KR20160090879A - Liquid crystal aligning agent and liquid crystal display element using same - Google Patents

Abstract

A polyimide precursor comprising a diamine-containing diamine component represented by the following formulas (1) and (2), a polyimide precursor obtained by reaction of a tetracarboxylic acid derivative, and a polyimide obtained by imidizing the polyimide precursor, Liquid crystal aligning agent. N in the formula (2) is an integer of 1, 3 or 5.

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal aligning agent and a liquid crystal display element using the liquid crystal aligning agent.

The present invention relates to a liquid crystal aligning agent used in the production of a liquid crystal display element, a liquid crystal alignment film obtained from the liquid crystal aligning agent, and a liquid crystal display element using the liquid crystal alignment film.

BACKGROUND ART A liquid crystal display device is known as a lightweight, thin and low power consumption display device. In recent years, even in the fixed three liquid crystal display devices for cellular phones and tablet-type terminals, which have rapidly increased their share, a remarkable development has been achieved in which high display quality is required.

A liquid crystal display element is constituted by sandwiching a liquid crystal layer by a pair of transparent substrates provided with electrodes. In the liquid crystal display element, an organic film made of an organic material is used as a liquid crystal alignment film so that the liquid crystal is in a desired alignment state between the substrates. That is, the liquid crystal alignment film is formed as a constituent member of the liquid crystal display element on the surface of the substrate which holds the liquid crystal in contact with the liquid crystal, and plays a role of orienting the liquid crystal in a certain direction between the substrates. This liquid crystal alignment film plays a major role in the liquid crystal display element because it determines the alignment uniformity of the liquid crystal molecules and the pretilt angle with respect to the substrate and greatly affects the electric characteristics of the display element.

Among them, the pretilt angle of the liquid crystal is one of important parameters that determine display characteristics, and it is required to control the pretilt angle to a proper value in accordance with the mode of the liquid crystal display element. For example, in a mode called IPS (In Plane Switching) or FFS (Fringe Field Switching), it is considered that the lower the pretilt angle, the wider the viewing angle and the better the color reproducibility. It is known that a liquid crystal alignment layer having an alkylene structure in the main chain of polyimide is obtained (see Patent Documents 1 and 2).

Japanese Patent Application Laid-Open No. 10-123532 Japanese Patent Application Laid-Open No. 2000-80164

However, in recent years, along with the enhancement of performance of mobile phones and tablet-type terminals, not only a good orientation but also a lower tilt angle are required. On the other hand, a liquid crystal alignment film containing a polyamic acid or a polyamic acid ester using 1,2-bis (4-aminophenoxy) ethane as a diamine component has a favorable alignment property and a remarkably low pretilt angle However, such a polyamic acid or polyamic acid ester is one of the main solvents for liquid crystal aligning agents, and has excellent printability and thickening property, and has low concern for regulatory matters. And the lack of solubility in water. An object of the present invention is to provide a liquid crystal aligning agent which realizes good liquid crystal alignability and low tilt angle and is highly soluble in? -Butyrolactone.

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above problems, and have completed the present invention. That is, the gist of the present invention is as follows.

1. A polyimide precursor obtained by reaction of a diamine component containing diamines of the following formulas (1) and (2) with a tetracarboxylic acid derivative and at least one polymer selected from a polyimide obtained by imidizing the polyimide precursor Containing liquid crystal aligning agent.

[Chemical Formula 1]

N in the formula (2) is an integer of 1, 3 or 5.

2. The liquid crystal aligning agent according to 1 above, wherein the diamine of the formula (1) is 10 to 90 mol% of the diamine component.

3. The liquid crystal aligning agent according to 1 or 2 above, wherein the diamine of the formula (2) is 10 to 90 mol% of the diamine component.

4. The liquid crystal aligning agent according to any one of 1 to 4 above, wherein the tetracarboxylic acid derivative contains an aliphatic structure or an alicyclic group structure in its structure.

5. The liquid crystal aligning agent according to any one of 1 to 4 above, wherein the tetracarboxylic acid derivative containing an aliphatic structure or alicyclic group structure in the structure is 10 to 100 mol% of the total tetracarboxylic acid derivative.

6. The liquid crystal aligning agent according to any one of 1 to 5 above, wherein the carboxylic acid derivative is a dicarboxylic acid diester.

7. A liquid crystal alignment film obtained by applying the liquid crystal aligning agent according to any one of 1 to 6 above to a substrate and baking.

8. A liquid crystal display element having the liquid crystal alignment film according to 7 above.

By using the liquid crystal aligning agent of the present invention, it is possible to produce a liquid crystal display element having good liquid crystal alignability and low tilt angle characteristics, and therefore, it can be suitably used for a liquid crystal display having a large screen and a high screen resolution. Further, since the polymer used in the liquid crystal aligning agent of the present invention has good solubility to? -Butyrolactone, the liquid crystal aligning agent of the present invention has good storage stability and excellent printing property and thickening property .

<Specific diamine>

The liquid crystal aligning agent of the present invention is a polyimide precursor obtained by reacting a diamine component containing a diamine of the following formulas (1) and (2) with a tetracarboxylic acid derivative, and a polyimide precursor And is a liquid crystal aligning agent containing one kind of polymer.

(2)

N in the formula (2) is an integer of 1, 3 or 5.

Among the polymers, the polyamic acid ester using the diamine of the formula (1) contributes to the improvement of the liquid crystal alignability and the low-tilt angle characteristics, but the contribution to the improvement of the solubility to the? -Butyrolactone is small.

On the other hand, the polyamic acid ester using the diamine of the formula (2) contributes to improvement in the solubility of the polymer, but has a small contribution to the low pretilt angularity and liquid crystal alignability.

That is, at least one kind of polymer selected from the polyamic acid ester obtained by the reaction of the diamine component containing the diamine of the formula (1) and the formula (2) with the dicarboxylic acid diester and the polyimide obtained by imidating it , The above three characteristics can be satisfied at the same time.

The diamine of the formula (1) is preferably 10 to 90 mol%, more preferably 10 to 70 mol%, of the total diamine component.

The diamine of the formula (2) is preferably 10 to 90 mol%, more preferably 30 to 90 mol%, of the total diamine component.

<Polymer>

The polyimide precursor obtained by the reaction of the diamine-containing diamine component of the above formulas (1) and (2) with the tetracarboxylic acid derivative can be represented as follows.

(3)

In the formula (3), Y is a divalent organic group derived from a diamine component, X is a tetravalent organic group derived from a tetracarboxylic acid derivative, A ¹ and A ² are each independently a hydrogen atom or a substituent An alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms which may have a substituent, an alkynyl group having 1 to 10 carbon atoms which may have a substituent, R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, Y (4) and (5).

[Chemical Formula 4]

In the formula (5), n is an integer of 1, 3 or 5.

&Lt; Tetracarboxylic acid derivative &gt;

The tetracarboxylic acid derivative used in the synthesis of the liquid crystal aligning agent of the present invention includes tetracarboxylic acid dianhydride, tetracarboxylic acid monoanhydride, tetracarboxylic acid, dicarboxylic acid dialkyl ester, dicarboxylic acid chloride di Alkyl esters and the like, but the reaction is not limited to these as long as the reaction with the diamine proceeds.

In the formula (3), X is a tetravalent organic group derived from a tetracarboxylic acid derivative, and its structure is not particularly limited. Specific examples of X include X-1 to X-44 shown below.

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

In the formula (X-1), R ² to R ⁵ each independently represent a hydrogen atom, a methyl group or a phenyl group.

In the formula (3), X may be one kind or two or more kinds may be mixed, and it is preferable that at least one X having an alicyclic structure or an aliphatic structure is contained. The preferred ratio of X having an alicyclic structure or aliphatic structure is 10 mol% or more, more preferably 30 mol% or more, and even more preferably 50 mol% or more of the total amount of X.

(X-1) to (X-16), (X-23) to (X-27) and (X-41) to (X-43) are preferable as the structure of X having an alicyclic structure or an aliphatic structure (X-1), (X-7), (X-9), (X-23) and (X-24).

Specific examples of the alkyl group in R ¹ in the formula (3) include methyl, ethyl, propyl, i-propyl, n-butyl, i- N-pentyl group, and the like.

In formula (3), A ¹ and A ² each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, an alkenyl group having 1 to 10 carbon atoms which may have a substituent, An alkynyl group having 1 to 10 carbon atoms.

Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a hexyl group, an octyl group, a decyl group, a cyclopentyl group, a cyclohexyl group and a bicyclohexyl group. As the alkenyl group, those having at least one CH-CH structure present in the alkyl group described above are substituted with a C = C structure, and more specifically, a vinyl group, an aryl group, a 1-propenyl group, A phenyl group, a 2-butenyl group, a 1,3-butadienyl group, a 2-pentenyl group, a 2-hexenyl group, a cyclopropenyl group, a cyclopentenyl group and a cyclohexenyl group. As the alkynyl group, those having at least one CH ₂ -CH ₂ structure present in the above alkyl group substituted with a C≡C structure can be mentioned, and more specifically, an ethynyl group, 1-propynyl group, 2-propynyl group And the like.

The above alkyl group, alkenyl group and alkynyl group may have a substituent, or may form a cyclic structure by a substituent. The formation of a ring structure by a substituent means that a substituent group or a substituent group and a part of the parent skeleton are bonded to form a ring structure.

Examples of the substituent include a halogen group, a hydroxyl group, a thiol group, a nitro group, an aryl group, an organoxy group, an organotio group, an organosilyl group, an acyl group, an ester group, a thioester group, , An alkenyl group, and an alkynyl group.

Examples of the halogen group as a substituent include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

As the aryl group as a substituent, a phenyl group can be mentioned. These aryl groups may be further substituted with other substituents described above.

The organoxy group as a substituent may represent a structure represented by O-R. These R may be the same or different and may be exemplified by the alkyl, alkenyl, alkynyl, and aryl groups described above. These R may be further substituted with the aforementioned substituents. Specific examples of the organoxy group include a methoxy group, ethoxy group, propyloxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group and octyloxy group.

The organotio group which is a substituent may represent a structure represented by -S-R. As R, examples of the alkyl group, alkenyl group, alkynyl group, aryl group and the like can be mentioned. These R may be further substituted with the aforementioned substituents. Specific examples of the organotitanium group include methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, heptylthio group and octylthio group.

The organosilyl group as a substituent may represent a structure represented by -Si- (R) ₃ . These R may be the same or different and may be exemplified by the alkyl, alkenyl, alkynyl, and aryl groups described above. These R may be further substituted with the aforementioned substituents. Specific examples of the organosilyl group include a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a tripentylsilyl group, a trihexylsilyl group, a pentyldimethylsilyl group, a hexyldimethylsilyl group, .

The acyl group as a substituent may represent a structure represented by -C (O) -R. As R, examples of the alkyl group, alkenyl group, aryl group, and the like may be mentioned. These R may be further substituted with the aforementioned substituents. Specific examples of the acyl group include a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group, and a benzoyl group.

The ester group as a substituent may represent a structure represented by -C (O) O-R or -OC (O) -R. As R, examples of the alkyl group, alkenyl group, alkynyl group, aryl group and the like can be mentioned. These R may be further substituted with the aforementioned substituents.

The thioester group which is a substituent may represent a structure represented by -C (S) O-R or -OC (S) -R. As R, examples of the alkyl group, alkenyl group, alkynyl group, aryl group and the like can be mentioned. These R may be further substituted with the aforementioned substituents.

The phosphoric acid ester group which is a substituent may represent a structure represented by -OP (O) - (OR) ₂ . These R may be the same or different and may be exemplified by the alkyl, alkenyl, alkynyl, and aryl groups described above. These R may be further substituted with the aforementioned substituents.

Examples of the amide group as the substituent include a group represented by -C (O) NH ₂ or a group represented by -C (O) NHR, -NHC (O) R, -C (O) N (R) ₂ or -NRC Lt; / RTI &gt; These R may be the same or different and may be exemplified by the alkyl, alkenyl, alkynyl, and aryl groups described above. These R may be further substituted with the aforementioned substituents.

Examples of the aryl group as the substituent include the same aryl groups as those described above. These aryl groups may be further substituted with other substituents described above.

Examples of the alkyl group as the substituent include the same alkyl groups mentioned above. These alkyl groups may be further substituted with other substituents described above.

Examples of the alkenyl group as the substituent include the same alkenyl groups as those described above. This alkenyl group may be further substituted with another substituent as described above.

Examples of the alkynyl group as the substituent include the same alkynyl groups as mentioned above. These alkynyl groups may be further substituted with other substituents described above.

In general, when introducing a bulky structure, there is a possibility that the reactivity of the amino group and the liquid crystal orientation may be lowered. Therefore, as A ¹ and A ² , a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent is more preferable And a hydrogen atom, a methyl group or an ethyl group is particularly preferable.

<Other diamines>

In formula (3), at least a part of Y is a structure of formula (4) and formula (5), but Y is not limited to them and may include other structures. Examples of other structures of Y include Y-1 to Y-115 shown below.

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 22]

(23)

&Lt; EMI ID =

(25)

[Chemical Formula 1]

(In the formula (Y-102), m and n are each an integer of 1 to 11, and m + n is an integer of 2 to 12. In the formula (Y-107), h is an integer of 1 to 3, (Y-104) and (Y-111), j is an integer of 0 to 3. In the formulas (Y-113) to (Y-115), Boc is a t-butoxycarbonyl group.

Of these, Y-7, Y-21, Y-22, Y-23, Y-25, Y-26, Y-27, Y-43, Y- , A high linearity structure such as Y-56, Y-64, Y-66, Y-67, Y-68, Y-91, Y-92 and Y-93, . Y-70, Y-71, Y-72, Y-73, Y-74, Y-75, Y-76, Y- Chain alkyl group, an aromatic ring such as a long chain alkyl group, or a branched chain alkyl group such as Y-81, Y-82, Y-83, Y-84, Y-85, Y-86, Y-87, Y- , An aliphatic ring, a steroid skeleton, or a combination thereof can increase the pretilt angle of the liquid crystal when the liquid crystal alignment film is used. In addition, a structure such as Y-112 can obtain a good rubbing resistance when used as a liquid crystal alignment film.

The polyimide precursor used in the present invention is obtained from the reaction of a diamine component and a tetracarboxylic acid derivative, and examples thereof include polyamic acid and polyamic acid ester.

<Production method of polyamic acid>

Polyamic acid, which is a polyimide precursor used in the present invention, can be synthesized by the following method.

Specifically, the tetracarboxylic acid dianhydride and the diamine are reacted in the presence of an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C for 30 minutes to 24 hours, preferably 1 to 12 hours And then synthesized.

The organic solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone or? -Butyrolactone from the solubility of the monomer and the polymer, May be mixed and used. The concentration of the polymer is preferably from 1 to 30 mass%, more preferably from 5 to 20 mass%, from the viewpoint that the polymer does not easily precipitate and a high molecular weight product is easily obtained.

The polyamic acid thus obtained can be recovered by precipitating the polymer by injecting the reaction solution into a poor solvent with good stirring. Further, the precipitation is carried out several times, followed by washing with a poor solvent, followed by drying at room temperature or by heating, whereby a purified polyamic acid powder can be obtained. Examples of the poor solvent include, but are not limited to, water, methanol, ethanol, hexane, butyl cellosolve, acetone, and toluene.

<Production method of polyamic acid ester>

The polyamic acid ester used as the polyimide precursor used in the present invention can be synthesized by the following methods (1) to (3).

(1) Synthesis from polyamic acid

The polyamic acid ester can be synthesized by esterifying a polyamic acid obtained from a tetracarboxylic acid dianhydride and a diamine.

Concretely, by reacting the polyamic acid and the esterifying agent in the presence of an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C, for 30 minutes to 24 hours, preferably 1 to 4 hours Can be synthesized.

The esterifying agent is preferably one which can be easily removed by purification. Examples of the esterifying agent include N, N-dimethylformamide dimethylacetal, N, N-dimethylformamide diethyl acetal, N, N-dimethylformamide dipropyl acetal, N, N-dimethylformamide dineopentylbutyl acetal, N, N-dimethylformamide di-t-butyl acetal, 1-methyl-3-p-tolyltriazine, , 1-propyl-3-p-tolyltriazine, and 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride. The addition amount of the esterifying agent is preferably 2 to 6 molar equivalents relative to 1 mol of the repeating unit of the polyamic acid.

The solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone or? -Butyrolactone from the solubility of the polymer, May be used. The concentration at the time of the synthesis is preferably from 1 to 30% by mass, and more preferably from 5 to 20% by mass, from the viewpoint that the polymer does not easily precipitate and a high molecular weight product is easily obtained.

(2) Synthesis by reaction of dicarboxylic acid diester dichloride with diamine

Polyamic acid esters can be synthesized from dicarboxylic acid diester dichloride and diamines.

Specifically, the dicarboxylic acid diester dichloride and the diamine are reacted in the presence of a base and an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C for 30 minutes to 24 hours, For 4 hours.

As the base, pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used, but pyridine is preferred since the reaction proceeds mildly. The amount of the base to be added is preferably 2 to 4 times as much as the dicarboxylic acid diester dichloride from the viewpoint of easy removal and high molecular weight.

The solvent to be used in the above reaction is preferably N-methyl-2-pyrrolidone or? -Butyrolactone from the viewpoint of the solubility of the monomer and the polymer, and they may be used alone or in combination of two or more. The concentration of the polymer in the synthesis is preferably from 1 to 30 mass%, more preferably from 5 to 20 mass%, from the viewpoint that the polymer does not easily precipitate and a high molecular weight product is easily obtained. In order to prevent the hydrolysis of the dicarboxylic acid diester dichloride, it is preferable that the solvent used for the synthesis of the polyamic acid ester is dehydrated as much as possible, and it is preferable to prevent the ambient air from being mixed in a nitrogen atmosphere.

(3) Synthesis of polyamic acid from dicarboxylic acid diester and diamine

The polyamic acid ester can be synthesized by polycondensation of a dicarboxylic acid diester and a diamine.

Concretely, the dicarboxylic acid diester and diamine are reacted in the presence of a condensing agent, a base and an organic solvent at 0 ° C to 150 ° C, preferably 0 ° C to 100 ° C for 30 minutes to 24 hours, Followed by reaction for 15 hours.

Examples of the condensing agent include triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3- dimethylaminopropyl) carbodiimide hydrochloride, N, N'-carbonyldiimidazole, dimethoxy- N, N ', N'-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) 1-yl) -N, N, N ', N'-tetramethyluronium hexafluorophosphite, diphenyl (2,3-dihydro-2-thioxo-3-benzoxazolyl) Can be used. The amount of the condensing agent to be added is preferably 2 to 3 times as much as the dicarboxylic acid diester.

As the base, a tertiary amine such as pyridine or triethylamine can be used. The amount of the base to be added is preferably 2 to 4 times the amount of the diamine component, from the viewpoint of easy removal and high molecular weight.

In addition, in the above reaction, the reaction proceeds efficiently by adding Lewis acid as an additive. As the Lewis acid, lithium halides such as lithium chloride and lithium bromide are preferable. The addition amount of the Lewis acid is preferably from 0 to 1.0 times the amount of the diamine component.

Among the methods for synthesizing the above three polyamic acid esters, a polyamic acid ester having a high molecular weight can be obtained, and the synthesis method of the above (3) is particularly preferable.

The solution of the polyamic acid ester obtained as described above can be precipitated by injecting it into a poor solvent while stirring well. After several times of precipitation, it is washed with a poor solvent, and then heated or dried at room temperature to obtain a purified polyamic acid ester powder. Examples of the poor solvent include, but are not limited to, water, methanol, isopropyl alcohol, ethanol, hexane, butyl cellosolve, acetone, and toluene.

&Lt; Process for producing imidized polymer &

The imidized polymer used in the present invention can be prepared by imidizing the polyimide precursor. In the case of preparing an imidized polymer from a polyimide precursor, chemical imidization by adding a basic catalyst to the polyimide precursor solution is simple. The chemical imidization is preferable because the imidization reaction proceeds at a relatively low temperature and the molecular weight of the polymer is not lowered in the process of imidization.

The chemical imidization can be carried out by stirring the polyimide precursor to be imidized in an organic solvent in the presence of a basic catalyst. As the organic solvent, a solvent used in the polymerization reaction described above may be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Among them, triethylamine and pyridine are preferred because they have a basicity suitable for proceeding the reaction. As the acid anhydride, acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like can be given. Among them, acetic anhydride is preferable because the purification after completion of the reaction becomes easy.

The temperature at which the imidization reaction is carried out is from -20 占 폚 to 140 占 폚, preferably from 0 占 폚 to 100 占 폚, and the reaction time is from 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the polyimide precursor. The imidization rate of the resulting polymer can be controlled by adjusting the amount of catalyst, temperature, and reaction time. Since the added catalyst remains in the solution after the imidization reaction, it is preferable to recover the imidized polymer obtained by means described below and redissolve it with an organic solvent to obtain the liquid crystal aligning agent of the present invention .

The solution of the imidized polymer obtained as described above can be precipitated by pouring into a poor solvent while stirring well. Precipitation is carried out several times, washed with a poor solvent, and then heated or dried at room temperature to obtain a purified imidized polymer powder.

Examples of the poor solvent include, but are not limited to, methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene and benzene.

<Liquid Crystal Aligner>

The liquid crystal aligning agent used in the present invention has a form of a solution in which the above-described polyimide precursor or its imidized polymer (hereinafter referred to as a specific structure polymer) is dissolved in an organic solvent. The molecular weight of the polymer having a specific structure is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, and still more preferably 8,000 to 100,000 in terms of weight average molecular weight. The number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and still more preferably 4,000 to 50,000.

The concentration of the polymer of the liquid crystal aligning agent used in the present invention can be appropriately changed depending on the setting of the thickness of the coating film to be formed, but it is preferably 1% by weight or more from the viewpoint of forming a uniform and defect- It is preferably 10% by weight or less from the viewpoint of storage stability.

The organic solvent contained in the liquid crystal aligning agent used in the present invention is not particularly limited as long as the polymer having a specific structure is uniformly dissolved. Specific examples thereof include N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methyl- , N-methylcaprolactam, 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethylsulfoxide, dimethylsulfone,? -Butyrolactone, 1,3-dimethyl-imidazolidinone, N, N-dimethylpropanamide, and the like. These may be used alone or in combination of two or more. The solvent may be mixed with the organic solvent as long as the solvent alone can not uniformly dissolve the polymer and the polymer does not precipitate.

The liquid crystal aligning agent used in the present invention may contain, in addition to an organic solvent for dissolving a polymer having a specific structure, a solvent for improving the film uniformity when the liquid crystal aligning agent is applied to the substrate. Such a solvent generally uses a solvent having a lower surface tension than the organic solvent. Specific examples thereof include ethylcellosolve, butylcellosolve, ethylcarbitol, butylcarbitol, ethylcarbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy- 2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether- Propanol, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid, isoamyl acetate, Esters and the like. These solvents may be used in combination of two or more.

The liquid crystal aligning agent of the present invention may contain other than the polymer described in the present invention and a dielectric or conductive material for changing electrical characteristics such as dielectric constant and conductivity of the liquid crystal alignment film, , A silane coupling agent for improving the adhesion between the liquid crystal alignment film and the substrate, a crosslinkable compound for increasing the hardness and density of the film when the film is used as a liquid crystal alignment film, and further imidized by heating the polyimide precursor And an imidization promoter for the purpose of efficiently promoting the reaction of the reaction product.

&Lt; Liquid crystal alignment film &

The liquid crystal alignment film of the present invention is a film obtained by applying the above liquid crystal aligning agent to a substrate, followed by drying and firing. The substrate to which the liquid crystal aligning agent of the present invention is applied is not particularly limited as long as it is a substrate having high transparency. A plastic substrate such as a glass substrate, a silicon nitride substrate, an acrylic substrate or a polycarbonate substrate can be used. It is preferable from the viewpoint of simplification of the process. Further, in a reflective liquid crystal display element, it may be opaque, such as a silicon wafer, only on a substrate on one side. In this case, a material that reflects light such as aluminum may also be used.

Examples of the application method of the liquid crystal aligning agent of the present invention include a spin coating method, a printing method, and an ink jet method. The drying and firing steps after the application of the liquid crystal aligning agent of the present invention can be carried out at arbitrary temperature and time. Normally, it is dried at 50 ° C to 120 ° C for 1 minute to 10 minutes and then at 150 ° C to 300 ° C for 5 minutes to 120 minutes in order to sufficiently remove the contained organic solvent. Thickness of the coated film after firing is not particularly limited, but if it is too thin, the reliability of the liquid crystal display element may deteriorate. Therefore, it is 5 to 300 nm, preferably 10 to 200 nm.

Examples of a method for aligning the obtained liquid crystal alignment film include a rubbing method and an optical alignment treatment method.

As a specific example of the photo-alignment treatment method, there is a method of irradiating the surface of the above-mentioned coating film with radiation deflected in a predetermined direction and, if necessary, further heating treatment at a temperature of 150 to 250 ° C to give a liquid crystal aligning ability . As the radiation, ultraviolet rays and visible rays having a wavelength of 100 nm to 800 nm can be used.

[Liquid crystal display element]

The liquid crystal display element of the present invention is obtained by obtaining a substrate on which a liquid crystal alignment film is formed from the liquid crystal aligning agent of the present invention by the above-mentioned technique and subjecting the substrate to an alignment treatment by rubbing treatment or the like, .

The method of producing the liquid crystal cell of the liquid crystal display element is not particularly limited. For example, a pair of substrates on which the liquid crystal alignment film is formed is preferably 1 to 30 mu m, more preferably 2 to 30 mu m, A spacer having a size of 10 mu m is interposed therebetween, and then the periphery is fixed with a sealant, and liquid crystal is injected and sealed. The method of enclosing the liquid crystal is not particularly limited, and examples thereof include a vacuum method in which a liquid crystal cell is made in a reduced pressure and a liquid crystal is injected, and a dropping method in which liquid crystal is dropped and then encapsulation is performed. Since the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention has excellent properties as described above, the liquid crystal alignment film of VA, TN, STN, TFT, transverse electric field type, and the like can be used. Further, for liquid crystal display devices of ferroelectric and antiferroelectric Can be used as a liquid crystal alignment layer.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

The abbreviations of the compounds used in this example and the comparative examples and the method of evaluating the properties are as follows.

X-1: 2,4-bis (methoxycarbonyl) cyclobutane-1,3-dicarboxylic acid

X-2: 1,2,3,4-Cyclobutane tetracarboxylic acid dianhydride

Y-1: bis (4-aminophenoxy) methane

Y-2: 1,2-bis (4-aminophenoxy) ethane

Y-3: 1,3-bis (4-aminophenoxy) propane

Y-4: 1,5-bis (4-aminophenoxy) pentane

Y-5: 1,3-bis (4-aminophenethyl) urea

DBOP: diphenyl (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonite

(26)

Each measurement method is shown below.

[Viscosity]

In the synthesis examples, the viscosity of the polyamic acid solution or the polyamic acid ester solution was measured using a E-type viscometer TVE-22H (manufactured by TOKI INDUSTRIAL CO., LTD.) With a sample amount of 1.1 ml, cone rotor TE-1 ) And a temperature of 25 캜.

[Solid content concentration]

In the synthesis examples, the solid content concentration of the polyamic acid solution or the polyamic acid ester solution was calculated in the following manner.

Approximately 1.1 g of the solution was weighed in an aluminum cup No. 2 (manufactured by Asuzen Corporation) with a handle and heated at 200 ° C for 2 hours with an oven DNF 400 (manufactured by Yamato), then left at room temperature (23 ° C) for 5 minutes, The weight of the solid remaining in the aluminum cup was weighed. The solid content concentration was calculated from the value of the solid content weight and the value of the original solution weight.

[Molecular Weight]

The molecular weight of the polyamic acid and the polyamic acid ester is measured by a GPC (room temperature gel permeation chromatography) apparatus, and the number average molecular weight (hereinafter also referred to as Mn) and the weight average molecular weight (hereinafter also referred to as Mw) as polyethylene glycol and polyethylene oxide equivalent ).

GPC apparatus: manufactured by Shodex Co., Ltd. (GPC-101)

Column: manufactured by Shodex Co., Ltd. (serial of KD803, KD805)

Column temperature: 50 ° C

Eluent: 30 mmol / l of lithium bromide-hydrate (LiBr 占 O 2O), 30 mmol / l of phosphoric anhydride crystal (o-phosphoric acid), 30 ml of tetrahydrofuran (THF ) &Lt; / RTI &gt; 10 ml / l)

Flow rate: 1.0 ml / min

Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (weight average molecular weight (Mw) of about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation and polyethylene glycol (peak top molecular weight (Mp) 4,000, 1,000). In order to avoid peaks overlapping, two samples of samples mixed with four types of 900,000, 100,000, 12,000 and 1,000 and three samples of 150,000, 30,000 and 4,000 were separately measured.

[VHR Aging Resistance]

The prepared liquid crystal cell was subjected to aging in an oven at 60 ° C for 48 hours under an LED light source (10,000 rpm). The voltage retention rate before and after aging was measured, and when the aging was 90% or more and after aging was 85% or more, the result was &quot; Good &quot;;

-VHR measurement condition-

A voltage of 1 V was applied for 60 seconds, and a voltage after 100 ms was measured, and the variation from the initial value was calculated as VHR (voltage holding ratio). The temperature of the liquid crystal cell was measured at 60 캜.

[Liquid crystal alignment property]

An AC voltage having a relative transmittance of 100% at a frequency of 30 Hz was applied for 168 hours under a constant temperature environment of 60 占 폚.

Thereafter, the pixel electrode and the counter electrode of the liquid crystal cell were short-circuited, and left at room temperature for one day.

After leaving the liquid crystal cell, the liquid crystal cell was placed between two polarizers arranged so that the polarization axis thereof was orthogonal to each other. The backlight was turned on in a voltage-unapplied state and the angle of arrangement of the liquid crystal cells was adjusted so that the luminance of transmitted light was minimized. Then, the angle of rotation when the liquid crystal cell was rotated from the angle at which the second area of the first pixel was darkest to the angle at which the first area became darkest was calculated as angle DELTA. Similarly, in the second pixel, the second region and the first region were compared to calculate the same angle DELTA. The average value of the angle DELTA values of the first pixel and the second pixel was calculated as the angle DELTA of the liquid crystal cell. A case where the angle DELTA of the liquid crystal cell was less than 0.05 degrees was defined as &amp; cir &amp;

[Pretilt angle]

And the pretilt angle was measured. An AxoScan Muller Matrix Polarimeter manufactured by Optometrics was used for the measurement. A pretilt of less than 1.0 占 was rated as?, And a retardation of 1.0 占 or more was evaluated as 占.

[Solubility of GBL (? -Butyrolactone)] [

6 wt% of polymer solid, 30 wt% of N-methyl-2-pyrrolidone, 44 wt% of? -Butyrolactone, and 10 wt% of polyamic acid solution or polyamic acid ester powder obtained in Synthesis Examples 1 to 10, Butyl cellosolve: 20 wt% diluted solution was prepared. This solution was allowed to stand at 23 占 폚 for 5 days. When the change in viscosity before and after being left standing was less than 10 mPa 占 에는, it was rated?, And when it was 10 mPa 占 퐏 or more,

(Synthesis Example 1)

174.9 g (672.0 mmol) of (X-1) was added to a 5000 ml four-necked flask equipped with a stirrer, and 3153 g of N-methyl-2-pyrrolidone was added and dissolved by stirring. Then 148.7 g (1470 mmol) of triethylamine and 161.2 g (700.0 mmol) of (Y-1) were added and dissolved by stirring.

While this solution was stirred, 563.5 g (1470 mmol) of DBOP was added, and further 433.1 g of N-methyl-2-pyrrolidone was added and stirred at room temperature for 12 hours to obtain a solution of the polyamic acid ester. The viscosity of the polyamic acid ester solution at 25 캜 was 61.1 mPa..

This polyamic acid ester solution was poured into methanol {27800 g}, and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and then dried under reduced pressure at a temperature of 100 ° C to obtain a powder of polyamic acid ester. The molecular weight of this polyamic acid ester was Mn = 13,400 and Mw = 34,600.

(Synthesis Example 2)

86.6 g (333.0 mmol) of (X-1) was added to a 3000 ml four-necked flask equipped with a stirrer, and 1644 g of N-methyl-2-pyrrolidone was added and dissolved by stirring. Then, 76.5 g (756 mmol) of triethylamine and 87.9 g (360.0 mmol) of (Y-2) were added and dissolved by stirring.

While this solution was stirred, 289.8 g (756 mmol) of DBOP was added, 225.8 g of N-methyl-2-pyrrolidone was further added, and the mixture was stirred at room temperature for 12 hours to obtain a solution of the polyamic acid ester. The viscosity of the polyamic acid ester solution at 25 캜 was 65.3 mPa..

This polyamic acid ester solution was poured into methanol {14500 g}, and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and then dried under reduced pressure at a temperature of 100 ° C to obtain a powder of polyamic acid ester. The molecular weight of this polyamic acid ester was Mn = 13,200 and Mw = 25,900.

(Synthesis Example 3)

After adding 12.2 g (47.0 mmol) of (X-1) to a 500 ml four-necked flask equipped with a stirrer, 232 g of N-methyl-2-pyrrolidone was added and dissolved by stirring. Subsequently, 10.2 g (100.8 mmol) of triethylamine and 12.4 g (48.0 mmol) of (Y-3) were added and dissolved by stirring.

While stirring the solution, 38.6 g (100.8 mmol) of DBOP was added, and further 31.9 g of N-methyl-2-pyrrolidone was added and stirred at room temperature for 12 hours to obtain a solution of the polyamic acid ester. The viscosity of this polyamic acid ester solution at a temperature of 25 캜 was 213.2 mPa s.

This polyamic acid ester solution was added to methanol {2020 g}, and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and then dried under reduced pressure at a temperature of 100 ° C to obtain a powder of polyamic acid ester. The molecular weight of this polyamic acid ester was Mn = 24,700 and Mw = 59,300.

(Synthesis Example 4)

11.0 g (42.1 mmol) of (X-1) was added to a 500 ml four-necked flask equipped with a stirrer, and 220 g of N-methyl-2-pyrrolidone was added and dissolved by stirring. Subsequently, 9.14 g (90.3 mmol) of triethylamine and 12.3 g (43.0 mmol) of (Y-4) were added and dissolved by stirring.

While this solution was stirred, 34.6 g (90.3 mmol) of DBOP was added, and further 30.2 g of N-methyl-2-pyrrolidone was added and stirred at room temperature for 12 hours to obtain a solution of the polyamic acid ester. The viscosity of this polyamic acid ester solution at 25 캜 was 348.0 mPa s.

This polyamic acid ester solution was poured into methanol {1900 g}, and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and then dried under reduced pressure at a temperature of 100 ° C to obtain a powder of polyamic acid ester. The molecular weight of this polyamic acid ester was Mn = 26,800 and Mw = 66,500.

(Synthesis Example 5)

7.45 g (28.7 mmol) of (X-1) was added to a 500 ml four-necked flask equipped with a stirrer, and 138 g of N-methyl-2-pyrrolidone was added and dissolved by stirring. Subsequently, 6.38 g (63.0 mmol) of triethylamine and 5.87 g (25.5 mmol) of (Y-1) and 1.34 g (4.5 mmol) of (Y-5) were added and dissolved by stirring.

While stirring the solution, 24.2 g (63.0 mmol) of DBOP was added, and further 18.9 g of N-methyl-2-pyrrolidone was added and stirred at room temperature for 12 hours to obtain a solution of the polyamic acid ester. The viscosity of this polyamic acid ester solution at 25 캜 was 65.0 mPa s.

This polyamic acid ester solution was poured into methanol {1200 g}, and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and then dried under reduced pressure at a temperature of 100 ° C to obtain a powder of polyamic acid ester. The molecular weight of this polyamic acid ester was Mn = 14,200 and Mw = 35,300.

(Synthesis Example 6)

114.9 g (441.6 mmol) of (X-1) was added to a 5000 ml four-necked flask equipped with a stirrer, and then 2226 g of N-methyl-2-pyrrolidone was added and dissolved by stirring. Subsequently, 102.0 g (1008.0 mmol) of triethylamine, 99.67 g (408.0 mmol) of (Y-2) and 21.48 g (72.0 mmol) of (Y-5) were added and dissolved by stirring.

While this solution was stirred, 386.4 g (1008.0 mmol) of DBOP was added, and further 305.8 g of N-methyl-2-pyrrolidone was added and stirred at room temperature for 12 hours to obtain a solution of the polyamic acid ester. The viscosity of this polyamic acid ester solution at 25 캜 was 88.5 mPa s.

This polyamic acid ester solution was poured into methanol {19500 g}, and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and then dried under reduced pressure at a temperature of 100 ° C to obtain a powder of polyamic acid ester. The molecular weight of this polyamic acid ester was Mn = 16,400 and Mw = 33,200.

(Synthesis Example 7)

In a 100 ml four-necked flask equipped with a stirrer, 8.52 g (37.0 mmol) of (Y-1) was taken, 112.0 g of N-methyl-2-pyrrolidone was added and dissolved with stirring while nitrogen was being supplied. While this diamine solution was stirred, 6.89 g (35.2 mmol) of (X-2) was added, and further 27.7 g of N-methyl-2-pyrrolidone was added and stirred at 23 占 폚 for 5 hours under a nitrogen atmosphere A polyamic acid solution was obtained. The viscosity of the polyamic acid solution at 25 캜 was 436 mPa.. The molecular weight of this polyamic acid was Mn = 18400 and Mw = 47000.

(Synthesis Example 8)

23.9 g (92.0 mmol) of (X-1) was added to a 1000 ml four-necked flask equipped with a stirrer, and 448 g of N-methyl-2-pyrrolidone was added and dissolved by stirring. Subsequently, 21.2 g (210 mmol) of triethylamine, 11.51 g (50.0 mmol) of (Y-1) and 12.21 g (50.0 mmol) of Y-2 were added and dissolved by stirring.

While stirring this solution, 80.5 g (210 mmol) of DBOP was added, 61.6 g of N-methyl-2-pyrrolidone was further added, and the mixture was stirred at room temperature for 12 hours to obtain a solution of the polyamic acid ester. The viscosity of this polyamic acid ester solution at 25 캜 was 35.2 mPa..

The polyamic acid ester solution was poured into methanol {660 g}, and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and then dried under reduced pressure at a temperature of 100 ° C to obtain a powder of polyamic acid ester. The molecular weight of this polyamic acid ester was Mn = 10,100 and Mw = 19,200.

(Synthesis Example 9)

17.8 g (68.4 mmol) of (X-1) was added to a 1000 ml four-necked flask equipped with a stirrer, and then 345 g of N-methyl-2-pyrrolidone was added and dissolved by stirring. Subsequently, 15.4 g (152 mmol) of triethylamine and 6.12 g (26.6 mmol) of (Y-1), 9.28 g (38.0 mmol) of (Y- g &lt; / RTI &gt; (11.4 mmol) and stirred to dissolve.

While stirring the solution, 58.3 g (152 mmol) of DBOP was added, and further 47.4 g of N-methyl-2-pyrrolidone was added and stirred at room temperature for 12 hours to obtain a solution of the polyamic acid ester. The viscosity of this polyamic acid ester solution at 25 캜 was 36.2 mPa s.

This polyamic acid ester solution was added to methanol {3020 g}, and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and then dried under reduced pressure at a temperature of 100 ° C to obtain a powder of polyamic acid ester. The molecular weight of this polyamic acid ester was Mn = 8,600 and Mw = 18,900.

(Synthesis Example 10)

After 7.38 g (28.4 mmol) of (X-1) was added to a 500 ml four-necked flask equipped with a stirrer, 140 g of N-methyl-2-pyrrolidone was added and dissolved by stirring. Subsequently, 6.17 g (61.0 mmol) of triethylamine and 3.51 g (15.3 mmol) of (Y-1), 2.61 g (10.7 mmol) of (Y- g (4.58 mmol) was added and dissolved by stirring.

While this solution was stirred, 23.4 g (61.0 mmol) of DBOP was added, and further 19.2 g of N-methyl-2-pyrrolidone was added and stirred at room temperature for 12 hours to obtain a solution of the polyamic acid ester. The viscosity of this polyamic acid ester solution at 25 캜 was 43.4 mPa s.

This polyamic acid ester solution was poured into methanol {1220 g}, and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and then dried under reduced pressure at a temperature of 100 ° C to obtain a powder of polyamic acid ester. The molecular weight of this polyamic acid ester was Mn = 10,200 and Mw = 23,700.

(Comparative Example 1)

1.77 g of the polyamic acid ester powder obtained in Synthesis Example 1 was taken in a 100 ml Erlenmeyer flask containing 27.7 g of N-methyl-2-pyrrolidone and stirred for dissolution at room temperature for 18 hours. Subsequently, 9.85 g of butyl cellosolve was added and stirred for 2 hours to obtain a polyamic acid ester solution having a solid content concentration of 4.34 mass%.

(Comparative Example 2)

3.87 g of the polyamic acid ester powder obtained in Synthesis Example 2 was placed in a 100 ml Erlenmeyer flask containing 60% by weight of an agitator and 60.6 g of N-methyl-2-pyrrolidone was added thereto and dissolved by stirring at room temperature for 18 hours. Subsequently, 21.5 g of butyl cellosolve was added and stirred for 2 hours to obtain a polyamic acid ester solution having a solid content concentration of 4.30 mass%.

(Comparative Example 3)

3.51 g of the polyamic acid ester powder obtained in Synthesis Example 3 was placed in a 100 ml Erlenmeyer flask containing an agitator, and 55.0 g of N-methyl-2-pyrrolidone was added thereto and dissolved by stirring at room temperature for 18 hours. Subsequently, 19.5 g of butyl cellosolve was added and stirred for 2 hours to obtain a polyamic acid ester solution having a solid content concentration of 4.20 mass%.

(Comparative Example 4)

3.48 g of the polyamic acid ester powder obtained in Synthetic Example 4 was placed in a 100 ml Erlenmeyer flask containing an agitator and 54.5 g of N-methyl-2-pyrrolidone was added thereto and dissolved by stirring at room temperature for 18 hours. Subsequently, 19.3 g of butyl cellosolve was added and stirred for 2 hours to obtain a polyamic acid ester solution having a solid content concentration of 4.20 mass%.

(Comparative Example 5)

3.94 g of the polyamic acid ester powder obtained in Synthetic Example 5 was placed in a 100 ml Erlenmeyer flask containing an agitator and 61.8 g of N-methyl-2-pyrrolidone was added and dissolved by stirring at room temperature for 18 hours. Subsequently, 21.9 g of butyl cellosolve was added and stirred for 2 hours to obtain a polyamic acid ester solution having a solid content concentration of 4.28 mass%.

(Comparative Example 6)

3.25 g of the polyamic acid ester powder obtained in Synthetic Example 6 was placed in a 100 ml Erlenmeyer flask containing 50 ml of an agitator and 50.9 g of N-methyl-2-pyrrolidone was added and dissolved by stirring at room temperature for 18 hours. Subsequently, 18.1 g of butyl cellosolve was added and stirred for 2 hours to obtain a polyamic acid ester solution having a solid content concentration of 4.38 mass%.

(Comparative Example 7)

10.3 g of the polyamic acid solution obtained in Synthesis Example 7 was put into a 100 ml Erlenmeyer flask containing an agitator, 18.7 g of N-methyl-2-pyrrolidone and 9.68 g of butyl cellosolve were added, and 2 g of 2 Followed by stirring for a period of time to obtain a polyamic acid solution having a solid content concentration of 4.00 mass%.

(Example 1)

4.10 g of the polyamic acid ester powder obtained in Synthetic Example 8 was placed in a 100 ml Erlenmeyer flask containing an agitator and 64.2 g of N-methyl-2-pyrrolidone was added and dissolved by stirring at room temperature for 18 hours. Subsequently, 22.8 g of butyl cellosolve was added and stirred for 2 hours to obtain a polyamic acid ester solution having a solid content concentration of 4.40% by mass.

(Example 2)

3.81 g of the polyamic acid ester powder obtained in Synthesis Example 9 was taken in a 100 ml Erlenmeyer flask containing 59.7 g of N-methyl-2-pyrrolidone and stirred for dissolving at room temperature for 18 hours. Subsequently, 21.2 g of butyl cellosolve was added and stirred for 2 hours to obtain a polyamic acid ester solution having a solid content concentration of 4.41 mass%.

(Example 3)

4.21 g of the polyamic acid ester powder obtained in Synthesis Example 10 was placed in a 100-ml Erlenmeyer flask containing 66% by weight of an agitator, followed by addition of 66.0 g of N-methyl-2-pyrrolidone and dissolution by stirring at room temperature for 18 hours. Subsequently, 23.4 g of butyl cellosolve was added and stirred for 2 hours to obtain a polyamic acid ester solution having a solid content concentration of 4.45 mass%.

Claims (8)

A polyimide precursor comprising a diamine-containing diamine component represented by the following formulas (1) and (2), a polyimide precursor obtained by reaction of a tetracarboxylic acid derivative, and a polyimide obtained by imidizing the polyimide precursor, Liquid crystal aligning agent.
[Chemical Formula 1]

In the formula (2), n is an integer of 1, 3 or 5. The method according to claim 1,
Wherein the diamine of the formula (1) is 10 to 90 mol% of the diamine component. 3. The method according to claim 1 or 2,
Wherein the diamine of the formula (2) is 10 to 90 mol% of the diamine component. 4. The method according to any one of claims 1 to 3,
Wherein the tetracarboxylic acid derivative contains an aliphatic structure or an alicyclic group structure in its structure. 5. The method according to any one of claims 1 to 4,
Wherein the tetracarboxylic acid derivative containing an aliphatic structure or alicyclic group structure in the structure is 10 to 90 mol% of the total tetracarboxylic acid derivative. 6. The method according to any one of claims 1 to 5,
Wherein the carboxylic acid derivative is a dicarboxylic acid diester. A liquid crystal alignment film obtained by applying and firing the liquid crystal aligning agent according to any one of claims 1 to 6 on a substrate. 9. A liquid crystal display element having the liquid crystal alignment film according to claim 7.