TWI504676B - Polyamide liquid crystal aligning agent and liquid crystal alignment film using the same - Google Patents

Description

Polyphthalate liquid crystal alignment agent and liquid crystal alignment film using same

The present invention relates to a liquid crystal alignment film obtained by preparing a liquid crystal alignment agent containing a polyphthalate for a liquid crystal alignment film and the liquid crystal alignment agent.

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

With the high refinement of the liquid crystal display element, the liquid crystal alignment film has high pre-tilt angle (Pretiltangle) and high voltage for suppressing the decrease in the contrast of the liquid crystal display element or reducing the image sticking phenomenon. It is important to maintain the rate, suppress the residual image generated by the AC drive, generate less residual charge when applying a DC voltage, and/or ease the characteristics of the residual charge accumulated by the DC voltage in advance.

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 of the amine group (for example, Patent Document 1) or a liquid crystal alignment agent containing a soluble polyimine having a specific diamine compound such as a pyridine skeleton as a raw material (for example, Patent Document 2). Further, the liquid crystal alignment film having a high voltage holding ratio and shortening the time from the occurrence of the residual voltage due to the DC voltage, for example, a polyamine or a ruthenium imidized polymer thereof can be used. A liquid crystal alignment agent other than a compound containing one carboxylic acid group in the molecule, a compound containing one carboxylic acid anhydride group in the molecule, and a compound selected from a compound having one tertiary amino group in the molecule (for example, Patent Document 3) And other proposals.

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 thereof obtained from tetracarboxylic dianhydride and a specific diamine compound with cyclobutane (for example, Patent Document 4). Further, in a liquid crystal display device of a lateral electric field driving method, a method of suppressing image sticking due to AC driving is known, and it has been known to use a liquid crystal alignment property and have a large interaction with liquid crystal molecules. A method of a specific liquid crystal alignment film (for example, Patent Document 5).

However, in recent years, 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, in the polymer component constituting the polyimine-based liquid crystal alignment agent, when the polyglycolate is heat-treated during the imidization of the oxime, the molecular weight is not lowered, so that stability can be obtained. Report on liquid crystal alignment, excellent reliability, and the like (for example, Patent Document 6). However, polyglycolate generally has a problem of generating a large amount of residual electric charge when a DC voltage is applied due to high volume resistance. However, there has been no method for improving the properties of a polyimine-based liquid crystal alignment agent containing the polyphthalate.

[Previous Technical Literature]

[Patent Literature]

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

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

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

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

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

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

The present inventors have begun research on a liquid crystal alignment obtained by blending a polyglycolate with a polyglycine having excellent electrical properties in a method for improving the characteristics of a liquid crystal alignment agent containing the above polyphthalate. Agent. However, the liquid crystal alignment film obtained by the liquid crystal alignment agent obtained by mixing the polyphthalate with polyphthalic acid has not been satisfactory in terms of liquid crystal alignment and electrical properties.

That is, the liquid crystal alignment film obtained by the liquid crystal alignment agent containing the polyphthalate and the poly-proline does not cause white turbidity, and in the case where the liquid crystal display element is used at a high temperature, the voltage retention rate is lowered. When the DC voltage is accumulated, image sticking occurs, and an image or the like is caused by an AC drive.

The present invention provides a liquid crystal alignment agent containing a polyphthalate and a polyaminic acid, which can have excellent liquid crystal alignment and electrical properties, and can also have transparency without white turbidity. A liquid crystal alignment agent for a liquid crystal alignment film is intended.

As a result of analysis by a liquid crystal alignment film formed of a liquid crystal alignment agent containing a polyphthalate and polyphthalic acid, it was confirmed that fine irregularities were formed on the surface of the film. Further, in the case where a polyphthalate having a specific structure was used, it was confirmed that the fine unevenness on the surface of the film was further enlarged. However, the fine concavities and convexities generated on the surface of the film may be an organic solvent used in the liquid crystal alignment agent, and may contain two or more organic solvents having a high affinity with a polyglycolate having a specific structure. When a mixed solvent of a solvent such as an organic solvent having a high affinity with polyglycine is used, when the ratio of the two or more organic solvents is controlled, it is found that the phase of the polyglycolate and the poly-proline Separating, the fine concavities and convexities can be suppressed to a low degree, and when the fine concavities and convexities generated on the surface of the film are lowered, the liquid crystal alignment agent obtained by mixing the polyphthalate with the polyamic acid can have the above-mentioned Various difficulties are eliminated, thus completing the present invention.

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

A liquid crystal alignment agent containing the following components (A), (B) and (C).

(A) Ingredients:

a tetracarboxylic acid dialkyl ester derivative containing 60 mol% or more of a dicarboxylic acid dialkyl ester derivative represented by the following formula (1) in the tetracarboxylic acid dialkyl ester derivative, and

a diamine containing at least one diamine selected from the group consisting of diamines represented by the following formulas (2) to (5)

The resulting polyphthalate,

(In the formula (1), R ₁ is an alkyl group having 1 to 5 carbon atoms, and R ₂ is a hydroxyl group or a chlorine atom).

(In the formulae (2) to (5), A ₁ is a single bond, an ester bond, a guanamine bond, a thioester bond, or an organic group having a carbon number of 2 to 10, and A ₂ is a halogen atom. a hydroxyl group, an amine group, a thiol group, a nitro group, a phosphoric acid group, or a monovalent organic group having 1 to 20 carbon atoms, a is an integer of 1 to 4, and a is 2 or more, and the structure of A ₂ may be the same Or different);

(B) component: polyamic acid obtained from tetracarboxylic dianhydride and diamine;

(C) component: at least one organic solvent (C1) selected from the group consisting of γ-butyrolactone or a derivative thereof, and N-methyl-2-pyrrolidone, 1,3-dimethyl a mixed solvent of at least one organic solvent (C2) selected from the group consisting of 1,3-Dimethylimidazolidinone or a derivative thereof, which is an organic solvent (C2) content, relative to The mixed solvent of the organic solvent (C1) and the organic solvent (C2) in a total amount of 2% by mass to 30% by mass.

2. The liquid crystal alignment agent according to the above aspect, wherein the content ratio of the component (A) to the component (B) is 1/9 to 9/1 in the mass ratio (A/B), and the component (C) The content is 70% by mass or more based on the total amount of the component (A), the component (B), and the component (C).

3. The liquid crystal alignment agent according to the above 1 or 2, wherein the component (A) is a diamine represented by the above formulas (2) to (5) in an amount of 40 to 100 mol% based on the total diamine. A polyglycolate obtained by grouping a diamine of at least one selected diamine.

4. The liquid crystal alignment agent according to any one of the above-mentioned items 1 to 3, wherein the component (A) is a group comprising a diamine represented by the formula (2) and a diamine represented by the formula (3) a diamine of at least one selected from the group consisting of a diamine selected from the group consisting of a diamine represented by the formula (4) and a diamine represented by the formula (5), and a diamine obtained The resulting polyphthalate.

5. The liquid crystal alignment agent according to any one of the above-mentioned, wherein the component (A) is a diamine represented by the formula (2) and a diamine represented by the formula (4). A polyphthalate obtained from a diamine of at least one diamine selected from the group.

In the liquid crystal alignment agent of the above formula (4), A ₂ of the above formula (4) is a structure represented by the following formula (6).

[Chemical 4]

─A ₃ -R ₃ (6)

(A ₃ in the formula (6) is a single bond, -O-, -S-, -NR' ₃ -, an ester bond, a guanamine bond, a thioester bond, a urea bond, a carbonate bond, Or a urethane linkage, R ₃ is selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkynyl group, an aryl group, and a combination thereof, which may have a substituent, and the groups may be selected. There are substituents. R' _{3 is selected} from a hydrogen atom, or an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and a combination obtained by the combination, and the groups may have a substituent).

7. The liquid crystal alignment agent according to any one of the above-mentioned items 1 to 6, wherein the component (A) is selected by using a group containing diamines of the following formulas (A-1) to (A-5). A polyphthalate obtained from at least one diamine diamine.

The liquid crystal alignment agent according to any one of the above-mentioned items (1), wherein the component (A) is a diamine containing the above formula (1), and the above formula (A-1) to (A-5) a polyphthalate obtained from a diamine of at least one diamine selected in the group.

The liquid crystal alignment agent according to any one of the above-mentioned items 1 to 8, wherein the component (B) is formed by using a tetracarboxylic dianhydride containing the following formulas (B-1) to (B-9). The polyamic acid obtained from at least one of the tetracarboxylic dianhydrides selected from the group.

The liquid crystal alignment agent of any one of the above-mentioned (1), wherein the component (B) is the above formula (B-1) to (20% by mole or more based on the total tetracarboxylic dianhydride). B-9) Polyphthalic acid obtained by grouping at least one tetracarboxylic dianhydride of a tetracarboxylic dianhydride and a diamine.

The liquid crystal alignment agent according to any one of the above-mentioned items 1 to 10, wherein the component (B) contains at least one selected from the group consisting of the following formulas (B-10) to (B-13). The polyamine obtained by the diamine.

The liquid crystal alignment agent according to any one of the above-mentioned items (1), wherein the component (B) contains the above formula (B-10) to (B-) in an amount of 20 mol% or more based on the total diamine. 13) Polylysine obtained by grouping at least one of the diamine diamines selected.

The liquid crystal alignment agent according to any one of the above 1 to 12, wherein the organic solvent (C1) of the component (C) is γ-butyrolactone, and the organic solvent (C2) is N-methyl-2- Pyrrolidone.

The liquid crystal alignment agent according to any one of the above-mentioned, wherein the component (C) is a mixed solvent of γ-butyrolactone and N-methyl-2-pyrrolidone, and the component (C) The total amount of the components (A), (B), and (C) is 80% by mass or more.

A liquid crystal alignment film obtained by coating and baking a liquid crystal alignment agent according to any one of the above 1 to 14.

A liquid crystal alignment film obtained by applying and baking a liquid crystal alignment agent according to any one of the above 1 to 14 and irradiating the radiation of polarized light.

The present invention provides an effect of having low fine concavities and convexities on the surface of a liquid crystal alignment film regardless of a coating method such as relief printing or inkjet coating. In addition, the obtained liquid crystal alignment film can reduce the residual image caused by the AC driving, thereby improving the interface characteristics between the liquid crystal and the liquid crystal alignment film, and can also improve the electrical characteristics such as voltage holding ratio, ion density, and DC voltage residual. A liquid crystal alignment agent that enhances reliability.

In the present invention, the organic solvent used for the liquid crystal alignment agent contains two or more organic solvents having a high affinity with a polyglycolate having a specific structure, and has a high affinity with polyglycine. When a mixed solvent of an organic solvent such as an organic solvent is used to control the ratio of the two or more organic solvents, the fine unevenness generated on the surface of the film is lowered, and the polyglycolate is contained. In the case of a liquid crystal alignment agent of polylysine, the above problems can be eliminated, and the reason is not clear, but the effect obtained by the following reason is almost the same.

The polyglycolate having the specific structure described in the present invention has high affinity for γ-butyrolactone and its derivative (organic solvent (C1)), N-methyl-2-pyrrolidone or 1 , 3-dimethyltetrahydroimidazolone and its derivatives (organic solvent (C2)) have a tendency to have low affinity. Further, polylysine generally has a high affinity for the above organic solvent (C2). The present inventors have found that when a polyglycolate obtained by dissolving in an organic solvent (C1) is blended with a polylysine dissolved in an organic solvent (C2), it is subjected to formation of polyamine. The effect of the organic solvent (C2) of the poor solvent of the acid ester changes the polylysine and the polyamic acid to a phase separation state.

This phenomenon is presumed to be related to the solubility of the above polyglycolate and polylysine. Conventionally, after coating a liquid crystal alignment agent by letterpress printing or inkjet coating, the organic solvent (C1) having a high vapor pressure is dried compared to the organic solvent (C2) when the coating film is dried at 50 to 120 °C. It is volatilized earlier than the organic solvent (C2). Thus, the organic solvent (C2) which forms the poor solvent of the polyphthalate in the film exhibits an excessive state, which promotes aggregation or precipitation of the polyphthalate, so that before the polyglycolate moves to the surface layer of the film, Since agglomerates of polyphthalate are formed in the polyamine acid phase, a film having a large number of fine irregularities formed on the surface of the film is formed.

Further, when the organic solvent (C2) is too small, the aggregation or precipitation of the polyaminic acid is promoted, and the aggregate of the polyaminic acid is formed in the polyphthalate phase, so that a film having a large number of fine irregularities formed on the surface of the film is formed.

On the other hand, the liquid crystal alignment agent of the present invention, even in the case of using a polyglycolate having a specific structure, is controlled by the ratio of the organic solvent (C1) to the organic solvent (C2). The polylysine is phase-dissociated without agglomeration or precipitation, and the polyphthalate is not mixed with the poly-proline in the vicinity of the surface of the membrane, and the poly-proline is not present in the membrane and at the substrate interface. A state in which it is mixed with a polyphthalate.

That is, since the surface of the obtained liquid crystal alignment film is separated from the polylysine by phase separation, a smooth surface can be formed without forming irregularities, and the phenomenon of white turbidity of the film due to occurrence of unevenness can be reduced. Subsequently, the liquid crystal alignment film having a smooth surface having no unevenness covers the surface of the film having a polyamic acid ester having an orientation stability and excellent reliability, and has excellent electrical properties due to the inside of the film and the electrode interface. It has excellent properties due to reasons such as polyamine.

[Embodiment of the Invention]

<(A) component>

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

In the (A) component of the present invention, the tetracarboxylic acid dialkyl ester derivative of the tetracarboxylic acid dialkyl ester represented by the following formula (1) is contained in the tetracarboxylic acid dialkyl ester derivative, and is contained in the tetracarboxylic acid dialkyl ester derivative. A polyglycolate obtained by a polycondensation reaction with a diamine containing at least one diamine selected from the group consisting of the diamines represented by the following formulas (2) to (5).

In the formula (1), R ₁ is an alkyl group having 1 to 4 carbon atoms, and R ₂ is a hydroxyl group or a chlorine atom. Me is a methyl group.

Specific examples of R ₁ include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group and the like. The polyglycolate is an increase in the number of carbon atoms in the alkyl group, and the temperature at which the ruthenium is increased is increased. Therefore, the viewpoint of how R ₁ is easily imidized by heat is methyl or ethyl. For better, methyl is especially good.

It is more preferable that R ₂ is a chlorine atom to form a bis(chlorocarbonyl) compound which is highly reactive with a diamine.

The diamine which is polycondensed with the dicarboxylic acid dialkyl ester derivative represented by the formula (1), and which is at least one selected from the group consisting of the diamines represented by the formulas (2) to (5). a diamine in which at least one diamine selected from the group consisting of the diamine represented by the formula (2) and the diamine represented by the formula (3), and the diamine represented by the formula (4) Further, in the case where at least one of the diamines selected from the group consisting of the diamines represented by (5) is used, the solubility of γ-butyrolactone can be improved, and it is more preferable. In particular, in the case of a diamine containing at least one diamine selected from the group consisting of the diamine represented by the formula (2) and the diamine represented by the formula (4), a liquid crystal alignment property can be obtained. The liquid crystal alignment film is better.

In the formulae (3) and (5), A ₁ is a single bond, an ester bond, a guanamine bond, a thioester bond, or an organic group having a carbon number of 2 to 10 valence.

In A ₁ , the ester linkage is represented by -C(O)O-, or -OC(O)-.

The guanamine bond is a structure represented by -C(O)NH-, or -C(O)NR-, -NHC(O)-, -NRC(O)-. R is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a thioester bond having a carbon number of 1 to 10, or a combination thereof.

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 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. An aryl group such as a phenyl group or the like. The thioester linkage is such as that represented by -C(O)S-, or -SC(O)-.

When A ₁ is an organic group having 2 to 10 carbon atoms, it may be represented by the structure of the following formula (6).

[化12]

─A ₄ -R ₄ -A ₅ -R ₅ -A ₆ ─ (6)

In the formula (6), A ₄ , A ₅ and A ₆ are each independently a single bond, or, -O-, -S-, -NR ₈ -, an ester bond, a guanamine bond, a thioester bond, a urea Bonding, carbonate bonding, urethane bonding. R ₈ is a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof, and is, for example, the same as the above-mentioned alkyl group, alkenyl group, alkynyl group or aryl group. An illustration.

In A ₄ , A ₅ and A ₆ , the ester bond, the guanamine bond, and the thioester bond have the same structure as the ester bond, the guanamine bond, and the thioester bond described above.

A urea bond, such as the structure represented by -NH-C(O)NH-, or -NR-C(O)NR-. R is an alkyl group, an alkenyl group, an alkynyl group or an aryl group having 1 to 10 carbon atoms, or a combination thereof, and examples thereof include the same examples as the alkyl group, the alkenyl group, the alkynyl group and the aryl group described above.

Carbonate linkage, such as the structure represented by -O-C(O)-O-.

A urethane linkage, such as -NH-C(O)-O-, -OC(O)-NH-, -NR-C(O)-O-, or -OC(O)-NR- Indicates the construction. R is an alkyl group, an alkenyl group, an alkynyl group or an aryl group having 1 to 10 carbon atoms, or a combination thereof, and examples thereof include the same examples as the alkyl group, the alkenyl group, the alkynyl group and the aryl group described above.

In the formula (6) R ₄ and R _5, each independently represent a single bond, or a C 1-10 alkyl of extension, alkenylene group, an alkynyl group extends, an arylene group, and combination group of the plurality of the resultant Alternatively, the groups may have a substituent. In the case where any one of R ₄ and R ₅ is a single bond, R ₄ or R _{5 is a} group derived from an alkyl group having 2 to 10 carbon atoms, an alkenyl group, an alkynylene group, an extended aryl group, and a combination thereof. Selected, the groups may have a substituent.

The alkylene group is, for example, a structure obtained by removing one hydrogen atom from the alkyl group. More specifically, for example, methyl, 1,1-extended ethyl, 1,2-extended ethyl, 1,2-extended propyl, 1,3-extended propyl, 1,4-tert-butyl 1,2-terminated butyl, 1,2-extended pentyl, 1,2-extended hexyl, 2,3-butylene, 2,4-extended pentyl, 1,2-cyclopropyl, 1 , 2-cyclobutylene, 1,3-cyclobutylene, 1,2-cyclopentyl, 1,2-cyclohexyl, and the like.

The above-described alkenyl group is, for example, a structure obtained by removing one hydrogen atom from the above alkenyl group. More specifically, for example, 1,1-extended vinyl, 1,2-extended vinyl, 1,2-extended ethylene methyl, 1-methyl-1,2-vinyl, 1,2- Ethylene-1,1-extended ethyl, 1,2-extended ethylene-1,2-extended ethyl, 1,2-extended ethylene-1,2-extended propyl, 1,2-extended ethylene-1, 3-propyl, 1,2-extended ethylene-1,4-butylene, 1,2-extended ethylene-1,2-butylene, and the like.

An alkynyl group, for example, a structure obtained by removing one hydrogen atom from the alkynyl group described above. More specifically, for example, an ethynyl group, an exoacetylene methyl group, an exoacetylene-1,1-extended ethyl group, an exoacetylene-1,2-extended ethyl group, an exoacetylene-1,2-propanyl group, Ethylene acetyl-1,3-propanyl, ethene-1,4-butylene, acetylene-1,2-butylene and the like.

The aryl group is, for example, a structure obtained by removing one hydrogen atom from the above aryl group. More specifically, for example, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, and the like.

The alkyl group, the alkenyl group, the alkynylene group, the extended aryl group, and the group obtained by combining the above may have a substituent at a carbon number of 1 to 20, and may further form a ring via a substituent. structure. 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 organic oxy group, an organic thio group, an organic decyl group, a decyl group, an ester group, a thioester group, a phosphate group, a decyl group, and an aryl group. , alkyl, alkenyl, alkynyl and the like.

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

The organooxy group in the substituent, such as an alkoxy group, an alkenyloxy group, an aryloxy group or the like, is represented by -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 alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group and the like.

The organothio group in the substituent, for example, the structure represented by -S-R such as an alkylthio group, an alkenethio group, an arylthio group or the like. This R is, for example, the aforementioned alkyl group, alkenyl group, aryl group or the like. These R may be further substituted by the aforementioned substituents. Specific examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio 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, and may be, for example, the aforementioned alkyl group, aryl group or the like. These R may be further substituted by the aforementioned substituents. Specific examples of the alkyl fluorenyl group include a trimethyl decyl group, a triethyl decyl group, a tripropyl decyl group, a tributyl 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. 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.

The thioester group in the substituent, such as -C(S)O-R, or the structure represented by -OC(S)-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.

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

When a diamine having a high linear structure or a rigid structure is used, since a liquid crystal alignment film having a good liquid crystal alignment property can be obtained, the structure of A ₁ is a single bond, or the following formula (A1-1) to (A1) 23) The construction is better.

In the above formulas (4) and (5), A ₂ is a halogen atom, a hydroxyl group, an amine group, a thiol group, a nitro group, a phosphoric acid group, or an organic group having a carbon number of 1 to 20, and a is 1 to An integer of 4, where a is 2 or more, the configurations of A ₂ may be the same or different.

The halogen atom is, for example, the same as the above-described halogen atom.

The amine group may be represented by a structure represented by -NH ₂ , -NHR, or -NR(R)-. R is an alkyl group, an alkenyl group, an alkynyl group or an aryl group having 1 to 10 carbon atoms, or a combination thereof, and examples thereof include the same examples as the alkyl group, the alkenyl group, the alkynyl group and the aryl group described above.

An organic group having a carbon number of 1 to 20, for example, an organic oxy group, an organic thio group, an organic decyl group, a decyl group, an ester group, a thioester group, a phosphate group, a decyl group, an alkyl group, an alkenyl group, Alkynyl, aryl, and the like.

The organic oxy group is, for example, a structure represented by -O-R such as an alkoxy group, an alkenyloxy group or an aryloxy group. This R is, for example, the aforementioned alkyl group, alkenyl group, aryl group or the like. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group and the like.

The organic sulfur group is, for example, a structure represented by -S-R such as an alkylthio group, an arylthio group or an arylthio group. This R is, for example, the aforementioned alkyl group, alkenyl group, aryl group or the like. Specific examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group and the like.

Alkyl silicones, for example, -Si- (R) ₃ represented by the structure. The R may be the same or different, and may be, for example, the aforementioned alkyl group, aryl group or the like. Specific examples of the alkyl fluorenyl group include a trimethyl decyl group, a triethyl decyl group, a tripropyl decyl group, a tributyl decyl group, and the like.

A thiol group, such as the structure represented by -C(O)-R. This R is, for example, the aforementioned alkyl group, alkenyl group, aryl group or the like. 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.

An ester group such as -C(O)O-R, or a structure represented by -OC(O)-R. This R is, for example, the aforementioned alkyl group, alkenyl group, aryl group or the like.

A thioester group such as -C(S)O-R, or a structure represented by -OC(S)-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.

Phosphate group, for example, a structure represented by -OP(O) to (OR) ₂ . The R may be the same or different, and may be, for example, the aforementioned alkyl group, aryl group or the like.

a structure represented by amidino group, such as -C(O)NH ₂ , or -C(O)NHR, -NHC(O)R, -C(O)N(R) ₂ , -NRC(O)R . The R may be the same or different, and may be, for example, the aforementioned alkyl group, aryl group or the like.

The alkyl group, the alkenyl group, the alkynyl group, and the aryl group have the same contents as the alkyl group, the alkenyl group, the alkynyl group, and the aryl group described above.

The above-mentioned alkyl group, alkenyl group, alkynyl group, and aryl group may have a substituent when the total number of carbon atoms is 1 to 20, and may further form a ring structure via a substituent. Further, the formation of a ring structure via a substituent means that the substituents are bonded to each other or a part of the substituent is bonded to a part of the parent skeleton to form a ring structure.

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

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

The organooxy group in the substituent, such as an alkoxy group, an alkenyloxy group, an aryloxy group or the like, is represented by -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 alkoxy 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, a decyloxy group, a decyloxy group, and a lauryloxy group. Base.

The organothio group in the substituent, for example, the structure represented by -S-R such as an alkylthio group, an alkenethio group, an arylthio group or the like. This R is, for example, the aforementioned alkyl group, alkenyl group, aryl group or the like. These R may be further substituted by the aforementioned substituents. Specific examples of the alkylthio group are, for example, methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio, heptylthio, octylthio, decylthio , mercaptothio group, laurylthio 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, and may be, for example, the aforementioned alkyl group, aryl group or the like. These R may be further substituted by the aforementioned substituents. Specific examples of the alkyl fluorenyl group are, for example, trimethyldecyl, triethyl decyl, tripropyl decyl, tributyl decyl, tripentyl decyl, trihexyl decyl, pentyl dimethyl decyl And hexyl dimethyl decyl, octyl dimethyl decyl, decyl dimethyl decyl 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. 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.

The thioester group in the substituent, such as -C(S)O-R, or the structure represented by -OC(S)-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.

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

The urethane group as a substituent is, for example, a structure represented by -OC(O)NH ₂ or -OC(O)NHR, -NHC(O)-OR, or -NR-C(O)OR. The R may be the same or different, and may be, for example, the aforementioned alkyl group, aryl group or 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 the formulae (4) and (5), A ₂ is a group having an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof, and the carbon number thereof is preferably from 1 to 14. When A ₂ is an alkyl group, an alkenyl group, an alkynyl group, an aryl group having a carbon number of 15 or more, or a combination of these, it may cause a decrease in the liquid crystal alignment property accompanying the introduction amount, or may cause difficulty in controlling the pretilt angle. possibility.

A ₂ in the above formula (4) and formula (5) is preferably a structure represented by the following formula (6).

[化18]

─A ₃ -R ₃ (6)

A ₃ in the formula (6) is a single bond, -O-, -S-, -NR' ₃ -, an ester bond, a guanamine bond, a thioester bond, a urea bond, a carbonate bond, or Carbamate-bonded, R ₃ is an alkyl group, an alkenyl group, an alkynyl group, an aryl group having a carbon number of 1 to 10, preferably 1 to 5 which may have a substituent, and a combination thereof Alternatively, the groups may have a substituent. R' _{3 is selected} from a hydrogen atom, or an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and a combination obtained by the combination, and the groups may have a substituent).

Further, the configuration of A ₂ is a structure having a dissociation group which is dissociated by heating, and the solubility of the polymer can be improved without affecting the liquid crystal alignment property, the pretilt angle, and the like. The structure of A ₂ having a dissociation group which is dissociated by heating is preferably a structure represented by the following formulas (A2-1) to (A2-24).

The ratio of the diamine represented by the above formulas (2) to (5) is preferably from 5 mol% to 100 mol% in the total diamine. When the ratio of the diamine represented by the above formulas (2) to (5) is higher, a liquid crystal alignment film having a good liquid crystal alignment property can be obtained, and it is more preferably 40 mol% to 100 mol%. It is preferably from 60 mol% to 100 mol%.

Further, the diamine which is a raw material of the component (A) is at least one selected from the group consisting of a diamine represented by the formula (2) and a diamine represented by the formula (3), and It is preferred that at least one diamine selected from the group consisting of the diamine represented by the formula (4) and the diamine represented by the formula (5). The diamine which is a raw material of the component (A) is, in particular, a diamine containing the diamine represented by the formula (2) and at least one selected from the group consisting of the diamine represented by the formula (4). good. Thus, in particular, the solubility in γ-butyrolactone as a solvent can be improved.

In this case, the amount of the diamine represented by the formula (2), or the total amount of the diamine represented by the formula (2) and the diamine represented by the formula (3), and the formula (4) The amount of the diamine used, or the total amount of the diamine represented by the formula (4) and the diamine represented by the formula (5), is preferably 95/5 to 60/40 in terms of the molar ratio, more preferably Good for 90/10 ~ 80/20.

The diamine has a structure in which it is structurally rigid, and in order to obtain a liquid crystal alignment film having excellent liquid crystal alignment, a diamine of the polyphthalate of the present invention is obtained to contain a formula (A) a diamine of at least one diamine selected from the group consisting of -1) to (A-5), particularly a diamine obtained by containing the diamine and the diamine represented by the above formula (2) good. In this case, the amount of the diamine used in the above formula (2) and the amount of the diamine selected from the group of the formula (A-1) to the formula (A-5) of the diamine are used. The molar ratio is preferably 95/5 to 60/40, more preferably 90/10 to 80/20.

In the present invention, the tetracarboxylic acid dialkyl ester preferably contains 60 mol% or more of the tetracarboxylic acid dialkyl ester represented by the above formula (1), more preferably 80 mol% or more. In this case, the tetracarboxylic acid dialkyl ester derivative represented by the above formula (1) and the tetracarboxylic acid dialkyl ester derivative represented by the following formulas (10) to (11) can be used as the tetracarboxylic acid. derivative.

In the above formulae (10) to (11), X is a tetravalent organic group, and R ₁ includes a preferred embodiment, and is also the same as in the case of the formula (1). X is not particularly limited, and specific examples thereof include, for example, the structures represented by the following X-1 to X-46. Further, these tetracarboxylic acid derivatives may be used singly or in combination of two or more.

Further, in the present invention, the diamine represented by the above formulas (2) to (5) is preferably contained in an amount of from 5 to 100 mol%, more preferably from 50 to 100 mol%, based on the total diamine. The diamine represented by the following formula (12) can also be used together with the diamine represented by the above formulas (2) to (5).

In the formula (12), R ₆ and R ₇ 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. Specific examples of the above alkyl group, alkenyl group, and alkynyl group are the same as those described above.

The above-mentioned 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 and the like. Specific examples of the respective substituents are the same as those 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, so that R ₆ and R _{7 have} a hydrogen atom or a carbon number of 1 to 5 which may have a substituent. The alkyl group is more preferably a hydrogen atom, a methyl group or an ethyl group.

In the above formula (12), Y is a divalent organic group. Y is not particularly limited, and specific examples thereof include, for example, the structures represented by the following formulas Y-1 to Y113. Further, two or more kinds of diamine compounds may also be used. Among them, the viewpoint of good liquid crystal alignment is obtained, and it is preferable to introduce a diamine having high linearity into the polyphthalate, and Y ₁ is Y-7, Y-10, Y-11, Y-12. , Y-13, Y-21, Y-22, Y-23, Y-25, Y-26, Y-27, Y-41, Y-42, Y-43, Y-44, Y-45, Y -46, Y-48, Y-61, Y-63, Y-64, Y-71, Y-72, Y-73, Y-74, Y-75, Y-98 diamine are more preferred. Further, in order to increase the pretilt angle, it is preferred to introduce a diamine having a long-chain alkyl group, an aromatic ring, an aliphatic ring, a steroid skeleton, or a combination thereof in a side chain into a polyphthalate. Y ₁ is Y-76, Y-77, Y-78, Y-79, Y-80, Y-81, Y-82, Y-83, Y-84, Y-85, Y-86, Y- 87. Y-88, Y-89, Y-90, Y-91, Y-92, Y-93, Y-94, Y-95, Y-96, or Y-97 diamine is more preferred. These diamines may have an arbitrary pretilt angle when 1 to 50 mol% is added to the total diamine, and more preferably 5 to 20 mol%.

[(B) ingredients]

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

The component (B) of the present invention is a polyamic acid obtained by polycondensation of a tetracarboxylic dianhydride and a diamine. The tetracarboxylic dianhydride can be represented by the following formula (13), wherein X ₁ is a tetravalent organic group, and the structure thereof is not particularly limited. When specific examples are given, for example, the structures of the above formulas (X-1) to (X-46) and the like.

The diamine compound can be represented by the following formula (14): wherein Y ₁ is a divalent organic group, and the structure thereof is not particularly limited. For the specific examples, for example, the structures of the above formulae (Y-1) to (Y-99) and (Y-110) to (Y-113) are used.

(wherein R ₆ and R ₇ are the same as defined in the above formula (12)).

When the component (B) is deposited on the surface of the film, there is a possibility that the alignment of the liquid crystal is hindered. Further, when the component (A) can be deposited on the surface of the film, a liquid crystal alignment film having excellent reliability or image retention characteristics can be obtained in addition to the liquid crystal alignment property. Therefore, the polyamic acid of the component (B) is preferably a polyamic acid having a high polarity which can improve the surface transition property of the component (A) and a high solubility. In view of the above, the tetracarboxylic dianhydride and the diamine containing at least one of the tetracarboxylic dianhydrides selected from the group of the above formulas (B-1) to (B-9) are used. Polyglycine is preferred. The ratio of use of at least one of the tetracarboxylic dianhydrides selected in the group of (B-1) to (B-9) is preferably from 5 mol% to 100 mol% based on the total tetracarboxylic dianhydride. . The higher the ratio of use, the higher the polarity and solubility of the polymer, and more preferably from 20 mol% to 100 mol%, and most preferably from 40 mol% to 100 mol%.

From the same viewpoint, the use of a diamine having a substituent having a high polarity can also cause the polyamic acid of the component (B) to be interposed between the inside of the film and the substrate interface. The diamine having a highly polar substituent is preferably, for example, a diamine having a secondary or tertiary amine group, a hydroxyl group, a guanamine group, a urea group, or a carboxyl group. Specifically, for example, Y _{1 of the} above formula (14) is contained in Y-19, Y-31, Y-40, Y-45, Y-49 to Y-51, Y-61, Y-98, Y-99, etc. Y-98 and Y-99 of the carboxyl group are more preferred.

The amount of the diamine compound having a substituent having a high polarity is preferably from 5 mol% to 100 mol% based on the total diamine. When the amount of use is higher, the polarity of the polymer can be increased, and from the viewpoint of increasing the film surface ratio of the component (A), it is preferably from 10 mol% to 100 mol%, and more preferably from 30 mol% to 100 mol%. % is the best.

The tetracarboxylic dianhydride of the raw material of the component (B) contains at least one kind of tetracarboxylic acid selected from the group consisting of the tetracarboxylic dianhydrides of the following formulas (B-1) to (B-9). Acid dianhydride is preferred.

At least one type of tetracarboxylic dianhydride selected from the group consisting of the formulae (B-1) to (B-9) is used as the tetracarboxylic dianhydride used as a raw material of the component (B). More than 20% by mole, more preferably 40% by mole or more.

Further, the diamine which is a raw material of the component (B) is preferably at least one type of diamine selected from the group consisting of the following formulas (B-10) to (B-13).

At least one type of diamine selected in the group of the above formulas (B-10) to (B-13) is preferably used in the total diamine used as the raw material of the component (B). More than %, more preferably 40% by mole or more.

[(C) ingredient]

The component (C) of the present invention contains at least one organic solvent (C1) selected from the group consisting of γ-butyrolactone and a derivative thereof, and N-methyl-2-pyrrolidone, 1 , at least one organic solvent (C2) selected from the group consisting of 3-dimethyltetrahydroimidazolidone and a derivative thereof, and the content of the organic solvent (C1) relative to the organic solvent (C1) The total amount of the organic solvent (C2) is a mixed solvent of 2 to 30% by mass.

The γ-butyrolactone of the organic solvent (C1) and the derivative thereof are not particularly limited as long as it is an organic solvent having a lactone structure, but are suitable as a polycondensate for dissolving the component (A) of the present invention. When the solvent of the amine ester is used, γ-butyrolactone and γ-valerolactone are particularly preferred.

An organic solvent (C2) such as N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, or a derivative thereof such as N-methyl-2-pyrrolidone, N Ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, 1,3-dimethylimidazolidinone and the like. When the boiling point is too high, the solvent will remain in the film, and there is a possibility that the characteristics of the liquid crystal alignment film are deteriorated, so N-methyl-2-pyrrolidone and 1,3-dimethyl-2-tetra Hydrozimidazolone is preferred, and N-methyl-2-pyrrolidone is more preferred.

The polyphthalate ester of the component (A) of the present invention has a high affinity for the organic solvent (C1) and is easily dissolved in the organic solvents. However, the polyamine amide of the component (A) of the present invention has a low affinity for the organic solvent (C2), and when the content is too large, the polyamine amide of the component (A) precipitates or may affect the polymerization. The possibility of phase separation of the phthalate and polylysine. Therefore, in the component (C) of the present invention, the content of the organic solvent (C2) is preferably 2% by mass to 30% by mass based on the total amount of the organic solvent (C1) and the organic solvent (C2), more preferably It is 2% by mass to 20% by mass, and particularly preferably 5% by mass to 15% by mass.

The content of the organic solvent (C2) varies depending on the coating method of the liquid crystal alignment agent. In the case of the letterpress printing method, the solvent composition is not easily changed at the time of coating, generally 5 The mass % to 30% by mass is more preferably 5% by mass to 15% by mass.

Further, in the case of the inkjet coating method, since the liquid crystal alignment agent forms minute droplets at the time of coating, the composition of the solvent before coating and the composition of the solvent after the liquid crystal alignment agent adheres to the substrate There are different possibilities. Specifically, when γ-butyrolactone and a derivative thereof having a high vapor pressure are applied, volatilization occurs, and the content of γ-butyrolactone and a derivative thereof when attached to a substrate is lowered. Therefore, the solvent composition having a large amount of the organic solvent (C1) is preferred, and the content of the organic solvent (C2) is more preferably 2% by mass to 15% by mass, and most preferably 2% by mass to 10% by mass.

[Method for producing polyamidomate]

The component (A) of the liquid crystal alignment agent of the present invention and the polyglycolate can be produced by a known production method, and specifically, for example, the methods (a) and (b), but are not limited thereto.

(a) The case of producing a polyamidate from an acid chloride and a diamine compound

Polyammonium esters can be prepared from bis(chlorocarbonyl) compounds and diamine compounds.

Specifically, the bis(chlorocarbonyl) compound and the diamine compound are carried out in the presence of a base and an organic solvent at -20 ° C to 140 ° C, preferably 0 ° C to 50 ° C, for 30 minutes to 24 hours. It can be prepared by a reaction of 1 to 4 hours. As the base, pyridine, triethylamine or 4-dimethylaminopyridine can be used, but from the viewpoint that the reaction proceeds stably, it is preferred to use pyridine. When the amount of the base added is too small, it is not easy to remove. When the amount is too small, the molecular weight is too small. Therefore, the bis(chlorocarbonyl) compound is preferably 2 to 4 times moles.

The solvent used in the production of the polyamidolate of the above formula (i) is preferably N-methyl-2-pyrrolidone or γ-butyrolactone in terms of the solubility of the monomer and the polymer. These may be used alone or in combination of two or more. When the concentration at the time of production is too high, the precipitation of the polymer is likely to occur, and when the molecular weight is too low, the molecular weight cannot be increased. Therefore, it is preferably 1 to 30% by mass based on the total amount of the bis(chlorocarbonyl) compound and the diamine compound in the reaction liquid. It is more preferably 5 to 20% by mass. Further, in order to prevent hydrolysis of the bis(chlorocarbonyl) compound, it is preferred that the solvent used in the production of the polyglycolate is dehydrated as much as possible, and it is preferred to prevent the incorporation of other gases in a nitrogen atmosphere.

(b) The case of producing a polyamidate from a dialkyl dicarboxylate and a diamine compound

The polyamine ester can be obtained by condensing a dialkyl tetracarboxylate with a diamine compound via a condensing agent.

Specifically, the dicarboxylic acid dialkyl ester and the diamine compound are carried out in the presence of a condensing agent, a base, and an organic solvent at 0 ° C to 140 ° C, preferably 0 ° C to 100 ° C, for 30 minutes to 24 hours. It can be obtained in an hour, preferably from 3 to 15 hours.

Among the above condensing agents, triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, N,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-Dihydro-2-thio(keto)-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 dialkyl dicarboxylate.

As the base, a tertiary amine such as pyridine or triethylamine can be used. When the amount of the base is too large, it is not easy to remove. When the amount is too small, the molecular weight is too small, and it is generally 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 method for producing the above three polyphthalate esters, a high molecular weight polyglycolate or the like can be obtained, and the production method of (a) 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.

[Manufacture of polyamide]

The component (B) of the liquid crystal alignment agent of the present invention, for example, the polyamic acid which is a raw material of the polyphthalamide of the component (A), can be subjected to condensation polymerization of a tetracarboxylic dianhydride and a diamine compound. be made of.

In the case of producing polyamic acid, the tetracarboxylic dianhydride and the diamine compound are preferably carried out in the presence of an organic solvent at -20 ° C to 140 ° C, preferably 0 ° C to 50 ° C, for 30 minutes to 24 hours. It can be obtained in an hour, preferably from 1 to 12 hours. The solvent used in the production of polylysine of the above formula (iii), in terms of the solubility of the monomer and the polymer, N,N-dimethylformamide, N-methyl-2-pyrrolidine The ketone and γ-butyrolactone are preferred, and one type of these may be used alone or two or more types may be used in combination. When the concentration at the time of production is too high, the precipitation of the polymer is likely to occur, and when the molecular weight is too low, the molecular weight cannot be increased. Therefore, it is preferably 1 to 30% by mass based on the total amount of the tetracarboxylic dianhydride and the diamine compound in the reaction liquid. It is more preferably 5 to 20% by mass.

The polyamine acid obtained by the above method can be used as the component (B). However, in the case where the liquid crystal alignment agent does not contain the solvent used for the polymerization, the polymer is recovered as a solid, and then The component (B) of the present invention is preferably used.

The polymer can be injected into a poor solvent while the reaction solution is sufficiently stirred, and then the polymer is precipitated and recovered. The precipitated powder is washed several times, washed with a poor solvent, and dried at room temperature or by heating to obtain a powder of purified polylysine.

The poor solvent is not particularly limited, and is generally, for example, water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene or the like.

The ratio of the diamine component used in the polymerization reaction to the tetracarboxylic acid derivative (tetracarboxylic dianhydride or tetracarboxylic acid dialkyl derivative) is from 1:0.7 to 1:1.2 in terms of molecular weight control. It is better. The closer the molar ratio is 1:1, the larger the molecular weight of the resulting polyimine precursor. The molecular weight of polyglycolate and polyaminic acid will affect the viscosity of the varnish or the physical strength of the polyimide film. Therefore, when the molecular weight of polyglycolate and poly-proline is too large, it will cause varnish coating. In the case where the workability of the cloth or the uniformity of the coating film is deteriorated, if the molecular weight is too small, the strength of the obtained polyimide film may be insufficient.

Therefore, the molecular weight of the polyperurethane and polylysine of the present invention is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, particularly preferably 10,000 to 100,000.

[Liquid alignment agent]

The liquid crystal alignment agent of the present invention contains a polyglycolate ((A) component) having a specific structure and polyglycine ((B) component), and an organic solvent (C1) and an organic solvent as described above. a mixed solvent of solvent (C2) (component (C)). In the liquid crystal alignment agent of the present invention, the ratio of the component (A) to the component (B) is preferably from 1/9 to 9/1 by mass ratio (A/B), and more preferably from 3/7 to 7/3. good. When the ratio is in this range, a liquid crystal alignment agent which is excellent in liquid crystal alignment properties or electrical properties can be provided.

In the liquid crystal alignment agent of the present invention, the content of the component (C) is preferably 70% by mass or more, and preferably 80% by mass or more based on the total amount of the component (A), the component (B), and the component (C). For better, 90% by mass or more is the best. When the content of the component (C) is too small, there is a possibility that the polymer is precipitated, and if it is too large, the concentration of the polymer may be lowered, and a coating film having a sufficient film thickness may not be obtained, which is not preferable.

Further, the total content (concentration) of the component (A) and the component (B) in the liquid crystal alignment agent of the present invention can be appropriately changed in accordance with the thickness setting of the liquid crystal alignment film to be formed, but uniform and non-formed. In view of the coating film of the defect, the component (C) is preferably contained in an amount of 0.5% by mass or more based on the organic solvent, and is preferably 15% by mass or less, particularly preferably 1% to 10% by mass, from the viewpoint of storage stability of the solution.

The liquid crystal alignment agent of the present invention is characterized by the component (C) having an organic solvent, but may contain other solvents. The solvent used for the liquid crystal alignment agent of the present invention can, for example, dissolve a solvent of a polyphthalate and a poly-proline (hereinafter also referred to as a good solvent) and a coating film can be applied when a liquid crystal alignment agent is applied to a substrate. Two types of solvents (hereinafter, also referred to as poor solvents) of uniformity.

The good solvent is not particularly limited as long as it can dissolve the polyamine amide of the component (A) and the solvent of the poly phthalic acid of the component (B). That is, when specific examples are given, for example, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N-ethyl-2-pyrrole Pyridone, N-methyl caprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl hydrazine, dimethyl hydrazine, hexamethylarylene , γ-butyrolactone, 3-methoxy-N,N-dimethylpropionamide, and the like. These may be used alone or in combination of two or more. In addition, even if the solvent of the polymer cannot be dissolved alone, a mixed solvent may be used in the range in which the polymer is not precipitated, or two or more kinds may be used as the mixed solvent.

The poor solvent is not particularly limited as long as it has a low surface tension and can improve the uniformity of the coating film. That is, when specific examples are given, for example, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy- 2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, Propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, butyl cellosolve acetate, dipropylene glycol, 2-(2-ethoxypropoxyl ) propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, and the like. These solvents may be used in combination of two or more.

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 effect of adhesion will not be exhibited, so 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, it is preferred to prevent the precipitation of the polymer and to add the solvent to improve the uniformity of the coating film. Further, in the case where a decane coupling agent is added, it may be added to the polyphthalate solution, the polyaminic acid solution, or the polyamine solution before the polyamine solution and the polyaminic acid solution are mixed. 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 (D-1) to (D-17) independently represents a tert-butoxycarbonyl group or a 9-fluorenylmethoxycarbonyl group. Further, in the case of (D-14) to (D-17), when a plurality of Ds exist 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 polyglycolate is obtained, and is contained under the polyphthalate ester of the liquid crystal alignment agent. The valinate moiety of the 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 hydrazine imidization promoter remaining in the film after baking is reduced to a minimum amount which adversely affects various characteristics of the liquid crystal alignment film, and is relative to the liquid crystal alignment agent. The valerate moiety of the following formula (12) contained in the polyamidolate has a molar concentration of 2 moles or less, more preferably 1 mole or less, and most preferably Below 0.5 m.

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.

In the liquid crystal alignment agent of the present invention, it is of course possible to add various additives such as a crosslinking agent. Further, the polyamic acid of the component (A) of the present invention and the polyamic acid of the component (B) may be used alone or in combination of two or more.

The concentration (content) of the polymer containing the polyphthalate ((A) component) and the poly-proline (component (B)) in the liquid crystal alignment agent of the present invention can be blended with the desired polyimine The thickness of the film is appropriately changed, and it is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, based on the organic solvent. When it is less than 1% by mass, it is not easy to form a uniform and defect-free coating film, and when it exceeds 10% by mass, the solution storage stability may be deteriorated.

[Method of Manufacturing Liquid Crystal Aligning Agent]

The liquid crystal alignment agent of the present invention is characterized by containing a polyphthalate ((A) component) having a specific structure and polyamic acid (component (B)).

The ratio of the component (A) is preferably 5% by mass to 95% by mass based on the total amount of the component (A) and the component (B). When the ratio of the component (A) is too small, sufficient liquid crystal alignment property may not be obtained, and when the ratio of the component (B) is too small, the effect described in the present invention may not be obtained. Therefore, the ratio of the component (A) is more preferably 20% by mass to 80% by mass, and most preferably 30% by mass to 70% by mass.

(A) A method in which the component (B) is mixed with the component (B), for example, a method in which a polyammonium ester of the component (A) and a polyamic acid powder of the component (B) are mixed and dissolved in an organic solvent, and (A) a method of mixing a powder of a polyammonium ester of a component with a polyamic acid solution of the component (B), mixing a solution of the polyamine derivative of the component (A) with a powder of the polyamide derivative of the component (B) A method, a method of mixing a polyamidate solution of the component (A) with a polyamine solution of the component (B), and the like. In the case where the polyglycolate which dissolves the component (A) is different from the good solvent of the polylysine of the component (B), a homogeneous poly (A) component of the (A) component can also be obtained (B) The method of mixing the polyamic acid mixed solution of the component is more preferably a method of mixing the polyamidate solution of the component (A) with the polyamic acid solution of the component (B).

A method of producing a polyamine phthalate solution of the component (A), preferably a method of dissolving a powder of the polyamidate of the component (A) in γ-butyrolactone or a derivative thereof or other good solvent A method of dissolving using γ-butyrolactone or a derivative thereof is more preferable. In this case, the polymer concentration is preferably from 10 to 30%, particularly preferably from 10 to 15%. Further, when the polyamine amide of the component (A) is dissolved, heating may be carried out. The heating temperature is preferably from 20 ° C to 150 ° C, and particularly preferably from 20 ° C to 80 ° C.

A method for producing a polyaminic acid solution of the component (B), for example, dissolving a powder of polyproline in N-methyl-2-pyrrolidone, 1,3-dimethylpyrrolidone, or the above-mentioned good solvent The method of using the polyaminic acid solution, and the method of using the polymerization reaction solution without treatment, and the method of using the polymerization reaction solution without treatment are more preferable. a solvent for polymerizing polyamic acid to use γ-butyrolactone or a derivative thereof, and N-methyl-2-pyrrolidone, 1,3-dimethylpyrrolidone or a derivative thereof as a mixed solvent. The method of preparing a polyamidonic acid solution is more preferable. In the case where the polyproline powder is redissolved, the polymer concentration is preferably from 10 to 30%, particularly preferably from 10 to 15%. Further, heat treatment can be performed while dissolving the powder of the polymer. The heating temperature is preferably from 20 ° C to 150 ° C, and particularly preferably from 20 ° C to 80 ° C.

When a decane coupling agent is added, it may be added to the polyamidomate solution of the component (A) before mixing the polyphthalate solution of the component (A) with the polyaminic acid solution of the component (B). a polylysine solution of the component, or both of a polyamidate solution of the component (A) and a polyamic acid solution of the component (B). Further, it may be added to a mixed solution of the polyperuric acid ester of the (A) component and the polyamic acid of the component (B). 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 interface of the substrate (B). After the polymer is sufficiently reacted with the decane coupling agent, it is preferably mixed with the polyamine amide solution of the component (A). When the amount of the decane coupling agent is too large, the unreacted substance will have an adverse effect on the alignment of the liquid crystal. If the amount is too small, the effect of the adhesion will not be exhibited. Therefore, the solid content of the polymer is 0.01 to 5.0. The mass % is preferably from 0.1 to 1.0% by mass.

When the polyammonium ester solution of the component (A) is mixed with the polyamic acid solution of the component (B), the polymer concentration is preferably from 10 to 30%, particularly preferably from 10 to 15%. Further, heat treatment may be carried out at the time of mixing, and the heating temperature is preferably 20 ° C to 100 ° C, and particularly preferably 20 ° C to 60 ° C.

In the case where a decane coupling agent or a crosslinking agent is added, in order to prevent precipitation of the polymer, it is preferred to add it before adding a poor solvent. Further, in the case of baking the coating film, a ruthenium imidization accelerator may be added in order to efficiently carry out the ruthenium imidization of the polyamidite. 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.

After adding the above-mentioned good solvent and the above-mentioned poor solvent to the mixed solution of the polyamine derivative of the component (A) and the polyamine derivative of the component (B), the mixture is diluted to a specific polymer concentration, and then obtained. The liquid crystal alignment agent of the present invention.

g. [Liquid alignment film]

In the liquid crystal alignment film of the present invention, the liquid crystal alignment agent described above is preferably filtered, applied to a substrate, dried, and fired to form a coating film. 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 which can reflect light can be used as the electrode.

The coating method of the liquid crystal alignment agent of the present invention may, for example, be a spin coating method, a printing method, an inkjet method or the like. After the liquid crystal alignment agent of the present invention is applied, it is preferably dried and baked. In order to sufficiently remove the organic solvent contained in the liquid crystal alignment agent, it is preferably at 50 to 120 ° C, preferably dried for 1 to 10 minutes. Next, it is preferred to carry out baking at 150 to 300 ° C, more preferably 150 to 250 ° C. The baking time varies depending on the baking temperature, and is preferably from 5 to 120 minutes, more preferably from 5 to 60 minutes.

The thickness of the liquid crystal alignment film of the present invention 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 coating film surface can be used as a liquid crystal alignment film after being subjected to alignment treatment such as rubbing.

A method of performing the alignment treatment on the coating film, for example, a rubbing method, a photo-alignment treatment method, or the like.

In the liquid crystal alignment film of the present invention, a liquid crystal alignment film having a liquid crystal alignment energy can be formed by irradiation of polarized light. Further, when the liquid crystal alignment film of the present invention is compared with a conventional light alignment liquid crystal alignment film, it has a light irradiation range in which a wider liquid crystal alignment property can be obtained, and even if the irradiation intensity is uneven in the substrate surface, A liquid crystal alignment film having uniform and good liquid crystal alignment properties can be obtained.

Specifically, for example, a method of irradiating the surface of the coating film with energy in a specific direction by polarized light, and if necessary, heat-treating at a temperature of 150 to 250 ° C to impart a liquid crystal alignment energy thereto. For the radiation, ultraviolet rays and visible rays having a wavelength of 100 to 800 nm can be used. In this case, ultraviolet rays having a wavelength of 100 to 400 nm are preferable, and ultraviolet rays having a wavelength of 200 to 400 nm are particularly preferable. Moreover, from the viewpoint of improving the alignment of the liquid crystal, the coated substrate may be heated to 50 to 250 ° C, and radiation may be used. Irradiation amount of the radiation, in the range of 1 ~ 10,000mJ / cm ² of preferably, in the range of 100 ~ 5,000mJ / cm ² is the particularly preferred.

[Examples]

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

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

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

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellulolytic

GBL: γ-butyrolactone

BCA: butyl cellosolve acetate

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

[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]

The molecular weight of the polyglycolate is measured by a GPC (normal temperature gel permeation chromatography) apparatus, and the number average molecular weight (hereinafter, also referred to as Mn) is calculated from the values of polyethylene glycol and polyethylene oxide. Weight average molecular weight (hereinafter, also referred to as Mw).

GPC device: made by Shodex (GPC _- 101)

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

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 the peaks, four kinds of mixed samples of 900,000, 100,000, 12,000, and 1,000, and two samples of three kinds of mixed samples of 150,000, 30,000, and 4,000 were respectively measured.

[Toppan Printing]

Angstromer (S-15 type) (made by Nippon Photo Printing Co., Ltd.), which is equipped with a 250-line/inch chrome-plated anilox roller (Anilox Roller) and a 400-line/inch APR resin printing plate, was used. The solid content of the solid content was adjusted to 6% by mass of the liquid crystal alignment agent.

[Inkjet coating]

A liquid crystal alignment agent having a solid content adjusted to 3.6% by mass was applied using an inkjet coating device (manufactured by Hitachi High-Technologies Corporation).

[Determination of the average thickness of the centerline]

The coating film of the liquid crystal alignment agent obtained by letterpress printing or inkjet coating is dried on a hot plate at a temperature of 80 ° C for 5 minutes, and baked in a hot air circulating oven at a temperature of 230 ° C for 30 minutes to 1 hour to form a film thickness. 130 nm coating film. The surface of the film of the coating film was observed using an atomic force microscope (AFM), and the average thickness (Ra) of the center line of the film surface was measured to evaluate the flatness of the film surface.

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

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

On the glass substrate, an ITO electrode having a first layer having a film thickness of 50 nm as an electrode, a second layer having a thickness of 500 nm as an insulating film, and a third layer having a comb shape as an electrode were formed. A glass substrate of an electrode for driving an edge of an ITO electrode (electrode width: 3 μm, electrode spacing: 6 μm, electrode height: 50 nm), which is driven by a fringe field switching (hereinafter referred to as FFS), is coated with liquid crystal by inkjet coating. Agent. After drying on a hot plate at 80 ° C for 5 minutes, it was baked in a hot air circulating oven at 230 ° C for 60 minutes to form a coating film having a film thickness of 100 nm. The coating film surface was irradiated with ultraviolet rays of 254 nm at 400 mJ/cm ² through a polarizing plate to obtain a substrate with a liquid crystal alignment film. Further, a glass substrate having a columnar distance controller having a height of 4 μm 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.

A rectangular wave of ±4 V/120 Hz for 4 hours was applied after the V-T characteristic (voltage-transmittance characteristic) of the FFS-driven liquid crystal cell at a temperature of 58 ° C was measured. After 4 hours, the voltage was turned off, and after leaving it at a temperature of 58 ° C for 60 minutes, the 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. Cutting the DC voltage, as determined by AC driving transmittance (Tb) 10 minutes later, the difference between the T _a and T _b of calculating remaining in transmittance difference arising from the voltage within the liquid crystal display element.

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) 220 g (0.981 mol), with methanol 2200 g (6.87 mol, 10wt times relative to 1,3-DM-CBDA), heated under reflux at 65 ° C, formed uniformly in 30 minutes Solution. The reaction solution was stirred under heating and reflux for 4 hours and 30 minutes in this state. This reaction liquid was measured using a high-speed liquid chromatography analyzer (hereinafter, abbreviated as HPLC). The analysis contents of the measurement results are as described later.

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-d6, δ ppm); 12.82 (s, 2H), 3.60 (s, 6H), 3.39 (s, 2H), 1.40 (s, 6H).

A-2. Synthesis of 1,3-DM-CBDE-C1

Under a nitrogen flow, a compound (1-1) 234.15 g (0.81 mol) and n-heptane 1170.77 g (11.68 mol. 5 wt times) were added to a three-liter four-necked flask, and then 0.64 g (0.01 mol) of pyridine was added thereto. The magnetic stirrer was heated and stirred to 75 ° C with stirring. Subsequently, 289.93 g (11.68 mol) of sulfinium chloride was added dropwise over 1 hour. The foaming started immediately after the dropping, and the reaction solution formed a uniform solution 30 minutes after the completion of the dropping, and the foaming was stopped. Subsequently, in this state, after stirring at 75 ° C for 1 hour and 30 minutes, the solvent was distilled off to an amount of 924.42 g in an evaporator and a 40 ° C water bath. Further, the mixture was heated at 60 ° C to dissolve the crystals precipitated when the solvent was distilled off, and the insoluble matter was distilled off by hot filtration at 60 ° C, and then the filtrate was cooled to 25 ° C at a rate of 1 ° C per 10 minutes. After stirring at 25 ° C for 30 minutes in this state, the precipitated white crystals were taken out by filtration, and the crystals were washed with n-heptane 264.21 g. After drying under reduced pressure, 226.09 g of white crystals were obtained.

Subsequently, 226.09 g of the white crystals obtained and 452.18 g of n-heptane obtained above were added to a three-liter four-necked flask under a nitrogen stream, and the mixture was heated and stirred at 60 ° C to dissolve the crystals. Subsequently, the mixture was cooled and stirred at 25 ° C at a rate of 1 ° C per 10 minutes to precipitate crystals. After stirring for 1 hour at 25 ° C in this state, the precipitated white crystals were taken out by filtration, and the crystals were washed with n-hexane 113.04 g, and then dried under reduced pressure to give 203.91 g of white crystals. This crystal was analyzed by ¹ H NMR to confirm that the compound (3-1) was dimethyl-1,3-bis(chlorocarbonyl)-1,3-dimethylcyclobutane-2,4-dicarboxylate. Acid ester (1,3-DM-CBDE-C1) (relative area of HPLC 99.5%) (yield 77.2%).

1H NMR (CDCl3, δ ppm): 3.78 (s, 6H), 3.72 (s, 2H), 1.69 (s, 6H).

(Synthesis Example 1) Synthesis of A-5

The diamine compound (A-5) was synthesized by the 4-step process shown below.

Step 1: Synthesis of Compound (A5)

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

Step 2: Synthesis of Compound (A6)

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

Step 3: Synthesis of Compound (A7)

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

Step 4: Reduction of Compound (A7)

The above 2-{3-(Nt-butoxycarbonyl-Nt-butoxycarbonylmethylamino)-1-propynyl)}-4-nitroaniline (22.0 g, was added to a 500 mL four-necked flask. 54.2 mmol) and ethanol (200 g) were substituted with nitrogen in the reaction system, and then palladium carbide (2.20 g) was substituted with hydrogen in the reaction system, and stirred at 50 ° C for 48 hours. After completion of the reaction, palladium carbide was removed by filtration through cerite, activated carbon was added to the filtrate, and the mixture was stirred at 50 ° C for 30 minutes. Subsequently, the activated carbon is filtered, and the organic solvent is distilled off under reduced pressure, and the residual oil is dried under reduced pressure to give the diamine compound (A-5). The yield was 19.8 g and the yield was 96%.

The diamine compound (A-5) was confirmed by ¹ H NMR.

¹ H NMR (DMSO-d ₆ ): δ 6.54-6.42 (m, 3H, Ar), 3.49, 3.47 (eachs, 2H, NCH ₂ CO ₂ t-Bu), 3.38-3.30 (m, 2H, CH ₂ CH ₂ N), 2.51-2.44 (m, 2H, ArCH ₂ ), 1.84-1.76 (m, 2H, CH ₂ CH ₂ CH ₂ ), 1.48-1.44 (m, 18H, NCO ₂ t-Bu and CH ₂ CO ₂ t -Bu).

(Synthesis Example 2) Synthesis of A-2

The diamine compound (A-2) was synthesized by the two-step process shown below.

Step 1: Synthesis of Compound (A8)

To a four-necked flask after nitrogen substitution, 2-iodo-4-nitroaniline (5.11 g, 19.4 mmol), bis(triphenylphosphine)palladium(II) dichloride (281.7 mg, 0.401 mmol) was added. Copper iodide (160.7 mg, 0.844 mmol) and diethylamine 30 ml were stirred at room temperature (20 ° C) for 10 minutes. Subsequently, t-butyl N-propargylaminoacetate (Compound (A5)) (3.72 g, 24.0 mmol) was added, and the mixture was stirred at room temperature (20 ° C) for 4 hours. After confirming the disappearance of the raw material by HPLC, 200 ml of ethyl acetate and 200 ml of a 1 M aqueous ammonium chloride solution were added, followed by extraction. The obtained organic layer was washed twice with a 1M aqueous solution of ammonium chloride and dried over anhydrous magnesium sulfate. After the desiccant was removed, the filtrate was concentrated and refined by a cerium oxide gel column chromatography (ethyl acetate:hexane = 3:7). The yield was 4.97 g and the yield was 88.0%.

Step 2: Synthesis of Compound (A-2)

The above dinitrogen (A8) (12.45 g, 42.7 mmol) was added to a four-necked flask, and suspended in 200 ml of ethanol. After degassing and nitrogen substitution, palladium carbide (1.23 g) was added, and the mixture was replaced with hydrogen, and stirred at room temperature (20 ° C) for 2 days. After filtering with vermiculite, the palladium carbide was removed and the solvent was distilled off. After the obtained solid was dissolved in 100 ml of toluene, 50 ml of hexane was added to carry out recrystallization. The obtained solid was dried under reduced pressure to give a pale brown solid. (yield: 9.13 g, yield: 80.6%)

The ¹ H-NMR of the obtained solid was confirmed to be a diamine (A-2).

¹ H-NMR (DMSO-d ₆ , δ ppm): 1.38 (s, 9H), 1.57 (q, J = 7.2 Hz, 2H), 2.30 (t, J = 7.2 Hz, 2H), 2.94 (quin, J = 6.0 Hz, 2H), 3.88 to 4.22 (m, 4H), 6.22 (dd, J = 2.1 Hz, 8.1 Hz, 1H), 6.25 (d, J = 2.1 Hz, 1H), 6.37 (d, J = 8.1 Hz) , 1H), 6.84 (t, J = 6.0 Hz, 1H).

<Synthesis Example 3>

In a 3 L four-necked flask equipped with a stirring device, 44.04 g (0.407 mol) of p-phenylenediamine, 43.59 g (0.115 mol) of diamine (A-5), and 1891 g of NMP were added as a base under a nitrogen atmosphere. 92.19 g (1.17 mol) of pyridine was stirred and dissolved. Next, the diamine solution was stirred, and 1,3DM-CBDE-C1 157.90 g (0.486 mol) was added, and the mixture was reacted under water cooling for 4 hours. To the solution of the obtained polyphthalate, 101 g of NMP was added, and the mixture was stirred for 30 minutes to obtain a polyglycolate solution having a solid content of 5 wt%. The polyglycolate solution was poured into 21012 g of water under stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 21012 g of water, washed with 21012 g of ethanol once, and washed with 5253 g of ethanol three times. After drying, 175.94 g of a white polyphthalate resin powder was obtained. The yield was 83.7%. Further, the molecular weight of the polyphthalate was Mn = 13,350 and Mw = 28,323.

11.1148 g of the obtained polyphthalate resin powder was placed in a 200 ml Erlenmeyer flask, and 73.8905 g of GBL was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyglycolate solution having a solid content of 13% by weight. PAE-1).

<Synthesis Example 4>

In a 3 L four-necked flask equipped with a stirring device, 34.01 g (0.315 mol) of p-phenylenediamine, 15.65 g (0.059 mol) of diamine (A-2), and diamine (A-5) were added under a nitrogen atmosphere. 7.46 g (0.0197 mol) was further added to 1344 g of NMP and 69.41 g (0.878 mol) of pyridine as a base, followed by stirring to dissolve. Next, the diamine solution was stirred, and 1,3DM-CBDE-C1 118.9 g (0.366 mol) was added, and the mixture was reacted for 4 hours under water cooling. To the solution of the obtained polyphthalate, 1493 g of NMP was added, and the mixture was stirred for 30 minutes to obtain a polyglycolate solution having a solid content of 5 wt%. The polyamine lysate solution was placed in 14934 g of water under stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 14934 g of water, washed once with 14934 g of ethanol, and washed with 3373 g of ethanol three times. After drying, 127.23 g of a white polyphthalate resin powder was obtained. The yield was 85.2%. Further, the molecular weight of the polyphthalate was Mn = 13,442 and Mw = 29,570.

15.5374 g of the obtained polyamidite resin powder was placed in a 200 ml Erlenmeyer flask, and GBL 138.4228 g was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyglycolate solution having a solid content of 10% by weight. PAE-2).

<Synthesis Example 5>

4,4'-diaminodiphenylamine 3.986 g (20.0 mmol) and 3,5-diaminobenzoic acid 4.5681 g (30.0) were weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube. Methanol), 11.05 g of NMP and 27.60 g of GBL were added, and the mixture was continuously stirred and supplied with nitrogen to dissolve. This diamine solution was added with BDA 9.9036 g (49.99 mmol), and further added with GBL to have a solid content concentration of 25% by mass, and stirred at room temperature for 24 hours to obtain a polyamidonic acid solution (PAA-1). Make the ratio of NMP/GBL 2/8. The polyamic acid solution has a viscosity of 8830 mPa ‧ at a temperature of 25 ° C. Further, the molecular weight of the polyamic acid was Mn = 12,509 and Mw = 27,832.

<Synthesis Example 6>

4,4'-diaminodiphenyl ether 4.0048 g (20.0 mmol) and 3,5-diaminobenzoic acid 4.5676 g (30.0) were weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube. Methyl) 11.08 g of NMP and 27.72 g of GBL were added, and the mixture was continuously stirred and supplied with nitrogen to dissolve. This diamine solution was added with BDA 9.9046 g (49.99 mmol), and further added with GBL to have a solid content concentration of 25% by mass, and stirred at room temperature for 24 hours to obtain a polyamidonic acid solution (PAA-2). Make the ratio of NMP/GBL 2/8. The polyamic acid solution had a viscosity of 3,607 mPa ‧ at a temperature of 25 ° C. Further, the molecular weight of the polyamic acid was Mn = 10,788 and Mw = 22,416.

<Example 1>

In a 100 ml Erlenmeyer flask equipped with a stirrer, 5.5334 g of the polyamidate solution (PAE-1) obtained in Synthesis Example 3 and 3.4645 g of the polyaminic acid solution (PAA-1) obtained in Synthesis Example 5 were weighed. After adding NMP 1.6968 g, GBL 34.3647 g, and BCA 5.0620 g, the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (Ia). (NMP/GBL ratio: 5/95)

<Example 2>

In a 100 ml Erlenmeyer flask equipped with a stirrer, 5.5491 g of the polyamidate solution (PAE-1) obtained in Synthesis Example 3 and 3.4078 g of the polyaminic acid solution (PAA-1) obtained in Synthesis Example 5 were weighed. After adding NMP 2.7897 g, GBL 33.2928 g, and BCA 5.0429 g, the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (Ib). (solid content concentration: 3.6 wt%, NMP/GBL ratio: 7.5/92.5)

<Example 3>

In a 100 ml Erlenmeyer flask equipped with a stirrer, 5.5354 g of the polyamidate solution (PAE-1) obtained in Synthesis Example 3 and 3.4191 g of the polyaminic acid solution (PAA-1) obtained in Synthesis Example 5 were weighed. After adding NMP 6.0227 g, GBL 30.1129 g, and BCA 5.0263 g, the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (Ic). (solid content concentration: 3.6 wt%, NMP/GBL ratio: 15/85)

<Comparative Example 1>

In a 100 ml Erlenmeyer flask equipped with a stirrer, 5.5499 g of the polyamidomate solution (PAE-1) obtained in Synthesis Example 3 and 3.4118 g of the polyaminic acid solution (PAA-1) obtained in Synthesis Example 5 were weighed. After adding NMP 8.23 g, GBL 27.8722 g, and BCA 5.0610 g, the mixture was stirred for 30 minutes in a magnetic stirrer to obtain a liquid crystal alignment agent (Id). (solid content concentration: 3.6 wt%, NMP/GBL ratio: 20/80)

<Comparative Example 2>

In a 100 ml Erlenmeyer flask equipped with a stirrer, 5.5545 g of the polyamidomate solution (PAE-1) obtained in Synthesis Example 3 and 3.4429 g of the polyaminic acid solution (PAA-1) obtained in Synthesis Example 5 were weighed. After adding NMP 12.5101 g, GBL 23.5576 g, and BCA 5.0314 g, the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (Ie). (solid content concentration: 3.6 wt%, NMP/GBL ratio: 30/70)

<Example 4>

In a 100 ml Erlenmeyer flask equipped with a stirrer, 7.2090 g of the polyamidate solution (PAE-2) obtained in Synthesis Example 4 and 3.4230 g of the polyamidic acid solution (PAA-2) obtained in Synthesis Example 4 were weighed. After adding NMP 0.6286 g, GBL 33.7993 g, and BCA 5.0192 g, the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (II-a). (solid content concentration: 3.6 wt%, NMP/GBL ratio: 2.5/97.5)

<Example 5>

In a 100 ml Erlenmeyer flask equipped with a stirrer, 7.2068 g of the polyamidomate solution (PAE-2) obtained in Synthesis Example 4 and 3.4458 g of the polyaminic acid solution (PAA-1) obtained in Synthesis Example 5 were weighed. After adding NMP 1.6911g, GBL32.6904g, and BCA5.0167g, the mixture was stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal alignment agent (II-b). (NMP/GBL ratio: 5/95)

<Example 6>

In a 100 ml Erlenmeyer flask equipped with a stirrer, 7.2094 g of the polyamidate solution (PAE-2) obtained in Synthesis Example 4 and 3.4142 g of the polyaminic acid solution (PAA-1) obtained in Synthesis Example 5 were weighed. After adding N728 (2.7728 g), GBL 31.6135 g, and BCA5.0049 g, the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (II-c). (solid content concentration: 3.6 wt%, NMP/GBL ratio: 7.5/92.5)

<Comparative Example 3>

In a 100 ml Erlenmeyer flask equipped with a stirrer, 7.29 g of the polyamidomate solution (PAE-2) obtained in Synthesis Example 4 and 3.4260 g of the polyaminic acid solution (PAA-1) obtained in Synthesis Example 5 were weighed. After adding NMP 6.0261 g, GBL 28.3758 g, and BCA 5.0213 g, the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (II-d). (solid content concentration: 3.6 wt%, NMP/GBL ratio: 15/85)

<Comparative Example 4>

In a 100 ml Erlenmeyer flask equipped with a stirrer, 7.2006 g of the polyamidate solution (PAE-2) obtained in Synthesis Example 4 and 3.4327 g of the polyaminic acid solution (PAA-1) obtained in Synthesis Example 5 were weighed. After adding NMP8.1874g, GBL26.2167g, and BCA5.0089g, it stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (II-e). (solid content concentration: 3.6 wt%, NMP/GBL ratio: 20/80)

<Comparative Example 5>

In a 100 ml Erlenmeyer flask equipped with a stirrer, 7.2175 g of the polyamidate solution (PAE-2) obtained in Synthesis Example 4 and 3.4183 g of the polyaminic acid solution (PAA-1) obtained in Synthesis Example 5 were weighed. After adding NMP 12.4940 g, GBL 21.9220 g, and BCA 5.0327 g, the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (11-f). (solid content concentration: 3.6 wt%, NMP/GBL ratio: 30/70)

<Example 7>

In a 20 ml sample tube provided with a stirrer, 1.8711 g of the polyamidomate solution (PAE-1) obtained in Synthesis Example 3 and 1.1123 g of the polyaminic acid solution (PAA-1) obtained in Synthesis Example 5 were weighed. NMP 0.2143g, GBL4.8191g, BCS2.0020g were added, and N-α-(9-fluorenylmethoxycarbonyl)-Nt-butoxycarbonyl-L-histidine was added as a ruthenium promoter. Hereinafter, 0.0584 g of Fmoc-His is abbreviated, and the mixture was stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal alignment agent (III-a). (solid content concentration: 6.0wt%, NMP/GBL ratio: 5/95)

<Example 8>

In a 20 ml sample tube provided with a stirrer, 1.8648 g of the polyamidomate solution (PAE-1) obtained in Synthesis Example 3 and 1.1533 g of the polyaminic acid solution (PAA-1) obtained in Synthesis Example 5 were weighed. NMP 0.59 g, GBL 4.4782 g, and BCS 2.0022 g were added, and then 0.0606 g of Fmoc-His as a ruthenium iodide promoter was added, and the mixture was stirred for 30 minutes in a magnetic stirrer to obtain a liquid crystal alignment agent (III-b). (solid content concentration: 6.0 wt%, NMP/GBL ratio: 10/90)

<Example 9>

In a 20 ml sample tube provided with a stirrer, 1.8791 g of the polyamidate solution (PAE-1) obtained in Synthesis Example 3 and 1.1632 g of the polyaminic acid solution (PAA-1) obtained in Synthesis Example 5 were weighed. After adding NMP 1.3395 g, GBL 3.6976 g, and BCS 2.0394 g, and adding 0.0575 g of Fmoc-His as a ruthenium iodide promoter, the mixture was stirred for 30 minutes in a magnetic stirrer to obtain a liquid crystal alignment agent (III-c). (solid content concentration: 6.0wt%, NMP/GBL ratio: 20/80)

<Example 10>

In a 20 ml sample tube provided with a stirrer, 1.8635 g of the polyamidomate solution (PAE-1) obtained in Synthesis Example 3 and 1.1301 g of the polyaminic acid solution (PAA-1) obtained in Synthesis Example 5 were weighed. NMP 2.0570g, GBL2.9560g, BCS2.0165g were added, and Fmoc-His 0.0580 as a ruthenium promoter was added, and the mixture was stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal alignment agent (III-d). (solid content concentration: 6.0wt%, NMP/GBL ratio: 30/70)

<Comparative Example 6>

In a 20 ml sample tube provided with a stirrer, 1.8638 g of the polyamidomate solution (PAE-1) obtained in Synthesis Example 3 and 1.1340 g of the polyaminic acid solution (PAA-1) obtained in Synthesis Example 5 were weighed. After adding NMP 2.8074 g, GBL 2.2311 g, and BCS 2.0313 g, and adding 0.0549 g of Fmoc-His as a ruthenium iodide promoter, the mixture was stirred for 30 minutes in a magnetic stirrer to obtain a liquid crystal alignment agent (III-e). (solid content concentration: 6.0wt%, NMP/GBL ratio: 40/60)

<Comparative Example 7>

In a 20 ml sample tube provided with a stirrer, 1.8653 g of the polyamidomate solution (PAE-1) obtained in Synthesis Example 3 and 1.1766 g of the polyaminic acid solution (PAA-1) obtained in Synthesis Example 5 were weighed. After adding NMP 3.5495 g, GBL 1.4903 g, BCS 2.0125 g, and adding 0.0589 g of Fmoc-His as a ruthenium promoter, the mixture was stirred for 30 minutes in a magnetic stirrer to obtain a liquid crystal alignment agent (III-f). (solid content concentration: 6.0wt%, NMP/GBL ratio: 50/50)

<Example 11>

In a 20 ml sample tube provided with a stirrer, 1.8748 g of the polyamidomate solution (PAE-1) obtained in Synthesis Example 3 and 1.98 g of the polyaminic acid solution (PAA-2) obtained in Synthesis Example 6 were weighed. After adding NMP 0.2291 g, GBL 4.8059 g, and BCS 2.0692 g, the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (-a). (solid content concentration: 6.0wt%, NMP/GBL ratio: 5/95)

<Comparative Example 8>

In a 20 ml sample tube provided with a stirrer, 1.8504 g of the polyamidate solution (PAE-1) obtained in Synthesis Example 3 and 1.1918 g of the polyaminic acid solution (PAA-2) obtained in Synthesis Example 6 were weighed. After adding NMP 2.8065 g, GBL 2.1576 g, and BCs 2.0034 g, the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (-b). (solid content concentration: 6.0wt%, NMP/GBL ratio: 40/60)

<Example 12>

The liquid crystal alignment agent (I-a) obtained in Example 1 was filtered through a 1.0 μm filter, and the liquid crystal alignment agent was applied by inkjet coating onto a glass substrate with an ITO transparent electrode. The obtained coating film was dried on a hot plate at a temperature of 80 ° C for 5 minutes, and baked for 1 hour in a hot air circulating oven at a temperature of 230 ° C to form a coating film having a film thickness of 130 nm. The film surface of the coating film was observed using an atomic force microscope (AFM), and the average thickness (Ra) of the center line of the film surface was measured to evaluate the flatness of the film surface. The results are shown in Table 1 below.

<Examples 13 to 17 and Comparative Examples 9 to 13>

Except that each of the liquid crystal alignment agents (Ia) to (II-c) and the liquid crystal alignment agents (Id) to (II-f) obtained in the above Examples 2 to 4 and Comparative Examples 1 to 4 were used, respectively, Each of the coating films was prepared in the same manner. The film surface of each coating film was observed using an atomic force microscope (AFM). Further, the average thickness (Ra) of the center line of each of the coating films was measured to evaluate the flatness of the film surface. The measurement results are shown in Table 1 below.

As shown in Table 1, it was found from the results of Examples 12 to 17 and Comparative Examples 9 to 13 that depending on the composition of the polyglycolate and the polyamic acid, the optimum solvent ratio was different, and NMP was used. The amount is, in the total amount of NMP and GBL, in the case of inkjet coating, when it is 2.5% by mass to 15% by mass, and the microphase separation of the polyglycolate and the polylysine is reduced. Concavity and convexity, it was confirmed that a flat film was obtained.

<Example 18>

After the liquid crystal alignment agent (III-a) obtained in Example 7 was filtered through a 1.0 μm filter, the liquid crystal alignment agent was applied by letterpress printing onto a glass substrate with an ITO transparent electrode. The obtained coating film was dried on a hot plate at a temperature of 80 ° C for 5 minutes, and baked in a hot air circulating oven at a temperature of 230 ° C for 30 minutes to form a coating film having a film thickness of 130 nm. 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. The results are shown in Table 2 below.

<Examples 19 to 22 and Comparative Examples 14 to 16>

Except for the liquid crystal alignment agents (III-b) to (-a) and the liquid crystal alignment agents (III-e) to (-b) obtained in the above Examples 8 to 4 and Comparative Examples 1 to 5, respectively, A coating film was produced in the same manner as in Example 18. The surface of each film of the coating film was observed using an atomic force microscope (AFM), and the average thickness (Ra) of the center line of the film surface was measured to evaluate the flatness of the film surface. The results are shown in Table 2 below.

As shown in Table 2, it is known from the results of Examples 18 to 22 and Comparative Examples 14 to 16 that depending on the composition of the polyglycolate and the poly-proline, the optimum solvent ratio is different, and the amount of NMP is different. With respect to the total amount of NMP and GBL, in the case of the relief printing, when the content is set to 5 mass% to 30 mass%, the fine unevenness caused by the phase separation of the polyphthalate and the polyamic acid can be reduced. Confirm that a flat film can be obtained.

<Example 23>

The liquid crystal alignment agent (Ib) obtained in Example 2 was filtered using a 1.0 μm filter, and then applied onto a glass substrate by inkjet coating to form an ITO electrode having a first layer of 50 nm in thickness and a second layer. A glass substrate of an FFS driving electrode having an insulating film of 500 nm in thickness and a third layer of a comb-shaped ITO electrode (electrode width: 3 μm, electrode spacing: 6 μm, electrode height: 50 nm). After drying on a hot plate at 80 ° C for 5 minutes, it was baked in a hot air circulating oven at 230 ° C for 60 minutes to form a coating film having a film thickness of 130 nm. The coating film surface was irradiated with ultraviolet rays of 254 nm at 400 mJ/cm ² through a polarizing plate to obtain a substrate to which a liquid crystal alignment film was attached. 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 Japan Co., Ltd.) was injected by a vacuum injection method, and the injection port was closed to obtain an FFS-driven liquid crystal cell.

The FFS was used to drive the liquid crystal cell, and the AC drive burn-in and charge accumulation characteristics were evaluated. The results are shown in Table 3 below.

<Example 24>

An FFS-driven liquid crystal cell was produced in the same manner as in Example 23 except that the liquid crystal alignment agent (II-b) obtained in Example 5 was used. The FFS was used to drive the liquid crystal cell, and the AC drive burn-in and charge accumulation characteristics were evaluated. The results are shown in Table 3 below.

<Comparative Example 17>

An FFS-driven liquid crystal cell was produced in the same manner as in Example 23 except that the liquid crystal alignment agent (I-d) obtained in Comparative Example 1 was used. The FFS was used to drive the liquid crystal cell, and the AC drive burn-in and charge accumulation characteristics were evaluated. The results are shown in Table 3 below.

<Comparative Example 18>

An FFS-driven liquid crystal cell was produced in the same manner as in Example 23 except that the liquid crystal alignment agent (II-e) obtained in Comparative Example 4 was used. The FFS was used to drive the liquid crystal cell, and the AC drive burn-in and charge accumulation characteristics were evaluated. The results are shown in Table 3 below.

From the results of Examples 23 to 24 and Comparative Examples 17 to 18, it was confirmed that the result of the fine unevenness which was caused by the phase separation of the polyphthalate and the poly-proline was confirmed to be more excellent in AC-driven baking and A liquid crystal alignment film having a charge accumulation property.

‧ Synthesis of diamine compound (A-1)

(Precursor Synthesis 1)

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

(Precursor Synthesis 2)

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

(synthesis of DA-2)

To the 100 mL eggplant type flask, the Boc adduct (5.0 g, 18.7 mmol) and ethanol (40 ml) were added, and after the reaction was replaced with nitrogen, platinum oxide (500 mg) was added, and the reaction was replaced with hydrogen. The reaction mixture which formed a yellow suspension was stirred at room temperature for 15 hours. After the completion of the reaction, ethanol was added to dissolve the precipitated white solid, and the catalyst was removed by filtration with vermiculite. The filtrate was concentrated and the obtained EtOAc (EtOAc m. The yield was 3.40 g and the yield was 77%.

The ¹ H-NMR of the obtained solid was measured, but the term was A-1.

¹ H-NMR (DMSO-d ₆ , δ ppm): 1.44 (s, 9H), 3.87 (d, J = 6.3 Hz, 2H), 4.10 to 4.30 (m, 4H), 6.27 (dd, J = 2.4 Hz) , 8.1 Hz, 1H), 6.31 (d, J = 2.4 Hz, 1H), 6.38 (d, J = 8.1 Hz), 7.14 (t, J = 6.3 Hz, 1H).

(Synthesis Example 7)

A 300 mL four-necked flask equipped with a stirring device was set in a nitrogen atmosphere, and p-PDA 2.52 g (23.30 mmol), (A-1) 1.3725 g (5.78 mmol), and NMP 97.20 g, as a base pyridine were placed. After 5.21 g (65.89 mmol), it was stirred to dissolve. Next, the diamine solution was stirred, and 8.930 g (27.47 mmol) of 1,3DM-CBDE-Cl was added, and the mixture was reacted under water cooling for 4 hours. After 4 hours, 107.94 g of NMP was added to the reaction solution, and the mixture was stirred at room temperature (20 ° C) for 15 minutes. The obtained polyglycolate solution was poured into 1080 g of water with stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 1080 g of water, once with 1080 g of ethanol, and washed with 270 g of ethanol. Three times, after drying, a white polyphthalate resin powder was obtained. The molecular weight of the polyphthalate was Mn = 12,119 and Mw = 25,695.

In a 100 ml Erlenmeyer flask, 7.7151 g of the obtained polyphthalate resin powder was weighed and added to GBL 69.4528 g, and then stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-3).

(Synthesis Example 8)

A 300 mL four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, and 2.8118 g (26.0 mmol) of p-phenylenediamine, 1.0964 g (2.89 mmol) of (A-5), and 51.99 g of NMP were added, and 155.97 of GBL was added. g. 5.16 g (65.18 mmol) of pyridine as a base, and stirred to dissolve. Next, the diamine solution was stirred, and 1,3DM-CBDE-Cl 8.8301 g (27.16 mmol) was added, and the mixture was reacted for 4 hours under water cooling. After 4 hours, 0.7532 g (8.32 mmol) of acrylonitrile chloride was added, and the mixture was reacted for 30 minutes under water cooling. The obtained polyamidate solution was poured into 905 g of 2-propanol with stirring, and the precipitate was separated by filtration, and then washed with 448 g of 2-propanol for 5 times, and dried to obtain poly-proline. Ester resin powder.

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

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

(Synthesis Example 9)

A 300 mL four-necked flask equipped with a stirring device was set in a nitrogen atmosphere, and 2.7958 g (13.17 mmol) of 4,4'-ethylenediphenylamine and 1.2493 g (3.41 mmol) of (A-5) were added, and NMP 35.40 g was further added. After adding GBL 35.39 g and 2.87 g (36.34 mmol) as a base pyridine, the mixture was stirred and dissolved. Next, the diamine solution was stirred, and 1,3DM-CBDE-Cl 4.9228 g (15.14 mmol) was added, and the mixture was reacted for 4 hours under water cooling. After 4 hours, 35.40 g of NMP and 35.40 g of GBL were added to the reaction solution, and the mixture was stirred at room temperature (20 ° C) for 15 minutes. The obtained polyglycolate solution was poured into 786 g of water with stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 786 g of water, washed once with 786 g of ethanol, and washed with 197 g of ethanol. Three times, after drying, a white polyphthalate resin powder was obtained. The molecular weight of the polyphthalate was Mn = 16710 and Mw = 32,198.

In a 100 ml Erlenmeyer flask, 4.7855 g of the obtained polyphthalate resin powder was weighed and added to GBL 32.0428 g, and stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-5).

(Synthesis Example 10)

A 500 mL four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, and p-phenylenediamine 5.5027 g (50.88 mmol) and (A-1) 1.0521 g (4.43 mmol) were placed, and then NMP 95.07 g and GBL 285.21 were added. g. 9.87 g (124.7 mmol) of pyridine as a base, followed by stirring to dissolve. Next, the diamine solution was stirred, and 1,3DM-CBDE-CL 16.8956 g (51.97 mmol) was added, and the mixture was reacted under water cooling for 4 hours. After 4 hours, 1.4410 g (15.92 mmol) of propylene hydrazine chloride was added, and the mixture was reacted for 30 minutes under water cooling. The obtained polyamidate solution was poured into 1658 g of 2-propanol with stirring, and the precipitate was separated by filtration, and then washed with 829 g of 2-propanol for 5 times, and dried to obtain poly-proline. Ester resin powder. The molecular weight of the polyphthalate was Mn = 15623 and Mw = 30510.

In a 200 ml Erlenmeyer flask, 12.8231 g of the obtained polyphthalate resin powder was weighed, and GBL 115.4259 g was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-6).

(Synthesis Example 11)

A 300 mL four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, and 2.03 g (18.77 mmol) of p-PDA and 1.2280 g (4.63 mmol) of (A-2) were placed, and then 167.80 g of NMP was added thereto as a base. After 4.21 g (53.26 mmol) of pyridine, it was stirred and dissolved. Next, the diamine solution was stirred, and 1,3DM-CBDE-Cl 7.2182 g (22.20 mmol) was added, and the mixture was reacted for 4 hours under water cooling. The obtained solution of the polyglycolate was put into 885 g of water with stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 885 g of water, once with 885 g of ethanol, and washed with 220 g of ethanol. Then, after drying, a white polyphthalate resin powder was obtained. The molecular weight of the polyamidomate was Mn = 14116 and Mw = 27044.

In a 100 ml Erlenmeyer flask, 7.2601 g of the obtained polyphthalate resin powder was weighed, and GBL 65.3489 g was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-7).

(Synthesis Example 12)

A 500 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, and (093-1 g (16.89 mmol) of (A-1) was added, and 156.7 g of NMP and 3.20 g (40.42 mmol) of pyridine as a base were added, followed by stirring. Let it dissolve. Next, the diamine solution was stirred, and 1,3DM-CBDE-Cl 5.4798 g (16.85 mmol) was added, and the mixture was reacted for 4 hours under water cooling. The obtained polyamidate solution was poured into 825 g of water with stirring, and the deposited precipitate was collected by filtration, and then washed once with 825 g of water, once with 825 g of ethanol, and washed with 200 g of ethanol three times. After drying, a white polyphthalate resin powder was obtained. The molecular weight of the polyphthalate was Mn = 17330 and Mw = 39,781.

In a 100 ml Erlenmeyer flask, 7.1430 g of the obtained polyphthalate resin powder was weighed and added to GBL 64.2906 g, and then stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-8).

(Synthesis Example 13)

A 300 mL four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, and p-phenylenediamine (2.0044 g (18.54 mmol)) and 4,4'-diaminodiphenylmethane 1.6278 g (8.21 mmol) were placed. After adding 48.15 g of NMP, 144.44 g of GBL, and 4.77 g (60.27 mmol) of pyridine as a base, it was stirred and dissolved. Next, the diamine solution was stirred, and 1,3DM-CBDE-Cl 8.1678 g (25.12 mmol) was added, and the mixture was reacted for 4 hours under water cooling. The obtained polyglycolate solution was poured into 835 g of 2-propanol with stirring, and the precipitate was separated by filtration, and then washed with 413 g of 2-propanol for 5 times, and dried to obtain poly-proline. Ester resin powder. The molecular weight of the polyphthalate was Mn = 13107 and Mw = 29,407.

In a 100 ml Erlenmeyer flask, 9.7076 g of the obtained polyphthalate resin powder was weighed, and after adding GB. 87.3683 g, it was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-9).

(Synthesis Example 14)

A 300 mL four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, and 4,4'-diaminodiphenylacetylene 2.0030 g (9.62 mmol) and 4,4'-diaminodiphenylmethane 1.9063 g were placed. (9.62 mmol), 40.90 g of NMP, 122.69 g of GBL, and 3.46 g (43.79 mmol) of pyridine as a base were added, followed by stirring to dissolve. Next, the diamine solution was stirred, and 1,3DM-CBDE-Cl 5.9360 g (18.26 mmol) was added, and the mixture was reacted for 4 hours under water cooling. The obtained polyamidate solution was poured into 706 g of 2-propanol with stirring, and the precipitate was separated by filtration, and then washed with 349 g of 2-propanol for 5 times, and dried to obtain poly-proline. Ester resin powder. The molecular weight of the polyglycolate was Mn = 9380 and Mw = 32,567.

In a 100 ml Erlenmeyer flask, 8.2385 g of the obtained polyphthalate resin powder was weighed, and after adding GBL 74.1537 g, it was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-10).

(Synthesis Example 15)

A 300 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, and p-phenylenediamine (3.1482 g (29.11 mmol) and (A-5): 1.2270 g (3.23 mmol) were placed, and then NMP 59.66 g, GBL 178.98 was added. g. 5.77 g (72.94 mmol) of pyridine as a base, and stirred to dissolve. Next, the diamine solution was stirred, and 1,3DM-CBDE-CL 9.8861 g (30.41 mmol) was added, and the mixture was reacted under water cooling for 4 hours. After 4 hours, 1.5885 g (9.31 mmol) of 4-methoxybenzimidyl chloride was added, and the mixture was reacted for 30 minutes under water cooling. The obtained polyamidate solution was put into 1040 g of 2-propanol with stirring, and the precipitate was separated by filtration, and then washed with 515 g of 2-propanol for 5 times, and dried to obtain poly-proline. Ester resin powder.

The molecular weight of the polyamidomate was Mn=16781 and Mw=32537.

In a 200 ml Erlenmeyer flask, 10.20 g of the obtained polyphthalate resin powder was weighed, and 91.80 g of GBL was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-11).

(Synthesis Example 16)

Into a 500 mL four-necked flask equipped with a stirring device and a nitrogen gas introduction tube, 6.087 g (40.01 mmol) of 3,5-diaminobenzoic acid was weighed, and 71.04 g of NMP was added thereto, and the mixture was continuously stirred for nitrogen gas to be dissolved. Next, 31.88 g (160 mmol) of 4,4'-diaminodiphenylamine and 124.30 g of GBL were added, and the mixture was continuously stirred and supplied with nitrogen to be dissolved. This diamine solution was stirred, and BDA 31.70 g (160 mmol) was added, and the mixture was stirred under water cooling for 2 hours. Next, adding GBL 88.78g, stirring for 10 minutes, and then allowing the reaction solution to continue stirring, adding 8.51 g (39.0 mmol) of pyromellitic dianhydride, and adding GBL to make the solid content concentration up to 18% by mass, under water cooling. Stir for 24 hours. The resulting polyamic acid solution had a viscosity of 2864 mPa ‧ at a temperature of 25 ° C. Further, the molecular weight of the polyamic acid was Mn = 14435 and Mw = 30525.

Further, 77.81 g of a solution of 3-glycidoxypropylmethyldiethoxy decane diluted to 0.3% by mass with a mixed solvent of N/GBL ratio of 2/8 was added to obtain a polyamidonic acid solution. (PAA-3).

(Synthesis Example 17)

In a 500 mL four-necked flask equipped with a stirring device and a nitrogen gas introduction tube, 3.0402 g (19.98 mmol) of 3,5-diaminobenzoic acid was weighed, and 17.37 g of NMP was added thereto, and the mixture was continuously stirred and supplied with nitrogen to dissolve. Next, 17.081 g (86.60 mmol) of 4,4'-diaminodiphenyl-N-methylamine and 86.87 g of GBL were added, and the mixture was continuously stirred and supplied with nitrogen to dissolve. This diamine solution was stirred, and BDA 17.1588 g (80.10 mmol) was added, and the mixture was stirred under water cooling for 2 hours. Next, after adding GBL 34.75g and stirring for 10 minutes, the reaction solution was further stirred, and 2.1847 g (10.02 mmol) of pyromellitic dianhydride was added, and GBL was added to make the solid content concentration up to 18% by mass under water cooling. Stir for 24 hours. The resulting polyamic acid solution had a viscosity of 534 mPa ‧ at a temperature of 25 ° C. Further, the molecular weight of the polyamic acid was Mn = 9287 and Mw = 18,703.

Further, 38.14 g of a solution of 3-glycidoxypropylmethyldiethoxydecane diluted to 0.3% by mass in a mixed solvent of NMP/GBL ratio of 1/9 was added to obtain a polyamidonic acid solution ( PAA-4).

(Synthesis Example 18)

In a 500 mL four-necked flask equipped with a stirring device and a nitrogen gas introduction tube, 4.5648 g (30.0 mmol) of 3,5-diaminobenzoic acid was weighed, and 15.8 g of NMP was added thereto, and the mixture was continuously stirred for nitrogen gas to be dissolved. Next, 2.1625 g (20.0 mmol) of m-phenylenediamine and 11.90 g of GBL were added, and the mixture was continuously stirred and supplied with nitrogen to be dissolved. This diamine solution was stirred, and 2.9736 g (15.01 mmol) of BDA was added, and the mixture was stirred under water cooling for 2 hours. Next, after adding 23.68g of GBL, stirring for 10 minutes, the reaction solution was further stirred, adding 7.6308 g (34.99 mmol) of pyromellitic dianhydride, and adding GBL to make the solid content concentration up to 18% by mass, under water cooling. Stir for 24 hours. The resulting polyamic acid solution had a viscosity of 2084 mPa ‧ at a temperature of 25 ° C. Further, the molecular weight of the polylysine was Mn = 19201 and Mw = 52329.

Further, 17.33 g of a solution of 3-glycidoxypropylmethyldiethoxydecane diluted to 0.3% by mass in a mixed solvent of N/GB ratio of 2/8 was added to obtain a polyamidonic acid solution. (PAA-5).

(Synthesis Example 19)

To a 200 mL four-necked flask equipped with a stirring device and a nitrogen gas introduction tube, 8.2176 g (54.01 mmol) of 3,5-diaminobenzoic acid and 28.31 g of NMP were added, and the mixture was continuously stirred and dissolved in nitrogen gas to dissolve. Next, DA-7 8.7267 g (36.02 mmol) and NMP 56.62 g were added, and the mixture was continuously stirred and supplied with nitrogen to dissolve. This diamine solution was stirred, and BDA 12.4025 g (62.60 mmol) was added, and the mixture was stirred under water cooling for 2 hours. Next, 28.30g of GBL was added, and after stirring for 10 minutes, the reaction solution was further stirred, and 6.0594 g (25.01 mmol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride was added, and NMP was added to make solid form. The concentration was 20% by mass, and the mixture was stirred under water cooling for 24 hours. The resulting polyamic acid solution had a viscosity of 372 mPa ‧ at a temperature of 25 ° C. Further, the molecular weight of the polyamic acid was Mn = 7517 and Mw = 15376.

Further, 0.1062 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyamic acid solution (PAA-6).

(Synthesis Example 20)

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 was weighed, and 12.52 g of NMP was added thereto, and the mixture was continuously stirred for nitrogen gas to be dissolved. Next, DA-7 3.8765 g (16.41 mmol) and GBL 25.02 g were added, and the mixture was continuously stirred and supplied with nitrogen to dissolve. This diamine solution was added with stirring, 5.5501 g (28.01 mmol) of BDA, and stirred under water cooling for 2 hours. Next, after adding GBL 12.52g, stirring for 10 minutes, the reaction solution was further stirred, adding 2.5736 g (11.8 mmol) of pyromellitic dianhydride, and adding GBL to make the solid content concentration up to 20% by mass, under water cooling. Stir for 24 hours. The resulting polyamic acid solution had a viscosity of 1313 mPa ‧ at a temperature of 25 ° C. Further, the molecular weight of the polyproline was Mn = 7841 and Mw = 15,582.

Further, 15.65 g of a solution of 3-glycidoxypropylmethyldiethoxydecane diluted to 0.3% by mass in a mixed solvent of N/GB ratio of 2/8 was added to obtain a polyamidonic acid solution. (PAA-7).

(Synthesis Example 21)

In a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 2.4435 g (16.06 mmol) of 3,5-diaminobenzoic acid was weighed, and 1,3-dimethyl-2-tetrahydroimidazolone 25.20 was added. g, stirring and allowing to dissolve by continuously feeding nitrogen gas. Next, 4.7794 g (23.99 mmol) of 4,4'-diaminodiphenylamine and 42.0 g of GBL were added, and the mixture was continuously stirred and supplied with nitrogen to dissolve. The diamine solution was stirred, and 7.6070 g (38.79 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was added, and then GBL was added to make the solid content concentration 15% by mass, and the mixture was stirred under water cooling. hour. The resulting polyamic acid solution had a viscosity of 1380 mPa ‧ at a temperature of 25 ° C. Further, the molecular weight of the polyproline was Mn = 13275 and Mw = 28,956.

Further, 0.0445 g of 3-glycidoxypropylmethyldiethoxydecane was added to obtain a polyamic acid solution (PAA-8).

(Embodiment 25)

A stirrer was placed in a 100 ml Erlenmeyer flask, and 7.202 g of the polyamidate solution (PAE-3) obtained in Synthesis Example 7 and 5.5201 g of the polyamidic acid solution (PAA-6) obtained in Synthesis Example 19 were weighed and added. NMP 2.9310 g, GBL 29.3534 g, and BCA 5.0297 g were further added with Fmoc-His 0.1859 g of a ruthenium iodide promoter, and stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (V-1). (solid content concentration: 3.6 wt%, NMP/GBL ratio: 15/85)

(Comparative Example 19)

The stirrer was placed in a 100 ml Erlenmeyer flask, and 7.2075 g of the polyamidate solution (PAE-3) obtained in Synthesis Example 7 and 5.5385 g of the polyamidic acid solution (PAA-6) obtained in Synthesis Example 19 were weighed and added. NMP 13.7383g, GBL 18.5640g, and BCA 4.9927g were further added with 0.1858 g of Fmoc-His of a ruthenium iodide promoter, and stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (Va). (solid content concentration: 3.6 wt%, NMP/GBL ratio: 40/60)

(Example 26)

The stirrer was placed in a 100 ml Erlenmeyer flask, and 5.5452 g of the polyamidate solution (PAE-5) obtained in Synthesis Example 9 and 6.7566 g of the polyamidic acid solution (PAA-5) obtained in Synthesis Example 18 were weighed and added. NMP 1.0141 g, GBL 31.6599 g, and BCA 4.9937 g, and Fmoc-His 0.1460 g of a ruthenium iodide promoter were further added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (V-2). (solid content concentration: 3.6 wt%, NMP/GBL ratio: 5/95)

(Example 27)

A stirrer was placed in a 100 ml Erlenmeyer flask, and 7.2138 g of the polyamidate solution (PAE-4) obtained in Synthesis Example 8 and 6.6321 g of the polyamidic acid solution (PAA-4) obtained in Synthesis Example 17 were weighed and added. NMP 1.0482 g, GBL 30.1339 g, and BCA 5.0290 g were further added with Froc-His 0.1811 g of a ruthenium iodide promoter, and stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (V-3). (solid content concentration: 3.6 wt%, NMP/GBL ratio: 5/95)

(Embodiment 28)

A stirrer was placed in a 100 ml Erlenmeyer flask, and 7.2162 g of the polyamidate solution (PAE-8) obtained in Synthesis Example 12 and 6.0871 g of the polyamidic acid solution (PAA-7) obtained in Synthesis Example 20 were weighed and added. NMP 5.4631 g, GBL 26.2444 g, and BCA 5.0040 g, and further added 0.1510 g of Fmoc-His of a ruthenium iodide promoter, and stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (V-4). (solid content concentration: 3.6 wt%, NMP/GBL ratio: 15/95)

(Example 29)

A stirrer was placed in a 100 ml Erlenmeyer flask, and 4.4308 g of the polyamidate solution (PAE-1) obtained in Synthesis Example 3 and 4.8860 g of the polyamidic acid solution (PAA-7) obtained in Synthesis Example 20 were weighed and added. NMP 7.8416 g, GBL 18.8822 g, and BCA 4.0082 g were further added with Fmoc-His 0.1347 g of a ruthenium iodide promoter, and stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (V-5). (solid content concentration: 3.6 wt%, NMP/GBL ratio: 20/80)

(Embodiment 30)

A stir bar was placed in a 100 ml Erlenmeyer flask, and 7.2170 g of the polyamidate solution (PAE-6) obtained in Synthesis Example 10 and 6.6319 g of the polyamidic acid solution (PAA-4) obtained in Synthesis Example 17 were weighed and added. NMP 1.0542g, GBL 30.1156g, and BCA 5.0141g were further added with 0.159 g of Fmoc-His of a ruthenium promoter, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (V-6). (solid content concentration: 3.6 wt%, NMP/GBL ratio: 5/95)

(Example 31)

A stirrer was placed in a 100 ml Erlenmeyer flask, and 7.2141 g of the polyamidate solution (PAE-9) obtained in Synthesis Example 13 and 6.7968 g of the polyamidic acid solution (PAA-5) obtained in Synthesis Example 18 were weighed and added. NMP 1.0209 g, GBL 30.1030 g, and BCA 5.0183 g were further added with Fromacl-His 0.1636 g of a ruthenium iodide promoter, and stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (V-7). (solid content concentration: 3.6 wt%, NMP/GBL ratio: 5/95)

(Example 32)

A stirrer was placed in a 100 ml Erlenmeyer flask, and 13.30 g of the polyamidomate solution (PAE-4) obtained in Synthesis Example 8 and 12.26 g of the polyamidonic acid solution (PAA-3) obtained in Synthesis Example 16 were weighed and added. NMP 2.52 g, GBL 62.49 g, and BCA 10.05 g, and further added F46-g of Fmoc-His of the ruthenium hydride promoter, and stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (V-8). (solid content concentration: 3.3wt%, NMP/GBL ratio: 5/95)

(Example 33)

A stirrer was placed in a 100 ml Erlenmeyer flask, and 7.229 g of the polyamidate solution (PAE-10) obtained in Synthesis Example 14 and 6.7899 g of the polyamidic acid solution (PAA-5) obtained in Synthesis Example 18 were weighed and added. NMP 1.0185g, GBL 30.1015g, and BCA 5.0143g were further added with 0.162 g of Fmoc-His of a ruthenium iodide promoter, and stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (V-9). (solid content concentration: 3.6 wt%, NMP/GBL ratio: 5/95)

(Example 34)

A stirrer was placed in a 100 ml Erlenmeyer flask, and 1.9916 g of the polyamidate solution (PAE-3) obtained in Synthesis Example 7 and 1.6669 g of the polyamidonic acid solution (PAA-7) obtained in Synthesis Example 20 were weighed and added. NMP 1.2121 g, GBL 2.0042 g, and BCS 1.6075 g were further added with 0.0698 g of Fmoc-His of a ruthenium iodide promoter, and stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (VI-1). (solid content concentration: 6.0wt%, NMP/GBL ratio: 25/75)

(Example 35)

A stirrer was placed in a 100 ml Erlenmeyer flask, and 1.9393 g of the polyamidate solution (PAE-7) obtained in Synthesis Example 11 and 1.7745 g of the polyamidonic acid solution (PAA-3) obtained in Synthesis Example 16 were weighed and added. NMP 0.2977 g, GBL 2.4057 g, and BCS 1.6293 g were further added with 0.0819 g of Fmoc-His of a ruthenium iodide promoter, and stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (VI-2). (solid content concentration: 6.0 wt%, NMP/GBL ratio: 10/90)

(Example 36)

A stirrer was placed in a 100 ml Erlenmeyer flask, and 1.9957 g of the polyamidate solution (PAE-4) obtained in Synthesis Example 8 and 1.7908 g of the polyamidic acid solution (PAA-3) obtained in Synthesis Example 16 were weighed and added. NMP 0.3158 g, GBL 2.4442 g, and BCS 1.6242 g, and further added with a methane imidization accelerator Fmoc-His 0.0653 g, and stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (VI-3). (solid content concentration: 6.0wt%, NMP/GBL ratio: 5/95)

(Example 37)

A stirrer was placed in a 100 ml Erlenmeyer flask, and 1.925 g of the polyamidate solution (PAE-8) obtained in Synthesis Example 12 and 1.4775 g of the polyamidonic acid solution (PAA-6) obtained in Synthesis Example 19 were weighed and added. NMP 0.5335 g, GBL 2.4708 g, and BCS 1.6135 g, and further added Fmoc-His 0.0570 g of a hydrazine imidization accelerator, and stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (VI-4). (solid content concentration: 6.0wt%, NMP/GBL ratio: 25/75)

(Example 38)

A stirrer was placed in a 100 ml Erlenmeyer flask, and 1.985 g of the polyamidate solution (PAE-9) obtained in Synthesis Example 13 and 1.9556 g of the polyamidic acid solution (PAA-8) obtained in Synthesis Example 21 were weighed and added. 1,3-Dimethyl-2-tetrahydroimidazolidone (hereinafter abbreviated as DMI) 0.0996g, GBL 2.4600g, and BCS 1.6048g, and added Fmoc-His 0.0617g of hydrazine imidization accelerator, using magnetic stirrer After stirring for 30 minutes, a liquid crystal alignment agent (VI-5) was obtained. (solid content concentration: 6.0wt%, DMI/GBL ratio: 10/90)

(Example 39)

A stirrer was placed in a 100 ml Erlenmeyer flask, and 3.6113 g of the polyamidate solution (PAE-11) obtained in Synthesis Example 15 and 2.7746 g of the polyamidonic acid solution (PAA-6) obtained in Synthesis Example 19 were weighed and added. NMP 0.5025 g, GBL 5.968 g, and BCS 2.9958 g, and further added Fruc-His 0.1223 g of a hydrazine imidization accelerator, and stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (VI-6). (solid content concentration: 6.0wt%, NMP/GBL ratio: 20/80)

(Comparative Example 20)

A stirrer was placed in a 100 ml Erlenmeyer flask, and 1.9418 g of the polyamidate solution (PAE-3) obtained in Synthesis Example 7 and 1.6452 g of the polyamidonic acid solution (PAA-7) obtained in Synthesis Example 20 were weighed and added. NMP 2.1092g, GBL 0.7577g, and BCS 1.6097g were further added with 0.0725 g of Fmoc-His of a ruthenium iodide promoter, and stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (VI-a). (solid content concentration: 6.0wt%, NMP/GBL ratio: 40/60)

(Comparative Example 21)

A stirrer was placed in a 100 ml Erlenmeyer flask, and 1.9606 g of the polyamidate solution (PAE-9) obtained in Synthesis Example 13 and 1.9393 g of the polyamidic acid solution (PAA-8) obtained in Synthesis Example 21 were weighed and added. DMI 1.8650g, GBL 0.6754g, and BCS 1.6059g, followed by addition of Fmoc-His 0.0618g of a ruthenium iodide promoter, and stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (VI-b). (solid content concentration: 6.0wt%, DMI/GBL ratio: 40/60)

(Embodiment 40)

The liquid crystal alignment agent (V-1) obtained in Example 25 was filtered through a 1.0 μm filter, and the liquid crystal alignment agent was applied by inkjet coating onto a glass substrate with an ITO transparent electrode. The obtained coating film was dried on a hot plate at a temperature of 80 ° C for 5 minutes, and baked in a hot air circulating oven at a temperature of 230 ° C for 20 minutes to form a coating film having a film thickness of 130 nm. The surface of the film of the coating film was observed using an atomic force microscope (AFM), and the average thickness (Ra) of the center line of the film surface was measured to evaluate the flatness of the film surface. The results are shown in Table 4 below.

(Examples 41 to 45 and Comparative Example 22)

Each of the coating films was formed in the same manner as in Example 40 except that each of the liquid crystal alignment agents obtained in the above Examples 27 to 31 and Comparative Example 19 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.

(Example 46)

The liquid crystal alignment agent (VI-1) obtained in Example 34 was filtered through a 1.0 μm filter, and the liquid crystal alignment agent was applied by letterpress printing onto a glass substrate with an ITO transparent electrode. The obtained coating film was dried on a hot plate at a temperature of 80 ° C for 5 minutes, and baked in a hot air circulating oven at a temperature of 230 ° C for 20 minutes to form a coating film having a film thickness of 130 nm. The surface of the film of the coating film was observed using an atomic force microscope (AFM), and the average thickness (Ra) of the center line of the film surface was measured to evaluate the flatness of the film surface. The results are shown in Table 5 below.

(Examples 46 to 49 and Comparative Example 23)

Each of the coating films was formed in the same manner as in Example 46 except that each of the liquid crystal alignment agents obtained in the above Examples 35 to 37 and Comparative Example 20 was used. The film surface of each coating film was observed using AFM. Further, the average thickness (Ra) of the center line of each coating film was measured. The measurement results are shown in Table 5 below.

(Example 50 and Comparative Example 24)

Each of the coating films was formed in the same manner as in Example 46 except that each of the liquid crystal alignment agents obtained in the above Example 38 and Comparative Example 21 was used. The film surface of each coating film was observed using AFM. Further, the average thickness (Ra) of the center line of each coating film was measured. The measurement results are shown in Table 6 below.

[Industrial use]

The liquid crystal alignment agent of the present invention can reduce the fine unevenness on the surface of the obtained liquid crystal alignment film, reduce the image sticking caused by the AC driving, and improve the interface characteristics between the liquid crystal and the liquid crystal alignment film, and can also improve the voltage holding ratio. Electrical characteristics such as ion density and residual DC voltage. As a result, the present invention can be widely applied to TN elements, STN elements, TFT liquid crystal elements, and even vertical alignment type liquid crystal display elements.

Claims (16)

A liquid crystal alignment agent comprising a liquid crystal alignment agent of the following (A) component, (B) component, and (C) component, and (A) component: 60 mol of a tetracarboxylic acid dialkyl ester derivative % or more of the dicarboxylic acid dialkyl ester derivative of the tetracarboxylic acid dialkyl ester derivative represented by the following formula (1), and the diamine represented by the following formulas (2) to (5) a polyglycolate obtained from a diamine of at least one diamine selected from the group; (In the formula (1), R ₁ is an alkyl group having 1 to 5 carbon atoms, and R ₂ is a hydroxyl group or a chlorine atom) (In the formulae (2) to (5), A ₁ is a single bond, an ester bond, a guanamine bond, a thioester bond, or an organic group having a carbon number of 2 to 10, and A ₂ is a halogen atom. a hydroxyl group, an amine group, a thiol group, a nitro group, a phosphoric acid group, or an organic group having a carbon number of 1 to 20, a is an integer of 1 to 4, and a is 2 or more, and the structure of A ₂ may be the same Or different); (B) component: polyamic acid obtained from tetracarboxylic dianhydride and diamine; (C) component: at least one selected from the group consisting of γ-butyrolactone and its derivatives The organic solvent (C1) and at least one selected from the group consisting of N-methyl-2-pyrrolidone, 1,3-dimethyl-2-tetrahydroimidazolidone, and derivatives thereof The organic solvent (C2) and the organic solvent (C2) are a mixed solvent of 2% by mass to 30% by mass based on the total amount of the organic solvent (C1) and the organic solvent (C2). The liquid crystal alignment agent of the first aspect of the invention, wherein the ratio of the component (A) to the component (B) is 1/9 to 9/1 in the mass ratio (A/B), and the component (C) The content is 70% by mass or more based on the total amount of the component (A), the component (B), and the component (C). The liquid crystal alignment agent of claim 1 or 2, wherein the component (A) is a compound represented by the above formula (2) to formula (5) which contains 40 to 100 mol% based on the total diamine. A polyglycolate obtained from a diamine of at least one diamine selected from a group of amines. The liquid crystal alignment agent of the first aspect of the invention, wherein the component (A) is at least one selected from the group consisting of a diamine represented by the formula (2) and a diamine represented by the formula (3). The diamine is selected from the group consisting of the diamine represented by the formula (4) and the diamine represented by the formula (5). The diamine of one of the diamines is less, and the polyamine obtained by the obtained diamine. The liquid crystal alignment agent of claim 1, wherein the component (A) is at least one selected from the group consisting of the diamine represented by the formula (2) and the diamine represented by the formula (4). A polyphthalate obtained from a diamine of one of the diamines. The liquid crystal alignment agent of the first aspect of the invention, wherein A ₂ of the above formula (4) is a structure represented by the following formula (6), [Chemical 4]-A ₃ -R ₃ (6) (formula ( 6) A ₃ is a single bond, -O-, -S-, -NR' ₃ -, ester bond, guanamine bond, thioester bond, urea bond, carbonate bond, or amine group a formate linkage; R _{3 is selected} from an alkyl group, an alkenyl group, an alkynyl group, an aryl group having a carbon number of 1 to 10 which may have a substituent, and a combination of the groups, and the group may have a substituent ; R' _{3 is selected} from a hydrogen atom, or an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and a combination obtained by the combination, and the groups may have a substituent). The liquid crystal alignment agent of the first aspect of the invention, wherein the component (A) is at least one selected from the group consisting of diamines of the following formulas (A-1) to (A-5). a polyglycolate obtained from an amine diamine, The liquid crystal alignment agent of claim 7, wherein the component (A) is a diamine containing the above formula (2) and is contained in the group consisting of the above formulas (A-1) to (A-5). The at least one diamine selected, the polyamine obtained from the obtained diamine. The liquid crystal alignment agent of claim 1, wherein the component (B) is at least one selected from the group consisting of tetracarboxylic dianhydrides of the following formulas (B-1) to (B-9). Kind of polyamic acid obtained from tetracarboxylic dianhydride, The liquid crystal alignment agent of claim 9, wherein the component (B) is the above formula (B-1) to formula (B-9) having 20 mol% or more relative to the total tetracarboxylic dianhydride. A tetracarboxylic dianhydride of at least one selected tetracarboxylic dianhydride and a polyamic acid obtained from the diamine. The liquid crystal alignment agent of the first or ninth aspect of the invention, wherein the component (B) is obtained by using a diamine having at least one selected from the following formula (B-10) to formula (B-13). Polylysine, The liquid crystal alignment agent of claim 11, wherein the component (B) is selected from the above formula (B-10) to (B-13) by using at least 20 mol% or more based on the total diamine. Polylysine obtained from a diamine of at least one diamine. The liquid crystal alignment agent of claim 1, wherein the organic solvent (C1) of the component (C) is γ-butyrolactone, and the organic solvent (C2) is N-methyl-2-pyrrolidone. The liquid crystal alignment agent of claim 1, wherein the component (C) is a mixed solvent of γ-butyrolactone and N-methyl-2-pyrrolidone, and the content of the component (C) is relative to (A) The total amount of the component, the component (B), and the component (C) is 80% by mass or more. A liquid crystal alignment film obtained by coating and baking a liquid crystal alignment agent according to any one of claims 1 to 14. A liquid crystal alignment film obtained by applying, baking, and irradiating a polarized ultraviolet ray to a liquid crystal alignment agent according to any one of claims 1 to 14.