TWI742094B - Method of producing liquid crystal alignment film and liquid crystal display - Google Patents

Abstract

The present invention provides a method of producing a liquid crystal alignment film and a liquid crystal display. In the method, a liquid crystal alignment agent with specific composition, formed by a specific method, is coated on a thin film transistor (TFT) substrate to form a pre-coated layer. The pre-coated layer is then subjected to a pre-bake treatment, a post-bake treatment and an alignment treatment, thereby forming a liquid crystal alignment film having a proper stability of resistance after exposure to light. The TFT substrate includes an active layer formed by a material of indium gallium zinc oxide. The liquid crystal display including the liquid crystal alignment film has good ability of eliminating accumulated charges.

Description

Method for manufacturing liquid crystal alignment film and liquid crystal display element

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

In recent years, the development of new liquid crystal display elements has been vigorously developed. For example, the industry has developed a liquid crystal display element that drives liquid crystal by arranging two electrodes on a single-sided substrate in a comb-tooth manner to generate a parallel electric field on the surface of the substrate. , To control the liquid crystal molecules. The above-mentioned liquid crystal display element is generally called a lateral electric field effect type (IPS type), and it is known that it has excellent wide viewing angle characteristics. However, the aforementioned IPS-type liquid crystal display element still has the problem of image retention due to excessively high ion density.

Japanese Patent Laid-Open No. 2006-259716 discloses a low ion density liquid crystal alignment film and a piperazine structure-containing diamine compound for preparing the liquid crystal alignment film. By using a diamine compound containing a piperazine structure, the resulting alignment film can improve the problem of excessively high ion density. However, when the liquid crystal alignment film prepared by the above liquid crystal alignment agent is applied to an IPS-type liquid crystal display device, the accumulated charge is still slowly eliminated, resulting in excessively high residual charge, and the problem of image sticking. It can be seen from the above that, in order to meet the requirements of the current IPS type liquid crystal display industry, it is an effort by those in the art to provide a liquid crystal alignment film that can form a liquid crystal display element with good accumulated charge elimination performance, and a liquid crystal alignment agent for forming the liquid crystal alignment film. The goal of the research.

Therefore, one aspect of the present invention is to provide a method for manufacturing a liquid crystal alignment film, which is coated on a thin film transistor substrate containing an active layer of Indium Gallium Zinc Oxide (IGZO). The liquid crystal alignment agent with a specific composition is obtained by the method to form a liquid crystal alignment film. In particular, the present invention is characterized in that the above-mentioned liquid crystal alignment film has a specific impedance and light stability, so as to produce a liquid crystal display element with good accumulated charge elimination properties.

Another aspect of the present invention is to provide a liquid crystal display element, which includes a liquid crystal alignment film manufactured by the above-mentioned method for manufacturing a liquid crystal alignment film.

Please refer to FIG. 1, which shows a schematic diagram of the detection unit 100 according to an embodiment of the present invention. The impedance optical stability of the present invention is performed by the following measuring method: (1) First, the detection unit 100 is assembled. The detection unit 100 is composed of a substrate 110, a pixel electrode 120, and the aforementioned liquid crystal alignment film 130. The pixel electrode 120 is formed on the surface of the substrate 110 in a comb-tooth pattern, and the liquid crystal alignment film 130 is formed on the pixel The surface of the electrode 120; (2) Next, use an ion density measurement system manufactured by TOYO Corporation (TOYO Corporation; model 6254), set the frequency to 0.01 Hz and the amplitude to a voltage of 10V, and use the above-mentioned detection unit 100 _{Measure the first impedance R i of the} detection unit 100 with the current flowing in and the corresponding voltage, where the above current is 3.16 nA, and the above measurement is performed in an environment with a temperature of 23° C. and a humidity of 50%; (3) ) Then, the detection unit 100 is irradiated with a backlight unit with an illuminance of 6mW/cm ² _{for 300 seconds, and the second impedance R f is} measured. The backlight unit is a white light-emitting diode, and the white light-emitting diode has a light-emitting diode. The main peak range of the spectrum is the light-emitting layer of the wafer with the main peak range of 430nm~500nm, and a photoluminescent phosphor; Group IV compound semiconductors, Group IV-VI compound semiconductors, or these combinations; (4) and, using the following formula (1) to calculate the impedance light stability (△R ^UV ): △R ^UV =R _i- R _f formula (1).

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

If the impedance light stability of the liquid crystal alignment film is not within the above range, the resulting liquid crystal display element has poor elimination of accumulated charges.

According to the above aspect of the present invention, a method for manufacturing a liquid crystal alignment film is first proposed, which includes coating a liquid crystal alignment agent on a thin film transistor substrate to form a pre-coating layer, and subjecting the pre-coating layer to pre-heating treatment and then The liquid crystal alignment film is prepared by heat treatment and alignment treatment, wherein the thin-film transistor substrate includes an active layer made of IGZO, and the above-mentioned liquid crystal alignment film has an impedance light stability of less than 500GΩ. The manufacturing methods of the liquid crystal alignment agent and the liquid crystal alignment film are respectively described below.

Liquid crystal alignment agent

The liquid crystal alignment agent of the present invention includes a polymer (A) and a solvent (B), which are described below.

Polymer (A)

The polymer (A) of the present invention is obtained by reacting a mixture, wherein the mixture contains the tetracarboxylic dianhydride component (a) and the diamine component (b).

Preferable specific examples of the above-mentioned polymer (A) are polyimide polymers, polyimide polymers, polyimine-based block copolymers, or a combination of these. Among them, preferred specific examples of polyimide block copolymers are polyimide block copolymers, polyimide block copolymers, polyimide-polyimide block copolymers, and polyimide block copolymers. Polymer, or a combination of them.

Tetracarboxylic dianhydride component (a)

The preferred specific examples of the tetracarboxylic dianhydride component (a) according to the present invention are (1) aliphatic tetracarboxylic dianhydride compound, (2) alicyclic tetracarboxylic dianhydride compound, (3) aromatic Tetracarboxylic dianhydride compounds or (4) tetracarboxylic dianhydride compounds having formulas (a-1) to (a-6), etc.

The (1) aliphatic tetracarboxylic dianhydride compound according to the present invention includes but is not limited to aliphatic tetracarboxylic dianhydride compounds such as ethane tetracarboxylic dianhydride or butane tetracarboxylic dianhydride.

The (2) alicyclic tetracarboxylic dianhydride compound according to the present invention includes but is not limited to 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3 ,4-Cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dichloro-1,2,3, 4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopenta Alkyltetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, cis-3,7-di Butylcycloheptyl-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride or bicyclo[2.2.2]- Alicyclic tetracarboxylic dianhydride compounds such as oct-7-ene-2,3,5,6-tetracarboxylic dianhydride.

Specific examples of (3) aromatic tetracarboxylic dianhydride compound according to the present invention may include, but are not limited to, 3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, benzene S-tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3 ',4,4'-Biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3' -4,4'-Diphenylethane tetracarboxylic dianhydride, 3,3',4,4'-Dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3',4,4'- Tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4 ,4'-Diphenyl ether tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 2,3,3',4'-diphenyl sulfide Ether tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) diphenyl dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene diphthalic dianhydride, 2,2' ,3,3'-Diphenyltetracarboxylic dianhydride, 2,3,3',4'-Diphenyltetracarboxylic dianhydride, 3,3',4,4'-Diphenyltetracarboxylic acid Dianhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) bis Anhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, ethylene glycol- Bis (anhydro trimellitate), propylene glycol-bis (anhydro trimellitate), 1,4-butanediol-bis (anhydro trimellitate), 1,6-hexanediol-bis ( Dehydrated trimellitate), 1,8-octanediol-bis(dehydrated trimellitate), 2,2-bis(4-hydroxyphenyl)propane-bis(dehydrated trimellitate), 2,3,4,5-Tetrahydrofurantetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-diside oxy-3-furanyl) -Naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-methyl-5-(tetrahydro-2,5- Di-side oxy-3-furyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-ethyl- 5-(Tetrahydro-2,5-diside oxy-3-furyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5, 9b-hexahydro-7-methyl-5-(tetrahydro-2,5-di-side oxy-3-furyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-ethyl-5-(tetrahydro-2,5-dioxo-3-furyl)-naphtho[1,2-c ]-Furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl )-Naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-ethyl-5-(tetrahydro-2,5 -Di-side oxy-3-furyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5,8- Dimethyl-5-(tetrahydro-2,5-diside oxy-3-furyl)-naphtho[1,2-c]-furan-1,3-dione, 5-(2,5 -Di-side oxytetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride and the like.

The tetracarboxylic dianhydride compound represented by formula (a-1) to formula (a-6) according to (4) of the present invention is described in detail as follows.

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

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

The above-mentioned tetracarboxylic dianhydride component (a) can be used singly or as a mixture of plural kinds.

Based on the use amount of the diamine component (b) is 100 mol, the use amount of the tetracarboxylic dianhydride component (a) is in the range of 20 mol to 200 mol; preferably 30 mol to 120 mol.

Diamine component (b)

In one embodiment, the diamine component (b) of the present invention includes at least the diamine compound (b1) represented by formula (b-1). In another embodiment, the diamine component (b) of the present invention includes the above-mentioned diamine compound (b1) and the diamine compound (b2) represented by formula (b-2). In the above embodiments, the diamine component (b) of the present invention may further include other diamine compounds (b3).

Diamine compound (b1)

The aforementioned diamine compound (b1) represented by formula (b-1) is represented as follows:

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

Specifically, the diamine compound (b1) represented by the formula (b-1) includes a diamine compound having a structure represented by the following formula (b-1-1) to formula (b-1-3):

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

Specific examples of the aforementioned diamine compound having the structure shown in formula (b-1-1) can be bis(4-aminophenoxy)methane, 1,2-bis(4-aminophenoxy)ethane Alkyl, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane Alkane, 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 any combination of the above compounds.

Specific examples of the aforementioned diamine compound having the structure shown in formula (b-1-2) can be bis(2-aminophenoxy)methane, 1,2-bis(2-aminophenoxy)ethane Alkyl, 1,3-bis(2-aminophenoxy)propane, 1,4-bis(2-aminophenoxy)butane, 1,5-bis(2-aminophenoxy)pentane Alkane, 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 any combination of the above compounds.

Specific examples of the aforementioned diamine compound having the structure shown in formula (b-1-3) can be bis(3-aminophenoxy)methane, 1,2-bis(3-aminophenoxy)ethane Alkyl, 1,3-bis(3-aminophenoxy)propane, 1,4-bis(3-aminophenoxy)butane, 1,5-bis(3-aminophenoxy)pentane Alkane, 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 any combination of the above compounds.

Preferably, specific examples of the diamine compound (b1) represented by the formula (b-1) may be 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-amino) Phenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,7-bis(4-amine Phenyloxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,3-bis(2-aminophenoxy)propane, 1,4-bis(2-amine Phenyloxy)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- Aminophenoxy)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, etc.

Based on the total usage amount of the diamine component (b) is 100 mol, the usage amount of the diamine compound (b1) is 15 mol to 95 mol, preferably 20 to 93 mol, more preferably 25 Mo ears to 90 moles.

If the diamine component (b) does not contain the diamine compound (b1) represented by the formula (b-1), the liquid crystal display element containing the liquid crystal alignment film prepared by the liquid crystal alignment agent will not have the accumulated charge elimination performance good.

Diamine compound (b2)

The aforementioned diamine compound (b2) represented by formula (b-2) is represented as follows:

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

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

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

The diamine compound (b2) represented by the formula (b-2) can be used singly or in combination of multiple types.

Based on the total usage amount of the diamine component (b) being 100 mol, the usage amount of the diamine compound (b2) is 5 mol to 50 mol, preferably 7 mol to 45 mol, more preferably 10 mol Ears to 40 moles.

When the diamine compound (b2) is used in the liquid crystal alignment agent, the accumulated charge elimination property of the formed liquid crystal display element can be further improved.

Secondly, the molar ratio [(b1)/(b2)] of the aforementioned diamine compound (b1) and diamine compound (b2) may be 0.5 to 10.0, preferably 1.0 to 8.0, and more preferably 1.5 to 5.0. If the molar ratio [(b1)/(b2)] of the diamine compound (b1) to the diamine compound (b2) is in the aforementioned range, the accumulated charge elimination property of the formed liquid crystal display element can be further improved.

Other diamine compounds (b3)

The other diamine compound (b3) of the present invention may include, but is not limited to, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diamine Pentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diamine Decane, 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 Base) ethane, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylamine, 1,3-diaminocyclohexane , 1,4-Diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentadiene diamine, tricyclic (6.2.1.02,7)-undecene dimethyl Diamine, 4,4'-methylenebis(cyclohexylamine), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'- Diaminodiphenyl sulfide, 4,4'-diaminobenzaniline, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,5 -Diaminonaphthalene, 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylhydroindene, 6-amino-1-(4'-aminophenyl) )-1,3,3-trimethylindenyl, hexahydro-4,7-methane-bridged indenyldimethylene diamine, 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)hexafluoropropane, 2,2-bis[4-(4-aminobenzene) (Oxy) phenyl) chrysene, 1,4-bis(4-aminophenoxy)cyclohexane, 1,5-bis(4-aminophenoxymethylene)adamantane, 1,4- Bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis( 4-aminophenyl)-10-hydroanthracene, 9,10-bis(4-aminophenyl)anthracene [9,10-bis(4-aminophenyl)anthracene], 2,7-diaminophenyl, 9,9-bis(4-aminophenyl)sulfuric acid, 4,4'-methylene-bis(2-chloroaniline), 4,4'-(p-phenylene isopropylidene) bisaniline , 4,4'-(m-phenylene isopropylidene)bisaniline, 2,2'-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoro Propane, 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-aminophenoxy)phenyl]-4-(4-ethyl phenyl) cyclohexane} or other diamine compounds represented by the following formulas (b-3-1) to (b-3-29).

、

、

、

或

，且X₇代表含甾基團、三氟甲基、氟基、碳數為2至30之烷基或衍生自吡啶、嘧啶、三嗪、哌啶及哌嗪等含氮原子環狀結構的一價基團。 In formula (III-1), X ₆ represents -O-,

,

,

,

or

, And X ₇ represents a steroid group, a trifluoromethyl group, a fluoro group, an alkyl group with a carbon number of 2 to 30, or those derived from pyridine, pyrimidine, triazine, piperidine and piperazine and other nitrogen-containing cyclic structures Monovalent group.

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

、

、

、

或

，X₉及X₁₀表示伸脂肪族環、伸芳香族環或伸雜環基團，且X₁₁代表碳數為3至18之烷基、碳數為3至18之烷氧基、碳數為1至5之氟烷基、碳數為1至5之氟烷氧基、氰基或鹵素原子。 In formula (b-3-2), X ₈ represents -O-,

,

,

,

or

, X ₉ and X ₁₀ represent an aliphatic ring, an aromatic ring or a heterocyclic ring group, and X ₁₁ represents an alkyl group with a carbon number of 3 to 18, an alkoxy group with a carbon number of 3 to 18, and a carbon number It is a fluoroalkyl group of 1 to 5, a fluoroalkoxy group of 1 to 5 carbon atoms, a cyano group or a halogen atom.

The other diamine compound represented by the above formula (b-3-2) may preferably be the diamine compound represented by the following formula (b-3-2-1) to formula (b-3-2-13):

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

In the formula (b-3-3), X ₁₂ represents a hydrogen atom, an acyl group having a carbon number of 1 to 5, an alkyl group having a carbon number of 1 to 5, an alkoxy group having a carbon number of 1 to 5, or a halogen. X ₁₃ is an integer of 1 to 3. When X _{13 is} greater than 1, a plurality of X ₁₂ may be the same or different.

The diamine compound represented by the above formula (b-3-3) is preferably selected from (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'-di Amino biphenyl, 3,3'-dichloro-4,4'-diamino biphenyl, 2,2',5,5'-tetrachloro-4,4'-diamino biphenyl, 2, 2'-Dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl or 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl Etc.; (3) X ₁₃ is 3: 1,4-bis(4'-aminophenyl) benzene, etc., more preferably selected from p-diaminobenzene, 2,5-diaminotoluene, 4,4 '-Diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl or 1,4-bis(4'-aminophenyl)benzene.

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

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

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

In the formula (b-3-7), X ₂₄ represents -O- or cyclohexylene, X ₂₅ represents -CH ₂ -, X ₂₆ represents phenylene or cyclohexylene, and X ₂₇ represents hydrogen Atom or heptyl.

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

Other diamine compounds represented by formula (b-3-8) to formula (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 component (b3) may preferably include, but is not limited to, 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, ethyl 2,4-diaminophenylformate, 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), a compound represented by formula (b-3-2-11), formula (b-3-7-1), formula (b-3-25), or formula (b-3-28).

The aforementioned diamine component (b3) can be used alone or in combination.

Based on the total usage amount of the diamine component (b) is 100 mol, the usage amount of the other diamine compound (b3) is 0 to 80 mol, preferably 0 to 73 mol, more preferably 0 to 65 mol Ear.

Manufacturing method of polymer (A)

The preparation of the polyamide acid polymer according to the present invention can be a general method. Preferably, the preparation method of the polyamide acid polymer includes the following steps: combining the tetracarboxylic dianhydride component (a) and the diamine The mixture of component (b) is dissolved in a solvent, and the polycondensation reaction is carried out at a temperature of 0°C to 100°C and reacted for 1 hour to 24 hours, and then the above reaction solution is subjected to vacuum distillation with an evaporator. The polyamide acid polymer can be obtained, or the above reaction solution is poured into a large amount of poor solvent to obtain the precipitate, and then the precipitate is dried through the vacuum drying method to obtain the polyamide acid polymer .

The solvent used in the polycondensation reaction may be the same as or different from the solvent in the following liquid crystal alignment agent, and the solvent used in the polycondensation reaction is not particularly limited, as long as it can dissolve the reactants and products. Preferably, the solvent includes but is not limited to (1) aprotic polar solvent, for example: N-methyl-2-pyrrolidinone (NMP), N,N-dimethylacetamide , N,N-dimethylformamide, dimethylsulfide, γ-butyrolactone, tetramethylurea or hexamethylphosphoric triamine such as aprotic polar solvents; (2) phenolic solvents, For example: phenolic solvents such as m-cresol, xylenol, phenol or halogenated phenols. The usage amount based on the mixture is 100 parts by weight, and the usage amount of the solvent used in the polycondensation reaction is preferably 200 parts by weight to 2000 parts by weight, more preferably 300 parts by weight to 1800 parts by weight.

In particular, in the polycondensation reaction, the solvent can be used in combination with an appropriate amount of poor solvent, where the poor solvent will not cause the precipitation of the polyamide acid polymer. The poor solvent can be used alone or in a mixture of multiple, and it includes but is not limited to (1) alcohols, for example: methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butane Alcohols such as alcohol or triethylene glycol; (2) Ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; (3) Esters, such as: Esters such as methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate or ethyl 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 dimethyl ether (5) Halogenated hydrocarbons, such as dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene or o-dichloro Halogenated hydrocarbons such as benzene; (6) Hydrocarbons, such as hydrocarbons such as tetrahydrofuran, hexane, heptane, octane, benzene, toluene or xylene, or any combination of the above solvents. Based on 100 parts by weight of the diamine component (b), the amount of the poor solvent is preferably 0 parts by weight to 60 parts by weight, more preferably 0 parts by weight to 50 parts by weight.

The preparation of the polyimide polymer according to the present invention can be a general method. Preferably, the preparation method of the polyimide polymer first dissolves a mixture in a solution, wherein the mixture contains the tetracarboxylic dianhydride component (a) and the diamine component (b), and carry out a polymerization reaction to form a polyamide acid polymer. Then, in the presence of a dehydrating agent and a catalyst, further heating and dehydration and ring-closing reaction are carried out, so that the amide functional group in the polyamide acid polymer is converted into an amide functional group (ie, amide) through the dehydration ring-closing reaction. Amination) to obtain a polyimide polymer.

The solvent used in the dehydration and ring-closing reaction can be the same as the solvent in the following liquid crystal alignment agent, so no further description is given. Based on the usage amount of the polyamide acid polymer being 100 parts by weight, the usage amount of the solvent used in the dehydration ring-closing reaction is preferably 200 parts by weight to 2000 parts by weight, more preferably 300 parts by weight to 1800 parts by weight.

In order to obtain a better degree of imidization of the polyamide acid polymer, the operation temperature of the dehydration ring-closure reaction is preferably 40°C to 200°C, more preferably 40°C to 150°C. If the operating temperature of the dehydration ring-closure reaction is lower than 40°C, the imidization reaction is incomplete, and the degree of imidization of the polyamide acid polymer is reduced. However, if the operating temperature of the dehydration and ring-closure reaction is higher than 200°C, the weight average molecular weight of the obtained polyimide polymer is low.

The dehydrating agent used in the dehydration ring-closing reaction can be selected from acid anhydride compounds, specifically such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride. Based on 1 mol of the polyamide acid polymer, the amount of the dehydrating agent used is 0.01 mol to 20 mol. The catalyst used in the dehydration ring-closing reaction can be selected from (1) pyridine compounds, such as pyridine, collidine or lutidine; (2) tertiary amine compounds, such as: Tertiary amine compounds such as triethylamine. Based on the use amount of the dehydrating agent is 1 mol, the use amount of the catalyst is 0.5 mol to 10 mol.

The preferred specific examples of the polyimide block copolymers according to the present invention are polyimide block copolymers, polyimide block copolymers, polyimide-polyimine block copolymers, and polyimide block copolymers. Segment copolymers, or any combination of these.

The preparation of the polyimine-based block copolymer according to the present invention can be a general method. Preferably, the preparation method of the polyimine-based block copolymer is to first dissolve a starting material in a solvent, and A polycondensation reaction is carried out, wherein the starting material includes the above-mentioned at least one polyamide acid polymer and/or the above-mentioned at least one polyimide polymer, and may further include a tetracarboxylic dianhydride component (a ) And the diamine component (b).

The tetracarboxylic dianhydride component (a) and diamine component (b) of the starting material are the same as the tetracarboxylic dianhydride component (a) and The diamine component (b) is the same, and the solvent used in the polycondensation reaction can be the same as the solvent in the following liquid crystal alignment agent, which will not be repeated here.

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

Preferably, the starting material includes but is not limited to (1) two kinds of polyimide polymers with different end groups and different structures; (2) two kinds of polyimide polymers with different end groups and different structures Polymers; (3) Polyamide polymers and polyimide polymers with different end groups and different structures; (4) Polyamide acid polymers, tetracarboxylic dianhydride compounds and diamine compounds, Among them, at least one of the tetracarboxylic dianhydride compound and the diamine compound is different in structure from the tetracarboxylic dianhydride component (a) and the diamine component (b) used to form the polyamide acid polymer (5) Polyimide polymer, tetracarboxylic dianhydride compound and diamine compound, wherein at least one of the tetracarboxylic dianhydride compound and diamine compound is used to form the polyimide polymer The structure of tetracarboxylic dianhydride component (a) and diamine component (b) are different; (6) polyamide acid polymer, polyimide polymer, tetracarboxylic dianhydride compound and diamine Compound, wherein at least one of tetracarboxylic dianhydride compound and diamine is combined with tetracarboxylic dianhydride component (a) and diamine component used to form polyamide acid polymer or polyimide polymer (b) Different structures; (7) Two kinds of polyamide polymers, tetracarboxylic dianhydride compounds and diamine compounds with different structures; (8) Two kinds of polyimide polymers with different structures , Tetracarboxylic dianhydride compounds and diamine compounds; (9) Two kinds of polyamide acid polymers and diamine compounds with acid anhydride groups and different structures; (10) Two kinds of end groups are amine groups and structures Different polyimide polymers and tetracarboxylic dianhydride compounds; (11) Two kinds of polyimide polymers and diamine compounds whose end groups are acid anhydride groups and have different structures; (12) Two kinds of end groups Polyimide polymers and tetracarboxylic dianhydride compounds with different structures.

In the range that does not affect the efficacy of the present invention, preferably, the polyimide polymer, the polyimide polymer and the polyimine-based block copolymer may be the terminal after the molecular weight is adjusted first. Modified polymer. By using end-modified polymers, the coating performance of the liquid crystal alignment agent can be improved. The method of preparing the terminal modified polymer can be prepared by adding a monofunctional compound while the polyamide acid polymer undergoes a polycondensation reaction. The monofunctional compound includes but is not limited to (1) monobasic anhydride, For example: maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride or n-hexadecyl succinic anhydride and other monobasic acid anhydrides; (2) Monoamine compounds, such as: aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-ten Monoamine compounds such as dialkylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine or n-eicosylamine ; (3) Monoisocyanate compounds, such as monoisocyanate compounds such as phenyl isocyanate or naphthyl isocyanate.

The polymer (A) of the present invention has a weight average molecular weight of 10,000 to 90,000, preferably 12,000 to 75,000, and more preferably 15,000 to 60,000 as measured by polystyrene conversion according to gel permeation chromatography.

The polymer (A) of the present invention includes at least one polyamide acid polymer, polyimine polymer or polyimine-based block copolymer prepared in the following manner. Specific examples of this method include batch addition of tetracarboxylic dianhydride component during polycondensation reaction, batch addition of diamine component during polycondensation reaction, batch addition of solvent during polycondensation reaction, or temperature change control during polycondensation reaction.

When the polymer (A) does not contain the polyimide polymer, polyimide polymer or polyimide block copolymer prepared in the above manner, the resistance of the prepared liquid crystal alignment film Poor light stability.

Solvent (B)

The solvent 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 arbitrary components and does not react with them, preferably the same as in the aforementioned synthetic polyamide acid The solvent used can also be used in combination with the poor solvent used when synthesizing the polyamide acid.

Specific examples of the solvent (B) include, but are not limited to, N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone, NMP), γ-butyrolactone, γ-butyrolactone, 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 n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetic acid Ester, 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 (N,N-dimethyl acetamide), etc. The solvent (B) can be used alone or in combination of multiple types.

Based on 100 parts by weight of the polymer (A), 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 1000 to 3000 parts by weight.

Additive (C)

Within the scope of the efficacy of the present invention, the liquid crystal alignment agent can be optionally added with an additive (C), and the additive (C) is an epoxy compound or a silane compound with a functional group, etc. The function of the additive (C) is to improve the adhesion of the liquid crystal alignment film to the surface of the substrate. Additives (C) can be used alone or in combination of plural kinds.

The aforementioned epoxy compounds may include, but are not limited to, 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'-Tetraglycidyl-M-Di Toluene diamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraepoxypropyl-4,4'-di Amino diphenylmethane, N,N-glycidyl-p-glycidoxyaniline, 3-(N-allyl-N-glycidoxypropyl)aminopropyl trimethoxysilane, 3-(N,N-diepoxypropyl)aminopropyl trimethoxysilane, etc.

Based on the usage amount of the polymer (A) being 100 parts by weight, the usage amount of the epoxy compound is generally 40 parts by weight or less, preferably 0.1 to 30 parts by weight.

The above-mentioned silane compounds with functional groups may include, but are not limited to, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2- Aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyl 3-ureidopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane Triethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyl trimethylenetriamine, N-trimethoxysilylpropyl trimethylene Triamine, 10-trimethoxysilyl-1,4,7-triazdecane, 10-triethoxysilyl-1,4,7-triazdecane, 9-trimethoxysilyl- 3,6-Diazinonyl acetate, 9-triethoxysilyl-3,6-diazenonyl 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, etc.

Based on the usage amount of the polymer (A) being 100 parts by weight, the usage amount of the silane compound is generally 10 parts by weight or less, preferably 0.5 to 10 parts by weight.

Method for preparing liquid crystal alignment agent

The preparation method of the liquid crystal alignment agent of the present invention is not particularly limited, and general mixing methods can be used, such as first mixing the tetracarboxylic dianhydride component (a) and the diamine component (b) uniformly to form a Polymer (A). Then, the polymer (A) is added to the solvent (B) at a temperature of 0°C to 200°C, and optionally the additive (C) is added, and the stirring device is used to continue stirring until it is dissolved. Preferably, the polymer (A) is added to the solvent (B) at a temperature of 20°C to 60°C.

Method for forming liquid crystal alignment film

The present invention also provides a liquid crystal alignment film, which is manufactured from the aforementioned liquid crystal alignment agent.

Preferably, the method for forming the liquid crystal alignment film includes the steps of: applying the above-mentioned liquid crystal alignment agent to the existing liquid crystal alignment agent by roller coating method, spin coating method, printing method, ink-jet method, etc. A pre-coating layer is formed on the surface of the substrate where the pixel electrode is set, and then the pre-coating layer is processed by pre-bake treatment, post-bake treatment and alignment treatment. Thus, the film thickness of the film formed in the above manner is preferably 0.001 μm to 1 μm, more preferably 0.005 μm to 0.5 μm.

The substrate referred to herein includes at least one thin film transistor substrate, including: a first substrate (which may have the same material as the substrate 110 shown in FIG. 1), a plurality of thin film transistor units, and an insulating layer. Among them, the thin film transistor unit is disposed on the first substrate, and the thin film transistor unit respectively includes a gate insulating layer, an active layer, a source electrode and a drain electrode, and the material of the active layer is indium gallium zinc oxide (IGZO). In addition, the insulating layer is disposed on the thin film transistor unit and the insulating layer has a plurality of contact holes to respectively expose the drain of the thin film transistor unit; the pixel electrode is disposed on the insulating layer and extends toward the contact hole It is electrically connected to the drain electrode; and the alignment film covers the pixel electrode.

The purpose of the pre-heating treatment is to volatilize the organic solvent in the pre-coating layer. Preferably, the operating temperature range of the pre-heating treatment is 30°C to 120°C, more preferably 40°C to 110°C, and more preferably 50°C to 100°C.

The above-mentioned alignment treatment is not particularly limited, and cloth made of nylon, rayon, cotton and other fibers can be used to wind on the drum and rub in a certain direction for alignment. The above-mentioned alignment processing is well-known to those skilled in the art, so no further description will be given.

The purpose of the post-heating treatment step is to make the polymer in the pre-coating further undergo dehydration and ring-closure (imidization) reaction. Preferably, the operating temperature of the post-heating treatment ranges from 150°C to 300°C, more preferably from 180°C to 280°C, more preferably from 200°C to 250°C.

When the material of the active layer of the thin-film transistor unit does not include indium gallium zinc oxide (IGZO), the liquid crystal display device produced has poor elimination of accumulated charges.

In one embodiment, before forming the liquid crystal alignment film, the manufacturing method of the liquid crystal alignment film of the present invention further includes using the detection unit 100 as shown in FIG. The measurement and the specific detection method are as described in the aforementioned Figure 1 and the evaluation method of impedance optical stability described later.

Method for manufacturing liquid crystal display element

The present invention also provides a liquid crystal display element, which includes the aforementioned liquid crystal alignment film.

The manufacturing method of the liquid crystal display element is well known to those skilled in the art, therefore, the following is only briefly described.

Referring to FIG. 2, a preferred embodiment of the liquid crystal display element 200 of the present invention includes a first unit 210, a second unit 220, and a liquid crystal unit 230. The second unit 220 is spaced apart from the first unit 210, and the liquid crystal unit 230 is disposed in Between the first unit 210 and the second unit 220.

The first unit 210 includes a thin film transistor substrate 212, a pixel electrode 214, and a first liquid crystal alignment film 216. The pixel electrode 214 is formed on the surface of the thin film transistor substrate 212 in a comb-tooth pattern. A 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 units, and an insulating layer.

The second unit 220 includes a second substrate 222 and a second liquid crystal alignment film 226, wherein the second liquid crystal alignment film 226 is formed on the surface of the second substrate 222.

The above-mentioned first substrate and second substrate 222 are selected from transparent materials, etc., wherein the transparent materials include but are not limited to alkali-free glass, soda lime glass, hard glass (Pyles glass), quartz used in liquid crystal display devices. Glass, polyethylene terephthalate, polybutylene terephthalate, polyether terephthalate, polycarbonate, etc. The material of the pixel electrode 114 is _{a transparent electrode selected from tin oxide (SnO 2} ), indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ), etc.; or a metal electrode such as chromium.

The first liquid crystal alignment film 216 and the second liquid crystal alignment film 226 are the above-mentioned liquid crystal alignment films respectively, and their function is to make the liquid crystal cell 230 form a pretilt angle, and the liquid crystal cell 230 can be driven by the parallel electric field generated by the pixel electrode 214.

The liquid crystal used in the liquid crystal unit 230 can be used alone or in a mixture of multiple types. The liquid crystals include but are not limited to diaminobenzene type liquid crystals, pyridazine type liquid crystals, shiff base type liquid crystals, and azo group oxides. (azoxy) type liquid crystal, phenylcyclohexane type liquid crystal, biphenyl type liquid crystal, phenylcyclohexane type liquid crystal, ester type liquid crystal, terphenyl, biphenylcyclohexane Biphenylcyclohexane type liquid crystal, pyrimidine type liquid crystal, dioxane type liquid crystal, bicyclooctane type liquid crystal, cubane type liquid crystal, etc., and can be added such as chlorinated Cholesterol (cholesteryl chloride), cholesterol nonanoate (cholesteryl nonanoate), cholesterol carbonate (cholesteryl carbonate) and other cholesteric liquid crystals, or under the trade names "C-15", "CB-15" (Merck Company made ), such as chiral agents, or ferroelectric liquid crystals such as p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate.

The liquid crystal display element produced by the liquid crystal alignment agent of the present invention is suitable for various types of nematic liquid crystals, such as liquid crystal display elements such as TN, STN, TFT, VA, and IPS. In addition, depending on the selected liquid crystal, it can also be used in different liquid crystal display elements such as strong dielectric or anti-strong dielectric. Among the above-mentioned liquid crystal display elements, it is particularly suitable for IPS-type liquid crystal display elements.

The following examples are used to illustrate the present invention in detail, but it does not mean that the present invention is limited to the content disclosed by these examples.

100‧‧‧Detection unit

110‧‧‧Substrate

120‧‧‧Pixel electrode

130‧‧‧LCD alignment film

200‧‧‧Liquid crystal display element

210‧‧‧Unit 1

212‧‧‧Thin Film Transistor Substrate

214‧‧‧Pixel electrode

216‧‧‧The first liquid crystal alignment film

220‧‧‧Second Unit

222‧‧‧Second substrate

226‧‧‧Second liquid crystal alignment film

230‧‧‧LCD unit

In order to make the above and other objectives, features, advantages and embodiments of the present invention more comprehensible, the detailed description of the accompanying drawings is as follows: [FIG. 1] shows the detection unit according to an embodiment of the present invention Schematic.

[Fig. 2] is a schematic diagram showing the structure of a liquid crystal display element according to an embodiment of the present invention.

Synthesis example of polymer (A)

The following describes synthesis examples A-1-1 to A-1-12, synthesis examples A-2-1 to A-2-6, and comparative synthesis examples A'-1-1 to A'-1 of polymer (A) -4 and comparative synthesis examples A'-2-1 to A'-2-2, wherein the usage ratios of the components of the above-mentioned synthesis example and the comparative synthesis example are as shown in Table 1 and Table 2.

Synthesis Example A-1-1

A nitrogen inlet, a stirrer, a condenser, and a thermometer are set on a four-necked conical flask with a volume of 500 ml, and nitrogen is introduced. Then, add 1.73 grams (0.0075 mol) of bis(4-aminophenoxy) methane (referred to as b1-1) and 2.16 grams (0.02 mol) of p-diaminobenzene (referred to as B3-1), 4.96 grams (0.025 mol) of 4,4'-diaminodiphenylmethane (abbreviated as b3-2) and 80 grams of N-methyl-2-pyrrolidone (abbreviated as NMP), And stir at room temperature until dissolved. Then, 9.82 g (0.045 mol) of pyromellitic dianhydride (abbreviated as a-1) and 20 g of NMP were added, and after reacting at room temperature for 2 hours, 1.08 g (0.005 mol) of a-1 is added in three equal parts three times, with an interval of 20 minutes each time. After the completion of the reaction, the reaction solution was poured into 1500 ml of water to precipitate the polymer. Then, the obtained polymer was filtered, washed with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60° C. to obtain the polymer (A-1-1).

Synthesis Example A-1-2

A nitrogen inlet, a stirrer, a condenser, and a thermometer are set on a four-necked conical flask with a volume of 500 ml, and nitrogen is introduced. Then, in a four-necked conical flask, add 3.23 grams (0.0125 mol) 1,3-bis(4-aminophenoxy) propane (referred to as b1-2), 6.70 grams (0.025 mol) as the formula ( b-2-1) the diamine compound (referred to as b2-1), 2.50 grams (0.0125 mol) 4,4'-diaminodiphenyl ether (referred to as b3-3) and 80 grams of NMP, and stir at room temperature until dissolved. Then, 8.82 g (0.045 mol) of 1,2,3,4-cyclobutane tetracarboxylic dianhydride (abbreviated as a-2) and 20 g of NMP were added and reacted at room temperature for 2 hours. Add 0.99 g (0.005 mol) of a-2 in two equal portions with an interval of 20 minutes. After the completion of the reaction, the reaction solution was poured into 1500 ml of water to precipitate the polymer. Then, the obtained polymer was filtered, washed with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60° C. to obtain the polymer (A-1-2).

Synthesis Example A-1-3

A nitrogen inlet, a stirrer, a condenser, and a thermometer are set on a four-necked conical flask with a volume of 500 ml, and nitrogen is introduced. Then, add 3.58g (0.0125mol) of 1,5-bis(4-aminophenoxy)pentane (referred to as b1-3), 5.95g (0.03mol) of b3 in a four-necked conical flask -2, 0.50 g (0.0025 mol) of b3-3 and 80 g of NMP, and stir at room temperature to dissolve. Then, 11.21 g (0.05 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride (abbreviated as a-3) and 20 g of NMP were added, and after reacting at room temperature for 2 hours, 0.99 Grams (0.005 mol) of b3-2 was added in three equal portions three times, with an interval of 20 minutes each time. After the completion of the reaction, the reaction solution was poured into 1500 ml of water to precipitate the polymer. Then, the obtained polymer was filtered, washed with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60°C to obtain the polymer (A-1-3).

Synthesis Example A-1-4

A nitrogen inlet, a stirrer, a condenser, and a thermometer are set on a four-necked conical flask with a volume of 500 ml, and nitrogen is introduced. Then, add 3.14 g (0.01 mol) of 1,7-bis(3-aminophenoxy) heptane (referred to as b1-4), 8.40 g (0.025 mol) in a four-necked conical flask. The diamine compound represented by formula (b-2-4) (abbreviated as b2-2), 1.08 g (0.010 mol) of b3-1 and 80 g of NMP, 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 after reacting at room temperature for 2 hours, 0.54 g (0.005 mol) of b3-1 was added in three equal portions. Every 20 minutes interval. After the completion of the reaction, the reaction solution was poured into 1500 ml of water to precipitate the polymer. Then, the obtained polymer was filtered, washed with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60°C to obtain the polymer (A-1-4).

Synthesis Example A-1-5

A nitrogen inlet, a stirrer, a condenser, and a thermometer are set on a four-necked conical flask with a volume of 500 ml, and nitrogen is introduced. Then, add 4.60 grams (0.02 mol) of bis(2-aminophenoxy)methane (referred to as b1-5), 5.94 grams (0.03 mol) of b3-2, and 60 grams in a four-necked conical flask NMP, and stir at room temperature until dissolved. Next, 10.30 g (0.0525 mol) of a-2 and 20 g of NMP were added, and after reacting at room temperature for 1 hour, 20 g of NMP was added and reacted at room temperature for 1 hour. After the completion of the reaction, the reaction solution was poured into 1500 ml of water to precipitate the polymer. Then, the obtained polymer was filtered, washed with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60° C. to obtain the polymer (A-1-5).

Synthesis Example A-1-6

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

Synthesis Example A-1-7

A nitrogen inlet, a stirrer, a condenser, and a thermometer are set on a four-necked conical flask with a volume of 500 ml, and nitrogen is introduced. Then, add 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 in a four-necked conical flask , And stir 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 in an ice bath for 30 minutes, and then cooled to room temperature in an ice bath for reaction 30 minutes. After the completion of the reaction, the reaction solution was poured into 1500 ml of water to precipitate the polymer. Then, the obtained polymer was filtered, washed with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60° C. to obtain the polymer (A-1-7).

Synthesis Example A-1-8

A nitrogen inlet, a stirrer, a condenser, and a thermometer are set on a four-necked conical flask with a volume of 500 ml, and nitrogen is introduced. Then, add 9.43 g (0.03 mol) of b1-4, 1.76 g (0.005 mol) of the diamine compound represented by formula (b-2-23) (abbreviated as b2-5) in a four-necked conical flask ), 1.62 g (0.015 mol) of b3-1 and 80 g of NMP, and stirred at room temperature until dissolved. Next, add 9.81 g (0.05 mol) of a1-2 and 20 g of NMP, and react at 60°C for 1 hour, then cool down to 40°C in an ice bath and react for 30 minutes, then cool down to room temperature in an ice bath for reaction 30 minutes. After the completion of the reaction, the reaction solution was poured into 1500 ml of water to precipitate the polymer. Then, the obtained polymer was filtered, washed with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60° C. to obtain the polymer (A-1-8).

Synthesis Example A-1-9

A nitrogen inlet, a stirrer, a condenser, and a thermometer are set on a four-necked conical flask with a volume of 500 ml, and nitrogen is introduced. Then, in a four-necked conical flask, add 8.05 g (0.035 mol) of b1-1, 1.48 g (0.005 mol) of the diamine compound represented by formula (b-2-28) (abbreviated as b2-6) ), 1.98 g (0.010 mol) of b3-2 and 80 g of NMP, and stir at room temperature until dissolved. Next, add 9.53 g (0.0425 mol) of a-3 and 20 g of NMP, and react at 60°C for 1 hour, then cool down to 40°C in an ice bath and react for 30 minutes, then cool down to room temperature in an ice bath. 1.12 g (0.005 mol) of a-3 was added in three equal portions three times, with an interval of 10 minutes each time. After the completion of the reaction, the reaction solution was poured into 1500 ml of water to precipitate the polymer. Then, the obtained polymer was filtered, washed with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60° C. to obtain the polymer (A-1-9).

Synthesis Example A-1-10

A nitrogen inlet, a stirrer, a condenser, and a thermometer are set on a four-necked conical flask with a volume of 500 ml, and nitrogen is introduced. Then, add 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, 2.00 g (0.010 mol) in a four-necked conical flask Mol) b3-3 and 80 grams of NMP, and stirred at room temperature until dissolved. Next, add 9.82 g (0.045 mol) of a-1 and 20 g of NMP, and react at 60°C for 1 hour, then cool down to 40°C in an ice bath and react for 30 minutes, then cool down to room temperature in an ice bath. 1.08 g (0.005 mol) of a-1 was added in four equal portions in four times, with an interval of 10 minutes each time. After the completion of the reaction, the reaction solution was poured into 1500 ml of water to precipitate the polymer. Then, the obtained polymer was filtered, washed with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60° C. to obtain the polymer (A-1-10).

Synthesis Example A-1-11

A nitrogen inlet, a stirrer, a condenser, and a thermometer are set on a four-necked conical flask with a volume of 500 ml, and nitrogen is introduced. Then, 11.45 g (0.04 mol) of b1-3, 0.81 g (0.0075 mol) of b3-1, and 80 g of NMP were added to the 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 and reacted at 60°C for 1 hour, then cooled to 40°C in an ice bath for reaction 30 Minutes later, cool down to room temperature in an ice bath, and add 0.54 g (0.005 mol) of b3-1 in three equal portions three times with an interval of 10 minutes. After the completion of the reaction, the reaction solution was poured into 1500 ml of water to precipitate the polymer. Then, the obtained polymer was filtered, washed with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60°C to obtain the polymer (A-1-11).

Synthesis Example A-1-12

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

Synthesis Example A-2-1

A nitrogen inlet, a stirrer, a condenser, and a thermometer are set on a four-necked conical flask with a volume of 500 ml, and nitrogen is introduced. Then, add 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 in a four-necked conical flask , And stir 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 three equal portions three times with an interval of 20 minutes each time. After the reaction is over, 97 g of NMP, 2.55 g of acetic anhydride and 7.91 g of pyridine are added, the temperature is raised to 60° C., and stirring is continued for 2 hours to carry out the imidization reaction. After the completion of the reaction, the reaction solution was poured into 1500 ml of water to precipitate the polymer. Then, the obtained polymer was filtered, washed with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60° C. to obtain the polymer (A-2-1).

Synthesis Example A-2-2

A nitrogen inlet, a stirrer, a condenser, and a thermometer are set on a four-necked conical flask with a volume of 500 ml, and nitrogen is introduced. Then, add 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 in a four-necked conical flask. , And stir at room temperature until dissolved. Next, 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 three equal portions three times with an interval of 20 minutes each time. After the reaction is over, 97 g of NMP, 2.55 g of acetic anhydride and 7.91 g of pyridine are added, the temperature is raised to 60° C., and stirring is continued for 4 hours to carry out the imidization reaction. The reaction solution was poured into 1500 ml of water to precipitate the polymer. Then, the obtained polymer was filtered, washed with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60°C to obtain the polymer (A-2-2).

Synthesis Example A-2-3

A nitrogen inlet, a stirrer, a condenser, and a thermometer are set on a four-necked conical flask with a volume of 500 ml, and nitrogen is introduced. Then, add 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 in a four-necked conical flask , And stir at room temperature until dissolved. Next, 10.30 g (0.0525 mol) of a-2 and 20 g of NMP were added. After reacting at room temperature for 1 hour, 20 g of NMP was added and reacted at room temperature for 2 hours. After the reaction is over, 97 g of NMP, 5.1 g of acetic anhydride and 11.86 g of pyridine are added, the temperature is raised to 50° C., and stirring is continued for 2 hours to carry out the imidization reaction. After the completion of the reaction, the reaction solution was poured into 1500 ml of water to precipitate the polymer. Then, the obtained polymer was filtered, washed with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60° C. to obtain the polymer (A-2-3).

Synthesis Example A-2-4

A nitrogen inlet, a stirrer, a condenser, and a thermometer are set on a four-necked conical flask with a volume of 500 ml, and nitrogen is introduced. Then, add 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, 3.00 g (0.015 mol) into a four-necked conical flask Mol) b3-3 and 80 grams of NMP, and stirred 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 60°C for 1 hour, then cooled to 40°C in an ice bath for 1 hour, and then cooled to room temperature in an ice bath for reaction 1 hour. After the reaction is over, 97 g of NMP, 5.1 g of acetic anhydride and 11.86 g of pyridine are added, the temperature is raised to 50° C., and stirring is continued for 4 hours to carry out the imidization reaction. After the completion of the reaction, the reaction solution was poured into 1500 ml of water to precipitate the polymer. Then, the obtained polymer was filtered, washed with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60°C to obtain the polymer (A-2-4).

Synthesis example A-2-5

A nitrogen inlet, a stirrer, a condenser, and a thermometer are set on a four-necked conical flask with a volume of 500 ml, and nitrogen is 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 and reacted at 60°C for 1 hour, then cooled to 40°C in an ice bath for reaction 30 Minutes later, the temperature was cooled down to room temperature in an ice bath, and 1.12 g (0.005 mol) of a-3 was added in three equal portions three times, with an interval of 10 minutes each time. After the reaction is over, 97 g of NMP, 7.65 g of acetic anhydride and 19.78 g of pyridine are added, the temperature is raised to 50° C., and stirring is continued for 4 hours to carry out the imidization reaction. After the completion of the reaction, the reaction solution was poured into 1500 ml of water to precipitate the polymer. Then, the obtained polymer was filtered, washed with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60°C to obtain the polymer (A-2-5).

Synthesis Example A-2-6

A nitrogen inlet, a stirrer, a condenser, and a thermometer are set on a four-necked conical flask with a volume of 500 ml, and nitrogen is introduced. Then, add 10.97 g (0.0425 mol) of b1-2, 0.82 g (0.0025 mol) of b2-4, and 80 g of NMP into a four-necked conical flask, and stir at room temperature until dissolved. Next, add 10.91 g (0.05 mol) of a-1 and 20 g of NMP, and react at 60°C for 1 hour, then cool down to 40°C in an ice bath and react for 30 minutes, then cool down to room temperature in an ice bath. 1.29 g (0.005 mol) of b1-2 was added in four equal portions in four times, with an interval of 10 minutes each time. After the reaction is over, 97 g of NMP, 7.65 g of acetic anhydride and 19.78 g of pyridine are added, the temperature is raised to 50° C., and stirring is continued for 4 hours to carry out the imidization reaction. After the completion of the reaction, the reaction solution was poured into 1500 ml of water to precipitate the polymer. Then, the obtained polymer was filtered, washed with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60°C to obtain the polymer (A-2-6).

Comparative Synthesis Example A’-1-1

A nitrogen inlet, a stirrer, a condenser, and a thermometer are set on a four-necked conical flask with a volume of 500 ml, and nitrogen is introduced. Then, in a four-necked conical flask, add 6.7 grams (0.025 mol) referred to as b2-1, 2.48 grams (0.0125 mol) b3-2, 2.50 grams (0.0125 mol) b3-3, and 80 grams of NMP, And stir at room temperature until dissolved. Then, 8.82 g (0.045 mol) of a-2 and 20 g of NMP were added, and after reacting at room temperature for 2 hours, 0.99 g (0.005 mol) of a-2 was added in three equal portions. Every 20 minutes interval. After the completion of the reaction, the reaction solution was poured into 1500 ml of water to precipitate the polymer. Then, the obtained polymer was filtered, washed with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60°C to obtain the polymer (A'-1-1).

Comparative Synthesis Example A’-1-2

A nitrogen inlet, a stirrer, a condenser, and a thermometer are set on a four-necked conical flask with a volume of 500 ml, and nitrogen is introduced. Then, in a four-necked conical flask, add 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 of NMP, and Stir at room temperature until dissolved. Then, 10.91 g (0.05 mol) of a-1 and 20 g of NMP were added, and after reacting at room temperature for 2 hours, 0.54 g (0.005 mol) of b3-1 was added in three equal portions. Every 20 minutes interval. After the completion of the reaction, the reaction solution was poured into 1500 ml of water to precipitate the polymer. Then, the obtained polymer was filtered, washed with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60°C to obtain the polymer (A'-1-2).

Comparative Synthesis Example A’-1-3

A nitrogen inlet, a stirrer, a condenser, and a thermometer are set on a four-necked conical flask with a volume of 500 ml, and nitrogen is 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 of NMP in a four-necked Erlenmeyer 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 after reacting at room temperature for 1 hour, 20 g of NMP was added and reacted at room temperature for 1 hour. After the completion of the reaction, the reaction solution was poured into 1500 ml of water to precipitate the polymer. Then, the obtained polymer was filtered, washed with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60°C to obtain the polymer (A'-1-3).

Comparative Synthesis Example A’-1-4

A nitrogen inlet, a stirrer, a condenser, and a thermometer are set on a four-necked conical flask with a volume of 500 ml, and nitrogen is introduced. Then, add 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 in a four-necked conical flask , And stir at room temperature until dissolved. Next, 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 the completion of the reaction, the reaction solution was poured into 1500 ml of water to precipitate the polymer. Then, the obtained polymer was filtered, washed with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60°C to obtain the polymer (A'-1-4).

Comparative Synthesis Example A’-2-1

A nitrogen inlet, a stirrer, a condenser, and a thermometer are set on a four-necked conical flask with a volume of 500 ml, and nitrogen is introduced. Then, add 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 in a four-necked conical flask , And stir at room temperature until dissolved. Next, 9.81 g (0.05 mol) of a-2 and 20 g of NMP were added. After reacting at room temperature for 2 hours, 97 g of NMP, 2.55 g of acetic anhydride and 7.91 g of pyridine were added, the temperature was raised to 60° C., and stirring was continued for 2 hours to proceed the imidization reaction. After the completion of the reaction, the reaction solution was poured into 1500 ml of water to precipitate the polymer. Then, the obtained polymer was filtered, washed with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60°C to obtain the polymer (A'-2-1).

Comparative Synthesis Example A’-2-2

A nitrogen inlet, a stirrer, a condenser, and a thermometer are set on a four-necked conical flask with a volume of 500 ml, and nitrogen is introduced. Then, add 0.97 grams (0.003 mol) of b2-3, 5.95 grams (0.030 mol) of b3-2, 3.00 grams (0.015 mol) of b3-3, and 80 grams of NMP in a four-necked conical flask, And stir 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 in an ice bath for 1 hour, and then cooled to room temperature in an ice bath for reaction 1 hour. After the reaction is over, 97 g of NMP, 2.55 g of acetic anhydride and 7.91 g of pyridine are added, the temperature is raised to 60° C., and stirring is continued for 4 hours to carry out the imidization reaction. The reaction solution was poured into 1500 ml of water to precipitate the polymer. Then, the obtained polymer was filtered, washed with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60°C to obtain the polymer (A'-2-2).

Manufacturing liquid crystal alignment agent

Example 1

In Example 1, 100 parts by weight of the polymer (A-1-1) and 800 parts by weight of N-methyl-2-pyrrolidone (B-1) were mixed at room temperature to prepare the liquid crystal of Example 1. Alignment agent. The specific composition of the liquid crystal alignment agent of Example 1 and the subsequent evaluation results are shown in Table 3.

Preparation of liquid crystal alignment film and liquid crystal display element

The liquid crystal alignment agent obtained in the above-mentioned Example 1 was formed by spin coating on a thin film transistor substrate with pixel electrodes and an active layer of IGZO, wherein the pixel electrodes had a pair of ITO electrodes (electrode Width: 10μm, electrode spacing: 10μm, electrode height: 50nm) IPS driving electrodes, the pair of ITO electrodes have comb-tooth shapes, and the comb-tooth-like parts of each other are arranged in a separate and interlocking manner . After that, it was preheated on a hot plate at 80°C for 2 minutes, and then heat treated at 230°C for 20 minutes to obtain a coating film with a thickness of 100 nm. Then, after the alignment treatment, a thin film transistor substrate with a liquid crystal alignment film is formed. Furthermore, a coating film is also formed on a glass substrate with a columnar spacer with a height of 4 μm which is used as an opposing substrate without pixel electrodes formed, and is also subjected to alignment treatment to obtain another liquid crystal alignment film. Then, using the two substrates as a set, the two substrates were bonded together in such a way that the rubbing direction of the two substrates was 180 degrees opposite to each other. Then, the liquid crystal MLC-2041 (manufactured by Merck) was injected by the pressure-reduced injection method and used The ultraviolet light hardening glue seals the liquid crystal injection port, and the ultraviolet light hardening glue is irradiated by an ultraviolet lamp, which is the liquid crystal display element of Example 1.

Examples 2 to 18 and Comparative Examples 1 to 6

Examples 2 to 18 and Comparative Examples 1 to 6 were carried out using the same method as Example 1, except that Examples 2 to 18 and Comparative Examples 1 to 6 changed the polymer, solvent, additives and the liquid crystal alignment agent. /Or its usage. For specific compositions and evaluation results of the liquid crystal alignment agents of Examples 2 to 18 and Comparative Examples 1 to 6, please refer to Table 3 and Table 4.

Comparative example 7

Comparative Example 7 was also performed using a method similar to that of Example 2, except that the active layer of the thin film transistor substrate prepared by the liquid crystal alignment film of Comparative Example 7 was Low Temperature Poly-silicon (LTPS). Please refer to Table 4 for the specific composition and evaluation results of Comparative Example 7.

Evaluation method

1. Impedance light stability

The above-mentioned liquid crystal alignment agent was respectively coated on a glass substrate with a comb-tooth patterned pixel electrode made of ITO (indium tin oxide) using a printer (manufactured by Nippon Printing Co., Ltd., model S15-036), To form a pre-coating layer. After that, the glass substrate was placed on a hot plate, and pre-heating was performed on the conditions of a temperature of 100°C and a time of 5 minutes. Then, in a circulating oven, post-heat treatment is performed under the conditions of a temperature of 220°C and a time of 30 minutes to obtain a glass substrate on which a liquid crystal alignment film with a thickness of 100 nm is formed, which is used for measuring impedance and light stability. Detection unit.

Use an ion density measurement system (manufactured by TOYO corporation; model 6254), set the frequency to 0.01 Hz and the amplitude to a voltage of 10V, and use the current flowing in the above-mentioned detection unit and the corresponding voltage , Measure the first impedance R _{i of the} detection unit, where the above-mentioned current is 3.16nA, and the above-mentioned measurement is carried out in an environment with a temperature of 23°C and a humidity of 50%; then, a white light-emitting diode ^{with an illuminance of 6mW/cm 2} After the body is irradiated to the detection unit for 300 seconds, and the second impedance R _{f is} measured, the following formula (1) is used to calculate the impedance optical stability (△R ^UV ): △R ^UV =R _i -R _f (1)

◎: △R ^UV <300GΩ.

○: 300GΩ≦△R ^UV <400GΩ.

△: 400GΩ≦△R ^UV <500GΩ.

×: 500GΩ≦△R ^UV .

2. Elimination of accumulated charge

The liquid crystal display elements prepared in Examples 1 to 18 and Comparative Examples 1 to 7 were respectively applied with a DC voltage of 3 volts for 30 minutes, and then the liquid crystal display elements were measured with an electrical measuring machine (manufactured by TOYO Corporation, Model 6254) _{The accumulated voltage (V R1} ) after the voltage is released (V _{R1) and the accumulated voltage (V R2} ) 15 minutes after the voltage is released, the accumulated charge elimination slope (V _S ) is calculated by the following formula (IV), and the evaluation is based on the following criteria:

※: 80%<V _S.

◎: 75%<V _S ≦80%.

○: 70%<V _S ≦75%.

△: 65%<V _S ≦70%.

×: V _S ≦65%.

Please refer to Table 3. The polymer (A) in the liquid crystal alignment agent of Examples 1 to 18 of the present invention is prepared by a specific manufacturing method and a specific diamine compound (b1), and a liquid crystal prepared by the above polymer (A) All the alignment agents have good impedance and light stability. The liquid crystal alignment agent of the above embodiment can form a liquid crystal alignment film on a thin film transistor substrate with an IGZO active layer, so as to produce a liquid crystal display element with good accumulated charge elimination properties. Furthermore, when the polymer (A) of the liquid crystal alignment agent is synthesized using a diamine compound (b2), and/or when the molar ratio of the diamine compound (b1) to the diamine compound (b2) is [(b1) When /(b2)] is in a specific range, the elimination of accumulated charge of the liquid crystal display element can be further improved.

On the other hand, according to Table 4, it can be seen that if the polymer (A) claimed in the present invention is not used to prepare the liquid crystal alignment agent, the required impedance light stability cannot be achieved, and the liquid crystal alignment film formed by the liquid crystal alignment agent The liquid crystal display element has poor elimination of accumulated charge. In addition, even if the polymer (A) claimed in the present invention is used to form a liquid crystal alignment agent with good impedance and light stability, if the prepared liquid crystal alignment film is not matched with a thin film transistor substrate with an IGZO active layer, the liquid crystal The display element has poor elimination of accumulated charge.

Although the present invention has been disclosed in several embodiments as above, it is not intended to limit the present invention. Anyone with ordinary knowledge in the technical field to which the present invention belongs can make various modifications without departing from the spirit and scope of the present invention. Modifications and modifications, therefore, the scope of protection of the present invention shall be subject to those defined by the attached patent application scope.

200‧‧‧Liquid crystal display element

210‧‧‧Unit 1

212‧‧‧Thin Film Transistor Substrate

214‧‧‧Pixel electrode

216‧‧‧The first liquid crystal alignment film

220‧‧‧Second Unit

222‧‧‧Second substrate

226‧‧‧Second liquid crystal alignment film

230‧‧‧LCD unit

Claims (11)

A method for manufacturing a liquid crystal alignment film includes coating a liquid crystal alignment agent on a thin-film transistor substrate to form a pre-coating layer, and subjecting the pre-coating layer to a pre-heating treatment, a post-heating treatment, and a The liquid crystal alignment film is prepared by alignment treatment, wherein the thin film transistor substrate includes an active layer of indium gallium zinc oxide (Indium Gallium Zinc Oxide; IGZO), and the liquid crystal alignment agent includes: polymer (A) , Which is obtained by the reaction of a mixture, wherein the mixture contains the tetracarboxylic dianhydride component (a) and the diamine component (b), and the diamine component (b) contains the formula (b-1) Said diamine compound (b1):

In the formula (b-1), the h represents an integer from 1 to 12; and a solvent (B), and the liquid crystal alignment film has an impedance optical stability △R ^UV less than 500 GΩ, and the impedance optical stability △ R ^UV is measured through the following steps: providing a detection unit, wherein the detection unit is composed of a substrate, a pixel electrode on the substrate, and the liquid crystal alignment film on the pixel electrode; using an ion Density measurement system, the frequency is set to 0.01Hz and the amplitude is set to a voltage of 10V, and the first impedance R _{i of} the detection unit is measured by the current flowing in the detection unit and the corresponding voltage, where the current is 3.16nA, and operating the first measuring impedance R _i of the one carried out at a temperature of 23 ℃ one and 50% humidity; illuminance 6mW / cm ² of white light emitting diode illuminating the detection unit 300 seconds and the measured _{The second impedance R f} of one of the detection units; and the following formula (1) is used to calculate the impedance optical stability (△R ^UV ): △R ^UV =R _i -R _f formula (1). The method for manufacturing a liquid crystal alignment film as described in the first item of the scope of patent application, wherein the impedance light stability △R ^{UV of} the liquid crystal alignment film is less than 400GΩ. According to the method for manufacturing a liquid crystal alignment film as described in item 1 of the scope of patent application, the impedance optical stability △R ^{UV of} the liquid crystal alignment film is less than 300 GΩ. The method for manufacturing a liquid crystal alignment film as described in the first item of the scope of patent application, wherein the diamine component (b) includes a diamine compound (b2) represented by the formula (b-2):

In the formula (b-2), _{each R 1} independently represents a hydrogen atom, an alkyl group having 1 to 10 carbons, an alkoxy group having 1 to 10 carbons, an acetamido group, a fluorine atom, and a chlorine atom. Or a bromine atom; _{each R 2} independently represents an alkyl group having a carbon number of 1 to 3; each m independently represents an integer from 0 to 3; and, the n represents an integer from 0 to 4. The method for manufacturing a liquid crystal alignment film as described in item 4 of the scope of patent application, wherein in the diamine compound (b2) of the formula (b-2), the R ₁ each independently represents a hydrogen atom, and the carbon number is 1 to 10 An alkyl group, an alkoxy group having a carbon number of 1 to 10, or an acetamido group. The method for manufacturing a liquid crystal alignment film as described in the first item of the scope of patent application, wherein the total mol based on the diamine component (b) is 100 mol, and the diamine represented by the formula (b-1) The amount of compound (b1) used is 15 to 95 mol. The method for manufacturing a liquid crystal alignment film as described in item 4 of the scope of patent application, wherein the total mol based on the diamine component (b) is 100 mol, and the diamine represented by the formula (b-2) The amount of compound (b2) used is 5 to 50 mol. The method for manufacturing a liquid crystal alignment film according to item 4 of the scope of patent application, wherein the molar ratio of the diamine compound (b1) to the diamine compound (b2) [(b1)/(b2)] is 0.5 to 10.0 . According to the method for manufacturing a liquid crystal alignment film as described in item 1 of the scope of patent application, the total usage amount based on the polymer (A) is 100 parts by weight, and the usage amount of the solvent (B) is 800 to 4000 parts by weight. According to the method for manufacturing a liquid crystal alignment film according to claim 1, wherein the thin film transistor base material includes: a first substrate; and a plurality of thin film transistor units arranged on the first substrate, wherein the thin film transistors Each of the transistor units includes a gate insulating layer, the active layer, a source and a drain. A liquid crystal display element includes a liquid crystal alignment film manufactured by the method for manufacturing a liquid crystal alignment film according to any one of the scope of the patent application to the 10th item.

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