TWI622621B - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

The present invention provides a liquid crystal alignment agent which is a liquid crystal alignment agent containing polyphthalate (A) and polyglycine (B), and the polyphthalate (A) contains the following formula (1) Wherein, R ¹ to R ⁵ and Y ¹ are the same meanings as defined in the scope of the patent application and the specification; and the polyamine acid (B) is obtained by reacting a tetracarboxylic acid component with a diamine component, the aforementioned four The carboxylic acid component contains 20 mol% or more of the aromatic acid dianhydride, and the diamine component contains 30 mol% or more of the following formula (2b-1) (wherein R ¹⁰ and R ¹¹ , Y ² , Y ³ and Z systems) A diamine compound represented by the same meaning as defined in the scope of application and the specification.

Description

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

The present invention relates to a liquid crystal alignment agent containing a polyphthalamide having a cyclobutane structure and a polyamic acid having a (thio)urea structure, and a liquid crystal alignment film and a liquid crystal display element obtained from the liquid crystal alignment agent.

Liquid crystal display elements are widely used as display elements of digital cameras, personal computers, mobile terminals, and the like. The liquid crystal display element is generally composed of a constituent member such as a liquid crystal, a liquid crystal alignment film, an electrode, or a substrate, and various driving methods can be employed depending on the use thereof. For example, in order to realize a wide viewing angle of a liquid crystal display element, an IPS (registered trademark) (In Plane Switching) driving method and a modified FFS (Fringe-Field Switching) driving method of a horizontal electric field are used.

A liquid crystal alignment film for controlling the alignment state of liquid crystal molecules, and a polyimine-based liquid crystal alignment film is widely used. However, polyimine is generally poorly soluble and has difficulty in molding processability, so that a liquid crystal alignment agent for a liquid crystal alignment film is formed, and a polyimide precursor or a soluble polyglycol such as polyamic acid (also called polyamic acid) is contained. The quinone imine is a main component, and this is applied to a glass substrate or the like, and is fired to obtain a polyimine-based liquid crystal alignment film.

As the liquid crystal display element is highly refined, liquid crystal alignment properties or electrical characteristics excellent in characteristics of the liquid crystal alignment film are required. In particular, in addition to their characteristics, the characteristics of the liquid crystal alignment film used in the liquid crystal display device of the IPS and FFS driving modes are required to suppress the residual image caused by the AC driving or the DC voltage when driving the IPS or FFS. The characteristics of the rapid relaxation of the accumulated residual charge. In recent years, in the case of small and medium-sized products, and the power saving of the device is required, a technique of increasing the transmittance of the panel is required, and the liquid crystal alignment film itself also requires high transmittance.

In order to meet such requirements, it is proposed to provide liquid crystal alignment agents of various polyimine-based liquid crystal alignment films. For example, a liquid crystal alignment film having a short time until the residual image due to a DC voltage disappears, and a liquid crystal containing a specific structure of a tertiary amine in addition to a polyamic acid and/or a polyamido acid containing a quinone imine group. An alignment agent (for example, refer to Patent Document 1), a liquid crystal alignment agent containing a soluble polyimine which is used as a raw material, and a diamine compound having a ring structure containing a nitrogen atom such as a pyridine skeleton (see, for example, Patent Document 2). In addition, it is proposed to provide a liquid crystal alignment agent having a high voltage holding ratio and a liquid crystal alignment film having a short period of time due to the disappearance of a DC voltage, and it is proposed to contain a polyacrylic acid or a ruthenium iodide polymer. A liquid crystal alignment agent containing at least one compound selected from the group consisting of a compound containing one carboxylic acid group in the molecule, a compound containing one carboxylic acid anhydride group in the molecule, and a compound containing one tertiary amino group in the molecule (For example, refer to Patent Document 3).

Moreover, liquid crystal alignment of a liquid crystal alignment film which has good liquid crystal alignment, rubbing resistance and high transparency is provided. For example, a liquid crystal alignment agent containing a polylysine obtained by reacting a specific diamine compound having a urea or thiourea structure (also referred to as "(thio)urea structure") with a tetracarboxylic dianhydride (for example) In the case of the liquid crystal alignment film which is excellent in the step coverage, the carbon dioxide alignment film, for example, has a carbon number, and has a basic requirement such as a voltage retention ratio, a tilt alignment angle, a residual voltage, adhesion to a substrate, and printability. The alkyl ester having a large steric hindrance of 3 or more contains two kinds of polyamic acid esters (for example, refer to Patent Document 5).

A liquid crystal alignment agent for a liquid crystal alignment film which can reduce the fine unevenness on the surface of the liquid crystal alignment film which is obtained by the above, and which can suppress the residual image due to the AC drive and improve the electrical characteristics such as the relaxation of the charge accumulation characteristics due to the DC voltage. For example, there is a liquid crystal alignment agent in which various polyphthalates and polyglycines are blended (for example, refer to Patent Documents 6 to 9).

[prior technical literature] [Patent Document]

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

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

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

[Patent Document 4] International Publication No. 2011/136375

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2003-26918

[Patent Document 6] International Publication No. 2011/115077

[Patent Document 7] International Publication No. 2011/115078

[Patent Document 8] International Publication No. 2011/115080

[Patent Document 9] International Publication No. 2011/115118

[disclosure of the invention]

The present inventors have focused on providing a liquid crystal alignment agent which imparts a liquid crystal alignment film having excellent liquid crystal alignment or electrical properties and having a higher transmittance, a liquid crystal alignment agent containing a polyphthalate (Patent Document 4) or a blend. A liquid crystal alignment agent of polyglycolate and polyglycolic acid (Patent Documents 6 to 9) was carefully studied. However, it is still not possible to obtain all of these features.

Further, the liquid crystal alignment film obtained by blending a liquid crystal alignment agent of a polyphthalate and a poly-proline exhibits a slope in the thickness direction of the film for the concentration of the polyphthalate and the poly-proline, thereby exhibiting A property that is difficult to obtain with a single resin component. In particular, since the polyphthalate component does not exist in a state in which the surface of the film is not mixed with the polyaminic acid component, the image sticking due to the AC drive is suppressed, and the polyamine component is in the film interior and the substrate interface. Since it does not exist in a state in which it is mixed with a polyphthalate component, the adhesion to the substrate is improved or the charge accumulation characteristics due to the DC voltage are alleviated. In addition, the incorporation of polyperurethane and polyaminic acid forms aggregates, causing white turbidity, fear of damage and electrical properties or transparency of the resulting liquid crystal alignment film.

Therefore, the subject of the present invention is to provide a residual force generated by an AC drive that occurs in an IPS or FFS driving type liquid crystal display device. A liquid crystal alignment agent which exhibits a residual image caused by a residual charge accumulated by a DC voltage, and which provides a liquid crystal alignment film having a high transmittance, in particular, a polyphthalate and a polyaminic acid are blended. A novel liquid crystal alignment agent, and a liquid crystal alignment film and a liquid crystal display element obtained from the liquid crystal alignment agent.

The inventors of the present invention have intensively studied the results in view of the above-mentioned problems, and have found that a novel liquid crystal alignment agent having a polybuturide having a cyclobutane structure and a polyamic acid having a (thio)urea structure can provide excellent The liquid crystal alignment and electrical properties, liquid crystal alignment film having higher transmittance, and the present invention have been completed.

In other words, the present invention is as follows.

A liquid crystal alignment agent comprising a liquid crystal alignment agent of polyphthalate (A) and polyglycine (B), wherein the polyphthalate (A) comprises the following formula (1): Wherein R ¹ is an alkyl group having 1 to 6 carbon atoms, R ² to R ^{5 are} each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Y ¹ is a divalent organic group derived from a diamine compound. The aforementioned diamine compound contains the following formula (1b): (wherein, A ¹ is a single bond, an ester bond, a guanamine bond, a thioester bond or a divalent organic group having 2 to 10 carbon atoms, and m is 0 or 1) represents a repeating unit represented by a diamine compound; The proline (B) is obtained by reacting a tetracarboxylic acid component with a diamine component, and the tetracarboxylic acid component contains 20 mol% or more of the aromatic acid dianhydride, and the diamine component contains 30 mol% or more of the following formula ( 2b-1): (wherein R ¹⁰ and R ^{11 are} each independently an alkylene group having 1 to 3 carbon atoms, and Y ² and Y ^{3 are} independently a single bond, -O-, -S- or an ester bond, and Z is an oxygen atom or sulfur. Atom) represents a diamine compound.

2. The liquid crystal alignment agent according to the above 1, wherein the content ratio of the polyphthalate (A) component to the polyamic acid (B) component is 1/9 to 9/1 by mass ratio (A/B). The total solid content concentration of the component (A) and the component (B) is 0.5 to 10% by mass.

3. The liquid crystal alignment agent according to the above 1 or 2, wherein the diamine component of the polyamic acid (B) further contains 20 mol% or less of the following (2b-2): Diamine.

4. The liquid crystal alignment agent according to any one of the above 1 to 3, wherein the diamine component of the polyamic acid (B) further contains 70 mol% or less of the third diamine component.

5. The liquid crystal alignment agent according to 4 above, wherein the third diamine component of the polyamic acid (B) is the following (2b-3) to (2b-5): At least one diamine selected in the group.

6. The liquid crystal alignment agent according to any one of the above 1 to 5, wherein the aromatic acid dianhydride in the tetracarboxylic acid component of the polyamic acid (B) is the following (2a-1) and (2a-2) : At least one aromatic acid dianhydride selected in groups.

7. The liquid crystal alignment agent according to any one of the above 1 to 6, wherein the tetracarboxylic acid component of the polyamic acid (B) further contains (2a-3) to (2a-10): At least one selected from the group consisting of alicyclic acid dianhydrides.

8. The liquid crystal alignment agent according to any one of the above 1 to 7, wherein in the polyphthalate (A), the diamine compound represented by the formula (1b) is the following (1b-1) or (1b-2): Diamine.

9. The liquid crystal alignment agent according to the above 8, wherein in the polyphthalate (A), the diamine compound derived from Y ¹ contains 50 mol% or more of the diamine of the formula (1b-1) or (1b-2).

10. The liquid crystal alignment agent according to any one of the above 1-9, wherein, in the polyphthalate (A), the diamine compound derived from Y ¹ further contains 20 mol% or less of the following (1b-3) to (1b- 5): (wherein, Boc represents a t-butoxycarbonyl group, and t-Bu represents a t-butyl group).

11. The liquid crystal alignment agent according to any one of 1 to 10 above, which further contains an organic solvent component.

12. The liquid crystal alignment agent according to any one of the above 1 to 11, wherein the liquid crystal alignment agent is a liquid crystal alignment film which is subjected to photoalignment treatment.

A liquid crystal alignment film which is obtained by using the liquid crystal alignment agent according to any one of the above 1 to 12.

A liquid crystal alignment film characterized in that the liquid crystal alignment agent according to any one of the above 1 to 12 is applied onto a substrate on which an electrode is attached, and is obtained by photoalignment treatment.

A liquid crystal display element characterized by having a liquid crystal alignment film of 13 or 14 above.

The novel liquid crystal alignment agent blended with polyphthalate and polyamic acid of the invention can provide excellent liquid crystal alignment and electrical properties, especially in liquid crystal display elements of IPS and FFS driving modes, and inhibiting Residual or residual charge generated by the AC drive that occurs A liquid crystal alignment film having high transmittance is provided. Further, the liquid crystal alignment film of the present invention can impart liquid crystal alignment energy by photoalignment treatment. By the liquid crystal alignment film obtained by the photo-alignment treatment, it is expected that the contrast and viewing angle characteristics of the liquid crystal display element can be further improved as compared with the liquid crystal alignment film obtained by the rubbing treatment.

[Best Practice for Carrying Out the Invention] [Polyurethane (A)]

The polyphthalate used in the liquid crystal alignment agent of the present invention contains the following formula (1):

(wherein R ¹ is an alkyl group having 1 to 6 carbon atoms, and R ² to R ^{5 are} each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Y ¹ is a divalent organic group derived from a diamine compound) Represents the repeating unit.

The above-mentioned "alkyl group having 1 to 6 carbon atoms" means a monovalent group of a linear saturated, branched or cyclic aliphatic saturated hydrocarbon having 1 to 6 carbon atoms. It is preferably a linear or branched group, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, a pentyl group, and the like. Heji and so on.

R ² to R ⁵ in the formula (1) are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Among them, from the viewpoint of liquid crystal alignment, R ² and R ⁴ are preferably hydrogen, and R ³ and R ⁵ are an alkyl group having 1 to 6 carbon atoms, particularly a methyl group or an ethyl group, or R ² and R ⁴ are An alkyl group having 1 to 6 carbon atoms, particularly a methyl group or an ethyl group, and R ³ and R ⁵ are hydrogen.

Y ¹ in the formula (1) is a divalent organic group derived from a diamine compound represented by the formula: H ₂ NY ¹ -NH ₂ , and the diamine compound preferably has the following formula from the viewpoint of liquid crystal alignment. (1b): (wherein, A ¹ is a single bond, an ester bond, a guanamine bond, a thioester bond or a divalent organic group having 2 to 10 carbon atoms, and m is 0 or 1) is a diamine compound.

In A ¹ , "ester bond" means a structure represented by -C(O)O- or -OC(O)-.

The "melamine bond" means a structure represented by -C(O)NR ^a - or -NR ^a C(O)-. This R ^a is a hydrogen atom, or an alkyl group, a thermally detachable substituent, an alkenyl group, an alkynyl group, an aryl group, a thioester bond, or a combination thereof. Here, the thermally detachable substituent refers to a structure having a structure in which a detached group is removed by heating, and the solubility of the polymer is improved, and the liquid crystal alignment property is not affected. The "thioester bond" means a structure represented by -C(O)S- or -SC(O)-.

The above "alkyl group" means a monovalent group of a linear, branched or cyclic aliphatic saturated hydrocarbon. It is preferably an alkyl group having 1 to 10 carbon atoms, and specific examples thereof 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. Particularly preferred is the above "alkyl group having 1 to 6 carbon atoms". The above "alkenyl group" means a straight one having more than one carbon-carbon double bond. a monovalent group of a chain, branched or cyclic aliphatic unsaturated hydrocarbon. It is preferably an alkenyl group having 2 to 10 carbon atoms, and more specifically, for example, a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, a 2-butenyl group, a 1,3-butadienyl group, 2-pentenyl, 2-hexenyl, cyclopropenyl, cyclopentenyl, cyclohexenyl, and the like. The above "alkynyl group" means a monovalent group of a linear, branched or cyclic aliphatic unsaturated hydrocarbon having one or more carbon-carbon triple bonds. It is preferably an alkynyl group having 2 to 10 carbon atoms, and more specifically, for example, an ethynyl group, a 1-propynyl group, a 2-propynyl group or the like. The above "aryl group" means a monovalent group of an aromatic hydrocarbon. It is preferably an aryl group having 6 to 10 carbon atoms, and a specific example is a phenyl group or the like.

In A ¹ , the "two-valent organic group having 2 to 10 carbon atoms" can be represented by the structure of the following formula (3).

[12]-A ² ‧R ⁶ ‧A ³ ‧R ⁷ ‧A ⁴ - (3)

A ² , A ³ and A ⁴ in the formula (3) are each independently a single bond, or -O-, -S-, -NR ^b -, an ester bond, a guanamine bond, a thioester bond, a carbonate bond or A urethane bond. R ^b is a hydrogen atom or an amine protecting group, or an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a combination thereof, and examples thereof include the same examples as the above-mentioned alkyl group, alkenyl group, alkynyl group and aryl group.

The ester bond, the guanamine bond, and the thioester bond in A ² , A ³ and A ⁴ have the same structures as the above ester bond, guanamine bond and thioester bond.

The "carbonate bond" means a structure represented by -O-C(O)-O-.

The "carbamate bond" means a structure represented by -NR ^c -C(O)-O- or -OC(O)-NR ^c -. The R ^c hydrogen atom, or an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a combination thereof may be, for example, the same as the above-mentioned alkyl group, alkenyl group, alkynyl group or aryl group.

The "amino-protecting group" is not particularly limited as long as it is familiar to those skilled in the art and can protect the amine group in the method for producing a polyamidolate described later. Specific examples are t-butoxycarbonyl (Boc), carbobenzoxy (Cbz), 9-fluorenyl methoxycarbonyl (Fmoc) group, ethenyl group and the like.

R ⁶ and R ⁷ in the formula (3) are each independently a single bond or a group selected from the group consisting of an alkyl group, an alkenyl group, an alkynylene group, an extended aryl group, a heteroaryl group, and the like. Etc. may have a substituent. When one of R ⁶ and R ⁷ is a single bond, the other is a group selected from an alkyl group, an alkenyl group, an alkynyl group, an extended aryl group, a heteroaryl group, and the like, and these may have a substitution. base.

The above "alkylene group" means a structure (divalent group) obtained by removing one hydrogen atom from the above alkyl group. It is preferably an alkylene group having 1 to 10 carbon atoms, more specifically, for example, a methylene group, an ethylene group, an ethylidene group, a 1,2- or 1,3-propanediyl group, 1,2-, 1,4- or 2,3-butanediyl, 1,2- or 2,4-pentanediyl, 1,2-hexanediyl, 1,2-extended cyclopropyl, 1, 2- or 1,3-cyclopentene butyl, 1,2-extended cyclopentyl, 1,2-extended cyclohexyl, and the like.

The above-mentioned "alkenyl group" means a structure (divalent group) obtained by removing one hydrogen atom from the above alkenyl group. It is preferably an alkenyl group having 2 to 10 carbon atoms, and more specifically, for example, a vinylidene group, an ethenylene group, a propenyl group, a methylvinyl group, or a 3- Methyl-extended propylene, 1-exenbutenyl, 4-methyl-1-enbutenyl, 1-endopentenyl, 1-extenylhexenyl, 4-ethyl-1-cyclobutene Base.

The above "alkynyl group" is one hydrogen removed from the aforementioned alkynyl group. Structure after atom (bivalent group). It is preferably an alkynylene group having 2 to 10 carbon atoms, and more specifically, for example, an ethynyl group, a propynyl group, a methylpropynylene group, a 1-butenyl group, a 4-methyl-1- group. A butynyl group, a 1-exetylene group, a 1-hexenylene group, a 4-ethyl-1-butenyl group, and the like.

The above "extended aryl group" means a structure (divalent group) obtained by removing one hydrogen atom from an aryl group. More preferably, it is a aryl group having 6 to 10 carbon atoms, and more specifically, for example, a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group or the like.

The above "heteroaryl group" means a divalent group of a heteroaromatic compound, preferably a divalent group of a heteroaromatic compound of 5 to 10 members containing at least one hetero atom selected from oxygen, nitrogen and sulfur. More specifically, for example, furan-2,5-diyl, thiophene-2,5-diyl, pyrrole-2,5-diyl, 1-methyl-pyrrole-2,5-diyl, 1, 3,4-oxadiazole-2,5-diyl and the like.

The alkyl group, the alkenyl group, the alkynylene group, the aryl group, the heteroaryl group, and the combination thereof may have a substituent and may be formed by a substituent when the carbon number is 2 to 10 in total. Ring structure. Further, the formation of a ring structure by a substituent means that the substituents are bonded to each other or a part of the substituent and a part of the parent skeleton to form a ring structure.

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

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

The "organooxy group" of the substituent is a structure represented by -OR ^d such as an alkoxy group, an alkenyloxy group or an aryloxy group. This R ^d is an alkyl group, an alkenyl group, an aryl group or the like as described above. These R ^d may be 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" of the substituent is a structure represented by -SR ^d such as an alkylthio group, an alkenethio group or an arylthio group. The R ^d is the aforementioned alkyl group, alkenyl group, aryl group or the like. These R ^d may be 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.

The "organoalkylene group" of the substituent is a structure represented by -Si-(R ^e ) ₃ . Each of R ^e may be the same or different, and examples thereof include the aforementioned alkyl group, aryl group and the like. These R ^e may be substituted by the aforementioned substituents. Specific examples of the organic fluorenyl group include a trimethyl decyl group, a triethyl decyl group, a tripropyl decyl group, a tributyl decyl group, and the like.

The "mercapto group" of the substituent is a structure represented by -C(O)-R ^f . This R ^f is a hydrogen atom or the aforementioned alkyl group, alkenyl group, aryl group or the like. These R ^f may be 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 benzamidine group and the like.

The "ester group" of the substituent is a structure represented by -C(O)OR ^d or -OC(O)-R ^d . The R ^d is the aforementioned alkyl group, alkenyl group, aryl group or the like. These R ^d may be substituted by the aforementioned substituents.

The "thioester group" of the substituent is a structure represented by -C(S)OR ^d or -OC(S)-R ^d . The R ^d is the aforementioned alkyl group, alkenyl group, aryl group or the like. These R ^d may be substituted by the aforementioned substituents.

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

"Acyl group" based substituent of structure ^{-C (O) N (R g} ) 2 , or -NR ^g C (O) R ^g representation. Each R ^g may be the same or different and is a hydrogen atom or the aforementioned alkyl group, aryl group or the like. These R ^g may be substituted by the aforementioned substituents.

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

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

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

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

When a diamine having a linear structure or a rigid structure is used, a liquid crystal alignment film having a good liquid crystal alignment property can be obtained, so that the structure of A ¹ is more preferably a single bond or the following formula (A1-0)~( Structure of A1-24).

(wherein Boc represents t-butoxycarbonyl and t-Bu represents t-butyl)

The blending alignment agent which exhibits good liquid crystal alignment property and suppresses residual charge is a diamine compound represented by the formula (1b), more preferably a diamine of the following (1b-1) to (1b-2). The content is 50 mol% or more, more preferably 80 mol% or more.

The diamine compound derived from Y ¹ is more preferably contained in an amount of 20 mol% or less of the following (1b-3) to (1b-5) diamine, more preferably 10 mol% or less, from the viewpoint of improving the solubility of the polymer.

Further, the polyglycolate represented by the formula (1) used in the liquid crystal alignment agent of the present invention may have an amine group having a terminal group represented by the following formula (1c): (wherein, A ⁵ is a single bond, -O-, -S- or -NR ⁹ -, and R ⁸ and R ^{9 are} each independently an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group) , modified polyphthalate.

The above alkyl group, alkenyl group, alkynyl group and aryl group are as described above. These groups may be substituted by the other substituents described above. The monovalent group of the above-mentioned "heteroaryl" heteroaromatic compound is preferably a monovalent group of a heteroaromatic compound of 5 to 10 members containing at least one hetero atom selected from oxygen, nitrogen and sulfur, for example, Pyridine, imidazole, isoxazole, thiophene, furan, anthracene, benzene And imidazole, pyrrole, piperidinyl and the like. Further, the aryl group and the heterocyclic group may be substituted with a substituent such as the aforementioned halogen atom, hydroxyl group, thiol group, nitro group, alkyl group, alkoxy group, alkenyl group, alkynyl group, Aryl, fluorenyl and the like.

Among them, from the viewpoint of suppressing aggregation of polyphthalate, it is preferred that A ⁵ in the formula (1c) is a single bond or -O-, and R ⁸ is an alkyl group having 1 to 6 carbon atoms (particularly a methyl group). Or ethyl), an alkenyl group having 2 to 6 carbon atoms (especially a vinyl or isopropenyl group), a cycloalkyl group having 3 to 6 carbon atoms (particularly a cyclopentyl group) or a heterocyclic group (especially a thienyl group or Furyl), R ⁹ is hydrogen.

[polyglycine (B)]

The polyphthalic acid used in the liquid crystal alignment agent of the present invention is obtained by reacting a tetracarboxylic acid component with a diamine component, wherein the tetracarboxylic acid component contains 20 mol% or more of aromatic acid dianhydride, and the diamine component contains 30 mol%. The above is given by the following formula (2b-1): (wherein R ¹⁰ and R ^{11 are} each independently an alkylene group having 1 to 3 carbon atoms, and Y ² and Y ^{3 are} independently a single bond, -O-, -S- or an ester bond, and Z is an oxygen atom or sulfur. Atom) represents a diamine compound.

The above "alkylene group having 1 to 3 carbon atoms", when used alone or in combination with other terms, means a linear or branched aliphatic having 1 to 3 carbon atoms. The divalent group of the hydrocarbon may, for example, be a methylene group, an ethylidene group, a trimethylene group or a propyl group. Further, the ester bond is as described above.

<tetracarboxylic acid component>

The polyaminic acid of the present invention gives the following formula (2a): (wherein X ¹ is a tetravalent organic group), wherein the tetracarboxylic acid component and the diamine component are reacted, and the tetracarboxylic acid component contains 20 mol% or more of aromatic acid dianhydride (that is, in the formula (2a), X ¹ is a tetravalent group of aromatic hydrocarbons). Wherein the aromatic hydrocarbon may be a monocyclic aromatic hydrocarbon (for example, benzene), a condensed polycyclic aromatic hydrocarbon (for example, naphthalene) or a cyclic agglomerated hydrocarbon (for example, biphenyl), or these mutually via -O-, - The spacer of CH ₂ - or the like is a bonded hydrocarbon (for example, diphenyl ether or diphenylmethane). When the skeleton of the poly-proline is rigid, the hydrogen bond of the urea bond of the diamine compound represented by the formula (2b-1) becomes higher, and electron mobility is easily generated, thereby promoting the direct current voltage. The relaxation of the accumulated residual charge. Therefore, X ¹ may preferably be a monocyclic aromatic hydrocarbon, a condensed polycyclic aromatic hydrocarbon or a cyclic agglomerated hydrocarbon which imparts rigidity to polyamic acid.

Preferred examples of the aromatic acid dianhydride are, for example, the following (2a-1) and (2a-2): At least one aromatic acid dianhydride selected in groups. The tetracarboxylic acid component contains 20 mol% or more, preferably 20 to 80 mol%, more preferably 20 to 60 mol% of at least one aromatic acid selected from the group consisting of the formulae (2a-1) and (2a-2). Diacid anhydride.

As the tetracarboxylic acid component of the polyamic acid of the present invention, a tetracarboxylic dianhydride other than the aromatic acid dianhydride can be used. Typical examples of such tetracarboxylic dianhydrides are aliphatic acid dianhydrides (i.e., in the formula (2a), X ¹ is a tetravalent group of an aliphatic hydrocarbon) or an alicyclic acid dianhydride (i.e., formula (2a). In the formula, X ¹ is a 4-valent group of an alicyclic hydrocarbon). Wherein, the aliphatic hydrocarbon may be a linear or branched aliphatic saturated hydrocarbon (for example, butane), a linear or branched aliphatic unsaturated hydrocarbon having at least one double bond (for example, butene) or Any of linear or branched aliphatic unsaturated hydrocarbons having at least one triple bond (for example, butyne), the alicyclic hydrocarbon may be a saturated or partially unsaturated cyclic hydrocarbon (eg, cyclobutane, Cyclobutene).

Preferred examples of the tetracarboxylic dianhydride other than the aromatic acid dianhydride are, for example, the following (2a-3) to (2a-10): At least one selected from the group consisting of alicyclic acid dianhydrides. The tetracarboxylic dianhydride other than the aromatic acid dianhydride contains a group of the formula (2a-3) to (2a-10) which is less than 80 mol%, preferably 20 to 80 mol%, more preferably 20 to 60 mol%. At least one selected alicyclic acid dianhydride.

<Diamine component>

The polyglycine of the present invention is obtained by reacting a tetracarboxylic acid component with a diamine component, and the diamine component contains 30 mol% or more of the following formula (2b-1): (wherein R ¹⁰ and R ^{11 are} each independently an alkylene group having 1 to 3 carbon atoms, and Y ² and Y ^{3 are} independently a single bond, -O-, -S- or an ester bond, and Z is an oxygen atom or sulfur. Atom) represents a diamine compound.

R ¹⁰ and R ¹¹ in the formula (2b-1) are preferably a structure having a freely rotatable portion and a small steric hindrance, from the viewpoint of having both liquid crystal alignment property and charge image sticking property, specifically, Preferred are a methylene group, an ethyl group, and a trimethylene group. Y ² and Y ³ in the formula (2b-1) are preferably a structure which is as soft as possible and has a small steric hindrance from the viewpoint of having both liquid crystal alignment property and charge image retention property, and specifically, is preferably a single bond. , -O- or -S-. Z in the formula (2b-1) is preferably an oxygen atom from the viewpoint of high electric anion and easy collection by itself.

The diamine component of the polyaminic acid of the present invention may contain a diamine other than the diamine compound represented by the formula (2b-1). Such a diamine is, for example, the following (2b-2): Diamine. The carboxylic acid side chain of the diamine of the formula (2b-2) enhances the polarity of the polyproline of the present invention, but lacks polymerization reactivity due to electron attraction, which may result in formation of a low molecular weight polyamine. The low molecular weight polylysine tends to be on the surface of the film, and as a result, a polyphthalate component and a low molecular weight polyamine are mixed on the surface of the film to hinder the display of properties. Therefore, the diamine component is preferably a diamine containing 20 mol% or less of the formula (2b-2).

The diamine component of the polyaminic acid of the present invention may contain 70 mol% or less of the diamine compound represented by the formula (2b-1) and the third diamine other than the diamine of the formula (2b-2). The third bisamine component is, for example, at least one diamine selected from the group consisting of the following (2b-3) to (2b-24), but has a liquid crystal The diamine which is at least one selected from the group consisting of (2b-3) to (2b-5) is preferred from the viewpoint of the orientation property and the image retention characteristic caused by the residual charge.

[Method for Producing Polyamide (A)] <Method for producing polyamidomate>

The polyphthalate represented by the above formula (1) is represented by the following formula (1a) or (1a ' ): (wherein R ¹ to R ⁵ are the same as defined above, R is a hydroxyl group or a chlorine atom), and any one of the tetracarboxylic acid derivatives is reacted with a diamine compound represented by the formula: H ₂ NY ¹ —NH ₂ . .

The polyperurethane represented by the above formula (1) can be synthesized by using the above-mentioned monomers, for example, by the methods (i) to (iii) shown below.

(i) Method for producing from polyamic acid

The polyglycolic acid can be obtained by using the tetracarboxylic dianhydride represented by the formula (1a) and the diamine compound represented by the formula: H ₂ NY ¹ -NH ₂ (polylysine can be described later) [Manufactured by the method for producing poly-proline (B)], it is produced by esterification.

Specifically, the reaction is carried out for 30 minutes to 24 hours, preferably at a temperature of from -20 ° C to 150 ° C, preferably from 0 ° C to 50 ° C, in the presence of an organic solvent in the presence of an organic acid and an esterifying agent. Manufactured in 1~4 hours.

The esterifying agent is preferably one which can be easily removed by purification, for example, N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N - dimethylformamide dipropyl acetal, N,N-dimethylformamide dinepentyl butyl acetal, N,N-dimethylformamide di-t-butyl acetal , 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl-3-p-tolyltriazene, 4-(4,6- Dimethoxy-1,3,5-triazine-2- Base)-4-methylmorpholinium chloride and the like. The amount of the esterifying agent added is 1 mole per unit of repeating unit of polyamic acid, preferably 2 to 6 moles.

The organic solvent is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone or γ-butyrolactone from the viewpoint of solubility of the polymer, and one or a mixture of these may be used. Two or more types are used. The concentration at the time of production is less likely to cause precipitation of the polymer, and is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass, from the viewpoint of easily obtaining a high molecular weight body.

(ii) a method for producing a dicarboxylic acid dialkylate dichloride compound and a diamine compound

The polyperurethane can be produced by polycondensation of a dicarboxylic acid dialkylate dichloride represented by the formula (1a ' ) (where R is a chlorine atom) with a diamine compound represented by the formula (1b).

Specifically, the tetracarboxylic acid dialkyl ester dichloride and the diamine compound can be carried out in the presence of a base and an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C. It is synthesized in minutes to 24 hours, preferably 1 to 4 hours.

As the base, pyridine, triethylamine or 4-dimethylaminopyridine can be used, but from the viewpoint of stable reaction, pyridine is preferred. The amount of the base to be added is preferably from 2 to 4 moles per mol of the dicarboxylic acid dialkyl ester dichloride from the viewpoint of easy removal amount and easy availability of a high molecular weight body.

In view of the solubility of the monomer and the polymer, the organic solvent is preferably N-methyl-2-pyrrolidone or γ-butyrolactone. These may be used alone or in combination of two or more. The concentration of the polymer at the time of manufacture is not easy to cause precipitation of the polymer, and it is easy to obtain a view of the high molecular weight polymer. The point is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass. Further, in order to prevent hydrolysis of the dicarboxylic acid dialkyl ester dichloride, it is preferred that the solvent used for the production of the polyglycolate is dehydrated as much as possible, and it is preferable to prevent the outside air from being mixed in a nitrogen atmosphere. .

(iii) a method for producing a dicarboxylic acid tetraalkyl ester and a diamine compound

The polyperurethane can be produced by polycondensing a diamine tetracarboxylate represented by the formula (1a ' ) (where R is a hydroxyl group) with a diamine compound represented by the formula: H ₂ NY ¹ -NH ₂ .

Specifically, the tetracarboxylic acid dialkyl ester and the diamine compound can be carried out at 0 ° C to 150 ° C, preferably 0 ° C to 100 ° C in the presence of a condensing agent, a base and an organic solvent. Manufactured in minutes to 24 hours, preferably 3 to 15 hours.

As the condensing agent, triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, N, N'-carbonyldiimidazole, dimethoxy-1,3,5-triazinylmethylmorpholinium, O-(benzotriazol-1-yl)-N,N,N',N'- Tetramethyluronium tetrafluoroborate, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate, (2,3-dihydrogen) 2-thione (thioxo)-3-benzoxazolyl)phosphonic acid diphenyl ester. The amount of the condensing agent added is preferably 2 to 3 times moles relative to the dicarboxylic acid dialkyl ester.

As the base, a tertiary amine such as pyridine or triethylamine can be used. The amount of the base to be added is preferably from 2 to 4 times the molar amount of the diamine component from the viewpoint of easily removing the amount and easily obtaining a high molecular weight body.

The organic solvent is preferably N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, or N from the viewpoint of solubility of the dialkyl tetracarboxylate and the diamine. , N-dimethylacetamide, N-methyl caprolactam, dimethyl hydrazine, dimethyl hydrazine, hexamethyl fluorene. These may be used alone or in combination of two or more.

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

In the method for producing the above three polyglycolates, a high molecular weight polyglycolate can be obtained. Therefore, the production method of the above (i) or (ii) is particularly preferable.

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

<Method for producing terminal modified polyphthalate>

The terminal modified polyphthalate is a polyacetate having an amine group at the terminal obtained as described above, and the following formula (1c ' ) is made: (wherein, A ⁵ and R ⁸ are synonymous with the above) are obtained by reacting a chlorocarbonyl compound.

The chlorocarbonyl compound has a structure in which the carbon number is smaller, and the interaction between the terminals is smaller, and aggregation of the polyamidite can be suppressed. Therefore, the chlorocarbonyl compound is more preferably an acrylic acid chloride, a methacrylic acid chloride, a crotonic acid chloride, a 2-furanylmethyl chloride, a 2-thiophenemethyl chloride, an ethyl chloroformate or a vinyl chloroformate. , cyclopentyl chloroformate, S-phenyl chlorosulfate or C-29, more preferably acrylic acid chloride, methacrylic acid chloride, crotonic acid chloride, 2-furomethylguanidinyl chloride or 2-thiophene Formamyl chloride.

The terminal modified polyphthalate, for example, a powder of a polyphthalamide having an amine group at the end thereof is dissolved in an organic solvent, and then a carbon chlorocarbonyl compound is added in the presence of a base to cause a reaction. a method of reacting a diamine compound represented by the formula: H ₂ NY ¹ -NH ₂ with a dialkyl tetracarboxylate derivative represented by the formula (1a ' ) in an organic solvent to obtain a polyfluorene having an amine group at the terminal. In the case of an amine acid ester, a method in which a chlorocarbonyl compound is added to the reaction system and a polyamine derivative having an amine group at the terminal of the reaction system is not required to be isolated from the polyamine. Among them, the method of adding a chlorocarbonyl compound to the reaction system of the latter is preferable because the purification step of the polyphthalate is carried out by one reprecipitation.

In order to obtain the terminal modified polyphthalate of the present invention, it is necessary to produce a polyamine derivative having an amine group at the end of the main chain. Therefore, the molar ratio of the diamine compound represented by the formula (1b) to the dicarboxylic acid dialkyl ester derivative represented by the formula (1a ' ) is preferably from 1:0.7 to 1:1, more preferably 1:0.8. 1:1.

A method of adding a chlorocarbonyl compound to the above reaction system, for example, a method of simultaneously adding a dicarboxylic acid dialkyl ester derivative to a diamine to sufficiently react a dicarboxylic acid dialkyl ester derivative with a diamine A method of adding a chlorocarbonyl compound after producing a polyamine phthalate having an amine group at the end. From the viewpoint of easily controlling the molecular weight of the polymer, the latter method is more preferable.

In the case of preparing a terminally modified polyphthalate, the reaction of the amine group having a terminal amino group and the chlorocarbonyl compound is carried out in the presence of a base and an organic solvent at -20 to 150 ° C, preferably The reaction is carried out at 0 to 50 ° C for 30 minutes to 24 hours, preferably for 30 minutes to 4 hours.

The amount of the chlorocarbonyl compound to be added is one unit, preferably from 0.5 to 60 mol%, more preferably from 1 to 40 mol%, based on the repeating unit of the polyaminophthalate having an amine group at the end. When the amount of addition is large, unreacted chlorocarbonyl compound remains, which is difficult to remove, and is more preferably 1 to 20 mol%.

As the base, pyridine, triethylamine or 4-dimethylaminopyridine is preferably used, and for the reaction to be stable, pyridine is preferred. When the amount of the base added is too large, it is not easy to remove. When the amount is too small, the molecular weight is small, and therefore it is preferably 2 to 4 times moles based on the chlorocarbonyl compound.

The organic solvent used for the production of the terminal modified polyphthalate is preferably N-methyl-2-pyrrolidone or γ-butyrolactone from the viewpoint of 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 manufacture is too high, the polymer is likely to be precipitated. When the concentration is too low, the molecular weight cannot be increased, so it is preferably from 1 to 30% by mass, more preferably 5~20% by mass. Further, in order to prevent hydrolysis of the chlorocarbonyl compound, the organic solvent used for producing the terminal-modified polyphthalate is dehydrated as much as possible, and is stored in a nitrogen atmosphere to prevent the incorporation of outside air.

[Method for Producing Polylysine (B)]

The polyproline (B) of the present invention can be obtained by the following formula (2a): (wherein, X ¹ is a tetravalent organic group), wherein the tetracarboxylic acid component and the diamine component are reacted, and the tetracarboxylic acid component contains 20 mol% or more of aromatic acid dianhydride (that is, formula (2a) In the above, X ¹ is a tetravalent group of an aromatic hydrocarbon), and the diamine component contains 30 mol% or more of the following formula (2b-1): (wherein R ¹⁰ , R ¹¹ , Y ² , Y ³ and Z are synonymous with the above) are diamine compounds.

Specifically, the tetracarboxylic acid component and the diamine component are reacted in the presence of an organic solvent at -20 ° C to 150 ° C, preferably at 0 ° C to 50 ° C for 30 minutes to 24 hours, preferably 1 hour. Made in 12 hours.

The organic solvent is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone or γ-butyrolactone from the viewpoint of solubility of the monomer and the polymer, and one of these may be used. Or use in combination of 2 or more types. The concentration of the polymer to be produced is preferably from 1 to 30% by mass, and more preferably from 5 to 20% by mass, from the viewpoint that the polymer is less likely to precipitate and is easily obtained as a high molecular weight body.

The polyamic acid obtained as described above is obtained by injecting a weak solvent into a sufficiently stirred reaction solution to precipitate and recover the polymer. The precipitation is carried out several times, and after washing with a weak solvent, the purified polyaminic acid powder can be obtained after normal temperature or heating and drying. The weak solvent is not particularly limited, and examples thereof include water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene, and the like.

[Liquid alignment agent]

The liquid crystal alignment agent of the present invention is blended with the above polyglycolate (A) and polyglycolic acid (B), preferably having a polyphthalate (A) and a poly (trans) acid (B) dissolved. The form of the solution in an organic solvent. The molecular weight of the polyphthalate (A) is represented by its weight average molecular weight, preferably from 2,000 to 500,000, more preferably from 5,000 to 300,000, still more preferably from 10,000 to 100,000. Further, the number average molecular weight is preferably from 1,000 to 250,000, more preferably from 2,500 to 150,000, still more preferably from 5,000 to 50,000.

Further, the weight average molecular weight of the polyamic acid (B) is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, still more preferably 10,000 to 100,000. Further, the number average molecular weight is preferably from 1,000 to 250,000, more preferably from 2,500 to 150,000, still more preferably from 5,000 to 5,000. 50,000.

By making the molecular weight of the polyphthalate (A) smaller than the molecular weight of the poly-proline (B), minute irregularities due to phase separation can be further reduced. The difference in weight average molecular weight between the polyamidomate (A) and the polyamic acid (B) is preferably from 1,000 to 1,200,000, more preferably from 3,000 to 80,000, particularly preferably from 5,000 to 60,000.

The mass ratio of the polyglycolate (A) to the poly (transamine) (B) contained in the liquid crystal alignment agent of the present invention is preferably 1/9 to 9/ 1. The ratio is preferably 2/8 to 8/2, particularly preferably 3/7 to 7/3. By setting this ratio within this range, a liquid crystal alignment agent having good liquid crystal alignment properties and electrical characteristics can be provided.

The liquid crystal alignment agent of the present invention is preferably in the form of a solution in which a polyphthalate (A) and a poly (trans) acid (B) are dissolved in an organic solvent. The production method is not particularly limited, and examples thereof include a method in which a powder of a polyphthalate and a poly-proline is mixed, a method of dissolving in an organic solvent, a method of mixing a solution of a powder of a polyphthalate with a solution of poly-proline, and a mixed polymerization. A method of a solution of a proline ester and a powder of polylysine, a method of mixing a solution of a polyamidite with a solution of polylysine. A good solvent for dissolving polyglycolate and poly-proline, even if it is different, can obtain a uniform polyphthalate-polyaminic acid mixed solution, so it is more preferable to mix polyphthalate solution and polyfluorene. A method of an amine acid solution.

Further, when the polyperurate or the poly-proline is produced in an organic solvent, the "polyamidomate solution" and the "polyammonic acid solution" may be the respective reaction solutions themselves, or this may be The reaction solution is dissolved in a suitable solution Dilution of the agent. Further, when a polyphthalate or a poly-proline is formed into a powder, it may be those which dissolve the organic solvent to form a solution. In this case, the total polymer concentration is preferably from 10 to 30% by mass, particularly preferably from 10 to 15% by mass. Further, when the powder of the polyglycolate and/or the poly-proline is dissolved, heating can be performed. The heating temperature is preferably from 20 to 150 ° C, particularly preferably from 20 to 80 ° C.

The total content (solid content concentration) of the polyamidomate (A) and the polyaminic acid (B) in the liquid crystal alignment agent of the present invention can be set to be moderate by the thickness of the polyimide film to be formed. In the case of forming a coating film which is uniform and free from defects, it is preferably 0.5% by mass or more based on the organic solvent, and is preferably 15% by mass or less from the viewpoint of storage stability. More preferably, it is 0.5 to 10% by mass, and particularly preferably 1 to 10% by mass.

The liquid crystal alignment agent of the present invention may contain other polymers having liquid crystal alignment properties in addition to the polyphthalate (A) and the polyamic acid (B). Such other polymers include, for example, polyammonium esters other than polyglycolate (A), soluble polyamidiamines, and/or polylysines other than polyglycolic acid (B). polymer.

The organic solvent contained in the liquid crystal alignment agent of the present invention is not particularly limited as long as it can uniformly dissolve the polymer component of the polyphthalate (A) and polyphthalic acid (B). Specific examples thereof include N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyl hydrazine, dimethyl hydrazine, γ-butyrolactone, 1, 3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropionamide, and the like. These can be used 1 or mixed 2 More than one kind. Moreover, even if it is a solvent which cannot melt|dissolve a polymer component uniformly, it can mix with the above-mentioned organic solvent as long as the range of the polymer is not deposited.

The liquid crystal alignment agent of the present invention may contain a solvent which improves the uniformity of the coating film when the liquid crystal alignment agent is applied to the substrate, in addition to the organic solvent for dissolving the polymer component. This solvent is generally a solvent having a lower surface tension than the above organic solvent. Specific examples thereof include ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, and 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-ethoxypropoxy)propanol, Methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, and the like. These solvents can be used in combination of two types.

The liquid crystal alignment agent of the present invention may contain various additives such as a decane coupling agent or a crosslinking agent. When a decane coupling agent or a crosslinking agent is added, in order to prevent precipitation of a polymer, when a weak solvent is added to a liquid crystal alignment agent, it is preferable to add previously. Further, in the case of firing the coating film, in order to effectively carry out the ruthenium imidization of the polyphthalate (A) and the polyglycolic acid (B), a ruthenium amide promoter can be added.

When the decane coupling agent is added to the liquid crystal alignment agent of the present invention, it may be added to the polyamidate solution, the polyaminic acid solution, or the polyaminic acid before mixing the polyphthalate solution and the polyaminic acid solution. Both the ester solution and the polyaminic acid solution. Also, a decane coupling agent can be added to the polyphthalate- Polylysine mixed solution. The decane coupling agent is added in order to improve the adhesion between the polymer and the substrate. Therefore, the method of adding the decane coupling agent is added to the polyamic acid solution which can be located at the interface between the film and the substrate to make the polymer and the decane coupling agent. After sufficient reaction, the method of mixing with the polyamine solution is more preferable. When the amount of the decane coupling agent added is too large, the unreacted material may adversely affect the liquid crystal alignment property, and when it is too small, the adhesion property may not be exhibited. Therefore, the solid content of the polymer is preferably 0.01. ~5.0% by mass, more preferably 0.1 to 1.0% by mass.

Specific examples of the decane coupling agent are listed below, but the decane coupling agent which can be used for the liquid crystal alignment agent of the present invention is not limited thereto. For example, 3-aminopropyltriethoxydecane, 3-(2-aminoethyl)aminopropyltrimethoxydecane, 3-(2-aminoethyl)aminopropylmethyldi Methoxydecane, 3-aminopropyltrimethoxydecane, 3-phenylaminopropyltrimethoxydecane, 3-triethoxydecyl-N-(1,3-dimethyl-arylene An amine decane coupling agent such as propylamine, 3-aminopropyldiethoxymethyl decane, etc.; vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris (2-methoxy) Ethyl ethoxy) decane, vinyl methyl dimethoxy decane, vinyl triethoxy decane, vinyl triisopropoxy decane, allyl trimethoxy decane, p-styryl trimethoxy Vinyl decane coupling agent such as decane or the like; 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropylmethyl Epoxy decane such as bis-ethoxy decane, 3-glycidoxypropylmethyldimethoxy decane or 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane Coupling agent; 3-methacryloxypropylmethyldimethoxydecane, 3-methyl Bing Xixi a methacryl oxime group such as oxypropyltrimethoxydecane, 3-methacryloxypropylmethyldiethoxydecane or 3-methylpropenyloxypropyltriethoxydecane a decane coupling agent; an acrylonitrile-based decane coupling agent such as 3-acryloxypropyltrimethoxydecane; a urea-based decane coupling agent such as 3-ureidopropyltriethoxysilane; a sulfide-based decane coupling agent such as (triethoxyalkylalkyl)propyl)disulfide or bis(3-(triethoxydecyl)propyl)tetrasulfide; 3-hydrothiopropylpropyl Hydrogenthio-based decane coupling agent such as dimethoxy decane, 3-hydrothiopropyltrimethoxy decane, 3-octyl thiol-1-propyltriethoxy decane; 3-isocyanate propyl Isocyanate decane coupling agent such as triethoxy decane or 3-isocyanate propyl trimethoxy decane; aldehyde decane coupling agent such as triethoxy decyl butyl aldehyde; triethoxy decyl propyl methyl amide A urethane-based decane coupling agent such as a carbamic acid ester or a (3-triethoxydecylpropyl)-t-butyl urethane.

Specific examples of the ruthenium imidization accelerator of the polyglycolate (A) and the poly (proamino acid) (B) are exemplified below, but the ruthenium-based accelerator which can be used for the liquid crystal alignment agent of the present invention is not limited thereto.

Each of D in the above formulae (I-1) to (I-17) is independently a tert-butoxycarbonyl group, a 9-fluorenylmethoxycarbonyl group or a benzyloxycarbonyl group. Further, in (I-14) to (I-17), a plurality of D may exist in one formula, and these may be the same or different from each other.

The content of the ruthenium imidization accelerator is not particularly limited as long as the range of the effect of promoting the thermal imidization of the polyphthalate (A) and the poly (resource) (B) is obtained. When the lower limit is to be shown, it is preferably 0.01 mol or more, more preferably 0.05 mol or more, and still more preferably 0.1 mol, based on 1 part of the glutamic acid or its ester moiety contained in the polyperurethane. Above the ear. Further, the hydrazine imidization promoter itself remaining in the film after sintering, from the liquid From the viewpoint that the adverse effect of various characteristics of the crystal alignment film is reduced to a minimum, if the upper limit is to be shown, the proline or ester thereof contained in the polyphthalate and the poly (resource) of the present invention The moieties of the moieties are preferably 2 mol or less, more preferably 1 mol or less, and still more preferably 0.5 mol or less.

When a ruthenium hydride promoter is added, it can be imidated by heating, and it is preferable to add it after dilution with a good solvent and a weak solvent.

<Liquid alignment film>

The liquid crystal alignment film of the present invention is a coating film obtained by applying a liquid crystal alignment agent obtained as described above to a substrate, followed by drying and sintering. The liquid crystal alignment film to which the liquid crystal alignment energy is imparted is irradiated to the surface of the coating film by the polarized radiation.

The substrate to which the liquid crystal alignment agent of the present invention is applied is not particularly limited as long as it is a substrate having high transparency, and a plastic substrate such as a glass substrate, a tantalum nitride substrate, an acrylic substrate or a polycarbonate substrate can be used. From the viewpoint of simplification of the process, it is preferable to use a substrate on which an ITO electrode or the like is formed for driving a liquid crystal. Further, in the case of the reflective liquid crystal display element, an opaque object such as a germanium wafer may be used only for the substrate on one side, and in this case, a material such as aluminum which can reflect light may be used.

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.

The drying and sintering steps after applying the liquid crystal alignment agent of the present invention may be selected to any temperature and time. Usually, in order to sufficiently remove the organic solvent contained, it is dried at 50 ° C ~ 120 ° C for 1 minute to 10 minutes, but Sintering at 150 ° C ~ 300 ° C for 5 ~ 120 minutes. The thickness of the coating film after sintering is not particularly limited. However, when it is too thin, the reliability of the liquid crystal display element may be lowered, so it is usually 5 to 300 nm, preferably 10 to 200 nm.

The method of performing the alignment treatment on the coating film includes, for example, a rubbing method, a photoalignment treatment method, and the like. The liquid crystal alignment agent of the present invention is particularly useful when used in a photo-alignment treatment method.

Specific examples of the photo-alignment treatment method include, for example, a method of irradiating radiation on a surface of the coating film with a radiation that is polarized in a certain direction, and then heat-treating at a temperature of 150 to 250 ° C to impart alignment energy to the liquid crystal. For the radiation, for example, ultraviolet rays and visible rays having a wavelength of 100 to 800 nm can be used. Among them, ultraviolet rays having a wavelength of 100 to 400 nm are preferable, and those having a wavelength of 200 to 400 nm are particularly preferable. Further, in order to improve the liquid crystal alignment property, the coated substrate may be heated at 50 to 250 ° C to irradiate the radiation. The irradiation amount of the radiation is preferably in the range of 1 to 10,000 mJ/cm ² , particularly preferably in the range of 100 to 5,000 mJ/cm ² .

The liquid crystal alignment film produced as described above allows the liquid crystal molecules to be stably aligned in a certain direction.

[Liquid Crystal Display Element]

In the liquid crystal display device of the present embodiment, a liquid crystal alignment cell is produced by a liquid crystal alignment agent of the present embodiment, and a liquid crystal cell is produced by a known method.

An example of the production of a liquid crystal cell is as follows. First, a pair of substrates on which a liquid crystal alignment film is formed is prepared. Next to one of the substrates The separator is spread on the liquid crystal alignment film so that the liquid crystal alignment film surface becomes the inner side, and the other substrate is bonded, and the liquid crystal is injected under reduced pressure and sealed. Or the liquid crystal is dropped on the liquid crystal alignment film surface on which the separator is dispersed, and the substrate is bonded and sealed. The thickness of the separator at this time is preferably from 1 to 30 μm, more preferably from 2 to 10 μm.

The liquid crystal display element produced by using the liquid crystal alignment agent of the present embodiment is excellent in display quality and excellent in reliability, and is very suitable for a large-screen and high-definition liquid crystal television.

Example

The invention will be more specifically described below by way of examples. However, the invention is not limited to the embodiments.

The abbreviations of the compounds used in the examples and comparative examples and the methods for measuring the respective properties are as follows.

NMP: N-methyl-2-pyrrolidone

GBL: γ-butyrolactone

BCS: ethylene glycol monobutyl ether

IPA: 2-propanol

DE-1: Refer to the following formula (DE-1); DA-1: refer to the following formula (DA-1); DA-2: refer to the following formula (DA-2); DA-3: refer to the following formula (DA-3); DA-4: Refer to the following formula (DA-4); Additive A: N-α-(9-fluorenylmethoxycarbonyl)-N-τ-t-butoxy Carbonyl-L-histidine (see Formula I-16 above); Additive B: tris(benzyloxycarbonyl)-L-arginine (refer to Formula I-17 above).

The measurement method of each characteristic used in the examples is as follows.

[viscosity]

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

[molecular weight]

Further, the molecular weights of polyperurethane and polylysine are measured by a GPC (normal temperature gel permeation chromatography) apparatus, and the number average molecular weight is calculated in terms of polyethylene glycol (polyethylene oxide) ( Hereinafter, it is also referred to as Mn) and a weight average molecular weight (hereinafter also referred to as Mw).

GPC device: manufactured by Shodex (GPC-101)

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

Column temperature: 50 ° C

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

Flow rate: 1.0ml/min

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

[Measurement of transmittance]

The liquid crystal alignment agent was applied onto a quartz substrate by spin coating, and dried on a hot plate at 80 ° C for 2 minutes, and then fired in a hot air circulating oven at 230 ° C for 10 minutes to form a coating film having a film thickness of 100 nm. The transmittance of the obtained coating film was measured using an ultraviolet-visible spectrophotometer (UV-3100PC) manufactured by Shimadzu Corporation, and the average value of the transmittance of 360 nm to 800 nm was calculated. The average value of 99.5% or more was evaluated as good.

[Production of FFS-driven liquid crystal cell]

The liquid crystal alignment agent was applied onto a glass substrate by a spin coating method, and an ITO electrode having a film thickness of 50 nm as an electrode in the first layer and a tantalum nitride having a film thickness of 500 nm as an insulating film and a third layer were formed. The layer had a fringe field switching (Fringe Field Switching: hereinafter referred to as FFS) driving electrode on a glass substrate of a comb-shaped ITO electrode (electrode width: 3 μm, electrode spacing: 6 μm, electrode height: 50 nm) as an electrode. After drying on a hot plate at 80 ° C for 2 minutes, the film was fired in a hot air circulating oven at 230 ° C for 14 minutes to form a coating film having a film thickness of 100 nm. The 254 nm ultraviolet light was irradiated onto the coating film surface through a polarizing plate at 500 mJ/cm ² to obtain a substrate having a liquid crystal alignment film. Further, a coating film was formed in the same manner on the glass substrate having the columnar spacer having a height of 4 μm in which the electrode was not formed on the opposite substrate, and the alignment treatment was performed.

The two substrates are grouped together, and a sealant is printed on the substrate, and the other substrate is bonded so that the alignment direction of the liquid crystal alignment film becomes 0°, and the sealant is hardened to form 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.

(AC drive afterimage)

Using the liquid crystal cell prepared above, an AC voltage of ±10 V was applied for 144 hours at a frequency of 30 Hz in a constant temperature environment of 60 °C. Then, a state in which a short circuit between the pixel electrode and the counter electrode of the liquid crystal cell is formed is performed, and in this state, it is left at room temperature for one day.

After being placed, the liquid crystal cell is placed between two polarizing plates arranged in an orthogonal manner on the polarizing axis, and the backlight is turned on without applying a voltage, and the adjustment is performed. The arrangement angle of the liquid crystal cell minimizes the luminance of the transmitted light. Further, the second region of the first pixel is the darkest angle to the darkest angle of the first region, and the rotation angle when the liquid crystal cell is rotated is calculated as the angle Δ. Similarly, in the second pixel, the second region and the first region are compared, and the same angle Δ is calculated. Further, the average value of the angle Δ values of the first pixel and the second pixel is calculated as the angle Δ of the liquid crystal cell. The AC drive afterimage △ did not reach 0.1 and was evaluated as good.

[charge accumulation characteristics]

The liquid crystal cell was placed on a light source, and the VT characteristic (voltage-transmittance characteristic) at a temperature of 25 ° C was measured, and then the transmittance (Ta) of the liquid crystal cell in a state where a rectangular wave of ±3 V/120 Hz was applied was measured. . Then, a rectangular wave of ±3 V/120 Hz was applied at a temperature of 25 ° C for 10 minutes, and then DC 2 V was superposed and driven for 120 minutes. The DC voltage was cut, and the transmittance (Tb) of the liquid crystal cell at 60 minutes of AC driving was measured, and the difference in the initial transmittance (Ta) (ΔT) was calculated from the voltage remaining in the liquid crystal display element. The difference in rate. The transmittance difference ΔT was 2.0% or less, and it was evaluated as good.

<Synthesis Example 1>

A 500 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, and 4.58 g (42.4 mmol) of p-phenylenediamine, DA-1 (1.79 g) (4.71 mmol), NMP (84.7 g), GBL (254 g), and 8.40 g (106 mmol) of pyridine as a base was stirred and dissolved. Second, take this two The amine solution was stirred while adding DE-1 (14.4 g) (44.2 mmol) and reacted at 15 ° C overnight. After stirring overnight, 1.23 g (13.6 mmol) of acrylonitrile chloride was added, and the mixture was reacted at 15 ° C for 4 hours. The obtained polyglycolate solution was stirred and placed in 1477 g of IPA, and the precipitated white precipitate was obtained by filtration, followed by washing with 738 g of IPA for 5 times, and drying to obtain a white polyphthalate resin powder. 17.3g. The yield was 96.9%. Further, the molecular weight of the polyglycolate was Mn = 14,288 and Mw = 29,956.

3.69 g of the obtained polyphthalate resin powder was transferred to a 100 mL Erlenmeyer flask, and GBL (33.2 g) was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution PAE-1.

<Synthesis Example 2>

A 500 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, and 2.50 g (23.1 mmol) of p-phenylenediamine, DA-2 (0.59 g (1.22 mmol)), NMP (42.8 g), and GBL (129 g) were added. 4.34 g (54.9 mmol) of the base pyridine was stirred and dissolved. Next, the diamine solution was stirred while adding DE-1 (7.44 g) (22.9 mmol)), and the reaction was carried out at 15 ° C overnight. After stirring overnight, 0.63 g (7.01 mmol) of acrylonitrile chloride was added, and the mixture was reacted at 15 ° C for 4 hours. The obtained solution of the polyamidate was stirred and placed in 574 g of IPA, and the precipitated white precipitate was obtained by filtration, followed by washing 5 times with 382 g of IPA, and dried to obtain a white polyphthalate resin powder. 8.82g. The yield was 97.8%. Moreover, the molecular weight of the polyglycolate is Mn = 16,617 and Mw = 37,387.

0.80 g of the obtained polyphthalate resin powder was transferred to a 100 mL Erlenmeyer flask, and GBL (7.20 g) was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution PAE-2.

<Synthesis Example 3>

A 500 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, and 1.23 g (11.3 mmol) of p-phenylenediamine, 0.80 g (3.77 mmol) of 4,4'-diaminobibenzyl, and NMP (27.0 g) were added. GBL (91.2 g) and 2.69 g (34.0 mmol) of pyridine as a base were stirred and dissolved. Next, this diamine solution was stirred while adding DE-1 (4.61 g) (14.2 mmol), and it was made to react at 15 ° C overnight. After stirring for one night, 0.39 g (4.34 mmol) of acrylonitrile chloride was added, and the mixture was reacted at 15 ° C for 4 hours. The resulting solution of the polyglycolate was stirred and placed in 384 g of IPA, and the precipitated white precipitate was obtained by filtration, followed by washing 5 times with 256 g of IPA, and dried to obtain a white polyphthalate resin powder. 5.11g. The yield was 89.6%. Further, the molecular weight of the polyglycolate was Mn = 14,806 and Mw = 32,719.

0.80 g of the obtained polyphthalate resin powder was transferred to a 100 mL Erlenmeyer flask, and GBL (7.20 g) was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution PAE-3.

<Synthesis Example 4>

A 500 mL four-necked flask equipped with a stirring device was set to a nitrogen atmosphere, and 2.80 g (25.9 mmol) of p-phenylenediamine, DA-3 (1.45 g) (6.47 mmol), 111 g of NMP, and 6.18 g (78.1 mmol) of pyridine as a base were added, and the mixture was stirred and dissolved. Next, the diamine solution was stirred while adding DE-1 (9.89 g) (30.4 mmol), and reacted at 15 ° C overnight. After stirring for one night, 0.38 g (4.21 mmol) of acrylonitrile chloride was added, and the mixture was reacted at 15 ° C for 4 hours. The obtained solution of the polyglycolate was stirred and poured into 1230 g of water, and the precipitated white precipitate was obtained by filtration, followed by washing 5 times with 1230 g of IPA, and dried to obtain a white polyphthalate resin powder 10.2. g. The yield was 83.0%. Further, the molecular weight of the polyglycolate was Mn = 20,786 and Mw = 40,973.

0.798 g of the obtained polyphthalate resin powder was transferred to a 100 mL Erlenmeyer flask, and GBL (7.18 g) 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 5>

To a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 0.76 g (5.00 mmol) of 3,5-diaminobenzoic acid and 1,3-bis(4-aminophenethyl)urea 2.24 were added. G (7.51 mmol), 2.50 g (12.5 mmol) of 4,4'-diaminodiphenyl ether, and 12.1 g of NMP were stirred and dissolved while feeding nitrogen. To the diamine solution, 2.48 g (12.5 mmol) of 1,2,3,4-butanetetracarboxylic dianhydride was added thereto, and then 9.07 g of GBL was added thereto, followed by stirring at room temperature for 2 hours. Next, after adding 33.0 g of GBL and stirring, 2.72 g (12.5 mmol) of pyromellitic dianhydride was added, and 6.09 g of GBL was added, and it stirred at room temperature for 24 hours. The obtained polyaminic acid solution is viscous at 25 ° C The degree is 3,216mPa. s. Further, the molecular weight of polylysine was Mn = 18,890 and Mw = 44,017.

Further, 0.0321 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyaminic acid solution (PAA-1).

<Synthesis Example 6>

To a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 0.76 g (5.00 mmol) of 3,5-diaminobenzoic acid and 1,3-bis(4-aminophenethyl)urea 2.24 were added. g (7.51 mmol), 2.51 g (12.5 mmol) of 4,4'-diaminodiphenyl ether, 9.62 g of NMP, and 9.68 g of GBL were stirred and dissolved while feeding nitrogen. To the diamine solution, 3.97 g (20.0 mmol) of 1,2,3,4-butanetetracarboxylic dianhydride was added thereto, and then 7.24 g of GBL was added thereto, followed by stirring at room temperature for 2 hours. Next, after adding GBL 16.9g and stirring, 1.09 g (5.00 mmol) of pyromellitic dianhydride was added, and 4.83 g of GBL was added, and it stirred at room temperature for 24 hours. The obtained polyaminic acid solution has a viscosity of 2,236 mPa at 25 ° C. s. Further, the molecular weight of the polyproline was Mn = 11,687 and Mw = 27,080.

Further, 0.0316 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyaminic acid solution (PAA-2).

<Synthesis Example 7>

100mL four-necked flask with stirring device and nitrogen inlet tube Add 3,5-diaminobenzoic acid 0.76g (5.00mmol), 1,3-bis(4-aminophenethyl)urea 2.24g (7.51mmol), 4,4'-diaminodi 2.51 g (12.5 mmol) of phenyl ether, 9.67 g of NMP, and 9.64 g of GBL were stirred and dissolved while feeding nitrogen. To the diamine solution, 3.48 g (17.6 mmol) of 1,2,3,4-butanetetracarboxylic dianhydride was added thereto, and then 7.23 g of GBL was added thereto, followed by stirring at room temperature for 2 hours. Next, after stirring with GBL 16.9g, 1.64 g (7.52 mmol) of pyromellitic dianhydride was added, and 4.81 g of GBL was added, and it stirred at room temperature for 24 hours. The obtained polyaminic acid solution has a viscosity of 4,531 mPa at 25 ° C. s. Further, the molecular weight of the polyproline was Mn = 13,616 and Mw = 33,687.

Further, 0.0318 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyaminic acid solution (PAA-3).

<Synthesis Example 8>

To a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 0.76 g (5.00 mmol) of 3,5-diaminobenzoic acid and 1,3-bis(4-aminophenethyl)urea 2.23 were added. g (7.51 mmol), 2.50 g (12.5 mmol) of 4,4'-diaminodiphenyl ether, 9.70 g of NMP and 7.23 g of GBL were stirred and dissolved while feeding nitrogen. To the diamine solution, 2.98 g (15.0 mmol) of 1,2,3,4-butanetetracarboxylic dianhydride was added thereto, and then 7.28 g of GBL was added thereto, followed by stirring at room temperature for 2 hours. Next, after stirring to add 19.4 g of GBL, 2.18 g (9.99 mmol) of pyromellitic dianhydride was added, and 4.80 g of GBL was added, and the mixture was stirred at room temperature for 24 hours. Polylysine dissolved The viscosity of the liquid at 25 ° C is 4,804 mPa. s. Further, the molecular weight of the polyproline was Mn = 13,004 and Mw = 32,102.

Further, 0.0319 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyaminic acid solution (PAA-4).

<Synthesis Example 9>

The mixture was placed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube. Add 0.91 g (5.98 mmol) of 3,5-diaminobenzoic acid, 4.78 g (23.9 mmol) of 4,4'-diaminodiphenylamine, 13.3 g of NMP and 6.66 g of GBL, and stir while feeding nitrogen. Soluble. To the diamine solution, 4.76 g (24.0 mmol) of 1,2,3,4-butanetetracarboxylic dianhydride was added thereto, and then 9.99 g of GBL was added thereto, followed by stirring at room temperature for 2 hours. Next, after adding GBL 20.0g and stirring, 1.31 g (6.00 mmol) of pyromellitic dianhydride was added, and 4.80 g of GBL was added, and it stirred at room temperature for 24 hours. The obtained polyaminic acid solution has a viscosity at 25 ° C of 4,147 mPa. s. Further, the molecular weight of polylysine was Mn = 24,333 and Mw = 60,010.

Further, 0.0353 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyamidonic acid solution (PAA-5).

<Synthesis Example 10>

To a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 1.22 g (8.02 mmol) of 3,5-diaminobenzoic acid and 4,4'-di were added. 3.21 g (16.0 mmol) of aminodiphenyl ether, 3.41 g (16.0 mmol) of 4,4'-diaminodiphenylmethylamine, 13.6 g of NMP, and 10.1 g of GBL were stirred and dissolved while supplying nitrogen. To the diamine solution, 4.76 g (24.0 mmol) of 1,2,3,4-butanetetracarboxylic dianhydride was added thereto, and then 13.6 g of GBL was added thereto, followed by stirring at room temperature for 2 hours.

Next, after adding 13.6 g of GBL and stirring, 3.39 g (15.5 mmol) of pyromellitic dianhydride was added, and 17.00 g of GBL was added, and it stirred at room temperature for 24 hours. The obtained polyaminic acid solution has a viscosity at 25 ° C of 2,036 mPa. s. Further, the molecular weight of the polyproline was Mn = 13,234 and Mw = 29,677.

Further, 0.0479 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyaminic acid solution (PAA-6).

<Synthesis Example 11>

To a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 1.22 g (8.02 mmol) of 3,5-diaminobenzoic acid and 4.81 g (44.0 mmol) of 4,4'-diaminodiphenyl ether were added. ), 1.71 g (8.02 mmol) of 4,4'-diaminodiphenylmethylamine, 13.5 g of NMP, and 10.1 g of GBL, and stirred while being fed with nitrogen to dissolve. To the diamine solution, 4.76 g (24.0 mmol) of 1,2,3,4-butanetetracarboxylic dianhydride was added thereto, and then 13.6 g of GBL was added thereto, followed by stirring at room temperature for 2 hours.

Next, after adding GBL 13.5g for stirring, 3.40 g (15.5 mmol) of pyromellitic dianhydride was added, and 16.9 g of GBL was added, and it stirred at room temperature for 24 hours. The obtained polyaminic acid solution has a viscosity at 25 ° C of 3,678 mPa. s. Further, the molecular weight of polyproline was Mn = 13,586 and Mw = 30,870.

Further, 0.0476 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyaminic acid solution (PAA-7).

<Synthesis Example 12>

To a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 0.91 g (5.98 mmol) of 3,5-diaminobenzoic acid and 2.40 g of 4,4'-diaminodiphenyl ether (11.9 mmol) were added. 2,4'-Diaminodiphenylmethylamine 2.56 g (12.0 mmol), NMP 10.9 g, and GBL 8.10 g were stirred and dissolved while feeding nitrogen. To the diamine solution, 4.76 g (24.0 mmol) of 1,2,3,4-butanetetracarboxylic dianhydride was added thereto, and then 10.9 g of GBL was added thereto, followed by stirring at room temperature for 2 hours. Next, after adding GBL 10.8g for stirring, 1.31 g (6.01 mmol) of pyromellitic dianhydride was added, and 13.6 g of GBL was added, and the mixture was stirred at room temperature for 24 hours. The obtained polyaminic acid solution has a viscosity at 25 ° C of 1,441 mPa. s. Further, the molecular weight of polylysine was Mn = 13,165 and Mw = 29,510.

Further, 0.0358 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyaminic acid solution (PAA-8).

<Synthesis Example 13>

11.94 g (40.01 mmol) of 1,3-bis(4-aminophenethyl)urea was added to a 300 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube. 76.34 g of NMP was added, and it stirred by stirring with nitrogen. While stirring the diamine solution, 11.33 g (38.51 mmol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride was added, and NMP was added to make the solid content concentration 12% by mass, and the mixture was stirred at room temperature. A solution of polyaminic acid (PAA-9) was obtained in 24 hours. The viscosity of the polyaminic acid solution at a temperature of 25 ° C is 372 mPa. s. Further, the molecular weight of the polyamic acid was Mn = 17,076 and Mw = 32,617.

Further, 0.0186 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyamic acid solution (PAA-9).

<Synthesis Example 14>

A 500 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, and DA-4 (14.4 g) (58.8 mmol), DA-1 (2.48 g) (6.53 mmol), NMP 622 g, and base pyridine 11.6 g ( 147 mmol), stirred to dissolve. Next, this diamine solution was stirred while adding DE-1 (20.0 g) (61.4 mmol), and reacted at 15 ° C overnight. After stirring for one night, 1.70 g (18.8 mmol) of acrylonitrile chloride was added, and the mixture was reacted at 15 ° C for 4 hours. The obtained polyglycolate solution was stirred and poured into 2691 g of IPA, and the precipitated white precipitate was obtained by filtration, followed by washing with 1345 g of IPA for 5 times, and drying to obtain a white polyphthalate resin powder. 31.4g. The yield was 95.9%. Further, the molecular weight of the polyglycolate was Mn = 13,012 and Mw = 25,594.

3.70 g of the obtained polyphthalate resin powder was transferred to a 100 mL Erlenmeyer flask, and 33.3 g of NMP was added thereto, and the mixture was stirred at room temperature for 24 hours to dissolve. Solution, a polyphthalate solution PAE-5 was obtained.

<Synthesis Example 15>

1,3-bis(4-aminophenethyl)urea 1.43 g (4.79 mmol), 4,4'-diaminodiphenyl was added to a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube. 2.24 g (11.2 mmol) of ether, 8.00 g of NMP and 16.0 g of GBL were stirred and dissolved while feeding nitrogen. To the diamine solution, 1.59 g (8.02 mmol) of 1,2,3,4-butanetetracarboxylic dianhydride was added thereto, and then GBL 6.00 g was added thereto, followed by stirring at room temperature for 2 hours. Next, 0.49 g (1.60 mmol) of 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride was added, and 6.00 g of GBL was added thereto, followed by stirring at room temperature for 2 hours. Next, 1.31 g (6.01 mmol) of pyromellitic dianhydride was added, and 4.00 g of GBL was further added thereto, and the mixture was stirred at room temperature for 24 hours. The obtained polyaminic acid solution has a viscosity of 920 mPa at 25 ° C. s. Further, the molecular weight of the polyproline was Mn = 13,012 and Mw = 25,594.

Further, 0.018 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyaminic acid solution (PAA-10).

<Synthesis Example 16>

1,3-bis(4-aminophenethyl)urea 1.48 g (4.96 mmol), 4,4'-diaminodiphenyl was added to a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube. 2.31 g (11.5 mmol) of ether, 9.20 g of NMP, and 4.06 g of GBL were stirred and dissolved while feeding nitrogen. This diamine While stirring the solution, 3.03 g (9.89 mmol) of 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride was added, and 7.57 g of GBL was added thereto, and the mixture was stirred at room temperature for 2 hours. Next, after stirring with GBL 16.3g, 1.43 g (6.53 mmol) of pyromellitic dianhydride was added, and 9.32 g of GBL was added, and it stirred at room temperature for 24 hours. The obtained polyaminic acid solution has a viscosity at 25 ° C of 16,540 mPa. s. Further, the molecular weight of polylysine was Mn = 18,357 and Mw = 42,800.

Further, 0.0246 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyaminic acid solution (PAA-11).

<Synthesis Example 17>

To a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 0.70 g (4.60 mmol) of 3,5-diaminobenzoic acid and 1,3-bis(4-aminophenethyl)urea 2.06 were added. g (6.90 mmol), m-phenylenediamine 1.24 g (11.5 mmol), NMP 7.92 g, and GBL 5.94 g were stirred and dissolved while feeding nitrogen. To the diamine solution, 2.73 g (13.8 mmol) of 1,2,3,4-butanetetracarboxylic dianhydride was added thereto, and 5.94 g of GBL was added thereto, followed by stirring at room temperature for 2 hours. Next, after adding GBL 15.8g for stirring, 1.96 g (8.99 mmol) of pyromellitic dianhydride was added, and 3.96 g of GBL was added, and it stirred at room temperature for 24 hours. The obtained polyaminic acid solution has a viscosity at 25 ° C of 2,700 mPa. s. Further, the molecular weight of the polyproline was Mn = 14,012 and Mw = 26,594.

Further, 0.0258 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyamidonic acid solution. (PAA-12).

<Synthesis Example 18>

1,3-bis(4-aminophenethyl)urea 1.34 g (4.49 mmol), 4,4'-diaminodiphenyl was added to a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube. 2.08 g (10.5 mmol) of methane, 7.42 g of NMP, and 3.71 g of GBL were stirred and dissolved while feeding nitrogen. To the diamine solution, 1.49 g (7.52 mmol) of 1,2,3,4-butanetetracarboxylic dianhydride was added thereto, and 5.60 g of GBL was added thereto, and the mixture was stirred at room temperature for 2 hours. Next, 16.7 g of GBL was added, and after stirring, 1.64 g (7.52 mmol) of pyromellitic dianhydride was added, and 3.71 g of GBL was added, and the mixture was stirred at room temperature for 24 hours. The obtained polyaminic acid solution has a viscosity at 25 ° C of 7,230 mPa. s. Further, the molecular weight of polyproline was Mn = 15,838 and Mw = 42,677.

Further, 0.0479 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyaminic acid solution (PAA-13).

<Synthesis Example 19>

1,3-bis(4-aminophenethyl)urea 2.68 g (8.98 mmol) and 3,5-diaminobenzoic acid 3.19 were added to a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube. g (21.9 mmol), NMP 13.7 g, and GBL 13.7 g were stirred and dissolved while feeding nitrogen. To the diamine solution, 2.95 g (15.0 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was added thereto, and 20.6 g of GBL was added thereto, followed by stirring at room temperature for 2 hours. its After adding GBL 13.8 g and stirring, 3.27 g (15.0 mmol) of pyromellitic dianhydride was added, and 6.82 g of GBL was added, and the mixture was stirred at room temperature for 24 hours. The obtained polyaminic acid solution has a viscosity at 25 ° C of 12,290 mPa. s. Further, the molecular weight of polylysine was Mn = 21,677 and Mw = 76,020.

Further, 0.0362 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyaminic acid solution (PAA-14).

<Synthesis Example 20>

Into a 300 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 9.02 g (30.23 mmol) of 1,3-bis(4-aminophenethyl)urea was added, and 31.38 g of NMP was added thereto, and the mixture was stirred while being fed with nitrogen. Dissolved. After the diamine solution was stirred, 5.93 g (29.93 mmol) of 1,2,3,4-butanetetracarboxylic acid dianhydride was added, and 8.97 g of NMP was further added thereto, and the mixture was stirred at room temperature for 24 hours. The viscosity of the polyaminic acid solution at a temperature of 25 ° C is 7,600 mPa. s. Further, the molecular weight of the polyamic acid was Mn = 12,084 and Mw = 28,577.

Further, 0.0483 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyaminic acid solution (PAA-15).

<Synthesis Example 21>

To a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 0.48 g (3.15 mmol) of 3,5-diaminobenzoic acid and 2.56 g of 4,4'-diaminodiphenyl ether (12.8 mmol) were added. ), NMP 7.17g and GBL 3.60 g, stirred while being fed with nitrogen to dissolve. To the diamine solution, 1.90 g (9.59 mmol) of 1,2,3,4-butanetetracarboxylic dianhydride was added thereto, and 3.60 g of GBL was added thereto, and the mixture was stirred at room temperature for 2 hours. Next, after adding GBL 14.3g and stirring, 1.36 g (6.24 mmol) of pyromellitic dianhydride was added, and 7.13 g of GBL was added, and it stirred at room temperature for 24 hours. The obtained polyaminic acid solution has a viscosity of 418 mPa at 25 ° C. s. Further, the molecular weight of polylysine was Mn = 10,441 and Mw = 22,031.

Further, 0.019 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyaminic acid solution (PAA-16).

<Synthesis Example 22>

To a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 0.61 g (4.01 mmol) of 3,5-diaminobenzoic acid and 2.00 g (9.99 mmol) of 4,4'-diaminodiphenyl ether were added. , 4.20 g (6.02 mmol) of 4,4'-diaminodiphenylamine, 7.24 g of NMP and 5.40 g of GBL, and stirred while being fed with nitrogen to dissolve. To the diamine solution, 2.38 g (12.0 mmol) of 1,2,3,4-butanetetracarboxylic dianhydride was added thereto, and 5.30 g of GBL was added thereto, and the mixture was stirred at room temperature for 2 hours. Next, after adding GBL 14.4g and stirring, 1.70 g (7.75 mmol) of pyromellitic dianhydride was added, and 3.59 g of GBL was added, and it stirred at room temperature for 24 hours. The viscosity of the obtained polyaminic acid solution at 25 ° C is 1,773 mPa. s. Further, the molecular weight of polyproline was Mn = 12,285 and Mw = 26,366.

Further adding 3-glycidoxypropylmethyldiethoxy oxime to this solution 0.0237 g of alkane was stirred at room temperature for 24 hours to obtain a polyaminic acid solution (PAA-17).

<Synthesis Example 23>

To a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 1.72 g (12.6 mmol) of 3-((methylamino)methyl)aniline, 1,3-bis(4-aminophenylethyl) The base urea 1.61 g (5.40 mmol), NMP 7.91 g, and GBL 11.90 g were stirred and dissolved while feeding nitrogen. To the diamine solution, 2.14 g (10.8 mmol) of 1,2,3,4-butanetetracarboxylic dianhydride was added thereto, and 11.9 g of GBL was added thereto, followed by stirring at room temperature for 2 hours. Next, after stirring to add 3.97 g of GBL, 1.53 g (7.01 mmol) of tetracarboxylic dianhydride was added, and 3.97 g of GBL was added, and the mixture was stirred at room temperature for 24 hours. The obtained polyaminic acid solution has a viscosity of 118 mPa at 25 ° C. s. Further, the molecular weight of the polyproline was Mn = 8,646 and Mw = 15,794.

Further, 0.010 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyaminic acid solution (PAA-18).

<Synthesis Example 24>

To a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 1.89 g (12.6 mmol) of 4-(2-(methylamino)ethyl)aniline and 1,3-bis(4-amino group) were added. 1.61 g (5.40 mmol) of phenethyl)urea, 8.13 g of NMP and 12.09 g of GBL were stirred and dissolved while feeding nitrogen. Adding 1,2,3,4-butane tetracarboxylic acid while stirring the diamine solution 2.14 g (10.8 mmol) of dianhydride was added to 12.2 g of GBL, and the mixture was stirred at room temperature for 2 hours. Next, GBL 4.07g was added, and after stirring, 1.53 g (7.01 mmol) of pyromellitic dianhydride was added, and GBL 4.07 g was added, and the mixture was stirred at room temperature for 24 hours. The obtained polyaminic acid solution has a viscosity of 674 mPa at 25 ° C. s. Further, the molecular weight of polyproline was Mn = 12,584 and Mw = 39,895.

Further, 0.015 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyaminic acid solution (PAA-19).

<Synthesis Example 25>

To a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 0.76 g (5.00 mmol) of 3,5-diaminobenzoic acid and 1,3-bis(4-aminophenethyl)urea 2.23 were added. g (7.51 mmol), 2.50 g (12.5 mmol) of 4,4'-diaminodiphenyl ether, 9.85 g of NMP and 7.23 g of GBL were stirred and dissolved while feeding nitrogen. To the diamine solution, 3.15 g (15.0 mmol) of 1,2,3,4-cyclopentanetetracarboxylic dianhydride was added thereto, and 7.28 g of GBL was added thereto, and the mixture was stirred at room temperature for 2 hours. Next, after stirring to add 19.4 g of GBL, 2.18 g (9.99 mmol) of pyromellitic dianhydride was added, and 5.50 g of GBL was added, and the mixture was stirred at room temperature for 24 hours. The obtained polyaminic acid solution has a viscosity at 25 ° C of 3,004 mPa. s. Further, the molecular weight of polylysine was Mn = 12,004 and Mw = 30,102.

Further, 0.0319 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyamidonic acid solution. (PAA-20).

<Synthesis Example 26>

To a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 0.76 g (5.00 mmol) of 3,5-diaminobenzoic acid and 1,3-bis(4-aminophenethyl)urea 2.23 were added. g (7.51 mmol), 2.50 g (12.5 mmol) of 4,4'-diaminodiphenyl ether, 11.1 g of NMP and 7.23 g of GBL were stirred and dissolved while feeding nitrogen. The diamine solution was stirred while adding 4.50 g (15.0 mmol) of 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dianhydride, and added to GBL 7.28 g at room temperature. Stir for 2 hours. Next, after stirring to add 19.4 g of GBL, 2.18 g (9.99 mmol) of pyromellitic dianhydride was added, and 10.5 g of GBL was added, and the mixture was stirred at room temperature for 24 hours. The obtained polyaminic acid solution has a viscosity of 3,500 mPa at 25 ° C. s. Further, the molecular weight of the polylysine was Mn = 11,000 and Mw = 28,100.

Further, 0.0320 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyaminic acid solution (PAA-21).

<Synthesis Example 27>

To a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 0.76 g (5.00 mmol) of 3,5-diaminobenzoic acid and 1,3-bis(4-aminophenethyl)urea 2.23 were added. g (7.51 mmol), 2.50 g (12.5 mmol) of 4,4'-diaminodiphenyl ether, 10.1 g of NMP and 7.23 g of GBL were stirred and dissolved while feeding nitrogen. Add this diamine solution while stirring 2.36 g (15.0 mmol) of 2,3,5-tricarboxycyclopentyl acetic acid-1,4:2,3-dianhydride was added to 7.28 g of GBL, and stirred at room temperature for 2 hours. Next, after stirring to add 19.4 g of GBL, 2.18 g (9.99 mmol) of pyromellitic dianhydride was added, and 6.30 g of GBL was added, and the mixture was stirred at room temperature for 24 hours. The obtained polyaminic acid solution has a viscosity of 3,200 mPa at 25 ° C. s. Further, the molecular weight of the polyamic acid was Mn = 10,100 and Mw = 24,100.

Further, 0.0320 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyaminic acid solution (PAA-22).

<Synthesis Example 28>

To a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 0.76 g (5.00 mmol) of 3,5-diaminobenzoic acid and 1,3-bis(4-aminophenethyl)urea 2.23 were added. g (7.51 mmol), 2.50 g (12.5 mmol) of 4,4'-diaminodiphenyl ether, 10.4 g of NMP, and 7.23 g of GBL were stirred and dissolved while feeding nitrogen. The diamine solution was stirred while adding 3.75 g (15.0 mmol) of bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride, and 7.28 g of GBL was added thereto, and the mixture was stirred at room temperature for 2 hours. . Next, 19.4 g of GBL was added, and after stirring, 2.18 g (9.99 mmol) of pyromellitic dianhydride was added, and 7.72 g of GBL was added, and the mixture was stirred at room temperature for 24 hours. The obtained polyaminic acid solution has a viscosity at 25 ° C of 3,300 mPa. s. Further, the molecular weight of the polylysine was Mn = 11,100 and Mw = 25,100.

Further, 0.0320 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyamidonic acid solution. (PAA-23).

<Synthesis Example 29>

To a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 0.76 g (5.00 mmol) of 3,5-diaminobenzoic acid and 1,3-bis(4-aminophenethyl)urea 2.23 were added. g (7.51 mmol), 2.50 g (12.5 mmol) of 4,4'-diaminodiphenyl ether, 10.1 g of NMP and 7.23 g of GBL were stirred and dissolved while feeding nitrogen. To the diamine solution, 3.36 g (15.0 mmol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride was added thereto, and 7.28 g of GBL was added thereto, and the mixture was stirred at room temperature for 2 hours. Next, after stirring to add 19.4 g of GBL, 2.18 g (9.99 mmol) of pyromellitic dianhydride was added, and 6.29 g of GBL was added, and the mixture was stirred at room temperature for 24 hours. The obtained polyaminic acid solution has a viscosity at 25 ° C of 3,300 mPa. s. Further, the molecular weight of the polylysine was Mn = 9,100 and Mw = 20,100.

Further, 0.0320 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyamidonic acid solution (PAA-24).

<Synthesis Example 30>

To a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 0.46 g (3.00 mmol) of 3,5-diaminobenzoic acid and 3.00 g of 4,4'-diaminodiphenyl ether (15.0 mmol) were added. 2,4'-Diaminodiphenylmethylamine 2.56 g (12.0 mmol), NMP 11.0 g, and GBL 8.10 g were stirred and dissolved while feeding nitrogen. Add the 1,2,3,4- while stirring the diamine solution. Butane tetracarboxylic dianhydride 4.76 g (24.0 mmol) was added to 10.9 g of GBL and stirred at room temperature for 2 hours. Next, GBL 10.8g was added, and after stirring, 1.31 g (6.01 mmol) of pyromellitic dianhydride was added, and 14.3 g of GBL was added, and the mixture was stirred at room temperature for 24 hours. The viscosity of the obtained polyaminic acid solution at 25 ° C is 2,041 mPa. s. Further, the molecular weight of polylysine was Mn = 14,200 and Mw = 30,110.

Further, 0.0358 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyaminic acid solution (PAA-25).

[Modulation of Liquid Crystal Aligning Agent] (Example 1)

A stirrer was placed in a 50 ml Erlenmeyer flask, and 3.30 g of the polyamidate solution (PAE-1) obtained in Synthesis Example 1 and 3.81 g of the polyamidonic acid solution (PAA-1) obtained in Synthesis Example 5 were weighed. NMP 0.45 g, GBL 4.43 g, BCS 3.01 g, and additive A 0.117 g were added, and stirred with a magnetic stirrer (Magnetic Stirrer) for 30 minutes to obtain a liquid crystal alignment agent (VIII-1).

(Example 2)

A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.64 g of the polyamidate solution (PAE-1) obtained in Synthesis Example 1 and 2.46 g of the polyamidonic acid solution (PAA-2) obtained in Synthesis Example 6 were weighed. Add NMP 0.48g, GBL 4.02g, BCS 2.42g and additive A 0.092g, stir with a magnetic stirrer The liquid crystal alignment agent (VIII-2) was obtained in 30 minutes.

(Example 3)

A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.65 g of the polyamidate solution (PAE-1) obtained in Synthesis Example 1 and 2.51 g of the polyamidonic acid solution (PAA-3) obtained in Synthesis Example 7 were weighed. NMP 0.47 g, GBL 3.99 g, BCS 2.41 g, and additive A 0.092 g were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (VIII-3).

(Example 4)

A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.66 g of the polyamidomate solution (PAE-1) obtained in Synthesis Example 1 and 2.63 g of the polyamidonic acid solution (PAA-4) obtained in Synthesis Example 8 were weighed. NMP 0.44 g, GBL 3.90 g, BCS 2.45 g, and additive A 0.092 g were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (VIII-4).

(Comparative Example 1)

A stirrer was placed in a 50 ml Erlenmeyer flask, and 3.29 g of the polyamidate solution (PAE-1) obtained in Synthesis Example 1 and 2.86 g of the polyamidonic acid solution (PAA-17) obtained in Synthesis Example 22 were weighed. NMP 0.68 g, GBL 5.22 g, BCS 3.14 g, and additive A 0.1190 g were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (VIII-5).

(Comparative Example 2)

A stirrer was placed in a 50 ml Erlenmeyer flask, and 3.96 g of the polyamidate solution (PAE-1) obtained in Synthesis Example 1 and 3.73 g of the polyamidonic acid solution (PAA-6) obtained in Synthesis Example 10 were weighed. NMP 0.04 g, GBL 6.66 g, BCS 3.61 g, and additive A 0.139 g were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (VIII-6).

(Comparative Example 3)

A stirrer was placed in a 50 ml Erlenmeyer flask, and 3.97 g of the polyamidate solution (PAE-1) obtained in Synthesis Example 1 and 3.73 g of the polyamidonic acid solution (PAA-7) obtained in Synthesis Example 11 were weighed. NMP 0.04 g, GBL 6.67 g, BCS 3.62 g, and additive A 0.138 g were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (VIII-7).

(Comparative Example 4)

A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.64 g of the polyamidate solution (PAE-1) obtained in Synthesis Example 1 and 2.40 g of the polyamidonic acid solution (PAA-8) obtained in Synthesis Example 12 were weighed. NMP 0.05 g, GBL 4.52 g, BCS 2.41 g, and additive A 0.092 g were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (VIII-8).

(Comparative Example 5)

A stirrer was placed in a 50 ml Erlenmeyer flask, and 3.30 g of the polyamidate solution (PAE-1) obtained in Synthesis Example 1 and 2.00 g of the polyamidonic acid solution (PAA-8) obtained in Synthesis Example 12 were weighed. Add NMP 0.11g, GBL 4.19 g, BCS 2.41 g and additive A 0.090 g were stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (VIII-9).

[Evaluation of Membrane Transmittance] (Example 5)

The liquid crystal alignment agent (VIII-1) obtained in Example 1 was filtered through a 1.0 μm filter, and a coating film having a thickness of 100 nm was formed in accordance with the above-mentioned measurement of "transmittance measurement", and the transmittance was measured. The transmittance of the obtained film was 99.9%.

(Example 6)

The liquid crystal alignment agent (VIII-2) obtained in Example 2 was filtered through a 1.0 μm filter, and a coating film having a thickness of 100 nm was formed in accordance with the above-mentioned measurement of "transmittance measurement", and the transmittance was measured. The transmittance of the obtained film was 99.8%.

(Example 7)

The liquid crystal alignment agent (VIII-3) obtained in Example 3 was filtered through a filter of 1.0 μm, and a coating film having a thickness of 100 nm was formed in accordance with the above-mentioned measurement of "transmittance measurement", and the transmittance was measured. The transmittance of the obtained film was 99.9%.

(Example 8)

The liquid crystal alignment agent (VIII-4) obtained in Example 4 was used at 1.0 μm. After filtration by the filter, a coating film having a thickness of 100 nm was formed in accordance with the above description of [transmittance measurement], and the transmittance was measured. The transmittance of the obtained film was 99.9%.

(Comparative Example 6)

The liquid crystal alignment agent (VIII-5) obtained in Comparative Example 1 was filtered through a filter of 1.0 μm, and a coating film having a thickness of 100 nm was formed in accordance with the above-mentioned measurement of "transmittance measurement", and the transmittance was measured. The transmittance of the obtained film was 95.3%.

(Comparative Example 7)

The liquid crystal alignment agent (VIII-6) obtained in Comparative Example 2 was filtered through a filter of 1.0 μm, and a coating film having a thickness of 100 nm was formed in accordance with the above-mentioned measurement of "transmittance measurement", and the transmittance was measured. The transmittance of the obtained film was 96.3%.

(Comparative Example 8)

The liquid crystal alignment agent (VIII-7) obtained in Comparative Example 3 was filtered through a filter of 1.0 μm, and a coating film having a thickness of 100 nm was formed in accordance with the above-mentioned measurement of "transmittance measurement", and the transmittance was measured. The transmittance of the obtained film was 96.2%.

(Comparative Example 9)

The liquid crystal alignment agent (VIII-8) obtained in Comparative Example 4 was used at 1.0 μm. After filtration by the filter, a coating film having a thickness of 100 nm was formed in accordance with the above description of [transmittance measurement], and the transmittance was measured. The transmittance of the obtained film was 94.4%.

(Comparative Example 10)

The liquid crystal alignment agent (VIII-9) obtained in Comparative Example 5 was filtered through a filter of 1.0 μm, and a coating film having a thickness of 100 nm was formed in accordance with the above-mentioned measurement of "transmittance measurement", and the transmittance was measured. The transmittance of the obtained film was 96.5%.

The results of the transmittance of the film obtained above are shown in Table 1.

[Evaluation of charge accumulation characteristics] (Example 9)

The liquid crystal alignment agent (VIII-1) obtained in Example 1 was filtered using a 1.0 μm filter, and the above [FFS-driven liquid crystal cell production] was followed. The FFS is driven to drive the liquid crystal cell. As a result of the evaluation of the above-mentioned [charge accumulation characteristics], the liquid crystal cell was driven by the FFS, and ΔT after AC driving for 60 minutes was 1.9%.

(Embodiment 10)

The evaluation of the charge storage characteristics was carried out in the same manner as in Example 9 except that the liquid crystal alignment agent (VIII-2) obtained in Example 2 was used, and ΔT after AC driving for 60 minutes was 1.5%.

(Example 11)

The evaluation of the charge storage characteristics was carried out in the same manner as in Example 9 except that the liquid crystal alignment agent (VIII-3) obtained in Example 3 was used, and ΔT after AC driving for 60 minutes was 1.8%.

(Embodiment 12)

In the same manner as in Example 9, except that the liquid crystal alignment agent (VIII-4) obtained in Example 4 was used, the evaluation of the charge storage characteristics was carried out, and ΔT after AC driving for 60 minutes was 1.9%.

(Comparative Example 11)

The evaluation of the charge storage characteristics was carried out in the same manner as in Example 9 except that the liquid crystal alignment agent (VIII-5) obtained in Comparative Example 1 was used, and ΔT after AC driving for 60 minutes was 2.4%.

(Comparative Example 12)

The evaluation of the charge storage characteristics was carried out in the same manner as in Example 9 except that the liquid crystal alignment agent (VIII-6) obtained in Comparative Example 2 was used, and ΔT after AC driving for 60 minutes was 3.0%.

(Comparative Example 13)

In the same manner as in Example 9, except that the liquid crystal alignment agent (VIII-7) obtained in Comparative Example 3 was used, as a result of evaluation of charge storage characteristics, ΔT after AC driving for 60 minutes was 2.8%.

(Comparative Example 14)

In the same manner as in Example 9, except that the liquid crystal alignment agent (VIII-8) obtained in Comparative Example 4 was used, the charge storage characteristics were evaluated, and ΔT after AC driving for 60 minutes was 2.0%.

(Comparative Example 15)

The evaluation of the charge storage characteristics was carried out in the same manner as in Example 9 except that the liquid crystal alignment agent (VIII-9) obtained in Comparative Example 5 was used, and ΔT after AC driving for 60 minutes was 1.5%.

The results of evaluation of the charge accumulation characteristics obtained above are shown in Table 2.

[Evaluation of AC-driven afterimages] (Example 13)

The liquid crystal alignment agent (VIII-1) obtained in Example 1 was filtered using a 1.0 μm filter, and an FFS-driven liquid crystal cell was obtained in accordance with the above [Production of FFS-driven liquid crystal cell].

Using the liquid crystal cell produced as described above, the average value of the angle Δ of the first pixel and the second pixel is calculated as the result of calculating the angle Δ of the liquid crystal cell, and the residual image is Δ. It is 0.081.

(Example 14)

In the same manner as in Example 13, except that the liquid crystal alignment agent (VIII-2) obtained in Example 2 was used, the average value of the angle Δ values of the first pixel and the second pixel was used as the result of calculating the angle Δ of the liquid crystal cell. The AC drive residual image △ is 0.072.

(Example 15)

In the same manner as in Example 13, except that the liquid crystal alignment agent (VIII-3) obtained in Example 3 was used, the average value of the angle Δ values of the first pixel and the second pixel was used as the result of calculating the angle Δ of the liquid crystal cell. The AC drive residual image △ is 0.052.

(Embodiment 16)

In the same manner as in Example 13, except that the liquid crystal alignment agent (VIII-4) obtained in Example 4 was used, the average value of the angle Δ values of the first pixel and the second pixel was used as the result of calculating the angle Δ of the liquid crystal cell. The AC drive residual image △ is less than 0.001.

(Comparative Example 16)

In the same manner as in Example 13, except that the liquid crystal alignment agent (VIII-5) obtained in Comparative Example 1 was used, the average value of the angle Δ values of the first pixel and the second pixel was used as the result of calculating the angle Δ of the liquid crystal cell. The AC drive residual image △ is 0.125.

(Comparative Example 17)

In the same manner as in Example 13, except that the liquid crystal alignment agent (VIII-6) obtained in Comparative Example 2 was used, the average value of the angle Δ values of the first pixel and the second pixel was used as the result of calculating the angle Δ of the liquid crystal cell. The AC drive residual image △ is 0.109.

(Comparative Example 18)

In the same manner as in Example 13, except that the liquid crystal alignment agent (VIII-7) obtained in Comparative Example 3 was used, the average value of the angle Δ values of the first pixel and the second pixel was used as the result of calculating the angle Δ of the liquid crystal cell. The AC drive residual image △ is 0.140.

(Comparative Example 19)

In the same manner as in Example 13, except that the liquid crystal alignment agent (VIII-8) obtained in Comparative Example 4 was used, the average value of the angle Δ values of the first pixel and the second pixel was used as the result of calculating the angle Δ of the liquid crystal cell. The AC drive residual image Δ is 0.005.

(Comparative Example 20)

In the same manner as in Example 13, except that the liquid crystal alignment agent (VIII-9) obtained in Comparative Example 5 was used, the average value of the angle Δ values of the first pixel and the second pixel was used as the result of calculating the angle Δ of the liquid crystal cell. The AC drive residual image △ is 0.046.

The results of the evaluation of the AC-driven afterimage obtained above are shown in Table 3.

[Modulation of Liquid Crystal Aligning Agent] (Example 17)

A stirrer was placed in a 50 ml Erlenmeyer flask, and 8.40 g of the polyamidate solution (PAE-5) obtained in Synthesis Example 14 and 7.27 g of the polyaminic acid solution (PAA-9) obtained in Synthesis Example 13 were weighed. N3 32.3 g, BCS 12.0 g, and additive A 0.235 g were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (VIII-10).

(Embodiment 18)

A stirrer was placed in a 50 ml Erlenmeyer flask, and 3.35 g of the polyamidate solution (PAE-1) obtained in Synthesis Example 1 and 2.62 g of the polyamidonic acid solution (PAA-10) obtained in Synthesis Example 15 were weighed. NMP 0.43 g, GBL 3.26 g, BCS 2.40 g, and additive A 0.0914 g were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (VIII-11).

(Embodiment 19)

A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.74 g of the polyamidate solution (PAE-1) obtained in Synthesis Example 1 and 1.75 g of the polyamidonic acid solution (PAA-12) obtained in Synthesis Example 17 were weighed. NMP 0.46 g, GBL 3.06 g, BCS 2.00 g, and additive A 0.0806 g were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (VIII-12).

(Comparative Example 21)

A stirrer was placed in a 50 ml Erlenmeyer flask, and 3.96 g of the polyamidomate solution (PAE-1) obtained in Synthesis Example 1 and 5.27 g of the polyamidonic acid solution (PAA-5) obtained in Synthesis Example 9 were weighed. NMP 0.40 g, GBL 4.76 g, BCS 3.60 g, and additive B 0.1386 g were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (VIII-13).

[Evaluation of Membrane Transmittance] (Embodiment 20)

The liquid crystal alignment agent (VIII-10) obtained in Example 17 was filtered through a 1.0 μm filter, and a coating film having a film thickness of 100 nm was formed in accordance with the above-mentioned measurement of "transmittance measurement", and the transmittance was measured. The transmittance of the obtained film was 99.9%.

(Example 21)

The liquid crystal alignment agent (VIII-11) obtained in Example 18 was filtered through a 1.0 μm filter, and a coating film having a film thickness of 100 nm was formed in accordance with the above-mentioned measurement of "transmittance measurement", and the transmittance was measured. Film obtained The transmission rate is 99.9%.

(Example 22)

The liquid crystal alignment agent (VIII-12) obtained in Example 19 was filtered through a 1.0 μm filter, and a coating film having a film thickness of 100 nm was formed in accordance with the above-mentioned measurement of "transmittance measurement", and the transmittance was measured. The transmittance of the obtained film was 99.9%.

(Comparative Example 22)

The liquid crystal alignment agent (VIII-13) obtained in Comparative Example 21 was filtered through a 1.0 μm filter, and a coating film having a film thickness of 100 nm was formed in accordance with the above-mentioned [Transmission Rate Measurement], and the transmittance was measured. The transmittance of the obtained film was 96.4%.

The results of the transmittance of the film obtained above are shown in Table 4.

[Evaluation of charge accumulation characteristics] (Example 23)

The evaluation of the charge storage characteristics was carried out in the same manner as in Example 9 except that the liquid crystal alignment agent (VIII-10) obtained in Example 17 was used. As a result, ΔT after 60 minutes of AC driving was 0%.

(Example 24)

The evaluation of the charge storage characteristics was carried out in the same manner as in Example 9 except that the liquid crystal alignment agent (VIII-11) obtained in Example 18 was used, and the ΔT after AC driving for 60 minutes was 1.4%.

(Embodiment 25)

The evaluation of the charge storage characteristics was carried out in the same manner as in Example 9 except that the liquid crystal alignment agent (VIII-12) obtained in Example 19 was used, and ΔT after 60 minutes of AC driving was 0%.

(Comparative Example 23)

The evaluation of the charge storage characteristics was carried out in the same manner as in Example 9 except that the liquid crystal alignment agent (VIII-13) obtained in Comparative Example 21 was used, and ΔT after AC driving for 60 minutes was 3.1%.

The results of evaluation of the charge storage characteristic film obtained above are shown in Table 5.

[Evaluation of AC-driven afterimages] (Example 26)

In the same manner as in Example 13, except that the liquid crystal alignment agent (VIII-10) obtained in Example 17 was used, the average value of the angle Δ values of the first pixel and the second pixel was used as the result of calculating the angle Δ of the liquid crystal cell. The AC drive residual image △ is 0.015.

(Example 27)

In the same manner as in Example 13, except that the liquid crystal alignment agent (VIII-11) obtained in Example 18 was used, the average value of the angle Δ values of the first pixel and the second pixel was used as the result of calculating the angle Δ of the liquid crystal cell. The AC drive residual image △ is 0.056.

(Embodiment 28)

In the same manner as in Example 13, except that the liquid crystal alignment agent (VIII-12) obtained in Example 19 was used, the average value of the angle Δ values of the first pixel and the second pixel was used as the result of calculating the angle Δ of the liquid crystal cell. The AC drive residual image △ is 0.092.

(Comparative Example 24)

In the same manner as in Example 13, except that the liquid crystal alignment agent (VIII-13) obtained in Comparative Example 21 was used, the average value of the angle Δ values of the first pixel and the second pixel was used as the result of calculating the angle Δ of the liquid crystal cell. , The AC drive residual image Δ is 0.062.

The results of the evaluation of the AC-driven afterimage obtained above are shown in Table 6.

[Modulation of Liquid Crystal Aligning Agent] (Comparative Example 25)

A stirrer was placed in a 50 ml Erlenmeyer flask, and 3.30 g of the polyamidate solution (PAE-1) obtained in Synthesis Example 1 and 1.98 g of the polyaminic acid solution (PAA-15) obtained in Synthesis Example 20 were weighed. NMP 6.74 g, BCS 3.00 g, and additive A 0.1269 g were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (VIII-14).

(Comparative Example 26)

A stirrer was placed in a 50 ml Erlenmeyer flask, and 3.30 g of the polyamidate solution (PAE-1) obtained in Synthesis Example 1 and 3.31 g of the polyamidic acid solution (PAA-16) obtained in Synthesis Example 21 were weighed. NMP 0.58 g, GBL 4.83 g, BCS 3.01 g, and additive A 0.1092 g were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (VIII-15).

[Evaluation of Membrane Transmittance] (Comparative Example 27)

The liquid crystal alignment agent (VIII-14) obtained in Comparative Example 25 was filtered through a filter of 1.0 μm, and a coating film having a thickness of 100 nm was formed in accordance with the above-mentioned measurement of "transmittance measurement", and the transmittance was measured. The transmittance of the obtained film was 99.9%.

(Comparative Example 28)

The liquid crystal alignment agent (VIII-15) obtained in Comparative Example 26 was filtered through a 1.0 μm filter, and a coating film having a thickness of 100 nm was formed in accordance with the above description of [Transmission Measurement], and the transmittance was measured. The transmittance of the obtained film was 99.9%.

The results of the transmittance of the film obtained above are shown in Table 7.

[Evaluation of charge accumulation characteristics] (Comparative Example 29)

The results of evaluation of the charge storage characteristics were carried out in the same manner as in Example 9 except that the liquid crystal alignment agent (VIII-14) obtained in Comparative Example 25 was used, and ΔT after 60 minutes of AC driving was 0%.

(Comparative Example 30)

The evaluation of the charge storage characteristics was carried out in the same manner as in Example 9 except that the liquid crystal alignment agent (VIII-15) obtained in Comparative Example 26 was used, and ΔT after 60 minutes of AC driving was 8.0%.

The results of evaluation of the charge storage property film obtained above are shown in Table 8.

[Evaluation of AC-driven afterimages] (Comparative Example 31)

In the same manner as in Example 13, except that the liquid crystal alignment agent (VIII-14) obtained in Comparative Example 25 was used, the average value of the angle Δ values of the first pixel and the second pixel was used as the result of calculating the angle Δ of the liquid crystal cell. The AC drive residual image △ is 0.358.

(Comparative Example 32)

In the same manner as in Example 13, except that the liquid crystal alignment agent (VIII-15) obtained in Comparative Example 26 was used, the average value of the angle Δ values of the first pixel and the second pixel was used as the result of calculating the angle Δ of the liquid crystal cell. The AC drive residual image △ is 0.138.

The results of the evaluation of the AC-driven afterimage obtained above are shown in Table 9.

[Modulation of Liquid Crystal Aligning Agent] (Example 29)

A stirrer was placed in a 50 ml Erlenmeyer flask, and 3.32 g of the polyamidate solution (PAE-1) obtained in Synthesis Example 1 and 3.36 g of the polyamidonic acid solution (PAA-18) obtained in Synthesis Example 23 were weighed. NMP 0.55 g, GBL 4.81 g, BCS 3.02 g, and additive A 0.1173 g were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (VIII-16).

(Embodiment 30)

A stirrer was placed in a 50 ml Erlenmeyer flask, and 3.30 g of the polyamidate solution (PAE-1) obtained in Synthesis Example 1 and 3.32 g of the polyamidonic acid solution (PAA-19) obtained in Synthesis Example 24 were weighed. NMP 0.39 g, GBL 4.81 g, BCS 3.02 g, and additive A 0.1147 g were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (VIII-17).

(Example 31)

A stirrer was placed in a 50 ml Erlenmeyer flask, and the synthesis example 1 was weighed. The polyphthalate solution (PAE-1) was obtained in an amount of 3.32 g, and the polyaminic acid solution (PAA-14) obtained in Synthesis Example 19 was 1.75 g, and NMP 0.51 g, GBL 4.63 g, BCS 2.99 g, and additive A 0.1180 were added. g, stirring with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (VIII-18).

(Example 32)

A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.64 g of the polyamidate solution (PAE-2) obtained in Synthesis Example 2 and 2.46 g of the polyaminic acid solution (PAA-2) obtained in Synthesis Example 6 were weighed. NMP 0.48 g, GBL 4.02 g, BCS 2.42 g, and additive A 0.092 g were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (VIII-19).

(Example 33)

A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.64 g of the polyamidate solution (PAE-1) obtained in Synthesis Example 1 and 2.46 g of the polyamidonic acid solution (PAA-20) obtained in Synthesis Example 25 were weighed. NMP 0.48 g, GBL 4.02 g, BCS 2.42 g, and additive A 0.092 g were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (VIII-20).

(Example 34)

A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.64 g of the polyamidate solution (PAE-1) obtained in Synthesis Example 1 and 2.46 g of the polyamidonic acid solution (PAA-21) obtained in Synthesis Example 26 were weighed. Add NMP 0.48g, GBL 4.02g, BCS 2.42g and additive A 0.083g, stir with a magnetic stirrer A liquid crystal alignment agent (VIII-21) was obtained in 30 minutes.

(Example 35)

A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.64 g of the polyamidomate solution (PAE-1) obtained in Synthesis Example 1 and 2.46 g of the polyaminic acid solution (PAA-22) obtained in Synthesis Example 27 were weighed. NMP 0.48 g, GBL 4.02 g, BCS 2.42 g, and additive A 0.092 g were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (VIII-22).

(Example 36)

A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.64 g of the polyamidate solution (PAE-1) obtained in Synthesis Example 1 and 2.46 g of the polyaminic acid solution (PAA-23) obtained in Synthesis Example 28 were weighed. NMP 0.48 g, GBL 4.02 g, BCS 2.42 g, and additive A 0.092 g were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (VIII-23).

(Example 37)

A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.64 g of the polyamidate solution (PAE-1) obtained in Synthesis Example 1 and 2.46 g of the polyamidonic acid solution (PAA-24) obtained in Synthesis Example 29 were weighed. NMP 0.48 g, GBL 4.02 g, BCS 2.42 g, and additive A 0.092 g were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (VIII-24).

(Example 38)

A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.64 g of the polyamidate solution (PAE-3) obtained in Synthesis Example 3 and 2.46 g of the polyamidonic acid solution (PAA-2) obtained in Synthesis Example 6 were weighed. NMP 0.48 g, GBL 4.02 g, BCS 2.42 g, and additive A 0.092 g were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (VIII-25).

(Example 39)

A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.64 g of the polyamidate solution (PAE-4) obtained in Synthesis Example 4 and 2.46 g of the polyamidonic acid solution (PAA-2) obtained in Synthesis Example 6 were weighed. NMP 0.48 g, GBL 4.02 g, BCS 2.42 g, and additive A 0.092 g were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (VIII-26).

(Embodiment 40)

A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.64 g of the polyamidate solution (PAE-1) obtained in Synthesis Example 1 and 2.46 g of the polyamidonic acid solution (PAA-2) obtained in Synthesis Example 6 were weighed. NMP 0.48 g, GBL 4.02 g, BCS 2.42 g, and additive B 0.092 g were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (VIII-27).

(Comparative Example 33)

A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.64 g of the polyamidate solution (PAE-1) obtained in Synthesis Example 1 and 2.40 g of the polyamidonic acid solution (PAA-25) obtained in Synthesis Example 30 were weighed. Add NMP 0.05g, GBL 4.52 g, BCS 2.41 g and additive A 0.092 g were stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (VIII-28).

[Evaluation of Membrane Transmittance] (Example 41)

The liquid crystal alignment agent (VIII-16) obtained in Example 29 was filtered through a 1.0 μm filter, and a coating film having a film thickness of 100 nm was formed in accordance with the above-mentioned measurement of "transmittance measurement", and the transmittance was measured. The transmittance of the obtained film was 99.9%.

(Example 42)

The liquid crystal alignment agent (VIII-17) obtained in Example 30 was filtered through a 1.0 μm filter, and a coating film having a film thickness of 100 nm was formed in accordance with the above-mentioned measurement of "transmittance measurement", and the transmittance was measured. The transmittance of the obtained film was 99.9%.

(Example 43)

The liquid crystal alignment agent (VIII-18) obtained in Example 31 was filtered using a 1.0 μm filter, and a coating film having a film thickness of 100 nm was formed in accordance with the above-mentioned measurement of "transmittance measurement", and the transmittance was measured. The transmittance of the obtained film was 99.9%.

(Example 44)

The liquid crystal alignment agent (VIII-19) obtained in Example 32 was used. After filtering through a 1.0 μm filter, a coating film having a thickness of 100 nm was formed in accordance with the above-mentioned description of [transmittance measurement], and the transmittance was measured. The transmittance of the obtained film was 99.9%.

(Example 45)

The liquid crystal alignment agent (VIII-20) obtained in Example 33 was filtered through a 1.0 μm filter, and a coating film having a film thickness of 100 nm was formed in accordance with the above-mentioned measurement of "transmittance measurement", and the transmittance was measured. The transmittance of the obtained film was 99.9%.

(Example 46)

The liquid crystal alignment agent (VIII-21) obtained in Example 34 was filtered through a 1.0 μm filter, and a coating film having a thickness of 100 nm was formed in accordance with the above-mentioned [Transmission Measurement], and the transmittance was measured. The transmittance of the obtained film was 99.9%.

(Example 47)

The liquid crystal alignment agent (VIII-22) obtained in Example 35 was filtered through a 1.0 μm filter, and a coating film having a film thickness of 100 nm was formed in accordance with the above-mentioned measurement of "transmittance measurement", and the transmittance was measured. The transmittance of the obtained film was 99.9%.

(Example 48)

Use of the liquid crystal alignment agent (VIII-23) obtained in Example 36 After filtering through a 1.0 μm filter, a coating film having a thickness of 100 nm was formed in accordance with the above-mentioned description of [transmittance measurement], and the transmittance was measured. The transmittance of the obtained film was 99.9%.

(Example 49)

The liquid crystal alignment agent (VIII-24) obtained in Example 37 was filtered through a 1.0 μm filter, and a coating film having a film thickness of 100 nm was formed in accordance with the above-mentioned measurement of "transmittance measurement", and the transmittance was measured. The transmittance of the obtained film was 99.9%.

(Example 50)

The liquid crystal alignment agent (VIII-25) obtained in Example 38 was filtered through a 1.0 μm filter, and a coating film having a film thickness of 100 nm was formed in accordance with the above-mentioned measurement of "transmittance measurement", and the transmittance was measured. The transmittance of the obtained film was 99.9%.

(Example 51)

The liquid crystal alignment agent (VIII-26) obtained in Example 39 was filtered using a 1.0 μm filter, and a coating film having a film thickness of 100 nm was formed in accordance with the above-mentioned "transmittance measurement", and the transmittance was measured. The transmittance of the obtained film was 99.9%.

(Example 52)

The liquid crystal alignment agent (VIII-27) obtained in Example 40 was used. After filtering through a 1.0 μm filter, a coating film having a thickness of 100 nm was formed in accordance with the above-mentioned description of [transmittance measurement], and the transmittance was measured. The transmittance of the obtained film was 99.9%.

(Comparative Example 34)

The liquid crystal alignment agent (VIII-28) obtained in Comparative Example 33 was filtered through a 1.0 μm filter, and a coating film having a thickness of 100 nm was formed in accordance with the above-mentioned [Transmission Measurement], and the transmittance was measured. The transmittance of the obtained film was 95.0%.

[Evaluation of charge accumulation characteristics] (Example 53)

The evaluation of the charge storage characteristics was carried out in the same manner as in Example 9 except that the liquid crystal alignment agent (VIII-16) obtained in Example 29 was used. As a result, ΔT after 60 minutes of AC driving was 1.9%.

(Example 54)

The evaluation of the charge storage characteristics was carried out in the same manner as in Example 9 except that the liquid crystal alignment agent (VIII-17) obtained in Example 30 was used, and ΔT after AC driving for 60 minutes was 1.9%.

(Example 55)

The evaluation of the charge storage characteristics was carried out in the same manner as in Example 9 except that the liquid crystal alignment agent (VIII-18) obtained in Example 31 was used, and ΔT after AC driving for 60 minutes was 1.9%.

(Example 56)

The evaluation of the charge storage characteristics was carried out in the same manner as in Example 9 except that the liquid crystal alignment agent (VIII-19) obtained in Example 32 was used, and ΔT after AC driving for 60 minutes was 1.9%.

(Example 57)

The evaluation of the charge storage characteristics was carried out in the same manner as in Example 9 except that the liquid crystal alignment agent (VIII-20) obtained in Example 33 was used, and ΔT after AC driving for 60 minutes was 1.5%.

(Example 58)

In addition to using the liquid crystal alignment agent (VIII-21) obtained in Example 34 Further, in the same manner as in Example 9, as a result of evaluation of charge storage characteristics, ΔT after 60 minutes of AC driving was 1.5%.

(Example 59)

The evaluation of the charge storage characteristics was carried out in the same manner as in Example 9 except that the liquid crystal alignment agent (VIII-22) obtained in Example 35 was used, and ΔT after 60 minutes of AC driving was 1.6%.

(Embodiment 60)

The evaluation of the charge storage characteristics was carried out in the same manner as in Example 9 except that the liquid crystal alignment agent (VIII-23) obtained in Example 36 was used, and the ΔT after AC driving for 60 minutes was 1.4%.

(Example 61)

The evaluation of the charge storage characteristics was carried out in the same manner as in Example 9 except that the liquid crystal alignment agent (VIII-24) obtained in Example 37 was used, and ΔT after AC driving for 60 minutes was 1.7%.

(Example 62)

The evaluation of the charge storage characteristics was carried out in the same manner as in Example 9 except that the liquid crystal alignment agent (VIII-25) obtained in Example 38 was used, and ΔT after AC driving for 60 minutes was 1.9%.

(Example 63)

The evaluation of the charge storage characteristics was carried out in the same manner as in Example 9 except that the liquid crystal alignment agent (VIII-26) obtained in Example 39 was used, and ΔT after AC driving for 60 minutes was 1.9%.

(Example 64)

The evaluation of the charge storage characteristics was carried out in the same manner as in Example 9 except that the liquid crystal alignment agent (VIII-27) obtained in Example 40 was used, and ΔT after AC driving for 60 minutes was 1.5%.

(Comparative Example 35)

The evaluation of the charge storage characteristics was carried out in the same manner as in Example 9 except that the liquid crystal alignment agent (VIII-28) obtained in Comparative Example 33 was used, and ΔT after 60 minutes of AC driving was 2.0%.

[Evaluation of AC-driven afterimages] (Example 65)

In the same manner as in Example 13, except that the liquid crystal alignment agent (VIII-16) obtained in Example 29 was used, the average value of the angle Δ values of the first pixel and the second pixel was used as the result of calculating the angle Δ of the liquid crystal cell. The AC drive residual image △ is 0.092.

(Example 66)

In the same manner as in Example 13, except that the liquid crystal alignment agent (VIII-17) obtained in Example 30 was used, the average value of the angle Δ values of the first pixel and the second pixel was used as the result of calculating the angle Δ of the liquid crystal cell. The AC drive residual image △ is 0.091.

(Example 67)

In the same manner as in Example 13, except that the liquid crystal alignment agent (VIII-18) obtained in Example 31 was used, the average value of the angle Δ values of the first pixel and the second pixel was used as the result of calculating the angle Δ of the liquid crystal cell. The AC drive residual image △ is 0.090.

(Example 68)

In the same manner as in Example 13, except that the liquid crystal alignment agent (VIII-19) obtained in Example 32 was used, the average value of the angle Δ values of the first pixel and the second pixel was used as the result of calculating the angle Δ of the liquid crystal cell. The AC drive residual image △ is 0.092.

(Example 69)

In the same manner as in Example 13, except that the liquid crystal alignment agent (VIII-20) obtained in Example 33 was used, the average value of the angle Δ values of the first pixel and the second pixel was used as the result of calculating the angle Δ of the liquid crystal cell. The AC drive residual image △ is 0.047.

(Embodiment 70)

In the same manner as in Example 13, except that the liquid crystal alignment agent (VIII-21) obtained in Example 34 was used, the average value of the angle Δ values of the first pixel and the second pixel was used as the result of calculating the angle Δ of the liquid crystal cell. The AC drive residual image △ is 0.064.

(Example 71)

In the same manner as in Example 13, except that the liquid crystal alignment agent (VIII-22) obtained in Example 35 was used, the average value of the angle Δ values of the first pixel and the second pixel was used as the result of calculating the angle Δ of the liquid crystal cell. The AC drive residual image △ is 0.048.

(Example 72)

In the same manner as in Example 13, except that the liquid crystal alignment agent (VIII-23) obtained in Example 36 was used, the average value of the angle Δ values of the first pixel and the second pixel was used as the result of calculating the angle Δ of the liquid crystal cell. The AC drive residual image △ is 0.055.

(Example 73)

In the same manner as in Example 13, except that the liquid crystal alignment agent (VIII-24) obtained in Example 37 was used, the average value of the angle Δ values of the first pixel and the second pixel was used as the result of calculating the angle Δ of the liquid crystal cell. The AC drive residual image △ is 0.043.

(Example 74)

In the same manner as in Example 13, except that the liquid crystal alignment agent (VIII-25) obtained in Example 38 was used, the average value of the angle Δ values of the first pixel and the second pixel was used as the result of calculating the angle Δ of the liquid crystal cell. The AC drive residual image △ is 0.092.

(Example 75)

In the same manner as in Example 13, except that the liquid crystal alignment agent (VIII-26) obtained in Example 39 was used, the average value of the angle Δ values of the first pixel and the second pixel was used as the result of calculating the angle Δ of the liquid crystal cell. The AC drive residual image △ is 0.085.

(Example 76)

In the same manner as in Example 13, except that the liquid crystal alignment agent (VIII-27) obtained in Example 40 was used, the average value of the angle Δ values of the first pixel and the second pixel was used as the result of calculating the angle Δ of the liquid crystal cell. The AC drive residual image △ is 0.053.

(Comparative Example 36)

In the same manner as in Example 13, except that the liquid crystal alignment agent (VIII-28) obtained in Comparative Example 33 was used, the average value of the angle Δ values of the first pixel and the second pixel was used as the result of calculating the angle Δ of the liquid crystal cell. The AC drive residual image Δ is 0.001.

The evaluation results of the respective properties carried out by using the liquid crystal alignment agent of the present invention carried out in the above examples and comparative examples are shown in Table 13 below.

[Industrial Applicability]

By using the liquid crystal alignment agent of the present invention, a liquid crystal alignment film having excellent liquid crystal alignment property and electrical characteristics and having higher transmittance can be obtained. The liquid crystal alignment film obtained by the novel liquid crystal alignment agent of the present invention blended with a polydecylamine having a cyclobutane structure and a polyamic acid having a (thio)urea structure is in the thickness direction of the film, in a polyfluorene The concentration of the amine ester and the polyamic acid produces a slope which exhibits characteristics which are not easily obtained by a single resin component. By using the liquid crystal alignment agent of the present invention, it is possible to suppress the image sticking caused by the AC driving or the residual image caused by the residual charge generated by the DC voltage generated in the liquid crystal display device of the IPS or FFS driving method, and A liquid crystal alignment film having high transmittance can be obtained. Therefore, it can be used for a liquid crystal display element which requires high display quality.

Claims (15)

A liquid crystal alignment agent comprising a liquid crystal alignment agent of polyphthalate (A) and polyglycine (B), and the polyphthalate (A) contains the following formula (1): Wherein R ¹ is an alkyl group having 1 to 6 carbon atoms, R ² to R ^{5 are} each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Y ¹ is a divalent organic group derived from a diamine compound. The aforementioned diamine compound contains the following formula (1b): (wherein, A ¹ is a single bond, an ester bond, a guanamine bond, a thioester bond or a divalent organic group having 2 to 10 carbon atoms, and m is 0 or 1) represents a repeating unit represented by a diamine compound; The proline (B) is obtained by reacting a tetracarboxylic acid component with a diamine component, and the tetracarboxylic acid component contains 20 mol% or more of the aromatic acid dianhydride, and the diamine component contains 30 mol% or more of the following formula ( 2b-1): (wherein R ¹⁰ and R ^{11 are} each independently an alkylene group having 1 to 3 carbon atoms, and Y ² and Y ^{3 are} independently a single bond, -O-, -S- or an ester bond, and Z is an oxygen atom or sulfur. Atom) represents a diamine compound. The liquid crystal alignment agent of claim 1, wherein a content ratio of the polyphthalate (A) component to the polyamic acid (B) component is 1/9 to 9/1 by mass ratio (A/B), The total solid content concentration of the component (A) and the component (B) is 0.5 to 10% by mass. The liquid crystal aligning agent of claim 1, wherein the diamine component of the polyaminic acid (B) further contains 20 mol% or less of the following (2b-2): Diamine. The liquid crystal alignment agent according to any one of claims 1 to 3, wherein the diamine component of the polyamic acid (B) further contains 70 mol% or less of the third diamine component. The liquid crystal alignment agent of claim 4, wherein the third diamine component of the polyaminic acid (B) is the following (2b-3) to (2b-5): At least one diamine selected in the group. The liquid crystal alignment agent according to any one of claims 1 to 3, wherein the aromatic acid dianhydride in the tetracarboxylic acid component of the polyamic acid (B) is represented by the following (2a-1) and (2a-2) : At least one aromatic acid dianhydride selected in groups. The liquid crystal alignment agent according to any one of claims 1 to 3, wherein the tetracarboxylic acid component of the polyamic acid (B) further contains (2a-3) to (2a-10): At least one selected from the group consisting of alicyclic acid dianhydrides. The liquid crystal alignment agent according to any one of claims 1 to 3, wherein in the polyphthalate (A), the diamine compound represented by the formula (1b) is the following (1b-1) or (1b-2): Diamine. The liquid crystal aligning agent of claim 8, wherein the polyamine derivative (A), the diamine compound derived from Y ¹ contains 50 mol% or more of the diamine of the formula (1b-1) or (1b-2). The liquid crystal alignment agent according to any one of claims 1 to 3, wherein, in the polyphthalate (A), the diamine compound derived from Y ¹ further contains 20 mol% or less of the following (1b-3) to (1b- 5): (wherein, Boc represents a t-butoxycarbonyl group, and t-Bu represents a t-butyl group). The liquid crystal alignment agent according to any one of claims 1 to 3, which further contains an organic solvent component. The liquid crystal alignment agent according to any one of claims 1 to 3, wherein the liquid crystal alignment agent is a liquid crystal alignment film which is subjected to photoalignment treatment. A liquid crystal alignment film obtained by using the liquid crystal alignment agent according to any one of claims 1 to 12. A liquid crystal alignment film which is obtained by applying a liquid crystal alignment agent according to any one of claims 1 to 12 to a substrate on which an electrode is attached, and performing photoalignment treatment. A liquid crystal display element characterized by having a liquid crystal alignment film as claimed in claim 13 or 14.