 to 3500 parts by weight; more preferably from 1,000 to 3,000 parts by weight.

The liquid crystal alignment agent according to the present invention preferably contains an additive (C) within a range not impairing the efficacy of the present invention. The additive (C) is preferably a compound having at least two epoxy groups or a decane compound having a functional group. The additive (C) serves to improve the adhesion of the liquid crystal alignment film to the surface of the substrate. The additive (C) may be used singly or in combination of plural kinds.

The compound having at least 2 epoxy groups includes, but is not limited to, ethylene glycol diepoxypropyl ether, polyethylene glycol diepoxypropyl ether, propylene glycol diepoxypropyl ether, and tripropylene glycol diepoxypropyl group. Ether, polypropylene glycol diepoxypropyl ether, neopentyl glycol diepoxypropyl ether, 1,6-hexanediol diepoxypropyl ether, glycerol diepoxypropyl ether, 2,2- Dibromo neopentyl glycol diepoxypropyl ether, 1,3,5,6-tetraepoxypropyl-2,4-hexanediol, N,N,N',N'-tetraepoxypropyl -m-xylylenediamine, 1,3-bis(N,N-diepoxypropylaminomethyl)cyclohexane, N,N,N',N'-tetraepoxypropyl-4, 4'-Diaminodiphenylmethane, 3-(N-allyl-N-epoxypropyl)aminopropyltrimethoxydecane, 3-(N,N-diepoxypropyl)amine Propyltrimethoxydecane, and the like.

The compound having at least two epoxy groups is used in an amount of usually 40 parts by weight or less, preferably 0.1 parts by weight to 30 parts by weight, based on 100 parts by weight of the polymer composition (A).

The decane compound having a functional group includes, but is not limited to, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-amine Propyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyl Dimethoxydecane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxy Decane, N-ethoxycarbonyl-3-aminopropyltriethoxydecane, N-triethoxydecylpropyltriamine, N-trimethoxydecylpropyltriazine Amine, 10-trimethoxydecyl-1,4,7-trioxane, 10-three Ethoxy decyl-1,4,7-trioxane, 9-trimethoxydecyl-3,6-dimercaptoacetate, 9-triethoxydecyl-3,6-di Mercaptoacetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-amino Propyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N-bis(oxyethylene)-3-aminopropyltrimethoxydecane, N-bis(ethylene oxide) 3-aminopropyltriethoxydecane, and the like.

The functional group-containing decane compound is used in an amount of usually from 0 to 10 parts by weight, preferably from 0.5 part by weight to 10 parts by weight, based on 100 parts by weight of the polymer composition (A).

The preparation method of the liquid crystal alignment agent is not particularly limited, and a general mixing method such as first mixing the tetracarboxylic dianhydride component (a) and the diamine component (b) to form a polymer by reaction. Composition (A). Next, the polymer composition (A) is added to the solvent (B) at a temperature of from 0 ° C to 200 ° C, and the additive (C) may be optionally added, and stirring is continued until it is dissolved by a stirring device. Preferably, the solvent (B) is added to the polymer composition at a temperature of from 20 ° C to 60 ° C.

Preferably, the additive (C) is used in an amount of from 0.5 part by weight to 50 parts by weight based on the total amount of the polymer composition (A), and more preferably, the additive is used in an amount of 1 part by weight. Parts to 45 parts by weight.

The invention further provides a method for producing a liquid crystal alignment film, which comprises applying the liquid crystal alignment agent to a substrate.

The present invention also provides a liquid crystal alignment film which is produced by the aforementioned liquid crystal alignment agent.

Preferably, the liquid crystal alignment film is formed by coating the liquid crystal alignment agent by a roll coating method, a spin coating method, a printing method, an inkjet method, or the like. a precoat layer is formed on the surface of a substrate, and then the precoat layer is subjected to pre-bake treatment and post-bake treatment (post-bake) Treatment) and alignment treatment.

The purpose of this preheating treatment is to volatilize the organic solvent in the precoat layer. Preferably, the preheating treatment has an operating temperature in the range of 30 ° C to 120 ° C, more preferably 40 ° C to 110 ° C, still more preferably 50 ° C to 100 ° C.

The alignment treatment is not particularly limited, and a fabric made of fibers such as nylon, rayon, or cotton may be wound around a drum and rubbed in a certain direction to perform alignment. The alignment processing described above is well known to those skilled in the art and therefore will not be described again.

The post-heat treatment step is aimed at further subjecting the polymer in the precoat layer to a dehydration ring-closing (deuteration) reaction. Preferably, the post-heat treatment has an operating temperature in the range of from 150 ° C to 300 ° C, more preferably from 180 ° C to 280 ° C, still more preferably from 200 ° C to 250 ° C.

The present invention further provides a liquid crystal display element comprising the liquid crystal alignment film described above.

The manner in which the liquid crystal display element is fabricated is well known to those skilled in the art, and therefore, the following is merely a brief statement.

Referring to FIG. 1, a preferred embodiment of the liquid crystal display device of the present invention includes a first unit 11, a second unit 12 spaced apart from the first unit, and a first unit 11 and a second unit 12 interposed therebetween. The liquid crystal unit 13 is between.

The first unit 11 includes a first substrate 111, a first conductive film 112 formed on the surface of the first substrate 111, and a first liquid crystal alignment film 113 formed on the surface of the first conductive film 112.

The second unit 12 includes a second substrate 121, a second conductive film 122 formed on the surface of the second substrate 121, and a second liquid crystal alignment film 123 formed on the surface of the second conductive film 122.

The first substrate 111 and the second substrate 121 are selected from a transparent material or the like, and the transparent material includes, but is not limited to, an alkali-free glass, a soda-lime glass, and a hard glass (Pyrus glass) for a liquid crystal display device. , quartz glass, polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, and the like. The material of the first conductive film 112 and the second conductive film 122 is selected from tin oxide (SnO ₂ ), indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ), or the like.

The first liquid crystal alignment film 113 and the second liquid crystal alignment film 123 are respectively the liquid crystal alignment film described above, and the liquid crystal alignment layer 13 is formed to have a pretilt angle, and the liquid crystal cell 13 can be used by the first conductive film 112 and the first The two conductive films 122 are driven by the electric field generated.

The liquid crystal used in the liquid crystal cell 13 may be used singly or in combination, and the liquid crystal includes, but is not limited to, a diamine benzene liquid crystal, a pyridazine liquid crystal, a Schiff base liquid crystal, an azo group. (azoxy) liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, ester liquid crystal, terphenyl , biphenylcyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, cubane liquid crystal, etc. Further, a cholesteric liquid crystal such as cholesteryl chloride, cholesteryl nonanoate, or cholesteryl carbonate may be added, or the trade names "C-15" and "CB-15" ( A chiral agent manufactured by Merck & Co., or a ferroelectric liquid crystal such as p-methoxybenzylidene-p-amino-2-methylbutyl cinnamate.

The invention is illustrated by the following examples, which are not intended to be limited to the scope of the invention.

[Preparation of Polymer Composition (A)] <Synthesis Example A-1-1>

A nitrogen inlet, a stirrer, a condenser and a thermometer were placed on a four-necked conical flask having a volume of 500 ml, and nitrogen was introduced, and the feed composition was added to include: 0.075 mol of the compound represented by b-1-1, 0.1 mol. Compound of the ear b-2-1, 0.125 m Compound represented by b-3-1, 0.15 mol of p-diamine benzene (hereinafter referred to as b-4-1), 0.05 mol of 4,4'-diaminodiphenylmethane (hereinafter referred to as b-) 4-2), and 80 g of nitrogen-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), and stirred at room temperature until dissolved. Further, 0.5 mol of benzene tetracarboxylic dianhydride (hereinafter a-1) and 20 g of NMP were added, and the mixture was reacted at room temperature for 2 hours. After the reaction was completed, the reaction solution was poured into 1500 ml of water to precipitate a polymer. The polymer obtained by filtration was repeatedly washed with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60 ° C to obtain a polyamic acid polymer (A-1-1).

<Synthesis Examples A-1-2 to A-1-5>

Synthesis Examples A-1-2 to A-1-5 were prepared in the same manner as in Synthesis Example A-1-1 except that the type of the tetracarboxylic dianhydride compound or the diamine compound was changed. And its usage, as shown in Table 1.

<Synthesis Example A-2-1>

A nitrogen inlet, a stirrer, a heater, a condenser and a thermometer were placed on a four-necked flask of 500 ml volume, and a nitrogen gas was introduced, and the feed composition was added to include: 0.075 mol of the compound represented by b-1-1. 0.1 mol of the compound represented by b-2-1, 0.125 mol of the compound represented by b-3-1, 0.15 mol of p-diphenylbenzene (hereinafter referred to as b-4-1), 0.05 mol 4,4'-diaminodiphenylmethane (hereinafter abbreviated as b-4-2), and 80 g of NMP were stirred at room temperature until dissolved. Further, 0.5 mol of pyromellitic dianhydride and 20 g of NMP were added, and the mixture was reacted at room temperature for 6 hours, and then 97 g of NMP, 2.55 g of acetic anhydride and 19.75 g of pyridine were added, and the temperature was raised to 60 ° C. The mixture was stirred for 2 hours to carry out hydrazine imidation. After the reaction was completed, the reaction solution was poured into 1500 ml of water to precipitate a polymer. The polymer obtained by filtration was repeatedly washed with methanol and filtered three times, and placed in a vacuum oven at a temperature of 60 ° C. After drying, a polyimine polymer (A-2-1) is obtained.

<Synthesis Examples A-2-2 to A-2-10 and Comparative Synthesis Examples A-3-1 to A-3-10>

Synthesis Examples A-2-2 to A-2-10 and Comparative Synthesis Examples A-3-1 to A-3-10 were prepared in the same manner as in Synthesis Example A-2-1, and the difference was made. Depends on: change The types of the tetracarboxylic dianhydride component, the diamine component, the dehydrating agent or the catalyst and the amounts thereof used are shown in Tables 1 and 2.

In Table 1 and Table 2:

A-1 benzene tetracarboxylic dianhydride

A-2 1,2,3,4-cyclobutane tetracarboxylic dianhydride

A-3 2,3,5-tricarboxycyclopentyl acetic acid dianhydride

A-4 1,2,3,4-cyclobutane tetracarboxylic dianhydride

B-1-1

B-1-2

B-1-3

B-1-4

B-1-5

B-2-1

B-2-2

B-2-3

B-2-4

B-3-1

B-3-2

B-3-3

B-3-4

B-4-1 p-diamine benzene

B-4-2 4,4'-diaminodiphenylmethane

B-4-3 4,4'-Diaminodiphenyl ether

B-4-4 formula (4-1-2)

B-4-5 formula (4-1-6)

B-4-6 1-octadecyloxy-2,4-diaminobenzene

[Preparation of liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element] <Example 1>

100 parts by weight of the polymer composition (A-1-1) was weighed and added to 800 parts by weight of N-methyl-2-pyrrolidone (hereinafter referred to as B-1) and 800 parts by weight of ethylene glycol n-butyl ether (hereinafter In abbreviated as B-2), it is stirred and mixed at room temperature to form a liquid crystal alignment agent.

The liquid crystal alignment agent was evaluated for each test item, and the results are shown in Table 3.

<Examples 2 to 16 and Comparative Examples 1 to 10>

Examples 2 to 16 and Comparative Examples 1 to 10 were prepared in the same manner as in Example 1 except that the types of the polymer composition, the solvent and the additive and the amount thereof were changed, as shown in the table. 3 and 4 are shown. These liquid crystal alignment agents were evaluated for each test item, and the results obtained are shown in Tables 3 and 4.

In Tables 3 and 4:

B-1 N-methyl-2-pyrrolidone

B-2 ethylene glycol n-butyl ether

B-3 γ -butyrolactone

B-4 1,3-dimethyl-2-imidazolidinone

C-1 N,N,N',N'-tetraepoxypropyl-4,4'-diaminodiphenylmethane

C-2 1,3-bis(N,N-diepoxypropylaminomethyl)cyclohexane

[Test items] <醯imination rate>

The ruthenium amination rate means the ratio of the number of ruthenium rings calculated as a percentage based on the total number of guanamine functional groups and the number of quinone rings in the polymer, expressed as a percentage.

The detection method is that the polymer composition of the synthesis example is separately dried under reduced pressure, and then dissolved in a suitable deuteration solvent, for example, deuterated dimethyl hydrazine, using tetramethyl decane as a reference substance. , ¹ H- NMR results ^{(1 H-Nuclear magnetic resonance,} 1 H-NMR) was measured from room temperature (e.g. 25 ℃), can then be obtained by the following formula (PEI) ratio (%).

Δ1: peak area produced by chemical shift of the NH matrix near 10 ppm; Δ2: peak area of other protons; α: precursor of polymer composition (polyglycine) The ratio of the number of protons of the NH group to the number of other protons.

<Environment resistance>

The liquid crystal display elements of Examples 1 to 16 and Comparative Examples 1 to 10 were placed in an environment having a temperature of 65 ° C and a relative humidity of 85%, and after 120 hours, an electric measuring machine (Dongyang Co., Ltd.) was used. System, Model 6254) The ion density of the liquid crystal display elements of Examples 1 to 16 and Comparative Examples 1 to 10. The test conditions were to apply a 1.7 volt, 0.01 Hz triangular wave at a temperature of 60 ° C. In the current-voltage waveform, the ion density (pC) was measured by calculating the peak area in the range of 0 to 1 volt. The lower the ion density, the better the environmental resistance.

The evaluation criteria of the ion density are as follows.

◎: ion density <20

○: 20 ≦ ion density <40

△: 40 ≦ ion density <50

×: 50 ≦ ion density

The above-described embodiments are merely illustrative of the principles and effects of the invention, and are not intended to limit the invention. Modifications and variations of the embodiments described above will be apparent to those skilled in the art without departing from the spirit of the invention. The scope of the invention should be as set forth in the appended claims.

11‧‧‧ first unit

12‧‧‧Second unit

13‧‧‧Liquid Crystal Unit

111‧‧‧First substrate

112‧‧‧First conductive film

113‧‧‧First liquid crystal alignment film

121‧‧‧second substrate

122‧‧‧Second conductive film

123‧‧‧Second liquid crystal alignment film

Claims (9)

A liquid crystal alignment agent comprising: a polymer composition (A) obtained by reacting a mixture comprising a tetracarboxylic dianhydride component (a) and a diamine component (b); and a solvent (B) Wherein the diamine component (b) comprises at least one selected from the diamine compound (b-1) represented by the formula (1), the diamine compound (b-2) represented by the formula (2), and a carboxy group. a group consisting of acid-based diamine compounds (b-3); In the formula (1): Y ¹ represents a C ₁ to C ₂ alkylene group; and Y ² represents a nitrogen-containing aromatic heterocyclic group; In formula (2): R ¹⁵ is selected from -O-, , , , and a group consisting of; and R ¹⁶ represents an organic group represented by the formula (II-1): Wherein: R ¹⁷ represents hydrogen, fluorine or methyl; R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a single bond, -O-, , C ₁ to C ₃ alkylene; R ²¹ is selected from and a group consisting of: wherein R ²³ and R ²⁴ each independently represent hydrogen, fluorine or methyl; and R ²² is selected from the group consisting of hydrogen, fluorine, C ₁ to C ₁₂ alkyl, C ₁ to C ₁₂ fluoroalkyl a group of C ₁ to C ₁₂ alkoxy groups, -OCH ₂ F, -OCHF ₂ and -OCF ₃ ; k represents an integer of 1 or 2; w, m and t each independently represent an integer of 0 to 4 ; y, p and q each independently represent an integer from 0 to 3, and y+p+q≧3; and u and v each independently represent 1 or 2; when R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , When R ²¹ , R ²³ or R ²⁴ is plural, each may be the same or different. The liquid crystal alignment agent according to claim 1, wherein, in the formula (1), Y ² represents a pyrrolidinyl group, a piperazinyl group, a piperidinyl group or a pyridyl group. The liquid crystal alignment agent of claim 1, wherein the carboxylic acid group-containing diamine compound (b-3) is a compound represented by the following formula (3); In the formula (3), X represents an organic group containing a C ₆ to C ₃₀ aromatic ring; and n represents an integer of 1 to 4. The liquid crystal alignment agent according to claim 3, wherein the carboxylic acid group-containing diamine compound (b-3) is at least one selected from the group consisting of the following formulas (3-1) to (3-5); In the formula, X ₁ and X ₃ independently represent a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, - O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON(CH ₃₎ - or _{- N (CH 3) CO-;} X 2 represents a straight-chain alkyl or C ₁ to C ₅ C ₁ to C ₅ of the branched chain alkyl; N7 and n1 independently represents an integer of from 1 to 4; N2 and n3 independently represent an integer of 0 to 4, and n2+n3 is an integer of 1 to 4; and n4, n5, and n6 independently represent an integer of 1 to 5. The liquid crystal alignment agent of claim 1, wherein the total amount of the diamine component (b) used is 100 mol, and the diamine compound (b-1) represented by the formula (1) is used in an amount of 10 to 40 moles; the diamine compound (b-2) represented by the formula (2) is used in an amount of 10 to 40 mol; and the carboxylic acid group-containing diamine compound (b-3) is used in an amount of 20 To 80 moles. The liquid crystal alignment agent of claim 1, wherein the polymer composition (A) has a ruthenium iodide ratio ranging from 30 to 90%. A method of producing a liquid crystal alignment film comprising applying a liquid crystal alignment agent according to any one of claims 1 to 6 to a substrate. A liquid crystal alignment film formed by the liquid crystal alignment agent according to any one of claims 1 to 6. A liquid crystal display element comprising the liquid crystal alignment film according to claim 8.