TWI570183B - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Description

Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element, and more particularly to a liquid crystal alignment agent capable of forming a liquid crystal alignment film having excellent ultraviolet reliability, a liquid crystal alignment film formed of the above liquid crystal alignment agent, and having the above A liquid crystal display element of a liquid crystal alignment film.

In recent years, as consumer demand for wide viewing angle characteristics of liquid crystal displays has been increasing year by year, the requirements for electrical characteristics or display characteristics of wide viewing angle liquid crystal display elements have become more stringent than ever. Among the wide viewing angle liquid crystal display elements, vertical alignment type liquid crystal display elements are most often studied. Therefore, in order to have better electrical characteristics and display characteristics, the liquid crystal alignment film has become one of the important research objects for improving the characteristics of the vertical alignment type liquid crystal display element, especially after the large-size liquid crystal television has been widely put into practical use. For displays that mainly display text or still images, it is more necessary to maintain the reliability of long-term use.

Japanese Laid-Open Patent Publication No. 9-176651 discloses a liquid crystal having a high pretilt angle Orientation film. In the liquid crystal alignment film, a tetracarboxylic dianhydride compound containing a ruthenium-based skeleton and a diamine compound containing a ruthenium-based skeleton are simultaneously used, so that the liquid crystal alignment film can maintain a high pretilt angle after the reliability test. However, the liquid crystal alignment film has a problem of poor ultraviolet reliability. Specifically, when the liquid crystal alignment film is irradiated with ultraviolet rays for a certain period of time, the voltage holding ratio of the liquid crystal display is largely lowered, which causes problems such as a decrease in contrast of the liquid crystal display.

Therefore, how to provide a liquid crystal alignment agent capable of forming a liquid crystal alignment film having excellent ultraviolet reliability, and to apply the liquid crystal alignment film to a liquid crystal display element, the high voltage retention rate can be maintained under long-term irradiation of ultraviolet rays. It is a problem that those skilled in the art are currently trying to solve.

In view of the above, the present invention provides a liquid crystal alignment agent capable of forming a liquid crystal alignment film having excellent ultraviolet ray reliability, a liquid crystal alignment film formed of the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film.

The present invention provides a liquid crystal alignment agent comprising a polymer (A) and a solvent (B). The polymer (A) is obtained by reacting a mixture, wherein the mixture includes a tetracarboxylic dianhydride component (a) and a diamine component (b). The tetracarboxylic dianhydride component (a) includes the tetracarboxylic dianhydride compound (a-1) represented by the formula (1). The diamine component (b) includes the diamine compound (b-1) represented by the formula (2).

Specifically, the tetracarboxylic dianhydride compound (a-1) represented by the formula (1) is as follows.

In the formula (1), P ¹ , P ² , P ³ and P ⁴ each independently represent a single bond or a methylene group; and j represents an integer of 1 to 3.

Further, the diamine compound (b-1) represented by the formula (2) is shown below.

In the formula (2), Y ¹ represents an alkylene group having a carbon number of 1 to 12; Y ² represents a group having an anthracene skeleton or a group represented by the formula (2-1), wherein, represented by the formula (2-1) The base is as follows.

In the formula (2-1), R ¹ each independently represents a fluorine atom or a methyl group; and R ² represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, and carbon. Alkoxy groups of 1 to 12, -OCH ₂ F, -OCHF ₂ or -OCF ₃ ; Z ¹ , Z ² and Z ³ each independently represent a single bond, an alkylene group having 1 to 3 carbon atoms, -O -, , , , or ; Z ^{4 is} independent of each other or And R ^a and R ^b each independently represent a fluorine atom or a methyl group, h and i each independently represent 0, 1 or 2; a represents 0, 1 or 2; and b, c and d each independently represent an integer of 0 to 4; , f and g each independently represent an integer of 0 to 3, and e+f+g≧1.

In one embodiment of the present invention, the tetracarboxylic dianhydride compound (a-1) is used in an amount of 5 moles based on the total mole number of the tetracarboxylic dianhydride component (a). Up to 50 m.

In an embodiment of the invention, the diamine compound (b-1) is used in an amount of from 3 moles to 20 moles, based on the total mole number of the above diamine component (b) being 100 moles.

In an embodiment of the invention, the above polymer (A) has a ruthenium iodide ratio of 30% to 90%.

The present invention further provides a liquid crystal alignment film which is formed by the above liquid crystal alignment agent.

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

Based on the above, the liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention is excellent in ultraviolet ray reliability and is suitable for use in a liquid crystal display element.

In order to make the above features and advantages of the present invention more apparent, the following is a special The embodiments are described in detail below in conjunction with the drawings.

100‧‧‧Liquid display components

110‧‧‧ first unit

112‧‧‧First substrate

114‧‧‧First conductive film

116‧‧‧First liquid crystal alignment film

120‧‧‧Second unit

122‧‧‧second substrate

124‧‧‧Second conductive film

126‧‧‧Second liquid crystal alignment film

130‧‧‧Liquid Crystal Unit

1 is a side view of a liquid crystal display element in accordance with an embodiment of the present invention.

<Liquid alignment agent>

The present invention provides a liquid crystal alignment agent comprising a polymer (A) and a solvent (B). Further, the liquid crystal alignment agent may further include the additive (C), if necessary.

The respective components used in the liquid crystal alignment agent of the present invention will be described in detail below.

Here, the following description means that acrylic acid and/or methacrylic acid is represented by (meth)acrylic acid, and acrylate and/or methacrylate is represented by (meth)acrylate; similarly, (meth) The acryl fluorenyl group means an acryl fluorenyl group and/or a methacryl fluorenyl group.

Polymer (A)

The polymer (A) is obtained by reacting a mixture comprising a tetracarboxylic dianhydride component (a) and a diamine component (b).

In detail, the polymer (A) includes poly-proline, polyimine, poly-proline-polyimide block copolymer or a combination of these polymers. Wherein the polyamidene block copolymer comprises a polyphthalic acid block copolymer, a polyamidiene block copolymer, a poly-proline-polyimine block copolymer or the above polymerization a combination of things. The polyaminic acid polymer, the polyimine polymer, and the polyamido-polyimide block copolymer may be a mixture of the tetracarboxylic dianhydride component (a) and the diamine component (b). The reaction was prepared.

Tetracarboxylic dianhydride component (a)

The tetracarboxylic dianhydride component (a) includes a tetracarboxylic dianhydride compound (a-1) and a tetracarboxylic dianhydride compound (a-2).

Tetracarboxylic dianhydride compound (a-1)

The tetracarboxylic dianhydride compound (a-1) is a compound represented by the formula (1).

In the formula (1), P ¹ , P ² , P ³ and P ⁴ each independently represent a single bond or a methylene group; and j represents an integer of 1 to 3. In the formula (1), j preferably represents 1 to 2, and more preferably represents 1.

In the tetracarboxylic dianhydride compound (a-1) represented by the formula (1), specific examples in which j represents 1 include, but are not limited to, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid. Dihydride (compound represented by formula (1-1)), bicyclo[4.3.0]nonane-2,4,7,9-tetracarboxylic dianhydride (by a compound represented by the formula (1-2)), a bicyclo[4.4.0]nonane-2,4,8,10-tetracarboxylic dianhydride (a compound represented by the formula (1-3)), a bicyclo[4.4. 0] decane-2,4,7,9-tetracarboxylic dianhydride (compound represented by formula (1-4)), or a combination thereof.

Further, in the tetracarboxylic dianhydride compound (a-1) represented by the formula (1), specific examples in which j represents 2 include, but are not limited to, tricyclo [6.3.0.0 ^{2, 6} ] undecane-3, 5, 9,11-tetracarboxylic dianhydride (a compound represented by the formula (1-5)).

A specific example of the tetracarboxylic dianhydride compound (a-1) represented by the formula (1) preferably includes a bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride (by the formula) (1-1) the compound), bicyclo[4.3.0]nonane-2,4,7,9-tetracarboxylic dianhydride (compound represented by formula (1-2)), tricyclic [6.3. 0.0 ^2,6 ]undecane-3,5,9,11-tetracarboxylic dianhydride (compound represented by formula (1-5)), or a combination thereof.

The tetracarboxylic dianhydride compound (a-1) may have an isomer structure, and one type of isomer may be used or a mixture of isomers may be used. Taking bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride as an example, it may have the following formula (1-1-a), formula (1-1-b) Or the structure shown by the formula (1-1-c).

Bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride can be synthesized, for example, by the following method. First, 2,5-norbornadiene and dicyclopentadiene were reacted in an autoclave at 190 ° C for 20 hours to form a tetracyclic ring [6.2.1.1 ^3,6 .0 ^2,7 ]12-4,9-diene. Next, the obtained compound is subjected to ozonation reaction in methanol at -30 ° C, and then oxidatively decomposed using hydrogen peroxide in a mixed solvent of formic acid and acetic acid to form a bicyclo ring [3.3.0] Octane-2,4,6,8-tetracarboxylic acid (Bicyclo[3.3.0] octane-2,4,6,8-tetracarboxylic acid, abbreviated as BOTA). The BOTA is added to acetic anhydride and subjected to heat treatment to obtain bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride. Alternatively, BOTA can be formed by oxidizing tetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ]dodec-4,9-diene by potassium permanganate.

The tetracarboxylic dianhydride compound (a-1) may be used in an amount of from 5 moles to 50 moles, preferably 8 moles, based on the total amount of the tetracarboxylic dianhydride component (a) used in an amount of 100 moles. To 45 moles, more preferably 10 moles to 40 moles. When the liquid crystal alignment agent does not use the tetracarboxylic dianhydride compound (a-1), the liquid crystal alignment film has a problem that the ultraviolet ray reliability is not good.

Tetracarboxylic dianhydride compound (a-2)

The tetracarboxylic dianhydride compound (a-2) includes an aliphatic tetracarboxylic dianhydride compound, an alicyclic tetracarboxylic dianhydride compound, an aromatic tetracarboxylic dianhydride compound, and a formula (I-1) to At least one of the tetracarboxylic dianhydride compounds represented by I-6) or a combination of the above compounds.

Specific examples of the aliphatic tetracarboxylic dianhydride compound, the alicyclic tetracarboxylic dianhydride compound, and the aromatic tetracarboxylic dianhydride compound are listed below, but the present invention is not limited to these specific examples.

Specific examples of the aliphatic tetracarboxylic dianhydride compound may include, but are not limited to, ethane tetracarboxylic dianhydride, butane tetracarboxylic dianhydride or a combination of the above compounds.

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-ring Ding Alkanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid Dihydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, cis-3,7-dibutyl ring Heptyl-1,5-diene-1,2,5,6-tetracarboxylic dianhydride or 2,3,5-tricarboxycyclopentyl acetic acid dianhydride or a combination of the above compounds.

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, pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenylfluorene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylate Acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3'-4,4'-diphenylethane tetracarboxylic dianhydride, 3,3',4,4'- Dimethyldiphenylnonanetetracarboxylic dianhydride, 3,3',4,4'-tetraphenylnonanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4, 4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl phthalic anhydride, 4,4'- Bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluorohetero Propyldiphthalic acid dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(three Phenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, double (triphenylphthalic acid)-4,4'- Phenyl methane dianhydride, ethylene glycol-bis (hydrogen trimellitate), propylene glycol-bis (hydrogen trimellitate), 1,4-butanediol-bis (hydrogen trimellitate), 1,6-hexanediol-bis(anhydrotrimellitic acid ester), 1,8-octanediol-bis(anhydrotrimellitic acid ester), 2,2-bis(4-hydroxyphenyl)propane- Bis(hydrogen trimellitate), 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5- Bis-oxy-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione {(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-di-oxy-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a ,4,5,9b-hexahydro-5-ethyl-5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]-furan-1, 3-diketone, 1,3,3a,4,5,9b-hexahydro-7-methyl-5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1] ,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-ethyl-5-(tetrahydro-2,5-di-oxyl- 3-furyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydrogen) -2,5-di-oxy-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro- 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 Aromatic tetracarboxylic acid such as -1,3-diketone, 5-(2,5-di-oxo-tetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride An anhydride compound or a combination of the above compounds.

The tetracarboxylic dianhydride compound represented by the formula (I-1) to the formula (I-6) is as follows.

In the formula (I-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 independently represents a hydrogen atom or an alkyl group. Specific examples of the tetracarboxylic dianhydride compound represented by the formula (I-5) include at least one of the compounds represented by the formula (I-5-1) to the formula (I-5-3).

In the formula (I-6), A ⁴ represents a divalent group containing an aromatic ring; and A ⁵ and A ⁶ may be the same or different and each independently represents a hydrogen atom or an alkyl group. The tetracarboxylic dianhydride compound represented by the formula (I-6) is preferably a compound represented by the formula (I-6-1).

The tetracarboxylic dianhydride compound (a-2) can be used singly or in combination of two or more.

A specific example of the tetracarboxylic dianhydride compound (a-2) preferably includes 1,2,3,4-cyclobutane tetracarboxylic dianhydride (1,2,3,4-cyclobutane tetracarboxylic dianhydride), 1, 2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,2,4,5-cyclohexane Alkane tetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, pyromellitic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenylfluorene tetracarboxylic dianhydride, a compound represented by the formula (I-1) or a combination of the above compounds.

The total number of moles based on the tetracarboxylic dianhydride component (a) is 100 moles, tetracarboxylic acid The acid dianhydride compound (a-2) may be used in an amount of from 50 moles to 95 moles, preferably from 55 moles to 92 moles, and more preferably from 60 moles to 90 moles.

The total mole number based on the diamine component (b) is 100 moles, and the tetracarboxylic dianhydride component (a) is preferably used in an amount ranging from 20 moles to 200 moles, more preferably 30 moles. 120 moles.

Diamine component (b)

The diamine component (b) includes a diamine compound (b-1) and a diamine compound (b-2).

Diamine compound (b-1)

The diamine compound (b-1) is a compound represented by the formula (2).

In the formula (2), Y ¹ represents an alkylene group having a carbon number of 1 to 12; and Y ² represents a group having a skeleton of a steroid or a group represented by the formula (2-1).

The group represented by the formula (2-1) is as follows.

In the formula (2-1), R ¹ each independently represents a fluorine atom or a methyl group; and R ² represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, and carbon. Alkoxy groups of 1 to 12, -OCH ₂ F, -OCHF ₂ or -OCF ₃ ; Z ¹ , Z ² and Z ³ each independently represent a single bond, an alkylene group having 1 to 3 carbon atoms, -O -, , , , or ; Z ^{4 is} independent of each other or And R ^a and R ^b each independently represent a fluorine atom or a methyl group, h and i each independently represent 0, 1 or 2; a represents 0, 1 or 2; and b, c and d each independently represent an integer of 0 to 4; , f and g each independently represent an integer of 0 to 3, and e+f+g≧1.

Specific examples of the diamine compound (b-1) include at least one of the compounds represented by the formula (2-2) to the formula (2-19).

The diamine compound (b-1) can be produced by a general organic synthesis method. For example, the compound represented by the formula (2-2) to the formula (2-19) may be added to the maleic anhydride after the compound having an anthracene skeleton or the compound represented by the formula (2-20), respectively. In the presence of potassium, a dinitrophenylphosphonium chloride compound is added to carry out an esterification reaction. Then, a reduction reaction is carried out by adding an appropriate reducing agent such as tin chloride to synthesize the diamine compound (b-1).

In the formula (2-20), R ¹ , R ² , Z ¹ , Z ² , Z ³ , Z ⁴ , a, b, c, d, e, f and g are respectively defined in the formula (2-1) The definitions of R ¹ , R ² , Z ¹ , Z ² , Z ³ , Z ⁴ , a, b, c, d, e, f and g are the same and will not be further described herein.

The compound represented by the formula (2-20) can be obtained by a method such as a Grignard reaction or a Friedal-Crafts acylation reaction generally used for synthesizing a liquid crystal compound. synthesis.

The diamine compound (b-1) represented by the formula (2) is preferably selected from the formula (2-2), the formula (2-7), the formula (2-10), the formula (2-15), and the formula (2). 2-17) At least one of the group consisting of the diamine compounds represented by the formula (2-18).

The diamine compound (b-1) may be used in an amount of from 3 moles to 20 moles, preferably from 4 moles to 18 moles, based on the diamine component (b) used in an amount of 100 moles, and more preferably Good for 5 to 15 moles. When the liquid crystal alignment agent does not use the diamine compound (b-1), the liquid crystal alignment film has a problem that the ultraviolet light reliability is not good.

Diamine compound (b-2)

The diamine compound (b-2) includes an aliphatic diamine compound, an alicyclic diamine compound, an aromatic diamine compound, a diamine compound having the formula (II-1) to the formula (II-30), or combination.

Specific examples of the aliphatic diamine compound include, but are not limited to, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane 1,6-Diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane, 1,10-diaminodecane , 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-methyldecane, 2,11-diaminododecane, 1,12-diaminooctadecane, 1,2-bis(3-aminopropoxy)B Alkane, or a combination of the above compounds.

Specific examples of the alicyclic diamine compound include, but are not limited to, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylamine, 1, 3-diaminocyclohexane, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadiene diamine, tricyclo[6.2.1.0 ^2,7 ]- eleven Carboxydimethyldiamine, 4,4'-methylenebis(cyclohexylamine), or a combination of the above compounds.

Specific examples of the aromatic diamine compound include, but are not limited to, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl Bismuth, 4,4'-diaminobenzimidamide, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylhydroquinone, 6-amino-1-(4'-aminophenyl)-1,3, 3-trimethylhydroquinone, hexahydro-4,7-methyl bridge hydroquinone dimethylene diamine, 3,3'-diaminobenzophenone, 3,4'-diaminodi Benzophenone, 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]碸, 1,4-bis(4-aminophenoxyl) Benzo, 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, 2,7-diaminopurine, 9,9-bis (4- Aminophenyl)anthracene, 4,4'-methylene-bis(2-chloroaniline), 4,4'-(p-phenylphenylisopropylene)diphenylamine, 4,4'- -phenylene isopropylidene)diphenylamine, 2,2'-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-double [(4-Amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl, 5-[4-(4-n-pentylcyclocyclohexyl)cyclohexyl]phenyl-methylene-1 ,3-diaminobenzene {5-[4-(4-n-pentylcyclohexyl)cyclohexyl]phenylmethylene-1,3-diaminobenzene}, 1,1-bis[4-(4-aminophenoxy)phenyl -4-(4-ethylphenyl)cyclohexane {1,1-bis[4-(4-aminophenoxy)phenyl]-4-(4-ethylphenyl)cyclohexane}, or a combination of the above compounds.

The diamine compound having the structural formula (II-1) to the formula (II-30) is shown below.

In the formula (II-1), B ¹ represents -O-, , , , ,or B ² represents a group having a steroid (steroid) skeleton, a trifluoromethyl group, a fluorine group, an alkyl group having 2 to 30 carbon atoms, or a derivative derived from pyridine, pyrimidine, triazine, piperidine or piperazine. a monovalent group containing a cyclic structure of a nitrogen atom.

Specific examples of the compound represented by the formula (II-1) include, but are not limited to, 2,4-diaminophenyl ethyl formate, 3,5-diaminophenylethylate B 3,5-diaminophenyl ethyl formate, 2,4-diaminobenzene 2,4-diaminophenyl propyl formate, 3,5-diaminophenyl propyl formate, 1-dodecyloxy-2,4-diamine 1-dodecoxy-2,4-diaminobenzene, 1-hexadecoxy-2,4-diaminobenzene, 1-octadecyloxy- 2,4-diaminobenzene (1-octadecoxy-2,4-diaminobenzene), at least one of the compounds represented by the formula (II-1-1) to the formula (II-1-6), or the above compound The combination.

The compound represented by the formula (II-1-1) to the formula (II-1-6) is shown below.

, B ¹ same formula (II-2) with the formula B (II-1) is ^1, B ³ and B ⁴ each independently represents a divalent aliphatic ring, a divalent aromatic ring or a divalent heterocyclic group; B ⁵ represents an alkyl group having 3 to 18 carbon atoms, an alkoxy group having 3 to 18 carbon atoms, a fluoroalkyl group having 1 to 5 carbon atoms, a fluoroalkoxy group having 1 to 5 carbon atoms, or a cyano group or Halogen atom.

Specific examples of the compound represented by the formula (II-2) include at least one of the compounds represented by the formula (II-2-1) to the formula (II-2-13). Specifically, the compound represented by the formula (II-2-1) to the formula (II-2-13) is as follows.

In the formula (II-2-10) to the formula (II-2-13), s represents an integer of from 3 to 12.

In the formula (II-3), B ⁶ each independently 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 atom. And B ⁶ in each repeating unit may be the same or different; u represents an integer of 1 to 3.

Specific examples of the compound represented by the formula (II-3) include when p is 1: p-diamine benzene, m-diamine benzene, o-diamine benzene or 2,5-diaminotoluene, etc.; 2 hours: 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-di Aminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 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; or when u is 3: 1 , 4-bis(4'-aminophenyl)benzene, and the like.

Specific examples of the compound represented by the formula (II-3) preferably include p-diamine benzene, 2,5-diaminotoluene, 4,4'-diaminobiphenyl, 3,3'-dimethyl Alkoxy-4,4'-diaminobiphenyl, 1,4-bis(4'-aminophenyl)benzene or a combination of the above compounds.

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

In the formula (II-5), w represents an integer of 1 to 5. The compound represented by the formula (II-5) is preferably 4,4'-diamino-diphenyl sulfide.

In the formula (II-6), B ⁷ and B ⁹ each independently represent a divalent organic group, and B ⁷ and B ⁹ may be the same or different; B ⁸ represents a derivative derived from pyridine, pyrimidine, triazine, piperidine or piperidine. a divalent group of a cyclic structure containing a nitrogen atom such as a azine.

In the formula (II-7), B ¹⁰ , B ¹¹ , B ¹² and B ¹³ each independently represent a hydrocarbon group having 1 to 12 carbon atoms, and B ¹⁰ , B ¹¹ , B ¹² and B ¹³ may be the same or different; X1 Each represents an integer from 1 to 3; X2 represents an integer from 1 to 20.

In formula (II-8), B ¹⁴ represents an oxygen atom or group extending cyclohexane; B ¹⁵ represents a methylene group _{(methylene, -CH 2 -);} B 16 represents a phenylene group or cyclohexane extension; B ¹⁷ Represents a hydrogen atom or a heptyl group.

Specific examples of the compound represented by the formula (II-8) include a compound represented by the formula (II-8-1), a compound represented by the formula (II-8-2) or a combination of the above compounds.

The compound represented by the formula (II-9) to the formula (II-30) is shown below.

In the formulae (II-17) to (II-25), B ¹⁸ preferably represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms; and B ¹⁹ preferably represents 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 (b-2) can be used singly or in combination of two or more.

Specific examples of the diamine compound (b-2) include, but are not limited to, 1,2-diaminoethane, 4,4'-diaminodicyclohexylmethane, and 4,4'-diamino group II. Phenylmethane, 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, 1- Octadecyloxy-2,4-diaminobenzene, a compound represented by the formula (II-1-1), a compound represented by the formula (II-1-2), and a formula (II-1-4) a compound represented by the formula, a compound represented by the formula (II-1-5), a compound represented by the formula (II-2-1), a compound represented by the formula (II-2-11), p-diamine benzene, m-diamine benzene, o-diamine benzene, and a formula (II-8) A compound represented by the formula (1), a compound represented by the formula (II-26) to the formula (II-30), or a combination of the above compounds.

The diamine compound (b-2) may be used in an amount of from 80 moles to 97 moles, preferably from 82 moles to 96 moles, based on the amount of the diamine component (b) used in an amount of 100 moles, and more preferably Good for 85 to 95 moles.

When the polymer (A) in the liquid crystal alignment agent contains the diamine compound (b-2) represented by the formula (II-1), the formula (II-2), the formula (II-26) to the formula (II-30) At least one of them can further improve the ultraviolet reliability of the liquid crystal display element.

Method for preparing polymer (A)

The polymer (A) may include at least one of polyamic acid and polyimine. Further, the polymer (A) may further include a polyimide-based block copolymer. The preparation methods of the above various polymers are further explained below.

Method for preparing polylysine

The method for preparing polylysine is to first dissolve the mixture in a solvent, wherein the mixture comprises the tetracarboxylic dianhydride component (a) and the diamine component (b), and is polymerized at a temperature of 0 ° C to 100 ° C. Condensation reaction. After reacting for 1 hour to 24 hours, the reaction solution is subjected to distillation under reduced pressure with an evaporator to obtain a polyamic acid. Alternatively, the reaction solution is poured into a large amount of a poor solvent to obtain a precipitate. Next, the precipitate is dried by drying under reduced pressure to obtain polylysine.

The solvent used in the polycondensation reaction may be the same as or different from the solvent 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 a product. The solvent preferably includes, but is not limited to, (1) an aprotic polar solvent such as N-methyl-2-pyrrolidinone (NMP), N,N-dimethylacetamide, An aprotic polar solvent such as N,N-dimethylformamide, dimethylhydrazine, γ-butyrolactone, tetramethylurea or hexamethylphosphoric acid triamide; or (2) a 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, and more preferably from 300 parts by weight to 1800 parts by weight, based on 100 parts by weight of the total amount of the mixture.

It is worth noting that 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 polyamic acid. The poor solvent may be used singly or in combination of two or more, and includes, but is not limited to, (1) an alcohol such as methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, or 1,4-butane. An alcohol such as an alcohol or 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 of methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate or ethylene glycol ethyl ether acetate; (4) ethers such as 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 diethylene glycol An ether such as an ether; (5) a halogenated hydrocarbon such as dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene or o-dichloro a halogenated hydrocarbon such as benzene; or (6) a hydrocarbon such as tetrahydrofuran or Any combination of a hydrocarbon such as an alkane, heptane, octane, benzene, toluene or xylene or the above solvent. The amount of the poor solvent is preferably from 0 part by weight to 60 parts by weight, and more preferably from 0 part by weight to 50 parts by weight, based on 100 parts by weight of the diamine component (b).

Method for preparing polyimine

The method for preparing the polyimine is obtained by heating the polylysine prepared by the above method for preparing polyamic acid in the presence of a dehydrating agent and a catalyst. During heating, the proline functional group in the polylysine can be converted to a quinone imine functional group (ie, hydrazide) via a dehydration ring closure reaction.

The solvent used in the dehydration ring closure reaction may be the same as the solvent (B) in the liquid crystal alignment agent, and therefore will not be further described herein. The amount of the solvent used in the dehydration ring-closure reaction is preferably from 200 parts by weight to 2000 parts by weight, and more preferably from 300 parts by weight to 1800 parts by weight, based on 100 parts by weight of the polylysine.

In order to obtain a preferred degree of ruthenium iodide, the operating 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-closing reaction is lower than 40 ° C, the reaction of ruthenium imidization is incomplete, and the degree of ruthenium iodide of poly-proline 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 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 1 mol of the polyglycolic acid. The catalyst used in the dehydration ring closure reaction may be selected from the group consisting of (1) pyridine compounds, for example: a pyridine compound such as pyridine, trimethylpyridine or lutidine; or (2) a tertiary amine compound such as a tertiary amine compound such as triethylamine. The amount of the dehydrating agent used is 1 mole, and the catalyst can be used in an amount of 0.5 mole to 10 moles.

The ruthenium amination rate of the polymer (A) may be from 30% to 90%, preferably from 35% to 85%, and more preferably from 40% to 80%. When the ruthenium imidation ratio of the polymer (A) in the liquid crystal alignment agent is within the above range, the ultraviolet reliability of the formed liquid crystal alignment film can be further improved.

Method for preparing polyamidene block copolymer

The polyamidene block copolymer is selected from the group consisting of polyphthalic acid block copolymers, polyamidiene block copolymers, polyamido acid-polyimine block copolymers or the above polymerizations. Any combination of objects.

The method for preparing the polyimine-based block copolymer is preferably first dissolving the starting material in a solvent and performing a polycondensation reaction, wherein the starting material comprises at least one poly-proline and/or at least one polyfluorene. The imine, and may further comprise a carboxylic anhydride component and a diamine component.

The carboxylic anhydride component and the diamine component in the starting material may be the same as the tetracarboxylic dianhydride component (a) and the diamine component (b) used in the method for preparing the polyamic acid, and used for The solvent in the polycondensation reaction may be the same as the solvent 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, and more preferably 300, based on 100 parts by weight of the starting material. Parts by weight to 1800 parts by weight. The operation temperature of the polycondensation reaction is preferably from 0 ° C to 200 ° C, and more preferably from 0 ° C to 100 ° C.

Preferably, the starting material comprises, but is not limited to, (1) two polyamido acids having different terminal groups and different structures; (2) two kinds of polyamidiamines having different terminal groups and different structures; a poly-proline and a polyamidiamine having different terminal groups and different structures; (4) a poly-proline, a carboxylic anhydride component and a diamine component, wherein the carboxylic anhydride component and the diamine component At least one of the structure is different from the structure of the carboxylic anhydride component and the diamine component used to form the polyamic acid; (5) a polyimine, a carboxylic anhydride component and a diamine component, wherein the carboxylic anhydride group At least one of the diamine component and the carboxylic anhydride component used in forming the polyimine are different from the structure of the diamine component; (6) poly-proline, polyimine, and carboxylic anhydride components And a diamine component, wherein at least one of the carboxylic anhydride component and the diamine component is different from the structure of the carboxylic anhydride component and the diamine component used to form the polyamic acid or the polyimine; 7) two structurally different polylysine, carboxylic anhydride component and diamine component; (8) two structurally different polyimine, carboxylic anhydride component and diamine component; (9) Two terminal groups are anhydride groups and structures a different polyamic acid and a diamine component; (10) two polyamines having a terminal group which is an amine group and having a different structure, and a carboxylic anhydride component; (11) the two terminal groups are an acid anhydride group and a structural phase a different polyimine and a diamine component; or (12) a polyimine and a carboxylic anhydride component in which the terminal groups are amine groups and have different structures.

The polyproline, the polyimine, and the polyimide block copolymer are preferably end-modified polymers having a molecular weight adjusted first, within a range that does not impair the efficacy of the present invention. The coating property of the liquid crystal alignment agent can be improved by using a terminal-modified polymer. Poly-proline in the preparation of terminally modified polymers A polyfunctional condensation reaction is carried out while adding a monofunctional compound.

Specific examples of the monofunctional compound include, but are not limited to, (1) a monobasic acid anhydride such as maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, ortho-fourth a monobasic anhydride such as an alkyl succinic anhydride or n-hexadecyl succinic 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, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecaneamine, A monoamine compound such as n-octadecylamine or n-icosylamine; or (3) a monoisocyanate compound such as a monoisocyanate compound such as phenyl isocyanate or naphthyl isocyanate.

Solvent (B)

The solvent to be used in the liquid crystal alignment agent of the present invention is not particularly limited as long as it can dissolve the polymer (A) and other optional components and does not react therewith, and is preferably the same as the above-mentioned synthetic polylysine. The solvent to be used may be used in combination with the poor solvent used in the synthesis of the polyamic acid.

Specific examples of the solvent (B) include, but are not limited to, N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, 4-hydroxy-4-methyl-2-pentanone, and ethylene glycol. Monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxy propionate, 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, 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 or N, N-dimethyl Carbenamide or N,N-dimethylacetamide or the like. The solvent (B) may be used singly or in combination of two or more.

The solvent (B) is used in an amount of 800 to 4000 parts by weight, preferably 900 to 3500 parts by weight, and more preferably 1,000 to 3,000 parts by weight, based on 100 parts by weight of the polymer (A).

Additive (C)

The liquid crystal aligning agent may also optionally add the additive (C), wherein the additive (C) includes a compound having at least two epoxy groups, a decane compound having a functional group, within a range not affecting the efficacy of the present invention, Or a combination thereof.

Compounds having at least two epoxy groups include, but are not limited to, ethylene glycol diepoxypropyl ether, polyethylene glycol diepoxypropyl ether, propylene glycol diepoxypropyl ether, tripropylene glycol diepoxypropyl ether , polypropylene glycol diepoxypropyl ether, neopentyl glycol diepoxypropyl ether, 1,6-hexanediol diepoxypropyl ether, glycerol diepoxypropyl ether, 2,2-di Bromo 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,N-diepoxypropyl)aminopropyltrimethoxydecane, or a combination of the above compounds.

Compounds having at least two epoxy groups may be used alone or in combination use.

The compound having at least two epoxy groups may be used in an amount of from 0 to 40 parts by weight, and preferably from 0.1 part by weight to 30 parts by weight, based on 100 parts by weight of the polymer (A).

Specific examples of the decane compound having a functional group include, but are not limited to, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2 -Aminopropyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropyl Methyldimethoxydecane, 3-ureidopropyltrimethoxy silane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyl Trimethoxydecane, N-ethoxycarbonyl-3-aminopropyltriethoxydecane, N-triethoxydecylpropyltriamine, N-trimethoxydecylpropyltri Ethylenetriamine, 10-trimethoxydecyl-1,4,7-trioxane, 10-triethoxydecyl-1,4,7-trioxane, 9-trimethoxydecane 3-,6-dimercaptoacetate, 9-triethoxydecyl-3,6-dimercaptoacetate, N-benzyl-3-aminopropyltrimethoxydecane, N -benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N - Bis(ethylene oxide)-3-aminopropyltrimethoxydecane, N-bis(oxyethylene)-3-aminopropyltriethoxydecane, or a combination of the above compounds.

The decane compound having a functional group may be used singly or in combination of two or more.

The polymer (A) is used in an amount of 100 parts by weight, having a functional group The decane compound may be used in an amount of from 0 to 10 parts by weight, and preferably from 0.5 part by weight to 10 parts by weight.

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

<Preparation method of liquid crystal alignment agent>

The preparation method of the liquid crystal alignment agent is not particularly limited and can be produced by a general mixing method. For example, the polymer (A) is first added to the solvent (B) at a temperature of from 0 ° C to 200 ° C, and the additive (C) is selectively added. Next, stirring is continued until dissolved by using a stirring device. Further, in addition, it is preferred to add the solvent (B) at a temperature of from 20 ° C to 60 ° C.

<Preparation method of liquid crystal alignment film>

The liquid crystal alignment film of the present invention can be formed by the above liquid crystal alignment agent.

Specifically, the liquid crystal alignment film may be prepared by coating a liquid crystal alignment agent on a surface of a substrate by a roll coating method, a spin coating method, a printing method, or an ink-jet method. Forming a precoat. Next, the precoat layer is subjected to a pre-bake treatment, a post-bake treatment, and an alignment treatment to obtain a substrate on which a liquid crystal alignment film is formed.

The purpose of the prebaking treatment is to volatilize the organic solvent in the precoat layer. Pre The operating temperature of the baking treatment is preferably from 30 ° C to 120 ° C, and more preferably from 40 ° C to 110 ° C, particularly preferably from 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 be aligned.

The purpose of the post-baking treatment step is to further subject the polymer in the precoat layer to a dehydration ring-closing (deuteration) reaction. The post-baking treatment is preferably carried out at a temperature of from 150 ° C to 300 ° C, more preferably from 180 ° C to 280 ° C, still more preferably from 200 ° C to 250 ° C.

<Liquid crystal display element and its preparation method>

The liquid crystal display element of the present invention comprises a liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention. The liquid crystal display element of the present invention can be produced by the following method.

Two sheets of the substrate on which the liquid crystal alignment film was formed as described above were prepared, and liquid crystal was placed between the two substrates to produce a liquid crystal cell. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example.

The first method: first, the two substrates are arranged opposite each other with a gap (cell gap) so that the respective liquid crystal alignment films are opposed to each other; the peripheral portions of the two substrates are bonded together by using a sealant; The filling liquid crystal is injected into the cell gap divided by the sealant; and the injection hole is closed, so that the liquid crystal cell can be manufactured.

The second method: a method called the One Drop Fill (ODF) method. First, for example, an ultraviolet curable sealing material is applied to a predetermined portion of one of the two substrates on which the liquid crystal alignment film is formed, and liquid crystal is dropped on the liquid crystal alignment film surface; then, the other substrate is bonded to make the liquid crystal alignment film relatively Towards; The entire surface of the substrate is irradiated with ultraviolet rays to cure the sealant, whereby the liquid crystal cell can be produced.

In the case of any of the above methods, it is desirable to subsequently heat the liquid crystal cell to a temperature at which the liquid crystal used is in an isotropic phase, and then slowly cool to room temperature, thereby removing the flow alignment when the liquid crystal is filled.

Then, a liquid crystal display element of the present invention can be obtained by laminating a polarizer on the outer surface of the liquid crystal cell.

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

The polarizing plate used for the outer side of the liquid crystal cell is a polarizing film called "H film" obtained by sandwiching a polyvinyl acetate (vinyl acetate) protective film while absorbing iodine. a polarizing plate formed by the polarizing plate or the H film itself.

The liquid crystal display element of the present invention thus produced has excellent display performance and does not deteriorate in display performance even when used for a long period of time.

1 is a side view of a liquid crystal display element in accordance with an embodiment of the present invention. The liquid crystal display element 100 includes a first unit 110, a second unit 120, and a liquid crystal unit 130, wherein the second unit 120 is disposed separately from the first unit 110, and the liquid crystal unit 130 is disposed between the first unit 110 and the second unit 120.

The first unit 110 includes a first substrate 112, a first conductive film 114, and a first liquid crystal alignment film 116, wherein the first conductive film 114 is located between the first substrate 112 and the first liquid crystal alignment film 116, and the first liquid crystal alignment film 116 is located on one side of the liquid crystal cell 130.

The second unit 120 includes a second substrate 122, a second conductive film 124, and a second liquid crystal alignment film 126, wherein the second conductive film 124 is located between the second substrate 122 and the second liquid crystal alignment film 126, and the second liquid crystal alignment film 126 is located on the other side of the liquid crystal cell 130. In other words, the liquid crystal cell 130 is located between the first liquid crystal alignment film 116 and the second liquid crystal alignment film 126.

The first substrate 112 and the second substrate 122 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, a hard glass (Pyrus glass), a quartz glass for a liquid crystal display device. , polyethylene terephthalate, polybutene, terephthalate, polyether oxime or polycarbonate. The material of the first conductive film 114 and the second conductive film 124 is selected from tin oxide (SnO ₂ ), indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ), or the like.

Each of the first liquid crystal alignment film 116 and the second liquid crystal alignment film 126 is the liquid crystal alignment film described above, and functions to form the liquid crystal cell 130 to have a pretilt angle. In addition, when the voltages of the first conductive film 114 and the second conductive film 124 are applied, an electric field can be generated between the first conductive film 114 and the second conductive film 124. This electric field can drive the liquid crystal cell 130, thereby changing the alignment of the liquid crystal molecules in the liquid crystal cell 130. The liquid crystal used in the liquid crystal cell 130 may be used singly or in combination, and the liquid crystal includes, but not limited to, a diamino benzene liquid crystal, a pyridazine liquid crystal, a shiff base liquid crystal, an azo group ( Azoxy) liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, ester liquid crystal, terphenyl, biphenylcyclohexane liquid crystal, pyrimidine ( Pyrimidine) liquid crystal, dioxane liquid crystal, bicyclooctyl A bicyclooctane liquid crystal, a cubane liquid crystal, or the like, and optionally, cholesterol such as cholesteryl chloride, cholesterol cholesteryl carbonate, cholesterol ester carbonate, or the like may be added as needed. Liquid crystal, or chiral agent such as "C-15", "CB-15" (made by Merck), or p-methoxybenzylidene-p-amino-2 - Ferroelectric liquid crystal such as methyl butyl cinnamate.

Synthesis example of polymer (A)

The synthesis example A-1-1 to the synthesis example A-1-3 of the polymer (A) will be described below:

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 gas was introduced. Then, 1.51 g (0.0025 mol) of a diamine compound represented by the formula (2-10) (abbreviated as b-1-1) and 9.42 g (0.0475 mol) of 4, 4 were placed in a four-necked flask. '-Diaminodiphenylmethane (4,4'-diaminodiphenylmethane) is abbreviated as (b-2-1), and 80 g of N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone) Referred to as NMP), it is stirred until dissolved at room temperature. Next, 1.25 g (0.005 mol) of a tetracarboxylic dianhydride compound represented by the formula (1-1) (abbreviated as a-1-1) and 8.82 g (0.045 mol) of 1,2,3 were added. 4-cyclobutane tetracarboxylic dianhydride (abbreviated as a-2-1) and 20 g of NMP were reacted at room temperature for 2 hours. After the reaction is over, pour the reaction solution into 1500 m. The water is raised to precipitate the polymer. Then, the obtained polymer was filtered, washed repeatedly with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60 ° C to obtain a polymer (A-1-1).

Synthesis Example A-1-2 to Synthesis Example A-1-3

Synthesis Example A-1-2 to Synthesis Example A-1-3 The polymer (A-1-2) to the polymer (A-1-3) were separately prepared in the same manner as in Synthesis Example A-1-1. And the difference is: change the type of monomer and its use (as shown in Table 1).

Synthesis example of polymer

The synthesis examples A-2-1 to Synthesis A-2-10 of the polymer are explained below:

Synthesis Example A-2-1

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 gas was introduced. Then, 1.51 g (0.0025 mol) of a diamine compound represented by the formula (2-10) (abbreviated as b-1-1) and 9.42 g (0.0475 mol) of 4, 4 were placed in a four-necked flask. '-Diaminodiphenylmethane (4,4'-diaminodiphenylmethane) is abbreviated as (b-2-1), and 80 g of N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone) Referred to as NMP), it is stirred until dissolved at room temperature. Next, 1.25 g (0.005 mol) of a tetracarboxylic dianhydride compound represented by the formula (1-1) (abbreviated as a-1-1) and 8.82 g (0.045 mol) of 1,2,3 were added. 4-cyclobutane tetracarboxylic dianhydride (1,2,3,4-cyclobutane Tetracarboxylic dianhydride (abbreviated as a-2-1) and 20 g of NMP. After reacting at room temperature for 6 hours, 97 g of NMP, 2.55 g of acetic anhydride and 19.75 g of pyridine were added, the temperature was raised to 60 ° C, and stirring was continued for 2 hours to carry out the oxime imidization reaction. After the reaction was completed, the reaction solution was poured into 1500 ml of water to precipitate a polymer. Then, the obtained polymer was filtered, washed repeatedly with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60 ° C to obtain a polymer (A-2-1).

Synthesis Example A-2-2 to Synthesis Example A-2-10

Synthesis Example A-2-2 to Synthesis Example A-2-10 The same procedure as in Synthesis Example A-2-1 was carried out to prepare a polymer (A-2-2) to a polymer (A-2-10), respectively. And the difference is: change the type of monomer and its use (as shown in Table 1).

Comparative Synthesis Example A-3-1 to Comparative Synthesis Example A-3-3 of Polymer

Comparative Synthesis Example A-3-1 to Comparative Synthesis Example A-3-3 The same procedure as in Synthesis Example A-1-1 was carried out to prepare a polymer (A-3-1) to a polymer (A-3-, respectively). 3), and the difference is: change the type of monomer and its use (as shown in Table 2).

Comparative Synthesis Example A-3-4 of Polymer to Comparative Synthesis Example A-3-6

Comparative Synthesis Example A-3-4 to Comparative Synthesis Example A-3-6 The same procedure as in Synthesis Example A-2-1 was carried out to prepare a polymer (A-3-4) to a polymer (A-3-, respectively). 6), and the difference is: change the type of monomer, catalyst and dehydrating agent and its amount of use (As shown in table 2).

The compounds corresponding to the abbreviations in Table 1 and Table 2 are as follows.

Embodiments and Comparative Examples of Liquid Crystal Aligning Agent, Liquid Crystal Alignment Film, and Liquid Crystal Display Element

Hereinafter, Examples 1 to 13 and Comparative Examples 1 to 6 of the liquid crystal alignment agent, the liquid crystal alignment film, and the liquid crystal display element will be described:

a. Liquid crystal alignment agent

100 parts by weight of the polymer (A-1-1), 1200 parts by weight of N-methyl-2-pyrrolidone (abbreviated as B-1), and 600 parts by weight of ethylene glycol n-butyl ether (abbreviated as B) -2), and stirred and mixed at room temperature to form the liquid crystal alignment agent of Example 1.

b. Liquid crystal alignment film and liquid crystal display element

The liquid crystal alignment agent was applied to a glass substrate having a conductive film made of ITO (indium-tin-oxide) by a printing machine (manufactured by Nippon Photo Printing Co., Ltd., model No. S15-036) to form a pre-form. coating. Thereafter, the glass substrate was placed on a hot plate, and prebaked at a temperature of 100 ° C for 5 minutes. Next, post-baking was carried out in a circulating oven under the conditions of a temperature of 220 ° C and a time of 30 minutes. Finally, after the alignment treatment, the glass substrate on which the liquid crystal alignment film of Example 1 was formed was obtained.

The two glass substrates on which the liquid crystal alignment film was formed were obtained as described above, one of which was coated with a thermocompression adhesive, and the other was sprinkled with a 4 μm spacer. Next, the two glass substrates were bonded together, and a pressure of 10 kg was applied thereto by a hot press, and hot press bonding was carried out at a temperature of 150 °C. Then, with a liquid crystal injection machine (island Liquid crystal injection was carried out by Tsusho Manufacturing Co., Ltd., model number ALIS-100X-CH. Next, the liquid crystal injection port is sealed by ultraviolet light curing glue, and the ultraviolet light hardening glue is hardened by ultraviolet light illumination, and the liquid crystal tempering treatment is performed in an oven at a temperature of 60 ° C for 30 minutes. The liquid crystal display element of Example 1 was obtained.

The liquid crystal display elements of Example 1 were evaluated for each evaluation method described later, and the results are shown in Table 3.

Example 2 to Example 13

The liquid crystal alignment agent, the liquid crystal alignment film, and the liquid crystal display element of Example 2 to Example 13 were separately prepared in the same manner as in Example 1, and the difference was that the kind of the component and the amount thereof were changed, as shown in Table 3. Show. The liquid crystal display elements obtained in Examples 2 to 13 were evaluated in the evaluation methods described later, and the results are shown in Table 3.

Comparative Example 1 to Comparative Example 6

The liquid crystal alignment agent, the liquid crystal alignment film, and the liquid crystal display element of Comparative Example 1 to Comparative Example 6 were separately prepared in the same manner as in Example 1, except that the type of the component and the amount thereof were changed, as shown in Table 4. . The evaluation methods of the liquid crystal display elements obtained in Comparative Examples 1 to 6 were evaluated in the following, and the results are shown in Table 4.

The compounds corresponding to the abbreviations in Tables 3 and 4 are as follows.

Evaluation method a. oxime imidization rate

The ruthenium imidization ratio refers to the calculation of the number of ruthenium rings by the total number of guanamine functional groups and the number of quinone rings in the polymer. Proportion, expressed as a percentage.

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

Δ1: the peak area of the chemical shift of the NH proton near 10 ppm; Δ2: the peak area of other protons; α: the NH of the precursor of the polymer (polyproline) The ratio of the number of protons of a radical to the number of other protons.

b. UV reliability

The ultraviolet reliability of the liquid crystal alignment film is evaluated by the voltage holding ratio of the liquid crystal display element. Further, the method of measuring the voltage holding ratio of the liquid crystal display element is as follows.

The voltage holding ratios of the liquid crystal display elements of Examples 1 to 13 and Comparative Examples 1 to 6 were measured by an electric measuring machine (manufactured by Toyo Corporation, Model No. 6254). The test condition was that a voltage of 4 volts was applied, and the voltage was released after 2 milliseconds, and the voltage holding ratio after 1667 milliseconds was released (measured as VHR1). Next, after the liquid crystal display element was irradiated with ultraviolet light of 4200 mJ/cm ² (UV type irradiation machine model: KN-SH48K1; manufactured by Phonton Industrial Co., Ltd.), the voltage holding ratio after ultraviolet light irradiation was measured under the same test conditions (calculated as VHR2). Finally, the percentage change in voltage holding ratio (calculated as VHR ^UV (%)) can be obtained by mathematical formula (2). The lower the percentage change in voltage holding ratio, the better the reliability of the ultraviolet light.

The evaluation criteria for the percentage change in voltage holding ratio are as follows.

◎: VHR ^UV <5%

○: 5% ≦VHR ^UV <10%

△: 10% ≦VHR ^UV <20%

×: 20% ≦VHR ^UV

<evaluation result>

From Table 3 and Table 4, a liquid crystal alignment film formed by simultaneously using a tetracarboxylic dianhydride compound (a-1) and a diamine compound (b-1) in the polymer (A) (Example 1 to Example) In the case of Example 13), the liquid crystal alignment film (Comparative Examples 1, 3, 4, and 6) formed using the polymer (A) not containing the tetracarboxylic dianhydride compound (a-1) was inferior in ultraviolet reliability; Further, the liquid crystal alignment film (Comparative Examples 2, 3, 5, and 6) formed using the polymer (A) not containing the diamine compound (b-1) had poor ultraviolet reliability.

Further, when the ruthenium imidation ratio of the polymer (A) in the liquid crystal alignment agent is from 30% to 90%, the liquid crystal alignment film (Examples 7 to 12) formed is preferably excellent in ultraviolet ray reliability.

Further, when the polymer (A) in the liquid crystal alignment agent contains the diamine compound represented by the formula (II-1), the formula (II-2), the formula (II-26) to the formula (II-30) (b-2) In the case of the liquid crystal alignment film (Examples 3, 6, 9, and 12) formed, the ultraviolet ray reliability was particularly excellent.

As described above, the polymer in the liquid crystal alignment agent of the present invention is formed of a tetracarboxylic dianhydride component containing a tetracarboxylic dianhydride compound having a specific structure and a diamine component containing a diamine compound having a specific structure. Therefore, when the liquid crystal alignment agent is applied to a liquid crystal alignment film, the liquid crystal alignment film has high ultraviolet reliability and is therefore suitable for use in a liquid crystal display element.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and any one of ordinary skill in the art can make some changes and refinements without departing from the spirit and scope of the present invention. The scope of the invention is defined by the scope of the appended claims.

100‧‧‧Liquid display components

110‧‧‧ first unit

112‧‧‧First substrate

114‧‧‧First conductive film

116‧‧‧First liquid crystal alignment film

120‧‧‧Second unit

122‧‧‧second substrate

124‧‧‧Second conductive film

126‧‧‧Second liquid crystal alignment film

130‧‧‧Liquid Crystal Unit

Claims (5)

A liquid crystal alignment agent comprising: a polymer (A); and a solvent (B), wherein the polymer (A) is obtained by reacting a mixture comprising a tetracarboxylic dianhydride component (a) and a diamine component (b), the tetracarboxylic dianhydride component (a) comprising a tetracarboxylic dianhydride compound (a-1) represented by the formula (1), wherein the tetracarboxylic dianhydride is based The total mole number of component (a) is 100 moles, and the tetracarboxylic dianhydride compound (a-1) is used in an amount of 5 moles to 30 moles. In the formula (1), P ¹ , P ² , P ³ and P ⁴ each independently represent a single bond or a methylene group; j represents an integer of 1 to 3, and the diamine component (b) includes the formula (2) The diamine compound (b-1), In the formula (2), Y ¹ represents an alkylene group having a carbon number of 1 to 12; and Y ² represents a group having an anthracene skeleton or a group represented by the formula (2-1). In the formula (2-1), R ¹ each independently represents a fluorine atom or a methyl group; and R ² represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, and carbon. Alkoxy groups of 1 to 12, -OCH ₂ F, -OCHF ₂ or -OCF ₃ ; Z ¹ , Z ² and Z ³ each independently represent a single bond, an alkylene group having 1 to 3 carbon atoms, -O -, or Z ^{4 is} independent of each other or , R ^a and R ^b each independently represent a fluorine atom or a methyl group, h and i each independently represent 0, 1 or 2; a represents 0, 1 or 2; b, c and d each independently represent an integer of 0 to 4; , f and g each independently represent an integer of 0 to 3, and e+f+g≧1. The liquid crystal alignment agent according to claim 1, wherein the total amount of moles based on the diamine component (b) is 100 moles, and the amount of the diamine compound (b-1) is 3 moles to 20 moles. The liquid crystal alignment agent according to claim 1, wherein the polymer (A) has a ruthenium azide ratio of 30% to 90%. A liquid crystal alignment film which is formed by the liquid crystal alignment agent according to any one of claims 1 to 3. A liquid crystal display element comprising the liquid crystal alignment film according to item 4 of the patent application.