TW201407243A - Liquid crystal alignment agent containing polyamic acid ester, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

Provided is a liquid crystal alignment agent whereby the problems of printing properties and precipitation of contained polymers can be simultaneously overcome, and whereby a liquid crystal alignment film can be formed having minimal residual charge when a direct-current voltage is applied, rapid relaxation of residual charge, and high film permeation rate. A liquid crystal alignment agent characterized by containing an organic solvent and a polyamic acid ester having 30-100 mol% of structural units represented by formula (1) with respect to 1 mole of all structural units derived from a tetracarboxylic acid derivative, and 20-100 mol% of structural units represented by formula (2) with respect to 1 mole of all diamine-derived structural units. (In the formulae, X1 is a tetravalent aromatic organic group, R1 is an ethyl group, R2 is a hydrogen atom or a C1-C5 alkyl group, hydrogen atoms and C1-C5 alkyl groups may be mixed, and A1 and A2 are each independently a hydrogen atom or a methyl group.)

Description

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

The present invention relates to a liquid crystal alignment agent containing a polyphthalate, and a liquid crystal alignment film obtained from the liquid crystal alignment agent.

A liquid crystal display element used for a liquid crystal television, a liquid crystal display or the like is generally provided with a liquid crystal alignment film for controlling the arrangement state of the liquid crystal. The liquid crystal alignment film which has been mainly used so far is a liquid crystal alignment agent which is a solution of a polyiminoid precursor such as polyamindo acid or a solution of a soluble polyimine, and is coated on a glass substrate or the like. The obtained polyimine-based liquid crystal alignment film.

Along with the high refinement of the liquid crystal display element, it is required to suppress the contrast reduction of the liquid crystal display element and reduce the afterimage phenomenon. In addition to the excellent liquid crystal alignment and stable pretilt angle, the liquid crystal alignment film is mainly focused on The high voltage holding ratio suppresses the residual image caused by the AC drive, reduces the residual charge when the DC voltage is applied, and/or quickly relaxes the residual charge accumulated by the DC voltage.

In order to make the polyimine-based liquid crystal alignment film meet the above requirements Ask, there have been various proposals. For example, in order to shorten the erasing time of the afterimage caused by the DC voltage, the liquid crystal alignment film proposed is a polyamine containing a polyaminic acid or a ruthenium group, and a tertiary amine having a specific structure. For the liquid crystal alignment agent (for example, refer to Patent Document 1), a liquid crystal alignment agent containing a specific polyamine compound such as a pyridine skeleton and a soluble polyimine is used as a raw material (for example, refer to Patent Document 2).

Prior technical literature Patent literature

Patent Document 1: Japanese Patent Laid-Open No. Hei 9-316200

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

The liquid crystal display element having the liquid crystal alignment film obtained from the liquid crystal alignment agent of polylysine or polyimine, as described above, can quickly alleviate the residual charge accumulated by the DC voltage. However, it is known that the liquid crystal alignment film described above oxidizes nitrogen atoms in an amine group, an imine group, and a nitrogen-containing hetero ring by oxygen or the like in the air to lower the transmittance of the obtained film.

Further, the inventors of the present invention have found that the use of polyphthalamide by the polyimide precursor can quickly alleviate the residual charge accumulated by the DC voltage and increase the film transmittance.

That is, by using a liquid crystal alignment agent containing a polyamine amide having an amine group, an imine group, and a nitrogen-containing hetero ring, rapid relaxation can be caused by straight A liquid crystal alignment film in which a residual charge is accumulated by a voltage and a film transmittance is high.

However, in the liquid crystal alignment agent containing a polyamine using a 4,4'-diaminodiphenylamine or a derivative thereof and a tetracarboxylic acid derivative using an aromatic tetracarboxylic acid derivative, aromatic is used. The resulting product of the methyl ester of a tetracarboxylic acid has a problem of poor solubility of the polymer, precipitation of the polymer, and clogging of the filter.

Further, the ester of a long-chain alkyl group having 3 or more carbon atoms is used, and the printability is poor, and a uniform polyimide film cannot be obtained.

An object of the present invention is to provide a liquid crystal alignment agent which is capable of quickly alleviating a residual liquid charge which is accumulated by a DC voltage and which has a high transmittance of a liquid crystal, and which avoids the problem of precipitation of a polymer and a problem of printability.

The present inventors have found that a diamine using 4,4'-diaminodiphenylamine or a derivative thereof, and a tetracarboxylic acid derivative using a polytetradecyl ester of an aromatic tetracarboxylic acid derivative, by aroma The ester of the tetracarboxylic acid is an ethyl ester, which can quickly alleviate the residual charge accumulated due to the DC voltage, and improve the film transmittance, while avoiding the problem of polymer precipitation or filter blockage, and printability.

Therefore, the present invention is based on the above-described findings and has the following gist.

A liquid crystal alignment agent characterized by containing, under 30 to 100 mol%, relative to 1 mol of a total structural unit derived from a tetracarboxylic acid derivative The structural unit represented by the following formula (1), and having a structural unit of the following formula (2) of 20 to 100 mol% with respect to 1 mol of the total structural unit derived from diamine With organic solvents.

In the formula (1), X ¹ is a tetravalent aromatic group, and R ¹ is an ethyl group.

In the formula (2), R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, a hydrogen atom may be mixed with an alkyl group having 1 to 5 carbon atoms, and A ¹ and A ² are each independently a hydrogen atom or a methyl group.

2. The liquid crystal alignment agent according to the above 1, which further comprises a solvent having a lower surface tension than the organic solvent.

3. The liquid crystal alignment agent according to the above 1 or 2, wherein X ¹ of the formula (1) is a benzene ring.

4. The liquid crystal alignment agent according to any one of the above 1 to 3, wherein R ² of the formula (2) is a hydrogen atom or a methyl group.

5. The liquid crystal alignment agent according to any one of the above 1 to 4, wherein A ¹ and A ² of the formula (2) are a hydrogen atom.

The liquid crystal alignment agent according to any one of the above 1 to 5, wherein the polyglycolate has a weight average molecular weight of 5,000 to 300,000 and a number average molecular weight of 2,500 to 150,000.

The liquid crystal alignment agent according to any one of the above 1 to 6, wherein the concentration of the polyphthalate in the liquid crystal alignment agent is from 0.5 to 15% by mass.

A liquid crystal alignment film which is obtained by coating the liquid crystal alignment agent according to any one of the above 1 to 7 and calcining it.

9. The liquid crystal alignment film according to the above 8, wherein the film thickness after firing is 5 to 300 nm.

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

The liquid crystal alignment film obtained by the liquid crystal alignment agent of the present invention has 4,4'-diaminodiphenylamine or a derivative thereof as a diamine, and a polyfluorene of an aromatic tetracarboxylic acid derivative as a tetracarboxylic acid derivative. Since the amine ester structure is used, the transmittance can be improved, and the liquid crystal display element including the liquid crystal alignment film can quickly alleviate the residual charge accumulated by the DC voltage.

Further, since the liquid crystal alignment agent of the present invention is an ethyl ester, the polymer has good solubility, has no problem of precipitation or clogging of the filter, and has good printability with respect to the substrate. It is presumed that the cause is as follows, the alkyl ester moiety of the aromatic tetracarboxylic acid derivative is an ethyl group.

It is generally known that the more the alkyl carbon number of the alkyl ester, the higher the solubility with respect to the solvent. Further, when the polymer solution is applied to the substrate, when the drainage property of the polymer is too high, the substrate is bounced off and the coating cannot be uniformly applied. That is, the methyl ester has good printability with respect to the substrate, but the solubility is insufficient, and the long-chain alkyl ester having 3 or more carbon atoms has good solubility, but the printability with respect to the substrate is insufficient. Therefore, it is inferred that only ethyl ester can make solubility and printability stand.

Therefore, the liquid crystal alignment film obtained by the liquid crystal alignment agent of the present invention can improve the transmittance, and the liquid crystal display element including the liquid crystal alignment film can quickly alleviate the residual electric charge accumulated by the DC voltage. Further, the liquid crystal alignment agent of the present invention can simultaneously solve the problem of the precipitation of the polymer contained and the blockage of the filter, and the problem of printability.

Form of implementing the invention <Polyurethane>

The polyphthalate used in the liquid crystal alignment agent of the present invention is a polyimine precursor for producing a polyimide, and has a polymer which can be subjected to the following oxime imidization reaction by heating.

The polyglycolate has a structural unit derived from a tetracarboxylic acid derivative and a structural unit derived from a diamine, but the polyphthalate contained in the liquid crystal alignment agent of the present invention is relative to a derivative derived from a tetracarboxylic acid. The total structural unit 1 mol has a structural unit represented by the following formula (1) of 30 to 100 mol%, and has 20 to 100 mol% with respect to 1 mol of the total structural unit derived from diamine. A polyamine phthalate of the structural unit represented by the formula (2).

In the formula (1), X ¹ is a tetravalent aromatic group, and R ¹ is an ethyl group.

In the formula (2), R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, a hydrogen atom may be mixed with an alkyl group having 1 to 5 carbon atoms, and A ¹ and A ² are each independently a hydrogen atom or a methyl group.

In the formula (1), X ¹ is a tetravalent aromatic group. The tetravalent aromatic group is a tetravalent aromatic group selected from a benzene ring and a naphthalene ring, but preferably has a single bond, an oxygen atom, a sulfur atom, a nitrogen atom, a carbonium, a sulfonium group. Further, a tetravalent aromatic group having a structure obtained by bonding two benzene rings to an alkyl group is specifically exemplified below.

Among them, X ^{1 is} preferably X-1 from the viewpoint of availability and the like.

In the polyphthalate of the present invention, the structural unit of the formula (1) is preferably 30 to 100 mol% and 40 to 100 mol with respect to the total structural unit derived from the tetracarboxylic acid derivative. The ear % is preferably more preferably 50 to 100 mole %.

In the formula (2), A ¹ and A ² are each independently a hydrogen atom or a methyl group. Among them, a hydrogen atom is preferred.

In the formula (2), specific examples of the above alkyl group of R ² include, for example, methyl, ethyl, propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, N-hexyl and the like.

R ^{2 is} preferably a hydrogen atom, an ethyl group or a methyl group, more preferably a hydrogen atom, or a methyl group.

In the polyphthalate of the present invention, the structural unit of the formula (2) is preferably from 20 to 100 mol%, and from 40 to 100 mol%, based on 1 mol of the total structural unit derived from the diamine. Better, better 60% to 100%.

The polyphthalate used in the present invention may be such that the structural unit derived from the tetracarboxylic acid derivative contains a structural unit represented by the following formula (3).

In the formula (3), R ³ is an alkyl group having 1 to 5 carbon atoms, and X is a tetravalent organic group.

Specific examples of X may be X-101 to X-133 as listed below. Among them, in terms of monomer availability, X is preferably X-101, X-102, X-103, X-104, X-105, X-106, X-108, X-116, X-119, X- 121 or X-125.

In the formula (3), specific examples of the alkyl group of R ³ are, for example, methyl, ethyl, propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n. - amyl and the like.

When the ratio of the structural unit represented by the formula (3) in the polyglycolate used in the present invention is high, the effect of the present invention may be impaired, which is not preferable. Therefore, the ratio of the structural unit represented by the formula (3) is preferably 0 to 70 mol% with respect to the structural unit of the polyphthalate, and preferably 0 to 60 mol%, more preferably It is 0~50% by mole.

Further, the polyphthalate used in the present invention may be such that the structural unit derived from the diamine contains a structural unit represented by the following formula (4).

In the formula (4), A ³ and A ⁴ are each independently a hydrogen atom, a C 1-10 alkyl group which may have a substituent, a C 1-10 alkene group which may have a substituent, or may have The alkynyl group having 1 to 10 carbon atoms of the 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, one or more CH ₂ -CH ₂ structures present in the above alkyl group, and substituted by a CH=CH structure, more specifically, for example, a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group. , 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-hexenyl, cyclopropenyl, cyclopentenyl, cyclohexenyl, and the like.

The alkynyl group is a compound in which one or more CH ₂ -CH ₂ structures present in the alkyl group are substituted by a C≡CH structure, and more specifically, an ethynyl group, a 1-propynyl group, a 2-propynyl group or the like.

The above alkyl group, alkenyl group, and alkynyl group may have a substituent, and a substituent may form a ring structure. Further, the formation of a ring structure by a substituent means that a ring structure is formed by bonding a substituent phase or a substituent to a part of a parent skeleton.

Such substituents are, for example, halo, hydroxy, thiol, nitro, aryl, organooxy, organothio, organodecyl, decyl, ester, thioester, phosphate, guanamine, Alkyl, alkenyl, alkynyl and the like.

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

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

The organooxy group of the substituent may be represented by a 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 additionally 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 pentyloxy group, an octyloxy group and the like.

The organothio group of the substituent may be represented by the structure represented by -S-R. The R is as defined above for an alkyl group, an alkenyl group, an alkynyl group, an aryl group or the like. These R may be additionally 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 pentylthio group, an octylthio group and the like.

The organic decyl group of the substituent may be represented by a 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 additionally 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 of the substituent may be represented by a structure represented by -C(O)-R. The R is as defined above for an alkyl group, an alkenyl group, an aryl group or the like. These R may be additionally 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 benzoinyl group and the like.

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

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

The phosphate group of the substituent may be represented by a 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 additionally substituted by the aforementioned substituents.

The substituent amide group may be represented by -C(O)NH ₂ , -C(O)NHR, -NHC(O)R, -C(O)N(R) ₂ , or -NRC(O)R. Construct representation. When R is a nitrogen atom, R may be the same or different, and R is as defined above for an alkyl group, an alkenyl group, an alkynyl group, an aryl group or the like. These R may be additionally substituted by the aforementioned substituents.

The aryl group of the substituent may be the same as the aforementioned aryl group. The aryl group may be additionally substituted with other substituents as described above.

The alkyl group of the substituent may be the same as the aforementioned alkyl group. The alkyl group may be additionally substituted with other substituents as described above.

The alkenyl group of the substituent may be the same as the aforementioned alkenyl group. The alkenyl group may be additionally substituted with other substituents as described above.

The alkynyl group of the substituent may be the same as the aforementioned alkenyl group. The alkynyl group may be additionally substituted with other substituents as described above.

When a high-volume structure is introduced, the reactivity of the amine group and the liquid crystal alignment property may be lowered. Therefore, A ³ and A ^{4 are more} preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent, particularly preferably A hydrogen atom, a methyl group, or an ethyl group.

Y is a divalent organic group, and the structure is not particularly limited, and may be 2 Kind of above mixed. Specific examples thereof may be the following Y-1 to Y-118.

In order to obtain good liquid crystal alignment, it is preferred to introduce a diamine having a higher linearity into the polyphthalate, and Y is preferably Y-7, Y-21, Y-22, Y-23, Y-25. , Y-26, Y-27, Y-43, Y-44, Y-45, Y-46, Y-48, Y-63, Y-71, Y-73, Y-74, Y-75, Y -98, Y-99, Y-100. 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 nest skeleton, or a combination thereof in a branched chain, and Y is further Jia 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, Y-97.

Any pretilt angle can be found by adding 1 to 50 mol%, preferably 5 to 40 mol% of the diamine to the entire diamine.

Further, when it is desired to improve the rubbing resistance, Y is preferably a diamine having Y-118.

In the formula (Y-109), m and n are integers of 1 to 11 each independently, and m+n is an integer of 2 to 12. In the formula (Y-114), h is an integer of 1 to 3, and the formula (Y) In -111) and (Y-117), j is an integer from 0 to 3.

When the ratio of the structural unit represented by the formula (4) in the polyglycolate used in the present invention is high, the effect of the present invention may be impaired, which is not preferable. Therefore, the ratio of the structural unit represented by the formula (4) is preferably 0 to 80 mol% with respect to the structural unit of the polyphthalate, and preferably 0 to 60 mol%, more preferably It is 0~40% by mole.

<Method for producing polyamidomate>

The polyperurethane can be synthesized by the following methods (1) to (3) using a tetracarboxylic acid derivative and a diamine compound.

(1) When synthesized from polyaminic acid

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

Specifically, it can be -20 to 150 ° C in the presence of a solvent, preferably The polylysine is reacted with the esterifying agent at 0 to 50 ° C for 30 minutes to 24 hours, preferably 1 to 4 hours.

Preferably, the esterifying agent is purified 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-triazin-2-yl)-4-methylmorpholinium chloride or the like. The amount of the esterifying agent added is 1 mol, more preferably 2 to 6 mol parts, and more preferably 2.1 to 3 mol parts, relative to the repeating unit of polyamic acid.

The solvent used in the above reaction is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone or r-butyrolactone in terms of solubility of the polymer, and the like may be one or two. More than one kind of mixture is used.

The concentration at the time of synthesis is less likely to precipitate a polymer, and the viewpoint of easily obtaining a high molecular weight substance is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass.

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

The polyglycolate can be synthesized from a tetracarboxylic acid diester dichloride and a diamine.

Specifically, it can be synthesized by reacting a base with a solvent at -20 to 150 ° C, preferably at 0 to 50 ° C for 30 minutes to 24 hours, preferably 1 to 4 hours.

As the base, pyridine, triethylamine, 4-dimethylaminopyridine or the like can be used, but in order to carry out the reaction, pyridine is preferred. Amount of alkali added The amount which can be easily removed and which is easy to obtain a high molecular weight substance is preferably 2 to 4 times moles, more preferably 2.1 to 3 times moles, relative to the tetracarboxylic acid diester dichloride.

The solvent to be used for the above-mentioned reaction is preferably a mixture of a monomer and a polymer, and is preferably used in the form of N-methyl-2-pyrrolidone or r-butyrolactone.

The polymer concentration at the time of synthesis is less likely to precipitate a polymer, and the viewpoint of easily obtaining a high molecular weight substance 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, it is preferred to dehydrate the solvent used for the synthesis of the polyphthalate as much as possible, and it is preferred to prevent the external gas from being mixed in the nitrogen atmosphere.

(3) When synthesizing polyphthalate from tetracarboxylic acid diester and diamine

Polyammonium esters can be synthesized by polycondensation of a tetracarboxylic acid diester with a diamine.

Specifically, it can be synthesized by reacting in the presence of a condensing agent, a base, a solvent or the like at 0 to 150 ° C, preferably at 0 to 100 ° C for 30 minutes to 24 hours, preferably 3 to 15 hours.

As the condensing agent, triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, N, N' can be used. -Carbonium diimidazole, dimethoxy-1,3,5-triazinylmethylmorpholinium, O-(benzotriazol-1-yl)-N,N,N',N'-four Methylurea quinone tetrafluoroborate, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphorus An acid salt, diphenyl (2,3-dihydro-2-thio-3-benzoxazolyl)phosphonate or the like. The amount of the condensing agent added is preferably 2 to 3 moles, more preferably 2.1 to 2.5 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 added can be easily removed, and the viewpoint of easily obtaining a high molecular weight substance is preferably 0.1 to 4 times moles, more preferably 0.5 to 3 times moles, relative to the diamine component.

The solvent to be used for the above-mentioned reaction is preferably a mixture of a monomer and a polymer, and is preferably used in the form of N-methyl-2-pyrrolidone or r-butyrolactone.

The polymer concentration at the time of synthesis is not easily precipitated as a polymer, and is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass, from the viewpoint of easily obtaining a high molecular weight substance.

Further, in order to prevent hydrolysis of the condensing agent, it is preferred to dehydrate the solvent used in the synthesis of the polyglycolate as much as possible, and it is preferred to prevent the external gas from being mixed in the nitrogen atmosphere.

Further, in the above reactions (1) to (3), the Lewis acid to which the additive is added can be efficiently reacted. The Lewis acid is preferably a lithium halide such as lithium chloride or lithium bromide. The amount of Lewis acid added is preferably from 0 to 1.0 moles per mole of the diamine component.

In the method for synthesizing the above three polyglycolates, in order to obtain a high molecular weight polyphthalate, the synthesis method of the above (1) or (2) is particularly preferred.

Stir the same with the polyphthalate solution obtained above When injected into a weak solvent, the polymer can be precipitated. After several precipitations, it is washed with a weak solvent, and dried at room temperature or under heating to obtain a purified polyphthalate powder.

The weak solvent is not particularly limited, and examples thereof include water, methanol, ethanol, 2-propanol, hexane, butylcellulose, acetone, toluene, and the like. Among them, water, methanol, ethanol or 2-propanol is preferred.

<Liquid alignment agent>

The liquid crystal alignment agent of the present invention contains a polyperurethane having a structural unit represented by the above formula (1) and a structural unit represented by the formula (2), and an organic solvent.

The weight average molecular weight of the polyphthalate having the structural unit represented by the formula (1) and the structural unit represented by the formula (2) is preferably 5,000 to 300,000, more preferably 10,000 to 200,000. Further, the number average molecular weight is preferably from 2,500 to 150,000, more preferably from 5,000 to 10,000.

The liquid crystal alignment agent of the present invention is in the form of a solution in which the above polyglycolate is dissolved in an organic solvent. In this form, for example, when a polyphthalate is synthesized in an organic solvent, it may be the obtained reaction solution or the solution obtained by diluting the reaction solution with another solvent. Further, when the obtained polyphthalate is a powder, it may be a solution obtained by dissolving it in an organic solvent.

The content (concentration) of the polyglycolate (hereinafter also referred to as a polymer) in the liquid crystal alignment agent of the present invention can be appropriately changed by the thickness of the polyimide film to be formed, but uniform The viewpoint of the defect-free coating film is preferably 0.5 mass based on the content of the polymer component of the organic solvent. The viewpoint of the storage stability of the solution is preferably 15% by mass or less, and more preferably 1 to 10% by mass. Further, at this time, a concentrated solution of the polymer can be prepared in advance, and the thick solution is diluted into a liquid crystal alignment agent. The concentration of the concentrated solution of the polymer component is preferably from 10 to 30% by mass, more preferably from 10 to 15% by mass.

Further, when the powder of the polymer component is dissolved in the organic solvent preparation liquid, it can be heated. The heating temperature is preferably from 20 to 150 ° C, particularly preferably from 20 to 80 ° C.

The above organic solvent contained in the liquid crystal alignment agent of the present invention may be one which can uniformly dissolve the polymer component, and is not particularly limited. Specific examples thereof may be N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-B. Base-2-pyrrolidone, N-methyl caprolactam, 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyl hydrazine, dimethyl hydrazine, r-butyrolactone, 1,3-two Methyl-imidazolidinone, 3-methoxy-N,N-dimethylpropane decylamine, and the like. These may be used alone or in combination of two or more. Further, the solvent of the polymer component cannot be uniformly dissolved alone, and the organic solvent can be mixed in the range in which the polymer is not precipitated.

The liquid crystal alignment agent of the present invention may contain a solvent for improving the uniformity of the coating film when the liquid crystal alignment agent is applied to the substrate, in addition to the organic solvent for dissolving the polymer component. The solvent is generally a solvent having a lower surface tension than the above organic solvent. Specific examples thereof may be ethyl cellosolve, butyl cellosolve, butyl cellosolve acetate, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methyl Oxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diethyl Acid ester, propylene glycol-1-monomethyl ether-2-acetate, Propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, n-propyl lactate, N-butyl lactate, isoamyl lactate, and the like. Two or more solvents may be used in combination.

The amount of the solvent having a low surface tension is preferably from 1 to 50% by mass, more preferably from 10 to 30% by mass, based on the total solvent (100% by mass) contained in the liquid crystal alignment agent. From the viewpoint of the uniformity of the coating film of the liquid crystal alignment agent with respect to the substrate, 10% by mass or more is preferable, and from the viewpoint of solubility of the polymer component, 30% by mass or less is preferable.

In addition to the above, the liquid crystal alignment agent of the present invention can be added to a polymer other than the polyphthalate, and the purpose is to change the electrical properties such as the permittivity or conductivity of the liquid crystal alignment film. An electric or conductive material, a decane coupling agent for improving the adhesion between a liquid crystal alignment film and a substrate, and a crosslinkable compound for improving the hardness and fineness of a film when a liquid crystal alignment film is formed, and for the purpose of baking When the film is coated, it is effective to carry out a ruthenium imidization accelerator for the imidization of polyamine.

<Liquid alignment film>

The liquid crystal alignment film of the present invention is a film obtained by applying the liquid crystal alignment agent to a substrate, followed by drying and baking. The substrate to which the liquid crystal alignment agent of the present invention is applied is not particularly limited, and a glass substrate, a tantalum nitride substrate, an acrylic substrate, a plastic substrate such as a polycarbonate substrate, or the like can be used, but the steps are simplified. In view of the above, it is preferable to use a substrate on which an ITO electrode for liquid crystal driving or the like is formed. Further, in the reflective liquid crystal display element, even if only one side of the substrate is used, an opaque object such as a ruthenium sheet is used. As the electrode, a material that reflects light such as aluminum can also be used.

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

The method for the alignment treatment of the obtained liquid crystal alignment film is, for example, a rubbing method, a photoalignment treatment method, or the like.

Specifically, for example, a method in which radiation in a certain direction is irradiated onto the surface of the coating film and then heat-treated at a temperature of 150 to 250 ° C to impart a liquid crystal alignment energy.

Radiation can be used with ultraviolet light having a wavelength of 100 to 800 nm and visible light. Among them, ultraviolet rays having a wavelength of from 100 to 400 nm are preferable, and those having a wavelength of from 200 to 400 nm are particularly preferable. Further, in order to improve the liquid crystal alignment property, the coated substrate can be heated at 50 to 250 ° C while irradiating the radiation.

The irradiation amount of the radiation is preferably from 1 to 10,000 mJ/cm ² , particularly preferably from 100 to 5,000 mJ/cm ² .

In the liquid crystal alignment film produced as described above, the liquid crystal molecules can be stably aligned in a certain direction.

[Liquid Crystal Display Element]

In the liquid crystal display device of the present invention, the substrate of the liquid crystal alignment film is obtained by the liquid crystal alignment agent of the present invention, and then subjected to an alignment treatment, and a liquid crystal cell is produced by a known method as a liquid crystal display element.

The method for producing the liquid crystal cell is not particularly limited. For example, generally, one pair of substrates forming a liquid crystal alignment film is provided with the liquid crystal alignment film facing inner side, and preferably has a pitch of 1 to 30 μm, more preferably 2 to 10 μm. After the conditions of the device are set, the method of fixing the liquid around with the sealant and injecting the liquid crystal and sealing is performed. The method of injecting the liquid crystal is not particularly limited, and for example, a vacuum method in which the inside of the produced liquid crystal cell is decompressed and then injected into a liquid crystal, a dropping method in which liquid crystal is dropped, and sealing is performed.

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

The code numbers of the compounds used in the examples and comparative examples, and the methods for measuring the respective characteristics are as follows.

DBOP: diphenyl (2,3-dihydro-2-thio-3-benzoxazolyl)phosphonate

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellosolve

[viscosity]

The viscosity of the polyaminic acid solution or the polyamidomate solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) with a sample volume of 1.1 mL and a cone. The rotor TE-1 (1°34', R24) was measured and the temperature was measured at 25 °C.

[molecular weight]

The molecular weight of the polyglycolate is measured by a GPC (Cry Tone Gel Permeation Chromatograph) apparatus, and the number average molecular weight (hereinafter also referred to as Mn) and the weight average molecular weight of the polyethanol or polyethylene oxide equivalent value are calculated. It is also referred to below as Mw).

GPC device: manufactured by Shodex (GPC-101)

Column: Shodex company (inline KD803 and KD805)

Column temperature: 50 ° C

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

Flow rate: 1.0ml/min

Standard sample for the production of calibration lines: TSK standard polyethylene oxide (weight average molecular weight (Mw) of about 900,000, 150,000, 10,000 and 30,000) made by Dongsuo Co., Ltd., and polyethylene glycol (Ph. The top molecular weight (Mp) is about 12,000, 4,000 and 1,000).

In order to avoid peak overlap in the measurement, two samples of samples obtained by mixing 900,000, 100,000, 12,000, and 1,000 kinds of samples, and 150,000, 30,000, and 4,000 kinds of samples were separately measured.

[Measurement of solid content concentration]

The solid content concentration of the polyamine ester solution was calculated in the following manner.

Approximately 1.1 g of the polyglycolate solution was weighed in an aluminum cup No. 2 (manufactured by Yasushi Co., Ltd.), and then heated at 200 ° C for 2 hours using an oven DNF400 (manufactured by Yamato Co., Ltd.) and left at room temperature. For the next 5 minutes, the weight of the solid component remaining in the aluminum cup was measured. The solid component concentration was calculated from the weight of the solid component and the weight of the original solution.

(Synthesis Example 1)

After extracting 3.06 g (11.8 mmol) of DE-1 and 3.88 g (12.5 mmol) of DE-3 using a 200 mL four-necked flask to which a stir bar was added, 125 g of NMP was added and stirred to dissolve. Next, 5.32 g (52.5 mmol) of triethylamine, 1.99 g (10.0 mmol) of DA-1, 2.87 g (10.0 mmol) of DA-3, and 1.49 g (5.00 mmol) of DA-5 were added and dissolved by stirring. While stirring the solution, 20.1 g (52.5 mmol) of DBOP was added, and 17.7 g of NMP was added thereto, and the mixture was stirred under water cooling for 13 hours to obtain a solution of polyglycolate. The viscosity of the polyglycolate solution at a temperature of 25 ° C is 87.0 mPa. s.

The obtained polyphthalate solution was added while stirring 1089 g of methanol, and the precipitate formed was collected by filtration. The precipitate was washed three times with methanol, and then dried under reduced pressure at a temperature of 100 ° C to obtain a poly phthalate powder. The molecular weight of the polyphthalate was Mn = 24,700 and Mw = 54,500.

3.31 g of the obtained polyphthalate powder was weighed in a 100 mL Erlenmeyer flask placed in a stir bar, and then 24.3 g of NMP was added, and the mixture was stirred at room temperature for 20 hours to be dissolved. The solid concentration of the polyamine solution was 10.9% by mass. Next, 2.89 g of a 1.0 mass% NMP solution of 3-glycidoxypropylmethyldiethoxydecane was added, and the mixture was stirred at a temperature of 50 ° C for 20 hours. Time. Further, 27.9 g of NMP and 24.5 g of BCS were added, and the mixture was stirred at room temperature for 6 hours to obtain a polyamine solution having a solid concentration of 3.5% by mass.

(Synthesis Example 2)

After extracting 3.06 g (11.8 mmol) of DE-1 and 3.88 g (12.5 mmol) of DE-3 in a 200 mL four-necked flask placed in a stir bar, 123 g of NMP was added and stirred to dissolve. Next, 5.31 g (52.5 mmol) of triethylamine, 1.99 g (10.0 mmol) of DA-1, 2.58 g (10.0 mmol) of DA-4, and 1.50 g (5.00 mmol) of DA-5 were added and dissolved by stirring. While stirring the solution, 20.1 g (52.5 mmol) of DBOP was added, and 17.1 g of NMP was added thereto, and the mixture was stirred under water cooling for 13 hours to obtain a solution of polyglycolate. The viscosity of the polyglycolate solution at a temperature of 25 ° C is 75.0 mPa. s.

The obtained polyphthalate solution was added while stirring 1068 g of methanol, and the precipitate formed was collected by filtration. The precipitate was washed three times with methanol, and then dried under reduced pressure at a temperature of 100 ° C to obtain a poly phthalate powder. The molecular weight of the polyglycolate was Mn = 24,100 and Mw = 52,200.

3.24 g of the obtained polyphthalate powder was weighed in a 100 mL Erlenmeyer flask placed in a stir bar, and then 23.6 g of NMP was added, and the mixture was stirred at room temperature for 20 hours to be dissolved. The solid concentration of the polyamine solution was 10.9% by mass. Next, 2.79 g of a 1.0 mass% NMP solution of 3-glycidoxypropylmethyldiethoxydecane was added, and the mixture was stirred at a temperature of 50 ° C for 20 hours. Further, 27.0 g of NMP and 23.8 g of BCS were added, and the mixture was stirred at room temperature for 6 hours to obtain a polyamine solution having a solid concentration of 3.5% by mass.

(Synthesis Example 3)

3.06 g (11.8 mmol) of DE-1 and 3.88 g (12.5 mmol) of DE-3 were weighed in a 200 mL four-necked flask placed in a stir bar, and then 120 g of NMP was added and stirred to dissolve. Next, 5.33 g (52.5 mmol) of triethylamine, 2.99 g (15.0 mmol) of DA-1, 1.30 g (5.00 mmol) of DA-4, and 1.49 g (5.00 mmol) of DA-5 were added and dissolved by stirring. While stirring the solution, 20.1 g (52.5 mmol) of DBOP was added, and 16.8 g of NMP was added thereto, and the mixture was stirred under water cooling for 13 hours to obtain a solution of polyglycolate. The viscosity of the polyphthalate solution at a temperature of 25 ° C is 85.4 mPa. s.

The obtained polyphthalate solution was added while stirring 1045 g of methanol, and the precipitate formed was collected by filtration. The precipitate was washed three times with methanol, and then dried under reduced pressure at a temperature of 100 ° C to obtain a poly phthalate powder. The molecular weight of the polyphthalate was Mn = 23,300 and Mw = 47,500.

After 3.24 g of the obtained polyphthalate powder was weighed in a 100 mL Erlenmeyer flask placed in a stir bar, 23.8 g of NMP was added, and the mixture was stirred at room temperature for 20 hours to be dissolved. The solid concentration of the polyamine solution was 11.1% by mass. Next, 2.88 g of a 1.0 mass% NMP solution of 3-glycidoxypropylmethyldiethoxydecane was added, and the mixture was stirred at a temperature of 50 ° C for 20 hours. Further, 28.1 g of NMP and 24.4 g of BCS were added, and the mixture was stirred at room temperature for 6 hours to obtain a polyamine solution having a solid concentration of 3.5% by mass.

(Synthesis Example 4)

1. Take 1.57 g (6.00 mmol) of DE-1 and 5.43 g (17.5 mmol) of DE-3 in a 200 mL four-necked flask placed in a stir bar, and then add 120 g of NMP was stirred and dissolved. Next, 5.32 g (52.5 mmol) of triethylamine, 0.99 g (5.00 mmol) of DA-1, 3.23 g (12.5 mmol) of DA-4, and 1.49 g (7.50 mmol) of DA-6 were added and dissolved by stirring. While stirring the solution, 20.1 g (52.5 mmol) of DBOP was added, and 16.5 g of NMP was added thereto, and the mixture was stirred under water cooling for 16 hours to obtain a solution of a polyamine. The viscosity of the polyamine solution at 25 ° C is 26.4 mPa. s.

The obtained polyphthalate solution was added while stirring 1047 g of methanol, and the precipitate formed was collected by filtration. The precipitate was washed three times with methanol, and then dried under reduced pressure at a temperature of 100 ° C to obtain a poly phthalate powder. The molecular weight of the polyglycolate was Mn = 14,500 and Mw = 3,500.

After 4.01 g of the obtained polyphthalate powder was weighed in a 100 mL Erlenmeyer flask placed in a stir bar, 29.4 g of NMP was added, and the mixture was stirred at room temperature for 20 hours to be dissolved. The solid concentration of the polyamine solution was 10.9% by mass. Next, 3.50 g of a 1.0 mass% NMP solution of 3-glycidoxypropylmethyldiethoxydecane was added, and the mixture was stirred at a temperature of 50 ° C for 24 hours. Further, 5.20 g of NMP and 17.5 g of BCS were added, and the mixture was stirred at room temperature for 6 hours to obtain a polyamine solution having a solid concentration of 6.0% by mass.

(Synthesis Example 5)

1.56 g (6.00 mmol) of DE-1 and 5.43 g (17.5 mmol) of DE-3 were weighed in a 200 mL four-necked flask placed in a stir bar, and then 124 g of NMP was added and stirred to dissolve. Next, 5.31 g (52.5 mmol) of triethylamine, 0.99 g (5.00 mmol) of DA-1, 1.49 g (7.50 mmol) of DA-6, and 3.65 g (12.50 mmol) of DA-8 were added and stirred to dissolve. Stir the solution 20.1 g (52.5 mmol) of DBOP was added simultaneously with the solution, and 55.5 g of NMP was added thereto, and the mixture was stirred under water cooling for 18 hours to obtain a solution of polyglycolate. The viscosity of the polyglycolate solution at a temperature of 25 ° C is 8.6 mPa. s.

The obtained polyphthalate solution was added while stirring 1079 g of methanol, and the precipitated precipitate was collected by filtration. The precipitate was washed three times with methanol, and then dried under reduced pressure at a temperature of 100 ° C to obtain a poly phthalate powder. The molecular weight of the polyphthalate was Mn = 10,900 and Mw = 23,800.

After 2.19 g of the obtained polyphthalate powder was weighed in a 100 mL Erlenmeyer flask placed in a stir bar, 16.1 g of NMP was added, and the mixture was stirred at room temperature for 20 hours to be dissolved. The solid concentration of the polyamine solution was 10.3% by mass. Next, 5.30 g of NMP and 9.57 g of BCS were added, and the mixture was stirred at room temperature for 6 hours to obtain a polyamine solution having a solid concentration of 5.5% by mass.

(Synthesis Example 6)

5.86 g (22.5 mmol) of DE-1 and 7.75 g (25.0 mmol) of DE-3 were weighed in a 500 mL four-necked flask placed in a stir bar, and then 240 g of NMP was added and stirred to dissolve. Next, 10.6 g (105 mmol) of triethylamine, 2.99 g (15.0 mmol) of DA-1, 2.97 g (15.0 mmol) of DA-6, and 5.85 g (20.0 mmol) of DA-8 were added and dissolved by stirring. While stirring the solution, 40.3 g (105 mmol) of DBOP was added, and 32.5 g of NMP was added thereto, and the mixture was stirred under water cooling for 15 hours to obtain a solution of polyglycolate. The viscosity of the polyglycolate solution at 25 ° C is 18.0 mPa. s.

While stirring 2094 g of methanol, the obtained polyphthalate was dissolved. The solution was filtered to remove the precipitate. The precipitate was washed three times with methanol, and then dried under reduced pressure at a temperature of 100 ° C to obtain a poly phthalate powder. The molecular weight of the polyglycolate was Mn=12000 and Mw=25700.

After 2.18 g of the obtained polyphthalate powder was weighed in a 100 mL Erlenmeyer flask placed in a stir bar, 16.0 g of NMP was added, and the mixture was stirred at room temperature for 20 hours to be dissolved. The solid concentration of the polyamine solution was 11.2% by mass. Next, 7.16 g of NMP and 10.3 g of BCS were added, and the mixture was stirred at room temperature for 6 hours to obtain a polyamine solution having a solid concentration of 5.5% by mass.

(Synthesis Example 7)

5.86 g (22.5 mmol) of DE-1 and 7.75 g (25.0 mmol) of DE-3 were weighed in a 500 mL four-necked flask placed in a stir bar, and then 240 g of NMP was added and stirred to dissolve. Next, 10.6 g (105 mmol) of triethylamine, 3.00 g (15.0 mmol) of DA-1, 2.97 g (15.0 mmol) of DA-7, and 5.85 g (20.0 mmol) of DA-8 were added and dissolved by stirring. While stirring the solution, 40.3 g (105 mmol) of DBOP was added, and then 32.6 g of NMP was added, and the mixture was stirred under water cooling for 15 hours to obtain a solution of polyglycolate. The viscosity of the polyamine solution at 25 ° C is 14.0 mPa. s.

The obtained polyphthalate solution was added while stirring 2094 g of methanol, and the precipitated precipitate was collected by filtration. The precipitate was washed three times with methanol, and then dried under reduced pressure at a temperature of 100 ° C to obtain a poly phthalate powder. The molecular weight of the polyphthalate was Mn = 10,000 and Mw = 2,1600.

The obtained polyamine was weighed in a 100 mL Erlenmeyer flask placed in a stir bar. After 2.19 g of the acid ester powder, 16.1 g of NMP was added, and the mixture was stirred at room temperature for 20 hours to be dissolved. The solid concentration of the polyamine solution was 10.9% by mass. Next, 6.60 g of NMP and 10.1 g of BCS were added, and the mixture was stirred at room temperature for 6 hours to obtain a polyamine solution having a solid concentration of 5.5% by mass.

(Synthesis Example 8)

4.83 g (18.6 mmol) of DE-1 and 4.34 g (14.0 mmol) of DE-3 were weighed in a 300 mL four-necked flask placed in a stir bar, and then 174 g of NMP was added and stirred to dissolve. Next, 7.42 g (73.5 mmol) of triethylamine, 1.39 g (7.00 mmol) of DA-1, 3.62 g (14.0 mmol) of DA-4, and 4.17 g (14.0 mmol) of DA-5 were added, and the mixture was stirred and dissolved. While stirring the solution, 28.2 g (73.5 mmol) of DBOP was added, and 23.8 g of NMP was added thereto, and the mixture was stirred under water cooling for 16 hours to obtain a solution of polyglycolate. The polyglycolate solution has a viscosity of 31.5 mPa at 25 ° C. s.

The obtained polyphthalate solution was poured while stirring 5032 g of methanol, and the deposited precipitate was collected by filtration. The precipitate was washed three times with methanol, and then dried under reduced pressure at a temperature of 100 ° C to obtain a poly phthalate powder. The molecular weight of the polyphthalate was Mn = 10,500 and Mw = 25,500.

2.28 g of the obtained polyphthalate powder was weighed in a 100 mL Erlenmeyer flask placed in a stir bar, and then 26.4 g of NMP was added thereto, and the mixture was stirred at room temperature for 20 hours to be dissolved. The solid concentration of the polyamine solution was 7.4% by mass. Next, 1.81 g of a 1.0 mass% NMP solution of 3-glycidoxypropylmethyldiethoxydecane was added, and the mixture was stirred at a temperature of 50 ° C for 23 hours. Time. Further, 1.92 g of NMP and 12.1 g of BCS were added, and the mixture was stirred at room temperature for 6 hours to obtain a polyamine solution having a solid concentration of 4.5% by mass.

(Synthesis Example 9)

3.38 g (13.0 mmol) of DE-1 and 3.10 g (10.0 mmol) of DE-3 were weighed in a 200 mL four-necked flask placed in a stir bar, and then 121 g of NMP was added and stirred to dissolve. Next, 5.31 g (52.5 mmol) of triethylamine, 1.49 g (7.50 mmol) of DA-1, 2.59 g (10.0 mmol) of DA-4, and 2.24 g (7.50 mmol) of DA-5 were added and dissolved by stirring. While stirring the solution, 20.1 g (52.5 mmol) of DBOP was added, and 16.7 g of NMP was further added thereto, and the mixture was stirred under water cooling for 12 hours to obtain a solution of a polyamine. The viscosity of the polyamine solution at 25 ° C is 34.0 mPa. s.

The obtained polyphthalate solution was poured while stirring 2463 g of methanol, and the precipitated precipitate was collected by filtration. The precipitate was washed three times with methanol, and then dried under reduced pressure at a temperature of 100 ° C to obtain a poly phthalate powder. The molecular weight of the polyphthalate was Mn = 10,300 and Mw = 26,100.

After 3.19 g of the obtained polyphthalate powder was weighed in a 100 mL Erlenmeyer flask placed in a stir bar, 32.3 g of NMP was added, and the mixture was stirred at room temperature for 20 hours to be dissolved. The solid concentration of the polyamine solution was 8.3% by mass. Next, 2.83 g of a 1.0 mass% NMP solution of 3-glycidoxypropylmethyldiethoxydecane was added, and the mixture was stirred at a temperature of 50 ° C for 24 hours. Further, 7.04 g of NMP and 18.9 g of BCS were added, and the mixture was stirred at room temperature for 6 hours to obtain a polyamine solution having a solid concentration of 4.5% by mass.

(Synthesis Example 10)

2.86 g (11.0 mmol) of DE-1 and 3.88 g (12.5 mmol) of DE-3 were weighed in a 200 mL four-necked flask placed in a stir bar, and then 127 g of NMP was added and stirred to dissolve. Next, 5.01 g (49.4 mmol) of triethylamine, 1.50 g (7.50 mmol) of DA-1, 2.24 g (7.50 mmol) of DA-5, and 2.92 g (10.0 mmol) of DA-8 were added and dissolved by stirring. While stirring the solution, 18.9 g (49.4 mmol) of DBOP was added, and then 17.9 g of NMP was added, and the mixture was stirred under water cooling for 16 hours to obtain a solution of polyglycolate. The polyglycolate solution has a viscosity of 18.8 mPa at 25 ° C. s.

The obtained polyglycolate solution was added while stirring 1090 g of 2-propanol, and the precipitated precipitate was collected by filtration. The precipitate was washed three times with 2-propanol, and then dried under reduced pressure at a temperature of 100 ° C to obtain a poly phthalate powder. The molecular weight of the polyphthalate was Mn = 10,400 and Mw = 2,1000.

After 4.97 g of the obtained polyphthalate powder was weighed in a 100 mL Erlenmeyer flask placed in a stir bar, 36.5 g of NMP was added, and the mixture was stirred at room temperature for 20 hours to be dissolved. The solid concentration of the polyamine solution was 10.8% by mass. Next, 4.30 g of a 1.0 mass% NMP solution of 3-glycidoxypropylmethyldiethoxydecane was added, and the mixture was stirred at a temperature of 50 ° C for 20 hours. Further, 16.0 g of NMP and 25.8 g of BCS were added, and the mixture was stirred at room temperature for 6 hours to obtain a polyamine solution having a solid concentration of 5.0% by mass.

(Synthesis Example 11)

2.86 g (11.0 mmol) of DE-1 and 3.88 g (12.5 mmol) of DE-3 were weighed in a 200 mL four-necked flask placed in a stir bar, and then added. 127 g of NMP was stirred and dissolved. Next, 5.00 g (49.4 mmol) of triethylamine, 1.50 g (7.50 mmol) of DA-1, 2.98 g (10.0 mmol) of DA-5, and 2.19 g (7.50 mmol) of DA-8 were added and dissolved by stirring. While stirring the solution, 18.9 g (49.4 mmol) of DBOP was added, and 17.8 g of NMP was added thereto, and the mixture was stirred under water cooling for 16 hours to obtain a solution of a polyamine. The viscosity of the polyglycolate solution at 25 ° C is 20.4 mPa. s.

While the 1091 g of 2-propanol was stirred, the obtained polyphthalate solution was poured, and the precipitate which precipitated was collected by filtration. The precipitate was washed three times with 2-propanol, and then dried under reduced pressure at a temperature of 100 ° C to obtain a poly phthalate powder. The molecular weight of the polyphthalate was Mn = 11100 and Mw = 22,200.

After 5.01 g of the obtained polyphthalate powder was weighed in a 100 mL Erlenmeyer flask placed in a stir bar, 36.8 g of NMP was added, and the mixture was stirred at room temperature for 20 hours to be dissolved. The solid concentration of the polyamine solution was 10.8% by mass. Next, 4.33 g of a 1.0 mass% NMP solution of 3-glycidoxypropylmethyldiethoxydecane was added, and the mixture was stirred at a temperature of 50 ° C for 20 hours. Further, 16.1 g of NMP and 26.0 g of BCS were added, and the mixture was stirred at room temperature for 6 hours to obtain a polyamine solution having a solid concentration of 5.0% by mass.

(Synthesis Example 12)

2.15 g (8.25 mmol) of DE-1 and 4.65 g (15.0 mmol) of DE-3 were weighed in a 200 mL four-necked flask placed in a stir bar, and then 128 g of NMP was added and stirred to dissolve. Next, 4.94 g (48.8 mmol) of triethylamine, 1.50 g (7.50 mmol) of DA-1, 3.74 g (12.5 mmol) of DA-5, and 1.46 g (5.00 mmol) of DA-8 were added and dissolved by stirring. Stir the solution 18.7 g (48.8 mmol) of DBOP was added simultaneously with the solution, and then 17.9 g of NMP was added, and the mixture was stirred under water cooling for 20 hours to obtain a solution of polyglycolate. The viscosity of the polyamine solution at a temperature of 25 ° C is 19.1 mPa. s.

While the 1096 g of 2-propanol was stirred, the obtained polyphthalate solution was poured, and the precipitate formed was collected by filtration. The precipitate was washed three times with 2-propanol, and then dried under reduced pressure at a temperature of 100 ° C to obtain a poly phthalate powder. The molecular weight of the polyphthalate was Mn = 8700 and Mw = 20,000.

After 3.78 g of the obtained polyamidite powder was weighed in a 100 mL Erlenmeyer flask placed in a stir bar, 27.7 g of NMP was added, and the mixture was stirred at room temperature for 20 hours to be dissolved. The solid concentration of the polyamine solution was 10.7% by mass. Next, 3.20 g of a 1.0 mass% NMP solution of 3-glycidoxypropylmethyldiethoxydecane was added, and the mixture was stirred at a temperature of 50 ° C for 23 hours. Further, 4.26 g of NMP and 16.0 g of BCS were added, and the mixture was stirred at room temperature for 6 hours to obtain a polyamine solution having a solid concentration of 5.0% by mass.

(Synthesis Example 13)

After weighing 9.84 g (37.8 mmol) of DE-1 and 8.69 g (28.0 mmol) of DE-3 in a 500 mL four-necked flask placed in a stir bar, 352 g of NMP was added and stirred to dissolve. Next, 14.0 g (138 mmol) of triethylamine, 4.19 g (21.0 mmol) of DA-1, 8.35 g (28.0 mmol) of DA-5, and 6.14 g (21.0 mmol) of DA-8 were added and dissolved by stirring. While stirring the solution, 53.0 g (138 mmol) of DBOP was added, and then 48.2 g of NMP was added, and the mixture was stirred under water cooling for 14 hours to obtain a solution of a polyamine. The polyglycolate solution has a viscosity of 22.6 mPa at 25 ° C. s.

The obtained polyglycolate solution was added while stirring 3028 g of 2-propanol, and the precipitated precipitate was collected by filtration. The precipitate was washed three times with 2-propanol, and then dried under reduced pressure at a temperature of 100 ° C to obtain a poly phthalate powder. The molecular weight of the polyphthalate was Mn = 10,600 and Mw = 20,500.

11.7 g of the obtained polyphthalate powder was weighed in a 200 mL Erlenmeyer flask placed in a stir bar, and then 86.0 g of NMP was added thereto, and the mixture was stirred at room temperature for 20 hours to be dissolved. The solid concentration of the polyamine ester solution was 11.0% by mass. Next, 10.6 g of a 1.0 mass% NMP solution of 3-glycidoxypropylmethyldiethoxydecane was added, and the mixture was stirred at a temperature of 50 ° C for 21 hours. Further, 16.6 g of NMP and 52.8 g of BCS were added, and the mixture was stirred at room temperature for 6 hours to obtain a polyamine solution having a solid concentration of 6.0% by mass.

(Synthesis Example 14)

11.7 g (44.8 mmol) of DE-1 and 6.52 g (21.0 mmol) of DE-3 were weighed in a 500 mL four-necked flask placed in a stir bar, and then 349 g of NMP was added and stirred to dissolve. Next, 14.0 g (138 mmol) of triethylamine, 4.19 g (21.0 mmol) of DA-1, 8.35 g (28.0 mmol) of DA-5, and 6.14 g (21.0 mmol) of DA-8 were added and dissolved by stirring. While stirring the solution, 53.0 g (138 mmol) of DBOP was added, and then 47.9 g of NMP was added, and the mixture was stirred under water cooling for 16 hours to obtain a solution of a polyamine. The viscosity of the polyphthalate solution at a temperature of 25 ° C is 26.2 mPa. s.

The obtained polyglycolate solution was added while stirring 3002 g of 2-propanol, and the precipitated precipitate was collected by filtration. The precipitate was washed three times with 2-propanol, and then dried under reduced pressure at a temperature of 100 ° C to obtain a poly phthalate powder. The gathering The molecular weight of the amine ester was Mn = 10,300 and Mw = 20,600.

After 11.9 g of the obtained polyamidite powder was weighed in a 200 mL Erlenmeyer flask placed in a stir bar, 87.8 g of NMP was added, and the mixture was stirred at room temperature for 20 hours to be dissolved. The solid concentration of the polyamine ester solution was 11.0% by mass. Next, 10.8 g of a 1.0 mass% NMP solution of 3-glycidoxypropylmethyldiethoxydecane was added, and the mixture was stirred at a temperature of 50 ° C for 21 hours. Further, 17.3 g of NMP and 54.0 g of BCS were added, and the mixture was stirred at room temperature for 6 hours to obtain a polyamine solution having a solid concentration of 6.0% by mass.

(Synthesis Example 15)

6.67 g (25.6 mmol) of DE-1 and 3.73 g (12.0 mmol) of DE-3 were weighed in a 300 mL four-necked flask placed in a stir bar, and then 201 g of NMP was added and stirred to dissolve. Next, 8.00 g (79.0 mmol) of triethylamine, 2.57 g (12.0 mmol) of DA-2, 4.78 g (16.0 mmol) of DA-5, and 3.50 g (12.0 mmol) of DA-8 were added and dissolved by stirring. While stirring the solution, 30.3 g (79.0 mmol) of DBOP was added, and 27.5 g of NMP was added thereto, and the mixture was stirred under water cooling for 16 hours to obtain a solution of a polyamidite. The viscosity of the polyphthalate solution at a temperature of 25 ° C is 21.6 mPa. s.

While the 1728 g of 2-propanol was stirred, the obtained polyphthalate solution was poured, and the precipitate formed was collected by filtration. The precipitate was washed three times with 2-propanol, and then dried under reduced pressure at a temperature of 100 ° C to obtain a poly phthalate powder. The molecular weight of the polyphthalate was Mn = 9200 and Mw = 19,600.

2.95 g of the obtained polyphthalate powder was weighed in a 100 mL Erlenmeyer flask placed in a stir bar, and then 21.7 g of NMP was added, and the mixture was stirred at room temperature. Allow it to dissolve in an hour. The solid concentration of the polyamine ester solution was 11.0% by mass. Next, 2.53 g of a 1.0 mass% NMP solution of 3-glycidoxypropylmethyldiethoxydecane was added, and the mixture was stirred at a temperature of 50 ° C for 26 hours. Further, 9.90 g of NMP and 15.2 g of BCS were added, and the mixture was stirred at room temperature for 6 hours to obtain a polyamine solution having a solid concentration of 5.0% by mass.

(Comparative Synthesis Example 1)

1.56 g (6.00 mmol) of DE-1 and 4.94 g (17.5 mmol) of DE-2 were weighed in a 200 mL four-necked flask placed in a stir bar, and then 115 g of NMP was added and stirred to dissolve. Next, 5.32 g (52.5 mmol) of triethylamine, 1.00 g (5.00 mmol) of DA-1, 3.22 g (12.5 mmol) of DA-4, and 1.49 g (7.50 mmol) of DA-6 were added and dissolved by stirring. While stirring the solution, 20.1 g (52.5 mmol) of DBOP was added, and 15.8 g of NMP was added thereto, and the mixture was stirred under water cooling for 16 hours to obtain a solution of a polyamidite. The viscosity of the polyamine solution at 25 ° C is 24.0 mPa. s.

The obtained polyphthalate solution was added while stirring 1010 g of methanol, and the precipitated precipitate was collected by filtration. The precipitate was washed three times with methanol, and then dried under reduced pressure at a temperature of 100 ° C to obtain a poly phthalate powder. The molecular weight of the polyamidomate was Mn=11600 and Mw=36200.

After 3.96 g of the obtained polyphthalate powder was weighed in a 100 mL Erlenmeyer flask placed in a stir bar, 29.1 g of NMP was added, and the mixture was stirred at room temperature for 20 hours to be dissolved. The solid concentration of the polyamine solution was 11.4% by mass. Next, 3.64 g of a 1.0 mass% NMP solution of 3-glycidoxypropylmethyldiethoxydecane was added, and the mixture was stirred at a temperature of 50 ° C for 24 hours. After the precipitation appeared.

(Comparative Synthesis Example 2)

1.57 g (6.00 mmol) of DE-1 and 4.94 g (17.5 mmol) of DE-2 were weighed in a 200 mL four-necked flask placed in a stir bar, and then 115 g of NMP was added and stirred to dissolve. Next, 5.30 g (52.5 mmol) of triethylamine, 1.00 g (5.00 mmol) of DA-1, 3.22 g (12.5 mmol) of DA-4, and 1.49 g (7.50 mmol) of DA-7 were added and dissolved by stirring. While stirring the solution, 20.1 g (52.5 mmol) of DBOP was added, and 15.8 g of NMP was added thereto, and the mixture was stirred under water cooling for 16 hours to obtain a solution of a polyamidite. The viscosity of the polyglycolate solution at 25 ° C is 17.7 mPa. s.

The obtained polyphthalate solution was added while stirring 1010 g of methanol, and the precipitated precipitate was collected by filtration. The precipitate was washed three times with methanol, and then dried under reduced pressure at a temperature of 100 ° C to obtain a poly phthalate powder. The molecular weight of the polyphthalate was Mn = 10,300 and Mw = 26,100.

After 4.00 g of the obtained polyphthalate powder was weighed in a 100 mL Erlenmeyer flask placed in a stir bar, 29.4 g of NMP was added, and the mixture was stirred at room temperature for 20 hours to be dissolved. The solid concentration of the polyamine solution was 11.3% by mass. Next, 3.62 g of a 1.0 mass% NMP solution of 3-glycidoxypropylmethyldiethoxydecane was added, and the mixture was stirred at a temperature of 50 ° C for 24 hours. Further, 6.70 g of NMP and 18.2 g of BCS were added, and the mixture was stirred at room temperature for 6 hours to obtain a polyamine solution having a solid concentration of 6.0% by mass.

(Comparative Synthesis Example 3)

8.59 g (33.0 mmol) of DE-1 and 6.77 g (24.0 mmol) of DE-2 were weighed in a 500 mL four-necked flask placed in a stir bar, and then 270 g of NMP was added and stirred to dissolve. Next, 12.8 g (126 mmol) of triethylamine, 3.59 g (18.0 mmol) of DA-1, 6.20 g (24.0 mmol) of DA-4, and 3.57 g (18.0 mmol) of DA-6 were added and dissolved by stirring. While stirring the solution, 48.3 g (126 mmol) of DBOP was added, and then 37.0 g of NMP was added, and the mixture was stirred under water cooling for 18 hours to obtain a solution of polyglycolate. The viscosity of the polyamine solution at 25 ° C is 35.8 mPa. s.

The obtained polyphthalate solution was added while stirring 2378 g of methanol, and the precipitated precipitate was collected by filtration. The precipitate was washed three times with methanol, and then dried under reduced pressure at a temperature of 100 ° C to obtain a poly phthalate powder. The molecular weight of the polyphthalate was Mn = 12,400 and Mw = 26,200.

21.9 g of the obtained polyphthalate powder was weighed in a 500 mL Erlenmeyer flask placed in a stir bar, and then 161 g of NMP was added, and the mixture was stirred at room temperature for 20 hours to be dissolved. The solid concentration of the polyamine solution was 11.7% by mass. Next, 21.3 g of a 1.0 mass% NMP solution of 3-glycidoxypropylmethyldiethoxydecane was added, and the mixture was stirred at a temperature of 50 ° C for 24 hours. Further, 45.5 g of NMP and 106 g of BCS were added, and the mixture was stirred at room temperature for 6 hours to obtain a polyamine solution having a solid concentration of 6.0% by mass.

(Comparative Synthesis Example 4)

8.59 g (33.0 mmol) of DE-1 and 6.77 g (24.0 mmol) of DE-2 were weighed in a 500 mL four-necked flask placed in a stir bar, and then 270 g of NMP was added and stirred to dissolve. Next, add 12.8g (126mmol) of the third Ethylamine, 3.59 g (18.0 mmol) of DA-1, 6.20 g (24.0 mmol) of DA-4, and 3.57 g (18.0 mmol) of DA-7 were stirred and dissolved. While stirring the solution, 48.3 g (126 mmol) of DBOP was added, and then 37.0 g of NMP was added, and the mixture was stirred under water cooling for 18 hours to obtain a solution of polyglycolate. The viscosity of the polyglycolate solution at 25 ° C is 25.5 mPa. s.

The obtained polyphthalate solution was added while stirring 2378 g of methanol, and the precipitated precipitate was collected by filtration. The precipitate was washed three times with methanol, and then dried under reduced pressure at a temperature of 100 ° C to obtain a poly phthalate powder. The molecular weight of the polyphthalate was Mn = 10,900 and Mw = 23,900.

21.7 g of the obtained polyphthalate powder was weighed in a 500 mL Erlenmeyer flask placed in a stir bar, and then 159 g of NMP was added, and the mixture was stirred at room temperature for 20 hours to be dissolved. The solid concentration of the polyamine solution was 11.6% by mass. Next, 21.0 g of a 1.0 mass% NMP solution of 3-glycidoxypropylmethyldiethoxydecane was added, and the mixture was stirred at a temperature of 50 ° C for 24 hours. Further, 43.1 g of NMP and 104 g of BCS were added, and the mixture was stirred at room temperature for 6 hours to obtain a polyamine solution having a solid concentration of 6.0% by mass.

(Comparative Synthesis Example 5)

0.82 g (3.12 mmol) of DE-1 and 3.08 g (9.10 mmol) of DE-4 were weighed in a 100 mL four-necked flask placed in a stir bar, and then 67.1 g of NMP was added and stirred to dissolve. Next, 2.61 g (25.7 mmol) of triethylamine, 0.52 g (2.60 mmol) of DA-2, 0.77 g (3.90 mmol) of DA-6, and 1.90 g (6.50 mmol) of DA-8 were added and dissolved by stirring. 9.84 g (25.7 mmol) of DBOP was added while stirring the solution, and then 9.42 g was added. NMP was stirred under water cooling for 16 hours to obtain a solution of polyamine. The polyglycolate solution has a viscosity of 12.3 mPa at 25 ° C. s.

While stirring 575 g of 2-propanol, the obtained polyamine ester solution was poured, and the deposited precipitate was collected by filtration. The precipitate was washed three times with 2-propanol, and then dried under reduced pressure at a temperature of 100 ° C to obtain a poly phthalate powder. The molecular weight of the polyphthalate was Mn = 7800 and Mw = 20,000.

2.87 g of the obtained polyphthalate powder was weighed in a 100 mL Erlenmeyer flask placed in a stir bar, and then 21.1 g of NMP was added thereto, and the mixture was stirred at room temperature for 20 hours to be dissolved. The solid concentration of the polyamine solution was 10.6% by mass. Next, 2.38 g of a 1.0 mass% NMP solution of 3-glycidoxypropylmethyldiethoxydecane was added, and the mixture was stirred at a temperature of 50 ° C for 25 hours. Further, 8.42 g of NMP and 14.3 g of BCS were added, and the mixture was stirred at room temperature for 6 hours to obtain a polyamine solution having a solid concentration of 5.0% by mass.

(Comparative Synthesis Example 6)

1.49 g (5.72 mmol) of DE-1 and 2.20 g (6.50 mmol) of DE-4 were weighed in a 100 mL four-necked flask placed in a stir bar, and then 68.5 g of NMP was added and stirred to dissolve. Next, 2.61 g (25.7 mmol) of triethylamine, 0.52 g (2.60 mmol) of DA-2, 1.49 g (5.20 mmol) of DA-3, and 1.53 g (5.20 mmol) of DA-8 were added and dissolved by stirring. While stirring the solution, 9.83 g (25.7 mmol) of DBOP was added, and 9.53 g of NMP was added thereto, and the mixture was stirred under water cooling for 16 hours to obtain a solution of polyglycolate. The viscosity of the polyamine solution at a temperature of 25° is 24.3 mPa. s.

The 585 g of 2-propanol was stirred while the obtained polyphthalate was dissolved. The solution was filtered to remove the precipitate. The precipitate was washed three times with 2-propanol, and then dried under reduced pressure at a temperature of 100 ° C to obtain a poly phthalate powder. The molecular weight of the polyphthalate was Mn = 9000 and Mw = 24,500.

After 2.87 g of the obtained polyphthalate powder was weighed in a 100 mL Erlenmeyer flask placed in a stir bar, 21.0 g of NMP was added, and the mixture was stirred at room temperature for 20 hours to be dissolved. The solid concentration of the polyamine solution was 10.6% by mass. Next, 2.39 g of a 1.0 mass% NMP solution of 3-glycidoxypropylmethyldiethoxydecane was added, and the mixture was stirred at a temperature of 50 ° C for 25 hours. Further, 8.60 g of NMP and 14.3 g of BCS were added, and the mixture was stirred at room temperature for 6 hours to obtain a polyamine solution having a solid concentration of 5.0% by mass.

(Example 1)

The polyphthalate solution obtained in Synthesis Example 1 was filtered through a 1.0 μm filter, and then coated on a glass substrate with an ITO electrode using a spin coater (manufactured by Mi Nei Electronics Co., Ltd., width 380 × length 320 × thickness 1.1 ( On mm)), place it at room temperature for 10 minutes while blowing the air. Next, it was dried on a hot plate at a temperature of 50 ° C for 5 minutes, and then fired in an IR (far infrared heating) furnace at a temperature of 230 ° C for 30 minutes to obtain a transparent and uniform polyimide film having a film thickness of 100 nm.

(Example 2)

The same treatment as in Example 1 was carried out except that the polyphthalate solution obtained in Synthesis Example 2 was used, and a transparent and uniform polyimide film having a thickness of 100 nm was obtained.

(Example 3)

The same treatment as in Example 1 was carried out except that the polyphthalate solution obtained in Synthesis Example 3 was used, and a transparent and uniform polyimide film having a film thickness of 100 nm was obtained.

(Example 4)

The same treatment as in Example 1 was carried out except that the polyphthalate solution obtained in Synthesis Example 4 was used, and a transparent and uniform polyimide film having a film thickness of 100 nm was obtained.

(Example 5)

A transparent and uniform polyimide film having a thickness of 100 nm was obtained by the same treatment as in Example 1 except that the polyphthalate solution obtained in Synthesis Example 5 was used.

(Example 6)

The same treatment as in Example 1 was carried out except that the polyphthalate solution obtained in Synthesis Example 6 was used, and a transparent and uniform polyimide film having a thickness of 100 nm was obtained.

(Example 7)

The same treatment as in Example 1 was carried out except that the polyphthalate solution obtained in Synthesis Example 7 was used, and a transparent and uniform polymerization having a film thickness of 100 nm was obtained. 醯 imine film.

(Example 8)

The same treatment as in Example 1 was carried out except that the polyphthalate solution obtained in Synthesis Example 8 was used, and a transparent and uniform polyimide film having a thickness of 100 nm was obtained.

(Example 9)

The same treatment as in Example 1 was carried out except that the polyphthalate solution obtained in Synthesis Example 9 was used, and a transparent and uniform polyimide film having a film thickness of 100 nm was obtained.

(Embodiment 10)

The same treatment as in Example 1 was carried out except that the polyphthalate solution obtained in Synthesis Example 10 was used, and a transparent and uniform polyimide film having a thickness of 100 nm was obtained.

(Example 11)

The same treatment as in Example 1 was carried out except that the polyphthalate solution obtained in Synthesis Example 11 was used, and a transparent and uniform polyimide film having a film thickness of 100 nm was obtained.

(Embodiment 12)

Except that the polyphthalate solution obtained in Synthesis Example 12 was used, The same treatment as in Example 1 was carried out to obtain a transparent and uniform polyimide film having a film thickness of 100 nm.

(Example 13)

The same treatment as in Example 1 was carried out except that the polyphthalate solution obtained in Synthesis Example 13 was used, and a transparent and uniform polyimide film having a thickness of 100 nm was obtained.

(Example 14)

The same treatment as in Example 1 was carried out except that the polyphthalate solution obtained in Synthesis Example 14 was used, and a transparent and uniform polyimide film having a film thickness of 100 nm was obtained.

(Example 15)

The same treatment as in Example 1 was carried out except that the polyphthalate solution obtained in Synthesis Example 15 was used, and a transparent and uniform polyimide film having a film thickness of 100 nm was obtained.

(Comparative Example 1)

The polyphthalate solution obtained in Synthesis Example 2 was compared by filtration through a 1.0 μm filter, and as a result, it was not passed through the filter.

(Comparative Example 2)

The polyphthalate obtained in Comparative Example 3 was compared by filtration through a 1.0 μm filter. The solution, as a result, blocked the filter.

(Comparative Example 3)

The polyphthalate solution obtained in Synthesis Example 4 was compared by filtration through a 1.0 μm filter, and the filter was blocked.

(Comparative Example 4)

The same treatment as in Example 1 was carried out except that the polyphthalate solution obtained in Comparative Synthesis Example 5 was used, but a turbid and uneven polyimine film was obtained.

(Comparative Example 5)

The same treatment as in Example 1 was carried out except that the polyphthalate solution obtained in Comparative Synthesis Example 6 was used, but a turbid and uneven polyimine film was obtained.

The results of the synthesis examples, comparative synthesis examples, examples and comparative examples are shown in Table 1.

As shown in Table 1, the liquid crystal alignment agents of Examples 1 to 15 all had good solubility and printability. Further, in Comparative Examples 1 to 3, the solubility was poor, and printing was impossible.

Further, in the liquid crystal alignment agents of Comparative Examples 4 and 5, although the solubility was good, the printability was poor, and a uniform polyimide film could not be obtained.

Industrial use possibility

By using the liquid crystal alignment agent of the present invention, it is possible to obtain a liquid crystal alignment film which has a characteristic of reducing residual charge when a DC voltage is applied, and/or rapidly relaxing the residual charge which is accumulated by the DC voltage, and which improves the transmittance of the obtained film. As a result, the obtained liquid crystal alignment film can be widely applied to TN elements, STN elements, TFT elements, and vertical alignment type liquid crystal display elements.

In addition, the entire contents of the specification, the scope of the patent application and the abstract of the Japanese Patent Application No. 2012-155676, filed on Jul.

Claims (10)

A liquid crystal alignment agent comprising a structural unit represented by the following formula (1) having a total structural unit of 1 mol from a tetracarboxylic acid derivative and having a molecular weight of 30 to 100 mol%, and containing a monomolecular unit derived from a diamine, having a structural unit of polyamine amide and an organic solvent represented by the following formula (2) in an amount of 20 to 100 mol%; (In the formula (1), X ¹ is a tetravalent organic aromatic group, and R ¹ is an ethyl group) (In the formula (2), R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, a hydrogen atom may be mixed with an alkyl group having 1 to 5 carbon atoms, and A ¹ and A ² are each independently a hydrogen atom or a methyl group. ). The liquid crystal alignment agent of claim 1, which further comprises a solvent having a lower surface tension than the above organic solvent. The liquid crystal alignment agent of claim 1 or 2, wherein X ¹ of the formula (1) is a benzene ring. The liquid crystal alignment agent according to any one of the items 1 to 3, wherein R ² of the formula (2) is a hydrogen atom or a methyl group. The liquid crystal alignment agent of any one of Claims 1 to 4, wherein A ¹ and A ² of the formula (2) are a hydrogen atom. The liquid crystal alignment agent according to any one of claims 1 to 5, wherein the polyglycolate has a weight average molecular weight of 5,000 to 300,000 and a number average molecular weight of 2,500 to 150,000. The liquid crystal alignment agent according to any one of claims 1 to 6, wherein the concentration of the polyphthalate in the liquid crystal alignment agent is 0.5 to 15% by mass. A liquid crystal alignment film which is obtained by coating a liquid crystal alignment agent according to any one of Items 1 to 7 of the patent application, and calcining it. The liquid crystal alignment film of claim 8 is characterized in that the film thickness after baking is 5 to 300 nm. A liquid crystal display element characterized by having a liquid crystal alignment film according to claim 8 or 9.