TWI501998B - A liquid crystal aligning agent containing a polyamic acid ester, and a liquid crystal alignment film - Google Patents

Description

Liquid crystal alignment agent containing polyphthalate, and liquid crystal alignment film

The present invention relates to a liquid crystal alignment film obtained by using a liquid crystal alignment agent of a polyphthalamide having a thermally dissociable protecting group and a polyphthalic acid, and the liquid crystal alignment agent.

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

With the high definition of the liquid crystal display element, in order to suppress the decrease in the contrast of the liquid crystal display element or to reduce the image sticking phenomenon, in the liquid crystal alignment film, in addition to the excellent liquid crystal alignment property or the pretilt angle which produces stability, The high voltage holding ratio, the suppression of residual images due to AC driving, the generation of less residual charges when a DC voltage is applied, and/or the early relaxation of the characteristics of residual charges accumulated by the DC voltage are important.

Polyimide-based liquid crystal alignment films have been proposed in response to the above requirements. For example, a liquid crystal alignment film capable of shortening the time until the disappearance of a DC voltage to disappear is proposed, and a specific structure may be used in addition to a polyaminic acid or a polyamido acid containing a quinone imine group. A liquid crystal alignment agent (for example, Patent Document 1) of the amine group, or a liquid crystal alignment agent containing a soluble polyimine having a specific diamine compound such as a pyridine skeleton as a raw material (for example, Patent Document 2). Further, the liquid crystal alignment film having a high voltage holding ratio and shortening the time until the image is lost due to the DC voltage can be further contained, for example, in the form of polyacrylic acid or a ruthenium iodide polymer thereof. a small amount of a liquid crystal alignment agent of a compound selected from the group consisting of 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 (for example, Proposal of Patent Document 3).

Further, a liquid crystal alignment film having excellent liquid crystal alignment, high voltage holding ratio, low image sticking, excellent signal reliability, and high pretilt angle is known, for example, using a tetracarboxylic dianhydride having a specific structure and A liquid crystal alignment agent of cyclobutane obtained from a tetracarboxylic dianhydride and a specific diamine compound, or a quinone imidized polymer thereof (for example, Patent Document 4). Further, in a liquid crystal display device of a lateral electric field driving method, a method of suppressing image sticking due to AC driving is known, and it is known to use a liquid crystal alignment property and have a large interaction with liquid crystal molecules. A method of a specific liquid crystal alignment film (for example, Patent Document 5).

However, in recent years, large-screen and high-definition LCD TVs have been mainly used, and the requirements for image sticking have become increasingly stringent, and they are also required to withstand long-term use in harsh environments. At the same time, the liquid crystal alignment film used must have a higher reliability than the conventional one, so that various characteristics of the liquid crystal alignment film must have a good initial characteristic, for example, a long time even at a high temperature. Those who maintain good characteristics after exposure.

Further, among the polymer components constituting the polyimine-based liquid crystal alignment agent, the polyglycolate is proposed to be subjected to heat treatment at the time of ruthenium imidization treatment, and does not cause a problem of molecular weight reduction, and is excellent. Report on liquid crystal alignment stability and good reliability (for example, Patent Document 6). However, polyglycolate generally has problems such as high volume resistance and an increase in residual charge when a DC voltage is applied, so that there is still no improvement in the polyazide containing the polyphthalate. A method of characterizing an amine-based liquid crystal alignment agent.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-9-316200

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

[Patent Document 3] Japanese Patent Publication No. 8-76128

[Patent Document 4] Japanese Patent Publication No. 9-138414

[Patent Document 5] Japanese Patent Publication No. 11-38415

[Patent Document 6] JP-A-2003-26918

According to the present invention, in order to improve the characteristics of the liquid crystal alignment agent containing the above polyphthalate, a liquid crystal obtained by doping polyacrylic acid having excellent properties from the viewpoint of electrical properties has been studied. An aligning agent. However, the liquid crystal alignment film obtained by the liquid crystal alignment agent obtained by mixing the polyphthalate with polyamic acid has not reached a satisfactory stage in terms of liquid crystal alignment and electrical properties.

That is, the liquid crystal alignment film obtained by the liquid crystal alignment agent containing the polyphthalate and the poly-proline does not cause white turbidity, and the low voltage retention rate and DC voltage accumulation of the film under high temperature use are generated. The afterimage, and the poor performance of the residual image caused by the AC drive.

The present invention provides a liquid crystal alignment agent containing a polyphthalate and a poly-proline, which can have excellent liquid crystal alignment and electrical properties, and can also have transparency without white turbidity. The liquid crystal alignment agent of the liquid crystal alignment film is for the purpose.

As a result of analysis by a liquid crystal alignment film formed of a liquid crystal alignment agent containing a polyphthalate and a poly-proline, it was confirmed that fine irregularities were formed on the surface of the film. However, it has been found that when a polyglycolate having a specific structure having a functional group which can be substituted by a hydrogen atom by heat treatment is used, the fine unevenness formed on the surface of the film can be remarkably suppressed, and In order to reduce the fine unevenness generated on the surface of the film, the above problem can be eliminated by using a liquid crystal alignment agent containing a polyphthalate and polylysine.

Further, based on the results of the study by the present inventors, it has been found that a polyglycolate having a specific structure having a functional group which can be substituted by a hydrogen atom via the above heat treatment has an organic solvent even in the case of a high molecular weight. Good solubility, and the liquid crystal alignment agent containing the polyphthalate can form a liquid crystal alignment agent having a lower viscosity even when the organic solvent contains a high concentration, and thus, for example, using an inkjet method It is also easier to manufacture a liquid crystal alignment film, and it is also easy to manufacture a liquid crystal alignment film having a high thickness.

That is, the present invention has been completed based on the above findings, and has the following main contents.

A liquid crystal alignment agent comprising the following components (A) and (B),

(A) component: a polyphthalate having a repeating unit represented by the following formula (1), and a polyphthalate satisfying the conditions of any one of the following (i) to (iii).

(wherein X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, R ₁ is an alkyl group having 1 to 5 carbon atoms, and A ₁ and A ₂ each independently represent a hydrogen atom, or may have a substituent The alkyl group having 1 to 20 carbon atoms, an alkenyl group or an alkyl group).

(i) X ₁ , Y ₁ or both of the formula (1) is a monovalent or divalent substituent having a structure selected from at least one selected from the group consisting of the following formulas (2) and (3) .

(ii) A ₁ , A ₂ or both of the formula (1) is a monovalent or divalent substituent having a structure selected from at least one of the groups of the following formulas (2) and (3) .

(iii) X ₁ , Y ₂ or both of the formula (1) is a monovalent or divalent substituent having a structure selected from at least one of the groups of the following formulas (2) and (3) Further, A ₁ , A ₂ or both are monovalent or divalent substituents having at least one structure selected from the group consisting of the following formulas (2) and (3).

(Formula (2) and (3) of the D ₁ and D _2, respectively, via a heat treatment may be substituted with a hydrogen atom of the protecting group .B ₁ of a single bond or a divalent organic group. However, the formula (3) in the The atom to which the ester group is bonded is a carbon atom).

(B) component: Polyamino acid having a repeating unit represented by the following formula (4).

(wherein, X ₂ is a tetravalent organic group, Y ₂ is a divalent organic group, and A ₁ and A ₂ have the same definitions as those of the formula (1)).

2. The liquid crystal alignment agent according to the above 1, wherein the content of the component (A) and the content of the component (B) are from 1/9 to 9/1 by mass ratio (A/B).

3. The liquid crystal alignment agent according to the above 1 or 2, wherein the total content of the component (A) and the component (B) is 1 to 10% by mass based on the organic solvent.

4. The liquid crystal alignment agent according to any one of the above 1 to 3, wherein the protecting group D ₁ is at least one selected from the group consisting of tert-butoxycarbonyl and 9-fluorenylmethoxycarbonyl. base.

5. The liquid crystal alignment agent according to any one of the above 1 to 4, wherein the protecting group D ₂ is a tert-butyl group.

6. The liquid crystal alignment agent according to the above-mentioned 1 to 5, wherein the component (A) is a substituent represented by a structure having at least one selected from the group consisting of the following formulas (5) and (6). Polyphthalate.

(In the formula (5), B ₂ is a single bond and a divalent organic group, and R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or an organic group having a monovalent number of carbon atoms of 1 to 20).

(In the formula (6), B ₃ is a single bond or a divalent organic group, wherein the atom to which the t-butoxycarbonyl group disclosed by the formula (6) is bonded is a carbon atom).

The liquid crystal alignment agent according to any one of the above-mentioned items (1), wherein the component (A) has a structure of Y ₁ of the formula (1) and has a group of the formulas (5) and (6). A polyphthalate ester of a substituent represented by at least one of the structures selected.

8. The liquid crystal alignment agent according to any one of the above 1 to 7, wherein the component (A) is A ₁ or A _{2 of the} formula (1) or both of the formulas (5) and (6) A polyphthalate ester of a substituent represented by at least one of the selected structures selected in the group.

9. The liquid crystal described in any one of claims 1 to 8, the described alignment agent, wherein, (A) component, of formula (1) Y ₁ is of the following structure represented by formula (7) of the polyamide ester .

(wherein R ₅ is a single bond or a divalent organic group having 1 to 20 carbon atoms; and R _{6 is} a structure selected from at least one selected from the group consisting of formulas (5) and (6). a is 1 to 4 integer).

Item 10. The liquid crystal request of any of claims 1 to 9, according to the alignment agent, wherein, (A) component, of formula (1) of the selected Y ₁ having the formula The groups represented by the structure of at least one Construction.

In the liquid crystal alignment agent according to any one of the above-mentioned formulas (1) and (4), the structures of X ₁ and X ₂ are each independently represented by the following formula. Construct at least one of the selected groups.

In the formula (4), Y ₂ is at least one selected from the group consisting of the structures represented by the following formulas, in the liquid crystal alignment agent according to any one of the above formulas.

A liquid crystal alignment film obtained by coating and baking the liquid crystal alignment agent according to any one of the above 1 to 12.

A liquid crystal alignment film obtained by applying the liquid crystal alignment agent according to any one of the above 1 to 12, baking it, and irradiating the polarized ultraviolet light to obtain a liquid crystal alignment film.

The present invention provides a method for improving the interface characteristics of a liquid crystal and a liquid crystal alignment film by reducing fine irregularities on the surface of the obtained liquid crystal alignment film, reducing image sticking caused by AC driving, and the like, and improving voltage holding ratio, ion density, and direct current. A liquid crystal alignment agent that improves the electrical properties such as voltage residual and improves the reliability.

Moreover, even if the liquid crystal alignment agent of the present invention contains a high concentration in an organic solvent, since it has a low viscosity, for example, a method of producing a liquid crystal alignment film by an inkjet method can be made easier, and It is also easy to obtain the advantages of a liquid crystal alignment film having a relatively high thickness.

In the present invention, when a polyglycolate having a specific structure having a functional group substituted with a hydrogen atom via heat is used, why is it possible to reduce fine irregularities generated on the surface of the film, and to eliminate the conventional polyamine The disadvantages of the liquid crystal alignment agent of the acid ester and the poly-proline are still unclear, but it is presumed that the effect obtained by the following reason is almost the same.

That is, in the liquid crystal alignment film formed by removing the solvent from the liquid crystal alignment agent in which the polyphthalate and the polyphthalic acid are dissolved in the organic solvent, the ester polyglycine having a lower surface free energy than the poly-proline is biased. If the polyglycolate is separated from the polylysine, agglomerates of polyglycine will form in the polyphthalate phase, or poly(phthalic acid) will form a polypeptone. The agglomerate of the amine ester forms a film having a large number of fine irregularities on the surface of the film.

On the other hand, the liquid crystal alignment agent of the present invention is a polyphthalate having a specific structure having a functional group substituted with a hydrogen atom as described above by heat treatment, and the solvent is removed by the liquid crystal alignment agent to form a liquid crystal alignment film. In the meantime, the phase separation of the polyglycolate and the poly-proline can be promoted, so that the polyglycolate does not exist in a manner of mixing with the poly-proline which is present near the surface of the membrane, and the poly-proline does not It exists in a manner of mixing with the polyamidolate at the inside of the film and at the interface of the substrate.

That is, on the surface of the obtained liquid crystal alignment film, due to the phase separation state of the polyphthalate and the polyaminic acid, a rough surface can be formed without forming irregularities, and the film due to occurrence of irregularities can be reduced. White turbidity. Moreover, since the liquid crystal alignment film having a smooth surface having no unevenness and the like has an alignment stability on the surface, it is a highly reliable polyamine phthalate, and a polyamic acid having excellent electrical properties exists inside the film and at the electrode interface. Therefore, it is an alignment film with excellent characteristics.

Further, the functional group having the above specific structure of the polyphthalate can be replaced by a hydrogen atom by heating in the subsequent imidization or baking treatment, so that the obtained liquid crystal alignment film does not exist. Since the above-mentioned functional groups are not affected by the presence of the functional groups of the specific structures, a liquid crystal alignment film having the same characteristics in the case of using a polyamidomate having a functional group having no specific structure can be obtained.

[Embodiment of the Invention] <Polyurethane and polylysine>

The polyphthalate and polylysine used in the present invention are polyimine precursors used in the production of polyimine, and have a site capable of performing the oxime imidization reaction shown below by heating. polymer.

The polyphthalate and the polyglycolic acid contained in the liquid crystal alignment agent of the present invention each have the following formula (1) and the following formula (4).

In the above formula (1), R ₁ is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 2 carbon atoms ^. The polyglycolate increases the temperature at which the oxime imidization is accompanied by an increase in the number of carbon atoms in the alkyl group. Therefore, R ₁ is a viewpoint that heat is easy to carry out oxime imidization, and methyl is particularly preferable. In the formulae (1) and (4), A ₁ and A ₂ each independently represent a hydrogen atom, or an alkyl group, an alkenyl group or an alkynyl group having 1 to 20 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 structure in which one or more CH ₂ -CH ₂ structures present in the above alkyl group are substituted by a CH=CH structure. More specifically, for example, vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-hexenyl, Cyclopropenyl, cyclopentenyl, cyclohexenyl and the like. The above alkynyl group, for example, one or more CH ₂ -CH ₂ structures present in the upper alkyl group are substituted by a C≡C structure, more specifically, for example, ethynyl group, 1-propynyl group, 2-propene group Alkynyl and the like.

The above-mentioned alkyl group, alkenyl group or alkynyl group may have a substituent when the total number of carbon atoms is 1 to 20, and may further 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 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, and a decyl group. , alkyl, alkenyl, alkynyl and the like.

A halogen group in the substituent, such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like.

An aryl group in the substituent, such as phenyl or the like. The aryl group may be further substituted with the other substituents described above.

The organooxy group in the substituent, such as the structure represented by O-R. The 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. Specific examples of the organooxy 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 in the substituent, such as the structure represented by -S-R. The R may be, for example, the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group or 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.

An organic decyl group in the substituent, such as the structure represented by -Si-(R) ₃ . The 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. Specific examples of the organic decyl group are, for example, trimethyldecyl, triethyl decyl, tripropyl decyl, tributyl decyl, tripentyl decyl, trihexyl decyl, pentyl dimethyl decyl, Hexyl dimethyl decyl group and the like.

The thiol group in the substituent, for example, the 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 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 in the substituent, such as -C(O)O-R, or the structure represented by -OC(O)-R. The R may be, for example, the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group or the like. These R may be further substituted by the aforementioned substituents.

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

The phosphate group in the substituent, for example, the structure represented by -OP(O)-(OR) ₂ . The 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.

Amidino group in the substituent, such as -C(O)NH ₂ , or -C(O)NHR, -NHC(O)R, -C(O)N(R) ₂ , -NRC(O)R The structure represented. The 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 aryl group in the substituent is, for example, the same as the aforementioned aryl group. The aryl group may be further substituted with the other substituents described above.

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

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

The alkynyl group in 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 large-volume structure is introduced, there is a possibility that the reactivity of the amine group or the liquid crystal alignment property is lowered, and A ₁ and A ₂ are hydrogen atoms, or a carbon number of 1 to 5 which may have a substituent. The base is more preferably a hydrogen atom, a methyl group or an ethyl group.

In the above formulas (1) and (4), X ₁ and X ₂ each independently represent a tetravalent organic group, and Y ₁ and Y ₂ each independently represent a divalent organic group. When X ₁ and X ₂ are a tetravalent organic group, there is no particular limitation. In the polyimine precursor, X ₁ and X ₂ may be a mixture of two or more types. When specific examples of X ₁ and X _{2 are} listed, for example, X-1 to X-46 and the like which are each independently shown below. In terms of the easiness of monomer acquisition, X ₁ and X ₂ are independent 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 are preferred.

Further, in the formulae (1) and (4), when Y ₁ and Y ₂ are a divalent organic group, there is no particular limitation. In the polyimine precursor, Y ₁ and Y ₂ may be a mixture of two or more types which are independent of each other. Specific examples of Y ₁ and Y ₂ include, for example, Y-1 to Y-103 described below.

Among them, the viewpoint of good liquid crystal alignment is obtained, and it is preferable to introduce a diamine having high linearity into the polyphthalate, and Y ₁ is 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 diamine are more preferred. Further, in order to increase the pretilt angle, it is preferred to introduce a diamine having a long-chain alkyl group, an aromatic ring, an aliphatic ring, a steroid skeleton, or a combination thereof in a side chain into a polyphthalate. Y ₁ is 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 diamine is more preferred. When these diamines are added in an amount of 1 to 50 mol% based on the total diamine, an arbitrary pretilt angle can be obtained.

When the volume resistivity of the polyphthalate is lowered, the image sticking due to the accumulation of the DC voltage can be reduced, so that a structure having a hetero atom, a polycyclic aromatic structure, or a diamine having a biphenyl skeleton can be introduced into the poly It is preferred for proline, Y ₂ is 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, or Y-61, Y-98, or Y- 99 is more preferable, and Y-31, Y-40, Y-98, or Y-99 is more preferable.

Y ₁ in the above formula (1) is preferably a structure represented by the following formula (7).

In the formula (7), R ₅ is a single bond or an organic group having a carbon number of from 1 to 20, preferably from 1 to 12. The divalent organic group is preferably an alkyl group, an extended aryl group, or a combination thereof which may contain an ether bond, a guanamine bond, an ester bond, a thioester bond or a thioether bond. R _{6 is} a structure of at least one selected from the group consisting of the above formulas (5) and (6). a is an integer of 1 to 4, preferably 1 or 2.

Further, Y _{1 of} the formula (1) in the above formula (1) is preferably one having at least one selected from the group represented by the following formula.

Further, Y ₂ in the above formula (4) is particularly preferably at least one selected from the structures represented by the following formulas.

<Method for producing polyamidomate>

The polyamine derivative represented by the above formula (1) may be any one of the tetracarboxylic acid derivatives represented by the following formulas (10) to (12) and the diamine compound represented by the formula (13). It can be obtained by carrying out a polycondensation reaction.

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

The polyphthalate represented by the above formula (1) can be synthesized by the methods shown in the following (1) to (3) using the above monomers.

(1) The case of synthesis from polyaminic acid

The polyphthalate can be synthesized by esterifying a tetracarboxylic dianhydride with a polyamine obtained from a diamine.

Specifically, the polyamic acid and the esterifying agent are allowed to be carried out 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 Synthesis by 4 hours reaction.

The esterifying agent is preferably one which can be easily removed by refining, 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 condensate Aldehyde, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl-3-p-tolyltriazene, 4-(4,6 -Dimethoxy-1,3,5-triazabenzene-2-yl)-4-methylmorpholinium chloride and the like. The amount of the esterifying agent to be added is preferably 2 to 6 mol equivalents per 1 mol of the repeating unit of the polyamic acid.

The solvent used in the above reaction is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone or γ-butyrolactone in terms of solubility of the polymer. One type or two or more types may be used in combination. The concentration at the time of synthesis is less likely to cause precipitation of a polymer and 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) Synthesis by reaction of tetracarboxylic acid diester dichloride with diamine

Polyphthalate can be synthesized by subjecting a tetracarboxylic acid diester dichloride to a polycondensation reaction with a diamine.

Specifically, the tetracarboxylic acid diester dichloride and the diamine may be carried out in the presence of a base and an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C, for 30 minutes to 24 hours. It is preferably synthesized by a reaction of 1 to 4 hours.

As the base, pyridine, triethylamine, 4-dimethylaminopyridine or the like can be used, and from the viewpoint of stable reaction, pyridine is preferably used. The amount of the base to be added is easily removed, and the viewpoint of easily obtaining a high molecular weight body is preferably 2 to 4 times the molar amount of the tetracarboxylic acid diester dichloride.

The solvent to be used in the above reaction is preferably N-methyl-2-pyrrolidone or γ-butyrolactone for the solubility of the monomer and the polymer, and one type or two or more types may be used. Mixed use. The concentration at the time of synthesis is less likely to cause precipitation of a polymer and 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. Further, in order to prevent hydrolysis of the tetracarboxylic acid diester dichloride, the solvent used for the synthesis of the polyglycolate is preferably as far as possible, and it is preferable to prevent the outside air from being mixed in a nitrogen atmosphere. .

(3) The case of synthesizing poly-proline from tetracarboxylic acid diester and diamine

Polyphthalate can be synthesized by condensation polymerization of a tetracarboxylic acid diester and a diamine.

Specifically, the tetracarboxylic acid diester and the diamine are preferably used 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, preferably. It can be synthesized by reacting for 3 to 15 hours.

As the condensing agent, triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, N can be used. , N'-carbonyldiimidazole, dimethoxy-1,3,5-triazaphenylmethylmorpholinium, O-(benzotriazol-1-yl)-N,N,N', N'-tetramethylurea cation tetrafluoroborate, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethylurea cation hexafluorophosphate, (2,3 - Diphenyl-2-thio(keto)yl-3-benzoxazolyl)phosphonic acid diphenyl ester or the like. The amount of the condensing agent to be added is preferably 2 to 3 moles per mole of 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 easily removed, and the viewpoint of easily obtaining a high molecular weight body is preferably 2 to 4 times the molar amount of the diamine component.

Further, in the above reaction, when Lewis acid is used as an additive, the reaction can be efficiently carried out. The Lewis acid is preferably lithium halide such as lithium chloride or lithium bromide. The addition amount of the Lewis acid is preferably 0 to 1.0 times the molar amount of the diamine component.

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

The solution of the polyphthalate obtained by the above method can precipitate a polymer when it is injected into a poor solvent with sufficient stirring. After several times of precipitation and washing with a poor solvent, the purified polyphthalate powder can be obtained after normal temperature or heating and drying. The poor solvent is not particularly limited, and is generally, for example, water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene or the like.

<Method for producing polylysine>

The polyamic acid represented by the above formula (4) can be obtained by subjecting a tetracarboxylic dianhydride represented by the following formula (14) to a diamine compound represented by the formula (15).

Specifically, the tetracarboxylic dianhydride and the diamine are 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 Synthesis by ~12 hours reaction.

The organic solvent used in the above reaction is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone or γ-butyrolactone in terms of 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, more preferably from 5 to 20% by mass, from the viewpoint of not easily causing precipitation of the polymer and easily obtaining a high molecular weight body.

The polylysine obtained by the above method can be recovered after the polymer is precipitated by injecting a poor solvent into the reaction solution while stirring well. Further, after a plurality of precipitations and washing with a poor solvent, the purified polylysine powder can be obtained by drying at room temperature or by heating. The poor solvent is not particularly limited, and is generally, for example, water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene or the like.

<Polyurethane ester having a thermally dissociable protecting group>

The polyphthalate ester having a thermally dissociable protective group according to the present invention is a polyphthalate having a repeating unit represented by the above formula (1), and satisfies the following (i) to (iii). A polyglycolate of any of the conditions.

(i) X ₁ , Y ₁ or both of the formula (1) is a monovalent or divalent substituent having a structure selected from at least one selected from the group consisting of the following formulas (2) and (3) .

(ii) A ₁ , A ₂ or both of the formula (1) is a monovalent or divalent substituent having a structure selected from at least one of the groups of the following formulas (2) and (3) .

(iii) X ₁ , Y ₂ or both of the formula (1) is a monovalent or divalent substituent having a structure selected from at least one of the groups of the following formulas (2) and (3) Further, A ₁ , A ₂ or both are monovalent or divalent substituents having at least one structure selected from the group consisting of the following formulas (2) and (3).

In the formula (2), D ₁ is a protective group of an amine group, and the structure thereof is not particularly limited as long as it is a functional group which can be substituted by a hydrogen atom via heating. D ₁ is preferably a structure capable of efficiently performing a dissociation reaction at a baking temperature of from 150 ° C to 300 ° C at the time of producing a liquid crystal alignment film, and is tert-butoxycarbonyl or 9-fluorenylmethoxy. The carbonyl group is more preferred, and tert-butoxycarbonyl group is particularly preferred.

In the formula (3), B ₁ is a single bond or a divalent organic group. Preferred examples of the divalent organic group, such as an alkyl group, an extended aryl group, or the like, which may contain an ether bond, a guanamine bond, an ester bond, a thioester bond or a thioether bond. . Further, in the formula (3), the atom to which the ester group is bonded is carbon.

D ₁ is a monovalent or divalent substituent of a tert-butoxycarbonyl group or a 9-fluorenylmethoxycarbonyl group represented by the formula (2), for example, having a primary or secondary form represented by the following formula a method of reacting an amine-based compound with di-tert-butyl dicarbonate in the presence of a base, or a method of reacting a compound having a primary or secondary amino group in the presence of a -9-mercaptomethyl chloroformate base The preparation is not particularly limited as long as it is a known method.

The compound having a substituent prepared by the above method can be synthesized by adding a tetracarboxylic acid derivative or a precursor thereof or a diamine compound or a derivative thereof, and having a substituent having a functional group substituted by a hydrogen atom by heat treatment. The polycarboxylic acid derivative having the thermally dissociable protecting group of the present invention can be obtained from a raw material of a polyglycolate based on a tetracarboxylic acid derivative and/or a diamine.

In the formula (3), D ₂ is a protective group of a carboxyl group, and the structure thereof is not particularly limited as long as it is a functional group substituted by a hydrogen atom via heating. D ₂ is a structure which can effectively carry out the dissociation reaction at a baking temperature of 150 ° C to 300 ° C at the time of producing a liquid crystal alignment film, and is also represented by the following formula (D2-1) to (D2-5). The functional group is more preferably, and the following formula (D2-1) is more preferable.

In the formula (D2-2), R ₁₀ is an alkyl group having 1 to 5 carbon atoms, and specific examples thereof include a methyl (Me) group, an ethyl group, a propyl group, a butyl group, a pentyl group, or a tert-butyl group.

D ₂ is a monovalent substituent of the structure represented by the formula (3) of the above formula (D2-1), and for example, a method of reacting a carboxyl group represented by the following formula with tert-butyl alcohol, a carbon ruthenium chloride compound and The method of reacting tert-butyl alcohol or the method of reacting a carboxyl group with a halogenated tert-butyl group is not particularly limited as long as it is a known method. The compound having a substituent prepared by the above method is added to a tetracarboxylic acid derivative or a precursor thereof or a diamine compound or a precursor thereof to synthesize a substituent having a functional group substituted with a hydrogen atom via heat treatment. When the tetracarboxylic acid derivative and/or the diamine are used as a raw material of the polyglycolate, the polylysine having the thermally dissociable protecting group of the present invention can be obtained.

In the structural unit of the polylysine having a thermally dissociable protecting group of the present invention, the position of the substituent selected by at least one of the groups selected by the formulae (2) and (3) may be a formula ( 1) Any position of X ₁ , Y ₁ , A ₁ , A ₂ . Wherein the structure of Y ₁ of the formula (1) has a form of at least one substituent selected from the group consisting of the formulas (2) and (3), and A ₁ , A ₂ or the formula _{2 of the} formula (1) The form of at least one substituent selected in the group of the formulas (2) and (3), the simpleness of the monomer of the raw material of the polyphthalate, and the treatment of the monomer It is preferable from the viewpoint of easiness and the like.

The polylysine having a thermally dissociable protecting group of the present invention may contain the formula (1), and the formula (2) is not present at any of X ₁ , Y ₁ , A ₁ , and A ₂ . And the structural unit of the substituent represented by (3) may also be used. When the introduction amount of the substituent represented by the formulas (2) and (3) is too small, the effect of suppressing the fine unevenness due to the phase separation of the polyphthalate and the poly-proline is lowered, so X ₁ , Y ₁ , When the content of the substituent represented by the formulas (2) and (3) in the position of any one of A ₁ and A ₂ is based on the structural unit represented by the formula (1), it is preferably 0.05 or more. It is especially good for 0.10 or more.

In the above definition, for example, the structural unit represented by the formula (1) contained in the polyphthalate is only "X ₁ and Y ₁ of the formula (1), and each has one of the formulas (2) and (3). a polyamine which is a structural unit of one type of substituent selected in the group, and A ₁ or A ₂ is a structural unit of a substituent selected from the group of the formulas (2) and (3) The content of the substituent represented by the formulae (2) and (3) in the acid ester is 4.00. Specific examples of the substituent having a functional group substituted with a hydrogen atom by heat treatment represented by the above formulas (2) and (3) are, for example, the following (D-1) to (D-24), but are not limited thereto. The content.

In addition, the diamine compound containing a substituent having a functional group substituted with a hydrogen atom by heat treatment represented by the above formulas (2) and (3) is, for example, the following formula (D-25) to (D-35). The following diamine compounds are not limited to these contents.

<Liquid alignment agent>

The liquid crystal alignment agent of the present invention is in the form of a solution obtained by dissolving the polylysine having a thermally dissociable protecting group and polylysine in an organic solvent. The molecular weight of the polyamidomate having a thermally dissociable protecting group is preferably from 2,000 to 500,000, more preferably from 5,000 to 300,000, particularly preferably from 10,000 to 100,000. Further, the number average molecular weight is preferably from 1,000 to 250,000, more preferably from 2,500 to 150,000, particularly preferably from 5,000 to 50,000.

Further, the weight average molecular weight of the polyamic acid is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, particularly preferably 10,000 to 100,000. Further, the number average molecular weight is preferably from 1,000 to 250,000, more preferably from 2,500 to 150,000, particularly preferably from 5,000 to 50,000. The polyglycolate having a thermally dissociable protecting group has a smaller molecular weight than the polyglycolic acid, and the micro-concavity formed by phase separation can be further reduced. The difference in weight average molecular weight of the polyamidomate having a thermally dissociable protecting group is preferably from 1,000 to 200,000, more preferably from 5,000 to 150,000, even more preferably from 10,000 to 100,000. In the liquid crystal alignment agent of the present invention, the content ratio of the polyglycolate and the polyaminic acid having a thermal dissociation protecting group (polyperurethane/polyglycolic acid) is 1/9 of the mass basis. 9/1 is better. The ratio is preferably 2/8, and particularly preferably 3/7 to 7/3. When the ratio is within this range, a liquid crystal alignment agent having both excellent liquid crystal alignment properties and electrical properties can be provided. The liquid crystal alignment agent of the present invention does not need to be examined in the production method as long as it is in the form of a solution obtained by dissolving a polylysine having a thermally dissociable protecting group and a polylysine in an organic solvent. For example, a method in which a powder of a polyphthalate and a polyaminic acid is mixed, dissolved in an organic solvent, a method in which a powder of a polyphthalate is mixed with a solution of a polyaminic acid, a polyphthalate solution, and A method of mixing a powder of poly-proline, a method of mixing a polyphthalate solution with a poly-proline solution. In view of the fact that even if the good solvent used for dissolving the polyphthalate and the poly-proline is different, a homogeneous polyamine-polyamide mixture solution can be obtained to use the polyamine. The method of mixing the acid ester solution with the polyaminic acid solution is more preferable.

Further, in the case where the polylysine having a thermally dissociable protecting group and/or polylysine is produced in an organic solvent, it may be in the form of the obtained reaction solution, or the reaction solution may be diluted with a suitable solvent. Also available. Further, in the case where the polylysine having a thermally dissociable protecting group is produced in a powder form, a solution obtained by dissolving it in an organic solvent may be used. The concentration of the polyglycolate and polylysine in the liquid crystal alignment agent of the present invention (in the case of the present invention, also referred to as a polymer) can be appropriately changed depending on the thickness of the coating film to be formed. However, from the viewpoint of forming a coating film which is uniform and free from defects, it is preferably 1% by mass or more, and more preferably 10% by mass or less from the viewpoint of storage stability of the solution. The organic solvent containing the liquid crystal alignment agent of the present invention is not particularly limited as long as it can uniformly dissolve the solvent of the polymer component of the lysine and the polyaminic acid having a thermally dissociable protective group. Specific examples thereof include, for example, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone , N-ethyl-2-pyrrolidone, N-methyl caprolactam, 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyl hydrazine, dimethyl hydrazine, Γ-butyrolactone, 1,3-dimethyl-tetrahydroimidazolidone, 3-methoxy-N,N-dimethylpropionamide, and the like. These may be used alone or in combination of two or more. Further, even when a solvent which does not uniformly dissolve the polymer component is used alone, it may be mixed with the above organic solvent as long as it does not precipitate a polymer.

In the liquid crystal alignment agent of the present invention, when a decane coupling agent is added, it may be added to the polyphthalate solution, the polyaminic acid solution, or added to the polyphthalate solution and the polyaminic acid solution before being mixed. Both the polyamidate solution and the polyaminic acid solution are acceptable. Further, it may be added to a polyphthalate-polyaminic acid mixed solution. The decane coupling agent is added for the purpose of improving the adhesion between the polymer and the substrate, and the method of adding the decane coupling agent is, for example, added to a polyamic acid solution which can be interposed between the inside of the film and the substrate, and the polymer and After the decane coupling agent is sufficiently reacted, it is preferably mixed with the polyamidate solution. When the amount of the decane coupling agent is too large, the unreacted substance will have an adverse effect on the liquid crystal alignment property, and when it is too small, the adhesion effect will not be exhibited, so the solid content of the polymer is 0.01 to 5.0 by weight. % is preferably more preferably 0.1 to 1.0% by weight. The liquid crystal alignment agent of the present invention may further contain a solvent which can improve the uniformity of the coating film when the liquid crystal alignment agent is applied to the substrate, in addition to the organic solvent for the purpose of dissolving the polymer. The solvent is generally a solvent which has a lower surface tension than the above organic solvent. Specifically, for example, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-single Methyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, butyl cellosolve acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, lactic acid Methyl ester, 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 may contain various additives such as a decane coupling agent or a crosslinking agent. In the case where a decane coupling agent or a crosslinking agent is added, in order to prevent precipitation of a polymer, a poor solvent is added to the liquid crystal alignment agent, and it is preferred to add it beforehand. Further, in the case of baking the coating film, a ruthenium imidization accelerator may be added in order to efficiently carry out the ruthenium imidization of the polyamidite. Specific examples of the decane coupling agent will be listed below, but the decane coupling agent to be used in the liquid crystal alignment agent of the present invention is not limited to these contents. 3-aminopropyltriethoxydecane, 3-(2-aminoethyl)aminopropyltrimethoxydecane, 3-(2-aminoethyl)aminopropylmethyldimethoxy Baseline, 3-aminopropyltrimethoxydecane, 3-phenylaminopropyltrimethoxydecane, 3-triethoxydecyl-N-(1,3-dimethyl-butylene) An amine decane coupling agent such as propylamine or 3-aminopropyldiethoxymethyl decane; vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris (2-methoxy phenyl) Oxy) decane, vinyl methyl dimethoxy decane, vinyl triethoxy decane, vinyl triisopropoxy decane, allyl trimethoxy decane, p-styryl trimethoxy decane, etc. Vinyl decane coupling agent; 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropylmethyldiethoxydecane An epoxy-based decane coupling agent such as 3-glycidoxypropylmethyldimethoxydecane or 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane; 3-methyl Propylene methoxypropyl methyl dimethoxy decane, 3-methyl propylene oxypropyl trimethoxy a methacrylic decane coupling agent such as decane, 3-methacryl oxime propyl dimethyl diethoxy decane, 3-methyl propylene oxypropyl triethoxy decane or the like; 3-propene oxy propylene Acrylic decane coupling agent such as trimethoxy decane; urea-based decane coupling agent such as 3-ureidopropyltriethoxy decane; bis(3-(triethoxydecyl)propyl)disulfide a thioether decane coupling agent such as ether or bis(3-(triethoxydecyl)propyl)tetrasulfide; 3-hydrothiopropylmethyldimethoxydecane, 3-hydrothiopropylpropane Hydrogenthio-based decane coupling agent such as trimethoxy decane, 3-octyl thiol-1-propyltriethoxy decane; 3-isocyanate propyl triethoxy decane, 3-isocyanate propyl trimethoxy Isocyanate-based decane coupling agent such as decane or the like; aldehyde-based decane coupling agent such as triethoxy decyl butyl aldehyde; triethoxy decyl propyl methyl urethane, (3-triethoxy decane) A urethane-based decane coupling agent such as propyl)-t-butyl carbamic acid ester. Specific examples of the ruthenium imidization accelerator of the polyphthalate are as follows, but the ruthenium-based accelerator which can be used for the liquid crystal alignment agent of the present invention is not limited to these contents.

D in the above formulae (B-1) to (B-17) each independently represents a tert-butoxycarbonyl group or a 9-fluorenylmethoxycarbonyl group. Further, in the case of (B-14) to (B-17), when a plurality of Ds are present in one formula, they may be the same or different from each other. The content of the ruthenium iodide promoter is not particularly limited as long as the effect of promoting the heat imidization of the polyphthalate is obtained. In general, if the lower limit is to be expressed, it is preferably 0.01 mol or more, more preferably 0.05 mol, based on the valerate moiety of the following formula (16) contained in the polyglycolate. Above the ear, the best is 0.1 moles or more. Further, the main body of the hydrazine imidization promoter remaining in the film after baking is reduced to a minimum amount which adversely affects various characteristics of the liquid crystal alignment film, and more specifically, When it is an upper limit, it is preferably 2 mol or less, more preferably 2 mol or less, based on the valerate moiety of the following formula (16) contained in the polyphthalate of the present invention. 1 mole below, preferably 0.5 mole or less.

In the case where a ruthenium imidization accelerator is added, since it can be subjected to hydrazine imidization treatment by heating, it is preferably added after dilution with a good solvent and a poor solvent.

<Liquid alignment film>

In the liquid crystal alignment film of the present invention, the liquid crystal alignment agent obtained by the above method is applied to a substrate, and the coating film obtained by drying and baking is applied, and if necessary, the coating film surface may be subjected to an alignment treatment such as rubbing. The substrate to which the liquid crystal alignment agent of the present invention can be 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. Wait. Further, when a substrate such as an ITO electrode is used for the purpose of performing liquid crystal driving, it is preferable from the viewpoint of simplifying the process. Further, since the reflective liquid crystal display element is only a single-sided substrate, an opaque substance such as a germanium wafer can be used. In this case, a material such as aluminum that reflects light can be used as the electrode. The coating method of the liquid crystal alignment agent of the present invention, for example, a spin coating method, a printing method, an inkjet method, or 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, the organic solvent and the like are sufficiently removed, and 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, there may be a fear of lowering the reliability of the liquid crystal display element, 5 to 300 nm, preferably 10 to 200 nm. The method of performing the alignment treatment on the coating film is, for example, a rubbing method or a photo-alignment treatment method, but the liquid crystal alignment agent of the present invention is particularly useful for the case of using the photo-alignment treatment method.

Specifically, for example, a method of irradiating the surface of the coating film with a polarized light in a specific direction by an energy ray, and then heat-treating at a temperature of 150 to 250 ° C to impart a liquid crystal alignment energy thereto. It is also possible to use the wavelength of the radiation to be ultraviolet or visible light having a wavelength of 100 nm to 800 nm. Among them, ultraviolet rays having a wavelength of 100 nm to 400 nm are preferably used, and those having a wavelength of 200 nm to 400 nm are particularly preferable. Moreover, from the viewpoint of improving the alignment of the liquid crystal, the coated substrate may be heated to 50 to 250 ° C and irradiated with radiation. In the alignment treatment or the like, the irradiation amount of the radiation is preferably in the range of 1 to 10,000 mJ/cm ² , and particularly preferably in the range of 100 to 5,000 mJ/cm ² . According to the liquid crystal alignment film produced in the above manner, the liquid crystal molecules can form a stable alignment in a specific direction.

[Examples]

The invention will be described in more detail below by way of examples, but the invention is not limited thereto. In the following, the abbreviations of the compounds used in the 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

DA-1: The above formula (D-25)

BDA: 1,2,3,4-butane tetracarboxylic dianhydride

CBDA: 1,2,3,4-cyclobutane tetracarboxylic dianhydride

NMP: N-methyl-2-pyrrolidone

γ-BL: γ-butyrolactone

BCS: butyl cellulolytic

PAE: Polyamidomate

PAA: Polylysine

DA-2: The above formula (D-29)

DA-3: The above formula (D-30)

DA-4: The above formula (D-28)

DA-5: The above formula (DA-32)

DA-6: n=5 of the above formula (DA-35)

DA-7: the following formula (DA-7)

DA-8: The following formula (DA-8)

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

DAH-2: the following formula (DAH-2)

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

AD-2: the following formula (AD-2)

AD-3: the following formula (AD-3)

AD-4: The following formula (AD-4)

[viscosity]

In the synthesis example, the viscosity of the polyphthalate and the poly-proline solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), a sample volume of 1.1 mL, and a conical mixer 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) apparatus, and the number average molecular weight is calculated from 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: Shodex company (inline type KD803, KD805) column temperature: 50 ° C

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

Flow rate: 1.0 ml/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, two samples of a mixture of four types of 900,000, 100,000, 12,000, and 1,000, and two samples of a mixture of 150,000, 30,000, and 4,000 were measured.

[Determination of the average thickness of the centerline]

The coating film of the obtained liquid crystal alignment agent was applied by a spin coating method, dried on a hot plate at a temperature of 80 ° C for 5 minutes, and baked in a hot air circulating oven at a temperature of 250 ° C for 1 hour to form a film thickness of 100. Coating film of nm. The film surface of the coating film was observed using an atomic force microscope (AFM), and the average thickness (Ra) of the center line of the film surface was measured to evaluate the flatness of the film surface.

Measuring device: L-trace detection microscope (manufactured by SII‧ Technology Co., Ltd.)

[

Voltage retention rate]

The liquid crystal alignment agent was spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at a temperature of 80 ° C for 5 minutes, and baked in a hot air circulating oven at 250 ° C for 60 minutes to form a film thickness of 100 nm. Coating film. The 254 nm ultraviolet light was irradiated onto the coating film surface at 100 mJ/cm ² through a polarizing plate to obtain a substrate with a liquid crystal alignment film. Two sheets of the substrate with the liquid crystal alignment film were prepared, and the liquid crystal alignment film surface of the substrate on one side was dispersed with a particle sizer having a diameter of 6 μm, and then the two substrates were combined in an antiparallel manner to be retained only Outside the liquid crystal injection port, the other surrounding portions were sealed, and an empty cell having a cell gap of 6 μm was obtained. Liquid crystal (MLC-2041, manufactured by Merck) was injected into the empty cell at a normal temperature, and the liquid crystal cell was obtained by blocking the injection port. The method for measuring the voltage holding ratio of the liquid crystal cell is carried out in the following manner. The voltage of 4 V was applied for 60 μs, and the voltage after 16.67 ms was measured, and the fluctuation caused by the initial value was calculated as the voltage holding ratio. At the time of measurement, the temperature of the liquid crystal cell was set to 23 ° C, 60 ° C, and 90 ° C, and the respective temperatures were measured.

[ion density]

The measurement of the ion density of the liquid crystal cell described above was carried out in the following manner. The measurement was carried out using a 6254 liquid crystal property evaluation device manufactured by Dongyang Technology Co., Ltd. A triangular wave of 10 V and 0.01 Hz was applied, and the area corresponding to the ion density of the obtained waveform was calculated by a triangle approximation as the ion density. At the time of measurement, the temperature of the liquid crystal cell was set to 23 ° C and 60 ° C, and the respective temperatures were measured.

[FFS drives liquid crystal cell AC drive burn-in]

The liquid crystal alignment agent was applied onto a glass substrate by a spin coating method to form an ITO electrode having a first layer electrode shape of 50 nm in thickness and a second layer insulating film shape having a thickness of 500 nm. The three layers are fringe field switching (Fringe Field Switching: hereinafter, also referred to as FFS) driving electrodes of a comb-shaped ITO electrode (electrode width: 3 μm, electrode spacing: 6 μm, electrode height: 50 nm) as an electrode On the glass substrate. 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 254 nm ultraviolet light was irradiated onto the coating film surface at 100 mJ/cm ² through a polarizing plate to obtain a substrate with a liquid crystal alignment film. Further, a glass substrate having a columnar distance controller having a height of 4 μm on which the electrode was not formed on the substrate was formed into a coating film by the same method, and subjected to alignment treatment. The two substrates were used as a group, and the sealant was printed on the substrate, and the other substrate was bonded so that the alignment direction of the liquid crystal alignment film surface was 0°, and then the sealant was cured to prepare an empty 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. A rectangular wave of ±4 V/120 Hz for 4 hours was applied after the VT characteristic (voltage-transmittance characteristic) of the FFS-driven liquid crystal cell at a temperature of 58 ° C was measured. After 4 hours, the voltage was turned off, and after leaving it at a temperature of 58 ° C for 60 minutes, the VT characteristics were measured again, and the difference in voltage when the transmittance before and after the application of the rectangular wave was 50% was calculated.

[Evaluation of charge accumulation characteristics]

The FFS-driven liquid crystal cell was placed on a light source, and the VT characteristic (voltage-transmittance characteristic) was measured, and then the transmittance (Ta) in a state where a rectangular wave of ±1.5 V/60 Hz was applied was measured. Subsequently, after applying a rectangular wave of ±1.5 V/60 Hz for 10 minutes, DC 1V was overlapped and driven for 30 minutes. The DC voltage was cut, and the transmittance (T _b ) after 10 minutes of AC driving was measured, and the difference between the transmittance of the voltage remaining in the liquid crystal display element was calculated by the difference between T _b and T _a .

Synthesis of (a.) dimethyl 1,3-bis(chlorocarbonyl)-1,3-dimethylcyclobutane-2,4-dicarboxylate (1,3DMCBDE-Cl)

(a-1) Synthesis of dicarboxylic acid dialkyl ester

1,3-dimethylcyclobutane-1,2,3,4-tetracarboxylic dianhydride (a compound of formula (5-1), placed in a 3 L (liter) four-necked flask under a nitrogen stream, Hereinafter, abbreviated as 1,3-DM-CBDA) 220 g (0.981 mol), and methanol 2200 g (6.87 mol, 10wt times relative to 1,3-DM-CBDA), heated at 65 ° C under reflux, to 30 A uniform solution is formed in minutes. The reaction solution was stirred in this state under heating and reflux for 4 hours and 30 minutes. This reaction liquid was measured using a high-speed liquid chromatography analyzer (hereinafter, abbreviated as HPLC). After the solvent was distilled off using an evaporator, 1301 g of ethyl acetate was added, and the mixture was heated to 80 ° C, and refluxed for 30 minutes. Subsequently, the internal temperature was cooled to 25 ° C at a rate of 2 to 3 ° C per 10 minutes, and stirred in this state at 25 ° C for 30 minutes. The precipitated white crystals were taken out by filtration, and the crystals were washed twice with ethyl acetate (141 g), and then dried over vacuo. This crystal was analyzed by ¹ H NMR, and the crystal structure was analyzed by X-ray analysis to confirm that it was Compound (1-1) (relative area of HPLC: 97.5%) (yield: 36.8%). ¹ H NMR (DMSO-d6, δ ppm); 12.82 (s, 2H), 3.60 (s, 6H), 3.39 (s, 2H), 1.40 (s, 6H).

(a-2) Synthesis of 1,3-DM-CBDE-C1

Under a nitrogen flow, a compound (1-1) 234.15 g (0.81 mol) and n-heptane 1170.77 g (11.68 mol. 5wt times) were added to a three-liter four-necked flask, and then 0.64 g (0.01 mol) of pyridine was added. The mixture was heated and stirred to 75 ° C with stirring using a magnetic stirrer. Subsequently, 289.93 g (11.68 mol) of sulfinium chloride was added dropwise over 1 hour. The foaming started immediately after the dropping, and the reaction solution formed a uniform solution 30 minutes after the completion of the dropping, and the foaming was stopped. Subsequently, in this state, after stirring at 75 ° C for 1 hour and 30 minutes, the solvent was distilled off to an amount of 924.42 g in an evaporator and a 40 ° C water bath. Further, the mixture was heated at 60 ° C to dissolve the crystals precipitated when the solvent was distilled off, and the insoluble matter was distilled off by hot filtration at 60 ° C, and then the filtrate was cooled to 25 ° C at a rate of 1 ° C per 10 minutes. After stirring at 25 ° C for 30 minutes in this state, the precipitated white crystals were taken out by filtration, and the crystals were washed with n-heptane 264.21 g. After drying under reduced pressure, 226.09 g of white crystals were obtained. Subsequently, 226.09 g of the white crystal obtained and 452.18 g of n-heptane obtained above were added to a three-liter four-necked flask under a nitrogen stream, and the mixture was heated and stirred at 60 ° C to dissolve the crystal. Subsequently, the mixture was cooled and stirred at 25 ° C at a rate of 1 ° C per 10 minutes to precipitate crystals. After stirring for 1 hour at 25 ° C in this state, the precipitated white crystals were taken out by filtration, and the crystals were washed with n-hexane 113.04 g, and then dried under reduced pressure to give 203.91 g of white crystals. This crystal was analyzed by ¹ H NMR to confirm that the compound (3-1) was dimethyl-1,3-bis(chlorocarbonyl)-1,3-dimethylcyclobutane-2,4-dicarboxylate. Acid ester (1,3-DM-CBDE-C1) (relative area of HPLC 99.5%) (yield 77.2%). ^{1 H NMR (CDCl3, δppm)} : 3.78 (s, 6H), 3.72 (s, 2H), 1.69 (s, 6H).

(Synthesis Example 1)

The diamine compound (DA-1) was synthesized by the 4-step process shown below.

Step 1: Synthesis of Compound (A5)

In a 500 mL eggplant flask, propargylamine (8.81 g, 160 mmol), N,N-dimethylformamide (112 mL), potassium carbonate (18.5 g, 134 mmol) were added sequentially. The solution obtained by dissolving t-butyl bromoacetate (21.9 g, 112 mmol) in N,N-dimethylformamide (80 mL) at 0 ° C was added dropwise over a period of about 1 hour. among them. After the completion of the dropwise addition, the reaction solution was returned to room temperature and stirred for 20 hours. Subsequently, the solid matter was removed by filtration, and 1 L of ethyl acetate was added to the filtrate, and washed with 300 mL of water for 4 times and 300 mL of saturated saline for 1 time. Subsequently, the organic layer was dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. Finally, the residual oil was distilled under reduced pressure at 0.6 Torr and 70 ° C to give N-propargylaminoacetic acid t-butyl ester (compound (A5)) as a colorless liquid. The yield was 12.0 g and the yield was 63%.

Step 2: Synthesis of Compound (A6)

In a 1 L eggplant type flask, the above-mentioned N-propargylaminoacetic acid t-butyl (12.0 g, 70.9 mmol) and dichloromethane (600 mL) were added as a solution, and the dicarbonic acid was dissolved in ice-cooled stirring. A solution of di-t-butyl ester (15.5 g, 70.9 mmol) in dichloromethane (100 mL) was added dropwise over 1 hour. After the completion of the dropwise addition, the reaction solution was returned to room temperature and stirred for 20 hours. After completion of the reaction, the reaction solution was washed with 300 mL of saturated brine and dried over magnesium sulfate. Subsequently, the solvent was distilled off under reduced pressure to give N-propargyl-N-t-butoxycarbonylaminoacetic acid t-butyl ester (compound (A6)) as a pale yellow liquid. The yield was 18.0 g and the yield was 94%.

Step 3: Synthesis of Compound (A7)

In a 300 mL four-necked flask, 2-iodo-4-nitroaniline (22.5 g, 85.4 mmol), bis(triphenylphosphine)palladium dichloride (1.20 g, 1.71 mmol), copper iodide ( 0.651 g, 3.42 mmol), after substitution with nitrogen, diethylamine (43.7 g, 598 mmol), N,N-dimethylformamide (128 mL) was added and stirred under ice-cooling - Propargylamino-Nt-butoxycarbonyl acetic acid t-butyl ester (27.6 g, 102 mmol) was stirred at room temperature for 20 hr. After completion of the reaction, 1 L of ethyl acetate was added, and the mixture was washed three times with 150 mL of a 1 mol/L aqueous solution of ammonium chloride, and once with 150 mL of saturated brine, and dried over magnesium sulfate. Subsequently, the solid which was obtained by distilling off the solvent under reduced pressure was dissolved in ethyl acetate (200 mL), and 1 L of hexane was added, followed by recrystallization. The solid was collected by filtration and dried <RTI ID=0.0> Aniline (compound (A7)). The yield was 23.0 g and the yield was 66%.

Step 4: Reduction of Compound (A7)

The above 2-{3-(Nt-butoxycarbonyl-Nt-butoxycarbonylmethylamino)-1-propynyl)}-4-nitroaniline (22.0 g) was added to a 500 mL four-necked flask. 54.2 mmol), and ethanol (200 g), after the reaction was replaced with nitrogen, palladium carbide (2.20 g) was added, and the reaction was replaced with hydrogen, and stirred at 50 ° C for 48 hours. After completion of the reaction, palladium carbide was removed by filtration through cerite, activated carbon was added to the filtrate, and the mixture was stirred at 50 ° C for 30 minutes. Subsequently, the activated carbon was filtered, and the organic solvent was distilled off under reduced pressure. The residue was dried under reduced pressure to give the diamine compound (DA-1). The yield was 19.8 g and the yield was 96%. The diamine compound (DA-1) was confirmed by using ¹ H NMR. ¹ H NMR (DMSO-d ₆ ): δ 6.54-6.42 (m, 3H, Ar), 3.49, 3.47 (each s, 2H, NCH ₂ CO ₂ t-Bu), 3.38-3.30 (m, 2H, CH ₂ CH ₂ N), 2.51-2.44 (m, 2H, ArCH ₂ ), 1.84-1.76 (m, 2H, CH ₂ CH ₂ CH ₂ ), 1.48-1.44 (m, 18H, NCO ₂ t-Bu and CH ₂ CO ₂ t-Bu).

(Synthesis Example 2)

A 300 mL four-necked flask equipped with a stirring device was set in a nitrogen atmosphere, and 4.48 g (22.63 mmol) of 4,4'-diaminodiphenylmethane was placed, and DA-12.147 g (5.658 mmol) was weighed and added. 121.37 g of NMP and 5.16 g (65.19 mmol) of pyridine as a base were stirred and dissolved. Next, the diamine solution was stirred, and 1,3DM-CBDE-Cl 8.8384 g (27.16 mmol) was added, and the mixture was reacted under water cooling for 4 hours. After 4 hours, 134.86 g of NMP was added to the reaction solution, and the mixture was stirred at room temperature (20 ° C) for 15 minutes. The obtained polyglycolate solution was poured into 1349 g of water with stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 1349 g of water, washed once with 1349 g of ethanol, and washed with 337 g of ethanol. After 3 times, 11.04 g of a white polyphthalate resin powder was obtained after drying. The yield was 81.9%. Further, the molecular weight of the polyphthalate was Mn = 15,205 and Mw = 30,219. 10.9690 g of the obtained polyphthalate resin powder was placed in a 200 ml Erlenmeyer flask, and after adding 98.7394 g of NMP, it was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-1). .

(Comparative Synthesis Example 1)

A 300 mL four-necked flask equipped with a stirring device was set in a nitrogen atmosphere, and after placing 4,4'-diaminodiphenylmethane 8.0102 g (40.35 mmol), 158.1 g of NMP and 7.20 g of pyridine as a base were added. After (91.03 mmol), it was stirred to dissolve. Next, the diamine solution was stirred, and 1,3DM-CBDE-C1 12.3419 g (37.93 mmol) was added, and the mixture was reacted under water cooling for 4 hours. The obtained polyglycolate solution was poured into 1757 g of water with stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 1757 g of water, 1757 g of ethanol, and 439 g of ethanol. After 3 times, 16.63 g of a white polyphthalate resin powder was obtained after drying. The yield was 94.6%. Further, the molecular weight of the polyamidomate was Mn = 10,180 and Mw = 21,476. 14.8252 g of the polyacetate resin powder obtained by weighing was placed in a 200 ml Erlenmeyer flask, and NMP99.3048 g was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-2). ).

(Synthesis Example 3)

In a 100 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube, 7.9693 g (40 mmol) of 4,4'-diaminodiphenylamine was weighed, and 31.7 g of NMP was added thereto, and the mixture was continuously stirred with nitrogen. Let it dissolve. The diamine solution was stirred, and BDA 7.1339 g (36.01 mmol) was added thereto, and NMP was added thereto to have a solid content concentration of 25% by mass, and stirred at room temperature for 24 hours to obtain a solution of poly-proline (PAA-1). . The polyamic acid solution has a viscosity of 2680 mPa ‧ at a temperature of 25 ° C. Further, the molecular weight of the polyamic acid was Mn = 8,176 and Mw = 16,834.

(Synthesis Example 4)

4,4'-diaminodiphenylamine 5.9791 g (30.01 mmol) and 3,5-diaminobenzoic acid 3.0446 g were weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube. 20.01 mmol), 39.69 g of NMP was added, and it was stirred and continuously dissolved in nitrogen gas to dissolve. This diamine solution was added with 9.8379 g (49.65 mmol) of BDA, and NMP was added thereto so that the solid content concentration was 25% by mass, and the mixture was stirred at room temperature for 24 hours to obtain a solution of poly-proline. The polyamic acid solution has a viscosity of 8000 mPa ‧ at a temperature of 25 ° C. Further, the molecular weight of the polyamic acid was Mn = 13,696 and Mw = 28,619. 5.5355 g of the obtained polyaminic acid solution was placed in a 50 ml Erlenmeyer flask, and 8.3744 g of NMP was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a 10 mass% polyamine solution (PAA-2). .

(Synthesis Example 5)

4. 666652 g (18.39 mmol) of 4,4'-diaminodiphenylamine and 0.6992 g of 3,5-diaminobenzoic acid were weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube. 4.595 mmol), 39.36 g of NMP was added, and it was stirred and continuously dissolved in nitrogen. The diamine solution was stirred, and 4.3326 g (22.09 mmol) of CBDA was added thereto, and NMP was added thereto so that the solid content concentration was 15% by mass, and the mixture was stirred at room temperature for 24 hours to obtain polyacrylic acid (PAA-3). Solution. The polyamic acid solution has a viscosity of 669 mPa ‧ at a temperature of 25 ° C. Further, the molecular weight of the polyamic acid was Mn = 16,902 and Mw = 34,865.

(Synthesis Example 6)

4.48g (9.23 mmol) of 4,4'-diaminodiphenyl ether and 2.1025 g of 3,5-diaminobenzoic acid were weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube. 13.82 mmol), 39.7 g of NMP was added, and it was stirred and continuously dissolved in nitrogen gas to dissolve. The diamine solution was stirred, and 4.8162 g (22.08 mmol) of PMDA was added thereto, and NMP was added thereto so that the solid content concentration was 15% by mass, and the mixture was stirred at room temperature for 24 hours to obtain polyglycine (PAA-4). Solution. The polyglycine solution had a viscosity of 257 mPa ‧ at a temperature of 25 ° C. Further, the molecular weight of the polyproline was Mn = 13,620 and Mw = 28,299.

(Example 1)

1.5289 g of the polyphthalate solution (PAE-1) obtained in Synthesis Example 2 and 0.5184 g of the polyamidic acid solution (PAA-1) obtained in Synthesis Example 3 were placed in an Erlenmeyer flask, and NMP 2.0050 g and BCS1 were added. After .0011 g, the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (I).

(Example 2)

1.5246 g of the polyphthalate solution (PAE-1) obtained in Synthesis Example 2 and 1.4067 g of the polyamidic acid solution (PAA-2) obtained in Synthesis Example 4 were placed in an Erlenmeyer flask, and NMP 1.0960 g and BCS1 were added. After .0112 g, the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (II).

(Example 3)

1.5119 g of the polyphthalate solution (PAE-1) obtained in Synthesis Example 2 and 1.0074 g of the polyaminic acid solution (PAA-3) obtained in Synthesis Example 5 were placed in an Erlenmeyer flask, and NMP 1.5183 g and BCS1 were added. After .0313 g, the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (III).

(Example 4)

1.5018 g of the polyphthalate solution (PAE-1) obtained in Synthesis Example 2 and 1.1008 g of the polyaminic acid solution (PAA-4) obtained in Synthesis Example 6 were placed in an Erlenmeyer flask, and NMP 1.4859 g and BCS1 were added. After .0214 g, it was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (IV).

(Comparative Example 1)

3.00 g of the polyphthalate solution (PAE-2) obtained in Comparative Synthesis Example 1 and 1.021 g of the polyamic acid solution (PAA-1) obtained in Synthesis Example 3 were placed in an Erlenmeyer flask, and NMP 3.99 g was added thereto. After BCS 2.0128g, it was stirred by a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (a).

(Comparative Example 2)

1.5119 g of the polyphthalate solution (PAE-2) obtained in Comparative Synthesis Example 1 and 1.4334 g of the polyamic acid solution (PAA-2) obtained in Synthesis Example 4 were placed in an Erlenmeyer flask, and NMP 1.0903 g was added thereto. After BCS 1.0271 g, the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (b).

(Comparative Example 3)

3.00 g of the polyphthalate solution (PAE-2) obtained in Comparative Synthesis Example 1 and 2.0141 g of the polyamic acid solution (PAA-3) obtained in Synthesis Example 5 were placed in an Erlenmeyer flask, and NMP 3.01 g was added thereto. After BCS 2.0111g, the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (c).

(Comparative Example 4)

1.5206 g of the polyphthalate solution (PAE-2) obtained in Comparative Synthesis Example 1 and 1.0258 g of the polyaminic acid solution (PAA-4) obtained in Synthesis Example 6 were placed in an Erlenmeyer flask, and NMP 1.4838 g was added thereto. After BCS 1.0418g, it was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (d).

(Comparative Example 5)

Synthesis Example 2 was weighed ester was obtained from the polyamide (PAE-1) 3.1281g into Erlenmeyer flask, added NMP1.0911g, after ^BCS1.0532g, using a magnetic stirrer for 30 minutes to give liquid crystal alignment agent (e) .

(Example 5)

The liquid crystal alignment agent (I) obtained in Example 1 was filtered using a 1.0 μm filter, and then spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at a temperature of 80 ° C for 5 minutes, and passed through a temperature of 250. After baking at ° C for 1 hour, a coating film having a film thickness of 100 nm was formed. The average thickness (Ra) of the center line of the coating film was measured. The measurement results are shown in Table 1 below.

(Examples 6 to 9 and Comparative Examples 7 to 10)

Each of the coating films was formed in the same manner as in Example 5 except that each of the liquid crystal alignment agents (II) to (IV) and (a) to (d) obtained in the above Examples 2 to 4 and Comparative Examples 1 to 4 was used. . The film surface of each coating film was observed using AFM. Further, the average thickness (Ra) of the center line of each coating film was measured. The measurement results are shown in Table 1 below.

As shown in Table 1, as is apparent from the results of Examples 5 to 9 and Comparative Examples 7 to 10, the liquid crystal alignment agent of the present invention was confirmed to reduce the phase separation of the polyphthalate and the polyaminic acid. The tiny bumps give a smooth film surface.

(Embodiment 10)

The liquid crystal alignment agent (I) obtained in Example 1 was filtered using a 1.0 μm filter, and then spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at a temperature of 80 ° C for 5 minutes, and passed through a temperature of 250. After baking at ° C for 1 hour, a coating film having a film thickness of 100 nm was formed. The 254 nm ultraviolet light was irradiated onto the coating film surface at 100 mJ/cm ² through a polarizing plate to obtain a substrate with a liquid crystal alignment film. Prepare two sheets of the substrate with the liquid crystal alignment film, and spread the 6 μm distance adjuster on the liquid crystal alignment film surface of one of the substrates, and then combine the alignment of the two substrates in an anti-parallel manner to retain only the liquid crystal. Except for the inlet, the other circumferences were sealed, and an empty cell with a cell gap of 6 μm was produced. Liquid crystal (MLC-2041, manufactured by Merck Co., Ltd.) was vacuum-injected into the empty cell at normal temperature, and the liquid crystal cell was obtained by blocking the injection port. The liquid crystal cell was measured for its voltage holding ratio, and then its ion density was measured. Voltage retention and ion density. The measurement results are shown in Table 2 below.

(Examples 11 to 13 and Comparative Examples 11 to 15)

A liquid crystal crystal was produced in the same manner as in Example 10 except that each of the liquid crystal alignment agents (II) to (IV) and (a) to (e) obtained in the above Examples 2 to 4 and Comparative Examples 1 to 5 was used. Cell. The voltage holding ratio of each liquid crystal cell was measured, and then the ion density was measured. The measurement results of these voltage holding ratios and ion densities are shown in Table 2 below.

As shown in Table 2, it was confirmed from the results of Examples 10 to 13 and Comparative Example 15 that it was confirmed that the liquid crystal alignment agent of the present invention can be obtained equivalent or more with respect to the liquid crystal alignment agent obtained by containing only the polyphthalate. A reliable liquid crystal alignment film. Further, as a result of Examples 10 to 13 and Comparative Examples 11 to 14, it was confirmed that the liquid crystal alignment agent of the present invention is related to a polyphthalamide and a polydecylamine containing a low-polarity substituent which does not dissociate via heat. The acid liquid crystal alignment agent can obtain a liquid crystal alignment film having higher letterability.

(Example 14)

The liquid crystal alignment agent (I) obtained in Example 1 was filtered using a 1.0 μm filter, and then applied onto a glass substrate by spin coating to form an ITO electrode having a first layer of 50 nm and a second layer. The insulating film has a thickness of 500 nm of tantalum nitride, and the third layer is 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). 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 254 nm ultraviolet light was irradiated onto the coating film surface at 100 mJ/cm ² through a polarizing plate to obtain a substrate with a liquid crystal alignment film. Further, a coating film was formed in the same manner as the glass substrate having the columnar distance controller having a height of 4 μm on the opposite substrate, and the alignment treatment was performed.

The two substrates were used as a group, and the sealant was printed on the substrate, and the other substrate was bonded so that the alignment direction of the liquid crystal alignment film surface was 0°, and then the sealant was cured to prepare 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 driving liquid crystal cell. The FFS drives the liquid crystal cell, and its AC drive burn-off characteristics and charge accumulation characteristics are evaluated. The results are shown in Table 3 below.

(Examples 15 to 17 and Comparative Example 16)

An FFS-driven liquid crystal cell was separately produced in the same manner as in Example 14 except that each of the liquid crystal alignment agents (II) to (IV) and (e) obtained in the above Examples 2 to 4 and Comparative Example 5 was used. The evaluation of the AC drive burn-up characteristics and the charge accumulation characteristics of each FFS-driven liquid crystal cell was performed. The results are shown in Table 3 below.

As shown in Table 3, as a result of Examples 14 to 17 and Comparative Example 16, it was confirmed that the liquid crystal alignment agent of the present invention can obtain a liquid crystal alignment having a small AC drive burnt degree and having a small residual voltage. membrane.

(Synthesis Example 7) Synthesis of Diamine Compound (DA-2) (Precursor Synthesis 1)

A 1 L four-necked flask connected with a Dimroth tube and a 100 mL dropping funnel was added with 2-cyano-4-nitroaniline (15 g, 92 mmol). After the reaction was replaced with nitrogen, THF 400 was added. mL, cooled to 0 °C. Next, a boron-THF complex (1 M in THF, 100 mL, 100 mmol) was added dropwise via a dropping funnel over 30 minutes. It was confirmed that a gas was generated from the reaction system, and a yellow solid was precipitated. After the completion of the dropwise addition, the mixture was stirred at room temperature for 2 days. After completion of the reaction, hydrochloric acid (2N, 200 mL) was added, and the mixture was stirred at room temperature for 2 hr, and then aqueous sodium hydroxide (2N, 250 mL) was added at 10 ° C to make it basic. The organic layer was washed with brine (500 mL) and dried over magnesium sulfate. The yield was 11.9 g and the yield was 77%.

(precursor synthesis 2)

To the 1 L eggplant flask, the above-mentioned cyano reducing body (4.60 g, 27.5 mmol) and dichloromethane (900 mL) were added as a solution, and diter-butyl dicarbonate (6.00 g, 27.5 mmol) was added to the chamber. Stir at temperature (20 ° C) for 3 days. After completion of the reaction, the reaction solution was washed with brine and dried over magnesium sulfate. The organic layer was concentrated under reduced pressure. The yield was 5.25 g and the yield was 71%.

(synthesis of DA-2)

The above Boc adduct (5.0 g, 18.7 mmol) and ethanol (40 ml) were added to a 100 mL eggplant flask, and after the reaction was replaced with nitrogen, platinum oxide (500 mg) was added, and the reaction system was replaced with hydrogen. . The reaction mixture which formed a yellow suspension was stirred at room temperature for 15 hours. After the completion of the reaction, ethanol was added to dissolve the precipitated white solid, and the catalyst was removed by filtration with vermiculite. The filtrate was concentrated and the obtained EtOAc (EtOAc m. The yield was 3.40 g and the yield was 77%. The ¹ H-NMR of the obtained solid was measured to confirm the formation of DA-2. ¹ H-NMR (DMSO-d ₆ , δ ppm): 1.44 (s, 9H), 3.87 (d, J = 6.3 Hz, 2H), 4.10 to 4.30 (m, 4H), 6.27 (dd, J = 2.4 Hz, 8.1 Hz, 1H), 6.31 (d, J = 2.4 Hz, 1H), 6.38 (d, J = 8.1 Hz), 7.14 (t, J = 6.3 Hz, 1H).

(Synthesis Example 8) Synthesis of diamine compound (DA-3) (synthesis of N-Boc-propargylamine)

In a four-necked flask, after adding propargylamine (25.18 g, 0.448 mol), triethylamine (55.52 g, 0.549 mol), and 400 ml of dichloromethane, the reaction solution was cooled in a water bath (20 ° C) to Di-tert-butyl dicarbonate (118.15 g, 0.541 mol) was added dropwise over 30 minutes. After the completion of the dropwise addition, the mixture was stirred for 2 hours, and then 300 ml of saturated brine and 200 ml of dichloromethane were added to the reaction mixture, followed by extraction. The resulting organic layer was dried over magnesium sulfate. After removing the desiccant, the resulting solution was distilled off to give a pale yellow oil (Oil). Purification by recrystallization (hexane) gave N-Boc-propargylamine as a white solid (yield: 47.01 g, yield: 67.6%).

(synthesis of nitrosome)

To a four-necked flask after nitrogen substitution, 2-iodo-4-nitroaniline (5.11 g, 19.4 mmol), bis(triphenylphosphine)palladium(II) dichloride (281.7 mg, 0.401 mmol) was added. Copper iodide (160.7 mg, 0.844 mmol) and diethylamine 30 ml were stirred at room temperature (20 ° C) for 10 minutes. Subsequently, Boc-propargylamine (3.72 g, 24.0 mmol) was added, and the mixture was stirred at room temperature (20 ° C) for 4 hours. After confirming the disappearance of the raw material by HPLC, 200 ml of ethyl acetate and 200 ml of a 1 M aqueous ammonium chloride solution were added, followed by extraction. The obtained organic layer was washed twice with a 1M aqueous solution of ammonium chloride and dried over anhydrous magnesium sulfate. After the desiccant was removed, the filtrate was concentrated and purified by a cerium oxide gel column chromatography (ethyl acetate:hexane = 3:7). The yield was 4.97 g and the yield was 88.0%.

(synthesis of DA-3)

The above nitro group (12.45 g, 42.7 mmol) was added to a four-necked flask, and suspended in 200 ml of ethanol. After degassing and nitrogen substitution, palladium carbide (1.23 g) was added, and the mixture was replaced with hydrogen, and stirred at room temperature (20 ° C) for 2 days. After filtering with vermiculite, the palladium carbide was removed and the solvent was distilled off. After the obtained solid was dissolved in 100 ml of toluene, 50 ml of hexane was added to carry out recrystallization. The obtained solid was dried under reduced pressure to give pale brown solid (yield: 9.13 g, yield: 80.6%). The ¹ H-NMR of the obtained solid was measured to confirm the formation of DA-B. ¹ H-NMR (DMSO-d ₆ , δ ppm): 1.38 (s, 9H), 1.57 (q, J = 7.2 Hz, 2H), 2.30 (t, J = 7.2 Hz, 2H), 2.94 (quin, J = 6.0 Hz, 2H), 3.88 to 4.22 (m, 4H), 6.22 (dd, J = 2.1 Hz, 8.1 Hz, 1H), 6.25 (d, J = 2.1 Hz, 1H), 6.37 (d, J = 8.1 Hz) , 1H), 6.84 (t, J = 6.0 Hz, 1H).

(Synthesis Example 9) Synthesis of diamine compound (DA-4)

In a 500 mL eggplant flask, p-phenylenediamine (16.2 g, 150 mmol), N,N-dimethylformamide (200 mL), potassium carbonate (49.8 g, 360 mmol) were added and cooled to - 20 ° C. A solution of N,N-dimethylformamide (100 mL) in which t-butyl bromoacetate (58.5 g, 300 mmol) was dissolved was dropped over 3 hours. Subsequently, it was stirred at room temperature for 20 hours. After filtering the solid in the reaction mixture by filtration, 6 L of water was poured into the filtrate to recover a crude product of the precipitated diamine compound (D). The obtained crude product was dissolved in 100 mL of N,N-dimethylformamide, and poured into 2 L of water to precipitate a solid. This solid was washed with methanol and dried under reduced pressure to give a diamine compound (DA-4) as a pale solid. The yield was 25.1 g and the yield was 50%. The structure of the diamine compound (D-4) was confirmed by using ¹ H NMR. ¹ H NMR (DMSO-d ₆ ): δ 6.39 (s, 4H, Ar), 5.09 (t, J = 6.6 Hz, 2H, NH), 3.64 (d, J = 6.6 Hz, 4H, CH ₂ ), 1.39 (s, 18H, t-Bu).

(Synthesis Example 10) Synthesis of diamine compound (DA-5) (synthesis of nitro group)

To a four-necked flask after nitrogen substitution, Boc-glycine (10.17 g, 58.05 mmol) was added and dissolved in 150 ml of THF. Thereto, N-methylmorpholine (11.93 g, 117.9 mmol) was added and cooled to -20 °C. Isobutyl chloroformate (9.99 g, 73.14 mmol) was added dropwise to the solution. At this time, be careful not to let the temperature of the reaction solution reach 0 ° C or higher. After dripping, it was stirred at -20 ° C for 10 minutes. At this time, the reaction solution became cloudy. After 10 minutes, 360 ml of 2-amino-4-nitroaniline (8.86 g, 57.86 mmol) in THF was added dropwise using a dropping funnel. After the completion of the dropwise addition, the mixture was stirred at -20 ° C for 1 hour, followed by stirring at room temperature (20 ° C) for 18 hours. After 18 hours, the precipitated solid was filtered off, and the solvent of the obtained filtrate was evaporated to give a concentrated liquid. 200 ml of ethyl acetate and 200 ml of a 1 M aqueous potassium dihydrogen phosphate solution were added to the concentrate to carry out extraction. The obtained organic layer was washed once with 1 M potassium dihydrogen phosphate aqueous solution, once with saturated brine, twice with saturated aqueous sodium hydrogen carbonate solution, and once with saturated brine. The obtained organic layer was dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was distilled off from the filtrate to give an orange solid. The solid was suspended in 300 ml of toluene and stirred under heating for 30 minutes. The solid was collected by absorption, and the NMR of the obtained solid was observed to obtain the desired nitrobenzene (yield: 9.85 g, yield: 54.9%).

(synthesis of DA-5)

To the eggplant flask, the above nitro group (9.85 g, 31.75 mmol) was added, followed by 150 ml of ethanol. After the reaction vessel was replaced with nitrogen, palladium carbide (1.11 g, 10 mass% based on the mass of the nitro group) was added, and the mixture was replaced with nitrogen. Subsequently, the reaction vessel was replaced with hydrogen and stirred at 20 ° C for 48 hours. After completion of the reaction, the palladium carbide was removed by filtration using vermiculite, and the solvent was removed from the filtrate. To the obtained concentrate, 150 ml of toluene was added, and the mixture was heated under reflux to precipitate a solid. The precipitated solid was filtered through heat to give a thin purple solid. The yield was 8.05 g and the yield was 90.4%. The ¹ H-NMR of the obtained solid was measured to confirm the formation of DA-5. ¹ H-NMR (DMSO-d ₆ , δ ppm): 1.40 (s, 9H), 3.70 (d, J = 6.0 Hz, 2H), 4.04 (bs, 2H), 4.35 (bs, 2H), 6.23 (dd, J=2.4 Hz, 8.0 Hz, 1H), 6.48 (d, J=8.0 Hz, 1H), 6.61 (d, J=2.4 Hz, 1H), 7.05 (t, J=6.0 Hz, 1H), 8.94 (s) , 1H).

(Synthesis Example 11) Synthesis of diamine compound (DA-6) (precursor synthesis 1)

Into a 2 L four-necked flask, 50.00 g (489.3 mmol) of 1,5-diaminopropane, 270.5 g (1.957 mol) of potassium carbonate, and 400 g of dimethyl hydrazine were placed, and the mixture was stirred under heating at 100 °C. Next, 138.09 g (978.7 mmol) of 4-fluoronitrobenzene and 100 g of dimethyl hydrazine were added, and the mixture was stirred under heating at 100 ° C for 4 hours. After 4 hours, the reaction solution was poured into 5 L of water with stirring, and the precipitated yellow solid was collected by filtration. The obtained solid was washed with 3 L of water and 556 g of methanol, and dried to give a yellow solid (the precursor-1). The yield was 152.71 g. The resulting solid (precursor-1) was transferred to the reaction which was subsequently used.

(precursor synthesis 2)

Into a 2 L four-necked flask, 100 g (290.4 mmol) of the above (precursor-1), 7.10 g (58.08 mmol) of N,N-dimethylaminopyridine, and 800 g of tetrahydrofuran were placed, and the mixture was stirred and dissolved at 10 °C. Next, 152.10 g (697.0 mmol) of diter-butyl dicarbonate was placed in a dropping funnel, and the solution was dropped into a four-necked flask over 1 hour. After the completion of the dropwise addition, the reaction liquid was distilled off using an evaporator to obtain a yellow oily substance. To the oil of the oil, ethyl acetate was added, and 500 ml of a 10 wt% aqueous hydrogen chloride solution was added thereto, followed by extraction. The obtained organic layer was washed with 500 ml of a 10 wt% aqueous hydrogen chloride solution and washed with 500 ml of water twice, and the organic layer obtained was washed with magnesium sulfate. After removing the desiccant, the solvent was distilled off to obtain a yellow oily substance. The yellow oil (Oil)-like material was allowed to stand overnight to change to a yellow solid. After adding 400 g of 2-propanol to the solid, it was washed, and the solid was collected by filtration and dried to give a white solid (yield-2). The yield was 124.32 g. The resulting solid (Precursor-2) can then be used in the subsequent reaction.

(Synthesis of DA-6)

To the 2 L four-necked flask, 100.0 g (183.6 mmol) of the above precursor-2 and 1500 g of 1,4-dioxane were added. After the reaction vessel was replaced with nitrogen, palladium carbide (10.00 g, 10 mass% based on the mass of the nitro group) was added, and the mixture was replaced with nitrogen. Subsequently, the reaction vessel was replaced with hydrogen and stirred at 20 ° C for 24 hours. To the precipitated white solid, 800 g of acetonitrile was added to dissolve it. The reaction solution was filtered using a membrane filter (1.0 μm) to remove palladium carbide. The solvent was removed from the filtrate to give a white solid. To the white solid, 350 g of 2-propanol was added, and the mixture was stirred for 1 hour. After 1 hour, the solid was collected by filtration, and 300 g of 2-propanol was added to the obtained solid, and the mixture was washed with an ultrasonic apparatus, and then filtered and dried to obtain DA-6 as a white solid. The yield was 65.50 g and the yield was 74%. The ¹ H-NMR of the obtained solid was measured to confirm the formation of DA-6. ¹ H-NMR (DMSO-d ₆ , δ ppm): 1.10 to 1.23 (m, 6H), 1.32 (s, 18H), 3.40 (t, J = 6.8 Hz, 4H), 5.03 (s, 4H), 6.49 ( d, 8.0 Hz, 1H), 6.48 (d, J = 8.4 Hz, 4H), 6.77 (d, J = 8.4 Hz, 4H).

(Synthesis Example 12) Synthesis of 1,3-bis(4-aminophenethyl)urea

2-(4-Nitrophenyl)ethylamine hydrochloride [A] (52.50 g, 259 mmol), bis(4-nitrobenzene) at room temperature in a 4-neck flask substituted with nitrogen Base) [B] (37.53 g, 123 mmol) and THF (1877 g), to which were added triethylamine (74.90 g, 740 mmol) and 4-N,N-dimethylaminopyridine (3.01 g, 24.7 mmol) After that, stirring was carried out using a mechanical stirrer. The reaction was traced using HPLC. After completion of the reaction, the reaction solution was poured into pure water (9 L) and stirred for 30 minutes. Subsequently, filtration was carried out, and washed with pure water (1 L) to give a crude product as a white solid. The obtained white solid was dispersed and washed with methanol (488 g) using an ultrasonic apparatus, and then filtered and dried to obtain a dinitro compound [C] as a white solid (yield: 42.3 g, yield: 96%). ¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 8.11-8.08 (4H, m), 7.43-7.40 (4H, m), 5.89 (2H, t), 3.24 - 3.19 (4H, q), 2.76 ( 4H, t).

A mixture of the compound [C] (42.32 g, 118 mmol), 5% palladium carbide (4.23 g, 10 wt%), 1,4-dioxane (2031 g) was substituted with nitrogen, replaced with hydrogen, and hydrogen. Stirring was carried out at room temperature in the presence. The reaction was followed by HPLC. After the reaction was completed, the catalyst was filtered using a vermiculite, and the solvent was evaporated under reduced pressure to give a crude product as a white solid. To the crude product, 2-propanol (85 g) was added, and after dispersing and washing with an ultrasonic apparatus, it was filtered and dried to obtain a white solid 1,3-bis(4-aminophenethyl)urea (yield 31.9 g, yield 91%). ^{1 H-NMR (400MHz, DMSO} -d 6, δppm): 6.85-6.82 (4H, m), 6.51-6.48 (4H, m), 5.78 (2H, t), 4.83 (4H, s), 3.14-3.09 (4H, m), 2.50-2.45 (4H, m).

(Synthesis Example 13)

In a 500 mL reaction vessel, compound (b) (50.00 g, 229 mmol), pyridine (0.500 g, 0.632 mmol), compound (c) (63.02, 504 mmol), acetonitrile (300 g) were added under a nitrogen atmosphere. The reaction was carried out by heating under reflux. After completion of the reaction, the mixture was cooled to 20 ° C, and then filtered and washed with acetonitrile (100 g) to give a crude product. Next, 2-propanol (300 g) and distilled water (100 g) were added to the crude product, and the mixture was heated under reflux. Subsequently, it was cooled to 20 ° C, and the solid was filtered, washed with 2-propanol (100 g), and dried to give Compound (d) (yield: 37.8 g, yield: 37%).

¹ H-NMR ( ¹ H NMR spectrometry) (400 MHz, DMSO-d ₆ , σ (ppm)): 8.07 (2H, s), 5.15-5.14 (2H, m), 4.62 (2H, t), 4.59- 4.49 (4H, m), 4.38 (2H, q).

Compound (d) (20.00 g, 44.0 mmol) and sulfinium chloride (120.0 g, 1.01 mol) were added to a 500 mL reaction vessel, and the mixture was heated under reflux. After 30 minutes, after cooling to 20 ° C, sulfinium chloride (120.0 g, 1.01 mol) was added, and the mixture was heated under reflux for 2 hours. After completion of the reaction, excess sulfinium chloride was distilled off under reduced pressure and washed with hexane (200 g). Next, in the crude product, dichloromethane (200 g) was added at 20 ° C, followed by stirring to obtain a solution of the compound (c) (12.1 g, 96.8 mmol), pyridine (13.93 g, 176 mmol), dichloromethane (100 g). Slowly drip into it. After stirring for 1 hour, compound (c) (12.1 g, 96.8 mmol) and pyridine (13.93 g, 176 mmol) were further added. After completion of the reaction, the solvent was distilled off and washed with distilled water (144 g) to give a crude product. Tetrahydrofuran (144 g) was added to the crude product, and the mixture was washed at 23 ° C, filtered, and washed with tetrahydrofuran (130 g), distilled water (170 g), methanol (150 g), and dried to give (AD-4) ( Yield: 17.72 g, yield: 62%).

¹ H-NMR ( ¹ H NMR spectrometry) (400 MHz, DMSO-d ₆ , σ (ppm)): 8.17 (2H, s), 5.18-5.13 (2H, m), 4.64 - 4.53 (6H, m), 4.37 (2H, q).

(Synthesis Example 14)

In a 300 mL four-necked flask equipped with a stirring device, 10.2046 g (39.22 mmol) of 2,4-bis(methoxycarbonyl)cyclobutane-1,3-dicarboxylic acid was weighed and added to 181.2 g of NMP. Stir to dissolve. Subsequently, 8.90 g (87.90 mmol) of triethylamine, 3.8987 g (36.05 mmol) of p-phenylenediamine, and DA-20.9528 g (4.02 mmol) were weighed and stirred, and dissolved. This solution was stirred, and after adding (2,3-dihydroxy-2-thio(keto)yl-3-benzoxazolinyl)phosphonic acid diphenyl 33.74 g (88.01 mmol), NMP 32 g was added. , reacted under water cooling for 4 hours. The obtained polyamidate solution was put into 1090 g of 2-propanol under stirring, and the precipitate was separated by filtration, and then washed with 540 g of 2-propanol for 5 times, and dried to obtain poly-proline. Ester resin powder.

The molecular weight of the polyphthalate was Mn = 5210 and Mw = 8755.

In a 50 ml Erlenmeyer flask, 2.4495 g of the obtained polyphthalate resin powder was weighed, and 22.511 g of NMP was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-3).

(Synthesis Example 15)

2,5-bis(methoxycarbonyl)terephthalic acid 1.2736g (4.51 mmol), 2,4-bis(methoxycarbonyl)cyclobutene was weighed in a 200 mL four-necked flask equipped with a stirring device. 2.6915 g (10.34 mmol) of alkane-1,3-dicarboxylic acid was added to 73.20 g of NMP, followed by stirring to dissolve. Subsequently, 3.34 g (33.01 mmol) of triethylamine, 3.4376 g (12.01 mmol) of 1,3-bis(4-aminophenoxy)propane, and 0.7122 g (3.00 mmol) of DA-2 were weighed and stirred. It dissolves. The solution was stirred, and 12.6 g (33.0 mmol) of (2,3-dihydroxy-2-thio(keto)-3-benzoxazolinyl)phosphonic acid diphenyl was added, followed by NMP 10 g. The reaction was carried out for 4 hours under water cooling. The obtained polyamidate solution was poured into 530 g of 2-propanol with stirring, and the precipitate was separated by filtration, and then washed with 210 g of 2-propanol for 5 times, and dried to obtain poly-proline. Ester resin powder.

The molecular weight of the polyphthalate was Mn = 10,281 and Mw = 23,163.

In a 50 ml Erlenmeyer flask, 2.5429 g of the obtained polyphthalate resin powder was weighed, and 2.93458 g of NMP was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-4).

(Synthesis Example 16)

A 300 mL four-necked flask equipped with a stirring device was set in a nitrogen atmosphere, and 4,4'-diaminodiphenylmethane 5.067 g (25.25 mmol) and DA-6 3.0573 g (6.31 mmol) were placed, and NMP was added. 139 g of 5.57 g (70.36 mmol) of pyridine as a base was stirred and dissolved. Next, the diamine solution was stirred, and 1,3DM-CBDE-Cl 9.5299 g (29.31 mmol) was added, and the mixture was reacted under water cooling for 4 hours. The obtained polyglycolate solution was poured into 1545 g of pure water with stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 1545 g of pure water, once with 1545 g of ethanol, and then with 386 g of ethanol. After washing three times, it was dried to obtain a white polyphthalate resin powder. The molecular weight of the polyphthalate was Mn = 14359 and Mw = 31558.

12.31 g of the obtained polyphthalate resin powder was weighed and placed in a 50 ml Erlenmeyer flask, and 110.79 g of NMP was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-5).

(Synthesis Example 17)

In a 200 mL four-necked flask equipped with a stirring device, 5.5958 g (19.83 mmol) of 2,5-bis(methoxycarbonyl)terephthalic acid was weighed, and 68.70 g of NMP was added thereto, followed by stirring to dissolve. Subsequently, 4.01 g (39.63 mmol) of triethylamine, 1.961 g (16.05 mmol) of 3-aminobenzylamine, and 0.9493 g (4.00 mmol) of DA-2 were added, followed by stirring to dissolve. This solution was stirred with the addition of 4-(4,6-dimethoxy-1,3,5-triazabenzene-2-yl)-4-methylmorpholinium chloride (15 ± 2 weight) 16.40 g of % water and water, and 7.72 g of NMP were added, and reacted under water cooling for 4 hours. The obtained polyamidate solution was poured into 633 g of 2-propanol with stirring, and the precipitate was separated by filtration, and then washed with 210 g of 2-propanol for 5 times, and dried to obtain polylysine. Ester resin powder. The molecular weight of the polyamidomate was Mn = 5152 and Mw = 8788.

In a 50 ml Erlenmeyer flask, 2.5630 g of the obtained polyphthalate resin powder was weighed, and 23.011 g of NMP was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-6).

(Synthesis Example 18)

A 300 mL four-necked flask equipped with a stirring device was set in a nitrogen atmosphere, and after adding 4,4'-diaminodiphenylmethane 1.5163 g (7.65 mmol) and DA-12.8712 g (7.57 mmol), NMP was added. 73.3 g of 2.82 g (35.59 mmol) of pyridine as a base was stirred and dissolved. Next, the diamine solution was stirred, and 1,3DM-CBDE-Cl 4.8583 g (14.94 mmol) was added, and the mixture was reacted for 4 hours under water cooling. After 4 hours, 81.44 g of NMP was added to the reaction solution, and the mixture was stirred at room temperature (20 ° C) for 15 minutes. The obtained solution of the polyglycolate was poured into 850 g of 2-propanol with stirring, and the precipitated white precipitate was collected by filtration, and then washed with 170 g of 2-propanol for 5 times, and dried to obtain a white aggregate. A phthalate resin powder. The molecular weight of the polyglycolate was Mn = 21514 and Mw = 43900.

2.1684 g of the obtained polyphthalate resin powder was placed in a 50 ml Erlenmeyer flask, and NMP 19.2226 g was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-7).

(Synthesis Example 19)

In a 200 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube, 1.7312 g (16.01 mmol) of p-phenylenediamine and 0.9444 g (3.98 mmol) of DA-2 were weighed, and 32.47 g of NMP was added thereto, and continuously fed. Stir in nitrogen to dissolve. This diamine solution was stirred, and 4.4841 g (20.0 mmol) of 2.3.5-tricarboxycyclopentyl acetic acid dianhydride was added, and NMP was added to make the solid content concentration 15% by mass, and the mixture was stirred at room temperature for 24 hours. The solution had a viscosity of 580 mPa ‧ at 25 ° C. To the solution, 23.28 g of NMP was added to give a solid concentration of 10% by mass, and then 6.04 g (40.5 mmol) of 1-methyl-3-p-toluenetriazene was added thereto, and the mixture was stirred at room temperature for 4 hours. After 4 hours, the reaction solution was poured into 286 g of 2-propanol with stirring, and the precipitate was separated by filtration, and then washed with 140 g of 2-propanol for 5 times, and dried to obtain a polyacetate resin. powder. The molecular weight of the polyglycolate was Mn=16532 and Mw=50698.

In a 50 ml sample tube in which a stirrer was placed, 2.2078 g of the obtained polyphthalate resin powder was weighed, and 19.784 g of NMP was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution ( PAE-8).

(Synthesis Example 20)

A 300 mL four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, and 1.9995 g (13.28 mmol) of 4-amino-N-methylphenylethylamine and 0.9379 g (3.35 mmol) of DA-5 were placed. 130.70 g of NMP and 3.80 g (37.54 mmol) of pyridine as a base were stirred and dissolved. Next, the diamine solution was stirred, and 1,3DM-CBDE-Cl 5.0894 g (15.65 mmol) was added, and the mixture was reacted for 4 hours under water cooling. The obtained solution of the polyglycolate was poured into 688 g of 2-propanol with stirring, and the precipitated white precipitate was collected by filtration, and then washed with 172 g of 2-propanol for 5 times, and dried to give a white pigment. Amine resin powder. The molecular weight of the polyglycolate was Mn = 7331 and Mw = 14716.

1.9755 g of the obtained polyacetate resin powder was placed in a 50 ml Erlenmeyer flask, and 17.5314 g of NMP was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-9).

(Synthesis Example 21)

A 100 mL four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, and p-phenylenediamine 0.6005 g (5.55 mmol), DA-4 0.2334 g (0.694 mmol), DA-3 0.1849 g (0.693 mmol) were placed. Thereafter, 49.80 g of NMP and 1.15 g (14.56 mmol) of pyridine as a base were added, followed by stirring to dissolve. Next, this diamine solution was stirred, and 1.2550 g (6.94 mmol) of 1,3DM-CBDE-Cl was added, and the reaction was carried out for 4 hours under water cooling. The obtained solution of the polyglycolate was poured into 277 g of water with stirring, and the precipitated white precipitate was collected by filtration, and then washed 5 times with 69 g of water, and dried to obtain a white polyphthalate resin powder. The molecular weight of the polyamidomate was Mn=16919 and Mw=27982.

2.0204 g of the obtained polyphthalate resin powder was placed in a 50 ml Erlenmeyer flask, and 18.l836 g of GBL was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-10).

(Synthesis Example 22)

2,5-bis(methoxycarbonyl)terephthalic acid 2.2570g (8.00 mmol), 2,4-bis(methoxycarbonyl)cyclobutene was weighed in a 300 mL four-necked flask equipped with a stirring device. 3.0206 g (11.61 mmol) of alkane-1,3-dicarboxylic acid, and after adding 100.35 g of NMP, it was stirred and dissolved. Subsequently, 4.45 g (43.98 mmol) of triethylamine, 3.0934 g (11.98 mmol) of 1,5-bis(4-aminophenoxy)propane, and 1,3-bis(4-aminophenethyl) were added. After 1.2018 g (4.03 mmol) of urea and 1.0653 g (4.02 mmol) of DA-3, the mixture was stirred and dissolved. This solution was stirred, and (2,3-dihydroxy-2-thio(keto)yl-3-benzoxazolinyl)phosphonic acid diphenyl 16.92 g (44.14 mmol) was added, followed by NMP 13.14 g. , reacted under water cooling for 4 hours. The obtained polyamidate solution was poured into 890 g of 2-propanol under stirring, and the precipitate was separated by filtration, and then washed with 300 g of 2-propanol for 5 times, and dried to obtain poly-proline. Ester resin powder.

The molecular weight of the polyglycolate was Mn=9170 and Mw=19990.

1.8720 g of the obtained polyphthalate resin powder was placed in a 50 ml Erlenmeyer flask, and 16.53 g of NMP was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-11).

(Synthesis Example 23)

A 300 mL four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, and 3.02 g (27.93 mmol) of p-phenylenediamine, 173.0 g of NMP, and 5.16 g (65.25 mmol) of pyridine as a base were placed, and then stirred. Dissolved. Next, this diamine solution was stirred, and 8.09 g (27.23 mmol) of dimethyl 2,4-bis(chlorocarbonyl)cyclobutane-1,3-dicarboxylate was added, and the mixture was reacted for 2 hours under water cooling. The obtained solution of the polyglycolate was poured into 1000 g of water, and the precipitated white precipitate was collected by filtration, and then washed with 300 g of 2-propanol for 5 times, and dried to obtain a white polyphthalate resin powder. The molecular weight of the polyglycolate was Mn = 10,820 and Mw = 29,197.

The polyacetate resin powder 1.5309 obtained by weighing was placed in a 50 ml Erlenmeyer flask, and 13.771 g of NMP and 16.69279 g of N,N-dimethylformamide were added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved. Polyammonium ester solution (PAE-12).

(Synthesis Example 24)

2. 1.7779 g (6.30 mmol) of 2,5-bis(methoxycarbonyl)terephthalate and 2,4-bis(methoxycarbonyl)cyclobutene were weighed in a 200 mL four-necked flask equipped with a stirring device. 3.7712 g (14.49 mmol) of alkane-1,3-dicarboxylic acid, and after adding 14.67 g of NMP, it was stirred and dissolved. Subsequently, 4.25 g (42.0 mmol) of triethylamine and 5.4239 g (21.0 mmol) of 1,3-bis(4-aminophenoxy)propane were added, followed by stirring to dissolve. This solution was stirred, and 16.91 g (44.11 mmol) of (2,3-dihydroxy-2-thio(keto)yl-3-benzoxazolinyl)phosphonic acid diphenyl ester was added, followed by NMP 25.81 g. , reacted under water cooling for 4 hours. The obtained polyamidate solution was poured into 1224 g of methanol under stirring, and the deposited precipitate was collected by filtration, and then washed four times with 408 g of methanol, and dried to obtain a polyphthalate resin powder. The molecular weight of the polyglycolate was Mn=15,103 and Mw=324,83.

1.0172 g of the obtained polyphthalate resin powder was weighed and placed in a 50 ml Erlenmeyer flask, and 9.4167 g of NMP was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-13).

(Synthesis Example 25)

A 300 mL four-necked flask equipped with a stirring device was set in a nitrogen atmosphere, and 4,4'-diaminodiphenylmethane, 5.0086 g (25.26 mmol), 1,5-bis(4-aminophenoxyl) was placed. After 1.8064 g (6.31 mmol) of pentane, 272 g of NMP and 5.69 g (71.88 mmol) of pyridine as a base were added, followed by stirring to dissolve. Next, the diamine solution was stirred, and 1,3DM-CBDE-Cl 9.7356 g (29.94 mmol) was added, and the mixture was reacted under water cooling for 4 hours. The obtained solution of the polyglycolate was put into 1436 g of pure water under stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 1436 g of pure water, once with 1436 g of ethanol, and then washed with 386 g of ethanol. After 3 times, it was dried to obtain a white polyphthalate resin powder. The molecular weight of the polyphthalate was Mn = 15205 and Mw = 30,219.

11.89 g of the obtained polyphthalate resin powder was placed in a 50 ml Erlenmeyer flask, and 107.01 g of NMP was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-14).

(Synthesis Example 26)

After 3.7141 g (13.16 mmol) of 2,5-bis(methoxycarbonyl)terephthalic acid was weighed in a 200 mL four-necked flask equipped with a stirring device, 72.31 g of NMP was added, and the mixture was stirred and dissolved. Subsequently, 0.71 g (7.01 mmol) of triethylamine and 1.7112 g (14.01 mmol) of 3-aminobenzylamine were added, followed by stirring to dissolve. This solution was stirred with the addition of 4-(4,6-dimethoxy-1,3,5-triazabenzene-2-yl)-4-methylmorpholinium chloride (15 ± 2 weight) 11.26258 g of % water and water, and 12.91 g of NMP were further added, and the reaction was carried out for 4 hours under water cooling. The obtained polyamidate solution was poured into 616 g of methanol under stirring, and the deposited precipitate was collected by filtration, and then washed four times with 616 g of methanol, and dried to obtain a polyphthalate resin powder. The molecular weight of the polyphthalate was Mn = 7234 and Mw = 15577.

1.1325 g of the obtained polyphthalate resin powder was weighed and placed in a 50 ml Erlenmeyer flask, and 10.1925 g of NMP was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-15).

(Synthesis Example 27)

A 300 mL four-necked flask equipped with a stirring device was set in a nitrogen atmosphere, and after placing 7.01 g (64.82 mmol) of p-phenylenediamine, 108 g of NMP, 324 g of γ-BL, and 11.55 g of pyridine as base were added (146 mmol). After that, it is stirred to dissolve. Next, the diamine solution was stirred, and 1,3DM-CBDE-Cl 19.7838 g (60.85 mmol) was added, and the mixture was reacted under water cooling for 4 hours. The obtained polyphthalate solution was poured into 1881 g of 2-propanol under stirring, and the precipitated white precipitate was collected by filtration, followed by washing with 940 g of 2-propanol for 5 times, and dried to obtain a white polyamine. Resin powder. The molecular weight of the polyglycolate was Mn = 11325 and Mw = 24,387.

1.2019 g of the obtained polyphthalate resin powder was placed in a 50 ml Erlenmeyer flask, and 10.81171 g of N,N-diethylformamide was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamine. Acid solution (PAE-16).

(Synthesis Example 28)

A 300 mL four-necked flask equipped with a stirring device was set in a nitrogen atmosphere, and 3.0144 g (20.07 mmol) of 4-amino-N-methylphenethylamine was placed, and 148.88 g of NMP was added, and 4.65 g of pyridine as a base was added. (46.01 mmol), stir and dissolve. Next, this diamine solution was stirred, and 6.2390 g (19.19 mmol) of 1,3DM-CBDE-Cl was added, and the reaction was carried out for 4 hours under water cooling. The obtained solution of the polyglycolate was poured into 784 g of water with stirring, and the precipitated white precipitate was collected by filtration, and then washed with 784 g of water and 196 g of 2-propanol for 3 times, and dried to obtain a white pigment. Amine resin powder. The molecular weight of the polyglycolate was Mn=8691 and Mw=20311.

1.9144 g of the obtained polyacetate resin powder was placed in a 50 ml Erlenmeyer flask, and NMP 17.2026 g was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-17).

(Synthesis Example 29)

In a 100 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube, 20.0838 g (132.0 mmol) of 3,5-diaminobenzoic acid and 21.3254 g (88.0 mmol) of DA-7 were weighed and added to NMP 268.48 g. The mixture was continuously stirred and supplied with nitrogen to dissolve. The diamine solution was stirred, and 4,24,946 g (216.7 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was added, and NMP was added thereto to have a solid concentration of 20% by mass, and stirred at room temperature. In hours, a solution of polyamine acid (PAA-5) was obtained. The polyamic acid solution has a viscosity of 2156 mPa ‧ at a temperature of 25 ° C. Further, the molecular weight of the polyamic acid was Mn = 18,794 and Mw = 63,387.

(Synthesis Example 30)

4,4'-diaminodiphenylamine 3.5843g (17.99 mmol), DA-72.9064g (12.0 mmol), and NMP 55.58 were added to a 100 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube. g, stirring and allowing to dissolve by continuously feeding nitrogen gas. The diamine solution was stirred, and 5.7653 g (29.40 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was added, and NMP was added to make the solid content concentration 15% by mass at room temperature. Stir for 24 hours. The resulting polyamic acid solution had a viscosity of 1269 mPa ‧ at a temperature of 25 ° C. Further, the molecular weight of the polyamic acid was Mn = 15559 and Mw = 43390.

Further, 0.0368 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyamic acid solution (PAA-6).

(Synthesis Example 31)

3.13 g (7.97 mmol) of 3,5-diaminobenzoic acid and 4,4'-diaminodiphenyl-N-A were weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube. 6.8216 g (31.98 mmol) of the base-amine was added to 44.03 g of NMP, and it was stirred and continuously dissolved in nitrogen gas to dissolve. This diamine solution was stirred, and BDA 7.1310 g (36.0 mmol) was added, and the mixture was stirred at room temperature for 2 hours. Next, 14.62 g of NMP and 0.8713 g (3.99 mmol) of pyromellitic dianhydride were added. Further, NMP was added to have a solid content concentration of 18% by mass, and the mixture was stirred at room temperature for 24 hours. The resulting polyamic acid solution had a viscosity of 577 mPa ‧ at a temperature of 25 ° C. Further, the molecular weight of the polyamic acid was Mn = 12,656 and Mw = 28,487.

Further, 0.0480 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyamidonic acid solution (PAA-7).

(Synthesis Example 32)

3. 356541 g (24.02 mmol) of 3,5-diaminobenzoic acid and 1,4-bis(4-aminophenyl)peridine were weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube. 4.2931 g (16.00 mmol), 36.48 g of NMP was added, and it was stirred and continuously dissolved in nitrogen gas to dissolve. This diamine solution was stirred, and BDA 4.7522 g (23.99 mmol) was added, and the mixture was stirred at room temperature for 2 hours. Next, 36.50 g of NMP and 3.4084 g (15.63 mmol) of pyromellitic dianhydride were added. Further, NMP was added to have a solid content concentration of 15% by mass, and the mixture was stirred at room temperature for 24 hours. The resulting polyamic acid solution had a viscosity of 1166 mPa ‧ at a temperature of 25 ° C. Further, the molecular weight of the polyamic acid was Mn = 19,307 and Mw = 42,980.

Further, 0.0483 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyamidonic acid solution (PAA-8).

(Synthesis Example 33)

3. 356536 g (24.01 mmol) of 3,5-diaminobenzoic acid, 3.8715 g (15.98 mmol) of DA-7, and 31.75 g of NMP were added to a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube. The mixture was stirred and continuously dissolved in nitrogen. This diamine solution was stirred, and BDA 3.9621 g (20.0 mmol) was added, and the mixture was stirred at room temperature for 2 hours. Next, 452776 g (19.97 mmol) of 25.42 g of NMP and 1,2,4,5-cyclohexanetetracarboxylic dianhydride were added. Further, NMP was added to have a solid content concentration of 20% by mass, and the mixture was stirred at room temperature for 24 hours. The resulting polylysine solution had a viscosity of 417 mPa ‧ at a temperature of 25 ° C. Further, the molecular weight of the polyproline was Mn = 13291 and Mw = 54029.

Further, 0.0476 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyamic acid solution (PAA-9).

(Synthesis Example 34)

3,5-diaminobenzoic acid 2.7365g (17.99 mmol), 2,2'-dimethyl-4,4'-two were weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube. 2.5471 g (12.0 mmol) of aminobiphenyl was added to 27.32 g of NMP, and it was stirred and continuously dissolved in nitrogen gas to dissolve. This diamine solution was stirred, and 2.2562 g (9.02 mmol) of bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride was added, and the mixture was stirred at 80 ° C for 3 hours. After the reaction solution was cooled to room temperature, 27.32 g of NMP and 4.5715 g (20.96 mmol) of pyromellitic dianhydride were added. Further, NMP was added to have a solid content concentration of 15% by mass, and the mixture was stirred at room temperature for 24 hours. The resulting polyamic acid solution had a viscosity of 2190 mPa ‧ at a temperature of 25 ° C. Further, the molecular weight of the polyproline was Mn = 23632 and Mw = 56881.

Further, 0.0360 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyamidonic acid solution (PAA-10).

(Synthesis Example 35)

In a 100 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube, 6.0854 g (40.0 mmol) of 3,5-diaminobenzoic acid was weighed, and 65.56 g of NMP was added thereto, and the mixture was continuously stirred and dissolved in nitrogen to dissolve. . This diamine solution was stirred, 8.5449 g (39.18 mmol) of pyromellitic dianhydride was added, and NMP was added so that the solid content concentration might be 15 mass%, and it stirred at room temperature for 24 hours. The resulting polyamic acid solution had a viscosity of 523 mPa ‧ at a temperature of 25 ° C. Further, the molecular weight of the polyamic acid was Mn = 20,565 and Mw = 47,912.

Further, 13.79 g of a 0.3 mass% 3-glycidoxypropylmethyldiethoxydecane NMP solution was added to the solution to obtain a polyamidonic acid solution (PAA-11).

(Synthesis Example 36)

4. In a 100 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube, weighed 3.2080 g (16.02 mmol) of 4,4'-diaminodiphenyl ether, DA-75.8147 (24.0 mmol), and added NMP 60.42 g. The mixture was continuously stirred and supplied with nitrogen to dissolve. The diamine solution was stirred, 7.7658 g (39.60 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was added, and NMP was added to make the solid content concentration 20% by mass, and stirred at room temperature. hour. The resulting polyamic acid solution had a viscosity of 1972 mPa‧s at a temperature of 25 °C. Further, the molecular weight of the polyamic acid was Mn = 15159 and Mw = 38,251.

Further, 0.0504 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyamic acid solution (PAA-12).

(Synthesis Example 37)

In a 100 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube, 2.4301 g (15.97 mmol) of 3,5-diaminobenzoic acid, DA-8 9.4204 g (24.0 mmol), and NMP 44.60 g were added. The mixture was stirred and continuously dissolved in nitrogen. This diamine solution was stirred, and 4.7505 g (23.98 mmol) of BDA was added, and the mixture was stirred at room temperature for 2 hours. Next, 41.59 g of NMP and 3.1054 g (15.84 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride were added. Further, NMP was added to have a solid content concentration of 15% by mass, and the mixture was stirred at room temperature for 24 hours. The resulting polyamic acid solution had a viscosity of 802 mPa at a temperature of 25 °C. s. Further, the molecular weight of the polyproline was Mn = 13261 and Mw = 32,078.

Further, 0.0590 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyamidonic acid solution (PAA-13).

(Synthesis Example 38)

3. 356504 g (23.69 mmol) of 3,5-diaminobenzoic acid, 3.8718 g (15.98 mmol) of DA-7, and 68.6 g of NMP were added to a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube. The mixture was stirred and continuously dissolved in nitrogen. This diamine solution was stirred and DAH-111.5387 g (39.21 mmol) was added. Further, NMP was added to have a solid content concentration of 20% by mass, and the mixture was stirred at room temperature for 24 hours. The resulting polyamic acid solution had a viscosity of 736 mPa ‧ at a temperature of 25 ° C. Further, the molecular weight of the polylysine was Mn=10091 and Mw=19511.

Further, 0.0572 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyamic acid solution (PAA-14).

(Synthesis Example 39)

3. 356603 g (24.06 mmol) of 3,5-diaminobenzoic acid and 1,3-bis(4-aminophenethyl)urea were weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube. 4.7740 g (16.0 mmol), 28.59 g of NMP was added, and it was stirred and continuously dissolved in nitrogen gas to dissolve. This diamine solution was stirred, and BDA 2.3782 g (12.0 mmol) was added, and the mixture was stirred at room temperature for 2 hours. Next, 38.13 g of NMP and 6.0903 g (27.92 mmol) of pyromellitic dianhydride were added. Further, NMP was added to have a solid content concentration of 15% by mass, and the mixture was stirred at room temperature for 24 hours. The resulting polyamic acid solution had a viscosity of 744 mPa ‧ at a temperature of 25 ° C. Further, the molecular weight of the polyproline was Mn = 17771 and Mw = 38,991.

Further, 0.0505 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyamic acid solution (PAA-15).

(Synthesis Example 40)

3,5-diaminobenzoic acid 0.6123 g (4.00 mmol) and 4,4-diaminodiphenylamine 3.199 g (16.06) were weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube. Mg), 19.64 g of NMP was added, and it was stirred and continuously dissolved in nitrogen gas to dissolve. This diamine solution was stirred, and BDA 3.1780 g (16.04 mmol) was added, and the mixture was stirred at room temperature for 2 hours. Next, 8.93 g of NMP and 0.8736 g (4.01 mmol) of pyromellitic dianhydride were added. Further, NMP was added to have a solid content concentration of 18% by mass, and the mixture was stirred at room temperature for 24 hours. The resulting polyamic acid solution had a viscosity of 8100 mPa ‧ at a temperature of 25 ° C. Further, the molecular weight of the polyamic acid was Mn = 22,537 and Mw = 72,601.

Further, 0.0235 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-16).

(Synthesis Example 41)

3. 356516 g (24.0 mmol) of 3,5-diaminobenzoic acid and 2.4070 g of 4-amino-N-methylphenethylamine were weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube. (16.02 mmol), NMP 66.21 g was added, and it was stirred and continuously dissolved in nitrogen gas to dissolve. This diamine solution was stirred, and 8.5972 g (39.42 mmol) of pyromellitic dianhydride was added. Further, NMP was added to have a solid content concentration of 15% by mass, and the mixture was stirred at room temperature for 24 hours. The resulting polyamic acid solution had a viscosity of 488 mPa ‧ at a temperature of 25 ° C. Further, the molecular weight of the polyamic acid was Mn = 13205 and Mw = 33511.

Further, 0.0438 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyamic acid solution (PAA-17).

(Synthesis Example 42)

3. In a 100 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube, 3.6532 g (24.01 mmol) of 3,5-diaminobenzoic acid, DA-7 3.8790 g (16.01 mmol), and NMP 70.32 g were added. The mixture was stirred and continuously dissolved in nitrogen. This diamine solution was stirred, and DAH-2 12.0709 g (39.41 mmol) was added. Further, NMP was added to have a solid content concentration of 20% by mass, and the mixture was stirred at room temperature for 24 hours. The resulting polyamic acid solution had a viscosity of 207 mPa ‧ at a temperature of 25 ° C. Further, the molecular weight of the polyamic acid was Mn = 5269 and Mw = 12,875.

Further, 0.0586 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyamidonic acid solution (PAA-18).

(Embodiment 18)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 3.6139 g of the polyamidate solution (PAE-3) obtained in Synthesis Example 14 and 2.709 g of the polyamidonic acid solution (PAA-5) obtained in Synthesis Example 29 were weighed. NMP 5.7093g, BCS 3.01g, and 0.1284 g of 4-(t-butoxycarbonylamino)pyridine (hereinafter abbreviated as Boc-AP) of a hydrazine imidization accelerator were added, and stirred for 30 minutes using a magnetic stirrer. A liquid crystal alignment agent (I-1) was obtained.

(Embodiment 19)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4040 g of the polyamidomate solution (PAE-4) obtained in Synthesis Example 15 and the polyamidonic acid solution (PAA-6) obtained in Synthesis Example 48 (2.4687 g) were weighed. NMP 3.2072g and BCS 2.0348g were added, and Boc-AP 0.0542 g of a ruthenium iodide promoter was added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (I-2).

(Embodiment 20)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4548 g of the polyamidate solution (PAE-4) obtained in Synthesis Example 15 and the polyamidic acid solution (PAA-6) obtained in Synthesis Example 31 were weighed 2.0213 g. NMP 3.6200 g, BCS 2.0116g, and Boc-AP 0.0415g of a hydrazine imidization accelerator were added, and it stirred for 30 minutes using the magnetic stirring machine, and liquid-crystal-aligning agent (I-3) was obtained.

(Example 21)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4232 g of the polyamidomate solution (PAE-5) obtained in Synthesis Example 16 and the polylysine solution (PAA-9) obtained in Synthesis Example 33 (2.4189 g) were weighed. N-3.2-(N-(9-fluorenylmethoxycarbonyl)-Nt-butoxycarbonyl-L-histidine acid (hereinafter, abbreviated as NMP) was added to NMP 3.2928g and BCS 2.0272g. Fmoc-His) 0.01416 g, which was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (I-4).

(Example 22)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4232 g of the polyamidate solution (PAE-5) obtained in Synthesis Example 16 and the polylysine solution (PAA-9) obtained in Synthesis Example 33 were weighed 1.8681 g. NMP 3.6548g and BCS 2.0158g were added, and 0.0372 g of Fmoc-His of a ruthenium iodide promoter was further added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (I-5).

(Example 23)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4356 g of the polyamidomate solution (PAE-6) obtained in Synthesis Example 17 and the polyamic acid solution (PAA-10) obtained in Synthesis Example 34 were weighed 2.5278 g. NMP 3.2644 g, BCS 2.0366g, and Fmoc-His 0.0550 g of a ruthenium iodide promoter were added, and stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (I-6).

(Example 24)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4012 g of the polyamidomate solution (PAE-7) obtained in Synthesis Example 18 and the polyamidic acid solution (PAA-11) obtained in Synthesis Example 35 (2.4115 g) were weighed. NMP 2.6514 g and BCS 2.0052g were added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (II-1).

(Embodiment 25)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4130 g of the polyamidate solution (PAE-7) obtained in Synthesis Example 18 and the polyamidic acid solution (PAA-11) obtained in Synthesis Example 35 (2.4216 g) were weighed. Adding NMP 2.6780g, BCS 2.0198g, and adding 0.3062g of a 20% by mass NMP solution of (AD-1) as a polyfunctional epoxy compound as a crosslinking agent, and stirring for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent ( II-2).

(Example 26)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4302 g of the polyamidate solution (PAE-4) obtained in Synthesis Example 15 and the polylysine solution (PAA-12) obtained in Synthesis Example 36 were weighed 1.8678 g. NMP 3.8086g and BCS 2.0060g were added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (II-3).

(Example 27)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4144 g of the polyamidate solution (PAE-4) obtained in Synthesis Example 15 and the polyamidic acid solution (PAA-12) obtained in Synthesis Example 36 were weighed. NAD 3.8184 g, BCS 2.0168 g, and 0.040 g of (AD-2) as a polyfunctional hydroxy group-containing compound as a crosslinking agent were added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (II-4).

(Embodiment 28)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4015 g of the polyamidate solution (PAE-4) obtained in Synthesis Example 15 and the polyamine acid solution (PAA-13) obtained in Synthesis Example 37 were weighed 1.8005 g. NMP 3.8063 g and BCS 2.0011g were added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (II-5).

(Example 29)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4120 g of the polyamidate solution (PAE-8) obtained in Synthesis Example 19 and the polyamine acid solution (PAA-14) obtained in Synthesis Example 38 were weighed 1.8389 g. NMP 3.8639 g and BCS 2.0181 g were added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (II-6).

(Embodiment 30)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4120 g of the polyamidate solution (PAE-8) obtained in Synthesis Example 19 and the polyamine acid solution (PAA-14) obtained in Synthesis Example 38 were weighed 1.8389 g. NPON 3.8639 g, BCS 2.0181g, and (318 g) of (AD-4) which is a polyfunctional cyclic carbonate compound as a crosslinking agent were added, and it stirred by the magnetic stirring machine for 30 minutes, and liquid-crystal-aligning agent (II-7) was obtained.

(Example 31)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 1.2268 g of the polyamidate solution (PAE-9) obtained in Synthesis Example 20 and 3.2687 g of the polyamidic acid solution (PAA-15) obtained in Synthesis Example 39 were weighed. NMP 3.6154g and BCS 2.0591g were added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (II-8).

(Example 32)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4236 g of the polyamidomate solution (PAE-10) obtained in Synthesis Example 21 and the polyamidic acid solution (PAA-16) obtained in Synthesis Example 40 were weighed 2.3539 g. NMP 0.3782 g, γ-BL 3.0639 g, and BCS 2.0178 g were added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (II-9).

(Example 33)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 4.2045 g of the polyamidate solution (PAE-5) obtained in Synthesis Example 16 and the polyamidic acid solution (PAA-17) obtained in Synthesis Example 41 were weighed to 1.2281 g. NMP 2.6041g and BCS 2.0112g were added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (II-10).

(Example 34)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4195 g of the polyamidomate solution (PAE-11) obtained in Synthesis Example 22 and the polyamidic acid solution (PAA-5) obtained in Synthesis Example 29 were weighed 1.8484 g. NMP 3.8069 g and BCS 2.0204g were added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (II-11).

(Example 35)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4176 g of the polyamidomate solution (PAE-6) obtained in Synthesis Example 17 and the polylysine solution (PAA-18) obtained in Synthesis Example 42 (2.0148 g) were weighed. NMP 3.8182 g and BCS 2.0129 g were added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (II-12).

(Example 36)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 2.3987 g of the polyamidate solution (PAE-6) obtained in Synthesis Example 17 and the polyamidic acid solution (PAA-18) obtained in Synthesis Example 42 were weighed 2.1543 g. After adding NMP 3.8130 g, BCS 2.0374 g, and (AD-3) 0.0460 g of a polyfunctional propylene oxide compound as a crosslinking agent, the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (I-13).

(Comparative Example 17)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 7.2164 g of the polyamidate solution (PAE-12) obtained in Synthesis Example 23 and 2.7470 g of the polyamidic acid solution (PAA-5) obtained in Synthesis Example 29 were weighed. NMP 2.1068 g, BCS 3.0264 g, and Boc-AP 0.1396 g of a ruthenium iodide promoter were added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (a-1).

(Comparative Example 18)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4504 g of the polyamidate solution (PAE-13) obtained in Synthesis Example 24 and the polyamidic acid solution (PAA-6) obtained in Synthesis Example 48 were weighed 2.4805 g. NMP 3.2447g and BCS 2.0226g were added, and Boc-AP 0.0547 g of a ruthenium iodide promoter was added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (a-2).

(Comparative Example 19)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4012 g of the polyamidate solution (PAE-14) obtained in Synthesis Example 25 and the polyamidic acid solution (PAA-9) obtained in Synthesis Example 33 were weighed 1.8320 g. NMP 3.8172 g and BCS 2.0195 g were added, and then FDMC-His 0.0433 g of a ruthenium iodide promoter was added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (a-5).

(Comparative Example 20)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4017 g of the polyamidate solution (PAE-15) obtained in Synthesis Example 26 and the polyamine acid solution (PAA-9) obtained in Synthesis Example 33 were weighed 2.5777 g. NMP 3.2518 g, BCS 2.000 g, and Fmoc-His 0.0550 g of a ruthenium iodide promoter were added, and stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (a-6).

(Comparative Example 21)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4335 g of the polyamidomate solution (PAE-2) obtained in Comparative Synthesis Example 1 and the polyaminic acid solution (PAA-11) 2.4013 obtained in Synthesis Example 35 were weighed. g, NMP 2.6238 g, BCS 2.0105g were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (b-1).

(Comparative Example 22)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4264 g of the polyamidate solution (PAE-13) obtained in Synthesis Example 24 and the polyamidic acid solution (PAA-12) obtained in Synthesis Example 1.8 (1.8157 g) were weighed. NMP 3.8352g and BCS 2.0448g were added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (b-3).

(Comparative Example 23)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 1.2049 g of the polyamidomate solution (PAE-17) obtained in Synthesis Example 28 and 3.298 g of the polyaminic acid solution (PAA-15) obtained in Synthesis Example 39 were weighed. NMP 3.6342 g and BCS 2.0694 g were added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (b-9).

(Comparative Example 24)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4025 g of the polyamidomate solution (PAE-16) obtained in Synthesis Example 27 and the polyamidic acid solution (PAA-16) obtained in Synthesis Example 42 were weighed 2.2514 g. NMP 0.3792 g, γ-BL 3.0007 g, and BCS 2.0015 g were added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (b-10).

(Comparative Example 25)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 4.2242 g of the polyamidate solution (PAE-14) obtained in Synthesis Example 25 and the polyamidic acid solution (PAA-17) obtained in Synthesis Example 41 were weighed 1.2473 g. NMP 2.6481 g and BCS 2.0664 g were added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (b-11).

(Comparative Example 26)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4260 g of the polyamidate solution (PAE-15) obtained in Synthesis Example 26 and the polyamic acid solution (PAA-18) obtained in Synthesis Example 42 were weighed 2.2122 g. NMP 3.8118 g and BCS 2.0585 g were added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (b-13).

(Example 37)

The liquid crystal alignment agent (I-1) obtained in Example 18 was filtered using a 1.0 μm filter, and then spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at a temperature of 80 ° C for 5 minutes. The temperature-circulating oven at a temperature of 230 ° C was baked for 20 minutes to obtain a yttrium imidized film having a thickness of 100 nm. The average thickness (Ra) of the center line of the ruthenium-imided film was measured. The measurement results are shown in Table 4 below.

(Examples 38 to 52 and Comparative Examples 27 to 35)

Each of the coating films was formed in the same manner as in Example 37 except that each of the liquid crystal alignment agents obtained in the above Examples 19, 22, 24 to 27, and 29 to 36, and Comparative Examples 17 to 19 and 21 to 26 was used. The film surface of each coating film was observed using AFM. Further, the average thickness (Ra) of the center line of each coating film was measured. The measurement results are shown in Table 4 below.

[Industrial use]

The liquid crystal alignment agent of the present invention can reduce the surface unevenness of the liquid crystal and the liquid crystal alignment film by reducing the fine unevenness on the surface of the obtained liquid crystal alignment film, thereby improving the voltage retention rate. Electrical characteristics such as ion density and residual DC voltage. As a result, it has been found that the liquid crystal alignment agent of the present invention can be widely used for TN elements, STN elements, TFT liquid crystal elements, and even vertical alignment type liquid crystal display elements.

The specification, the scope of the patent application, and the abstract of the Japanese Patent Application No. 2010-058552, filed on March 15, 2010, are hereby incorporated by reference in In the context of the invention.

Claims (13)

A liquid crystal alignment agent comprising the following components (A) and (B); and component (A) having a repeating unit represented by the following formula (1), and satisfying the following (i) to (iii) a polyglycolate of any one of the conditions, (wherein X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, R ₁ is an alkyl group having 1 to 5 carbon atoms, and A ₁ and A ₂ each independently represent a hydrogen atom, or may have a substituent The alkyl group having 1 to 20 carbon atoms, alkenyl group or alkynyl group) (i) X ₁ , Y _{1 of the} formula (1) or both of them have a group consisting of the following formulas (2) and (3) a monovalent or divalent substituent of at least one selected structure, (ii) A ₁ , A _{2 of the} formula (1) or both thereof having a group consisting of the following formulas (2) and (3) a monovalent or divalent substituent of at least one selected structure, (iii) X ₁ , Y _{1 of the} formula (1), or both thereof having the following formulas (2) and (3) a monovalent or divalent substituent of at least one structure selected from the group, and A ₁ , A ₂ or both are at least selected from the group consisting of the following formulas (2) and (3) a monovalent or divalent substituent of one type of structure; (In the formulae (2) and (3), B ₁ is a single bond or a divalent organic group, and D ₁ is at least one selected from the group consisting of a third butoxycarbonyl group and a 9-fluorenylmethoxycarbonyl group. And D ₂ is at least one selected from the group consisting of the following formulas (D2-1) to (D2-5); however, the atom bonded to the ester group in the formula (3) is carbon atom) (In the formula (D2-2), R ₁₀ is an alkyl group having 1 to 5 carbon atoms); (B) component: a polylysine having a repeating unit represented by the following formula (4), (wherein, X ₂ is a tetravalent organic group, Y ₂ is a divalent organic group, and A ₁ and A ₂ have the same definitions as in the formula (1)). For example, the liquid crystal alignment agent of claim 1 of the patent scope, wherein (A) The content of the component and the content of the component (B) are 1/9 to 9/1 by mass ratio (A/B). The liquid crystal alignment agent of the first or second aspect of the invention, wherein the total content of the component (A) and the component (B) is 1 to 10% by mass based on the organic solvent. The liquid crystal alignment agent of claim 1, wherein D ₂ is a third butyl group. The liquid crystal alignment agent of the first aspect of the invention, wherein the component (A) is a polyfluorene having a substituent represented by at least one of the groups selected by the following formulas (5) and (6) Amino acid ester, (In the formula (5), B ₂ is a single bond or a divalent organic group, and R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or an organic group having a carbon number of 1 to 20; (In the formula (6), B ₃ is a single bond or a divalent organic group; wherein the atom to which the third butoxycarbonyl group in the formula (6) is bonded is a carbon atom). The liquid crystal alignment agent of claim 5, wherein the component (A) has at least one selected from the group consisting of formulas (5) and (6) in the structure of Y ₁ of the formula (1). A polyamine phthalate of the substituents constructed. The liquid crystal alignment agent of claim 5, wherein the component (A) is that A ₁ , A _{2 of the} formula (1) or both are selected by the groups of the formulas (5) and (6). A polyglycolate of a substituent of at least one of the structures. The scope of the patent application of the liquid crystal alignment agent according to Item 1, wherein, (A) component, of formula (1) Y ₁ is a polyamide acid ester of (7) of the structure represented by the following formula, (wherein R ₅ is a single bond or a divalent organic group having 1 to 20 carbon atoms; and R _{6 is} a structure selected from at least one selected from the group consisting of formulas (5) and (6); a is 1~ 4 integer). The liquid crystal alignment agent of the first aspect of the invention, wherein the component (A) is a structure in which Y ₁ of the formula (1) is at least one selected from the group consisting of the structures represented by the following formula, The liquid crystal alignment agent of the first aspect of the invention, wherein, in the above formulas (1) and (4), X ₁ and X ₂ each independently represent at least one selected from the group consisting of the structures represented by the following formulas. , The liquid crystal alignment agent of claim 1 or 10, wherein, in the formula (4), Y ₂ is at least one selected from the group consisting of the structures represented by the following formulas, A liquid crystal alignment film obtained by coating and baking a liquid crystal alignment agent according to any one of claims 1 to 11. A liquid crystal alignment film which is obtained by coating, baking, and irradiating a liquid crystal alignment agent according to any one of claims 1 to 11 with a polarized ultraviolet light.