JP7164325B2 - Manufacturing method of liquid crystal alignment film and liquid crystal display element - Google Patents

Description

The present invention relates to a method for manufacturing a liquid crystal alignment film and a liquid crystal display device, and more particularly to a method for manufacturing a liquid crystal alignment film provided on a substrate of a thin film transistor including an active layer of indium gallium zinc oxide (IGZO), and a liquid crystal display device. It relates to a liquid crystal display element.

In recent years, new liquid crystal display devices have been actively developed. A liquid crystal display element that controls liquid crystal molecules by driving is developed. The liquid crystal display device is generally called an in-plane switching (IPS) type, and is known to be excellent in wide viewing angle characteristics. However, the IPS-type liquid crystal display element still has the problem of an afterimage due to the excessively high ion density.

Japanese Patent Publication No. 2006-259716

Japanese Patent Publication No. 2006-259716 discloses a low ion density liquid crystal alignment film and a diamine compound containing a piperazine structure used for the preparation of the liquid crystal alignment film. By using a piperazine structure-containing diamine compound, the problem that the produced alignment film has too high an ion density is improved. However, when the liquid crystal alignment film produced from the above liquid crystal alignment agent is applied to an IPS-type liquid crystal display device, the residual charge is too high due to the slow removal of the accumulated charge, resulting in a problem of causing an afterimage. After all there is. As can be seen from the above, a liquid crystal alignment film capable of forming a liquid crystal display element having good accumulated charge removal property, and a liquid crystal alignment for forming the liquid crystal alignment film, so as to meet the demands of current IPS type liquid crystal display manufacturers. Providing agents is a striving goal of those skilled in the art.

Therefore, one aspect of the present invention is to apply a liquid crystal aligning agent having a specific composition obtained by a specific manufacturing method to a thin film transistor substrate including an active layer of Indium Gallium Zinc Oxide (IGZO). It is therefore an object of the present invention to provide a method for manufacturing a liquid crystal alignment film that forms a liquid crystal alignment film. In particular, a feature of the present invention is that the liquid crystal alignment film has a specific resistive photostability so as to produce a liquid crystal display device with good accumulated charge removal properties.

Another aspect of the present invention is to provide a liquid crystal display element including a liquid crystal alignment film manufactured by the above method for manufacturing a liquid crystal alignment film.

See FIG. FIG. 1 is a schematic diagram of a test cell 100 according to one embodiment of the invention. The resistance light stability of the present invention is measured by the following survey method. (1) First, the inspection cell 100 is assembled. The inspection cell 100 is composed of a substrate 110 , a pixel electrode 120 and the liquid crystal alignment layer 130 . A pixel electrode 120 is formed on the surface of the substrate 110 in a comb-like pattern. A liquid crystal alignment layer 130 is formed on the surface of the pixel electrode 120 . (2) Then, using an ion density measurement system (manufactured by TOYO Corporation; standard 6254 type), the frequency is 0.01 Hz, the voltage is 10 V amplitude, and the current flowing through the inspection cell 100 and the corresponding The voltage applied measures the first resistance R _i of the test cell 100 . The current is 3.16 nA and the survey is performed in an atmosphere with a temperature of 23° C. and a humidity of 50%. (3) After that, the test cell 100 is illuminated for 300 seconds by a backlight cell with an illuminance of 6 mW/cm ² to measure the second resistance _Rf . The backlight cell is a white light emitting diode with a chip emitting layer and a photoluminescent phosphor, the main peak value of the emission spectrum of which is in the range of 430 nm to 500 nm. The constituent material of the chip light-emitting layer is selected from nitride compound semiconductors, III-V group compound semiconductors, II-IV group compound semiconductors, IV-VI group compound semiconductors, or combinations thereof. (4) Also, the resistance photostability (ΔR ^UV ) is calculated based on the following formula (1).
ΔR ^UV =R _i -R _f formula (1).

The resistance light stability (ΔR ^UV ) of the liquid crystal alignment film is less than 500 GΩ, preferably less than 400 GΩ, more preferably less than 300 GΩ.

If the resistive photostability of the liquid crystal alignment film does not fall within the above range, the liquid crystal display device produced has poor accumulated charge removal properties.

According to the above aspect of the present invention, the step of applying a liquid crystal aligning agent to a substrate of a thin film transistor to form a pre-coating layer, and performing pre-baking treatment, post-baking treatment and alignment treatment on the pre-coating layer to form a liquid crystal alignment film and a method for manufacturing a liquid crystal alignment film. The substrate of the thin film transistor includes an active layer whose material is IGZO, and the liquid crystal alignment film has a resistance photostability of less than 500 GΩ. Hereinafter, the manufacturing method of the liquid crystal aligning agent and liquid crystal aligning film which were described is each demonstrated.

Liquid crystal aligning agent The liquid crystal aligning agent of this invention contains a polymer (A) and a solvent (B). They will be described separately below.

Polymer (A)
The polymer (A) of the present invention is obtained by reacting a mixture containing the tetracarboxylic dianhydride composition (a) and the diamine composition (b).

Preferred specific examples of the polymer (A) include polyamic acid polymers, polyimide polymers, polyimide-based block copolymers, and combinations thereof. Suitable specific examples of polyimide-based block copolymers include polyamic acid block copolymers, polyimide block copolymers, polyamic acid-polyimide block copolymers, or combinations of one thereof.

Tetracarboxylic dianhydride composition (a)
Suitable specific examples of the tetracarboxylic dianhydride composition (a) according to the present invention include (1) an aliphatic tetracarboxylic dianhydride compound, (2) an alicyclic tetracarboxylic dianhydride compound, (3) aromatic tetracarboxylic dianhydride compounds or (4) tetracarboxylic dianhydride compounds having formulas (a-1) to (a-6).

The (1) aliphatic tetracarboxylic dianhydride compound according to the present invention may include an aliphatic tetracarboxylic dianhydride compound such as ethanetetracarboxylic dianhydride or butanetetracarboxylic dianhydride, but not limited to.

The (2) alicyclic tetracarboxylic dianhydride compound related to the present invention is 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-cyclobutanetetracarboxylic dianhydride , 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4 ,5-cyclohexanetetracarboxylic dianhydride, 3,3′,4,4′-dicyclohexyltetracarboxylic dianhydride, cis-3,7-dibutyl-cycloheptyl-1,5-diene-1,2, 5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride or bicyclo[2.2.2]-oct-7-ene-2,3,5,6-tetracarboxylic Including, but not limited to, alicyclic tetracarboxylic dianhydride compounds such as dianhydrides.

Specific examples of (3) the aromatic tetracarboxylic dianhydride compound according to the present invention include 3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride and pyromellitic acid. dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'- Diphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3'-4,4' -diphenylethanetetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3',4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 2,3,3′,4′-diphenyl ether tetracarboxylic dianhydride, 3,3′,4,4′-diphenyl ether tetracarboxylic dianhydride 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfide dianhydride, 2,3,3',4'-diphenylsulfide tetracarboxylic acid dianhydride, 3,3',4,4 '-diphenylsulfidetetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane di anhydride, 3,3′,4,4′-perfluoroisopropylidene diphthalic dianhydride, 2,2′,3,3′-diphenyltetracarboxylic dianhydride, 2,3,3′,4 '-diphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid ) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4′-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4′ -diphenylmethane dianhydride, ethylene glycol-bis (trimellitic anhydride), propylene glycol-bis (trimellitic anhydride), 1,4-butanediol-bis (trimellitic anhydride), 1,6-hexanediol- Bis(trimellitic anhydride), 1,8-octanediol-bis(trimellitic anhydride), 2,2- Bis(4-hydroxyphenyl)propane-bis(trimellitic anhydride), 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-( Tetrahydro-2,5-dioxo-3-furan)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-methyl-5- (Tetrahydro-2,5-dioxo-3-furan)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-ethyl-5 -(Tetrahydro-2,5-dioxo-3-furan)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-methyl- 5-(Tetrahydro-2,5-dioxo-3-furan)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-ethyl -5-(tetrahydro-2,5-dioxo-3-furan)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8- Methyl-5-(tetrahydro-2,5-dioxo-3-furan)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8 -ethyl-5-(tetrahydro-2,5-dioxo-3-furan)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro- 5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furan)-naphtho[1,2-c]-furan-1,3-dione, 5-(2,5-dioxotetrahydrofuran) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride and the like, but not limited thereto.

(4) The tetracarboxylic dianhydride compounds represented by formulas (a-1) to (a-6) according to the present invention are described in detail below.

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

式（ａ－６）において、Ａ_４は芳香環含有の２価基を表し、Ａ_５及びＡ_６は同一又は異なってもよく、且つそれぞれ水素原子又はアルキル基を表す。好ましくは、式（ａ－６）に示すテトラカルボン酸二無水物化合物は、下記式（ａ－６－１）に示す化合物から選ばれてよい。

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

The above tetracarboxylic dianhydride composition (a) may be used alone or in combination of multiple types.

The amount of the tetracarboxylic dianhydride composition (a) used is in the range of 20 mol to 200 mol with respect to 100 mol of the diamine composition (b). It is preferably 30 mol to 120 mol.

Diamine composition (b)
In one embodiment, the diamine composition (b) of the present invention contains at least a diamine compound (b1) represented by formula (b-1). In another embodiment, the diamine composition (b) of the present invention comprises the diamine compound (b1) and the diamine compound (b2) represented by formula (b-2). In the above examples, the diamine composition (b) of the present invention may further contain another diamine compound (b3).

式（ｂ－１）において、ｈは１～１２の整数を表す。 Diamine compound (b1)
The diamine compound (b1) represented by the above formula (b-1) is represented as follows.

In formula (b-1), h represents an integer of 1-12.

式（ｂ－１－１）～式（ｂ－１－３）において、ｈは１～１２の整数を表す。 Specifically, the diamine compound (b1) represented by the formula (b-1) includes diamine compounds having structures represented by the following formulas (b-1-1) to (b-1-3).

In formulas (b-1-1) to (b-1-3), h represents an integer of 1-12.

Specific examples of the diamine compound having the structure represented by the formula (b-1-1) include bis(4-aminophenoxy)methane, 1,2-bis(4-aminophenoxy)ethane, 1,3-bis( 4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,7- Bis(4-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)nonane, 1,10-bis(4-aminophenoxy)decane or the above compounds may be any combination of

Specific examples of the diamine compound having the structure represented by the formula (b-1-2) include bis(2-aminophenoxy)methane, 1,2-bis(2-aminophenoxy)ethane, 1,3-bis( 2-aminophenoxy)propane, 1,4-bis(2-aminophenoxy)butane, 1,5-bis(2-aminophenoxy)pentane, 1,6-bis(2-aminophenoxy)hexane, 1,7- Bis(2-aminophenoxy)heptane, 1,8-bis(2-aminophenoxy)octane, 1,9-bis(2-aminophenoxy)nonane, 1,10-bis(2-aminophenoxy)decane or the above compounds may be any combination of

Specific examples of the diamine compound having the structure represented by the formula (b-1-3) include bis(3-aminophenoxy)methane, 1,2-bis(3-aminophenoxy)ethane, 1,3-bis( 3-aminophenoxy)propane, 1,4-bis(3-aminophenoxy)butane, 1,5-bis(3-aminophenoxy)pentane, 1,6-bis(3-aminophenoxy)hexane, 1,7- Bis(3-aminophenoxy)heptane, 1,8-bis(3-aminophenoxy)octane, 1,9-bis(3-aminophenoxy)nonane, 1,10-bis(3-aminophenoxy)decane or the above compounds may be any combination of

Preferably, specific examples of the diamine compound (b1) represented by formula (b-1) include 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1, 5-bis(4-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,3-bis(2-aminophenoxy)propane, 1,4-bis(2-aminophenoxy)butane, 1,5-bis(2-aminophenoxy)pentane, 1,6-bis(2-aminophenoxy) Hexane, 1,7-bis(2-aminophenoxy)heptane, 1,8-bis(2-aminophenoxy)octane, 1,3-bis(3-aminophenoxy)propane, 1,4-bis(3-amino phenoxy)butane, 1,5-bis(3-aminophenoxy)pentane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(3-aminophenoxy)heptane or 1,8-bis(3 -aminophenoxy)octane and the like.

The amount of the diamine compound (b1) used is 15 mol to 95 mol, preferably 20 to 93 mol, more preferably 25 mol to 90 mol, per 100 mol of the total amount of the diamine composition (b) used.

When the diamine composition (b) does not contain the diamine compound (b1) represented by the formula (b-1), the liquid crystal display element including the liquid crystal alignment film produced by the liquid crystal alignment agent has poor accumulated charge removal properties. .

式（ｂ－２）において、Ｒ_１はそれぞれ独立に水素原子、炭素数１～１０のアルキル基、炭素数１～１０のアルコキシ基、アセチルアミノ基、フッ素原子、塩素原子又は臭素原子を表し、Ｒ_２はそれぞれ独立に炭素数１～３のアルキル基を表し、ｍはそれぞれ独立に０～３の整数を表し、ｎは０～４の整数を表す。 Diamine compound (b2)
The diamine compound (b2) represented by the above formula (b-2) is represented as follows.

In formula (b-2), each R ₁ independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an acetylamino group, a fluorine atom, a chlorine atom or a bromine atom; Each R ₂ independently represents an alkyl group having 1 to 3 carbon atoms, each m independently represents an integer of 0 to 3, and n represents an integer of 0 to 4.

In formula (b-2), each R ₁ preferably independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an acetylamino group.

Specific examples of the diamine compound (b2) represented by formula (b-2) include, but are limited to, at least one of the diamine compounds represented by formulas (b-2-1) to (b-2-28). not.

The diamine compound (b2) represented by formula (b-2) may be used either singly or in combination.

The diamine compound (b2) is used in an amount of 5 mol to 50 mol, preferably 7 mol to 45 mol, more preferably 10 mol to 40 mol, per 100 mol of the total amount of the diamine composition (b) used.

When the diamine compound (b2) is used as the liquid crystal aligning agent, it is possible to further improve the accumulated charge removal property of the formed liquid crystal display element.

Next, the molar ratio [(b1)/(b2)] between the diamine compound (b1) and the diamine compound (b2) may be from 0.5 to 10.0, preferably from 1.0 to 8.0. 0, and more preferably 1.5 to 5.0. When the molar ratio [(b1)/(b2)] between the diamine compound (b1) and the diamine compound (b2) is within the above range, the liquid crystal display device formed can further improve the ability to remove accumulated charges. .

Other diamine compounds (b3)
Other diamine compounds (b3) of the present invention include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1, 7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 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-methylnonane, 2,11-diaminododecane, 1,12-diaminooctadecane, 1,2-bis(3-aminopropoxy)ethane, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3 , 3′-dimethyldicyclohexylamine, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienediamine, tricyclo(6.2.1.02,7)-undecylenedimethyldiamine, 4, 4'-methylenebis(cyclohexylamine), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminobenzanilide, 4,4'-diamino Diphenyl ether, 3,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane, 6-amino-1-(4'- aminophenyl)-1,3,3-trimethylindane, hexahydro-4,7-methanoindanylene dimethylenediamine, 3,3′-diaminobenzophenone, 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)hexa fluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)cyclohexane, 1,5-bis(4-aminophenoxymethylene)adamantane, 1, 4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy) oxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 9,10-bis(4-aminophenyl)anthracene [9,10 -bis(4-aminophenyl)anthracene], 2,7-diaminofluorene, 9,9-bis(4-aminophenyl)fluorene, 4,4'-methylene-bis(2-chloroaniline), 4,4'- (p-phenyleneisopropylidene)bisaniline, 4,4′-(m-phenyleneisopropylidene)bisaniline, 2,2′-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4′-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl, 5-[4-(4-n-pentylcyclohexyl)cyclohexyl]phenylmethylene-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-aminophenyl)phenyl]-4-(4-ethylphenyl)cyclohexane} or other diamines represented by the following formulas (b-3-1) to (b-3-29) It may include, but is not limited to, compounds.

式（ｂ－３－１）において、Ｘ_６は

を表し、且つＸ_７はステロイド含有基、トリフルオロメチル、フッ素基、炭素数２～３０のアルキル基又はピリジン、ピリミジン、トリアジン、ピペリジン及びピペラジン等から誘導された窒素原子環状構造を含む１価基を表す。

In formula (b-3-1), X ₆ is

and X ₇ is a steroid-containing group, trifluoromethyl, a fluorine group, an alkyl group having 2 to 30 carbon atoms, or a monovalent group containing a nitrogen atom cyclic structure derived from pyridine, pyrimidine, triazine, piperidine, piperazine, etc. represents

Other diamine compounds represented by the above formula (b-3-1) are preferably 2,4-diaminophenyl ethyl formate, 3,5-diaminophenyl ethyl formate (3 ,5-diaminophenyl ethyl formate), 2,4-diaminophenyl propyl formate, 3,5-diaminophenyl propyl formate, 1-dodecoxy- 2,4-diaminobenzene (1-dodecoxy-2,4-diamino-benzene), 1-hexadecoxy-2,4-diaminobenzene (1-hexadecoxy-2,4-diaminobenzene), 1-octadecoxoxy-2,4- It may be diaminobenzene (1-octadecoxy-2,4-diaminobenzene) or other diamine compounds represented by the following formulas (b-3-1-1) to (b-3-1-6).

式（ｂ－３－２）において、Ｘ_８は

を表し、Ｘ_９及びＸ_１０は２価の脂肪族環、２価の芳香環又は２価の複素環基を表し、且つＸ_１１は炭素数３～１８のアルキル基、炭素数３～１８のアルコキシ基、炭素数１～５のフルオロアルキル基、炭素数１～５のフルオロアルコキシ基、シアノ基又はハロゲン原子を表す。

In formula (b-3-2), X ₈ is

, X ₉ and X ₁₀ each represent a divalent aliphatic ring, a divalent aromatic ring or a divalent heterocyclic group, and X ₁₁ is a C 3-18 alkyl group, a C 3-18 represents an alkoxy group, a fluoroalkyl group having 1 to 5 carbon atoms, a fluoroalkoxy group having 1 to 5 carbon atoms, a cyano group or a halogen atom;

式（ｂ－３－２－１０）～式（ｂ－３－２－１３）において、ｓは、３～１２の整数を表してよい。 Other diamine compounds represented by the above formula (b-3-2) may preferably be diamine compounds represented by the following formulas (b-3-2-1) to (b-3-2-13).

In formulas (b-3-2-10) to (b-3-2-13), s may represent an integer of 3-12.

式（ｂ－３－３）において、Ｘ_１２は水素原子、炭素数１～５のアシル基、炭素数１～５のアルキル基、炭素数１～５のアルコキシ基又はハロゲンを表す。Ｘ_１３は１～３の整数である。Ｘ_１３が１より大きくなると、複数のＸ_１２は同一又は異なってもよい。

In formula (b-3-3), X ₁₂ represents a hydrogen atom, an acyl 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 halogen. X ₁₃ is an integer of 1-3. When X ₁₃ is greater than 1, multiple X ₁₂ may be the same or different.

The diamine compound represented by the above formula (b-3-3) is: (1) X ₁₃ is 1: p-diaminobenzene, m-diaminobenzene, o-diaminobenzene or 2,5-diaminotoluene, etc., (2) X ₁₃ is 2: 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 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, etc. , (3) X ₁₃ is preferably selected from 3:1,4-bis(4′-aminophenyl)benzene and the like, p-diaminobenzene, 2,5-diaminotoluene, 4,4′-diaminobiphenyl, It is more preferably selected from 3,3'-dimethoxy-4,4'-diaminobiphenyl or 1,4-bis(4'-aminophenyl)benzene.

式（ｂ－３－４）において、Ｘ_１４は１～５の整数を表す。前記式（ｂ－３－４）は、好ましくは４，４’－ジアミノジフェニルスルフィドから選ばれる。

In formula (b-3-4), X ₁₄ represents an integer of 1-5. The formula (b-3-4) is preferably selected from 4,4'-diaminodiphenyl sulfide.

式（ｂ－３－５）において、Ｘ_１５及びＸ_１７は同一又は異なってもよく、且つそれぞれ２価の有機基を表し、Ｘ_１６はピリジン、ピリミジン、トリアジン、ピペリジン及びピペラジン等から誘導された窒素原子環状構造を含む２価基を表す。

In formula (b-3-5), X ₁₅ and X ₁₇ may be the same or different and each represents a divalent organic group, X ₁₆ is derived from pyridine, pyrimidine, triazine, piperidine, piperazine, etc. Represents a divalent group containing a nitrogen atom ring structure.

式（ｂ－３－６）において、Ｘ_１８、Ｘ_１９、Ｘ_２０及びＸ_２１はそれぞれ同一又は異なってもよく、且つ炭素数１～１２のアルキル基を表してよい。Ｘ_２２は１～３の整数を表し、且つＸ_２３は１～２０の整数を表す。

In formula (b-3-6), X ₁₈ , X ₁₉ , X ₂₀ and X ₂₁ may be the same or different and may represent an alkyl group having 1 to 12 carbon atoms. X ₂₂ represents an integer of 1-3 and X ₂₃ represents an integer of 1-20.

式（ｂ－３－７）において、Ｘ_２４は

又はシクロへキシレン基を表し、Ｘ_２５は

を表し、Ｘ_２６はフェニレン基又はシクロへキシレン基を表し、且つＸ_２７は水素原子又はヘプチル基を表す。

In formula (b-3-7), X ₂₄ is

or represents a cyclohexylene group, and X ₂₅ is

, X ₂₆ represents a phenylene group or a cyclohexylene group, and X ₂₇ represents a hydrogen atom or a heptyl group.

The diamine compound represented by the above formula (b-3-7) is preferably selected from diamine compounds represented by the following formulas (b-3-7-1) and (b-3-7-2).

式（ｂ－３－１６）～式（ｂ－３－１９）において、Ｘ_２８は、炭素数１～１０のアルキル基又は炭素数１～１０のアルコキシ基が好ましい。式（ｂ－３－２０）～式（ｂ－３－２４）において、Ｘ_２９は、水素原子、炭素数１～１０のアルキル基又は炭素数１～１０のアルコキシ基が好ましい。 Other diamine compounds represented by formulas (b-3-8) to (b-3-29) are as follows.

In formulas (b-3-16) to (b-3-19), X ₂₈ is preferably an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. In formulas (b-3-20) to (b-3-24), X ₂₉ is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

The diamine composition (b3) is preferably 1,2-diaminoethane, 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, 2,4-diamino Phenyl ethyl formate, p-diaminobenzene, m-diaminobenzene, o-diaminobenzene, formula (b-3-1-1), formula (b-3-1-2), formula (b-3-1- 5), formula (b-3-2-1), formula (b-3-2-11), formula (b-3-7-1), formula (b-3-25) or formula (b-3 -28), including but not limited to.

The diamine composition (b3) may be used singly or in combination of multiple types.

The amount of the other diamine compound (b3) used is 0 to 80 mol, preferably 0 to 73 mol, more preferably 0 to 65 mol, per 100 mol of the total amount of the diamine composition (b) used.

Method of Making Polymer (A) The preparation of polyamic acid polymers according to the invention may be conventional methods. Preferably, the method of preparing the polyamic acid polymer comprises the following steps. A mixture containing the tetracarboxylic dianhydride composition (a) and the diamine composition (b) is dissolved in a solvent and subjected to a polycondensation reaction at a temperature of 0° C. to 100° C. for 1 hour to 24 hours. , the above reaction solution is distilled under reduced pressure using an evaporator to obtain a polyamic acid polymer. Alternatively, the above reaction solution is put into a large amount of a poor solvent to obtain a precipitate, and the precipitate is dried by drying under reduced pressure to obtain a polyamic acid polymer.

The solvent used in the polycondensation reaction may be the same as or different from the solvent in the liquid crystal aligning agent described below, and is not particularly limited as long as it dissolves the reactants and products. Preferably, the solvent is (1) for example N-methyl-2-pyrrolidinone (NMP), N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone (2) phenolic solvents such as, but not limited to, m-cresol, xylenol, phenol or halogenated phenols. The amount of the solvent used in the polycondensation reaction is preferably 200 to 2000 parts by weight, more preferably 300 to 1800 parts by weight, per 100 parts by weight of the mixture.

In particular, in the polycondensation reaction, an appropriate amount of poor solvent that does not precipitate the polyamic acid polymer may be used in combination with the solvent. Poor solvents may be used singly or in combination, and (1) for example, methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol or alcohols such as triethylene glycol; (2) ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone; (3) such as methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate or esters such as ethylene glycol monoethyl ether acetate; (4) for example, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol normal propyl ether, ethylene glycol isopropyl ether, ethylene glycol normal butyl ether, ethylene glycol dimethyl ether or Ethers such as diethylene glycol dimethyl ether; (5) Halogenated hydrocarbons such as, for example, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene or o-dichlorobenzene; (6) For example, tetrahydrofuran, Including, but not limited to, hydrocarbons such as hexane, heptane, octane, benzene, toluene or xylene or any combination of the above solvents. The amount of the poor solvent is preferably 0 to 60 parts by weight, more preferably 0 to 50 parts by weight, per 100 parts by weight of the diamine composition (b).

Preparation of polyimide polymers according to the present invention may be conventional. Preferably, the polyimide polymer is prepared by dissolving a mixture containing the tetracarboxylic dianhydride composition (a) and the diamine composition (b) in a solution and conducting a polymerization reaction to form the polyamic acid polymer. Then, in the presence of a dehydrating agent and a catalyst, the amic acid functional group in the polyamic acid polymer is further heated to become an imide functional group (i.e., imidization) by a dehydration ring-closure reaction to perform a dehydration ring-closure reaction, and the polyimide polymer get

The solvent used for the dehydration ring-closure reaction may be the same as the solvent in the liquid crystal aligning agent described below, and will not be described in detail here. The amount of the solvent used in the dehydration ring closure reaction is preferably 200 to 2000 parts by weight, more preferably 300 to 1800 parts by weight, per 100 parts by weight of the polyamic acid polymer.

The operating temperature of the dehydration ring closure reaction is preferably between 40°C and 200°C, more preferably between 40°C and 150°C, so as to obtain a suitable degree of imidization of the polyamic acid polymer. When the operating temperature of the dehydration ring-closing reaction is lower than 40°C, the imidization reaction is incomplete and the degree of imidization of the polyamic acid polymer decreases. However, when the operating temperature of the dehydration ring closure reaction is higher than 200°C, the weight average molecular weight of the obtained polyimide polymer is rather 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 and trifluoroacetic anhydride. The dehydrating agent is used in an amount of 0.01 to 20 mol per 1 mol of the polyamic acid polymer. The catalyst used for the dehydration ring-closure reaction may be selected from (1) pyridine compounds such as pyridine, trimethylpyridine and dimethylpyridine; (2) tertiary amine compounds such as triethylamine. The amount of the catalyst used is 0.5 mol to 10 mol per 1 mol of the dehydrating agent.

Preferred specific examples of polyimide-based block copolymers according to the present invention include polyamic acid block copolymers, polyimide block copolymers, polyamic acid-polyimide block copolymers, or any combination thereof.

Preparation of the polyimide-based block copolymer according to the present invention may be a conventional method. Preferably, as a method for preparing a polyimide-based block copolymer, a tetracarboxylic dianhydride composition (a) and a diamine composition containing at least one polyamic acid polymer and/or at least one polyimide polymer described above The initiator, which may further contain (b), is dissolved in a solvent to carry out a polycondensation reaction.

The tetracarboxylic dianhydride composition (a) and the diamine composition (b) in the initiator are the tetracarboxylic dianhydride composition (a) and the diamine composition (b) used in the prepared polyamic acid polymer. The same solvent used in the polycondensation reaction may be the same as the solvent in the liquid crystal aligning agent described below, so detailed description is omitted here.

The amount of the solvent used in the polycondensation reaction is preferably 200 to 2000 parts by weight, more preferably 300 to 1800 parts by weight, per 100 parts by weight of the initiator. The operating temperature of the polycondensation reaction is preferably 0°C to 200°C, more preferably 0°C to 100°C.

Preferably, the initiators are: (1) two polyamic acid polymers with different end groups and different structures; (2) two polyimide polymers with different end groups and different structures; (3) different end groups and (4) polyamic acid polymer, tetracarboxylic dianhydride compound and diamine compound, provided that at least one of the tetracarboxylic dianhydride compound and the diamine compound forms the polyamic acid polymer; (5) a polyimide polymer, a tetracarboxylic dianhydride compound and a diamine compound, provided that the tetracarboxylic dianhydride (6) polyamic acid polymer, polyimide polymer, tetra A carboxylic dianhydride compound and a diamine compound, provided that at least one of the tetracarboxylic dianhydride compound and the diamine is a tetracarboxylic dianhydride composition (a) and a diamine composition for forming a polyamic acid polymer or a polyimide polymer (7) two types of polyamic acid polymers, tetracarboxylic dianhydride compounds and diamine compounds with different structures; (8) two types of polyimide polymers with different structures, tetracarboxylic dianhydrides (9) Two types of polyamic acid polymers and diamine compounds having anhydride terminal groups and different structures; (10) Two types of polyamic acid polymers having amino terminal groups and different structures and a tetracarboxylic dianhydride compound; (11) two types of polyimide polymers and diamine compounds whose terminal groups are anhydride groups and have different structures; (12) two types of polyimides whose terminal groups are amino and have different structures Including, but not limited to, polymers and tetracarboxylic dianhydride compounds.

Preferably, the polyamic acid polymer, the polyimide polymer, and the polyimide-based block copolymer are end-modified polymers whose molecular weights are adjusted, as long as they do not affect the effects of the present invention. By using a terminal-modified polymer, the applicability of the liquid crystal aligning agent can be improved. As a method for preparing the terminal-modified polymer, a polyamic acid polymer polycondensation reaction may be performed and a monofunctional compound may be added. Monofunctional compounds include (1) for example maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride or n-hexa (2) for example, aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine or monoamine compounds such as n-eicosylamine; (3) monoisocyanate compounds such as phenyl isocyanate or naphthyl isocyanate, including but not limited to.

The polystyrene equivalent weight average molecular weight measured by gel infiltration chromatography of the polymer (A) of the present invention is 10,000 to 90,000, preferably 12,000 to 75,000, more preferably 15 ,000 to 60,000.

Polymer (A) of the present invention comprises at least one of polyamic acid polymers, polyimide polymers or polyimide-based block copolymers prepared as described below. Specific examples of the method include adding a lot of the tetracarboxylic dianhydride composition during the polycondensation reaction, adding a lot of the diamine composition during the polycondensation reaction, and adding a lot of the diamine composition during the polycondensation reaction. Including lot addition of solvent or control by varying the temperature during the polycondensation reaction.

When the polymer (A) does not contain the polyamic acid polymer, polyimide polymer or polyimide-based block copolymer prepared as described above, the resistance photostability of the prepared liquid crystal alignment film is poor.

Solvent (B)
The solvent used for the liquid crystal aligning agent of the present invention is not particularly limited as long as it can dissolve the polymer (A) and any other components without reacting, and is preferably the same as the solvent used for the synthetic polyamic acid. At the same time, it may be used in combination with the poor solvent used when synthesizing the polyamic acid.

Specific examples of the solvent (B) include N-methyl-2-pyrrolidinone (NMP), γ-butyrolactone, γ-butyrolactam, 4-hydroxy-4-methyl-2-pentanone, ethylene Glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol normal propyl ether, ethylene glycol isopropyl ether, ethylene glycol normal butyl ether (ethylene glycol n- butyl ether), ethylene glycol dimethyl ether, ethylene glycol monoethyl 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-dimethylformamide or N , N-dimethylacetamide, and the like. A solvent (B) may be used individually or may be used in combination of multiple types.

The amount of the solvent (B) used is 800 to 4000 parts by weight, preferably 900 to 3500 parts by weight, and more preferably 1000 to 3000 parts by weight with respect to 100 parts by weight of the polymer (A). be.

Additive (C)
An additive (C) such as an epoxy compound or a functional group-containing silane compound may be selectively added to the liquid crystal aligning agent as long as it does not affect the effects of the present invention. The additive (C) is for improving the adhesion between the liquid crystal alignment film and the surface of the substrate. The additive (C) may be used alone or in combination of multiple types.

The above epoxy compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol. diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetra glycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N-glycidyl -p-epoxypropoxyaniline, 3-(N-allyl-N-glycidyl)aminopropyltrimethoxysilane, 3-(N,N-diglycidyl)aminopropyltrimethoxysilane, and the like.

The amount of the epoxy compound used is generally 40 parts by weight or less, preferably 0.1 to 30 parts by weight, per 100 parts by weight of the polymer (A).

The functional group-containing silane compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl) -3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxy Carbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1 ,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate , N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N -bis(oxyethylene)-3-aminopropyltrimethoxysilane, N-bis(oxyethylene)-3-aminopropyltriethoxysilane, but are not limited to.

The amount of the silane compound used is generally 10 parts by weight or less, preferably 0.5 to 10 parts by weight, per 100 parts by weight of the polymer (A).

Method for Preparing Liquid Crystal Aligning Agent The method for preparing the liquid crystal aligning agent of the present invention is not particularly limited as long as a general mixing method is employed. For example, first, the tetracarboxylic dianhydride composition (a) and the diamine composition (b) are uniformly mixed and reacted to form the polymer (A). Then, the solvent (B) is added to the polymer (A) at a temperature of 0° C. to 200° C., and the additive (C) may be optionally added, and continuously stirred with a stirring device until dissolved. do it. Polymer (A) is added to solvent (B), preferably at a temperature between 20°C and 60°C.

Method for Forming Liquid Crystal Alignment Film The present invention also provides a liquid crystal alignment film produced from the liquid crystal alignment agent.

Preferably, as a method for forming a liquid crystal alignment film, the liquid crystal alignment agent is applied to a substrate provided with pixel electrodes by a method such as a roll coating method, a spin coating method, a printing method, an ink-jet method, or the like. to form a pre-coating layer, and then the pre-coating layer is manufactured by pre-bake treatment, post-bake treatment and alignment treatment. The film thickness of the film formed as described above is preferably 0.001 μm to 1 μm, more preferably 0.005 μm to 0.5 μm.

The substrate referred to herein of the present invention includes at least one thin film transistor substrate. , the thin film transistor substrate includes a first substrate (which may have the same material as the substrate 110 shown in FIG. 1), a plurality of thin film transistor cells and an insulating layer. A thin film transistor cell is provided on the first substrate and includes a gate insulating layer, an active layer, a source and a drain, respectively. And the material of the active layer is Indium Gallium Zinc Oxide (IGZO). Also, the insulating layer has a plurality of contact holes provided in the thin film transistor cells and exposing the drains of the thin film transistor cells respectively. A pixel electrode is provided on the insulating layer and extends to the contact hole so as to be electrically connected to the drain. The alignment film covers the pixel electrodes.

The pre-baking process is for volatilizing the organic solvent in the pre-coating layer. Preferably, the operating temperature of the pre-baking treatment is in the range of 30°C to 120°C, more preferably 40°C to 110°C, even more preferably 50°C to 100°C.

The orientation treatment described above is not particularly limited, and may be oriented by winding a cloth made of fibers such as nylon, rayon, cotton, etc. around a roll and rubbing it in a given direction. The alignment treatment is well known to those skilled in the art, and will not be described in detail.

The post-baking process is for further dehydration ring closure (imidization) reaction to the polymer in the pre-coating layer. Preferably, the post-baking operating temperature is in the range of 150°C to 300°C, preferably 180°C to 280°C, more preferably 200°C to 250°C.

If the material of the active layer of the thin film transistor cell does not contain indium gallium zinc oxide (IGZO), the liquid crystal display device produced has poor accumulated charge removal properties.

In one embodiment, prior to forming the liquid crystal alignment film, the manufacturing method of the liquid crystal alignment film of the present invention is applied to the liquid crystal alignment film formed by the liquid crystal alignment agent by the inspection cell 100 shown in FIG. making a survey of A specific inspection method is as described in FIG.

Method for Manufacturing Liquid Crystal Display Device The present invention also provides a liquid crystal display device including the liquid crystal alignment film.

Since the method of manufacturing the liquid crystal display element is well known to those skilled in the art, it will be briefly described below.

Please refer to FIG. A preferred embodiment of the liquid crystal display element 200 of the present invention includes a first cell 210, a second cell 220 and a liquid crystal cell 230. FIG. A second cell 220 and a first cell 210 face each other with a gap therebetween, and a liquid crystal cell 230 is provided between the first cell 210 and the second cell 220 .

The first cell 210 includes a thin film transistor substrate 212 , a pixel electrode 214 and a first liquid crystal alignment layer 216 . A pixel electrode 214 is formed on the surface of the substrate 212 of the thin film transistor so as to be patterned in a comb shape, and a first liquid crystal alignment film 216 is formed on the surface of the pixel electrode 214 . The thin film transistor substrate 212 includes a first substrate, a plurality of thin film transistor cells and an insulating layer.

A second cell 220 includes a second substrate 222 and a second liquid crystal alignment layer 226 . A second liquid crystal alignment film 226 is provided on the surface of the second substrate 222 .

The first substrate and the second substrate 222 are selected from transparent materials or the like. Transparent materials include alkali-free glass, soda lime glass, hard glass (Pyrex glass), quartz glass, polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, and polycarbonate used in liquid crystal display devices. etc., but is not limited thereto. The material of the pixel electrode 114 is selected from transparent electrodes such as tin oxide (SnO ₂ ) and indium oxide-tin oxide (In ₂ O ₃ --SnO ₂ ), or metal electrodes such as chromium.

The first liquid crystal alignment film 216 and the second liquid crystal alignment film 226 are the liquid crystal alignment films described above, respectively, and are for forming a pretilt angle in the liquid crystal cell 230, and the liquid crystal cell 230 is formed by the pixel electrode 214. Driven by a parallel electric field.

The liquid crystals used in the liquid crystal cell 230 may be used singly or in combination. Liquid crystals include diaminobenzene liquid crystals, pyridazine liquid crystals, shiff base liquid crystals, azoxy liquid crystals, phenylcyclohexane liquid crystals, biphenyl liquid crystals, and phenylcyclohexane liquid crystals. liquid crystal, ester liquid crystal, terphenyl, biphenylcyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, cubane Liquid crystals include, but are not limited to, and if necessary, cholesterol-based liquid crystals such as cholesteryl chloride, cholesteryl nonanoate, cholesteryl carbonate, etc., or the trade name " C-15”, “CB-15” (a chiral agent manufactured by Merck Co. Ltd.), or strong agents such as p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate. A ferroelectric liquid crystal may also be added.

A liquid crystal display device manufactured using the liquid crystal aligning agent of the present invention is suitably used for various nematic liquid crystals such as liquid crystal display devices such as TN, STN, TFT, VA, and IPS. Also, depending on the liquid crystal selected, it may be used in different liquid crystal display elements such as ferroelectric or antiferroelectric. In the above liquid crystal display device, it is particularly suitable for use in an IPS type liquid crystal display device.

The following examples illustrate the invention in detail, but are not intended to limit the invention to what is disclosed in those examples.

The following detailed description of the drawings is intended to make these and other objects, features, advantages and embodiments of the present invention more comprehensible.

1 is a schematic diagram showing an inspection cell according to one embodiment of the present invention; FIG. 1 is a structural schematic diagram showing a liquid crystal display element according to one embodiment of the present invention; FIG.

Synthesis Examples of Polymer (A) Hereinafter, Synthesis Examples A-1-1 to A-1-12 of Polymer (A), Synthesis Examples A-2-1 to A-2-6, Comparative Synthesis Example A'-1- 1 to A'-1-4 and Comparative Synthesis Examples A'-2-1 to A'-2-2. Tables 1 and 2 show the usage ratio of each component in the above Synthesis Example and Comparative Synthesis Example.

Synthesis example A-1-1
A four-necked conical flask with a capacity of 500 ml was equipped with a nitrogen gas inlet, a stirrer, a condenser tube and a thermometer, and nitrogen gas was introduced. Then, in a four-necked conical flask, 1.73 g (0.0075 mol) bis(4-aminophenoxy)methane (abbreviated as b1-1), 2.16 g (0.02 mol) p-diaminobenzene (b3-1 and abbreviation), 4.96 g (0.025 mol) 4,4′-diaminodiphenylmethane (abbreviated as b3-2) and 80 g of N-methyl-2-pyrrolidinone (abbreviated as NMP) were added and stirred at room temperature until dissolved. . Then, after adding 9.82 g (0.045 mol) of pyromellitic dianhydride (abbreviated as a-1) and 20 g of NMP and reacting for 2 hours at room temperature, 1.08 g (0.005 mol) of a -1 was added in 3 equal portions every 20 minutes. After completion of the reaction, the reaction solution was put into 1500 ml of water to precipitate the polymer. After that, the polymer obtained was filtered, washed with methanol, and filtered three times, and then 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
A four-necked conical flask with a capacity of 500 ml was equipped with a nitrogen gas inlet, a stirrer, a condenser tube and a thermometer, and nitrogen gas was introduced. Then, in a four-necked conical flask, 3.23 g (0.0125 mol) 1,3-bis(4-aminophenoxy)propane (abbreviated as b1-2), 6.70 g (0.025 mol) formula (b-2) -1) Diamine compound (abbreviated as b2-1), 2.50 g (0.0125 mol) 4,4'-diaminodiphenyl ether (abbreviated as b3-3) and 80 g of NMP were added and stirred at room temperature until dissolved. did. Then, after adding 8.82 g (0.045 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (abbreviated as a-2) and 20 g of NMP and reacting for 2 hours at room temperature, 0.99 g (0.005 mol) of a-2 was added in two equal portions every 20 minutes. After completion of the reaction, the reaction solution was put into 1500 ml of water to precipitate the polymer. Thereafter, the polymer obtained was filtered, washed with methanol, and filtered three times, and then placed in a vacuum oven and dried at a temperature of 60° C. to obtain a polymer (A-1-2).

Synthesis Example A-1-3
A four-necked conical flask with a capacity of 500 ml was equipped with a nitrogen gas inlet, a stirrer, a condenser tube and a thermometer, and nitrogen gas was introduced. Then, in a four-necked conical flask, 3.58 g (0.0125 mol) 1,5-bis(4-aminophenoxy)pentane (abbreviated as b1-3), 5.95 g (0.03 mol) b3-2, 0.50 g (0.0025 mol) of b3-3 and 80 g of NMP were added and stirred at room temperature until dissolved. Then, 11.21 g (0.05 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride (abbreviated as a-3) and 20 g of NMP were added and reacted at room temperature for 2 hours. 99 g (0.005 mol) of b3-2 was added in 3 equal portions every 20 minutes. After completion of the reaction, the reaction solution was put into 1500 ml of water to precipitate the polymer. Thereafter, the polymer obtained was filtered, washed with methanol, and filtered three times, and then placed in a vacuum oven and dried at a temperature of 60° C. to obtain a polymer (A-1-3).

Synthesis Example A-1-4
A four-necked conical flask with a capacity of 500 ml was equipped with a nitrogen gas inlet, a stirrer, a condenser tube and a thermometer, and nitrogen gas was introduced. Then, in a four-necked conical flask, 3.14 g (0.01 mol) of 1,7-bis(3-aminophenoxy)heptane (abbreviated as b1-4), 8.40 g (0.025 mol) of formula (b- The diamine compound (abbreviated as b2-2) shown in 2-4), 1.08 g (0.010 mol) of b3-1 and 80 g of NMP were added and stirred at room temperature until dissolved. Then, add 10.91 g (0.05 mol) of a-1 and 20 g of NMP, react for 2 hours at room temperature, then add 0.54 g (0.005 mol) of b3-1 every 20 minutes, etc. The amount was added in three portions. After completion of the reaction, the reaction solution was put into 1500 ml of water to precipitate the polymer. Thereafter, the polymer obtained was filtered, washed with methanol, and filtered three times, and then placed in a vacuum oven and dried at a temperature of 60° C. to obtain a polymer (A-1-4).

Synthesis Example A-1-5
A four-necked conical flask with a capacity of 500 ml was equipped with a nitrogen gas inlet, a stirrer, a condenser tube and a thermometer, and nitrogen gas was introduced. Then, in a four-necked conical flask, 4.60 g (0.02 mol) bis(2-aminophenoxy)methane (abbreviated as b1-5), 5.94 g (0.03 mol) b3-2 and 60 g NMP Add and stir at room temperature until dissolution. Then, 10.30 g (0.0525 mol) of a-2 and 20 g of NMP were added and reacted at room temperature for 1 hour, then 20 g of NMP was added and reacted at room temperature for 1 hour. After completion of the reaction, the reaction solution was put into 1500 ml of water to precipitate the polymer. Thereafter, the polymer obtained was filtered, washed with methanol, and filtered three times, and then placed in a vacuum oven and dried at a temperature of 60° C. to obtain a polymer (A-1-5).

Synthesis Example A-1-6
A four-necked conical flask with a capacity of 500 ml was equipped with a nitrogen gas inlet, a stirrer, a condenser tube and a thermometer, and nitrogen gas was introduced. Then, in a four-necked conical flask, 6.45 g (0.025 mol) 1,3-bis(2-aminophenoxy)propane (abbreviated as b1-6), 3.24 g (0.010 mol) formula (b-2) -14), 4.92 g (0.015 mol) of the diamine compound (abbreviated as b2-3) shown in formula (b-2-19) (abbreviated as b2-4) and 60 g of NMP were added, Stir at room temperature until dissolved. Then, 11.21 g (0.05 mol) of a-3 and 20 g of NMP were added and reacted at room temperature for 1 hour, then 20 g of NMP was added and reacted at room temperature for 1 hour. After completion of the reaction, the reaction solution was put into 1500 ml of water to precipitate the polymer. Thereafter, the polymer obtained was filtered, washed with methanol, and filtered three times, and then placed in a vacuum oven and dried at a temperature of 60° C. to obtain a polymer (A-1-6).

Synthesis Example A-1-7
A four-necked conical flask with a capacity of 500 ml was equipped with a nitrogen gas inlet, a stirrer, a condenser tube and a thermometer, and nitrogen gas was introduced. Then, in a four-necked conical flask, 2.58 g (0.01 mol) of b1-2, 4.29 g (0.015 mol) of b1-3, 5.01 g (0.025 mol) of b3-3 and 80 g of NMP was added and stirred at room temperature until dissolved. Then, 10.91 g (0.05 mol) of a-1 and 20 g of NMP were added and reacted at 60 ° C. for 1 hour, then cooled to 40 ° C. with an ice bath and reacted for 30 minutes. The mixture was cooled to room temperature and reacted for 30 minutes. After completion of the reaction, the reaction solution was put into 1500 ml of water to precipitate the polymer. Thereafter, the obtained polymer was filtered, washed with methanol, and filtered three times, and then placed in a vacuum oven and dried at a temperature of 60° C. to obtain a polymer (A-1-7).

Synthesis Example A-1-8
A four-necked conical flask with a capacity of 500 ml was equipped with a nitrogen gas inlet, a stirrer, a condenser tube and a thermometer, and nitrogen gas was introduced. Then, in a four-necked conical flask, 9.43 g (0.03 mol) of b1-4, 1.76 g (0.005 mol) of the diamine compound (abbreviated as b2-5) represented by formula (b-2-23), 1.62 g (0.015 mol) of b3-1 and 80 g of NMP were added and stirred at room temperature until dissolved. Then, 9.81 g (0.05 mol) of a1-2 and 20 g of NMP were added, reacted at 60 ° C. for 1 hour, cooled to 40 ° C. with an ice bath and reacted for 30 minutes, and again with an ice bath. The mixture was cooled to room temperature and reacted for 30 minutes. After completion of the reaction, the reaction solution was put into 1500 ml of water to precipitate the polymer. Then, the polymer obtained was filtered, washed with methanol, and filtered three times, and then placed in a vacuum oven and dried at a temperature of 60° C. to obtain a polymer (A-1-8).

Synthesis Example A-1-9
A four-necked conical flask with a capacity of 500 ml was equipped with a nitrogen gas inlet, a stirrer, a condenser tube and a thermometer, and nitrogen gas was introduced. Then, in a four-necked conical flask, 8.05 g (0.035 mol) of b1-1, 1.48 g (0.005 mol) of the diamine compound (abbreviated as b2-6) represented by formula (b-2-28), 1.98 g (0.010 mol) of b3-2 and 80 g of NMP were added and stirred at room temperature until dissolved. Then, 9.53 g (0.0425 mol) of a-3 and 20 g of NMP were added, reacted at 60 ° C. for 1 hour, cooled to 40 ° C. with an ice bath, reacted for 30 minutes, and added ice. The bath was cooled to room temperature and 1.12 g (0.005 mol) of a-3 was added in 3 equal portions every 10 minutes. After completion of the reaction, the reaction solution was put into 1500 ml of water to precipitate the polymer. Thereafter, the obtained polymer was filtered, washed with methanol, and filtered three times, and then placed in a vacuum oven and dried at a temperature of 60° C. to obtain a polymer (A-1-9).

Synthesis Example A-1-10
A four-necked conical flask with a capacity of 500 ml was equipped with a nitrogen gas inlet, a stirrer, a condenser tube and a thermometer, and nitrogen gas was introduced. Then, 3.45 g (0.015 mol) of b1-1, 5.16 g (0.020 mol) of b1-2, 1.13 g (0.0035 mol) of b2-3, 2.3 g (0.0035 mol) of b2-3, 2.45 g (0.015 mol) of b1-1, 5.16 g (0.020 mol) of b1-2, 1.13 g (0.0035 mol) of b2-3, and 2.5 g (0.0035 mol) of b2-3 are added to a four-necked conical flask. 00 g (0.010 mol) of b3-3 and 80 g of NMP were added and stirred at room temperature until dissolved. Then, 9.82 g (0.045 mol) of a-1 and 20 g of NMP were added, reacted at 60 ° C. for 1 hour, cooled to 40 ° C. with an ice bath, reacted for 30 minutes, and added ice. The bath was cooled to room temperature and 1.08 g (0.005 mol) of a-1 was divided into 4 equal portions every 10 minutes. After completion of the reaction, the reaction solution was put into 1500 ml of water to precipitate the polymer. After that, the polymer obtained was filtered, washed with methanol, and filtered three times, and then placed in a vacuum oven and dried at a temperature of 60° C. to obtain a polymer (A-1-10).

Synthesis Example A-1-11
A four-necked conical flask with a capacity of 500 ml was equipped with a nitrogen gas inlet, a stirrer, a condenser tube and a thermometer, and nitrogen gas was introduced. Then, 11.45 g (0.04 mol) of b1-3, 0.27 g (0.0025 mol) of b3-1 and 80 g of NMP were added to a four-necked conical flask and stirred at room temperature until dissolved. Then, 3.27 g (0.015 mol) of a-1, 6.86 g (0.035 mol) of a-2 and 20 g of NMP were added, reacted at 60 ° C. for 1 hour, and then cooled to 40 ° C. with an ice bath. After cooling to room temperature and reacting for 30 minutes, the temperature was cooled to room temperature again with an ice bath, and 0.54 g (0.005 mol) of b3-1 was added in three equal portions every 10 minutes. After completion of the reaction, the reaction solution was put into 1500 ml of water to precipitate the polymer. After that, the polymer obtained was filtered, washed with methanol, and filtered three times, and then placed in a vacuum oven and dried at a temperature of 60° C. to obtain a polymer (A-1-11).

Synthesis Example A-1-12
A four-necked conical flask with a capacity of 500 ml was equipped with a nitrogen gas inlet, a stirrer, a condenser tube and a thermometer, and nitrogen gas was introduced. Then, 13.35 g (0.0425 mol) of b1-4, 1.34 g (0.004 mol) of b2-2 and 80 g of NMP were added to a four-necked conical flask and stirred at room temperature until dissolved. Then, 11.21 g (0.05 mol) of a1-3 and 20 g of NMP were added, reacted at 60 ° C. for 1 hour, cooled to 40 ° C. with an ice bath, reacted for 30 minutes, and added ice. The bath was cooled to room temperature and 1.57 g (0.005 mol) of b1-4 was added in 3 equal portions every 10 minutes. After completion of the reaction, the reaction solution was put into 1500 ml of water to precipitate the polymer. After that, the polymer obtained was filtered, washed with methanol, and filtered three times, and then placed in a vacuum oven and dried at a temperature of 60° C. to obtain a polymer (A-1-12).

Synthesis Example A-2-1
A four-necked conical flask with a capacity of 500 ml was equipped with a nitrogen gas inlet, a stirrer, a condenser tube and a thermometer, and nitrogen gas was introduced. Then, in a four-necked conical flask, 1.73 g (0.0075 mol) of b1-1, 2.68 g (0.01 mol) of b2-1, 6.94 g (0.035 mol) of b3-2 and 80 g of NMP was added and stirred at room temperature until dissolved. Then 8.82 g (0.045 mol) of a-2 and 20 g of NMP were added. After reacting for 2 hours at room temperature, 0.99 g (0.005 mol) of a-2 was added in 3 equal portions every 20 minutes. After the reaction was completed, 97 g of NMP, 2.55 g of acetic anhydride and 7.91 g of pyridine were added, heated to 60° C. and continuously stirred for 2 hours to carry out the imidization reaction. After completion of the reaction, the reaction solution was put into 1500 ml of water to precipitate the polymer. Then, the polymer obtained was filtered, washed with methanol, and filtered three times, and then 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
A four-necked conical flask with a capacity of 500 ml was equipped with a nitrogen gas inlet, a stirrer, a condenser tube and a thermometer, and nitrogen gas was introduced. Then, in a four-necked conical flask, 2.58 g (0.010 mol) of b1-2, 2.16 g (0.020 mol) of b3-1, 3.00 g (0.015 mol) of b3-3 and 80 g of NMP was added and stirred at room temperature until dissolved. Then 10.91 g (0.05 mol) of a-1 and 20 g of NMP were added. After reacting for 2 hours at room temperature, 1.00 g (0.005 mol) of b3-3 was added in 3 equal portions every 20 minutes. After the reaction was completed, 97 g of NMP, 2.55 g of acetic anhydride and 7.91 g of pyridine were added, heated to 60° C. and continuously stirred for 4 hours to carry out the imidization reaction. To precipitate the polymer by pouring the reaction solution into 1500 ml of water. Thereafter, the polymer obtained was filtered, washed with methanol, and filtered three times, and then placed in a vacuum oven and dried at a temperature of 60° C. to obtain a polymer (A-2-2).

Synthesis Example A-2-3
A four-necked conical flask with a capacity of 500 ml was equipped with a nitrogen gas inlet, a stirrer, a condenser tube and a thermometer, and nitrogen gas was introduced. Then, in a four-necked conical flask, 3.58 g (0.0125 mol) of b1-3, 8.40 g (0.025 mol) of b2-2, 2.48 g (0.0125 mol) of b3-2 and 60 g of NMP was added and stirred at room temperature until dissolved. Then 10.30 g (0.0525 mol) of a-2 and 20 g of NMP were added. After reacting for 1 hour at room temperature, 20 g of NMP was added and reacted for 2 hours at room temperature. After the reaction was completed, 97 g of NMP, 5.1 g of acetic anhydride and 11.86 g of pyridine were added, heated to 50° C. and continuously stirred for 2 hours to carry out the imidization reaction. After completion of the reaction, the reaction solution was put into 1500 ml of water to precipitate the polymer. Thereafter, the polymer obtained was filtered, washed with methanol, and filtered three times, and then placed in a vacuum oven and dried at a temperature of 60° C. to obtain a polymer (A-2-3).

Synthesis Example A-2-4
A four-necked conical flask with a capacity of 500 ml was equipped with a nitrogen gas inlet, a stirrer, a condenser tube and a thermometer, and nitrogen gas was introduced. Then, 2.86 g (0.010 mol) of b1-3, 6.28 g (0.020 mol) of b1-4, 0.97 g (0.003 mol) of b2-3, 3.5 g (0.003 mol) of b2-3, 3.5 g (0.003 mol) of b2-3, 2.86 g (0.010 mol) of b1-4, 0.97 g (0.003 mol) of b2-3, 3. 00 g (0.015 mol) of b3-3 and 80 g of NMP were added and stirred at room temperature until dissolved. Then, 11.21 g (0.05 mol) of a-3 and 20 g of NMP were added, reacted at 60 ° C. for 1 hour, cooled to 40 ° C. with an ice bath and reacted for 1 hour, and again with an ice bath. The mixture was cooled to room temperature and reacted for 1 hour. After the reaction was completed, 97 g of NMP, 5.1 g of acetic anhydride and 11.86 g of pyridine were added, heated to 50° C. and continuously stirred for 4 hours to carry out the imidization reaction. After completion of the reaction, the reaction solution was put into 1500 ml of water to precipitate the polymer. Thereafter, the polymer obtained was filtered, washed with methanol, and filtered three times, and then placed in a vacuum oven and dried at a temperature of 60° C. to obtain a polymer (A-2-4).

Synthesis Example A-2-5
A four-necked conical flask with a capacity of 500 ml was equipped with a nitrogen gas inlet, a stirrer, a condenser tube and a thermometer, and nitrogen gas was introduced. Then, 8.05 g (0.035 mol) of b1-1, 1.62 g (0.015 mol) of b3-1 and 80 g of NMP were added to a four-necked conical flask and stirred at room temperature until dissolved. Then, 2.94 g (0.015 mol) of a-2, 6.73 g (0.030 mol) of a-3 and 20 g of NMP were added, reacted at 60 ° C. for 1 hour, and then cooled to 40 ° C. with an ice bath. After cooling to room temperature and reacting for 30 minutes, the temperature was cooled to room temperature again with an ice bath, and 1.12 g (0.005 mol) of a-3 was added in three equal portions every 10 minutes. After the reaction was completed, 97 g NMP was added, 7.65 g acetic anhydride and 19.78 g pyridine, heated to 50° C. and continuously stirred for 4 hours to carry out the imidization reaction. After completion of the reaction, the reaction solution was put into 1500 ml of water to precipitate the polymer. Then, the polymer obtained was filtered, washed with methanol, and filtered three times, and then placed in a vacuum oven and dried at a temperature of 60° C. to obtain a polymer (A-2-5).

Synthesis Example A-2-6
A four-necked conical flask with a capacity of 500 ml was equipped with a nitrogen gas inlet, a stirrer, a condenser tube and a thermometer, and nitrogen gas was introduced. Then, 10.97 g (0.0425 mol) of b1-2, 0.82 g (0.0025 mol) of b2-4 and 80 g of NMP were added to a four-necked conical flask and stirred at room temperature until dissolved. Then, 10.91 g (0.05 mol) of a-1 and 20 g of NMP were added, reacted at 60 ° C. for 1 hour, cooled to 40 ° C. with an ice bath, reacted for 30 minutes, and The bath was cooled to room temperature and 1.29 g (0.005 mol) of b1-2 was divided into 4 equal portions every 10 minutes. After the reaction was completed, 97 g of NMP, 7.65 g of acetic anhydride and 19.78 g of pyridine were added, heated to 50° C. and continuously stirred for 4 hours for imidization reaction. After completion of the reaction, the reaction solution was put into 1500 ml of water to precipitate the polymer. Thereafter, the polymer obtained was filtered, washed with methanol, and filtered three times, and then placed in a vacuum oven and dried at a temperature of 60° C. to obtain a polymer (A-2-6).

Comparative Synthesis Example A'-1-1
A four-necked conical flask with a capacity of 500 ml was equipped with a nitrogen gas inlet, a stirrer, a condenser tube and a thermometer, and nitrogen gas was introduced. Then, in a four-necked conical flask, 6.7 g (0.025 mol) abbreviated b2-1, 2.48 g (0.0125 mol) b3-2, 2.50 g (0.0125 mol) b3-3 and 80 g NMP was added and stirred at room temperature until dissolved. Then, add 8.82 g (0.045 mol) of a-2 and 20 g of NMP, react for 2 hours at room temperature, then add 0.99 g (0.005 mol) of a-2 every 20 minutes, etc. The amount was added in three portions. After completion of the reaction, the reaction solution was put into 1500 ml of water to precipitate the polymer. Thereafter, the polymer obtained was filtered, washed with methanol, and filtered three times, and then placed in a vacuum oven and dried at a temperature of 60° C. to obtain a polymer (A′-1-1).

Comparative Synthesis Example A'-1-2
A four-necked conical flask with a capacity of 500 ml was equipped with a nitrogen gas inlet, a stirrer, a condenser tube and a thermometer, and nitrogen gas was introduced. Then, 8.40 g (0.025 mol) b2-2, 1.08 g (0.01 mol) b3-1, 1.98 g (0.01 mol) b3-2 and 80 g NMP were added to a four-necked conical flask. Add and stir at room temperature until dissolution. Then, add 10.91 g (0.05 mol) of a-1 and 20 g of NMP, react for 2 hours at room temperature, then add 0.54 g (0.005 mol) of b3-1 every 20 minutes, etc. The amount was added in three portions. After completion of the reaction, the reaction solution was put into 1500 ml of water to precipitate the polymer. Thereafter, the polymer obtained was filtered, washed with methanol, and filtered three times, and then placed in a vacuum oven and dried at a temperature of 60° C. to obtain a polymer (A′-1-2).

Comparative Synthesis Example A'-1-3
A four-necked conical flask with a capacity of 500 ml was equipped with a nitrogen gas inlet, a stirrer, a condenser tube and a thermometer, and nitrogen gas was introduced. Then add 3.24 g (0.010 mol) b2-3, 4.92 g (0.015 mol) b2-4, 2.7 g (0.025 mol) b3-1 and 60 g NMP to a four-necked conical flask, Stir at room temperature until dissolved. Then, 11.21 g (0.05 mol) of a-3 and 20 g of NMP were added and reacted at room temperature for 1 hour, then 20 g of NMP was added and reacted at room temperature for 1 hour. After completion of the reaction, the reaction solution was put into 1500 ml of water to precipitate the polymer. After that, the polymer obtained was filtered, washed with methanol, and filtered three times, and then placed in a vacuum oven and dried at a temperature of 60° C. to obtain a polymer (A′-1-3).

Comparative Synthesis Example A'-1-4
A four-necked conical flask with a capacity of 500 ml was equipped with a nitrogen gas inlet, a stirrer, a condenser tube and a thermometer, and nitrogen gas was introduced. Then, in a four-necked conical flask, 8.05 g (0.035 mol) of b1-1, 1.48 g (0.005 mol) of b2-6, 1.98 g (0.010 mol) of b3-2 and 80 g of NMP was added and stirred at room temperature until dissolved. Then, 10.64 g (0.0475 mol) of a-3 and 20 g of NMP were added and reacted at 60° C. for 2 hours. After completion of the reaction, the reaction solution was put into 1500 ml of water to precipitate the polymer. Thereafter, the polymer obtained was filtered, washed with methanol, and filtered three times, and then placed in a vacuum oven and dried at a temperature of 60° C. to obtain a polymer (A′-1-4).

Comparative Synthesis Example A'-2-1
A four-necked conical flask with a capacity of 500 ml was equipped with a nitrogen gas inlet, a stirrer, a condenser tube and a thermometer, and nitrogen gas was introduced. Then, in a four-necked conical flask, 1.73 g (0.0075 mol) of b1-1, 2.68 g (0.01 mol) of b2-1, 6.94 g (0.035 mol) of b3-2 and 80 g of NMP was added and stirred at room temperature until dissolved. Then 9.81 g (0.05 mol) of a-2 and 20 g of NMP were added. After reacting for 2 hours at room temperature, add 97 g of NMP, 2.55 g of acetic anhydride and 7.91 g of pyridine, heat up to 60° C., and continuously stir for 2 hours to initiate the imidization reaction. gone. After completion of the reaction, the reaction solution was put into 1500 ml of water to precipitate the polymer. Thereafter, the polymer obtained was filtered, washed with methanol, and filtered three times, and then placed in a vacuum oven and dried at a temperature of 60° C. to obtain a polymer (A′-2-1).

Comparative Synthesis Example A'-2-2
A four-necked conical flask with a capacity of 500 ml was equipped with a nitrogen gas inlet, a stirrer, a condenser tube and a thermometer, and nitrogen gas was introduced. Then, in a four-necked conical flask, add 0.97 g (0.003 mol) b2-3, 5.95 g (0.030 mol) b3-2, 3.00 g (0.015 mol) b3-3 and 80 g NMP was added and stirred at room temperature until dissolved. Then, 10.91 g (0.05 mol) of a-1 and 20 g of NMP were added and reacted at 60 ° C. for 1 hour, then cooled to 40 ° C. with an ice bath and reacted for 1 hour. The mixture was cooled to room temperature and reacted for 1 hour. After the reaction was completed, 97 g of NMP, 2.55 g of acetic anhydride and 7.91 g of pyridine were added, heated to 60° C. and continuously stirred for 4 hours to carry out the imidization reaction. To precipitate the polymer by pouring the reaction solution into 1500 ml of water. After that, the polymer obtained was filtered, washed with methanol, and filtered three times, and then placed in a vacuum oven and dried at a temperature of 60° C. to obtain a polymer (A′-2-2).

Production Example 1 of Liquid Crystal Aligning Agent
In Example 1, 100 parts by weight of the polymer (A-1-1) and 800 parts by weight of N-methyl-2-pyrrolidinone (B-1) were mixed at room temperature to obtain the liquid crystal aligning agent of Example 1. manufactured. Table 3 shows the specific composition of the liquid crystal aligning agent of Example 1 and the subsequent evaluation results.

Preparation of Liquid Crystal Alignment Film and Liquid Crystal Display Device The liquid crystal alignment agent obtained in Example 1 was formed on a substrate of a thin film transistor having pixel electrodes and an active layer made of IGZO by spin coating. The pixel electrode is an IPS driving electrode having a pair of ITO electrodes (electrode width: 10 μm, electrode spacing: 10 μm, electrode height: 50 nm). The ITO electrodes each have a comb-teeth shape and are arranged so that the comb-teeth portions are spaced apart from each other and mesh with each other. After that, it was pre-baked on a hot plate at 80° C. for 2 minutes and post-baked at 230° C. for 20 minutes to obtain a coating film with a thickness of 100 nm. After the orientation treatment, a thin film transistor substrate having a liquid crystal orientation film was formed. A glass substrate having columnar spacers with a height of 4 μm on which pixel electrodes are not formed as a counter substrate was similarly formed with a coating film and subjected to alignment treatment in the same manner to obtain another liquid crystal alignment film. rice field. After that, the two base materials are combined into one set, and after sticking the two base materials so that the friction direction is opposite to each other at 180 degrees, liquid crystal MLC-2041 (manufactured by Merck Co., Ltd.) is injected by a vacuum injection method. Then, the liquid crystal injection port was sealed with an ultraviolet curable gel, and the ultraviolet curable gel was cured with light from an ultraviolet lamp to obtain the liquid crystal display element of the first embodiment.

Examples 2-18 and Comparative Examples 1-6
Examples 2 to 18 and Comparative Examples 1 to 6 use the same method as Example 1, but in Examples 2 to 18 and Comparative Examples 1 to 6, the polymer, solvent, additive and/or Or differed by changing the amount used. See Tables 3 and 4 for specific compositions and evaluation results of the liquid crystal aligning agents of Examples 2 to 18 and Comparative Examples 1 to 6.

Comparative example 7
Comparative Example 7 also uses the same method as Example 2, but the active layer of the substrate of the thin film transistor prepared by the liquid crystal alignment film of Comparative Example 7 is Low Temperature Poly-silicon (LTPS). was different. See Table 4 for the specific composition and evaluation results of Comparative Example 7.

Evaluation method 1. Resistance light stability The above liquid crystal aligning agent is printed by a printer (manufactured by Nissha Co., Ltd., standard S15-036), and each pixel is patterned into a comb tooth shape composed of ITO (indium tin oxide). A pre-coating layer was formed by coating on a glass substrate having electrodes. After that, the glass substrate was placed on a heating plate and pre-baked at a temperature of 100° C. for 5 minutes. Next, in a circulation oven, a post-baking treatment is performed at a temperature of 220° C. for 30 minutes to obtain a glass substrate having a liquid crystal alignment film with a thickness of 100 nm formed on the upper surface, and to measure the resistance photostability. was the test cell.

Using an ion density measurement system (manufactured by Toyo Corporation; standard 6254 type), the frequency is 0.01 Hz, the voltage is set to an amplitude of 10 V, and the current flowing through the test cell and the corresponding voltage are used to determine the number of test cells. 1 resistance R _i was measured. The current was 3.16 nA and the measurements were performed in an atmosphere with a temperature of 23° C. and a humidity of 50%. After that, the test cell was illuminated with a white light emitting diode with an illuminance of 6 mW/cm ² for 300 seconds, and after measuring the second resistance R _f , the resistance photostability (ΔR ^UV ) was calculated.
ΔR ^UV =R _i -R _f (1)
A: ΔR ^UV <300 GΩ.
○: 300 GΩ≦ΔR ^UV <400 GΩ.
Δ: 400 GΩ≦ΔR ^UV <500 GΩ.
×: 500 GΩ≦ΔR ^UV .

※：８０％<Ｖ_Ｓ。
◎：７５％<Ｖ_Ｓ≦８０％。
○：７０％<Ｖ_Ｓ≦７５％。
△：６５％<Ｖ_Ｓ≦７０％。
×：Ｖ_Ｓ≦６５％。 2. Accumulated Charge Removability The liquid crystal display elements manufactured in Examples 1 to 18 and Comparative Examples 1 to 7 were each applied with a DC voltage of 3 V for 30 minutes, and the liquid crystal was measured by an electrical survey instrument (manufactured by TOYO Corporation; standard Model 6254). The accumulated voltage (V _R1 ) after the voltage release of the display element and the accumulated voltage (V _R2 ) for 15 minutes after the voltage release were measured, and the accumulated charge removal slope (V _S ) was calculated based on the following formula (IV). , was evaluated according to the following criteria.

*: 80%< _Vs .
A: 75% < V _S ≤ 80%.
◯: 70%<VS _≦ 75%.
Δ: 65%<VS _≦ 70%.
x: _VS≤65 %.

See Table 3. The polymer (A) in the liquid crystal aligning agents of Examples 1 to 18 of the present invention is produced by a specific production method and a specific diamine compound (b1), and the liquid crystal aligning agent prepared by the polymer (A) is any also has good resistance light stability. The liquid crystal aligning agents of the above examples can be used to form a liquid crystal aligning film on a substrate of a thin film transistor having an IGZO active layer, thereby producing a liquid crystal display device having good accumulated charge removing property. Furthermore, the polymer (A) of the liquid crystal aligning agent is synthesized with the diamine compound (b2), and/or the molar ratio [(b1)/(b2)] of the diamine compound (b1) and the diamine compound (b2) is Even when it is within a certain range, it is possible to further improve the ability to remove accumulated charges from the liquid crystal display element.

On the other hand, as can be seen from Table 4, unless the liquid crystal aligning agent is prepared from the claimed polymer (A) of the present invention, the desired resistance light stability cannot be achieved, and the liquid crystal aligning film formed from the liquid crystal aligning agent The accumulated charge removal property of the liquid crystal display element containing is poor. In addition, even if the polymer (A) claimed in the present invention forms a liquid crystal aligning agent with good resistive photostability, even if the manufactured liquid crystal alignment film is not combined with the substrate of a thin film transistor having an IGZO active layer, The liquid crystal display element has a poor ability to remove accumulated charges.

Although the present invention has been disclosed above through several embodiments, it is not intended to limit the present invention, and various changes and modifications can be made by those skilled in the art without departing from the spirit and scope of the present invention. be able to. The invention is defined by the claims.

100: Inspection cell 110: Substrate 120: Pixel electrode 130: Liquid crystal alignment film 200: Liquid crystal display element 210: First cell 212: Substrate of thin film transistor 214: Pixel electrode 216: First liquid crystal alignment film 220: Second Cell 222: Second substrate 226: Second liquid crystal alignment film 230: Liquid crystal cell

Claims (9)

A liquid crystal alignment film for manufacturing a liquid crystal alignment film by applying a liquid crystal alignment agent to a base material of a thin film transistor to form a pre-coating layer, and performing pre-baking treatment, post-baking treatment and alignment treatment on the pre-coating layer. In the manufacturing method of
The substrate of the thin film transistor includes an active layer whose material is Indium Gallium Zinc Oxide (IGZO), and the liquid crystal alignment agent is
obtained by reacting a mixture containing a tetracarboxylic dianhydride composition (a) and a diamine composition (b), and the diamine composition (b) is a diamine compound (b1) represented by formula (b-1) including

(In the formula (b-1), h represents an integer of 1 to 12) polymer (A),
and a solvent (B),
The resistance light stability ΔR ^UV of the liquid crystal alignment film is less than 300 GΩ , and the following steps:
(i) providing a test cell composed of a substrate, a pixel electrode on the substrate and the liquid crystal alignment film on the pixel electrode;
(ii) using an ion density measurement system with a frequency of 0.01 Hz and a voltage of 10 V amplitude, the current through the test cell and the corresponding voltage to measure the first resistance R _i of the test cell, the current is 3.16 nA and measuring the first resistance R _i at a temperature of 23° C. and a humidity of 50%;
(iii) illuminating the test cell with a white light emitting diode with an illuminance of 6 mW/ ^cm2 for 300 seconds to measure the second resistance _Rf of the test cell; and (iv) based on formula (1) below: Calculating the resistance photostability (ΔR ^UV ):
ΔR ^UV =R _i -R _f Formula (1 )
A method for manufacturing a liquid crystal alignment film measured by The diamine composition (b) contains a diamine compound (b2) represented by formula (b-2),

In the formula (b-2), each R ₁ independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an acetylamino group, a fluorine atom, a chlorine atom or a bromine atom. , wherein each R ₂ independently represents an alkyl group having 1 to 3 carbon atoms, each m independently represents an integer of 0 to 3, and each n represents an integer of 0 to 4. A method for manufacturing a liquid crystal alignment film. In the diamine compound (b2) of formula (b-2), each R ₁ independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an acetylamino group. 3. The method for producing a liquid crystal alignment film according to 2 . The liquid crystal alignment film according to claim 1, wherein the amount of the diamine compound (b1) represented by the formula (b-1) is 15 to 95 mol per 100 mol of the total number of moles of the diamine composition (b). Production method. The liquid crystal alignment film according to claim 2, wherein the amount of the diamine compound (b2) represented by the formula (b-2) is 5 to 50 mol per 100 mol of the total number of moles of the diamine composition (b). Production method. 3. The method for producing a liquid crystal alignment film according to claim 2, wherein the molar ratio [(b1)/(b2)] between the diamine compound (b1) and the diamine compound (b2) is 0.5 to 10.0. The method for producing a liquid crystal alignment film according to claim 1, wherein the amount of the solvent (B) used is 800 to 4000 parts by weight with respect to the total amount of the polymer (A) used of 100 parts by weight. The base material of the thin film transistor is
a first substrate;
a plurality of thin film transistor cells provided on the first substrate and each comprising a gate insulating layer, the active layer, a source and a drain;
The method for producing a liquid crystal alignment film according to claim 1, comprising: A liquid crystal display device comprising a liquid crystal alignment film manufactured by the method for manufacturing a liquid crystal alignment film according to any one of claims 1 to 8 .

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