TW201811864A - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display device - Google Patents

Abstract

A liquid crystal alignment agent capable of forming a liquid crystal alignment film with excellent accumulated charge removability, the liquid crystal alignment film, and the liquid crystal display element with the said liquid crystal alignment film are provided. The liquid crystal alignment agent includes a polymer (A), and a solvent (B). Polymer (A) is obtained by reacting a mixture. The mixture includes a tetracarboxylic dianhydride component (a) and a diamine component (b). The tetracarboxylic dianhydride component (a) includes a compound (a1) represented by formula (a-1).

Description

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

The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element, and more particularly to a liquid crystal alignment agent capable of quickly eliminating accumulated charge, a liquid crystal alignment film formed from the liquid crystal alignment agent, and the liquid crystal alignment film. Liquid crystal display element.

In recent years, various circles have been actively committed to the development of novel liquid crystal display elements. Taking a horizontal electric field type liquid crystal display element as an example, a horizontal electric field type liquid crystal display element has two electrodes on one side of a pair of opposing substrates, and the electrodes are dentate ( pectinate shape). These electrodes can generate an electric field parallel to the substrate, thereby controlling the liquid crystal molecules. The above-mentioned element is generally called an in-plane switching (IPS) type liquid crystal display element.

Japanese Patent Laid-Open No. 2002-131751 discloses a liquid crystal alignment agent using a diamine compound having a single benzene ring. Using the liquid crystal alignment agent, a liquid crystal alignment film having a pretilt angle of less than 2 ° can be obtained. A wide viewing angle and high contrast IPS type liquid crystal display element is obtained. However, the liquid crystal alignment agent has a problem that the accumulated charges are slowly eliminated, resulting in excessive residual charges, and further generation of afterimages. Therefore, how to provide a liquid crystal alignment agent capable of forming a liquid crystal alignment film with excellent charge storage elimination property, so that the formed liquid crystal alignment film can have better display quality when applied to a liquid crystal display element is actually a person skilled in the art. Problems to be solved.

In view of this, the present invention provides a liquid crystal alignment agent for a liquid crystal display element. The liquid crystal alignment film prepared by using the liquid crystal alignment agent can improve the problem of slow accumulation of charge elimination.

The invention provides a liquid crystal alignment agent, which includes a polymer (A) and a solvent (B). The polymer (A) is obtained by reacting a mixture, and the mixture includes a tetracarboxylic dianhydride component (a) and a diamine component (b). The tetracarboxylic dianhydride component (a) includes the compound (a1) represented by the formula (a-1): Formula (a-1) In formula (a-1), L ₁ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine atom, a chlorine atom, or bromine Atom; L ₂ each independently represents an alkyl group having 1 to 3 carbon atoms. a each independently represents an integer from 0 to 3; b represents an integer from 0 to 4.

In an embodiment of the present invention, the diamine component (b) includes a diamine compound (b1) represented by the formula (b-1): Formula (b-1) In formula (b-1), R ₁ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an acetamido group, or a fluorine atom. , A chlorine atom or a bromine atom; R ₂ each independently represents an alkyl group having 1 to 3 carbon atoms. m each independently represents an integer from 0 to 3; n represents an integer from 0 to 4.

In an embodiment of the present invention, in the formula (b-1), R ₁ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or acetamidine. Amine.

In an embodiment of the present invention, the diamine component (b) includes a diamine compound (b2) represented by the formula (b-2): Formula (b-2) In Formula (b-2), h represents an integer of 1-12.

In an embodiment of the present invention, the total mole number based on the tetracarboxylic dianhydride component (a) is 100 moles, and the amount of the compound (a1) represented by the formula (a-1) is 2 to 20 Mor.

In one embodiment of the present invention, the total mole number of the diamine component (b) is 100 moles, and the amount of the diamine compound (b1) represented by the formula (b-1) is 2 to 20 moles. ear.

In one embodiment of the present invention, the total mole number based on the diamine component (b) is 100 moles, and the amount of the diamine compound (b2) represented by the formula (b-2) is 10 to 80 moles. ear.

In one embodiment of the present invention, the total amount of the polymer (A) is 100 parts by weight, and the amount of the solvent (B) is 800 to 4000 parts by weight.

The present invention also provides a liquid crystal alignment film formed of the liquid crystal alignment agent as described above.

The present invention further provides a liquid crystal display device including the liquid crystal alignment film as described above.

Based on the above, since the liquid crystal alignment agent of the present invention contains the specific polymer (A), it is possible to form a liquid crystal alignment film that can quickly eliminate the accumulated charge.

In order to make the above features and advantages of the present invention more comprehensible, embodiments are hereinafter described in detail with reference to the accompanying drawings.

< Liquid crystal alignment agent > The present invention provides a liquid crystal alignment agent, which includes a polymer (A) and a solvent (B). In addition, if necessary, the liquid crystal alignment agent may further include an additive (C).

Hereinafter, each component of the liquid crystal alignment agent used in the present invention will be described in detail. Polymer ( A )

The polymer (A) is selected from a polyamic acid polymer, a polyimide polymer, a polyimide-based block copolymer, or any combination thereof. The polyimide-based block copolymer is selected from the group consisting of a polyimide block copolymer, a polyimide block copolymer, a polyimide-polyimide block copolymer, or Any combination of the above polymers.

The polyfluorinated acid polymer, the polyfluorinated imine polymer, and the polyfluorinated block copolymer in the polymer (A) may each include a tetracarboxylic dianhydride component (a) and a diamine component ( b) The mixture is prepared by reacting the tetracarboxylic dianhydride component (a), the diamine component (b), and the method for preparing the polymer (A) as follows. Tetracarboxylic dianhydride component ( a )

The tetracarboxylic dianhydride component (a) includes the compound (a1) represented by the formula (a-1), and other tetracarboxylic dianhydride compounds (a2). Compound ( a1 ) represented by formula (a-1 )

The compound (a1) represented by the formula (a-1) is shown below: Formula (a-1) In formula (a-1), L ₁ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine atom, a chlorine atom, or bromine Atom; L ₂ each independently represents an alkyl group having 1 to 3 carbon atoms. a each independently represents an integer from 0 to 3; b represents an integer from 0 to 4.

The compound (a1) represented by the formula (a-1) can be synthesized using a combination of standard methods of appropriate organic chemistry. Specific examples will be described below to describe the synthesis method of the compound (a1) represented by the formula (a-1).

Specifically, the compound (a1) represented by the formula (a-1) can be obtained through the following two-step reaction: Step (i): In the presence of a palladium compound, an organophosphorus compound, and a base, make it as follows The compound represented by the formula (a-1a) or (a-1b) is reacted in a solvent to form a compound represented by the following formula (a-1c). In this case, the solvent may contain a sulfinate. Step (ii): The carboxylic acid group in the compound represented by the following formula (a-1c) is subjected to a dehydration cyclization reaction to generate a tetracarboxylic dianhydride compound represented by the formula (a-1). In the formulae (a-1a) to (a-1c), the definitions of L ₁ , L ₂ , a, and b are the same as those in the formula (a-1). X represents a halogen atom, a substituted or unsubstituted alkylsulfonyloxy group, or a substituted or unsubstituted arylsulfonyloxy group. L ₃ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the alkyl group is a linear or branched type.

The alkyl group having a carbon number of 1 to 10 as defined by L ₃ may be methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, second butyl, n-pentyl, etc. Group.

Specific examples of the solvent include the following specific examples: methylene chloride, chloroform, dioxane, benzene, toluene, hexane, ethyl acetate, tetrahydrofuran, acetonitrile, acetone, and N, N-dimethylformamide. The solvent may be used singly or in combination of a plurality of solvents, and chloroform, toluene or hexane is preferred.

Specific examples of the palladium compound include the following specific examples: palladium acetate, palladium chloride, tris (dibenzylideneacetone) dipalladium, bis (dibenzylideneacetone) palladium, tetrakis (triphenylphosphine) palladium, [1,1'-bis (diphenylphosphine) ferrocene] dichloropalladium, bis (tri-o-tolylphosphine) palladium dichloride, bis (triphenylphosphine) palladium dichloride, acetamidine acetone Palladium, palladium carbon (Pd-C), dichlorobis (acetonitrile) palladium, di (phenylcyano) palladium chloride, (1,3-diisopropylimidazol-2-ylidene) (3-chloropyridyl) ) Palladium dichloride. The palladium compound is preferably palladium acetate, palladium chloride, or palladium carbon (Pd-C).

Specific examples of the organic phosphorus compound include the following specific examples: triphenylphosphine, tri (o-tolyl) phosphine, 9,9-dimethyl-4,5-bis (diphenylphosphino) xanthine, Tris (third butyl) phosphine, bis (third butyl) methylphosphine, diadamantylbutylphosphine, 1,1'-bis (diphenylphosphino) ferrocene, 1,2-di (Diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 2,2'-bis (diphenylphosphine) ) -1,1'-Binaphthyl, tricyclohexylphosphine, diphenylcyclohexylphosphine, dicyclohexylphenylphosphine, diphenylphosphinoferrocene, 2- (di-third-butylphosphino ) Biphenyl, tri (thirdbutyl) fluorene tetraphenylborate, and bis (thirdbutyl) methylfluorene tetraphenylborate. The organic phosphorus compound is preferably diadamantylbutylphosphine, tris (thirdbutyl) phosphine, tricyclohexylphosphine, or the like.

In addition, bis (tri-third-butylphosphine) palladium, dichlorobis (triphenylphosphine) palladium, dichlorobis (tricyclohexylphosphine) palladium, di (tri-cyclohexylphosphine) palladium, di Chlorobis (tri-o-tolylphosphine) palladium.

Specific examples of the base include the following specific examples: sodium tert-butoxide, sodium tert-pentoxide, cesium carbonate, sodium carbonate, potassium carbonate, and an aqueous solution of the aforementioned compound. The base is preferably sodium tripentoxide, sodium carbonate, potassium carbonate, or the like.

Specific examples of the sulfinate include the following specific examples: sodium methanesulfinate, sodium benzenesulfinate, and sodium p-toluenesulfinate. The sulfinate is preferably sodium benzenesulfinate or sodium p-toluenesulfinate.

In step (i), as a method of adding a compound represented by formula (a-1a), formula (a-1b), a palladium compound, an organic phosphorus compound, and a base to a solvent, the following method (a) can be used Any one of the methods (c): Method (a): All the compounds represented by formula (a-1a), formula (a-1b), palladium compound, organic phosphorus compound, and base are added to the solvent, and if necessary, The sulfinate is obtained by reacting at 15 ° C to the reflux temperature of the solvent. Method (b): first add the compound represented by formula (a-1a), palladium compound, organic phosphorus compound and base to the solvent, add sulfinate as needed, and react at 15-30 ° C for 15 minutes to 2 hours After that, the compound represented by the formula (a-1b) is added and reacted at a temperature of 15 ° C. to the reflux temperature of the solvent to obtain it. Method (c): First, add a palladium compound and an organic phosphorus compound to a solvent, and react at 15-30 ° C for 15 minutes to 2 hours; then, add a compound represented by formula (a-1a) and a base, as required Sulfinate is added; finally, the compound represented by formula (a-1b) is added and reacted at a temperature from 15 ° C to the reflux temperature of the solvent.

Among the above methods, method (b) is better than method (a) from the viewpoint of improving the stability of the reaction yield; method (c) is also better than method (b) from the viewpoint of improving the stability of the reaction yield during large-scale synthesis. Better.

The compound represented by formula (a-1c) obtained in step (i) can be first purified and purified by a known method such as column chromatography, recrystallization method or distillation method, and then carried out in step (ii). The reaction may be directly carried out in the step (ii) without going through the purification step.

The use amount of the compound represented by the formula (a-1a) is 1.0 mol, and the use amount of the compound represented by the formula (a-1b) is 1.0 to 4.0 mol, preferably 1.5 to 3.0 mol.

The use amount of the compound represented by the formula (a-1a) is 1.0 mol, and the use amount of the palladium compound is 0.004 to 0.4 mol, preferably 0.004 to 0.2 mol.

The use amount of the compound represented by the formula (a-1a) is 1.0 mol, and the use amount of the organic phosphorus compound is 0.004 to 0.4 mol, preferably 0.004 to 0.2 mol.

The use amount of the palladium compound is 1.0 mol, and the use amount of the organic phosphorus compound is 1.0 to 8.0 mol, preferably 1.0 to 2.0 mol.

The use amount of the compound represented by the formula (a-1a) is 1.0 mol, and the use amount of the base is 1.6 to 10.0 mol, preferably 4.0 to 6.0 mol.

The reaction temperature ranges from 15 ° C to the reflux temperature of the solvent, and the reaction time ranges from 1 hour to 24 hours.

In step (ii), as a method of subjecting a carboxylic acid group in the compound represented by the formula (a-1c) to a dehydration cyclization reaction, a known method such as an acetic anhydride method and a thermal dehydration method may be mentioned.

Specifically, when all of L ₃ in the compound represented by the formula (a-1c) is a hydrogen atom, as shown in the compound represented by the following formula (a-1d), a dehydration cyclization reaction can be performed to obtain the compound represented by the formula: Compound represented by (a-1): In the formula (a-1d), the definitions of L ₁ , L ₂ , a, and b are the same as those in the formula (a-1).

When the L ₃ moiety in the compound represented by the formula (a-1b) is a hydrogen atom, the compound represented by the formula (a-1c) formed with the compound represented by the formula (a-1a) is represented by the following formula (a- When shown in 1e), an intramolecular transesterification reaction can be performed to prepare a compound represented by formula (a-1): In the formula (a-1e), the definitions of L ₁ , L ₂ , a, and b are the same as those in the formula (a-1). L ₄ each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, wherein the alkyl group having 1 to 10 carbon atoms defined by L ₄ and the carbon number defined by L ₃ are The alkyl groups of 1 to 10 are the same and will not be repeated here.

Alternatively, when all of L ₃ in the compound represented by the formula (a-1c) is represented by L ₅ , as shown in the compound represented by the following formula (a-1f), it may be in the presence of an acid catalyst or a base catalyst. After the hydrolysis reaction with water to generate a compound represented by the formula (a-1d), a dehydration cyclization reaction is performed to obtain a compound represented by the formula (a-1): In the formula (a-1f), the definitions of L ₁ , L ₂ , a, and b are the same as those in the formula (a-1). L ₅ each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, wherein the alkyl group having 1 to 10 carbon atoms defined by L ₅ and the carbon number defined by L ₃ are The alkyl groups of 1 to 10 are the same and will not be repeated here.

Specific examples of the acid catalyst include, but are not limited to, hydrochloric acid, nitric acid, sulfuric acid, fluoric acid, oxalic acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acids or their anhydrides, ion exchange resins, and the like.

Specific examples of the base catalyst may include, but are not limited to, diethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethanolamine, triethanolamine, Sodium hydroxide, potassium hydroxide, amine-containing alkoxysilanes, ion exchange resins, etc.

Specific examples of the compound (a1) represented by the formula (a-1) include the following formulae (a-1-1) to (a-1-17), but are not limited to these specific examples: (A-1-1) (A-1-2) (A-1-3) (A-1-4) (A-1-5) (A-1-6) Formula (a-1-7) Formula (a-1-8) (A-1-9) Formula (a-1-10) (A-1-11) Formula (a-1-12) Formula (a-1-13) Formula (a-1-14) Formula (a-1-15) Formula (a-1-16) (A-1-17)

The total mole number based on the tetracarboxylic dianhydride component (a) is 100 moles, and the amount of the compound (a1) represented by the formula (a-1) is 2 to 20 moles, preferably 3 to 17 Mol, more preferably 4 to 15 Mol.

When the compound (a1) represented by the formula (a-1) is not contained in the tetracarboxylic dianhydride component (a), the accumulated charge elimination property of the obtained liquid crystal alignment film is not good. Other tetracarboxylic dianhydride compounds ( a2 )

Other tetracarboxylic dianhydride compounds (a2) include aliphatic tetracarboxylic dianhydride compounds, alicyclic tetracarboxylic dianhydride compounds, aromatic tetracarboxylic dianhydride compounds, from formula (a-2-1) to formula At least one of the tetracarboxylic dianhydride compounds represented by (a-2-6), or a combination of the aforementioned compounds.

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

Specific examples of the alicyclic tetracarboxylic dianhydride compound may include, but are not limited to, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4- Cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclo Butane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic acid Acid 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, bicyclo [2.2.2] -octane- 7-ene-2,3,5,6-tetracarboxylic dianhydride or a combination thereof.

Specific examples of the aromatic tetracarboxylic dianhydride compound may include, but are not limited to, 3,4-dicarboxyl-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, pyromellitic dianhydride, 2,2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'- Biphenylphosphonium tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3'-4,4'-di Phenylethane tetracarboxylic dianhydride, 3,3 ', 4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3', 4,4'-tetraphenylsilane tetracarboxylic acid 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 dianhydride, 3,3 ', 4,4'-diphenylsulfide tetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylarsine dianhydride, 4,4'-bis ( 3,4-dicarboxyphenoxy) diphenylpropane dianhydride (4,4'-bis (3,4-dicarboxy phenoxy) diphenylpropane dianhydride), 3,3 ', 4,4'-perfluoroisopropylidene Diphthalic 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 (tris Phenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride, ethylene glycol-bis (anhydrodehydrobenzene Triester), propylene glycol-bis (anhydrotrimellitate), 1,4-butanediol-bis (anhydrotrimellitate), 1,6-hexanediol-bis (anhydromellitate Esters), 1,8-octanediol-bis (anhydrotrimellitic acid esters), 2,2-bis (4-hydroxyphenyl) propane-bis (anhydrotrimellitic acid esters), 2,3,4 , 5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1 , 2-c] -furan-1,3-dione {(1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo- 3-furanyl) naphtho [1,2 -c] furan-1,3-dione)}, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5- (tetrahydro-2,5-dioxo-3- Furyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-ethyl-5- (tetrahydro-2 , 5-dioxo-3-furyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3, 3a, 4,5,9b-hexahydro-7-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1 , 3-diketone, 1,3,3a, 4,5,9b-hexahydro-7-ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ 1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo -3-furyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-ethyl-5- (tetra Hydrogen-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro -5,8-dimethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 5 -An aromatic tetracarboxylic dianhydride compound such as (2,5-dioxotetrahydrofuranyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride or a combination thereof.

The tetracarboxylic dianhydride compounds represented by the formula (a-2-1) to the formula (a-2-6) are shown below. (A-2-1) Formula (a-2-2) (A-2-3) (A-2-4) Formula (a-2-5) In formula (a-2-5), 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 Each may independently represent -H or alkyl. Specific examples of the tetracarboxylic dianhydride compound represented by the formula (a-2-5) include at least one of compounds represented by the formula (a-2-5-1) to the formula (a-2-5-3) . Formula (a-2-5-1) Formula (a-2-5-2) Formula (a-2-5-3) Formula (a-2-6) In formula (a-2-6), A ₄ represents a divalent group containing an aromatic ring; A ₅ and A ₆ may be the same or different, and each independently represents -H or an alkyl group. . The tetracarboxylic dianhydride compound represented by the formula (a-2-6) is preferably a compound represented by the formula (a-2-6-1). Formula (a-2-6-1)

Preferably, the other tetracarboxylic dianhydride compounds (a2) include, but are not limited to, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride Anhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetracarboxylic acid Hydronaphthalene-1-succinic dianhydride, pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, and 3,3', 4,4'-biphenyl Perylene tetracarboxylic dianhydride. The other tetracarboxylic dianhydride compounds (a2) may be used alone or in combination.

The total mole number based on the tetracarboxylic dianhydride component (a) is 100 moles, and the amount of the other tetracarboxylic dianhydride compound (a2) is 80 to 98 moles, preferably 83 to 97 moles. More preferably, it is 85 to 96 mol.

Based on the total mole number of the diamine component (b) is 100 moles, the amount of the tetracarboxylic dianhydride component (a) used is preferably from 20 moles to 200 moles; more preferably from 30 moles to 120 mol. Diamine component ( b )

The diamine component (b) includes a diamine compound (b1) represented by formula (b-1), a diamine compound (b2) represented by formula (b-2), and other diamine compounds (b3). Diamine compound ( b1 ) represented by formula (b-1 )

The diamine compound (b1) represented by the formula (b-1) is shown below: Formula (b-1) In formula (b-1), R ₁ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an acetamido group, or a fluorine atom. , A chlorine atom or a bromine atom; R ₂ each independently represents an alkyl group having 1 to 3 carbon atoms. m each independently represents an integer from 0 to 3; n represents an integer from 0 to 4.

In the formula (b-1), R ₁ is each preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an acetamido group.

Specific examples of the diamine compound (b1) represented by the formula (b-1) include, but are not limited to, at least one of the diamine compounds represented by the formula (b-1-1) to the formula (b-1-28). Formula (b-1-1) (B-1-2) Formula (b-1-3) Formula (b-1-4) Formula (b-1-5) Formula (b-1-6) Formula (b-1-7) Formula (b-1-8) Formula (b-1-9) Formula (b-1-10) Formula (b-1-11) Formula (b-1-12) Formula (b-1-13) Formula (b-1-14) Formula (b-1-15) Formula (b-1-16) (B-1-17) Formula (b-1-18) (B-1-19) Formula (b-1-20) Formula (b-1-21) Formula (b-1-22) Formula (b-1-23) Formula (b-1-24) Formula (b-1-25) (B-1-26) (B-1-27) Formula (b-1-28)

The diamine compound (b1) represented by the formula (b-1) may be used alone or in combination.

The total mole number based on the diamine component (b) is 100 moles, and the amount of the diamine compound (b1) represented by the formula (b-1) is 2 to 20 moles, preferably 3 to 17 moles. Ears, more preferably 4 to 15 moles.

When the diamine component (b) contains the diamine compound (b1) represented by the formula (b-1), the obtained liquid crystal alignment film has better accumulative charge elimination properties. Diamine compound ( b2 ) represented by formula (b-2 )

The diamine compound (b2) represented by the formula (b-2) is shown below: Formula (b-2) In Formula (b-2), h represents an integer of 1-12.

Specifically, the diamine compound (b2) represented by the formula (b-2) includes a diamine compound having a structure represented by the following formula (b-2-1) to formula (b-2-3): Formula (b-2-1) Formula (b-2-2) Formula (b-2-3) In formula (b-2-1) to formula (b-2-3), h represents an integer of 1 to 12.

Specific examples of the diamine compound having the structure represented by the formula (b-2-1) include bis (4-aminophenoxy) methane and 1,2-bis (4-aminophenoxy) ethyl. Alkane, 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 thereof.

Specific examples of the diamine compound having the structure represented by the formula (b-2-2) include bis (2-aminophenoxy) methane and 1,2-bis (2-aminophenoxy) ethyl. Alkane, 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 thereof.

Specific examples of the diamine compound having the structure represented by the formula (b-2-3) include bis (3-aminophenoxy) methane and 1,2-bis (3-aminophenoxy) ethyl. Alkane, 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 thereof.

Preferably, specific examples of the diamine compound (b2) represented by the formula (b-2) may be 1,3-bis (4-aminophenoxy) propane, 1,4-bis (4-amino group) Phenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) hexane, 1,7-bis (4-amine Phenylphenoxy) heptane, 1,8-bis (4-aminophenoxy) octane, 1,3-bis (2-aminophenoxy) propane, 1,4-bis (2-amine Phenylphenoxy) 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 and the like.

The total mole number based on the diamine component (b) is 100 moles, and the amount of the diamine compound (b2) represented by the formula (b-2) is 10 to 80 moles, preferably 15 to 75 moles. Ears, more preferably 20 to 70 moles.

When the diamine component (b) contains a diamine compound (b2) represented by the formula (b-2), the liquid crystal alignment film obtained has better charge accumulation eliminating ability. Other diamine compounds ( b3 )

Other diamine compounds (b3) include aliphatic diamine compounds, alicyclic diamine compounds, aromatic diamine compounds, and diamines having structures represented by formulae (b-3-1) to (b-3-29). An amine compound, or a combination thereof.

Specific examples of the aliphatic diamine compound include, but are not limited to, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane , 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-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) ethyl Alkane, or a combination of the above.

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

Specific examples of the aromatic diamine compound include, but are not limited to, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl Hydrazone, 4,4'-diaminobenzylanilide, 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-trimethylhydroindene, hexahydro-4,7-methyl bridged indenyl dimethylene diamine, 3,3'-diamino benzophenone, 3,4'-diamine di Benzophenone, 4,4'-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4- Aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] Hydrazone, 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 -Diaminofluorene, 9,9-bis (4-aminophenyl) fluorene, 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] hexafluoropropane, 4,4'-bis [(4-amino-2-trifluoro Methyl) phenoxy] -octafluorobiphenyl, 5- [4- (4-n-pentylcyclohexyl) cyclohexyl] phenyl-methylene-1,3-diaminobenzene {5- [ 4- (4-n-pentylcyclohexyl) cyclohexyl] phenylmethylene-1,3-diaminobenzene}, 1,1-bis [4- (4-aminophenoxy) phenyl] -4- (4-ethylphenyl ) Cyclohexane {1,1-bis [4- (4-aminophenoxy) phenyl] -4- (4-ethylphenyl) cyclohexane}, or a combination thereof.

The diamine compounds having structures represented by the formulae (b-3-1) to (b-3-29) are shown below. Formula (b-3-1) In formula (b-3-1), B ¹ represents , , , , ,or ; B ² represents a group having a steroid (cholesterol) skeleton, a trifluoromethyl group, a fluoro group, an alkyl group having 2 to 30 carbon atoms, or derived from pyridine, pyrimidine, triazine, piperidine, or piperazine, etc. A monovalent group containing a nitrogen atom ring structure.

Specific examples of the compound represented by the formula (b-3-1) include, but are not limited to, 2,4-diaminophenyl ethyl formate, 3,5-diaminophenyl Ethyl 3,5-diaminophenyl ethyl formate, 2,4-diaminophenyl propyl formate, 3,5-diaminophenyl propyl formate, 5-diaminophenyl propyl formate), 1-dodecoxy-2,4-diaminobenzene, 1-dodecoxy-2,4-diaminobenzene Benzene (1-hexadecoxy-2,4-diaminobenzene), 1-octadecoxy-2,4-diaminobenzene (1-octadecoxy-2,4-diaminobenzene), by the formula (b-3-1- 1) At least one of the compounds represented by the formula (b-3-1-6), or a combination of the aforementioned compounds.

The compounds represented by the formula (b-3-1-1) to the formula (b-3-1-6) are shown below. Formula (b-3-1-1) Formula (b-3-1-2) Formula (b-3-1-3) Formula (b-3-1-4) Formula (b-3-1-5) Formula (b-3-1-6)

In the formula (b-3-2) of formula (b-3-2), and B ¹ in the formula (b-3-1) B same as ^1, B ³ and B ⁴ each independently represents a divalent aliphatic ring, two Valent aromatic ring or divalent heterocyclic group; B ⁵ represents an alkyl group having 3 to 18 carbon atoms, an alkoxy group having 3 to 18 carbon atoms, a fluoroalkyl group having 1 to 5 carbon atoms, and a carbon number of 1 to 5 fluoroalkoxy, cyano or halogen atoms.

Specific examples of the compound represented by the formula (b-3-2) include at least one of compounds represented by the following formula (b-3-2-1) to the formula (b-3-2-13): Formula (b-3-2-1) Formula (b-3-2-2) Formula (b-3-2-3) Formula (b-3-2-4) Formula (b-3-2-5) Formula (b-3-2-6) Formula (b-3-2-7) Formula (b-3-2-8) Formula (b-3-2-9) Formula (b-3-2-10) Formula (b-3-2-11) Formula (b-3-2-12) Formula (b-3-2-13) In formula (b-3-2-1) to formula (b-3-2-13), s represents an integer of 3 to 12.

Formula (b-3-3) In formula (b-3-3), B ⁶ each independently represents a hydrogen atom, a fluorenyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, and a carbon number of 1 To 5 alkoxy or halogen atoms, and B ⁶ in each repeating unit may be the same or different; u represents an integer of 1 to 3.

Specific examples of the compound represented by the formula (b-3-3) include when u is 1: p-diaminebenzene, m-diaminebenzene, o-diaminebenzene, 2,5-diaminotoluene, and the like; When u 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 .; or when u is 3 : 1,4-bis (4'-aminophenyl) benzene and the like.

Specific examples of the compound represented by the formula (b-3-3) include preferably p-diaminebenzene, 2,5-diaminotoluene, 4,4'-diaminobiphenyl, 3,3'- Dimethoxy-4,4'-diaminobiphenyl, 1,4-bis (4'-aminophenyl) benzene or a combination thereof.

Formula (b-3-4) In Formula (b-3-4), w represents an integer of 1 to 5. The compound represented by the formula (b-3-4) is preferably 4,4'-diamino-diphenylsulfide.

Formula (b-3-5) In formula (b-3-5), B ⁷ and B ⁹ each independently represent a divalent organic group, and B ⁷ and B ⁹ may be the same or different; B ⁸ represents a derivative derived from pyridine , A divalent group having a cyclic structure containing a nitrogen atom such as pyrimidine, triazine, piperidine, or piperazine.

Formula (b-3-6) In formula (b-3-6), B ¹⁰ , B ¹¹ , B ^12, and B ¹³ each independently represent a hydrocarbon group having 1 to 12 carbon atoms, and B ¹⁰ , B ¹¹ , B ¹² And B ¹³ may be the same or different; x1 each independently represents an integer of 1 to 3; x2 represents an integer of 1 to 20.

Formula (b-3-7) In formula (b-3-7), B ¹⁴ represents an oxygen atom or a cyclohexyl group; B ¹⁵ represents a methylene group; B ¹⁶ represents a phenylene group or a cyclohexane group; B ¹⁷ represents a hydrogen atom or a heptyl group.

Specific examples of the compound represented by the formula (b-3-7) include a compound represented by the formula (b-3-7-1), a compound represented by the formula (b-3-7-2), or a combination thereof : Formula (b-3-7-1) Formula (b-3-7-2)

The compounds represented by the formula (b-3-8) to the formula (b-3-29) are shown below. Formula (b-3-8) Formula (b-3-9) Formula (b-3-10) Formula (b-3-11) Formula (b-3-12) Formula (b-3-13) Formula (b-3-14) Formula (b-3-15) Formula (b-3-16) Formula (b-3-17) Formula (b-3-18) Formula (b-3-19) Formula (b-3-20) Formula (b-3-21) Formula (b-3-22) Formula (b-3-23) Formula (b-3-24) Formula (b-3-25) Formula (b-3-26) Formula (b-3-27) Formula (b-3-28) Formula (b-3-29) In formulas (b-3-16) to (b-3-24), B ^{18 is} preferably an alkyl group having 1 to 10 carbon atoms or 1 to 10 carbon atoms. Alkoxy; B ¹⁹ preferably represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.

The other diamine compounds (b3) can be used alone or in combination.

Specific examples of other diamine compounds (b3) preferably include, but are not limited to, 1,2-diaminoethane, 4,4'-diaminodicyclohexylmethane, and 4,4'-diaminodiphenyl Methane, 4,4'-diaminodiphenyl ether, 5- [4- (4-n-pentylcyclohexyl) cyclohexyl] phenylmethylene-1,3-diaminobenzene, 1 , 1-bis [4- (4-aminophenoxy) phenyl] -4- (4-ethylphenyl) cyclohexane, ethyl 2,4-diaminophenylcarboxylate, p-di Amine benzene, m-diamine benzene, o-diamine benzene, compound represented by formula (b-3-1-1), compound represented by formula (b-3-1-2), 3-1-5), a compound represented by formula (b-3-2-1), a compound represented by formula (b-3-2-11), and a compound represented by formula (b-3-7-1 A compound represented by), a compound represented by formula (b-3-25), a compound represented by formula (b-3-28), or a combination thereof.

The total mole number based on the diamine component (b) is 100 moles, and the amount of other diamine compounds (b3) used is 0 to 88 moles, preferably 5 to 85 moles, and more preferably 10 to 80 Mor. Method for preparing polymer ( A )

The polymer (A) may include at least one of a polyamidic acid and a polyimide. The polymer (A) may further include a polyfluorene-based block copolymer. The methods for preparing the various polymers described above are further described below. Method for preparing polyamic acid

The method for preparing polyamic acid is to first dissolve the mixture in a solvent, wherein the mixture includes a tetracarboxylic dianhydride component (a) and a diamine component (b), and polymerize at a temperature of 0 ° C to 100 ° C. Condensation reaction. After reacting for 1 hour to 24 hours, the reaction solution is distilled under reduced pressure using an evaporator to obtain polyamic acid. Alternatively, the reaction solution is poured into a large amount of a lean solvent to obtain a precipitate. Then, the precipitate is dried under reduced pressure to obtain polyamic acid.

Based on the total mole number of the diamine component (b) is 100 moles, and the amount of the tetracarboxylic dianhydride component (a) is 20 to 200 moles; more preferably, the tetracarboxylic dianhydride group Part (a) is used in an amount of 30 to 120 mol.

The solvent used in the polycondensation reaction may be the same as or different from the solvent in the liquid crystal alignment agent described below, and the solvent used in the polycondensation reaction is not particularly limited as long as it can dissolve the reactant and the product. The solvent preferably includes, but is not limited to (1) an aprotic polar solvent, such as: N-methyl-2-pyrrolidinone (NMP), N, N-dimethylacetamide, Aprotic polar solvents such as N, N-dimethylformamide, dimethylmethylene sulfoxide, γ-butyrolactone, tetramethylurea or hexamethyl phosphate triamine; or (2) phenolic solvents, For example: m-cresol, xylenol, phenol or halogenated phenols. The use amount of the solvent used in the polycondensation reaction is preferably 200 parts by weight to 2000 parts by weight, and more preferably 300 parts by weight to 1800 parts by weight based on the total use amount of the mixture.

It is worth noting that in the polycondensation reaction, an appropriate amount of a lean solvent can be used in combination with the solvent, wherein the lean solvent does not cause the polyamic acid to precipitate. The lean solvent can be used singly or in combination, and it includes but is not limited to (1) alcohols, such as: methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butane Alcohols or alcohols such as triethylene glycol; (2) ketones, such as: ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; (3) esters, such as: Esters such as methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, or ethylene glycol ethyl ether acetate; (4) ethers, such as diethyl ether, Ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, or diethylene glycol dimethyl ether Ethers such as alkyl ethers; (5) halogenated hydrocarbons, such as: dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, or o-dichloro Halogenated hydrocarbons such as benzene; or (6) hydrocarbons, for example: hydrocarbons such as tetrahydrofuran, hexane, heptane, octane, benzene, toluene or xylene, or any combination of the above solvents. Based on the used amount of the diamine component (b) being 100 parts by weight, the amount of the lean solvent is preferably 0 to 60 parts by weight, and more preferably 0 to 50 parts by weight. Method for preparing polyfluorene

The method for preparing polyimide is obtained by heating the polyamidic acid prepared by the method for preparing polyamidic acid in the presence of a dehydrating agent and a catalyst. During the heating process, the arsenic acid functional group in the polyarsenic acid can be converted into the arsonimine functional group (that is, arsonimation) through a dehydration ring-closing reaction.

The solvent used in the dehydration ring-closing reaction may be the same as the solvent (B) in the liquid crystal alignment agent, so it will not be repeated here. The amount of the solvent used in the dehydration ring-closing reaction is preferably 200 to 2000 parts by weight, and more preferably 300 to 1800 parts by weight, based on 100 parts by weight of the polyamic acid used.

In order to obtain a better degree of polyimidation of the polyimide, the operating temperature of the dehydration ring-closing reaction is preferably 40 ° C to 200 ° C, and more preferably 40 ° C to 150 ° C. If the operating temperature of the dehydration ring-closing reaction is lower than 40 ° C, the imidization reaction is not complete, and the degree of imidization of the polyacid is reduced. However, if the operating temperature of the dehydration ring-closing reaction is higher than 200 ° C, the weight average molecular weight of the obtained polyfluorene imine is low.

The dehydrating agent used in the dehydration ring-closure reaction may be selected from acid anhydride compounds, and specific examples thereof include acid anhydride compounds such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride. Based on 1 mole of polyamic acid, the amount of dehydrating agent used is 0.01 to 20 moles. The catalyst used in the dehydration ring-closing reaction may be selected from (1) pyridine compounds, such as pyridine, trimethylpyridine, or dimethylpyridine; and (2) tertiary amine compounds, such as: Tertiary amines such as triethylamine. Based on the amount of dehydrating agent used is 1 mole, the amount of catalyst used can be 0.5 to 10 moles. Method for preparing polyfluorene imide block copolymer

The polyimide-based block copolymer is selected from the group consisting of a polyimide block copolymer, a polyimide block copolymer, a polyimide-polyimide block copolymer, or the above-mentioned polymerization. Any combination of things.

The method for preparing a polyfluorene-based block copolymer is preferably firstly dissolving a starting material in a solvent and performing a polycondensation reaction, wherein the starting material includes at least one polyamidic acid and / or at least one polyfluorene The imine may further include a tetracarboxylic dianhydride component (a) and a diamine component (b).

The tetracarboxylic dianhydride component and the diamine component in the starting material may be the same as the tetracarboxylic dianhydride component (a) and the diamine component (b) used in the method for preparing a polyamic acid, In addition, the solvent used in the polycondensation reaction may be the same as the solvent (B) in the liquid crystal alignment agent described below, and details are not described herein again.

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

The starting materials preferably include, but are not limited to, (1) two polyamido acids having different terminal groups and different structures; (2) two polyimines having different terminal groups and different structures; (3) ) Polyamidic acid and polyimide having different terminal groups and different structures; (4) Polyamidic acid, tetracarboxylic dianhydride component and diamine component, of which, tetracarboxylic dianhydride component And at least one of the diamine component is different from the structure of the tetracarboxylic dianhydride component and the diamine component used to form the polyamidic acid; (5) the polyamidoimide and the tetracarboxylic dianhydride group And diamine components, wherein at least one of the tetracarboxylic dianhydride component and the diamine component is different from the structure of the tetracarboxylic dianhydride component and the diamine component used to form the polyimide ; (6) at least one of a polyamine acid, a polyimide, a tetracarboxylic dianhydride component, and a diamine component, wherein at least one of the tetracarboxylic dianhydride component and the diamine component forms a polyamine The structure of the tetracarboxylic dianhydride component used by the acid or polyimide is different from that of the diamine component; (7) Two kinds of polyamidic acid, tetracarboxylic dianhydride component and diamine having different structures Component; (8) two structural phases Polyimide, tetracarboxylic dianhydride component and diamine component; (9) two polyamines and diamine components whose terminal groups are acid anhydride groups and different in structure; (10) two kinds of terminals Polyamines and tetracarboxylic dianhydride components whose groups are amine groups and are different in structure; (11) Polyimide and diamine components whose terminal groups are acid anhydride groups and are different in structure; or (12 ) Two kinds of polyimide and tetracarboxylic dianhydride components whose terminal groups are amine groups and have different structures.

As long as the efficacy of the present invention is not affected, the polyamidic acid, polyamidoimide, and polyamidoimide block copolymer are preferably terminally modified polymers after molecular weight adjustment. By using a terminal-modified polymer, the coating performance of the liquid crystal alignment agent can be improved. The method for preparing the terminal-modified polymer can be prepared by adding a polyfunctional compound while the polyamic acid is undergoing a polycondensation reaction.

Specific examples of monofunctional compounds include, but are not limited to (1) monobasic anhydrides, such as: maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecyl Monobasic anhydrides such as alkyl succinic anhydride or n-hexadecyl succinic anhydride; (2) monoamine compounds such as: aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, N-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecanylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecanylamine, Monoamine compounds such as n-octadecylamine or n-eicosylamine; or (3) monoisocyanate compounds, such as monoisocyanate compounds such as phenyl isocyanate or naphthyl isocyanate.

The polymer (A) of the present invention has a polystyrene-equivalent weight average molecular weight as measured by Gel Permeation Chromatography (GPC) of 5,000 to 50,000, preferably 6,000 to 48,000, and more preferably 7,000 to 45,000. Solvent ( B )

The solvent used in the liquid crystal alignment agent of the present invention is not particularly limited, as long as it is a soluble polymer (A) and any other component and does not react therewith, it is preferably the same as that in the aforementioned synthetic polyamide. The solvent to be used may be used in combination with the lean solvent used in the synthesis of the polyamic acid.

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

Based on 100 parts by weight of the polymer (A), 800 to 4000 parts by weight of the solvent (B), preferably 900 to 3500 parts by weight, and more preferably 1000 to 3000 parts by weight. Additive ( C )

To the extent that the efficacy of the present invention is not affected, the liquid crystal alignment agent may optionally add an additive (C), where the additive (C) includes an epoxy compound, a silane compound having a functional group, or a combination thereof. The function of the additive (C) is to improve the adhesion between the liquid crystal alignment film and the substrate surface.

Epoxy compounds 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 Propyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol di Glycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylylenediamine , 1,3-bis (N, N-diepoxypropylaminomethyl) cyclohexane, N, N, N ', N'-tetraepoxypropyl-4,4'-diaminodiamine Phenylmethane, 3- (N, N-diglycidyl) aminopropyltrimethoxysilane, or a combination of the foregoing.

The epoxy compound may be used alone or in combination.

The use amount of the epoxy compound may be 0 to 40 parts by weight, and preferably 0.1 to 30 parts by weight based on the use amount of the polymer (A).

Specific examples of the silane compound having a functional group include, but are not limited to, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2 -Aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyl Methyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyl Trimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriamine Ethylenetriamine, 10-trimethoxysilyl-1,4,7-triazine, 10-triethoxysilyl-1,4,7-triazine, 9-trimethoxysilane -3,6-diazinyl acetate, 9-triethoxysilyl-3,6-diazinyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N -Benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxy Silane, N- bis (oxyethylene) -3-aminopropyl trimethoxy Silane, N- bis (oxyethylene) -3-aminopropyl triethoxysilane Silane, or combinations of the above compounds.

The silane compound having a functional group may be used alone or in combination.

The use amount of the silane compound having a functional group may be 0 to 10 parts by weight, and preferably 0.5 to 10 parts by weight based on the use amount of the polymer (A).

The use amount of the additive (C) is preferably 0.5 to 50 parts by weight, and more preferably 1 to 40 parts by weight based on the total use amount of the polymer (A). < Manufacturing method of liquid crystal alignment agent >

The manufacturing method of the liquid crystal alignment agent is not particularly limited, and it can be prepared by a general mixing method. For example, the tetracarboxylic dianhydride component (a) and the diamine component (b) are first mixed uniformly to form a polymer (A). Next, the polymer (A) is added to the solvent (B) at a temperature of 0 ° C. to 200 ° C., and the additive (C) can be optionally added, and the stirring device can be continuously stirred until dissolved. Preferably, the solvent (B) is added to the polymer at a temperature of 20 ° C to 60 ° C. < Manufacturing method of liquid crystal alignment film >

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

Specifically, the preparation method of the liquid crystal alignment film may be, for example, applying a liquid crystal alignment agent on a surface of a substrate by a method such as a roll coating method, a spin coating method, a printing method, or an ink-jet method. To form a pre-coating. Then, a pre-bake treatment, a post-bake treatment, and an alignment treatment are performed on the pre-coat layer to obtain a substrate on which a liquid crystal alignment film is formed.

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

There is no particular limitation on the alignment treatment. Cloths made of fibers such as nylon, rayon, or cotton can be wound on a drum and aligned by rubbing in a certain direction.

The purpose of the post-baking treatment step is to make the polymer in the pre-coating layer undergo a further dehydration ring closure (fluorine imidization) reaction. The operating temperature of the post-baking treatment is preferably 150 ° C to 300 ° C, more preferably 180 ° C to 280 ° C, and even more preferably 200 ° C to 250 ° C. <Liquid crystal display device and manufacturing method>

The liquid crystal display element of the present invention includes a liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention. The manufacturing method of the liquid crystal display element is well known to those skilled in the art. Therefore, the following is simply stated.

FIG. 1 is a side view of a liquid crystal display element according to an embodiment of the present invention. The liquid crystal display element 100 includes a first unit 110, a second unit 120, and a liquid crystal unit 130. The second unit 120 is spaced apart from the first unit 110, and the liquid crystal unit 130 is disposed between the first unit 110 and the second unit 120. between.

The first unit 110 includes a first substrate 112, an electrode 114, and a first liquid crystal alignment film 116. The electrodes 114 are formed on the surface of the first substrate 112 in a dentate pattern, and the first liquid crystal alignment film 116 It is formed on the surface of the electrode 114.

The second unit 120 includes a second substrate 122 and a second liquid crystal alignment film 126. The second liquid crystal alignment film 126 is formed on a surface of the second substrate 122.

The first substrate 112 and the second substrate 122 are selected from transparent materials. The transparent materials include, but are not limited to, alkali-free glass, soda-lime glass, hard glass (Pales glass), and quartz glass used in liquid crystal display devices. , Polyethylene terephthalate, polybutylene terephthalate, polyether fluorene, polycarbonate, etc. The material of the electrode 114 is a transparent electrode selected from tin oxide (SnO ₂ ), indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ), or a metal electrode such as chromium.

The first liquid crystal alignment film 116 and the second liquid crystal alignment film 126 are the above-mentioned liquid crystal alignment films, respectively, and their function is to make the liquid crystal cell 130 form a pretilt angle, and the liquid crystal cell 130 can be driven by the parallel electric field generated by the electrode 114.

The liquid crystal used in the liquid crystal cell 130 may be used alone or in combination. The liquid crystal includes, but is not limited to, a diaminobenzene-based liquid crystal, a pyridazine-based liquid crystal, a shiff base-based liquid crystal, and an azo oxide. Azoxy liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, ester liquid crystal, terphenyl ), Biphenylcyclohexane-based liquid crystal, pyrimidine-based liquid crystal, dioxane-based liquid crystal, bicyclooctane-based liquid crystal, cubane-based liquid crystal, etc., and visible Need to add cholesterol type liquid crystals such as cholesterol (cholesteryl chloride), cholesterol nonanoate (cholesteryl nonanoate), cholesterol carbonate (cholesteryl carbonate), etc., or under the trade names "C-15", "CB-15 "Chiral" (manufactured by Merck), or ferroelectric liquid crystals such as p-decyloxymethylene-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 TN, STN, TFT, VA, IPS and other liquid crystal display elements. In addition, depending on the selected liquid crystal, it can also be used for liquid crystal display elements having different strong electromotive force or anti-strong electromotive force. Among the above-mentioned liquid crystal display elements, it is particularly suitable for an IPS-type liquid crystal display element.

Hereinafter, the present invention will be described in detail with examples, but the present invention is not limited to the contents disclosed in these examples. < Example > Synthesis example of tetracarboxylic dianhydride compound ( a1 )

The synthesis example a1-1 to a1-8 of the tetracarboxylic dianhydride compound (a1) will be described below: Synthesis example a1-1

A four-necked flask with a volume of 100 ml was provided with an argon inlet, a stirrer, a condenser, and a thermometer, and argon was introduced. Then, in a four-necked flask, 0.36 g (0.0042 mol) of piperazine, 36 mg (0.16 mmol) of palladium acetate, 56 mg (0.31 mmol) of sodium p-toluenesulfinate, 2.32 g (0.021 mole) of sodium tripentoxide was added to 14 ml of toluene. Then, 0.11 g (0.31 mmol) of diamantylbutylphosphine was added and stirred at room temperature for 30 minutes. Next, 1.06 g (0.0053 mole) of 4-chlorophthalic acid dissolved in 6 ml of toluene was added in an ice bath environment, and the reaction was stirred in the ice bath for 45 minutes. Next, 16 ml of 2 M hydrochloric acid was added in an ice-bath environment to generate a precipitate (a1-1 '). Finally, 1.08 g of the precipitate (a1-1 ′) and 21 g of acetic anhydride were subjected to a dehydration cyclization reaction at a temperature of 70 ° C. and a reaction time of 3 hours in a 50 ml reaction bottle. After the reaction is completed, the obtained product is filtered to obtain a tetracarboxylic dianhydride compound represented by formula (a-1-1). Synthesis example a1 -2

Synthesis Example a1-2 was prepared separately by the same procedure as Synthesis Example a1-1, and the difference was that 1.06 g (0.0053 mole) of 4-chlorophthalic acid was replaced with 1.54 g (0.0053 mole) Ear) of 3-iodophthalic acid to obtain a tetracarboxylic dianhydride compound represented by formula (a-1-15). Synthesis example a1 -3

Synthesis Example a1-3 was prepared separately by the same steps as Synthesis Example a1-1, and the difference was that 1.06 g (0.0053 mole) of 4-chlorophthalic acid was replaced with 1.58 g (0.0053 mole) Ear) of 5-bromo-3-butylphthalic acid to obtain a tetracarboxylic dianhydride compound represented by the formula (a-1-3). Synthesis example a1 -4

Synthesis Example a1-4 was prepared separately by the same procedure as Synthesis Example a1-1, and the difference was that 1.06 g (0.0053 mole) of 4-chlorophthalic acid was replaced with 1.86 g (0.0053 mole) Ear) of 5- (benzenesulfonyl) -3-methoxyphthalic acid to obtain a tetracarboxylic dianhydride compound represented by formula (a-1-6). Synthesis example a1 -5

Synthesis Example a1-5 was prepared separately by the same procedure as Synthesis Example a1-1, and the difference was that 1.06 g (0.0053 mole) of 4-chlorophthalic acid was replaced with 1.24 g (0.0053 mole) Ear) of 4,5-dichloro phthalic acid to obtain a tetracarboxylic dianhydride compound represented by the formula (a-1-8). Synthesis example a1 -6

A four-necked flask with a volume of 100 ml was provided with an argon inlet, a stirrer, a condenser, and a thermometer, and argon was introduced. Then, in a four-necked flask, 0.41 g (0.0041 mol) of 2-methylpiperazine, 36 mg (0.16 mmol) of palladium acetate, 56 mg (0.31 mmol) of p-toluenesulfinic acid Sodium, 2.32 g (0.021 mol) of sodium tertiary alcohol were added to 14 ml of toluene. Then, 0.11 g (0.31 mmol) of diamantylbutylphosphine was added and stirred at room temperature for 30 minutes. Next, 1.35 g (0.0052 mol) of 3,4-difluorodiethyl phthalate dissolved in 6 ml of toluene was added in an ice bath environment, and the reaction was stirred in the ice bath for 45 minutes. Next, 16 ml of 2 M hydrochloric acid was added in an ice-bath environment to generate a precipitate (a1-6 '). Next, 1.50 g of the precipitate (a1-6 ') and 20 ml of water, 2.4 g of potassium hydroxide, and 24 ml of ethanol were placed in a 100 ml three-necked flask at a temperature of 80 ° C for a reaction time of 3 hours The hydrolysis reaction was performed under the conditions of 2.5 ° C, and then sulfuric acid with a concentration of 2.5 M was added to make the reaction solution acidic to generate a precipitate (a1-6 ''). Finally, 1.21 g of the precipitate (a1-6 '') and 21 g of acetic anhydride were subjected to a dehydration cyclization reaction at a temperature of 70 ° C. and a reaction time of 3 hours in a 50 ml reaction bottle. After the reaction is completed, the obtained product is filtered to obtain a tetracarboxylic dianhydride compound represented by formula (a-1-12). Synthesis example a1 -7

Synthesis Example a1-7 was prepared separately by the same procedure as Synthesis Example a1-6, except that 0.36 g (0.0042 mol) of piperazine was replaced with 0.48 g (0.0042 mol) of 2,3 -Dimethylpiperazine to obtain a tetracarboxylic dianhydride compound represented by formula (a-1-2). Synthesis example a1-8

Synthesis Example a1-8 was prepared separately by the same procedure as Synthesis Example a1-6, and the difference was that 0.41 g (0.0041 mole) of 2-methylpiperazine was replaced with 0.59 g (0.0043 mole) 2,3,5,6-tetramethylpiperazine, replacing 1.35 g (0.0052 moles) of diethyl 3,4-difluorophthalate with 1.34 g of dichlorophthalate Ethyl dimethanol to obtain a tetracarboxylic dianhydride compound represented by formula (a-1-17). Synthesis example of polymer ( A )

Synthesis Example A-1-1 to Synthesis Example A-1-7, Synthesis Example A-2-1 to Synthesis Example A-2-7, and Comparative Synthesis Example A'-1-1, Polymer (A) will be described below. A'-2-1, A'-2-2: Synthesis example A-1-1

A 500 ml four-necked flask was provided with a nitrogen inlet, a stirrer, a condenser, and a thermometer, and nitrogen was introduced. Then, in a four-necked flask, 1.15 g (0.005 mole) of bis (4-aminophenoxy) methane (abbreviated as b2-1) and 2.16 g (0.02 mole) of p-diaminebenzene ( Referred to as b3-1), 4.96 g (0.025 mol) of 4,4'-diaminodiphenylmethane (referred to as b3-2) and 80 g of N-methyl-2-pyrrolidone (N-methyl -2-pyrrolidone (NMP), and stir at room temperature until dissolved. Next, 0.38 g (0.001 mole) of the tetracarboxylic dianhydride compound (abbreviated as a1-1) represented by the formula (a-1-1) and 9.6 g (0.049 mole) of 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride (abbreviated as a2-1) and 20 g of NMP, and reacted at room temperature for 2 hours. After the reaction is completed, the reaction solution is poured into 1500 ml of water to precipitate a polymer. Then, the obtained polymer was filtered, repeatedly washed with methanol and filtered three times, put into a vacuum oven, and dried at a temperature of 60 ° C. to obtain a polymer (A-1-1). Synthesis Example A-1-2 to A-1-7 and Comparative Synthesis Example A '-1-1

Synthesis Example A-1-2 to Synthesis Example A-1-7 and Comparative Synthesis Example A'-1-1 In the same procedure as Synthesis Example A-1-1, polymers (A-1-2) were prepared separately. To (A-1-7) and (A'-1-1), and the difference is that the type of monomer and its amount of use are changed (as shown in Table 1). Synthesis Example A-2-1

A 500 ml four-necked flask was provided with a nitrogen inlet, a stirrer, a condenser, and a thermometer, and nitrogen was introduced. Then, in a four-necked flask, 1.15 g (0.005 mol) of bis (4-aminophenoxy) methane (abbreviated as b2-1) and 3.97 g (0.020 mol) of 4,4'-di Amino diphenylmethane (abbreviated as b3-2), 10.86 g (0.025 mole) of a diamine compound (abbreviated as b3-3) represented by formula (b-3-28), and 80 g of N-formyl 2-Pyrrolidone (abbreviated as NMP), and stirred at room temperature until dissolved. Next, 0.38 g (0.001 mole) of a tetracarboxylic dianhydride compound (abbreviated as a1-1) represented by formula (a-1-1) and 14.7 g (0.049 mole) of 3,4-dicarboxyl were added. -1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride (abbreviated as a2-3) and 20 grams of NMP. After reacting at room temperature for 6 hours, 97 g of NMP, 2.55 g of acetic anhydride, and 19.75 g of pyridine were added, the temperature was raised to 60 ° C., and stirring was continued for 2 hours to carry out the imidization reaction. After the reaction is completed, the reaction solution is poured into 1500 ml of water to precipitate a polymer. Then, the obtained polymer was filtered, and repeatedly washed with methanol and filtered three times, put into a vacuum oven, and dried at a temperature of 60 ° C. to obtain a polymer (A-2-1). Synthesis Example A-2-2 to A-2-7 and Comparative Synthesis Example A '-2-1, A' -2-2

Synthesis Examples A-2-2 to A-2-7 and Comparative Synthesis Examples A'-2-1 and A'-2-2 were prepared in the same manner as in Synthesis Example A-2-1, respectively, and polymers (A -2-2) to (A-2-7) and (A'-2-1), (A'-2-2), and the difference is that: the type of monomer and its amount of use (as shown in the table 2).

The compounds corresponding to the numbers in Tables 1 and 2 are shown below.

[Table 1]

[Table 2] Examples and comparative examples of liquid crystal alignment agents, liquid crystal alignment films, and liquid crystal display elements

Examples 1 to 14 and Comparative Examples 1 to 3 of the liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element are described below: Example 1 a. Liquid crystal alignment agent

100 parts by weight of the polymer (A-1-1) and 800 parts by weight of N-methyl-2-pyrrolidone (abbreviated as B-1) were weighed and stirred at room temperature to form the liquid crystal of Example 1. Alignment agent. b. Liquid crystal alignment film and liquid crystal display element

The above-mentioned liquid crystal alignment agent was respectively applied to two glass substrates having a conductive film made of ITO (indium-tin-oxide) by a printer (manufactured by Japan Photo Printing Co., Ltd., model S15-036) to form a pre-form. coating. Thereafter, the glass substrate was placed on a hot plate, and pre-baked under conditions of a temperature of 100 ° C. and a time of 5 minutes. Next, post-baking was performed in a circulating oven under the conditions of a temperature of 220 ° C and a time of 30 minutes. Finally, after the alignment process, the glass substrate on which the liquid crystal alignment film of Example 1 is formed can be obtained.

One of the two glass substrates with the liquid crystal alignment film formed thereon was coated with hot-press adhesive, and the other one was coated with a 4 μm spacer. Next, the two glass substrates were bonded together, and then a pressure of 10 kg was applied with a hot press, and the bonding was performed by hot pressing at a temperature of 150 ° C. Then, liquid crystal injection was performed using a liquid crystal injection machine (made by Shimadzu Corporation, model number: ALIS-100X-CH). Next, the liquid crystal injection port is sealed with an ultraviolet curing adhesive, and the ultraviolet curing adhesive is hardened with the ultraviolet light, and the liquid crystal is subjected to an annealing treatment in an oven at a temperature of 60 ° C and a time of 30 minutes. That is, the liquid crystal display element of Example 1 can be obtained.

The liquid crystal display element of Example 1 was evaluated by each evaluation method described later, and the results are shown in Table 3. Examples 2 to 14

The liquid crystal alignment agent, the liquid crystal alignment film, and the liquid crystal display element of Example 2 to Example 14 were separately prepared in the same steps as in Example 1, and the difference was that the type of the component and its use amount were changed, as shown in Table 3, Table 4 shows. The liquid crystal display elements obtained in Examples 2 to 14 were evaluated in the evaluation method described later, and the results are shown in Tables 3 and 4. Comparative Examples 1 to 3

The liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element of Comparative Examples 1 to 3 were prepared in the same steps as in Example 1, except that the type of the component and the amount of use were changed, as shown in Table 4. . The liquid crystal display elements prepared in Comparative Examples 1 to 3 were evaluated in the evaluation method described later, and the results are shown in Table 4.

The compounds corresponding to the abbreviations in Tables 3 and 4 are shown below.

[table 3]

[Table 4] < Evaluation method > Elimination of accumulated charge

The liquid crystal display elements prepared in Examples 1 to 14 and Comparative Examples 1 to 3 were each applied with a DC voltage of 3 volts for 30 minutes, and then the liquid crystal display elements were measured with an electric measuring machine (manufactured by TOYO Corporation, model number 6254). to release accumulated voltage of the voltage (V _R1) and the voltage is released after 15 minutes accumulated voltage (V _R2), is calculated by the following formula (V) the accumulated charge elimination slope (V _S), and evaluated based on the following criteria: Formula (V) ◎: 70% <V _S. ○: 65% <V _S ≦ 70%. △: 60% <V _S ≦ 65%. ╳: V _S ≦ 60%. ＜ Evaluation results ＞

As can be seen from Tables 3 and 4, when the tetracarboxylic dianhydride component (a) of the polymer (A) in the liquid crystal alignment agent does not include the compound (a1) represented by the formula (a-1) (Comparative Example 1) To 3), the stored charge erasability of the liquid crystal display element is not good.

In addition, when the diamine component (b) of the polymer (A) in the liquid crystal alignment agent includes the diamine compound (b1) represented by the formula (b-1) (Examples 3 to 6, 10 to 13), It is also possible to further improve the stored charge erasability of the liquid crystal display element.

In addition, when the diamine component (b) of the polymer (A) in the liquid crystal alignment agent includes the diamine compound (b2) represented by the formula (b-2) (Examples 1 to 4, 8 to 11), It is possible to further improve the stored charge erasability of the liquid crystal display element.

In summary, in the liquid crystal alignment agent of the present invention, since the tetracarboxylic dianhydride component (a) in the mixture forming the polymer (A) includes the compound (a1) represented by the formula (a-1), The liquid crystal alignment film prepared by using the liquid crystal alignment agent can improve the problem of slow accumulation of charge and elimination.

On the other hand, in the liquid crystal alignment agent of the present invention, the diamine component (b) in the mixture forming the polymer (A) includes a diamine compound (b1) selected from the formula (b-1) and Any one or more of the diamine compounds (b2) represented by (b-2) can further improve the stored charge erasability of the liquid crystal display element, and is therefore suitable for producing a liquid crystal alignment film and a liquid crystal display element.

Although the present invention has been disclosed as above with the examples, it is not intended to limit the present invention. Any person with ordinary knowledge in the technical field can make some modifications and retouching without departing from the spirit and scope of the present invention. The protection scope of the present invention shall be determined by the scope of the attached patent application.

100‧‧‧LCD display element

110‧‧‧ Unit 1

112‧‧‧First substrate

114‧‧‧ electrode

116‧‧‧The first liquid crystal alignment film

120‧‧‧ Unit 2

122‧‧‧Second substrate

126‧‧‧Second LCD alignment film

130‧‧‧LCD unit

FIG. 1 is a side view of a liquid crystal display element according to an embodiment of the present invention.

Claims (10)

A liquid crystal alignment agent includes: a polymer (A); and a solvent (B), wherein the polymer (A) is obtained by reacting a mixture including a tetracarboxylic dianhydride component (a) and A diamine component (b), and the tetracarboxylic dianhydride component (a) includes a compound (a1) represented by the formula (a-1): Formula (a-1) In formula (a-1), L ₁ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine atom, a chlorine atom, or bromine An atom; L ₂ each independently represents an alkyl group having 1 to 3 carbon atoms; a each independently represents an integer of 0 to 3; b represents an integer of 0 to 4; The liquid crystal alignment agent according to item 1 of the scope of patent application, wherein the diamine component (b) includes a diamine compound (b1) represented by the formula (b-1): Formula (b-1) In formula (b-1), R ₁ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an acetamido group, or a fluorine atom. , A chlorine atom or a bromine atom; R ₂ each independently represents an alkyl group having 1 to 3 carbon atoms; m each independently represents an integer of 0 to 3; n represents an integer of 0 to 4; The liquid crystal alignment agent according to item 2 of the scope of patent application, wherein in the formula (b-1), each of R ₁ independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a carbon number of 1 to 10 Alkoxy or acetamido. The liquid crystal alignment agent according to item 1 of the scope of patent application, wherein the diamine component (b) includes a diamine compound (b2) represented by the formula (b-2): Formula (b-2) In Formula (b-2), h represents an integer of 1-12. The liquid crystal alignment agent according to item 1 of the scope of patent application, wherein the total mole number based on the tetracarboxylic dianhydride component (a) is 100 moles, and the compound represented by the formula (a-1) (A1) is used in an amount of 2 to 20 mol. The liquid crystal alignment agent according to item 2 of the scope of patent application, wherein the total mole number based on the diamine component (b) is 100 moles, and the diamine compound represented by formula (b-1) ( b1) is used in an amount of 2 to 20 moles. The liquid crystal alignment agent according to item 4 of the scope of patent application, wherein the total mole number based on the diamine component (b) is 100 moles, and the diamine compound represented by formula (b-2) ( b2) The amount used is 10 to 80 mol. The liquid crystal alignment agent according to item 1 of the scope of patent application, wherein based on the total used amount of the polymer (A) is 100 parts by weight, and the used amount of the solvent (B) is 800 to 4000 parts by weight. A liquid crystal alignment film is formed from the liquid crystal alignment agent according to any one of the first to eighth patent application scopes. A liquid crystal display element includes the liquid crystal alignment film according to item 9 of the scope of patent application.