TW201302856A - Liquid crystal aligning agent, and liquid crystal alignment film produced using same - Google Patents

Abstract

Provided are: a liquid crystal alignment film which enables the manufacture of a liquid crystal display element having a rapid rate of relaxing residual charge generated upon the application of a direct-current voltage; and a liquid crystal aligning agent which can be used for the manufacture of a liquid crystal alignment film. A liquid crystal aligning agent characterized by comprising: at least one polymer selected from the group consisting of polyimide precursors each having a structural unit represented by formula (1) and polymers produced by imidizing the polyimide precursors; a sulfonic acid ester represented by formula (2); and an organic solvent. (In formula (1), X1 represents a tetravalent organic group; Y1 represents a bivalent organic group; and R1 represents a hydrogen atom or an alkyl group having 1-5 carbon atoms.) [Formula 2] R2-SO2-OR3 (2) (In formula (2), R2 and R3 independently represent a monovalent organic group having 1-30 carbon atoms which may have a substituent, wherein R2 and R3 may be bound to each other to form a cyclic structure.)

Description

Liquid crystal alignment agent and liquid crystal alignment film using the same

The present invention relates to a liquid crystal alignment agent for producing a liquid crystal alignment film, and a liquid crystal alignment film obtained by the liquid crystal alignment agent. More specifically, the present invention provides a liquid crystal alignment film for a liquid crystal display element which can obtain a relaxation rate of a residual electric charge generated by a DC voltage, and a liquid crystal alignment agent for obtaining a liquid crystal alignment film.

In a liquid crystal display element used for a liquid crystal television, a liquid crystal display or the like, a liquid crystal alignment film for controlling a liquid crystal alignment state is usually provided in the element. In the liquid crystal alignment film, a liquid crystal alignment agent containing a polyimine acid precursor such as polyamido acid or a solution of a soluble polyimine is mainly applied to a glass substrate or the like, and is fired. Polyimine-based liquid crystal alignment film.

With the high definition of the liquid crystal display element, it is necessary to suppress the contrast of the liquid crystal display element to reduce or reduce the image sticking phenomenon, etc., and therefore, in the liquid crystal alignment film, in addition to exhibiting an excellent liquid crystal alignment or a stable pretilt angle, The high voltage holding ratio, the suppression of residual images due to AC driving, the residual charge which is less when a DC voltage is applied, and/or the rapid relaxation of residual charges due to DC voltage accumulation are also important.

Polyimine-based liquid crystal alignment films have various proposals in response to the above requirements. For example, a liquid crystal alignment film having a short time from the occurrence of a residual voltage due to a DC voltage, for example, a polyamic acid or a ruthenium is proposed. In addition to the amino group polyamine, a liquid crystal alignment agent containing a tertiary amine having a specific structure (see, for example, Patent Document 1), or a soluble polyazide containing a specific diamine compound having a pyridine skeleton or the like as a raw material is used. A liquid crystal alignment agent of an amine (see, for example, Patent Document 2).

In addition, a liquid crystal alignment film having a high voltage holding ratio and a short period of time from the occurrence of a residual voltage due to a DC voltage, for example, it is proposed to use, in addition to polyacrylic acid or a ruthenium iodide polymer thereof, A very small amount of a liquid crystal alignment agent of a compound selected from a compound having one carboxylic acid group in the molecule, a compound having one carboxylic acid anhydride group in the molecule, and a compound having one tertiary amino group in the molecule (refer to, for example, the patent document) 3).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. Hei 9-316200

[Patent Document 2] Japanese Patent Laid-Open No. Hei 10-104633

[Patent Document 3] Japanese Patent Laid-Open No. Hei 8-76128

[Summary of the Invention]

As described above, there are various methods for reviewing the image sticking of the liquid crystal display. However, in recent years, large-screen, high-definition LCD TVs have been used, and the requirements for image sticking are more stringent, and they are required to withstand long-term use in harsh environments. The present invention has been made in view of the above circumstances, and its object is to provide A liquid crystal alignment film of a liquid crystal display element having a rapid relaxation time of residual charges generated by a DC voltage and a liquid crystal alignment agent for obtaining the alignment film.

According to the study of the present inventors, the following new insights have been obtained, namely, a ruthenium imidized polymer from a polyimide precursor and/or the polyimide precursor and a liquid crystal alignment containing a specific amount of a specific sulfonate. The liquid crystal alignment film formed by the agent can obtain a liquid crystal display element which does not impair other characteristics and which has a relaxation time of residual charge due to a DC voltage.

The present invention is based on this insight and has the following essential elements.

A liquid crystal alignment agent characterized by comprising a group selected from the group consisting of a polyimine precursor having a repeating unit represented by the following formula (1) and a ruthenium imidized polymer of the polyimide precursor. At least one type of polymer, a sulfonate represented by the following formula (2), and an organic solvent, (In the formula (1), X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and each of A ₁ and A ₂ is independently a hydrogen atom. Or an alkyl group, an alkenyl group or an alkynyl group having 1 to 10 carbon atoms which may have a substituent. [Chemical 2]R ₂ -SO ₂ -OR ₃ (2) (in the formula (2), each of R ₂ and R ₃ is It is independently a monovalent organic group having 1 to 30 carbon atoms which may have a substituent, and R ₂ and R _{3 are} bonded to each other to form a ring structure).

2. The liquid crystal alignment agent according to the above item 1, wherein the content of the sulfonate is 0.01 parts by mass to 30 parts by mass based on 100 parts by mass of the polymer.

3. The liquid crystal alignment agent according to item 1 or 2 above, wherein R ₂ is a methyl group which may have a substituent.

4. The liquid crystal alignment agent according to any one of items 1 to 3 above, wherein R ₃ is a methyl group.

5. The liquid crystal alignment agent according to item 1 or 2 above, wherein the sulfonic acid ester is methyl trifluoromethanesulfonate or ethyl trifluoromethanesulfonate.

The liquid crystal alignment agent according to any one of items 1 to 5, wherein the polymer has a weight average molecular weight of 5,000 to 300,000.

The liquid crystal alignment agent according to any one of the above items, wherein the content of the polymer is from 0.5% by mass to 20% by mass based on the total amount of the organic solvent.

A liquid crystal alignment film obtained by coating and baking a liquid crystal alignment agent according to any one of items 1 to 7 above.

A liquid crystal alignment film obtained by coating and baking a liquid crystal alignment agent according to any one of items 1 to 7 above, which is irradiated with polarized radiation.

A liquid crystal display element comprising the liquid crystal alignment film according to item 8 or 9 above.

The liquid crystal alignment film formed by the polyamidiamine precursor and/or the ruthenium imidized polymer of the polyimide precursor and the liquid crystal alignment agent containing a specific amount of the specific sulfonate of the present invention can provide early liquid crystal The mitigation time of the residual charge generated by the DC voltage of the display element provides excellent liquid crystal alignment or a pretilt angle which exhibits stability, and provides an excellent liquid crystal display element.

The mechanism for obtaining the above effects by the liquid crystal alignment agent of the present invention is not clear, but is substantially as follows. When the sulfonate of the above formula (2) contained in the liquid crystal alignment agent of the present invention is present, the polyimine precursor of the liquid crystal alignment agent and/or the ruthenium imidized polymer of the polyimide precursor The carboxyl group or the amine group is reacted to form an anion represented by the following formula (3).

[Chemical 3] R ₂ -SO ₂ -O ^- (3)

The anion represented by the formula (3) is present in the liquid crystal alignment film formed by baking the coating film of the liquid crystal alignment agent, and the specific resistance of the obtained liquid crystal alignment film is lowered, and the DC voltage of the liquid crystal display element is increased. The effect of the relaxation rate of the residual charge.

[Formation of the Invention] <Polyimide precursor>

The polyimine precursor used in the present invention is a polymer having a site which can be subjected to the imidization reaction described below by heating or reacting with a ruthenium-catalyzed catalyst. In the following formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably 1 to 2 carbon atoms.

The ruthenium iodide polymer used in the present invention is a polymer obtained by heating the above polyimide precursor or reacting with a ruthenium catalyst.

The polyimine precursor contained in the liquid crystal alignment agent of the present invention has a polymer having the structural unit represented by the following formula (1).

In the above formula (1), R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably 1 to 2 carbon atoms. When R ₁ is an alkyl group, as the number of carbon atoms in the alkyl group increases, the temperature at which the oxime imidization progresses. Therefore, R _{1 is} particularly preferably a hydrogen atom or a methyl group from the viewpoint of easiness of imidization by heat generation. In the formula (1), each of A ₁ and A ₂ is independently a hydrogen atom or an alkyl group, an alkenyl group or an alkynyl group having 1 to 10 carbon atoms which may have a substituent. Specific examples of the above 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, a dicyclohexyl group and the like. The alkenyl group is, for example, a compound in which one or more CH-CH structures present in the above alkyl group are substituted with a C=C structure. More specifically, for example, a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, a 2-butenyl group, a 1,3-butadienyl group, a 2-pentenyl group, a 2-hexenyl group, Cyclopropenyl, cyclopentenyl, cyclohexenyl and the like. The alkynyl group is, for example, a structure in which one or more CH ₂ -CH ₂ structures present in the above alkyl group are substituted by a C≡C structure, and more specifically, for example, an ethynyl group, a 1-propynyl group, or a 2-propyne group. Base.

When the alkyl group, the alkenyl group, and the alkynyl group have a carbon number of 1 to 20 as a whole, they may have a substituent, and may further form a ring structure by a substituent. Further, the formation of a ring structure via a substituent means that the substituents are bonded to each other or a part of the substituent to a part of the parent skeleton 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 organic oxy group, an organic thio group, an organic decyl group, a decyl group, an ester group, a thioester group, a phosphate group, a decyl group, Alkyl, alkenyl, alkynyl.

The halogen group of the substituent includes, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The aryl group of the substituent is, for example, a phenyl group. This aryl group may be further substituted with the other substituents described above.

The organooxy group of the substituent has, for example, a structure represented by O-R. These R may be the same or different, and may, for example, be an alkyl group, an alkenyl group, an alkynyl group, an aryl group or the like as described above. These R may be further substituted by the aforementioned substituents. Specific examples of the organic oxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group and the like.

The organothio group of the substituent has, for example, a structure represented by -S-R. Examples of such R include the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like. These R may be further substituted by the aforementioned substituents. Specific examples of the organic sulfur group include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, a heptylthio group, an octylthio group and the like.

The organoalkylene group of the substituent has, for example, a structure represented by -Si-(R) ₃ . The R may be the same or different, and examples thereof include the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like. These R may be further substituted by the aforementioned substituents. Specific examples of the organic decyl group include, for example, trimethyldecyl, triethyldecyl, tripropyldecyl, tributyldecyl, tripentyldecyl, trihexyldecyl, pentyldimethylalkyl , hexyl dimethyl decyl and the like.

The thiol group of the substituent has, for example, a structure represented by -C(O)-R. Examples of such R include the aforementioned alkyl group, alkenyl group, aryl group and the like. These R may be further substituted by the aforementioned substituents. Specific examples of the fluorenyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentamidine group, an isovaleryl group, a hexyl group, and the like.

The ester group of the substituent has, for example, a structure represented by -C(O)O-R, or -OC(O)-R. Examples of such R include the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like. These R may be further substituted by the aforementioned substituents.

The thioester group of the substituent has, for example, a structure represented by -C(S)O-R, or -OC(S)-R. Examples of such R include the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like. These R may be further substituted by the aforementioned substituents.

The phosphate group of the substituent has, for example, a structure represented by -OP(O)-(OR) ₂ . These R may be the same or different, such as the aforementioned alkyl, alkenyl, alkynyl, aryl, and the like. These R may be further substituted by the aforementioned substituents.

The amine group of the substituent is represented, for example, by -C(O)NH ₂ or -C(O)NHR, -NHC(O)R, -C(O)N(R) ₂ , -NRC(O)R Structure. The R may be the same or different, and examples thereof include the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like. These R may be further substituted by the aforementioned substituents.

The aryl group of the substituent is, for example, the same as the aforementioned aryl group. This aryl group can It is then substituted by the other substituents mentioned above.

The alkyl group of the substituent is, for example, the same as the aforementioned alkyl group. This alkyl group may be further substituted with the other substituents described above.

The alkenyl group of the substituent is, for example, the same as the above alkenyl group. This alkenyl group may be further substituted with the other substituents described above.

The alkynyl group of the substituent is, for example, the same as the alkynyl group described above. This alkynyl group can be further substituted with the other substituents described above.

In general, when a structure having a relatively high bulk density is introduced, the reactivity of the amine group or the liquid crystal alignment property may be lowered. Therefore, A ₁ and A _{2 are} preferably a hydrogen atom or a carbon number of 1 to 5 which may have a substituent. An alkyl group, particularly preferably a hydrogen atom, a methyl group or an ethyl group.

In the above formula (1), X ₁ is a tetravalent organic group, and Y ₁ is a divalent organic group. X ₁ is a tetravalent organic group, and is not particularly limited. In the polyimine precursor, X ₁ may be mixed in two or more kinds. Specific examples of X ₁ include, for example, X-1 to X-46 shown below. Among them, from the viewpoint of monomer availability, X _{1 is} preferably X-1, X-2, X-3, X-4, X-5, X-6, X-8, X-16, X-. 19. X-21, X-25, X-26, X-27, X-28 or X-32.

Further, in the formula (1), Y ₁ is a divalent organic group, and is not particularly limited. In the polyimine precursor, Y ₁ may be mixed in two or more types. Y ₁ has the following specific examples of the Y-1 ~ Y-113.

Among them, in order to obtain a good liquid crystal alignment property, it is preferred to introduce a diamine having a high linearity into the polyphthalate. At this time, Y _{1 is more} preferably Y-7, Y-10, Y-11, Y-12, Y-13, Y-21, Y-22, Y-23, Y-25, Y-26, Y-27. , Y-41, Y-42, Y-43, Y-44, Y-45, Y-46, Y-48, Y-61, Y-63, Y-64, Y-71, Y-72, Y -73, Y-74, Y-75, Y-98, Y-100, Y-101, Y-102, Y-103, Y-0104, Y-105, Y-106, Y-107, Y-108 , Y-109, or Y-110 diamine.

Further, when the pretilt angle is to be increased, a diamine having a long-chain alkyl group, an aromatic ring, an aliphatic ring, a steroid skeleton, or a combination thereof in the side chain is introduced into the polyglycolate. Good, Y ₁ at this time is better Y-76, Y-77, Y-78, Y-79, Y-80, Y-81, Y-82, Y-83, Y-84, Y-85, Y-86, Y-87, Y-88, Y-89, Y-90, Y-91, Y-92, Y-93, Y-94, Y-95, Y-96, or Y-97 amine. Any pretilt angle can be obtained by adding 1 to 50 mol% of these diamines of the total diamine.

By reducing the volume resistivity of the polyimide precursor, the relaxation rate of the charge due to the accumulation of the DC voltage can be increased. Therefore, it is preferred to have a hetero atom structure, a polycyclic aromatic structure, or a biphenyl. The diamine of the skeleton is introduced into the polyamic acid. At this time, Y _{1 is more} preferably Y-19, Y-23, Y-25, Y-26, Y-27, Y-30, Y-31, Y- 32, Y-33, Y-34, Y-35, Y-36, Y-40, Y-41Y-42, Y-44, Y-45, Y-49, Y-50, Y-51, Y- 61, Y-110, Y-111, Y-112, or Y-113.

<sulfonate>

The sulfonic acid ester contained in the liquid crystal alignment agent of the present invention is represented by the following formula (2).

R ₂ -SO ₂ -OR ₃ (2)

In the above formula (2), each of R ₂ and R ₃ is independently a monovalent organic group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms which may have a substituent. The organic group is selected from the group consisting of an alkyl group, an alkenyl group, an alkynyl group and an aryl group, and R ₂ and R _{3 are} bonded to each other to form a ring structure.

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, a dicyclohexyl group and the like. The alkenyl group may be, for example, a structure in which one or more CH-CH structures present in the above alkyl group are substituted into a C=C structure. More specifically, for example, a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, a 2-butenyl group, a 1,3-butadienyl group, a 2-pentenyl group, a 2-hexenyl group, Cyclopropenyl, cyclopentenyl, cyclohexenyl and the like. The alkynyl group is, for example, a structure in which one or more CH ₂ -CH ₂ structures present in the above alkyl group are substituted into a C≡C structure, and more specifically, for example, an ethynyl group, a 1-propynyl group, or a 2-propynyl group. Wait. The aryl group is, for example, a phenyl group, an α-naphthyl group, a β-naphthyl group, an o-biphenyl group, an m-biphenyl group, a p-biphenyl group, a 1-fluorenyl group, a 2-fluorenyl group, a 9-fluorenyl group, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl and the like.

When the alkyl group, the alkenyl group, the alkynyl group, and the aryl group described above have a carbon number of 1 to 20, they may have a substituent and may form a ring structure via a substituent. Further, the formation of a ring structure via a substituent means that the substituents are bonded to each other or a part of the substituent is bonded to a part of the parent skeleton to form a ring structure.

Examples of the substituent include, for example, a halogen group, a hydroxyl group, a thiol group, a nitro group, an organic oxy group, an organic thio group, an organic decyl group, a decyl group, an ester group, a thioester group, a phosphate group, a decyl group, Aryl, alkyl, alkenyl, alkynyl and the like.

The halogen group of the substituent includes, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The organooxy group in the substituent, such as an alkoxy group, an alkenyloxy group, an aryloxy group or the like, has a structure represented by -O-R. This R is, for example, the aforementioned alkyl group, alkenyl group, aryl group or the like. These R can be further substituted by the aforementioned substituents. Specific examples of the alkyloxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and the like. Hexyloxy, heptyloxy, octyloxy, decyloxy, decyloxy, lauryloxy and the like.

The organothio group of the substituent is, for example, a structure represented by -S-R such as an alkylthio group, an arylthio group or an arylthio group. This R is, for example, the aforementioned alkyl group, alkenyl group, aryl group or the like. These R may be further substituted by the aforementioned substituents. Specific examples of the alkylthio group include methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, heptylthio group, octylthio group, mercaptothio group. , mercaptothio group, laurylthio group and the like.

The organoalkylene group of the substituent has, for example, a structure represented by -Si-(R) ₃ . These R may be the same or different, such as the aforementioned alkyl group, aryl group and the like. These R can be further substituted by the aforementioned substituents. Specific examples of the alkyl fluorenyl group are a trimethyl decyl group, a triethyl decyl group, a tripropyl decyl group, a tributyl decyl group, a tripentyl decyl group, a trihexyl decyl group, a pentyl dimethyl decyl group, Hexyl dimethyl decyl, octyl dimethyl decyl, decyl dimethyl decyl and the like.

The thiol group of the substituent is, for example, a structure represented by -C(O)-R. This R is, for example, the aforementioned alkyl group, alkenyl group, aryl group or the like. These R may be resubstituted by the aforementioned substituents. Specific examples of the mercapto group include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a amyl group, an isovaleryl group, a hexyl group, and the like.

The ester group of the substituent is, for example, a structure represented by -C(O)O-R or -OC(O)-R. This R is, for example, an alkyl group, an alkenyl group, an aryl group or the like as described above. These R may be substituted by the aforementioned substituents.

The thioester group of the substituent is, for example, a structure represented by -C(S)O-R, or -OC(S)-R. This R is, for example, an alkyl group, an alkenyl group, an aryl group or the like as described above. Such R may be substituted by the aforementioned substituents.

The phosphate group of the substituent is, for example, a structure represented by -OP(O)-(OR) ₂ . The R may be the same or different, and for example, the aforementioned alkyl group, aryl group or the like. These R may be substituted by the aforementioned substituents.

a substituent amide group, for example, -C(O)NH ₂ , -C(O)NHR, -NHC(O)R, -C(O)N(R) ₂ , or -NRC(O)R The structure of the representation. The R may be the same or different, and for example, the aforementioned alkyl group, aryl group or the like. These R may be substituted by the aforementioned substituents.

The aryl group of the substituent is, for example, the same as the aforementioned aryl group. This aryl group may be further substituted with the other substituents described above.

The alkyl group of the substituent is, for example, the same as the alkyl group described above. This alkyl group may be further substituted with the other substituents described above.

The alkenyl group of the substituent is, for example, the same as the above-mentioned alkenyl group. This alkenyl group may be further substituted with the other substituents described above.

The alkynyl group of the substituent is, for example, the same as the alkynyl group described above. This alkynyl group can be further substituted with the other substituents described above.

In order to reduce the molecular weight of the sulfonate, it is possible to obtain an effect in a small amount. In the above formula (2), R _{2 is} preferably an alkyl group having 1 to 4 carbon atoms which may have a substituent, or a phenyl group. It is preferably an alkyl group having 1 to 4 carbon atoms which may have a substituent, and more preferably a methyl group which may have a substituent.

The substituent which may be substituted for R ₂ in the above formula (2) is preferably an electron attracting group from the viewpoint of improving the stability of the anion formed by the sulfonate. Specific examples of the electron attracting group include a nitro group, a cyano group, a halogen atom, a hydroxyl group, an alkoxy group and the like, and more preferably a halogen atom, more preferably a fluorine atom.

Further, in the same manner as described above, the R ₃ in the above formula (2) is preferably an alkyl group having 1 to 4 carbon atoms or benzene, in order to reduce the molecular weight of the sulfonate by reducing the molecular weight of the sulfonate. The base is more preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group.

Preferred specific examples of the sulfonate used in the present invention are methyl trifluoromethanesulfonate, ethyl trifluoromethanesulfonate, methyl p-toluenesulfonate, methyl methanesulfonate, methanesulfonic acid 2,2, 2-Trifluoroethyl ester, 2-methoxyethyl methanesulfonate, propane sultone. More preferably, it is methyl trifluoromethanesulfonate or ethyl trifluoromethanesulfonate.

When the content of the sulfonate in the liquid crystal alignment agent of the present invention is too small, there is no effect, and when it is too large, other characteristics may be affected, and thus the polyimine precursor and/or the liquid crystal alignment agent are used. 100 parts by mass of the polymer composed of the ruthenium imidized polymer of the polyimide precursor, preferably 0.01 parts by mass to 30 parts by mass, more preferably 0.1 parts by mass to 10 parts by mass, still more preferably 0.1 parts by mass. ~5 parts by mass.

<Method for producing polyamidomate>

When the polyimide precursor of the present invention is a polyphthalate, the polyphthalate is one of the tetracarboxylic acid derivatives represented by the following formulas (4) to (6) and represented by the formula (7). The reaction of the diamine compound is obtained.

(wherein X ₁ , Y ₁ , R ₁ , A ₁ and A ₂ are respectively the same as defined in the above formula (1).)

The polyimine precursor represented by the above formula (1) can be synthesized by the above methods (1) to (3) using the above monomers.

(1) The case of synthesis from polyaminic acid

The polyglycolate can be synthesized by esterifying a polycarboxylic acid obtained by dicarboxylic acid dianhydride with a diamine.

Specifically, it can be carried out by using polylysine and an esterifying agent in the presence of an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C, preferably for 30 minutes to 24 hours. It is synthesized by a reaction of 1 to 4 hours.

The esterifying agent is preferably one which can be easily removed by purification, for example, N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N - dimethylformamide dipropyl acetal, N,N-dimethylformamide dinepentyl butyl acetal, N,N-dimethylformamide di-t-butyl acetal , 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl-3-p-tolyltriazene, 4-(4,6- Dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride and the like. The amount of esterification agent added is relative to the repeat of poly-proline The unit is 1 mole, preferably 2 to 6 mole equivalents.

The solvent for the above reaction is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone or γ-butyrolactone in terms of solubility of the polymer, and these may be used. Use 2 types or more. The concentration at the time of the synthesis is less likely to cause precipitation of the polymer and is easy to obtain a high molecular weight body, and is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass.

(2) A case synthesized by the reaction of a tetracarboxylic acid diester dichloride with a diamine

Polyammonium esters can be synthesized by tetracarboxylic acid diester dichlorides and diamines.

Specifically, it can be carried out by using a tetracarboxylic acid diester dichloride and a diamine 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. It is synthesized by reacting for 24 hours, preferably 1 to 4 hours.

As the base, pyridine, triethylamine or 4-dimethylaminopyridine can be used, but from the viewpoint of stable reaction, pyridine is preferred. The amount of the base to be added is preferably from 2 to 4 times the molar amount with respect to the tetracarboxylic acid diester dichloride from the viewpoint of easy removal amount and easy availability of a high molecular weight body.

The solvent to be used for the above-mentioned reaction is preferably N-methyl-2-pyrrolidone or γ-butyrolactone in terms of the solubility of the monomer and the polymer. These may be used alone or in combination of two or more. The concentration of the polymer 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 precipitation of the polymer is less likely to occur and the high molecular weight body is easily obtained. Further, in order to prevent hydrolysis of the tetracarboxylic acid diester dichloride, the synthesis of the polyamidite is used. The solvent is preferably dehydrated as much as possible, and in a nitrogen atmosphere, it is preferred to prevent external air incorporation.

(3) A case where a tetracarboxylic acid diester is synthesized with a diamine

Polyammonium esters can be synthesized by condensation polymerization of tetracarboxylic acid diesters and diamines.

Specifically, the tetracarboxylic acid diester and the diamine can be carried out in the presence of a condensing agent, a base or an organic solvent at 0 ° C to 150 ° C, preferably 0 ° C to 100 ° C, for 30 minutes to 24 hours. It is synthesized in an hour, preferably from 3 to 15 hours.

As the condensing agent, triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, N, N'-carbonyldiimidazole, dimethoxy-1,3,5-triazinylmethylmorpholinium, O-(benzotriazol-1-yl)-N,N,N',N'- Tetramethyluronium tetrafluoroborate, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate, (2,3-dihydrogen) 2-thione (thioxo)-3-benzoxazolyl)phosphonic acid diphenyl ester. The amount of the condensing agent added is preferably 2 to 3 times moles relative to the tetracarboxylic 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 from 2 to 4 times the molar amount of the diamine component from the viewpoint of easily removing the amount and easily obtaining a high molecular weight body.

Further, in the above reaction, Lewis acid is added as an additive, and the reaction can be carried out efficiently. The Lewis acid is preferably a lithium halide such as lithium chloride or lithium bromide. The amount of Lewis acid added is preferably 0 to 1.0 times mole relative to the diamine component.

In the method for synthesizing the above three polyglycolates, a high molecular weight polyglycolate can be obtained. Therefore, the synthesis method of the above (1) or (2) is particularly preferable.

The solution of the polyphthalate obtained by the above method is poured into a weak solvent with sufficient stirring to precipitate a polymer. After several times of precipitation, washing with a weak solvent, the purified polyphthalate powder can be obtained after normal temperature or heating and drying. The weak solvent is not particularly limited, and examples thereof include water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene, and the like.

<Method for producing polylysine>

When the polyamidiamine precursor used in the present invention is poly-proline, the polyamine can be reacted with the diamine compound represented by the above formula (7) by the tetracarboxylic dianhydride represented by the above formula (4). And got it.

Specifically, the tetracarboxylic dianhydride and the diamine can be used 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 of reaction to synthesize.

The organic solvent used in the above reaction is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone or γ-butyrolactone from the solubility of the monomer and the polymer. These may be used alone or in combination of two or more. The concentration of the polymer is preferably from 1 to 30% by mass, and more preferably from 5 to 20% by mass, from the viewpoint that the precipitation of the polymer is less likely to occur and the high molecular weight body is easily obtained.

As the polyamic acid obtained by the above method, the reaction solution can be sufficiently stirred while a weak solvent is injected to precipitate the polymer and then recovered. Further, it is precipitated several times, washed with a weak solvent, and dried at room temperature or under heating to obtain Purified poly-proline powder. The weak solvent is not particularly limited, and examples thereof include water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene, and the like.

<Method for producing polyimine]

The polyimine used in the present invention is produced by ruthenium imidization of a polyimine precursor composed of the above polyperurethane and/or polyamic acid. When the polyimine is produced from polyphthalate, the chemical property of the basic catalyst is added to the polyamic acid solution obtained by dissolving the polyphthalate solution or the polyphthalate resin powder in an organic solvent. The imidization of hydrazine is relatively simple. The chemical ruthenium imidization can be carried out at a relatively low temperature for the ruthenium imidization reaction, and it is preferred that the molecular weight of the polymer is not easily lowered during the ruthenium imidization.

The chemical oxime imidization system can be carried out by stirring a polyamine phthalate which is imidized in an organic solvent in the presence of a basic catalyst. As the organic solvent, the solvent used in the above polymerization reaction can be used.

The basic catalyst is, for example, pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine or the like. Among them, triethylamine is preferred because it has sufficient alkalinity for carrying out the reaction.

The temperature at which the ruthenium imidization reaction is carried out is -20 ° C to 140 ° C, preferably 0 ° C to 100 ° C, and the reaction time can be carried out within 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 moles of the valinate group, preferably 2 to 20 moles. The ruthenium imidization ratio of the obtained polymer can be controlled by adjusting the amount of the catalyst, the temperature, and the reaction time. Since the added catalyst or the like remains in the solution after the imidization reaction, the obtained quinone imidized polymer is recovered by the following means, and re-dissolved in an organic solvent is preferable as the liquid crystal alignment agent of the present invention.

When the polyimine is produced from polylysine, the chemical ruthenium imidization of the catalyst in the polyamic acid solution obtained by the reaction of the diamine component and the tetracarboxylic dianhydride is relatively simple. The chemical ruthenium imidization can be carried out at a relatively low temperature for the ruthenium imidization reaction, and it is preferred that the molecular weight of the polymer is not easily lowered during the ruthenium imidization.

The chemical oxime imidization system can be carried out by stirring a polymer which is imidized in an organic solvent in the presence of a basic catalyst and an acid anhydride. As the organic solvent, the solvent used in the above polymerization reaction can be used.

The basic catalyst is, for example, pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine or the like. Among them, pyridine is preferred because it has sufficient alkalinity for carrying out the reaction. The acid anhydride is, for example, acetic anhydride, trimellitic anhydride, benzene tetracarboxylic anhydride or the like. When an acid anhydride is used, purification after completion of the reaction becomes easier, which is preferable.

The temperature at which the ruthenium imidization reaction is carried out is -20 ° C to 140 ° C, preferably 0 ° C to 100 ° C, and the reaction time can be carried out within 1 to 100 hours. The amount of the alkaline catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the prolyl group, and the amount of the acid anhydride is 1 to 50 moles of the amidate group, preferably 3 to 3 30 times Mo. The ruthenium imidization ratio of the obtained polymer can be controlled by adjusting the amount of the catalyst, the temperature, and the reaction time.

The added catalyst or the like remains in the solution after the imidization reaction of the polyperurethane or the poly-proline, and the obtained ruthenium-imided polymer is recovered by the following means, followed by the organic solvent. Dissolution is preferred as the liquid crystal alignment agent of the present invention.

a solution of the polyimine obtained as described above, infused with a weak agitation In the agent, the polymer can be precipitated. After several times of precipitation, washing with a weak solvent, the purified polyphthalate powder can be obtained at room temperature or by heating.

The weak solvent is, for example, methanol, acetone, hexane, butyl sirolimus, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene or the like.

<Liquid alignment agent>

The liquid crystal alignment agent of the present invention contains at least one type of polymer selected from the group consisting of a polyimine precursor represented by the above formula (1) and a quinone imidized polymer of the polyimide precursor. The sulfonate represented by the above formula (2) and an organic solvent. The polymer contained in the liquid crystal alignment agent of the present invention is preferably a polyamidomate and/or a polyimide precursor composed of polyamic acid from the viewpoint of solubility in an organic solvent. Further, the polymer used in the present invention may be two or more types.

The weight average molecular weight of the polymer contained in the liquid crystal alignment agent of the present invention is preferably 5,000 to 300,000, more preferably 10,000 to 200,000. Further, the number average molecular weight is preferably from 2,500 to 150,000, more preferably from 5,000 to 100,000. The liquid crystal alignment agent of the present invention is preferably in the form of a solution in which the above polymer and a sulfonic acid ester are dissolved in an organic solvent.

The content (concentration) of the polymer and the sulfonate in the liquid crystal alignment agent of the present invention can be appropriately changed in accordance with the thickness setting of the polyimide film to be formed, but a uniform and defect-free coating film is formed. In view of the organic solvent, the content of the polymer component is preferably 0.5% by mass or more, and is preferably 20% by mass or less, and more preferably 1 to 15% by mass, from the viewpoint of storage stability. Moreover, at this time, a thick solution of the polymer can be prepared in advance. When the liquid crystal alignment agent is prepared from this concentrated solution, it can be diluted. The concentration of the concentrated solution of the polymer component is preferably from 10 to 30% by mass, more preferably from 10 to 15% by mass. Further, when a powder of a polymer component is dissolved in an organic solvent to prepare a solution, heating can be performed. The heating temperature is preferably from 20 ° C to 150 ° C, more preferably from 20 ° C to 80 ° C.

The organic solvent contained in the liquid crystal alignment agent of the present invention is not particularly limited as long as it is a solvent capable of uniformly dissolving the polymer and the sulfonic acid ester. Specific examples thereof include N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and N-B. Base-2-pyrrolidone, N-methyl caprolactam, 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyl hydrazine, dimethyl hydrazine, γ-butyrolactone, 1,3-two Methyl-imidazolidinone, 3-methoxy-N,N-dimethylpropionamide, and the like. These may be used alone or in combination of two or more. Moreover, even if it is a single solvent, when the solvent of a polymer component cannot be melt|dissolved uniformly, it can mix with the above-mentioned organic solvent as long as the polymer is not the precipitation.

The liquid crystal alignment agent of the present invention may further contain a solvent for improving the uniformity of the coating film when the liquid crystal alignment agent is applied to the substrate, in addition to the organic solvent for dissolving the polymer and the sulfonate. This solvent is generally a solvent having a lower surface tension than the above organic solvent. Specific examples include, for example, cellosolve, butyl sage, butyl succinate, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, and B. Glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoethyl Acid ester, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene Alcohol, 2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, and the like. These solvents may be used in combination of two types.

The liquid crystal alignment agent of the present invention preferably contains two or more kinds of organic solvents selected from the group consisting of N-methyl-2-pyrrolidone, γ-butyrolactone, and butyl sarbuta, and more preferably contains N-A. Peptidyl-2-pyrrolidone and butyl sarbuta, particularly preferably containing N-methyl-2-pyrrolidone, γ-butyrolactone and butyl sirolius.

The sulfonate is added to the concentrated solution or the diluted solution of the above polymer, and the liquid crystal alignment agent is prepared by stirring at 0 ° C to 100 ° C, preferably 20 ° C to 50 ° C. The stirring time is preferably from 1 hour to 48 hours, more preferably from 1 to 14 hours.

The liquid crystal alignment agent of the present invention may contain various additives such as a decane coupling agent or a crosslinking agent. The decane coupling agent is added in order to improve the adhesion of the substrate coated with the liquid crystal alignment agent to the liquid crystal alignment film formed thereon.

<Liquid alignment film>

The liquid crystal alignment film of the present invention is a film obtained by applying the above liquid crystal alignment agent to a substrate, drying and baking. The substrate to which the liquid crystal alignment agent of the present invention is applied is not particularly limited as long as it is a substrate having high transparency, and a plastic substrate such as a glass substrate, a tantalum nitride substrate, an acrylic substrate, or a polycarbonate substrate can be used. When a substrate such as an ITO electrode is formed for liquid crystal driving, it is preferable from the viewpoint of simplification of the process. Further, in the case of a reflective liquid crystal display element, opaque or the like can be used only when the substrate is on one side. The material at this time can also use a material such as aluminum that reflects light.

The method of applying the liquid crystal alignment agent of the present invention includes, for example, a spin coating method, a printing method, an inkjet method, and the like. The drying and baking steps after applying the liquid crystal alignment agent of the present invention may be selected to any temperature and time. Usually, in order to sufficiently remove the organic solvent contained, it is dried at 50 ° C to 120 ° C for 1 minute to 10 minutes, and then baked at 150 ° C to 300 ° C for 5 minutes to 120 minutes. The thickness of the coating film after baking is not particularly limited. Generally, when it is too thin, the reliability of the liquid crystal display element may be lowered, so it is usually 5 to 300 nm, preferably 10 to 200 nm.

The method of performing the alignment treatment of the obtained liquid crystal alignment film may be, for example, a rubbing method or a photoalignment treatment method.

Specific examples of the photo-alignment treatment method include, for example, a method in which a surface of the coating film is irradiated with radiation that is deflected in a certain direction, and if necessary, heat treatment is performed at a temperature of 150 to 250 ° C to impart energy to the liquid crystal alignment. For the radiation, for example, ultraviolet rays and visible rays having a wavelength of 100 nm to 800 nm can be used. Among them, ultraviolet rays having a wavelength of from 100 nm to 400 nm are preferred, and those having a wavelength of from 200 nm to 400 nm are particularly preferred. Further, in order to improve the liquid crystal alignment property, the coating film substrate may be heated at 50 to 250 ° C and irradiated with radiation. The irradiation amount of the radiation is preferably from 1 to 10,000 mJ/cm ² , particularly preferably from 100 to 5,000 mJ/cm ² . As the liquid crystal alignment film produced as described above, liquid crystal molecules can be stably aligned in a specific direction.

[Examples]

The invention is illustrated in more detail below by way of examples, but the invention is not limited thereto.

The abbreviations of the compounds used in the following examples and comparative examples, and the measurement methods of various characteristics are as follows.

1,3DMCBDE-C1: dimethyl 1,3-bis(chlorocarbonyl)-1,3-dimethylcyclobutane-2,4-dicarboxylate

NMP: N-methyl-2-pyrrolidone

GBL: γ-butyrolactone

BCS: Butyl Cyrus

DAH-1: the following formula (DAH-1)

[viscosity]

In the synthesis example, the viscosity of the polyphthalate and the poly-proline solution was E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), sample volume 1.1 mL, and rotor TE-1 (1) °34', R24), measured at a temperature of 25 °C.

[molecular weight]

Further, the molecular weight of the polyglycolate is measured by a GPC (Normal Temperature Gel Permeation Chromatography Analyzer) apparatus, and the number average molecular weight is calculated from the values of polyethylene glycol and polyethylene oxide (hereinafter, also referred to as Mn). ) with a weight average molecular weight (hereinafter, also referred to as Mw).

GPC device: manufactured by Shodex (GPC-101)

Pipe column: made by Shodex company (inline of KD803, KD805)

Column temperature: 50 ° C

Dissolution: N,N-dimethylformamide (additive lithium bromide-hydrate (LiBr.H ₂ O) is 30 mmol/L, phosphoric acid. Anhydrous crystal (o-phosphoric acid) is 30 mmol/L, tetrahydrofuran (THF) 10ml/L)

Flow rate: 1.0ml/min

Standard sample for making calibration lines: TSK standard polyethylene oxide manufactured by Tosoh Corporation (weight average molecular weight (Mw) of about 900,000, 150,000, 100,000, 30,000), and polyethylene glycol manufactured by Polymer Laboratories (peak top molecular weight (Mp) ) about 12,000, 4,000, 1,000). In the measurement, in order to avoid overlapping of the peaks, four types of samples of 900,000, 100,000, 12,000, and 1,000 were mixed, and two samples of three types of 150,000, 30,000, and 4,000 were mixed.

[FRY driving liquid crystal cell production]

On the glass substrate, an ITO electrode having a first layer having an electrode thickness of 50 nm as an electrode, a second layer having a thickness of 500 nm as an insulating film, and a third layer having a comb-like ITO electrode as an electrode were formed. On the glass substrate of the electrode for driving the edge electric field (Fringe Field Switching: hereinafter referred to as FFS), the liquid crystal alignment agent was applied by a spin coating method (electrode width: 3 μm, electrode spacing: 6 μm, electrode height: 50 nm) On it. After drying on a hot plate at 80 ° C for 5 minutes, it was baked in a hot air circulating oven at 250 ° C for 60 minutes to form a coating film having a film thickness of 100 nm. The surface of the coating film was irradiated with ultraviolet light or rubbed to obtain a substrate with a liquid crystal alignment film. Also, as a counter substrate A glass substrate having a columnar spacer having a height of 4 μm in which an electrode was not formed was also formed into a coating film, and subjected to alignment treatment.

Further, the two substrates are used as a group, and the sealant is printed on the substrate, and the other substrate is bonded to the liquid crystal alignment film surface, and the alignment direction is 0°, and then the sealant is cured to form an air crystal. Cell. In this empty cell, liquid crystal MLC-2041 (manufactured by Merck Co., Ltd.) was injected by a vacuum injection method, and the injection port was closed to obtain an FFS-driven liquid crystal cell.

[Charge mitigation characteristics]

The liquid crystal cell was placed on a light source, and the V-T characteristic (voltage-transmittance characteristic) was measured, and then the transmittance (Ta) of the liquid crystal cell in a state where a rectangular wave of ±1.5 V/60 Hz was applied was measured. Subsequently, after a rectangular wave of ±1.5 V/60 Hz was applied for 10 minutes, DC 2V was overlapped and driven for 120 minutes. The DC voltage was cut off, and the transmittance (Tb) of the liquid crystal cell at 0 minute, 5 minutes, 10 minutes, 20 minutes, and 60 minutes of the rectangular wave driving of only ±1.5 V/60 Hz was measured, and the transmittance from each time ( The difference between the transmittance (T) of the initial transmittance (Ta) and the initial transmittance (?T) is calculated as the difference in transmittance due to the voltage remaining in the liquid crystal display element.

(Synthesis Example 1)

5.8 g (30.0 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube, and NMP 64.08 g was added, and then fed. The nitrogen is simultaneously stirred. Next, the solution in the reaction vessel is stirred while adding p-phenylenediamine (hereinafter also referred to as p- PDA) 3.04 g (28.1 mmol), and further added NMP so that the solid content concentration became 10% by mass, and the mixture was stirred at room temperature for 24 hours to obtain a solution of polyamine acid (PAA-1). The polyamic acid solution has a viscosity of 171 mPa at a temperature of 25 ° C. s. Further, the molecular weight of the polyamic acid was Mn = 12,373 and Mw = 28,957.

(Synthesis Example 2)

3,5-diaminobenzoic acid (3.65 g (24.0 mmol) and DA-4 1.46 g (6.0 mmol) were weighed in a 100 mL four-necked flask equipped with a stirring apparatus and a nitrogen inlet tube, and NMP 55.74 g was added. Nitrogen is then fed while stirring to dissolve. The diamine solution was stirred while adding 5.83 g (29.7 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and NMP was added to make the solid content concentration 15% by mass, and the mixture was stirred at room temperature. In hours, a solution of polyaminic acid (PAA-2) was obtained. The polyamic acid solution has a viscosity of 264 mPa at a temperature of 25 ° C. s. Further, the molecular weight of the polyamic acid was Mn = 11630 and Mw = 30056.

(Synthesis Example 3)

In a 100 mL four-necked flask equipped with a stirring device and a nitrogen-introducing tube, 20.08 g (132 mm0) of 3,5-diaminobenzoic acid and 21.33 g (88.0 mmol) of DA-4 were weighed, and then NMP 268.48 g was added. Nitrogen is supplied and stirred to dissolve. The diamine solution was stirred while adding 42.49 g (217 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and NMP was added to make the solid content concentration 20% by mass, and stirred at room temperature. small At this time, a solution of polyaminic acid (PAA-3) was obtained. The viscosity of the polyamic acid solution at a temperature of 25 ° C is 2156 mPa. s. Further, the molecular weight of the polyamic acid was Mn = 18,794 and Mw = 63,387.

(Synthesis Example 4)

3,5-diaminobenzoic acid (3.65 g (24.0 mmol) was weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube, and 8.99 g of NMP was added thereto, and nitrogen was supplied thereto, and the mixture was stirred and dissolved. . Next, DA-4 1.46 g (6.01 mmol) was weighed, and GBL 15.75 g was added thereto, and nitrogen was supplied thereto while stirring to dissolve. The diamine solution was stirred while 4.16 g (21.0 mmol) of 1,2,3,4-butanetetracarboxylic dianhydride was added, and the mixture was stirred under water cooling for 2 hours. Next, GBL 11.18g was added, and 1.96 g (9.0 mmol) of pyromellitic dianhydride was added. Further, GBL was added to make the solid content concentration 20% by mass, and the mixture was stirred at room temperature for 24 hours. The obtained polyaminic acid solution has a viscosity of 1904 mPa at a temperature of 25 ° C. s. Further, the molecular weight of the polyamic acid was Mn = 8509 and Mw = 16774.

Further, 0.03 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyaminic acid solution (PAA-4).

(Synthesis Example 5)

In a 100 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube, 2.60 g (24.0 mmol) of m-phenylenediamine and 1.45 g (6.0 mmol) of DA-4 were weighed, and 53.69 g of NMP was added, followed by nitrogen. While stirring Mix and dissolve. The diamine solution was stirred while adding 6.41 g (39.4 mmol) of pyromellitic dianhydride, and NMP was added to make the solid content concentration 15% by mass, and stirred at room temperature for 24 hours to obtain polyglycine (PAA- 5) solution. The polyamic acid solution has a viscosity of 208 mPa at a temperature of 25 ° C. s. Further, the molecular weight of the polyproline was Mn = 1067 and Mw = 22,829.

(Synthesis Example 6)

4,4'-diaminodiphenyl ether 4.81 g (24.0 mmol) and DA-5 1.56 g (6.0 mmol) were weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube, and NMP 61.85 was added. g, nitrogen is fed and stirred to dissolve. The diamine solution was stirred while adding 5.77 g (29.4 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and NMP was added thereto to have a solid content concentration of 15% by mass, and stirred at room temperature. In hours, a solution of polyaminic acid (PAA-6) was obtained. The polyamic acid solution has a viscosity of 799 mPa at a temperature of 25 ° C. s. Further, the molecular weight of the polyamic acid was Mn = 12,569 and Mw = 27,653.

(Synthesis Example 7)

3,5-diaminobenzoic acid (3.65 g (24.0 mmol) and 2,6-diaminopyridine 0.66 g (6.0 mmol) were weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube. 51.67 g of NMP was added, nitrogen was supplied, and it stirred and it melt|dissolved. The diamine solution was stirred while adding 1.83 g (29.7 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and then added. NMP was adjusted to a solid content concentration of 15% by mass, and stirred at room temperature for 24 hours to obtain a solution of polyglycine (PAA-7). The polyamic acid solution has a viscosity of 60 mPa at a temperature of 25 ° C. s. Further, the molecular weight of the polyamic acid was Mn = 5090 and Mw = 7824.

(Synthesis Example 8)

In a 100 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube, 0.65 g (6.0 mmol) of m-phenylenediamine and 1.57 g (4.0 mol) of DA-6 were weighed, and 35.29 g of NMP was added, followed by nitrogen. While stirring, it is dissolved. The diamine solution was stirred, and 2.14 g (9.8 mmol) of pyromellitic dianhydride was added thereto, and NMP was added thereto so that the solid content concentration became 10% by mass, and the mixture was stirred at room temperature for 24 hours to obtain polylysine (PAA- 8) solution. The polyamic acid solution has a viscosity of 219 mPa at a temperature of 25 ° C. s. Further, the molecular weight of the polyproline was Mn = 15827 and Mw = 36626.

(Synthesis Example 9)

3,5-diaminobenzoic acid 0.31 g (2.0 mmol) and 1,4-bis(4-aminophenyl)piperazine were weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube. 0.81 g (3.0 mmol) was added to 33.70 g of NMP, and then nitrogen was supplied thereto while stirring to dissolve. The diamine solution was stirred while 0.97 g (5.0 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was added, and NMP was added to make the solid content concentration 10% by mass, and the mixture was stirred at room temperature. In hours, a solution of polyaminic acid (PAA-9) was obtained. The viscosity of the polyamic acid solution at a temperature of 25 ° C is 375 mPa. s. Polylysine The molecular weight was Mn = 14398 and Mw = 35,294.

(Synthesis Example 10)

A 300 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, and 1.51 g (14.0 mmol) of m-phenylenediamine and 0.84 g (3.5 mol) of DA-4 were placed, and 115.36 g of NMP and 3.16 g of pyridine as a base were added. (40.0 mmol) was stirred and dissolved. This diamine solution was stirred while adding 4.95 g (16.7 mmol) of dimethyl1,3-bis(chlorocarbonyl)cyclobutane-2,4-dicarboxylate, and reacted under water cooling for 4 hours. The obtained polyphthalate solution was simultaneously introduced into 607 g of water while stirring, and the precipitate was precipitated by filtration, and then washed once with 607 g of water, once with 607 g of ethanol, and washed with 125 g of ethanol. Three times, a polyphthalate resin powder was obtained by drying.

The molecular weight of this polyphthalate was Mn = 5967 and Mw = 12346.

2.75 g of the polyphthalate resin powder obtained above was weighed in a 100 ml Erlenmeyer flask, and 24.79 g of NMP was further added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamine ester solution (PAE-1).

(Synthesis Example 11)

A 300 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, and 2.01 g (13.2 mmol) of 3,5-diaminobenzoic acid and 0.80 g (3.3 mol) of DA-4 were added thereto, and 120.31 g of NMP was added thereto as a base. 2.99 g (37.9 mmol) of pyridine was stirred and dissolved. The diamine solution is stirred while adding dimethyl 1,3-bis(chlorocarbonyl)cyclobutane-2,4-dicarboxylate 4.69 g (15.8 mmol) was reacted for 4 hours under water cooling. The obtained polyphthalate solution was simultaneously introduced into 633 g of water under stirring, and the precipitate was precipitated by filtration, and then washed once with 633 g of water, once with 633 g of ethanol, and washed with 130 g of ethanol. Three times, a polyphthalate resin powder was obtained by drying.

The molecular weight of this polyphthalate was Mn = 6757 and Mw = 11827.

2.72 g of the polyphthalate resin powder obtained above was weighed in a 100 ml Erlenmeyer flask, and 24.46 g of NMP was further added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamine ester solution (PAE-2).

(Synthesis Example 12)

A 300 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, and 2.01 g (18.6 mmol) of p-phenylenediamine and 1.12 g (4.6 mmol) of DA-4 were added, and 164.36 g of NMP and 4.21 g of pyridine as a base were added. 53.3 mmol) was stirred to dissolve. The diamine solution was stirred while 7.2 g (22.2 mmol) of 1,3DM-CBDE-C1 was added, and the mixture was reacted for 4 hours under water cooling. The obtained polyphthalate solution was simultaneously introduced into 865 g of water under stirring, and the precipitated white precipitate was obtained by filtration, followed by washing once with 865 g of water, washing once with 865 g of ethanol, and washing with 180 g of ethanol. The white polyphthalate resin powder was obtained by drying three times. The molecular weight of this polyphthalate was Mn=14692 and Mw=31251.

Into a 50 ml Erlenmeyer flask, 2.14 g of the polyphthalate resin powder obtained above was weighed, and 20.35 g of NMP was further added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamine solution (PAE-3).

(Synthesis Example 13)

4,4'-diaminodiphenyl ether, 5.40 g (27.0 mmol) and DA-4 0.73 g (3.0 mmol) were weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube, and NMP 65.23 was added. g, then nitrogen is fed and stirred to dissolve. The diamine solution was stirred while adding 6.66 g (29.7 mmol) of 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, and NMP was added to make the solid concentration 15 The mass% was stirred at room temperature for 24 hours to obtain a polyaminic acid solution. The viscosity of the polyaminic acid solution at a temperature of 25 ° C is 233 mPa. s.

Next, 25.52 g of the above polyamic acid solution was weighed in a 100 ml eggplant type flask, and 37.53 g of NMP was added to form a solid content concentration of 6 mass%. To the polyamic acid solution, 16.93 g of acetic anhydride and 7.91 g of pyridine were added, and the mixture was stirred at 50 ° C for 3 hours. The obtained reaction solution was simultaneously introduced into 306 g of methanol under stirring, and the precipitated white precipitate was obtained by filtration, and then washed twice with 306 g of ethanol, washed three times with 100 g of ethanol, and dried to obtain a white aggregate. Yttrium imide resin powder. The polyimide imidization ratio of this polyimide resin was 98%. Further, the molecular weight of the polyimine resin was Mn = 10539 and Mw = 21428.

2.32 g of the polyimine resin powder obtained above was weighed in a 50 ml Erlenmeyer flask, and 20.92 g of NMP was further added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyimine solution (SPI-1).

(Synthesis Example 14)

3,5-diaminobenzoic acid (2.09 g (13.7 mmol), DA-4 1.51 g (6.2 mmol), DA-7 1.90 g were weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube. (5.0 mmol) and 41.22 g of NMP were stirred and dissolved at 40 °C. The diamine solution was stirred while adding 1.79 g (24.4 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and reacted at 40 ° C for 24 hours to obtain a polyaminic acid solution (PAA- 10). The molecular weight of this polyaminic acid was Mn = 15400 and Mw = 52,600.

(Synthesis Example 15)

3,5-diaminobenzoic acid 1.07 g (7.0 mmol), DA-4 1.70 g (7.0 mmol), DA-8 2.61 g were weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube. (6.0 mmol) and 27.37 g of NMP were stirred at 80 ° C to dissolve. The diamine solution was stirred while adding 3.75 g (15.0 mmol) of bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride, and reacted at 80 ° C for 5 hours. After 5 hours, 0.95 g (4.8 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 12.93 g of NMP were added, and the mixture was reacted at 40 ° C for 6 hours to obtain a polyaminic acid solution.

After adding NMP to 20.0 g of this polyaminic acid solution and diluting it to 6 mass%, 4.04 g of acetic anhydride and 1.25 g of pyridine as a ruthenium-imidation catalyst were added, and it reacted at 100 degreeC for 3 hours. The reaction solution was poured into 330 g of methanol under stirring, and the precipitate was collected by filtration, and then washed twice with 150 g of methanol to obtain a polyimide resin powder by drying. The polyimide imidization ratio of this polyimide resin was 80%. Further, the molecular weight of the polyimine resin was Mn = 19,100 and Mw = 6,1600.

Into a 100 ml Erlenmeyer flask, 5.02 g of the polyimine resin powder obtained above was weighed, and 33.60 g of NMP was further added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyimine solution (SPI-2).

(Synthesis Example 16)

4,4'-diaminodiphenyl-N-methylamine 0.43 (2.0 mmol) and 1,3-bis(4-amine) were weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube. 2.07 g (8.0 mol) of phenoxy)propane, and 37.68 g of NMP was added, and then nitrogen was supplied thereto while stirring to dissolve. The diamine solution was stirred, and 2.05 g (9.4 mmol) of pyromellitic dianhydride was added thereto, and NMP was added thereto so that the solid content concentration became 10% by mass, and the mixture was stirred at room temperature for 24 hours to obtain polylysine (PAA). -11) solution. The viscosity of the polyamic acid solution at a temperature of 25 ° C is 214 mPa. s. Further, the molecular weight of the polyamic acid was Mn = 17227 and Mw = 44,964.

(Synthesis Example 17)

A 300 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, and 2.81 g (26.0 mmol) of p-phenylenediamine and 1.10 g (2.89 mmol) of DA-1 were placed, and 51.99 g of NMP and 155.97 g of GBL were added as a base. 5.16 g (65.18 mmol) of pyridine was stirred and dissolved. This diamine solution was stirred while adding 8.83 g (27.2 mmol) of 1,3-bis(chlorocarbonyl)cyclobutane-2,4-dicarboxylate, and reacted under water cooling for 4 hours. After 4 hours, 0.75 g (8.3 mmol) of acrylonitrile chloride was added, and the mixture was reacted for 30 minutes under water cooling. The obtained polyphthalate solution was simultaneously charged with 905 g of 2- under stirring In the propanol, the precipitate was precipitated by filtration, and then washed with 448 g of 2-propanol for 5 times to obtain a polyphthalate resin powder by drying.

The molecular weight of this polyphthalate was Mn = 15623 and Mw = 30510.

10.10 g of the above obtained polyphthalate resin powder was weighed in a 100 ml Erlenmeyer flask, and further added with GBL 91.06 g, and stirred at room temperature for 24 hours to be dissolved to obtain a polyamine solution (PAE-4).

(Synthesis Example 18)

A 300 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, and p-PDA (2.03 g (18.8 mmol), DA-3 1.23 g (4.6 mmol) was added, and NMP 167.80 g was added as a base pyridine 4.21 g (53.3). Mmmol), stirring to dissolve. Next, this diamine solution was stirred while adding 7.22 g (22.2 mmol) of dimethyl1,3-bis(chlorocarbonyl)cyclobutane-2,4-dicarboxylate, and reacted under water cooling for 4 hours. The obtained polyphthalate solution was simultaneously introduced into 885 g of water while stirring, and the precipitated white precipitate was obtained by filtration, followed by washing once with 885 g of water, and once with 885 g of ethanol to give 220 g of ethanol. After washing three times, a white polyphthalate resin powder was obtained by drying. The molecular weight of this polyphthalate was Mn = 14116 and Mw = 27044.

7.26 g of the polyphthalate resin powder obtained above was weighed in a 100 ml Erlenmeyer flask, and 65.35 g of GBL was further added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamine solution (PAE-5).

(Synthesis Example 19)

Into a four-necked flask equipped with a stirring device and a nitrogen-introducing tube, 19.47 g (180 mmol) of p-phenylenediamine and 4.47 g (18.8 mmol) of DA-2 were weighed, and 50.03 g of NMP was added thereto, followed by nitrogen. At the same time, stirring was carried out to dissolve. The amine solution was stirred while adding 38.04 g (194 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and NMP was added thereto so that the solid content concentration became 10% by mass, and the mixture was stirred at room temperature for 24 hours. A solution of polyaminic acid (PAA-12) was obtained. The polyamic acid solution has a viscosity of 462 mPa at a temperature of 25 ° C. s. Further, the molecular weight of the polyamic acid was Mn = 16976 and Mw = 43749.

(Synthesis Example 20)

3.6 g (24.0 mmol) of 3,5-diaminobenzoic acid was weighed in a 100 mL four-necked flask equipped with a stirring apparatus and a nitrogen inlet tube, and 18.82 g of NMP was added thereto, and then nitrogen was supplied thereto and stirred. Dissolved. Next, DA-4 3.88 g (16.0 mmol) was weighed, and 18.81 g of GBL was added, and then nitrogen was supplied thereto while stirring to dissolve. The diamine solution was stirred while adding 1.47 g (27.6 mmol) of 1,2,3,4-butanetetracarboxylic dianhydride, and the mixture was stirred under water cooling for 2 hours. Next, 4.71 g of GBL was added, and 2.74 g (12.2 mmol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride was further added. Further, GBL was added to make the solid content concentration 25% by mass, and the mixture was stirred at room temperature for 24 hours. The obtained polyaminic acid solution has a viscosity of 2142 mPa at a temperature of 25 ° C. s. Further, the molecular weight of the polyamic acid was Mn = 6509 and Mw = 11481.

Further, 0.05 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyaminic acid solution ( PAA-13).

(Synthesis Example 21)

A 300 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, and 4.00 g (37.0 mmol) of p-phenylenediamine and 1.56 g (4.11 mol) of DA-4 were placed, and 76.32 g of NMP and 228.03 g of GBL were added as a base. 11.2 g (92.7 mmol) of 2,4,6-trimethylpyridine was stirred and dissolved. Then, the amine solution was stirred while 12.2 g (38.6 mmol) of dimethyl1,3-bis(chlorocarbonyl)cyclobutane-2,4-dicarboxylate was added, and the mixture was reacted for 4 hours under water cooling. After stirring for 4 hours, 0.878 g (4.93 mmol) of isonicotinic acid chloride was added, and the obtained polyglycolate solution was simultaneously added to 1335 g of ethanol under stirring, and the precipitate was precipitated by filtration, followed by 661 g of ethanol. It was washed 5 times, and the polyphthalate resin powder was obtained by drying.

The molecular weight of this polyphthalate was Mn = 14983 and Mw = 34,387.

3.45 g of the polyphthalate resin powder obtained above was weighed in a 100 ml Erlenmeyer flask, and 30.94 g of GBL was further added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamine solution (PAE-6).

(Synthesis Example 22)

A 300 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, and 3.09 g (28.6 mmol) of p-phenylenediamine and 1.21 g (3.18 mol) of DA-4 were placed, and 58.81 g of NMP and 176.42 g of GBL were added as a base. 5.67 g (71.7 mmol) of pyridine was stirred and dissolved. The amine solution is then stirred while adding dimethyl 1,3-bis(chlorocarbonyl)cyclobutane-2,4-dicarboxylic acid. The ester was 9.72 g (29.9 mmol) and reacted for 4 hours under water cooling. The obtained polyglycolate solution was simultaneously added to 1018 g of ethanol under stirring, and the precipitate thus obtained was filtered, and then washed with 504 g of ethanol for 5 times to obtain a polyphthalate resin powder by drying.

The molecular weight of this polyphthalate was Mn=16701 and Mw=33541.

0.40 g of the polyphthalate resin powder obtained above was weighed in a 100 ml Erlenmeyer flask, and 3.60 g of GBL was further added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyphthalate solution (PAE-7).

(Example 1)

A stir bar was placed in a 50 ml Erlenmeyer flask, and 6.12 g of the polyamidonic acid solution (PAA-1) obtained in Synthesis Example 1 was weighed, and 0.0639 g of methyl trifluoromethanesulfonate was added thereto, and the mixture was stirred at room temperature for 4 hours. Next, 1.76 g of NMP and 1.96 g of BCS were added, and the mixture was stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal alignment agent (A-1).

(Example 2)

A stirrer was placed in a 50 ml Erlenmeyer flask, and 6.23 g of a polyaminic acid solution (PAA-2) obtained in Synthesis Example 2 and 0.0770 g of methyl trifluoromethanesulfonate were weighed and stirred at room temperature for 4 hours to obtain a poly Proline solution (PAA-2S). Next, another 50 ml Erlenmeyer flask with a stirrer was placed, 2.25 g of polylysine solution (PAA-2S) was weighed, 2.57 g of NMP and 1.23 g of BCS were added, and stirred by a magnetic stirrer for 30 minutes. Liquid crystal alignment agent (A-2).

(Example 3)

A stirrer was placed in a 50 ml Erlenmeyer flask, and 4.53 g of the polyaminic acid solution (PAA-3) obtained in Synthesis Example 3 was weighed, and 0.1470 g of methyl trifluoromethanesulfonate was added thereto, and the mixture was stirred at room temperature for 4 hours to obtain Polylysine solution (PAA-3S). Next, in a 50 ml Erlenmeyer flask in which a stirrer was placed, 1.64 g of a polyaminic acid solution (PAA-3S) was weighed, and 3.32 g of NMP and 1.23 g of BCS were added, and the mixture was stirred for 30 minutes with a magnetic stirrer. A liquid crystal alignment agent (A-3) was obtained.

(Example 4)

A stirrer was placed in a 50 ml Erlenmeyer flask, 4.82 g of the polyaminic acid solution (PAA-4) obtained in Synthesis Example 4 was weighed, and 0.0754 g of methyl trifluoromethanesulfonate was added thereto, and the mixture was stirred at room temperature for 4 hours to obtain Polylysine solution (PAA-4S1). Next, 2.61 g of polylysine solution (PAA-4S1) was weighed in a 50 ml Erlenmeyer flask in which a stirrer was placed, 2.11 g of NMP and 1.19 g of BCS were added, and the mixture was stirred for 30 minutes with a magnetic stirrer. A liquid crystal alignment agent (A-4) was obtained.

(Example 5)

A stirrer was placed in a 50 ml Erlenmeyer flask, 4.82 g of the polyaminic acid solution (PAA-4) obtained in Synthesis Example 4 was weighed, and 0.0359 g of methyl trifluoromethanesulfonate was added thereto, and the mixture was stirred at room temperature for 4 hours to obtain Polylysine solution (PAA-4S2). Secondly, in addition to the other 50ml of the stirrer In a horn flask, 2.61 g of a polyaminic acid solution (PAA-4S2) was weighed, 2.22 g of NMP and 1.21 g of BCS were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (A-5).

(Example 6)

A stirrer was placed in a 50 ml Erlenmeyer flask, and 7.27 g of the polyaminic acid solution (PAA-5) obtained in Synthesis Example 5 was weighed, and 0.0856 g of methyl p-toluenesulfonate was added thereto, and the mixture was stirred at room temperature for 4 hours to obtain Polylysine solution (PAA-5S). Next, in an additional 50 ml Erlenmeyer flask in which a stirrer was placed, 2.61 g of polylysine solution (PAA-5S) was weighed, 2.20 g of NMP and 1.23 g of BCS were added, and the mixture was stirred for 30 minutes with a magnetic stirrer. A liquid crystal alignment agent (A-6) was obtained.

(Example 7)

A stirrer was placed in a 50 ml Erlenmeyer flask, and 6.88 g of the polyaminic acid solution (PAA-6) obtained in Synthesis Example 6 was weighed, and 0.0553 g of methyl methanesulfonate was added thereto, and the mixture was stirred at room temperature for 4 hours to obtain a polyfluorene. Amino acid solution (PAA-6S). Next, in an additional 50 ml Erlenmeyer flask in which a stirrer was placed, 2.66 g of polylysine solution (PAA-6S) was weighed, 2.34 g of NMP and 1.24 g of BCS were added, and the mixture was stirred for 30 minutes with a magnetic stirrer. A liquid crystal alignment agent (A-7) was obtained.

(Example 8)

A stirrer was placed in a 50 ml Erlenmeyer flask, and the synthesis example 7 was weighed. A polyamine acid solution (PAA-7) of 6.50 g was obtained, and 0.0836 g of methyl trifluoromethanesulfonate was added thereto, and the mixture was stirred at room temperature for 4 hours to obtain a polyaminic acid solution (PAA-7S1). Next, in an additional 50 ml Erlenmeyer flask equipped with a stirrer, 2.33 g of a polyaminic acid solution (PAA-7S1) was weighed, and NMP 2.55 g and BCS 1.20 g were added, and the mixture was stirred for 30 minutes with a magnetic stirrer. A liquid crystal alignment agent (A-8) was obtained.

(Example 9)

A stirrer was placed in a 50 ml Erlenmeyer flask, and 6.68 g of the polyaminic acid solution (PAA-7) obtained in Synthesis Example 7 was weighed, and 2,2,2-trifluoroethyl methanesulfonate (0.0462 g) was added thereto at room temperature. The mixture was stirred for 4 hours to obtain a polyaminic acid solution (PAA-7S2). Next, in an additional 50 ml Erlenmeyer flask in which a stirrer was placed, 2.34 g of a polyaminic acid solution (PAA-7S2) was weighed, 2.48 g of NMP and 1.24 g of BCS were added, and the mixture was stirred for 30 minutes with a magnetic stirrer. A liquid crystal alignment agent (A-9) was obtained.

(Embodiment 10)

A stirrer was placed in a 50 ml Erlenmeyer flask, 10.52 g of the polyaminic acid solution (PAA-8) obtained in Synthesis Example 8 was weighed, 0.2204 g of 2-methoxyethyl methanesulfonate was added, and the mixture was stirred at room temperature. In hours, a polyaminic acid solution (PAA-8S) was obtained. Next, in an additional 50 ml Erlenmeyer flask equipped with a stirrer, 3.77 g of a polyaminic acid solution (PAA-8S) was weighed, NMP 1.07 g, and BCS 1.22 g were added, and stirred with a magnetic stirrer for 30 minutes. A liquid crystal alignment agent (A-10) was obtained.

(Example 11)

A stirrer was placed in a 50 ml Erlenmeyer flask, and 9.87 g of the polyaminic acid solution (PAA-9) obtained in Synthesis Example 9 was weighed, 0.1875 g of methyl trifluoromethanesulfonate was added, and the mixture was stirred at room temperature for 4 hours to obtain Polylysine solution (PAA-9S). Next, in a 50 ml Erlenmeyer flask in which a stirrer was placed, 3.57 g of polylysine solution (PAA-9S) was weighed, NMP 1.25 g, and BCS 1.22 g were added, and stirred with a magnetic stirrer for 30 minutes. A liquid crystal alignment agent (A-11) was obtained.

(Embodiment 12)

A stirrer was placed in a 50 ml Erlenmeyer flask, and 10.01 g of the polyamidate solution (PAE-1) obtained in Synthesis Example 10 was weighed, and 0.0671 g of sultone was added thereto, and the mixture was stirred at room temperature for 4 hours. A polyphthalate solution (PAE-1S) was obtained. Next, in an additional 50 ml Erlenmeyer flask in which a stirrer was placed, 3.63 g of a polyamidate solution (PAE-1S) was weighed, 1.20 g of NMP and 1.21 g of BCS were added, and the mixture was stirred by a magnetic stirrer for 30 minutes. A liquid crystal alignment agent (A-12) was obtained.

(Example 13)

A stirrer was placed in a 50 ml Erlenmeyer flask, 10.31 g of the polyamidate solution (PAE-2) obtained in Synthesis Example 11 was weighed, and 0.0813 g of methyl trifluoromethanesulfonate was added thereto, and the mixture was stirred at room temperature for 4 hours. A polyphthalate solution (PAE-2S) was obtained. Secondly, in the other 50ml with a stirrer In a conical flask, 3.62 g of a polyamidate solution (PAE-2S) was weighed, 1.23 g of NMP and 1.21 g of BCS were added, and the mixture was stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal alignment agent (A-13).

(Example 14)

A stirrer was placed in a 50 ml Erlenmeyer flask, 10.32 g of the polyimine solution (SPI-1) obtained in Synthesis Example 13 was weighed, and 0.0352 g of methyl trifluoromethanesulfonate was added thereto, and the mixture was stirred at room temperature for 4 hours to obtain Polyimine solution (SPI-1S). Next, in an additional 50 ml Erlenmeyer flask with a stirrer, 3.61 g of a polyimine solution (SPI-1S) was weighed, 1.22 g of NMP and 1.20 g of BCS were added, and the mixture was stirred for 30 minutes with a magnetic stirrer. A liquid crystal alignment agent (A-14) was obtained.

(Example 15)

A stirrer was placed in a 50 ml Erlenmeyer flask, and 5.28 g of the polyaminic acid solution (PAA-10) obtained in Synthesis Example 14 was weighed, and 0.0813 g of methyl trifluoromethanesulfonate was added thereto, and the mixture was stirred at room temperature for 4 hours to obtain Polylysine solution (PAA-10S). Next, in an additional 50 ml Erlenmeyer flask in which a stirrer was placed, 1.85 g of polylysine solution (PAA-10S) was weighed, NMP 3.00 g, and BCS 1.21 g were added, and stirred with a magnetic stirrer for 30 minutes. A liquid crystal alignment agent (A-15) was obtained.

(Embodiment 16)

A stirrer was placed in a 50 ml Erlenmeyer flask, and the synthesis example 15 was weighed. 3.76 g of a polyimine solution (SPI-2) was obtained, and 0.0539 g of methyl trifluoromethanesulfonate was added thereto, and the mixture was stirred at room temperature for 4 hours to obtain a polyimine solution (SPI-2S). Next, NMP 0.32 g and BCS 4.05g were added, and the mixture was stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal alignment agent (A-16).

(Example 17)

A stirrer was placed in a 50 ml Erlenmeyer flask, and 9.91 g of the polyamidate solution (PAE-3) obtained in Synthesis Example 12 was weighed, and 0.0909 g of methyl trifluoromethanesulfonate was added thereto, and the mixture was stirred at room temperature for 4 hours. A polyphthalate solution (PAE-3S) was obtained. Next, in an additional 50 ml Erlenmeyer flask equipped with a stirrer, 3.60 g of a polyamidomate solution (PAE-3S) was weighed, 1.23 g of NMP and 1.22 g of BCS were added, and stirred by a magnetic stirrer for 30 minutes. A liquid crystal alignment agent (A-17) was obtained.

(Embodiment 18)

A stirrer was placed in a 50 ml Erlenmeyer flask, and 10.10 g of the polyamidonic acid solution (PAA-11) obtained in Synthesis Example 16 was weighed, and 0.0619 g of methyl trifluoromethanesulfonate was added thereto, and the mixture was stirred at room temperature for 4 hours to obtain Polylysine solution (PAA-11S). Next, in an additional 50 ml Erlenmeyer flask in which a stirrer was placed, 3.69 g of polylysine solution (PAA-11S) was weighed, NMP 1.12 g, and BCS 1.22 g were added, and stirred with a magnetic stirrer for 30 minutes. A liquid crystal alignment agent (A-18) was obtained.

(Embodiment 19)

To the sample tube in which 20 ml of the stirrer was placed, 2.24 g of the polyaminic acid solution (PAA-12) obtained in Synthesis Example 19 and 2.48 g of the polyamidic acid solution (PAA-2S) obtained in Example 2 were added. NMP 3.33 g and BCS 2.00 g were stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (A-19).

(Embodiment 20)

To the sample tube in which 20 ml of the stirrer was placed, 2.41 g of the polyamidate solution (PAE-5) obtained in Synthesis Example 18 and the polyamidic acid solution (PAA-3S1) obtained in Example 4 were 1.93 g. NMP 0.43g, GBL 3.27g, BCS 2.00g, and further added N-α-(9-fluorenylmethoxycarbonyl)-Nt-butoxycarbonyl-L-histidine as a ruthenium promoter (Histidine) (hereinafter abbreviated as Fmoc-His) 0.0844 g, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (A-20).

(Example 21)

A stirrer was placed in a 50 ml Erlenmeyer flask, and 30.70 g of the polyamidonic acid solution (PAA-13) obtained in Synthesis Example 20 was weighed, and 0.9011 g of methyl trifluoromethanesulfonate was added thereto, and the mixture was stirred at room temperature for 4 hours to obtain Polylysine solution (PAA-13S). Next, in an additional 50 ml Erlenmeyer flask in which a stirrer was placed, 2.02 g of polylysine solution (PAA-13S) was weighed, 4.68 g of NMP and 1.66 g of BCS were added, and the mixture was stirred for 30 minutes with a magnetic stirrer. A liquid crystal alignment agent (A-21) was obtained.

(Example 22)

To the sample tube in which 20 ml of the stirrer was placed, 3.36 g of the polyphthalate solution (PAE-4) obtained in Synthesis Example 17 and the polyamidic acid solution (PAA-13S) obtained in Example 21 were 2.24 g. NMP 1.37 g, GBL 4.22 g, and BCS 2.81 g were further added with Fmoc-His 0.1146 g as a hydrazine imidization accelerator, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (A-22).

(Embodiment 30)

A stir bar was placed in a 50 ml Erlenmeyer flask, and 4.00 g of the polyamidate solution (PAE-6) obtained in Synthesis Example 21 was weighed, and 0.019 g of methyl trifluoromethanesulfonate was added thereto, and the mixture was stirred at room temperature for 4 hours. Next, GBL 2.41g, BCS 1.61g, and Fmoc-His 0.1478g were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (A-23).

(Example 31)

A stir bar was placed in a 50 ml Erlenmeyer flask, and 4.00 g of the polyamidate solution (PAE-6) obtained in Synthesis Example 21 was weighed, and 0.0205 g of ethyl trifluoromethanesulfonate was added thereto, and the mixture was stirred at room temperature for 4 hours. Next, GBL 2.41g, BCS 1.61g, and Fmoc-His 0.1425g were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (A-24).

(Comparative Example 1)

In the sample tube in which 20 ml of the stirrer was placed, Synthesis Example 1 was added. The obtained polyaminic acid solution (PAA-1) 4.66 g, NMP 1.58 g, and BCS 1.57 g were stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (B-1).

(Comparative Example 2)

Into a sample tube in which 20 ml of a stirrer was placed, 2.46 g of a polyaminic acid solution (PAA-2) obtained in Synthesis Example 2, 2.34 g of NMP, and 1.21 g of BCS were added, and stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal. Orienting agent (B-2).

(Comparative Example 3)

Into a sample tube of 20 ml in which a stirrer was placed, 3.67 g of a polyaminic acid solution (PAA-11) obtained in Synthesis Example 16, 1.15 g of NMP, and 1.21 g of BCS were added, and stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal. Orienting agent (B-3).

(Comparative Example 4)

To a sample tube of 20 ml in which a stirrer was placed, 3.61 g of a soluble polyimine solution (SPI-1) obtained in Synthesis Example 13, 1.22 g of NMP, and 1.22 g of BCS were added, and stirred by a magnetic stirrer for 30 minutes. Liquid crystal alignment agent (B-4).

(Comparative Example 5)

In the sample tube in which 20 ml of the stirrer was placed, Synthesis Example 19 was added. 3.15 g of the obtained polyaminic acid solution (PAA-12), 3.46 g of polyamic acid solution (PAA-2) obtained in Synthesis Example 2, 4.62 g of NMP, and 2.81 g of BCS were stirred by a magnetic stirrer for 30 minutes. Liquid crystal alignment agent (B-5).

(Comparative Example 6)

To the sample tube in which 20 ml of the stirrer was placed, 3.37 g of the polyamidomate solution (PAE-5) obtained in Synthesis Example 18 and the polyamidic acid solution (PAA-4) obtained in Synthesis Example 3 were 2.69 g. NMP 0.61 g, GBL 4.56 g, and BCS 2.83 g were stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (B-6).

(Comparative Example 7)

To the sample tube in which 20 ml of the stirrer was placed, 3.37 g of the polyamidomate solution (PAE-4) obtained in Synthesis Example 17 and 2.25 g of the polyamidonic acid solution (PAA-13) obtained in Synthesis Example 20 were added. NMP 1.39 g, GBL 4.25 g, and BCS 2.80 g were stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (B-7).

(Comparative Example 15)

A stirrer was placed in a 50 ml Erlenmeyer flask, and 4.00 g of the polyamidate solution (PAE-7) obtained in Synthesis Example 22 was weighed, and 2.4 L of GBL, 1.60 g of BCS, and 0.1416 g of Fmoc-His were added to the magnetic force. The stirrer was stirred for 30 minutes to obtain a liquid crystal alignment agent (B-8).

(Example 23)

The liquid crystal alignment agent (A-1) obtained in Example 1 was filtered through a 1.0 μm filter, and then spin-coated on a glass substrate to form an ITO electrode having a first layer of 50 nm in thickness and a second layer as an insulating film. The tantalum nitride having a film thickness of 500 nm and the third layer were on a glass substrate of an FFS driving electrode having a comb-shaped ITO electrode (electrode width: 3 μm, electrode spacing: 6 μm, electrode height: 50 nm). The film was dried on a hot plate at a temperature of 80 ° C for 5 minutes, and baked in a warm air circulating oven at a temperature of 230 ° C for 30 minutes to form a coating film having a film thickness of 100 nm. The ultraviolet light of 254 nm was irradiated on the surface of the coating film with a polarizing plate at 1000 mJ/cm ^{2 to} obtain a substrate with a liquid crystal alignment film. Further, as a glass substrate having a columnar spacer having a height of 4 μm in which the electrode was not formed on the opposite substrate, a coating film was formed in the same manner, and an alignment treatment was performed.

The two substrates are one set, and a sealant is printed on the substrate, the liquid crystal alignment film is faced, and the other substrate is attached so that the alignment direction becomes 0°, and then the sealant is cured to form an empty cell. Liquid crystal MLC-2041 (manufactured by Merck Co., Ltd.) was injected into the empty cell by a vacuum injection method, and the injection port was closed to obtain an FFS-driven liquid crystal cell.

The FFS drives the liquid crystal cell to evaluate the charge relaxation characteristics, and the ΔT after AC driving for 0 minutes, 5 minutes, 10 minutes, 20 minutes, and 60 minutes is 34%, 0%, 0%, 0%, and 0, respectively. %.

(Example 24)

The liquid crystal alignment agent (A-7) obtained in Example 7 was used, and the number of roll rotations was 700 rpm, and the stage moving speed was replaced by light irradiation. An FFS-driven liquid crystal cell was produced in the same manner as in Example 23 except that rubbing treatment was carried out under the conditions of a pressure of 0.3 mm and a friction cloth pressure of 0.3 mm. The FFS drives the liquid crystal cell to evaluate the charge relaxation characteristics, and the ΔT after AC driving for 0 minutes, 5 minutes, 10 minutes, 20 minutes, and 60 minutes is 3%, 2%, 2%, 1%, and 0, respectively. %.

(Embodiment 25)

The liquid crystal alignment agent (A-14) obtained in Example 14 was used, and rubbing was carried out under the conditions of a roll rotation number of 700 rpm, a stage moving speed of 10 mm/s, and a rubbing cloth pressing pressure of 0.3 mm instead of light irradiation. An FFS-driven liquid crystal cell was produced in the same manner as in Example 23 except for the treatment. The FFS drives the liquid crystal cell to evaluate the charge relaxation characteristics, and the ΔT after AC driving for 0 minutes, 5 minutes, 10 minutes, 20 minutes, and 60 minutes is 32%, 0%, 0%, 0%, and 0, respectively. %.

(Example 26)

An FFS-driven liquid crystal cell was produced in the same manner as in Example 23 except that the liquid crystal alignment agent (A-18) obtained in Example 18 was used and irradiated with a polarized ultraviolet light of 100 mJ/cm ² . The FFS drives the liquid crystal cell to evaluate the charge relaxation characteristics, and the ΔT after AC driving for 0 minutes, 5 minutes, 10 minutes, 20 minutes, and 60 minutes is 27%, 1%, 1%, 1%, and 0, respectively. %.

(Example 27)

An FFS-driven liquid crystal cell was produced in the same manner as in Example 23 except that the liquid crystal alignment agent (A-19) obtained in Example 19 was used and irradiated with a polarized ultraviolet light of 750 mJ/cm ² . The FFS drives the liquid crystal cell to evaluate the charge relaxation characteristics, and the ΔT after AC driving for 0 minutes, 5 minutes, 10 minutes, 20 minutes, and 60 minutes is 31%, 0%, 0%, 0%, and 0, respectively. %.

(Embodiment 28)

An FFS-driven liquid crystal cell was produced in the same manner as in Example 23 except that the liquid crystal alignment agent (A-20) obtained in Example 20 was used and irradiated with a polarized ultraviolet light of 500 mJ/cm ² . The FFS drives the liquid crystal cell to evaluate the charge relaxation characteristics, and the ΔT after AC driving for 0 minutes, 5 minutes, 10 minutes, 20 minutes, and 60 minutes is 29%, 0%, 0%, 0%, and 0, respectively. %.

(Example 29)

An FFS-driven liquid crystal cell was produced in the same manner as in Example 23 except that the liquid crystal alignment agent (A-22) obtained in Example 22 was used and irradiated with a polarized ultraviolet light of 500 mJ/cm ² . The FFS drives the liquid crystal cell to evaluate the charge relaxation characteristics, and the ΔT after AC driving for 0 minutes, 5 minutes, 10 minutes, 20 minutes, and 60 minutes is 36%, 0%, 0%, 0%, and 0, respectively. %.

(Example 32)

An FFS-driven liquid crystal cell was produced in the same manner as in Example 23 except that the liquid crystal alignment agent (A-23) obtained in Example 30 was used and a polarized ultraviolet light of 500 mJ/cm ² was irradiated. The FFS drives the liquid crystal cell to evaluate the charge relaxation characteristics, and the ΔT after AC driving for 0 minutes, 5 minutes, 10 minutes, 20 minutes, and 60 minutes is 30%, 0%, 0%, 0%, and 0, respectively. %.

(Example 33)

An FFS-driven liquid crystal cell was produced in the same manner as in Example 23 except that the liquid crystal alignment agent (A-24) obtained in Example 31 was used and irradiated with a polarized ultraviolet light of 500 mJ/cm ² . The FFS drives the liquid crystal cell to evaluate the charge relaxation characteristics, and the ΔT after AC driving for 0 minutes, 5 minutes, 10 minutes, 20 minutes, and 60 minutes is 29%, 0%, 0%, 0%, and 0, respectively. %.

(Comparative Example 8)

Using the liquid crystal alignment agent (B-1) obtained in Comparative Example 1, an FFS-driven liquid crystal cell was produced in the same manner as in Example 23. The FFS drives the liquid crystal cell to evaluate the charge relaxation characteristics, and the ΔT after AC driving for 0 minutes, 5 minutes, 10 minutes, 20 minutes, and 60 minutes is 36%, 9%, 4%, 2%, and 1 respectively. %.

(Comparative Example 9)

In addition to using the liquid crystal alignment agent (B-2) obtained in Comparative Example 2, and taking An FFS-driven liquid crystal cell was produced in the same manner as in Example 23 except that the rubbing treatment was carried out under the conditions of a roller rotation number of 700 rpm, a stage moving speed of 10 mm/s, and a rubbing cloth pressing pressure of 0.3 mm. The FFS drives the liquid crystal cell to evaluate the charge relaxation characteristics, and the ΔT after AC driving for 0 minutes, 5 minutes, 10 minutes, 20 minutes, and 60 minutes is 4%, 3%, 2%, 2%, and 1 respectively. %.

(Comparative Example 10)

The liquid crystal alignment agent (B-3) obtained in Comparative Example 3 was used, and rubbing was performed under the conditions of a roll rotation number of 700 rpm, a stage moving speed of 10 mm/s, and a rubbing cloth pressing pressure of 0.3 mm instead of light irradiation. An FFS-driven liquid crystal cell was produced in the same manner as in Example 23 except for the treatment. The FFS drives the liquid crystal cell to evaluate the charge relaxation characteristics, and the ΔT after AC driving for 0 minutes, 5 minutes, 10 minutes, 20 minutes, and 60 minutes is 30%, 1%, 1%, 1%, and 0, respectively. %.

(Comparative Example 11)

An FFS-driven liquid crystal cell was produced in the same manner as in Example 23 except that the liquid crystal alignment agent (B-4) obtained in Comparative Example 4 was used and irradiated with a polarized ultraviolet light of 100 mJ/cm ² . The FFS drives the liquid crystal cell to evaluate the charge relaxation characteristics, and the ΔT after AC driving for 0 minutes, 5 minutes, 10 minutes, 20 minutes, and 60 minutes is 22%, 6%, 2%, 1%, and 0, respectively. %.

(Comparative Example 12)

An FFS-driven liquid crystal cell was produced in the same manner as in Example 23 except that the liquid crystal alignment agent (B-5) obtained in Comparative Example 5 was used and irradiated with a polarized ultraviolet light of 750 mJ/cm ² . The FFS drives the liquid crystal cell to evaluate the charge relaxation characteristics, and the ΔT after AC driving for 0 minutes, 5 minutes, 10 minutes, 20 minutes, and 60 minutes is 28%, 5%, 5%, 5%, and 4, respectively. %.

(Comparative Example 13)

An FFS-driven liquid crystal cell was produced in the same manner as in Example 23 except that the liquid crystal alignment agent (B-6) obtained in Comparative Example 6 was used and irradiated with a polarized ultraviolet light of 500 mJ/cm ² . The FFS drives the liquid crystal cell to evaluate the charge relaxation characteristics, and the ΔT after AC driving for 0 minutes, 5 minutes, 10 minutes, 20 minutes, and 60 minutes is 31%, 8%, 7%, 7%, and 4, respectively. %.

(Comparative Example 14)

An FFS-driven liquid crystal cell was produced in the same manner as in Example 23 except that the liquid crystal alignment agent (B-7) obtained in Comparative Example 7 was used and irradiated with a polarized ultraviolet light of 500 mJ/cm ² . The FFS drives the liquid crystal cell to evaluate the charge relaxation characteristics, and the ΔT after AC driving for 0 minutes, 5 minutes, 10 minutes, 20 minutes, and 60 minutes is 38%, 3%, 3%, 3%, and 1 respectively. %.

(Comparative Example 16)

An FFS-driven liquid crystal cell was produced in the same manner as in Example 23 except that the liquid crystal alignment agent (B-8) obtained in Comparative Example 15 was used and irradiated with a polarized ultraviolet light of 500 mJ/cm ² . The FFS drives the liquid crystal cell to evaluate the charge relaxation characteristics, and the ΔT after AC driving for 0 minutes, 5 minutes, 10 minutes, 20 minutes, and 60 minutes is 29%, 5%, 2%, 1%, and 0, respectively. %.

[Industrial availability]

The liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention can increase the relaxation rate of residual charges in the liquid crystal display element accumulated by the DC voltage. As a result, it can be widely used for TN elements, STN elements, TFT liquid crystal elements, and vertical alignment type liquid crystal display elements.

Reference is made to the Japanese patent application filed on March 31, 2011. The entire contents of the specification, patent application, drawings and abstracts of the specification 2011-078688 are incorporated in the specification of the present invention.

Claims (10)

A liquid crystal alignment agent characterized by containing at least 1 group selected from the group consisting of a polyimine precursor having a repeating unit represented by the following formula (1) and a ruthenium imidized polymer of the polyimide precursor. a type of polymer, a sulfonate represented by the following formula (2), and an organic solvent, (In the formula (1), X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and each of A ₁ and A ₂ is independently a hydrogen atom. Or an alkyl group, an alkenyl group or an alkynyl group having 1 to 10 carbon atoms which may have a substituent. [Chemical 2]R ₂ -SO ₂ -OR ₃ (2) (in the formula (2), each of R ₂ and R ₃ is It is independently a monovalent organic group having 1 to 30 carbon atoms which may have a substituent, and R ₂ and R _{3 are} bonded to each other to form a ring structure). The liquid crystal alignment agent of the first aspect of the invention, wherein the content of the sulfonate is 0.01 parts by mass to 30 parts by mass based on 100 parts by mass of the polymer. A liquid crystal alignment agent according to claim 1 or 2, wherein R ₂ is a methyl group which may have a substituent. The liquid crystal alignment agent according to any one of claims 1 to 3, wherein R ₃ is a methyl group. The liquid crystal alignment agent of claim 1 or 2, wherein the sulfonate is methyl trifluoromethanesulfonate or ethyl trifluoromethanesulfonate. The liquid crystal alignment agent according to any one of claims 1 to 5, wherein the polymer has a weight average molecular weight of 5,000 to 300,000. The liquid crystal alignment agent according to any one of claims 1 to 6, wherein the content of the polymer is from 0.5% by mass to 20% by mass based on the total amount of the organic solvent. A liquid crystal alignment film obtained by coating and baking a liquid crystal alignment agent according to any one of claims 1 to 7. A liquid crystal alignment film which is obtained by coating and baking a liquid crystal alignment agent according to any one of claims 1 to 7 to irradiate a polarized radiation. A liquid crystal display element characterized by comprising a liquid crystal alignment film according to claim 8 or 9.