TWI515227B - A liquid crystal aligning agent containing a polyamic acid ester and a polyamic acid, and a liquid crystal alignment film - Google Patents

Description

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

The present invention relates to a liquid crystal alignment agent containing a polyphthalate and a poly-proline, and a liquid crystal alignment film obtained by 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 baking is obtained.

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 addition to the excellent liquid crystal alignment property or the pretilt angle which can generate stability, the liquid crystal alignment film is used. It is important to change the characteristics such as the high voltage holding ratio, the suppression of the residual image due to the AC drive, the generation of less residual charge when the DC voltage is applied, and/or the early relaxation of the residual charge accumulated by the DC voltage.

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). In addition, the liquid crystal alignment film which has a high voltage holding ratio and can shorten the time until the image is lost due to the DC voltage, is also proposed to be used in addition to polyacrylic acid or its ruthenium iodide polymer. A very small amount of a liquid crystal alignment agent which is a compound selected from a compound having one carboxylic acid group in the molecule, a compound containing one carboxylic acid anhydride group in the molecule, and a compound having one tertiary amino group in the molecule (for example, Patent Literature) 3) Proposal. Further, a liquid crystal alignment film having excellent liquid crystal alignment, high voltage holding ratio, low image sticking, excellent reliability, and exhibiting a high pretilt angle is known, for example, using a tetracarboxylic dianhydride having a specific structure. A liquid crystal alignment agent of polyammonic acid or a quinone imidized polymer obtained from tetracarboxylic dianhydride and a specific diamine compound with cyclobutane (for example, Patent Document 4). Further, for example, 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 to have a good liquid crystal alignment property and 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, LCD TVs with large screens and high definition have been the main components, so the requirements for image sticking will be more 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. Therefore, in addition to having good initial characteristics, various characteristics of the liquid crystal alignment film are required, for example, a long time even at a high temperature. Those who maintain good characteristics after exposure.

Further, the polymer component constituting the polyimine-based liquid crystal alignment agent is highly reliable because it has high reliability, and does not cause a decrease in molecular weight in the heat treatment during the imidization. A report that the liquid crystal has a stable alignment property and excellent reliability can be provided (for example, Patent Document 6). However, polyglycolate generally has a problem of high volume resistance and a large amount of residual charge when a DC voltage is applied, so that there is no improvement in the polyimine containing the polyperurethane. A method of characterizing a liquid crystal alignment agent.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 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

The inventors of the present invention have begun research on a liquid crystal obtained by mixing polyglycine with a polyamic acid having excellent properties from the viewpoint of electrical characteristics, in order to improve the characteristics of the liquid crystal alignment agent containing the above polyphthalate. An aligning agent. However, the liquid crystal alignment film obtained by the liquid crystal alignment agent obtained by mixing the polyphthalate with polyphthalic acid has not yet satisfied the current demand regardless of the liquid crystal alignment property and electrical characteristics.

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 is excellent in terms of liquid crystal alignment and electrical properties, and also has transparency which does not cause white turbidity. A liquid crystal alignment agent for a liquid crystal alignment film is intended.

As a result of investigation by the present inventors, it has been found that the liquid crystal alignment film formed of a liquid crystal alignment agent containing a polyphthalate and a polyphthalic acid has been subjected to analysis, and it has been confirmed that fine irregularities are formed on the surface of the film. Further, the present inventors have found that the fine unevenness formed on the surface of the film, the weight average molecular weight of the polyphthalate contained in the liquid crystal alignment agent is smaller than the weight average molecular weight of the polyamic acid, and the fine unevenness can be suppressed. To a lesser extent. Moreover, the inventors of the present invention can eliminate the disadvantages caused by the liquid crystal alignment agent obtained by containing a polyphthalate and a polyphthalic acid when the fine unevenness generated on the surface of the film is lowered.

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 a polyphthalate having a repeating unit represented by the following formula (1) and a polyamine having a repeating unit represented by the following formula (2), And an organic solvent, and the weight average molecular weight of the polyacetamide is smaller than the weight average molecular weight of the polyamic acid,

(In the formulae (1) and (2), 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; and R ₁ is an alkyl group having 1 to 5 carbon atoms. The group, A ₁ and A ₂ each independently represent a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, an alkenyl group or an alkynyl group which may have a substituent.

2. The liquid crystal alignment agent according to the above 1, wherein the content of the polyphthalamide and the content of the polyamic acid are based on the mass of the polyglycolate/polyamide acid. The ratio is 1/9 to 9/1.

3. The liquid crystal alignment agent according to the above 1 or 2, wherein the total content of the polyphthalate and the polyamic acid is 0.5 to 15% 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 polyamine has a weight average molecular weight of from 1,000 to 100,000 less than a weight average molecular weight of the polyamic acid.

5. The liquid crystal alignment agent according to any one of the above-mentioned items 1 to 4, wherein X ₁ and X ₂ in the formulas (1) and (2) each independently represent a group represented by the following formula. At least one of the selected ones.

In the liquid crystal alignment agent according to any one of the above-mentioned items 1 to 5, Y ₁ is at least one selected from the group consisting of the structures represented by the following formulas.

7. In the liquid crystal alignment agent according to any one of the above-mentioned items, the Y ₂ is at least one selected from the group consisting of the structures represented by the following formulas.

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

A liquid crystal alignment film obtained by applying and baking a liquid crystal alignment agent according to any one of the above 1 to 7 to a liquid crystal alignment film obtained by irradiating a polarized radiation.

The present invention provides an electrical property which can reduce fine concavities and convexities on the surface of the obtained liquid crystal alignment film and improve liquid crystal alignment, and can also improve voltage retention, ion density, residual image caused by alternating current, residual DC voltage, and the like. A liquid crystal alignment agent that can improve reliability.

When the weight average molecular weight of the polyglycolate is smaller than the weight average molecular weight of the polyamic acid, why can the fine concavities and convexities generated on the surface of the film be lowered, and the liquid crystal alignment containing the polyphthalate and the poly-proline The reason why the difficulty of the agent has been eliminated is 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 free phthalic acid having a lower surface free energy than the poly-proline is present. If the polyglycolate is separated from the polylysine at the surface, a poly-proline condensate will form in the polyphthalate phase, or a polyamine will be formed in the poly-proline phase. The agglomerates of the acid ester form a film having a large number of fine irregularities on the surface of the film.

On the other hand, in the liquid crystal alignment agent of the present invention, when the weight average molecular weight of the polyphthalate is smaller than the weight average molecular weight of the polyamic acid, and the solvent is removed by the liquid crystal alignment agent to form a liquid crystal alignment film, It can promote the phase separation of polyglycolate and poly-proline, and form polyglycolate which does not exist in the vicinity of the surface of the membrane and is mixed with poly-proline, and the poly-proline is inside the membrane and the substrate interface. It does not exist in the presence of a polyphthalate.

Therefore, 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 caused by the occurrence of irregularities can be reduced. White turbidity. Therefore, in the liquid crystal alignment film having a smooth surface having no unevenness, the surface of the film is coated with a polyphthalate having a stable orientation and excellent reliability, and a polymer having excellent electrical properties exists inside the film and at the electrode interface. Proline is an alignment film with excellent properties.

[Embodiment of the Invention] <Polyurethane and polylysine>

The polyglycolate used in the present invention is a polyimine precursor used for producing a polyimine, and has a polymer which can carry out the site of the oxime imidization reaction shown below by heating.

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 (2).

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, it is particularly preferable that R ₁ is a viewpoint of how to carry out oxime imidization by heat. In the formulae (1) and (2), 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 10 carbon atoms which may have a substituent. Specific examples of the above alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a hexyl group, an octyl group, a decyl group, a cyclopentyl group, a cyclohexyl group, a dicyclohexyl group and the like. The alkenyl group, for example, one or more CH ₂ -CH ₂ structures present in the above alkyl group are substituted by a CH=CH structure, and more specifically, for example, a vinyl group, an allyl group, a 1-propenyl group, Isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-hexenyl, cyclopropenyl, cyclopentenyl, cyclohexenyl, and the like. An alkynyl group, for example, one or more CH ₂ -CH ₂ structures present in the aforementioned alkyl group are substituted by a C≡C structure, more specifically, for example, an ethynyl group, a 1-propynyl group, a 2-propene group Alkynyl and the like.

The above alkyl group, alkenyl group or alkynyl group may have a substituent when the total carbon number is from 1 to 10, 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.

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

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 (2), 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. Specific examples of X ₁ and X ₂ are, for example, X-1 to X-46 which are each independently shown below.

In addition, X ₁ and X _{2 are used} , and the ease of obtaining the monomers, etc., are independently represented by 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. The amount of the tetracarboxylic dianhydride having such preferred X ₁ and X ₂ is preferably from 2 to 100 mol%, more preferably from 40 to 100 mol%, based on the total tetracarboxylic dianhydride.

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

In view of the fact that a good liquid crystal alignment property can be obtained, and a diamine having a high linearity is introduced into the polyphthalate, Y ₁ has 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, or Y-98 diamine is preferred. The amount of the preferred diamine used in Y ₁ is preferably from 1 to 100 mol%, more preferably from 50 to 100 mol%, based on the total diamine.

Further, in order to increase the pretilt angle thereof, it is preferred to introduce a side chain having a long-chain alkyl group, an aromatic ring, an aliphatic ring, a steroid skeleton, or a diamine having a structure obtained by the combination into a polyphthalate. In this case, 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 is more preferred.

Among them, at least one selected from the structures represented by the following formula is particularly preferable.

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 In the case of lysine, 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 is better, Y-31, or Y-40 diamine is preferred. The amount of the preferred diamine used in Y ₂ is preferably from 1 to 100 mol%, more preferably from 50 to 100 mol%, based on the total diamine.

Among them, when the surface free energy of the poly-proline is increased, the phase separation of the polyphthalate and the poly-proline is further promoted, and the surface of the liquid crystal alignment film obtained by coating and baking is smoother. It is preferred to introduce a diamine containing a secondary amine group, a hydroxyl group, a guanamine group, a urea group, or a carboxyl group into the polyamic acid. Therefore, Y _{2 is more} preferably Y-19, Y-31, Y-40, Y-45, Y-98, or Y-99, and particularly preferably Y-98 or Y-99 having a carboxyl group. Y _{2 is} 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 (6) to (8) and the diamine compound represented by the formula (9). Produced by 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 or 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 may be used or two or more types may be used in combination. The concentration at the time of the synthesis is less likely to cause precipitation of the polymer, and from the viewpoint of easily obtaining a high molecular weight body, it 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

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

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 used in the above reaction is preferably N-methyl-2-pyrrolidone or γ-butyrolactone in terms of solubility of the monomer and the polymer, and one type or two types may be used. The above is mixed. The concentration of the polymer at the time of synthesis is less likely to cause precipitation of the polymer, and it is preferable to obtain a high molecular weight body, 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 (2) can be obtained by reacting a tetracarboxylic dianhydride represented by the following formula (10) with a diamine compound represented by the formula (11).

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

Specifically, the tetracarboxylic dianhydride and the diamine are 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 12 Synthesized in hours of reaction.

The organic solvent used in the above reaction is N,N-dimethylformamide, N-methyl-2-pyrrolidone, or γ-butyrolactone in terms of solubility of the monomer and the polymer. It is preferable to use one type or a mixture of two or more types. The concentration of the polymer is less likely to cause precipitation of the 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 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.

<Liquid alignment agent>

The liquid crystal alignment agent of the present invention contains the polyphthalate represented by the above formula (1) and the polyamic acid represented by the formula (2).

The weight average molecular weight of the polyphthalate is preferably from 5,000 to 300,000, more preferably from 10,000 to 200,000. Further, the number average molecular weight is preferably from 2,500 to 150,000, more preferably from 5,000 to 100,000.

Further, the weight average molecular weight of the polyamic acid is preferably from 10,000 to 305,000, more preferably from 20,000 to 210,000. Further, the number average molecular weight is preferably 5,000 to 152,500, more preferably 10,000 to 105,000.

In the present invention, the weight average molecular weight of the polyphthalate must be smaller than the weight average molecular weight of the polyamic acid. The difference between the weight average molecular weight of the polyperurethane and the polyglycolic acid is preferably from 1,000 to 100,000, more preferably from 3,000 to 80,000, still more preferably from 5,000 to 60,000. In the case where the difference in weight average molecular weight is in the range of 1,000 to 100,000, fine unevenness due to phase separation of the polyglycolate and polyglycolic acid can be effectively suppressed, which is good.

The content of the polylysine in the liquid crystal liquid crystal alignment agent of the present invention is from 1/9 to 9/ by mass of the polylysine (polyurethane/polyglycine). 1 is better, more preferably 2/8 to 8/2, and particularly preferably 3/7 to 7/3. When the ratio is limited to the range of from 1/9 to 9/1, it is possible to provide an effect of having both excellent liquid crystal alignment properties and a liquid crystal alignment agent.

The liquid crystal alignment agent of the present invention has a form of a solution obtained by dissolving the above polyamic acid ester and polylysine in an organic solvent. As long as it has such a form, for example, in the case where the polyamidomate and/or polyglycolic acid are synthesized in an organic solvent, the form of the obtained reaction solution may be used, or the reaction solution may be diluted with a suitable solvent. Also. Further, the polyphthalate and/or polyglycolic acid may be obtained in the form of a powder, or may be in the form of a solution obtained by dissolving it in an organic solvent.

In the liquid crystal alignment agent of the present invention, the content (concentration) of polylysine and polyphthalamide (hereinafter also referred to as polymer) can be appropriately changed in accordance with the thickness setting of the polyimide film to be formed. However, from the viewpoint of forming a uniform and non-defective coating film, the content of the polymer component is preferably 0.5% by mass or more based on the organic solvent, and 15% by mass in terms of solution stability. The following is more preferable, and it is especially preferably 1 to 10% by mass. Further, in this case, a thick solution of the polymer may be prepared in advance, and the thick solution may be diluted to prepare a liquid crystal alignment agent. The concentration of the concentrated solution having the polymer component is preferably 10 to 30% by mass, more preferably 10 to 15% by mass. Further, when the powder of the polymer component is dissolved in an organic solvent to prepare a solution, heating can be performed. The heating temperature is preferably from 20 ° C to 150 ° C, and particularly preferably from 20 ° C to 80 ° C.

The organic solvent contained in the liquid crystal alignment agent of the present invention is not particularly limited as long as it is a solvent capable of uniformly dissolving the polymer component. 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.

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 in which the polymer component is dissolved. The solvent is generally a solvent which has a lower surface tension than the above organic solvent. Specific examples thereof include, for example, ethyl cellosolve, butyl cellosolve, butyl cellosolve acetate, 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-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propane Alcohol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, and the like. These solvents may be used in combination of two types.

The liquid crystal alignment agent of the present invention may contain various additives such as a decane coupling agent or a crosslinking agent. The decane coupling agent is added for the purpose of improving the adhesion of the substrate coated with the liquid crystal alignment agent to the liquid crystal alignment film formed thereon. Specific examples of the decane coupling agent will be listed below, but are not limited thereto.

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.

When the amount of the above-mentioned 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 property will not be exhibited. Therefore, the solid content of the polymer is 0.01 to 5.0. The weight % is preferably from 0.1 to 1.0% by weight.

In the case where the above-described decane coupling agent is added, in order to prevent precipitation of the polymer, it is preferred to add the solvent before increasing the uniformity of the coating film. Further, in the case where a decane coupling agent is added, it may be added to the polyamidate solution, the polyaminic acid solution, or the polyphthalate solution before the polyphthalate solution is mixed with the polyaminic acid solution. Both can be used with polylysine solution. 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 baking coating film is baked, a ruthenium imidization promoter can be added in order to carry out the imidization of a poly phthalate. Specific examples of the ruthenium imidization accelerator of polyperurethane are exemplified below, but are not limited thereto.

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 imidization promoter is not particularly limited as long as the effect of promoting the heat imidization of the polyphthalate is obtained, and is contained in the polyphthalate in the liquid crystal alignment agent. The valinate moiety of the following formula (12) is preferably 1 mole or more, more preferably 0.05 mole or more, and most preferably 0.1 mole or more. Further, the main body of the ruthenium iodide promoter remaining in the baked film is reduced in concentration to a minimum amount which adversely affects various characteristics of the liquid crystal alignment film, and is concentrated with respect to the liquid crystal alignment agent. The guanamine ester moiety of the following formula (12) contained in the glutamate has a molar concentration of 2 moles or less, more preferably 1 mole or less, and most preferably 0.5. Moel below.

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>

The liquid crystal alignment film of the present invention is a film obtained by applying the above liquid crystal alignment agent to a substrate, drying and baking. The substrate to which the liquid crystal alignment agent of the present invention 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. When a substrate for forming an ITO electrode or the like for liquid crystal driving is used, it is preferable from the viewpoint of simplification of 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 is, 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 is a concern that the reliability of the liquid crystal display element is lowered. Therefore, it is usually 5 to 300 nm, preferably 10 to 200 nm.

The method of performing the alignment treatment on the obtained liquid crystal alignment film can be, for example, a rubbing method or a photo-alignment treatment method, and 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 a radiation line which is biased in a certain direction on the surface of the coating film, and heat-treating at a temperature of 150 to 250 ° C to impart a liquid crystal alignment energy to the surface of the coating film, for example. For the radiation, for example, ultraviolet rays and visible rays having a wavelength of 100 nm to 800 nm can be used. Among them, ultraviolet rays having a wavelength of from 100 nm to 400 nm are preferred, and those having a wavelength of from 200 nm to 400 nm are particularly preferred. 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. Radiation of the exposure to 1 ~ 10,000mJ / cm ² preferably, to 100 ~ 5,000mJ / cm ² is particularly preferred. In the liquid crystal alignment film produced in the above manner, the liquid crystal molecules can be stably aligned in a specific direction.

[Liquid Crystal Display Element]

In the liquid crystal display device of the present invention, a substrate having a liquid crystal alignment film can be obtained from the liquid crystal alignment agent of the present invention, and after the alignment treatment, a liquid crystal cell can be produced by a known method to obtain a liquid crystal display element.

The method for producing the liquid crystal cell is not particularly limited. For example, in a pair of substrates on which a liquid crystal alignment film is formed, for example, a liquid crystal alignment film surface is used as an inner side, and a crucible is preferably provided in a range of 1 to 30 μm. More preferably, after a distance of 2 to 10 μm, the surrounding area is fixed by a sealant, and then liquid crystal is injected and then closed. The method of encapsulating the liquid crystal is not particularly limited, and examples thereof include a vacuum method in which the liquid crystal cell to be produced is decompressed, a vacuum method in which a liquid crystal is injected, a dropping method in which a liquid crystal is dropped, and a sealing method in which sealing is performed.

[Examples]

The embodiments will be enumerated below, and the invention will be specifically described. However, the invention is not limited or construed by the embodiments.

Moreover, the abbreviation used in the examples and comparative examples, and the measurement methods of various characteristics are as follows.

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

ODA: 4,4'-diaminodiphenyl ether

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

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

NMP: N-methyl-2-pyrrolidone

Y-BL: γ-butyrolactone

BCS: butyl cellulolytic

PAE: Polyamidomate

PAA: Polylysine

[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: made by Shodex company (inline of 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 10ml/L)

Flow rate: 1.0ml/min

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

[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 then baked in a hot air circulating oven at a temperature of 250 ° C for 1 hour to obtain a film thickness of 100 nm. Coating film. The film surface of the coating film was observed by 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 obtain a film thickness of 100 nm. Polyimine 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 having 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. Outside 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) 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 first layer was formed on the glass substrate to have an ITO electrode having a film thickness of 50 nm as an electrode, the second layer was a tantalum nitride having a film thickness of 500 nm as an insulating film, and the third layer was a comb-shaped ITO electrode having an electrode ( Coating on a glass substrate obtained by driving a fringe field switching (Fringe Field Switching: hereinafter, also referred to as FFS) driving electrode with a width of the electrode: 3 μm, electrode spacing: 6 μm, electrode height: 50 nm), coating the liquid crystal alignment agent by spin coating On it. After drying on a hot plate at 80 ° C for 5 minutes, it was baked in a hot air circulating oven at 250 ° C for 60 minutes to form a coating film having a film thickness of 100 nm. The 254 nm ultraviolet light was irradiated onto the coating film surface at 100 mJ/cm ² through a polarizing plate to obtain a substrate having a liquid crystal alignment film. Further, a glass substrate having a columnar distance controller having a height of 4 μm in 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.

After measuring the V-T characteristics (voltage-transmittance characteristics) of the FFS-driven liquid crystal cell at a temperature of 58 ° C, a rectangular wave of ±4 V / 120 Hz was applied for 4 hours. After 4 hours, the voltage was turned off, and after leaving it at a temperature of 58 ° C for 60 minutes, the V-T 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 in transmittance due to the voltage remaining in the liquid crystal display element was calculated from the difference between T _b and T _a .

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

A-1: Synthesis of dialkyl tetracarboxylate

1,3-Dimethylcyclobutane-1,2,3,4-tetracarboxylic dianhydride (compound of formula (5-1) (hereinafter, abbreviated as follows) in a three-liter four-necked flask under a nitrogen stream 1,3-DM-CBDA) 220g (0.981mol), with methanol 2200g (68.7mol, 10wt times relative to 1,3-DM-CBDA), heated and refluxed at 65 ° C, forming a homogeneous solution in 30 minutes The reaction solution was stirred under heating and reflux for 4 hours and 30 minutes in this state. The reaction solution was measured using a high-speed liquid chromatography analyzer (hereinafter abbreviated as HPLC). The analysis contents of the measurement results are as follows. .

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, and it was confirmed that the compound (1-1) (the relative area of HPLC was 97.5%) (yield 36.8%).

_{1H NMR (DMSO-d 6,} 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 ‧5 wt.) were added to a three-liter four-necked flask, followed by the addition of 0.64 g (0.01 mol) of pyridine. The mixture was heated and stirred to 75 ° C with stirring using a magnetic stirrer. Subsequently, 289.93 g (2.44 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 placed in a three-liter four-necked flask under a nitrogen stream, and then 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, and it was confirmed that the compound (3-1) was dimethyl-1,3-bis(chlorocarbonyl)-1,3-dimethylcyclobutane-2,4-di. Carboxylic ester (1,3-DM-CBDE-Cl) (relative area of HPLC 99.5%) (yield 77.2%).

_{1H NMR (CDCl 3, δppm)} : 3.78 (s, 6H), 3.72 (s, 2H), 1.69 (s, 6H).

(Synthesis Example 1)

A 300 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, and ODA 8.0129 g (40.02 mmol) was placed, and then 157.25 g of NMP and 7.13 g (90.13 mmol) of pyridine as a base were added, followed by stirring and dissolving. Next, the diamine solution was stirred, and 1,3DM-CBDE-CL 12.2295 g (37.61 mmol) was added, and the mixture was reacted for 4 hours under water cooling. The obtained polyglycolate solution was poured into 1747 g of water with stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 1747 g of water, washed once with 1747 g of ethanol, and washed with 437 g of ethanol. After 3 times, 16.65 g of a white polyphthalate resin powder was obtained after drying. The yield was 95.3%. Further, the molecular weight of the polyphthalate was Mn = 13,104 and Mw = 29,112.

1.8731 g of the obtained polyphthalate resin powder was placed in a 50 ml Erlenmeyer flask, and 16.89 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 (A-1).

(Synthesis Example 2)

A 300 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, and ODA 7.0154 g (35.03 mmol) was placed, and then 140.77 g of NMP and 6.50 g (82.22 mmol) of pyridine as a base were added, followed by stirring to dissolve. Next, the diamine solution was stirred, and 1,3DM-CBDE-CL 11.1392 g (34.26 mmol) was added, and the mixture was reacted for 4 hours under water cooling. The obtained polyglycolate solution was poured into 1564 g of water under stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 1564 g of water, washed once with 1564 g of ethanol, and washed with 391 g of ethanol. After 3 times, 14.33 g of a white polyphthalate resin powder was obtained after drying. The yield was 91.6%. Further, the molecular weight of the polyglycolate was Mn = 24,228 and Mw = 61,076.

1.7324 g of the obtained polyphthalate resin powder was placed in a 50 ml Erlenmeyer flask, and 15.65 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 (A-2).

(Synthesis Example 3)

In a 100 mL four-necked flask equipped with a stirring device and a nitrogen gas introduction tube, 4.583 g (23.0 mmol) of 4,4'-diaminodiphenylamine was weighed and added to 62.9 g of NMP, and the mixture was continuously stirred and supplied with nitrogen gas to be stirred. It dissolves. The diamine solution was stirred, and 4.335 g (22.10 mmol) of CBDA was added thereto, and NMP was added thereto so that the solid content concentration was 10% by mass, and the mixture was stirred at room temperature for 24 hours to obtain a solution of polyglycine (B-1). . The polyglycine solution had a viscosity of 165.1 mPa ‧ at a temperature of 25 ° C. Further, the molecular weight of the polyamic acid was Mn = 17,171 and Mw = 35,201.

(Example 1)

1.5114 g of the polyphthalate solution (A-1) obtained in Synthesis Example 1 and 1.5048 g of the polyamic acid solution (B-1) obtained in Synthesis Example 3 were placed in an Erlenmeyer flask, and NMP 1.028 g and BCS 1.0016 were added. After g, it was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (I).

(Comparative Example 1)

1.5145 g of the polyphthalate solution (A-2) obtained in Synthesis Example 2 and 1.5241 g of the polyamic acid solution (B-1) obtained in Synthesis Example 3 were placed in an Erlenmeyer flask, and NMP 1.0331 g and BCS 1.0012 were added. After g, it was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (II).

(Comparative Example 2)

The polyperurethane solution (A-1) 4.2010g obtained in Synthesis Example 1 was placed in an Erlenmeyer flask, and NMP 0.5993 g and BCS 1.2519 g were added, and the mixture was stirred for 30 minutes in a magnetic stirrer to obtain a liquid crystal alignment agent (III).

(Example 2)

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, using a temperature of 250. The hot air circulating oven of °C was baked for 60 minutes to obtain a yttrium imidized film having a film thickness of 100 nm. The average thickness (Ra) of the center line was measured for the ruthenium-imided film. The measurement results are shown in Table 1 below.

(Comparative Example 3)

A ruthenium-imided film was produced in the same manner as in Example 2 except that the liquid crystal alignment agent (II) obtained in Comparative Example 1 was used. The average thickness (Ra) of the center line of the ruthenium-imided film was measured. The measurement results are shown in Table 1, which will be described later.

From the results of Example 2 and Comparative Example 3, it was found that the weight average molecular weight of PAE was smaller than that of PAA, and the fine concavities and convexities caused by the phase separation of polyglycolate and polyglycolic acid were suppressed to be smaller. Confirm that a smoother film is obtained.

(Example 3)

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 at 250 ° C. The hot air circulating oven was baked for 60 minutes to obtain a ruthenium imidized 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 having 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. Outside 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) was injected into the empty cell at a 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 the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 below.

(Comparative Example 4)

A liquid crystal cell was produced in the same manner as in Example 3 except that the liquid crystal alignment agent (II) obtained in Comparative Example 1 was used. The liquid crystal cell was measured for its voltage holding ratio, and then its ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 below.

(Comparative Example 5)

A liquid crystal cell was produced in the same manner as in Example 3 except that the liquid crystal alignment agent (III) obtained in Comparative Example 2 was used. The liquid crystal cell was measured for its voltage holding ratio, and then its ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 below.

From the results of Example 3 and Comparative Example 4, it was confirmed that it was possible to form a smoother film and to have a voltage holding ratio and an ion density at a high temperature. Further, from the results of Example 3 and Comparative Example 5, it was found that the polyphthalate was mixed with polylysine and a smooth film was obtained, in contrast to the case where the polyamidomate was used alone. In comparison, in order to have a higher voltage holding ratio and an ion density at a higher temperature, it was confirmed that a highly reliable liquid crystal alignment film can be obtained.

(Example 4)

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 a spin coating method to form an ITO electrode having a first layer of 50 nm in thickness, and the second layer was Fringe Field Switching (Fringe Field Switching: below, also known as a tantalum nitride of 500 nm in thickness of an insulating film, and an ITO electrode (electrode width: 3 μm, electrode spacing: 6 μm, electrode height: 50 nm) in which the third layer is a comb-like shape (Fringe Field Switching) On the glass substrate for the FFS) drive electrode. 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 130 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 having a liquid crystal alignment film. Further, a glass substrate having a columnar distance controller having a height of 4 μm in 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) was injected by a vacuum injection method, and the injection port was closed, and the FFS was used to drive the liquid crystal cell.

In this case, the FFS drives the liquid crystal cell, and the measurement of the liquid crystal alignment regulation force and the evaluation of the charge accumulation characteristics are performed. The results are shown in Table 3 below.

(Comparative Example 6)

An FFS-driven liquid crystal cell was produced in the same manner as in Example 4 except that the liquid crystal alignment agent (II) obtained in Comparative Example 1 was used. In this case, the FFS drives the liquid crystal cell, and the measurement of the liquid crystal alignment regulation force and the evaluation of the charge accumulation characteristics are performed. The results are shown in Table 3 below.

As a result of the results of Example 4 and Comparative Example 6, it was confirmed that the liquid crystal alignment film of the present invention was used, and it was confirmed that a liquid crystal alignment film having a small degree of AC drive sintering and a small residual voltage was obtained.

‧(AD-4) synthesis

Compound (b) (50.00 g, 229 mmol), pyridine (0.500 g, 0.632 mmol), compound (c) (63.02 g, 504 mmol), acetonitrile (300 g) were added to a 500 mL reaction vessel, and heated under a nitrogen atmosphere. Reflux to carry out the reaction. 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, followed by heating 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 further 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, and a solution of the compound (c) (12.1 g, 96.8 mmol), pyridine (13.93 g, 176 mmol), dichloromethane (100 g) was gradually stirred. Drop in 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 dispersed and washed at 23 ° C, filtered, and washed with tetrahydrofuran (130 g), distilled water (170 g), and 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 4)

A 300 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, and 5.028 g (25.11 mmol) of ODA was placed, and 202.80 g of NMP and 4.72 g (59.63 mmol) of pyridine as a base were added, followed by stirring to dissolve. Next, the diamine solution was stirred, and 1,3DM-CBDE-Cl 8.0794 g (24.85 mmol) was added, and the mixture was reacted for 4 hours under water cooling. The obtained solution of the polyglycolate was poured into 1127 g of water under stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 1127 g of water, once with 1127 g of ethanol, and washed with 282 g of ethanol. Three times, after drying, a white polyphthalate resin powder was obtained. The molecular weight of the polyglycolate was Mn = 6,394 and Mw = 13,794.

4.5796 g of the obtained polyphthalate resin powder was placed in a 50 ml Erlenmeyer flask, and 41.20 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 (A-3).

(Synthesis Example 5)

In a 100 mL four-necked flask equipped with a stirring device, 5.1584 g (19.82 mmol) of 2,4-bis(methoxycarbonyl)cyclobutane-1,3-dicarboxylic acid was weighed, and 68.12 g of NMP was added thereto, followed by stirring. It dissolves. Subsequently, 4.45 g (43.98 mmol) of triethylamine, 1.7315 g (16.01 mmol) of p-phenylenediamine, and 0.7922 g (3.99 mmol) of 4,4'-diaminodiphenylmethane were added, followed by stirring to dissolve. . While stirring this solution, 16.90 g (44.08 mmol) of (2,3-dihydroxy-2-thio(keto)yl-3-benzoxazolinyl)phosphonic acid diphenyl was added, followed by NMP 9.67 g. , reacted under water cooling for 4 hours. The obtained polyamidate solution was poured into 650 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 = 3,860 and Mw = 5,384.

In a 50 ml Erlenmeyer flask, 2.0332 g of the obtained polyphthalate resin powder was weighed, and 18.70708 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 (A-4).

(Synthesis Example 6)

A 100 mL four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, and 4,4'-diaminodiphenylmethane 2.01 g (10.09 mmol) and 3-amino-N-methylbenzylamine 0.92 g were placed. (6.73 mmol), 131.14 g of NMP and 3.83 g (37.93 mmol) of triethylamine as a base were added, and it stirred and it melt|dissolved. Next, the diamine solution was stirred, and 5.1407 g (15.81 mmol) of 1,3DM-CBDE-Cl was added, and the mixture was reacted for 4 hours under water cooling. The obtained solution of the polyglycolate was poured into 690 g of 2-propanol under stirring, and the precipitated white precipitate was collected by filtration, and then washed with 220 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 = 5064 and Mw = 11348.

2.0014 g of the obtained polyphthalate resin powder was placed in a 50 ml Erlenmeyer flask, and 18.2912 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 (A-5).

(Synthesis Example 7)

A 100 mL four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, and 4,4'-diaminodiphenylmethane 2.01 g (10.09 mmol) and 3-amino-N-methylbenzylamine 0.92 g were placed. (6.73 mmol), 135.18 g of NMP and 4.04 g (39.95 mmol) of triethylamine as a base were further added, and the mixture was stirred and dissolved. Next, the diamine solution was stirred, and 1,3DM-CBDE-Cl 5.4260 g (16.69 mmol) was added, and the mixture was reacted for 4 hours under water cooling. The obtained solution of the polyglycolate was poured into 711 g of 2-propanol with stirring, and the precipitated white precipitate was collected by filtration, and then washed with 230 g of 2-propanol for 5 times, and dried to give a white pigment. Amine resin powder. The molecular weight of the polyphthalate was Mn = 11820 and Mw = 28719.

2.4381 g of the obtained polyphthalate resin powder was placed in a 50 ml Erlenmeyer flask, and 21.4224 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 (A-6).

(Synthesis Example 8)

2,5-bis(methoxycarbonyl)terephthalic acid 2.2617 g (8.01 mmol), 2,4-bis(methoxycarbonyl)cyclobutane were weighed in a 300 mL four-necked flask equipped with a stirring device. 2.7808 g (10.61 mmol) of -1,3-dicarboxylic acid, and 102.82 g of NMP was added, followed by stirring to dissolve. Subsequently, 4.45 g (43.98 mmol) of triethylamine, 3.4396 g (12.01 mmol) of 1,5-bis(4-aminophenoxy)pentane, and 1,3-bis(4-aminophenethylethyl) were added. After 2.3914 g (8.01 mmol) of urea, it was stirred and dissolved. This solution was stirred with the addition of 4-(4,6-dimethoxy-1,3,5-triazabenzene-2-yl)-4-methylmorpholinium chloride (15 ± 2 weight) 16.60 g of % water and substance, and then added 14.12 g of NMP, and reacted under water cooling for 4 hours. The obtained polyamidate solution was poured into 890 g of 2-propanol with 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 polyphthalate was Mn = 9450 and Mw = 22588.

In a 50 ml Erlenmeyer flask, 1.1487 g of the obtained polyphthalate resin powder was weighed, and 19.1544 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 (A-7).

(Synthesis Example 9)

2,5-bis(methoxycarbonyl)terephthalic acid 2.2589 g (8.00 mmol) and 2,4-bis(methoxycarbonyl)cyclobutane were weighed in a 300 mL four-necked flask equipped with a stirring device. 3.0710 g (11.80 mmol) of -1,3-dicarboxylic acid, and 105.54 g of NMP was added, followed by stirring to dissolve. Subsequently, 4.45 g (43.98 mmol) of triethylamine, 3.4376 g (12.00 mmol) of 1,5-bis(4-aminophenoxy)pentane, and 1,3-bis(4-aminophenethylethyl) were added. After 2.3862 g (8.00 mmol) of urea, it was stirred and dissolved. This solution was stirred with the addition of 4-(4,6-dimethoxy-1,3,5-triazabenzene-2-yl)-4-methylmorpholinium chloride (15 ± 2 weight) 16.73 g of water and water, and then added to 14.50 g of NMP, and reacted under water cooling for 4 hours. The obtained polyamidate solution was poured into 910 g of 2-propanol with 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 polyphthalate was Mn = 18,067 and Mw = 46,973.

In a 50 ml Erlenmeyer flask, 1.3221 g of the obtained polyphthalate resin powder was weighed, and 24.8708 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 (A-8).

(Synthesis Example 10)

30.038 g (132.0 mmol) of 3,5-diaminobenzoic acid and 21.3254 g (88.0 mmol) of DA-1 were weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, and N268 was added to 268.48 g. Continue to feed nitrogen and stir 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 (B-2) was obtained. The polyglycine solution had 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 11)

In a 100 mL four-necked flask equipped with a stirring device and a nitrogen gas introduction 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 for nitrogen gas to be dissolved. The diamine solution was stirred, and 8.5449 g (39.18 mmol) of pyromellitic dianhydride was added thereto, and NMP was added thereto to have a solid content concentration of 15% by mass, followed by stirring 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 polyamic acid solution (B-3).

(Synthesis Example 12)

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 4.7522 g (23.99 mmol) of BDA was added, and the mixture was stirred at room temperature for 2 hours. Next, 36.50 g of NMP was added, and 3.4084 g (15.763 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 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 polyamic acid solution (B-4).

(Synthesis Example 13)

3. 356516 g (24.0 mmol) of 3,5-diaminobenzoic acid and 4-((2-methylamino)ethyl)aniline 2.4070 were weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube. g (16.02 mmol), 66.21 g of NMP was added, and it was stirred and continuously dissolved by nitrogen. 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 (B-5).

(Synthesis Example 14)

3,5-diaminobenzoic acid 0.6123 g (4.00 mmol) and 4,4-diaminodiphenylamine 3.199 g (16.06 mmol) were weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube. Then, 19.64 g of NMP was added, and the mixture was continuously stirred and supplied with nitrogen 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 was added, and 0.8736 g (4.01 mmol) of pyromellitic dianhydride was further 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 polyamine acid solution (B-6).

(Synthesis Example 15)

3. 356603 g (24.06 mmol) of 3,5-diaminobenzoic acid and 1,3-bis(4-aminophenethyl)urea 4.7740 were weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube. g (16.0 mmol), 28.59 g of NMP was added, and it was stirred and continuously dissolved by nitrogen gas. This diamine solution was stirred, and 2.378 g (12.0 mmol) of BDA 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 (B-7).

(Synthesis Example 16)

In a 100 mL four-necked flask equipped with a stirring device and a nitrogen gas introduction tube, 3.6536 g (24.01 mmol) of 3,5-diaminobenzoic acid and DA-13.8715 g (15.98 mmol) were weighed, and 31.75 g of NMP was added thereto. The mixture was stirred by nitrogen and dissolved. This diamine solution was added with stirring, 3.9621 g (20.0 mmol) of BDA, and stirred at room temperature for 2 hours. Next, 25.42 g of NMP and 4.4776 g (19.97 mmol) of 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 polyamic acid 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 (B-8).

(Synthesis Example 17)

3,5-diaminobenzoic acid 1.2133 g (7.97 mmol) and 4,4'-diaminodiphenyl-N-methyl 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 an amine, 44.03 g of NMP was added, and it was stirred and continuously dissolved by nitrogen gas. 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 was added, and 0.8713 g (3.99 mmol) of pyromellitic dianhydride was further 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 polyamic acid solution (B-9).

(Synthesis Example 18)

3. 365,365 (17.99 mmol) of 3,5-diaminobenzoic acid and 2,2'-dimethyl-4,4'-diamine 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 phenyl was added, and 27.32 g of NMP was added, 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 was added, and 4.5715 g (20.96 mmol) of pyromellitic dianhydride was further 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 polyamic acid solution (B-10).

(Example 5)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 3.0443 g of the polyamidomate solution (A-3) obtained in Synthesis Example 4 and 3.0126 g of the polyamidic acid solution (B-1) obtained in Synthesis Example 3 were weighed. Adding 1.7670 g of NMP, 2.083 g of BCS, and adding 0.2380 g of a 5 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 (I) -1).

(Example 6)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 3.0160 g of the polyamidate solution (A-3) obtained in Synthesis Example 4 and 3.1312 g of the polyamidic acid solution (B-1) obtained in Synthesis Example 3 were weighed. NAD 2.0339g and BCS 2.0099g were added, and 0.0274 g of (AD-2) as a polyfunctional hydroxy group-containing compound as a crosslinking agent was further added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (I-2).

(Example 7)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 3.0328 g of the polyamidate solution (A-3) obtained in Synthesis Example 4 and 3.0058 g of the polyamidic acid solution (B-1) obtained in Synthesis Example 3 were weighed. After adding NMP 2.0417g and BCS 2.0125g, 0.0366g of (AD-4) which added the polyfunctional cyclic carbonate compound as a crosslinking agent, and stirring with a magnetic stirrer for 30 minutes, and the liquid crystal alignment agent (I-3) was obtained.

(Example 8)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 3.0463 g of the polyamidomate solution (A-3) obtained in Synthesis Example 4 and 3.0433 g of the polyamidic acid solution (B-1) obtained in Synthesis Example 3 were weighed. After adding NMP 2.0306g, BCS 2.0367g, and 0.0454g of (AD-3) which added the polyfunctional propylene oxide compound as a crosslinking agent, it stirred by the magnetic stirring machine for 30 minutes, and liquid-crystal-aligning agent (I-4) was obtained.

(Example 9)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 3.0073 g of the polyamidomate solution (A-3) obtained in Synthesis Example 4 and 3.0197 g of the polyamidic acid solution (B-1) obtained in Synthesis Example 3 were weighed. Add NMP 2.0436g, BCS 2.0364g, and add N-α-(9-fluorenylmethoxycarbonyl)-Nt-butoxycarbonyl-L-histidine acid 0.0701g of hydrazine imidization accelerator, using magnetic stirrer After stirring for 30 minutes, a liquid crystal alignment agent (I-5) was obtained.

(Embodiment 10)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 3.0210 g of the polyamidate solution (A-3) obtained in Synthesis Example 4 and 3.0105 g of the polyamidic acid solution (B-1) obtained in Synthesis Example 3 were weighed. NMF 2.0140g, BCS 2.0246g, and 0.0341g of 4-(t-butoxycarbonylamino)pyridine of a ruthenium hydride promoter were added, and it stirred by the magnetic stirring machine for 30 minutes, and liquid crystal aligning agent (I-6) was obtained.

(Example 11)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 3.0021 g of the polyamidomate solution (A-3) obtained in Synthesis Example 4 and 3.1795 g of the polyamidic acid solution (B-1) obtained in Synthesis Example 3 were weighed. NMP 2.0480g and BCS 2.0062g were added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (I-7).

(Embodiment 12)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 1.8064 g of the polyamidate solution (A-3) obtained in Synthesis Example 4 and 2.1642 g of the polyamidic acid solution (B-2) obtained in Synthesis Example 10 were weighed. NMP 4.1032g and BCS 2.0388g were added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (II-1).

(Comparative Example 7)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 1.8510 g of the polyphthalate solution (A-2) obtained in Synthesis Example 2 and 2.1257 g of the polyamidic acid solution (B-2) obtained in Synthesis Example 10 were weighed. NMP 6.1321 g and BCS 2.0012 g were added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (II-2).

(Example 13)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 1.8212 g of the polyamidate solution (A-4) obtained in Synthesis Example 5 and 2.8206 g of the polyamidic acid solution (B-3) obtained in Synthesis Example 11 were weighed. NMP 3.4198 g and BCS 2.0629 g were added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (III-1).

(Example 14)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 4.2276 g of the polyphthalate solution (A-4) obtained in Synthesis Example 5 and 1.2331 g of the polyamidic acid solution (B-4) obtained in Synthesis Example 12 were weighed. NMP 2.6302 g and BCS 2.0189 g were added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (III-2).

(Example 15)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 3.0022 g of the polyamidate solution (A-4) obtained in Synthesis Example 5 and 2.3359 g of the polyamidic acid solution (B-5) obtained in Synthesis Example 13 were weighed. NMP 2.9918g and BCS 20168g were added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (III-3).

(Embodiment 16)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 3.0145 g of the polyamidate solution (A-5) obtained in Synthesis Example 6 and 1.7284 g of the polylysine solution (B-6) obtained in Synthesis Example 14 were weighed. NMP 3.3210 g and BCS 2.0155g were added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (IV-1).

(Example 17)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 3.0186 g of the polyamidate solution (A-6) obtained in Synthesis Example 7 and 1.7640 g of the polyamidic acid solution (B-6) obtained in Synthesis Example 14 were weighed. NMP 3.3171 g and BCS 2.0344 g were added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (IV-2).

(Embodiment 18)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 3.0250 g of the polyamidate solution (A-5) obtained in Synthesis Example 6 and 2.1211 g of the polyamidic acid solution (B-7) obtained in Synthesis Example 15 were weighed. NMP 3.0711g and BCS 2.0720g were added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (IV-3).

(Embodiment 19)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 3.0026 g of the polyamidate solution (A-6) obtained in Synthesis Example 7 and 2.0594 g of the polyamidic acid solution (B-7) obtained in Synthesis Example 15 were weighed. NMP 3.0194g and BCS 2.0030g were added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (IV-4).

(Embodiment 20)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 1.2318 g of the polyamidate solution (A-5) obtained in Synthesis Example 6 and 3.2286 g of the polyamidic acid solution (B-8) obtained in Synthesis Example 16 were weighed. NMP 3.6275 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 (IV-5).

(Example 21)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 4.8328 g of the polyamidomate solution (A-7) obtained in Synthesis Example 8 and 2.1984 g of the polyamidic acid solution (B-9) obtained in Synthesis Example 17 were weighed. NMP 1.2268g and BCS 2.0307g were added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (V-1).

(Comparative Example 8)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 4.8426 g of the polyphthalate solution (A-8) obtained in Synthesis Example 9 and 2.0480 g of the polyamidic acid solution (B-9) obtained in Synthesis Example 17 were weighed. NMP 1.2241 g and BCS 2.0380 g were added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (V-2).

(Example 22)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 4.8210 g of the polyamidomate solution (A-7) obtained in Synthesis Example 8 and 2.4526 g of the polyamidic acid solution (B-5) obtained in Synthesis Example 14 were weighed. NMP 0.8197g and BCS 2.0452g were added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (V-3).

(Comparative Example 9)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 4.7940 g of the polyamidate solution (A-8) obtained in Synthesis Example 9 and 2.5558 g of the polyamidic acid solution (B-5) obtained in Synthesis Example 14 were weighed. NMP 0.8545g and BCS 2.0254g were added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (V-4).

(Example 23)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 3.6281 g of the polyamidate solution (A-7) obtained in Synthesis Example 8 and 2.8751 g of the polyamidic acid solution (B-10) obtained in Synthesis Example 18 were weighed. NMP 1.6002 g and BCS 2.0514 g were added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (V-5).

(Example 24)

The stirrer was placed in a 50 ml Erlenmeyer flask, and 3.6507 g of the polyamidate solution (A-8) obtained in Synthesis Example 9 and 2.8195 g of the polyamidic acid solution (B-10) obtained in Synthesis Example 18 were weighed. NMP 1.6288g and BCS 1.9982g were added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (V-6).

(Embodiment 25)

The liquid crystal alignment agent (I-1) obtained in Example 5 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 film 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 26 to 45 and Comparative Examples 10 to 12)

Each of the coating films was formed in the same manner as in Example 25 except that each of the liquid crystal alignment agents obtained in the above Examples 6 to 24 and Comparative Examples 7 to 9 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 of these are shown in Table 4 below.

[Industrial use]

The liquid crystal alignment agent of the present invention can improve the liquid crystal alignment property by reducing fine irregularities on the surface of the obtained liquid crystal alignment film, and can also improve electrical properties such as voltage retention, ion density, residual image caused by alternating current, residual DC voltage, and the like. characteristic. As a result, it 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. 2010-058554, filed on March 15, 2010, are hereby incorporated herein in In the content.

Claims (9)

A liquid crystal alignment agent comprising: a polyphthalate having a repeating unit represented by the following formula (1); a polylysine having a repeating unit represented by the following formula (2); and an organic The solvent, in addition, the weight average molecular weight of the polyacetamide is smaller than the weight average molecular weight of the polyamic acid. (In the formulae (1) and (2), 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; and R ₁ is an alkyl group having 1 to 5 carbon atoms; The group, A ₁ and A ₂ each independently represent a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, or an alkynyl group which may have a substituent. The liquid crystal alignment agent of claim 1, wherein the content of the polylysine and the content of the polyamic acid are based on the mass of the polyglycolate/polylysine. The ratio is 1/9~9/1. The liquid crystal alignment agent of the first or second aspect of the invention, wherein the total content of the polyamic acid ester and the polyamic acid is 0.5 to 15% by mass based on the organic solvent. The liquid crystal alignment agent of claim 1, wherein the polyamic acid ester has a weight average molecular weight of from 1,000 to 100,000 smaller than a weight average molecular weight of the polyamic acid. The liquid crystal alignment agent of the first aspect of the invention, wherein X ₁ and X ₂ in the formulas (1) and (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 according to claim 1 or 5, wherein Y ₁ in the above formula (1) is 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 5, wherein, in the formula (2), 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 7. A liquid crystal alignment film obtained by coating and baking a liquid crystal alignment agent according to any one of claims 1 to 7 to irradiate a polarized radiation.