TWI522390B - A liquid crystal aligning agent containing a compound containing a thermal dissociative group, and a liquid crystal alignment film - Google Patents

Description

Liquid crystal alignment agent containing a compound containing a thermally dissociable group, and a liquid crystal alignment film

The present invention is excellent in mechanical strength, excellent in resistance to polishing treatment, and excellent in electric properties such as liquid crystal alignment, particularly at a high temperature, such as voltage holding ratio or ion density, and can also impart high pretreatment. A liquid crystal alignment agent for a liquid crystal alignment film having a large tilt angle, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element.

In a liquid crystal display element used in a liquid crystal television, a liquid crystal display or the like, a liquid crystal alignment film for controlling a liquid crystal alignment state is usually provided in the element. In the liquid crystal alignment film, a liquid crystal alignment agent containing a solution of a polyamidene precursor such as polyamic acid or a solution of a soluble polyimine as a main component is applied to a glass substrate or the like. A polyimine-based liquid crystal alignment film.

With the high definition of the liquid crystal display element, and the suppression of the contrast of the liquid crystal display element or the reduction of the image sticking phenomenon, in the liquid crystal alignment film, in addition to the excellent liquid crystal alignment and the stable pretilt performance, the high voltage is maintained. The rate, the suppression of the residual image due to the AC drive, the small amount of residual charge when a DC voltage is applied, and/or the early relaxation of the residual charge accumulated by the DC voltage are also becoming more important.

In the polyimine-based liquid crystal alignment agent, various proposals have been made in order to meet the above requirements. For example, in addition to a polyamic acid containing a polyaminic acid or a quinone imine group, there is a liquid crystal alignment agent containing a tertiary amine having a specific structure (refer to Patent Document 1), and a pyridine skeleton or the like is used in the raw material. A liquid crystal alignment agent of soluble polyimine which is formed by a specific diamine compound (refer to Patent Document 2) or the like is proposed.

Further, in addition to polylysine or a quinone imidized polymer thereof, it is known that a very small amount is selected from a compound containing one carboxylic acid group in a molecule, a compound containing one carboxylic anhydride group in a molecule, and a molecule. A liquid crystal alignment agent containing a compound of a compound of the third-order amine group (refer to Patent Document 3), a tetracarboxylic dianhydride having a specific structure, a tetracarboxylic dianhydride having a cyclobutane, and a specific diamine compound. A liquid crystal alignment agent obtained by the obtained polylysine or a quinone imidized polymer thereof (refer to Patent Document 4).

Further, a liquid crystal alignment agent obtained by adding a monomer having a specific structure of a quinone imine group or a monomer having a methionine moiety is proposed together with polyglycine or polyimine. Reference Patent Document 5), at least one polymer selected from a ruthenium imidized polymer of poly-proline and poly-proline, at least one compound selected from a proline compound and a quinone compound The resulting liquid crystal alignment agent (refer to Patent Document 6).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 9-316200

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

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

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

[Patent Document 5] Japanese Patent Publication No. 6-110061

[Patent Document 6] Japanese Patent Publication No. 9-269491

However, in recent years, with the high-definition liquid crystal television with a larger picture as the main body and the demand for liquid crystal display elements becoming more and more stringent, the liquid crystal alignment film which is closely related to the characteristics of the liquid crystal display element is required to have More excellent high-reliability characteristics, and while requiring this higher characteristic, not only the initial characteristics are good, but also the high reliability of good characteristics can be maintained even after exposure to high temperatures for a long time.

The present invention provides a liquid crystal alignment film which is excellent in mechanical strength, excellent in resistance to polishing treatment, and excellent in liquid crystal alignment properties, particularly electrical properties such as voltage holding ratio and ion density at high temperatures. Further, it is possible to form a liquid crystal alignment agent which imparts a high reliability to a liquid crystal alignment film having a high pretilt angle.

In order to achieve the above object, the inventors of the present invention have found that, in addition to the polyimine precursor obtained by reacting a diamine compound which has been conventionally a liquid crystal alignment agent component with a tetracarboxylic acid derivative, and/or the polymerization The quinone imine precursor may be exemplified by a ruthenium imidized polyamine, and may have an amine group which has a thermal dissociable group which can be substituted by hydrogen by heating, and has an anthracene. The liquid crystal alignment agent of a compound of an amine acid or a glutamate structure (hereinafter referred to as a compound containing a thermally dissociable group) can achieve the above object.

a compound having a lysine or glutamate structure (hereinafter referred to as a thermal dissociation) added to the liquid crystal alignment agent and having an amine group protected by a heat dissociable group which can be substituted by heating with hydrogen The compound of the nature) is a novel compound not described in the literature before the application of the present application, but when the compound containing the pyrolytic group is added to the liquid crystal alignment agent, it is found that the mechanical strength of the film can be formed. In addition, it is excellent in resistance to the polishing treatment, and is excellent in liquid crystal alignment, particularly in electrical properties such as voltage holding ratio and ion density at high temperatures, and can provide a liquid crystal alignment film having high pretilt angle reliability.

That is, the present invention has been made in view of the gist of the following.

A liquid crystal alignment agent comprising: a polyimide precursor obtained by reacting a diamine compound with a tetracarboxylic acid derivative; and/or a polyfluorene obtained by imidating the polyimine precursor An imine, a compound having a structure consisting of a proline or a guanamine ester having an amine group which is substituted by a heat dissociable group which is heated by heating at 80 to 300 ° C.

2. The liquid crystal alignment agent according to the above 1, wherein the polyimine precursor has a repeating unit represented by the following formula (7).

(wherein X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group; and R ₆ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. A ₁ and A ₂ are each independently a hydrogen atom or may have The alkyl group, alkenyl group or alkynyl group having 1 to 10 carbon atoms of the substituent.

3. The liquid crystal alignment agent according to the above 1 or 2, wherein the content of the polyimine precursor and the polyimine is 0.5 to 15% by mass based on the total amount of the liquid crystal alignment agent. And having a repeating unit of one unit having a polyimine precursor of the repeating unit represented by the above formula (7) and the quinone imidized polymer of the polyimine precursor Further, the compound of the guanamine or guanamine structure which can be substituted with the amine group protected by the thermally dissociable group of hydrogen contains 0.5 to 50 mol%.

4. The liquid crystal alignment agent according to any one of the above 1 to 3, wherein the compound having the structure of the proline or guanamine has a compound represented by the following formula (1).

(wherein X is a tetravalent organic group; R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; and Z is a structure represented by the following formula (2).)

(wherein Z ₁ is a single bond or a divalent organic group having 1 to 30 carbon atoms. R ₂ and R ₃ each independently represent a hydrogen atom or an alkyl group having 1 to 30 carbon atoms and an alkenyl group which may have a substituent. The alkynyl group, the aryl group or a combination thereof may also form a ring structure. R ₄ is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms which may have a substituent. D ₁ is a thermally dissociable group).

5. The liquid crystal alignment agent according to any one of the above 1 to 4, wherein the thermally dissociable group is a tert-butoxycarbonyl group or a 9-fluorenylmethoxycarbonyl group.

6. The liquid crystal alignment agent according to any one of the above-mentioned items, wherein the X is selected from the group consisting of the structures shown by the following formula.

7. A liquid crystal alignment film obtained by subjecting a film obtained by baking the liquid crystal alignment agent according to any one of the above 1 to 6 to a film.

8. The liquid crystal alignment film according to the above-mentioned item 7, wherein the alignment treatment is a polishing treatment or an irradiation treatment of a polarized radiation.

A liquid crystal display element comprising the liquid crystal alignment film according to the above 7 or 8.

A compound having a compound having a structure of a proline or a guanamine represented by the following formula (1).

(wherein X is a tetravalent organic group; R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; and Z is a structure represented by the following formula (2).)

(wherein Z ₁ is a single bond or a divalent organic group having 1 to 30 carbon atoms. R ₂ and R ₃ each independently represent a hydrogen atom or an alkyl group having 1 to 30 carbon atoms and an alkenyl group which may have a substituent. The alkynyl group, the aryl group or a combination thereof may also form a ring structure. R ₄ is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms which may have a substituent. D ₁ is a thermally dissociable group).

11. The compound according to the above 10, which is a chlorocarbonyl compound obtained by using a bischlorocarbonyl compound represented by the following formula (3) and a monoamine compound represented by the following formula (4) in the presence of a base; /Monamine) The molar ratio is 1/2 to 1/3 of the reaction.

(wherein X, Z ₁ ; R ₂ ; R ₃ ; R ₄ and D ₁ are the same as those of the above formulae (1) and (2); and R ₅ is an alkyl group having 1 to 5 carbon atoms).

12. The compound according to the above 10, which is obtained by using a tetracarboxylic acid derivative represented by the following formula (5) and a monoamine compound represented by the above formula (4) in the presence of a condensing agent ( The molar ratio of the tetracarboxylic acid derivative/monoamine is 1/2 to 1/3 of the reaction.

(wherein X and R ₅ are the same as defined in the above formulae (1) and (3).).

13. The compound according to the above 10, wherein the tetracarboxylic dianhydride represented by the following formula (6) and the monoamine compound represented by the above formula (4) are (tetracarboxylic dianhydride/monoamine) The molar ratio is 1/2 to 1/3 of the reaction.

(In the formula, the X system is synonymous with the above formula (1)).

14. The compound according to the above 10, which is characterized in that the tetracarboxylic acid dihydrate represented by the above formula (6) and the monoamine compound represented by the above formula (4) are (tetracarboxylic dianhydride/ The monoamine has a molar ratio of 1/2 to 1/3, and is obtained by esterifying a carboxyl group with an esterifying agent.

The compound according to any one of the above items 10 to 14, wherein the X is selected from the group consisting of the structures represented by the following formulas.

The compound according to any one of the above 10 to 15, wherein the above R ₁ is an alkyl group having 1 to 5 carbon atoms.

According to the present invention, it is possible to provide the obtained liquid crystal alignment film with high mechanical strength, excellent resistance to polishing treatment, and also performance in liquid crystal alignment, particularly at high temperature, such as voltage retention or ion density. It is excellent in the form of a liquid crystal alignment agent which provides a liquid crystal alignment film which is highly reliable to a high pretilt angle.

The liquid crystal alignment agent of the present invention can form a liquid crystal alignment film having the above-described excellent characteristics, and is excellent in long-term storage stability when stored before use of a liquid crystal alignment agent.

Further, the present invention also provides a novel compound which is a compound having an amine group protected by a thermally dissociable group contained in the liquid crystal alignment agent of the present invention and having a lysine or glutamate structure.

The reason why the liquid crystal alignment agent of the present invention has excellent characteristics as described above is not known, but it can be almost inferred as follows.

The thermally dissociable group-containing compound contained in the liquid crystal alignment agent of the present invention is coated with a liquid crystal alignment agent on a surface of a substrate and fired to form a liquid crystal alignment film, and is thermally decomposed at a temperature during the baking process. The base will decompose and produce a highly reactive grade 1 or 2 amine. The produced first- or second-order amine system promotes the ruthenium imidization reaction of the main component of the polyimine precursor and/or the polyimide of the polyimine contained in the liquid crystal alignment agent, and brings high At the same time as the imidization ratio, a crosslinking reaction occurs between the polymers, and the liquid crystal alignment film obtained by the liquid crystal alignment agent is imparted with a large mechanical strength. The increase in mechanical strength leads to an improvement in the polishing resistance and the stability of the liquid crystal properties at a high temperature.

Further, the thermally dissociable group-containing compound has a skeleton structure which is similar to the polymer of the polyimine precursor and/or the polyimine which is a main component contained in the liquid crystal alignment agent. Or the phthalate structure, when added to the liquid crystal alignment agent, it is obviously hindered by the alignment of the liquid crystal, but conversely brings about an improvement in the liquid crystal alignment property, and as a result, the voltage retention ratio, the ion density, The liquid crystal characteristics such as the pretilt angle are improved.

Further, the pyrolyzable group-containing compound does not decompose the thermally dissociable group of the compound before the high temperature is applied, and therefore does not adversely affect the storage stability of the liquid crystal alignment agent containing the compound.

According to the present invention, it is possible to provide a liquid crystal alignment agent which is excellent in mechanical strength and excellent in resistance to polishing treatment, and at the same time, in liquid crystal alignment, particularly at a high temperature, voltage retention or ion density. The electrical characteristics are excellent in point, and a liquid crystal alignment film which can provide a high pretilt angle with high reliability can be formed.

[Formation of the Invention] <The compound containing a thermally dissociable group>

In the present invention, the pyrolyzable group-containing compound to be added to the liquid crystal alignment agent is a compound having an amine group which is protected by a thermally dissociable group and has a lysine or guaninate structure, the compound At a temperature of 80 to 300 ° C, preferably 100 to 250 ° C, particularly preferably 150 to 230 ° C, the thermally dissociable group decomposes and is substituted with a hydrogen atom. Therefore, when the liquid crystal alignment agent is applied to the substrate of the liquid crystal display element and fired, the thermal dissociable group is dissociated at a general temperature of 150 to 300 ° C, and is replaced by hydrogen.

In the present invention, the thermally dissociable group-containing compound to be used is preferably represented by the following general formula (1).

In the formula, X is a tetravalent organic group; R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; and Z is a structure represented by the following formula (2).

In the formula, Z ₁ is a single bond or a divalent organic group having 1 to 30 carbon atoms; and R ₂ and R ₃ are each independently a hydrogen atom or an alkyl group having 1 to 30 carbon atoms which may have a substituent, an alkenyl group, and an alkyne a group, an aryl group or a combination thereof, which may also form a ring structure; R ₄ is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms which may have a substituent; and D ₁ is an amine group which is substituted with a hydrogen atom by heating. Protection base.

In the above formula (1), R ₁ is a hydrogen atom or a C 1-5 alkyl group. When R ₁ is a large structure, when it is used as a liquid crystal alignment film, R ₁ is preferably a hydrogen atom, a methyl group or an ethyl group, and more preferably a hydrogen atom or a methyl group.

In the above formula (1), X is a tetravalent organic group, and the structure thereof is not particularly limited. Specific examples of X include X-1 to X-46 as shown below. Among them, X-1, X-2, X-3, X-4, X-5, X-6, X-8, X-16, X-19, X-21, X-25, X- 26, X-27, X-28 or X-32 is better.

In the above formula (2), R ₂ and R ₃ each independently represent a hydrogen atom or an alkyl group having 1 to 30 carbon atoms which may have a substituent, an alkenyl group, an alkynyl group, an aryl group or a combination thereof, or may be formed. Ring construction.

Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a hexyl group, an octyl group, a decyl group, a cyclopentyl group, a cyclohexyl group, and a dicyclohexyl group. The alkenyl group may be one in which one or more CH-CH structures present in the above alkyl group are substituted with a C=C structure, and more specifically, a vinyl group, an allyl group, or a 1-propenyl group may be mentioned. Isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-hexenyl, cyclopropenyl, cyclopentenyl, cyclohexenyl, and the like. Examples of the alkynyl group include a structure in which one or more CH ₂ -CH ₂ structures present in the alkyl group are substituted with a C≡C structure, and more specifically, an ethynyl group, a 1-propynyl group, and 2 - propynyl and the like. Examples of the aryl group include a phenyl group, an α-naphthyl group, a β-naphthyl group, an o-biphenyl group, an m-biphenyl group, a p-biphenyl group, a 1-fluorenyl group, a 2-fluorenyl group, and a 9- Indenyl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl.

The above-mentioned alkyl group, alkenyl group, alkynyl group, and aryl group may have a substituent in the case of having 1 to 20 carbon atoms in total, and may further form a ring structure by a substituent. 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 is bonded to the parent skeleton.

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

In terms of a halogen group of a substituent, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The organooxy group of the substituent may, for example, be a structure represented by -O-R such as an alkoxy group, an alkenyloxy group or an aryloxy group. As the R aspect, an alkyl group, an alkenyl group, an aryl group or the like as described above can be exemplified. In the above R, the aforementioned substituent may be further substituted. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group, and a decyloxy group. , lauryloxy and the like.

The aspect of the organic thio group of the substituent may be a structure represented by -S-R such as an alkylthio group, an alkenylthio group or an arylthio group. As the R aspect, an alkyl group, an alkenyl group, an aryl group or the like as described above can be exemplified. In the above R, the aforementioned substituent may be further substituted. 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 a heptyl group. A thio group, an octylthio group, a mercaptothio group, a mercaptothio group, a laurylthio group, and the like.

The organoalkylene group of the substituent may represent a structure represented by -Si-(R) ₃ . These R may be the same or different, and may exemplify the aforementioned alkyl group, aryl group and the like. In the above R, the aforementioned substituent may be further substituted. Specific examples of the alkyl fluorenyl group include a trimethyl decyl group, a triethyl decyl group, a tripropyl decyl group, a tributyl decyl group, a tripentyl decyl group, a trihexyl decyl group, and a pentyl group. Methyl decyl, hexyl dimethyl decyl, octyl dimethyl decyl, decyl dimethyl decyl, and the like.

The thiol group of the substituent may represent a structure represented by -C(O)-R. As the R aspect, an alkyl group, an alkenyl group, an aryl group or the like as described above can be exemplified. In the above R, the aforementioned substituent may be further substituted. Specific examples of the mercapto 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 may be represented by a structure represented by -C(O)O-R or -OC(O)-R. As the R aspect, an alkyl group, an alkenyl group, an aryl group or the like as described above can be exemplified. In the above R, the aforementioned substituent may be further substituted.

The thioester group of the substituent may be represented by a structure represented by -C(S)O-R or -OC(S)-R. As the R aspect, an alkyl group, an alkenyl group, an aryl group or the like as described above can be exemplified. In the above R, the aforementioned substituent may be further substituted.

The aspect of the phosphate group of the substituent may represent a structure represented by -OP(O)-(OR) ₂ . These R may be the same or different, and may exemplify the aforementioned alkyl group, aryl group and the like. In the above R, the aforementioned substituent may be further substituted.

The amide group of the substituent may be represented by -C(O)NH ₂ or -C(O)NHR, -NHC(O)R, -C(O)N(R) ₂ , -NRC(O) The structure shown by R. These R may be the same or different, and may exemplify the aforementioned alkyl group, aryl group and the like. In the above R, the aforementioned substituent may be further substituted.

The aryl group of the substituent may be the same as the above aryl group. In the aryl group, the other substituents described above may be substituted.

The alkyl group of the substituent may be the same as the alkyl group described above. In the alkyl group, the other substituents described above may be further substituted.

The alkenyl group of the substituent may be the same as the above alkenyl group. In the alkenyl group, the other substituents described above may be further substituted.

The alkynyl group of the substituent may be the same as the alkynyl group described above. In the alkynyl group, the other substituents described above may be further substituted.

In the above formula (2), R ₄ is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms which may have a substituent. Specific examples of the alkyl group and the substituent include the same alkyl groups and substituents as described above.

In the above formula (2), Z ₁ is a single bond or a divalent organic group having 1 to 30 carbon atoms. When Z ₁ is a divalent organic group having 1 to 30 carbon atoms, it is preferably a divalent organic group represented by the following formula (8).

[Chemistry 14]

-B ₁ -R ₈ -B ₂ -R ₉ - (8)

(In the formula (8), B ₁ and B ₂ are each independently a single bond or a divalent linking group. However, at least one of B ₁ and B ₂ is a divalent linking group. Each of R ₈ and R ₉ Independently a single bond or a C1-C20 alkylene group, an alkenyl group, an alkynyl group, an extended aryl group or a combination thereof.

Specific examples of the above B ₁ and B ₂ can be expressed as follows, but are not limited thereto.

In the above B-5 to B-8, B-10, and B-11, R ¹⁰ and R ¹¹ are a hydrogen atom or an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a combination thereof which may have a substituent. A ring configuration can be formed. Specific examples of the alkyl group, the alkenyl group, the alkynyl group, the aryl group and the substituents are the same as those described above.

When R ¹⁰ and R ¹¹ are in a large structure such as an aromatic ring or an alicyclic structure, when used as a liquid crystal alignment film, liquid crystal alignment may be lowered, so that a methyl group, an ethyl group, a propyl group, a butyl group or the like may be used. The alkyl group or the hydrogen atom is preferred, and the hydrogen atom is more preferred.

In the formula (8), when R ₈ and R ₉ are an alkylene group having 1 to 20 carbon atoms, an alkenyl group, an alkynylene group, an extended aryl group or a combination thereof, the specific examples are as follows. But not limited to this.

The alkylene group may have a structure in which one hydrogen atom is removed from the alkyl group. More specifically, it may, for example, be a methyl group, a 1,1-extended ethyl group, a 1,2-extended ethyl group, a 1,2-extended propyl group, a 1,3-propanyl group or a 1,4-extended group. 1, 1, 2-butyl, 1,2-exylpentyl, 1,2-extension, 1,2-extension, 1,2-extension, 2,3-butyl, 2,4-Exylpentyl, 1,2-cyclopropyl, 1,2-cyclobutyl, 1,3-cyclobutyl, 1,2-cyclopentyl, 1,2-cyclode Hexyl, 1,2-ring extended fluorenyl, 1,2-ring extended dodecyl and the like. Examples of the alkenyl group include a structure in which one hydrogen atom is removed from an alkenyl group. More specifically, 1,1-vinylidene, 1,2-extended vinyl, 1,2-extended vinylmethyl, 1-methyl-1,2-vinyl, 1,2 -Extended vinyl-1,1-extended ethyl, 1,2-extended vinyl-1,2-extended ethyl, 1,2-extended vinyl-1,2-extended propyl, 1,2-extended Vinyl-1,3-propanyl, 1,2-extended vinyl-1,4-butylene, 1,2-vinyl-1,2-butylene, 1,2-vinyl -1,2-extended heptyl, 1,2-extended vinyl-1,2-extended thiol and the like. Examples of the alkynyl group include a structure in which one hydrogen atom is removed from an alkynyl group. More specifically, an ethynyl group, an exetylene group, a methyl group, an ethynyl group, a 1-ethylidene group, an ethynyl group, a 2-ethyl group, an ethynyl group-1,2- Propyl propyl, ethynyl-1,3-propanyl, ethynyl-1,4-butylene, ethynyl-1,2-butylene, ethynyl-1,2-extension Base, ethynyl-1,2-extension base, and the like. The aspect of the aryl group may be a structure in which one hydrogen atom is removed from an aryl group. More specifically, it may be 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,2-anthranyl, 1,4-naphthyl, 1, 5-naphthyl, 2,3-naphthyl, 2,6-anthranyl, 3-phenyl-1,2-phenylene, 2,2'-diphenyl.

The alkyl group, the alkenyl group, the alkynyl group, the aryl group, and the combination thereof are as a whole, and if they have a carbon number of 1 to 20, they may have a substituent and may be further substituted by The base forms a 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 is bonded to the parent skeleton.

Examples of such a substituent include the same as described above.

When R ₈ and R _{9 have} a small carbon number, when used as a liquid crystal alignment film, in order to enhance the liquid crystal alignment property, an alkylene group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, and carbon are used. The number 1 to 5 of the alkynyl group is preferred. More preferably, either or both of R ₈ and R ₉ are single bonds.

In the formula (2), the protective group of the D ₁ -based amine group is not particularly limited as long as it is a functional group substituted by a hydrogen atom by heating. From the viewpoint of preservation stability of the liquid crystal alignment agent of the present invention, the protective group D ₁ is preferably one which does not dissociate at room temperature, and is preferably a protective group which is deprotected by heat of 80 ° C or more. More preferably, it is a protective group which is deprotected by heat of 100 ° C or more. Further, from the viewpoint of promoting the efficiency of the thermal imidization of the polyphthalate and the crosslinking reaction with the polyimide precursor or the polyimine, the heat is deprotected at 300 ° C or lower. The protecting group is preferably a protecting group which is deprotected by heat of 250 ° C or less, and more preferably a protecting group which is deprotected by heat of 200 ° C or less. As the above structural aspect of D _{1 ,} an ester group represented by the following formula is preferred.

(wherein R ₁₁ is a hydrocarbon group having 1 to 22 carbon atoms.)

Specific examples of the ester group represented by the above formula (9) include a methoxycarbonyl group, a trifluoromethoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, and n. a -butoxycarbonyl group, a tert-butoxycarbonyl group, a sec-butoxycarbonyl group, an n-pentyloxycarbonyl group, an n-hexyloxycarbonyl group, a 9-fluorenylmethoxycarbonyl group or the like. Among these, a structure in which the dissociation reaction is efficiently carried out at a firing temperature of 150 ° C to 300 ° C at the time of obtaining a liquid crystal alignment film is preferable, and tert-butoxycarbonyl or 9-fluorenylmethoxy is used. More preferred is a carbonyl group and a tert-butoxycarbonyl group.

In the following, the structure represented by the formula (2) is specifically a structure of D-1 to D-24, but is not limited thereto.

Further, the compounds of the present invention may be exemplified by the following structures, but are not limited thereto.

[Synthesis method of the compound of the present invention]

The compound of the present invention is a bischlorocarbonyl compound represented by the following formula (3), a tetracarboxylic acid derivative represented by the following formula (5) or a tetracarboxylic dianhydride represented by the following formula (6), and The monoamine compound represented by the following formula (4) is used as a raw material, and is reacted and synthesized by various methods. Specifically, the methods (i) to (iii) are exemplified, but are not limited thereto.

(wherein R ₅ is an alkyl group having 1 to 5 carbon atoms; and X, Z ₁ , R ₂ , R ₃ , R ₄ and D _{1 are} each the same as defined in the formulae (1) and (2).)

The bischlorocarbonyl compound of the above formula (3), for example, may be a chlorinating agent after reacting the tetracarboxylic dianhydride of the above formula (6) with an alcohol represented by R ₅ OH to form a dialkyl tetracarboxylate. It is obtained by converting a carboxyl group into a chlorocarbonyl group.

The tetracarboxylic acid derivative of the above formula (5) can be obtained, for example, by reacting the tetracarboxylic dianhydride of the above formula (6) with an alcohol represented by R ₅ OH.

The monoamine compound of the above formula (4) may be a method in which a compound having a first- or second-order amine group represented by the following formula and a di-tert-butyl dicarbonate are allowed to act in the presence of a base. Among the compounds having a primary or secondary amine group, a method in which a -9-fluorenyl chloroformate is allowed to act in the presence of a base is not particularly limited as long as it is a known method.

The compound having a substituent obtained by the above method is added to a nitro compound, a monoamine compound, a diamine compound or a derivative thereof, and if necessary, a reduction of a nitro group or introduction of an amine group is carried out to obtain A monoamine compound of a thermally dissociable protecting group.

The method for synthesizing the compound of the present invention includes the following methods (i) to (iii), but is not limited thereto.

(i) a method for synthesizing a bischlorocarbonyl compound from a monoamine compound

The compound of the present invention can be synthesized by reacting a biscarbonyl compound represented by the above formula (3) with a monoamine compound represented by the above formula (4).

Specifically, the bischlorocarbonyl compound and the monoamine compound are reacted in the presence of an alkali and an organic solvent at -20 ° C to 80 ° C, preferably at 0 ° C to 50 ° C for 30 minutes to 24 hours. It is preferably synthesized in 1 to 4 hours.

In the case of the above-mentioned base, pyridine, triethylamine, 4-dimethylaminopyridine or the like can be used, but in order to carry out the reaction stably, pyridine is preferred. The amount of the base to be added is preferably from 2 to 4 moles per mole of the bischlorocarbonyl compound from the viewpoint of the amount easily removed.

(ii) a method for synthesizing a tetracarboxylic acid derivative from a monoamine compound

The compound of the present invention can be synthesized by subjecting a tetracarboxylic acid derivative represented by the above formula (5) to a monoamine compound represented by the above formula (4) by dehydration condensation.

Specifically, the tetracarboxylic acid derivative and the monoamine compound can be reacted in the presence of a condensing agent, a base or an organic solvent at 0 ° C to 80 ° C, preferably 0 ° C to 50 ° C, for 30 minutes to 24 hours. It is preferably synthesized in 3 to 15 hours.

As the condensing agent, triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride can be used. , N,N'-carbonyldiimidazole, dimethoxy-1,3,5-triazinylmethylmorpholinium, O-(benzotriazol-1-yl)-N,N,N', N'-tetramethylcarbonium tetrafluoroborate, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethylcarbonate hexafluorophosphate, (2,3 - Dihydro-2-thioketo-3-benzoxazolyl)phosphonic acid diphenyl or the like. The amount of the condensing agent to be added is preferably 2 to 3 moles per mole of the tetracarboxylic acid derivative.

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 the amount which is easily removed.

Further, in the above reaction, the addition of Lewis acid as an additive allows the reaction to proceed more efficiently. In terms of Lewis acid, lithium halide such as lithium chloride or lithium bromide is preferred. The addition amount of the Lewis acid is preferably 0 to 1.0 times the molar amount of the monoamine compound.

(iii) a method for synthesizing tetracarboxylic dianhydride from a monoamine compound

The compound of the present invention can be synthesized by reacting a tetracarboxylic dianhydride represented by the above formula (6) with a monoamine compound represented by the above formula (4).

Specifically, the tetracarboxylic dianhydride and the monoamine compound can be reacted in the presence of an organic solvent at -20 ° C to 80 ° C, preferably 0 ° C to 50 ° C, for 30 minutes to 24 hours. It is synthesized for 1 to 12 hours. The solvent used in the above reaction is, in view of the solubility of the tetracarboxylic dianhydride, the monoamine compound and the product, N-methyl-2-pyrrolidone, γ-butyrolactone, and N,N- Dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, chloroform, etc., wherein N-methyl-2-pyrrolidone, N,N-dimethylformamide or tetrahydrofuran It is preferable to use one type or a mixture of two or more types. The concentration at the time of the synthesis is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass.

Further, the compound of the present invention wherein R ₁ of the above formula (1) is an alkyl group having 1 to 5 carbon atoms is a compound which can be added to a reaction solution of a tetracarboxylic dianhydride and a monoamine compound. And the esterification of a carboxyl group is carried out to synthesize.

Specifically, the tetracarboxylic dianhydride, the monoamine compound, and the esterifying agent can be reacted in the presence of an organic solvent at -20 ° C to 80 ° C, preferably 0 ° C to 50 ° C, for 30 minutes to 24 hours. It is synthesized in an hour, preferably from 1 to 4 hours.

In terms of the esterifying agent, it is preferred to be easily removed by purification, and examples thereof include N,N-dimethylformamide dimethyl acetal and N,N-dimethylformamide diethyl condensate. Aldehyde, N,N-dimethylformamide dipropyl acetal, N,N-dimethylformamide dineopentyl 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-triazin-2-yl)-4-methylmorpholinium chloride or the like. The amount of the esterifying agent to be added is preferably 2 to 6 moles per equivalent of the tetracarboxylic dianhydride 1 mole.

The solvent used in the reaction of the above (i) to (iii) is N-methyl-2-pyrrolidone and γ-butyrolactone in view of the solubility of the monomer and the product used in the synthesis. , N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, chloroform, etc., among which N-methyl-2-pyrrolidone, N,N-dimethylmethyl The guanamine or the tetrahydrofuran is preferably used, and these may be used alone or in combination of two or more. The concentration at the time of the synthesis is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass. Further, when a bischlorocarbonyl compound is used, in order to prevent hydrolysis of the bischlorocarbonyl compound, it is preferred that the solvent used in the synthesis be dehydrated as much as possible, and it is preferable to avoid the incorporation of outside air in a nitrogen atmosphere.

The reaction solution obtained by the reaction of the above (i) to (iii) can be used as it is as the composition of the present invention. In particular, when the compound of the present invention in which R ₁ in the formula (1) is a hydrogen atom is obtained by the method of the above (iii), since it is a reaction between an acid anhydride and an amine, it does not contain a reaction by-product and The base or condensing agent that must be removed. Therefore, the compound of the present invention described above is particularly preferably used as a composition of the present invention by using a reaction solution.

Further, the reaction solution obtained by the reaction of the above (i) to (iii) is poured into a poor solvent while stirring, whereby the compound of the present invention can be precipitated. After several times of precipitation and washing with a poor solvent, the purified compound powder of the present invention can be obtained by normal temperature or heat drying. The poor solvent is not particularly limited, and examples thereof include water, methanol, ethanol, and hexane. When the purity of the obtained compound is low, when the film formed of the composition is used for an electronic material, it is preferable to purify it by various methods because the electrical characteristics may be deteriorated. Examples of the purification method include ruthenium dioxide colloid column chromatography, recrystallization, and washing with an organic solvent. However, from the viewpoints of ease of operation and purification efficiency, recrystallization is more preferable. The organic solvent used for the recrystallization may be an organic solvent capable of recrystallizing the compound of the present invention, and may be recrystallized by mixing solvents of two or more types without selecting a type thereof.

<Polyimide precursors and polyimines>

The polyimine precursor contained in the liquid crystal alignment agent of the present invention is a polymer having a site which can undergo the oxime imidization reaction shown below by heating.

The polyimine precursor system used in the present invention has a structure represented by the following formula (7).

In the above formula, R ₆ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably 1 to 2 carbon atoms. A ₁ and A ₂ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms which may have a substituent. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a hexyl group, an octyl group, a decyl group, a cyclopentyl group, a cyclohexyl group, and a dicyclohexyl group. The above alkyl group may have a substituent, and may further form a ring structure by a substituent. 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 is bonded to a part of the parent skeleton.

Examples of the substituent include a halogen group, a hydroxyl group, a thiol group, a nitro group, an aryl group, an organic oxy group, an organic thio group, an organic decyl group, a decyl group, an ester group, a thioester group, and a phosphoric acid group. Ester group, decylamino group, alkyl group, alkenyl group, alkynyl group.

In the polyimine precursor, when a large structure is introduced, the reactivity of the amine group or the liquid crystal alignment property may be lowered, and the A ₁ and A ₂ are hydrogen atoms or a carbon number which may have a substituent. The alkyl group of 5 is more preferable, and it is particularly preferably a hydrogen atom, a methyl group or an ethyl group.

Further, in the formula (7), the above X ₁ is a tetravalent organic group, and Y ₁ is a divalent organic group. In the polyimine precursor, X ₁ may be mixed in two or more types. In order to show a specific example, in the structure represented by the formula (2) of the preferred compound of the above-mentioned thermally dissociable group-containing compound, X is the same as described above, and X-1 to X-46 are mentioned.

Further, in the formula (7), the organic group in which Y ₁ is a divalent group is not particularly limited, and in the polyimine imide precursor, Y ₁ may be mixed in two or more types. Specific examples of Y ₁ include the following Y-1 to Y-97.

Among them, in order to obtain good liquid crystal alignment, it is preferable to introduce a highly linear diamine into a polyimine precursor or a polyimine, and in the Y ₁ aspect, Y-7, Y-10, Y-11. , Y-12, Y-13, Y-21, Y-22, Y-23, Y-25, Y-26, Y-27, Y-41, Y-42, Y-43, Y-44, Y -45, Y-46, Y-48, Y-61, Y-63, Y-64, Y-71, Y-72, Y-73, Y-74, Y-75, Y-98 diamine good. Further, when the pretilt angle is to be increased, a diamine having a structure of a long-chain alkyl group, an aromatic ring, an aliphatic ring, a steroid skeleton or a combination thereof may be introduced into the polyamidiene precursor or poly. Yttrium is preferred, Y ₁ is Y-76, Y-77, Y-78, Y-79, Y-80, Y-81, Y-82, Y-83, Y-84, Y -85, Y-86, Y-87, Y-88, Y-89, Y-90, Y-91, Y-92, Y-93, Y-94, Y-95, Y-96 or Y-97 The diamine is better. Any such pretilt angle can be expressed by adding these diamines in an amount of from 1 to 50 mol% of the total diamine.

<Method for producing polyimine precursor>

In the present invention, a polyphthalamide precursor or a poly-proline is mentioned. Among them, the polyphthalate ester can be obtained by reacting any one of the tetracarboxylic acid derivatives represented by the following formulas (10) to (12) with the diamine compound represented by the formula (13).

(wherein, X ₁ , Y ₁ , R ₆ , A ₁ and A ₂ are each the same as defined in the above formula (7).)

The polyperurethane represented by the above formula (1) can be synthesized by the methods (1) to (3) shown below by using the above monomers.

(1) Synthesis by polylysine

Polyurethane esters can be synthesized by esterifying a polyamic acid obtained from a tetracarboxylic dianhydride and a diamine.

Specifically, the polyglycine and the esterifying agent are reacted in the presence of an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C, for 30 minutes to 24 hours, preferably It can be synthesized in 1 to 4 hours.

In terms of the esterifying agent, it is preferably one which can be easily removed by purification, and examples thereof include N,N-dimethylformamide dimethyl acetal and N,N-dimethylformamide II. Acetal, N,N-dimethylformamide dipropyl acetal, N,N-dimethylformamide dinepentyl butyl acetal, N,N-dimethylformamide -t-butyl acetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl-3-p-tolyl III Nitroene, 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride, and the like. The amount of the esterifying agent to be added is preferably from 2 to 6 mol equivalents per 1 mol of the repeating unit of the polyamic acid.

The solvent used in the above reaction is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone or γ-butyrolactone from the viewpoint of solubility of the polymer. One type may be used or two or more types may be used in combination. The concentration at the time of the synthesis is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass, from the viewpoint that the polymer is difficult to precipitate and the high molecular weight body is easily obtained.

(2) Synthesis by reaction of tetracarboxylic acid diester dichloride with diamine

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

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

As the base, pyridine, triethylamine, 4-dimethylaminopyridine or the like can be used, but in order to carry out the reaction stably, pyridine is preferred. The amount of the base to be added is preferably from 2 to 4 moles per mole of the tetracarboxylic acid diester dichloride from the viewpoint of easy removal amount and easy availability of a high molecular weight body.

The solvent used in the above reaction is preferably N-methyl-2-pyrrolidone or γ-butyrolactone from the viewpoint of solubility of the monomer and the polymer, and one type or mixture of two can be used. More than one kind. The polymer concentration at the time of the synthesis is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass, from the viewpoint that the polymer is difficult to precipitate and the high molecular weight body is easily obtained. Further, in order to prevent hydrolysis of the tetracarboxylic acid diester dichloride, it is preferred that the solvent used in the synthesis of the polyphthalate is desalted as much as possible, and it is preferably placed in a nitrogen atmosphere to avoid intrusion of outside air.

(3) Synthesis by tetracarboxylic acid diester and diamine

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

Specifically, the reaction can be carried out by reacting a tetracarboxylic acid diester with a diamine in the presence of a condensing agent, a base or an organic solvent at 0 ° C to 150 ° C, preferably 0 ° C to 100 ° C, for 30 minutes to 24 hours. It is synthesized in an hour, preferably from 3 to 15 hours.

As the condensing agent, triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, N,N'-carbonyldiimidazole, dimethoxy-1,3,5-triazinylmethylmorpholinium, O-(benzotriazol-1-yl)-N,N,N',N '-Tetramethylcarbon 鎓tetrafluoroborate, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethylcarbon hexafluorophosphate, (2,3- Dihydro-2-thioketo-3-benzoxazolyl)phosphonic acid diphenyl and the like. The amount of the condensing agent to be added is preferably 2 to 3 times the molar amount of the tetracarboxylic acid diester.

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

Further, in the above reaction, the addition of Lewis acid as an additive allows the reaction to proceed more efficiently. In terms of Lewis acid, lithium halide such as lithium chloride or lithium bromide is preferred. The amount of the Lewis acid added is preferably from 0 to 1.0 times the molar amount of the diamine component.

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

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

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

Further, in the case where the polyimine precursor is poly-proline, the poly-proline can be obtained by the tetracarboxylic dianhydride represented by the following formula (12) and the formula (13) The amine compound is obtained by reaction.

(wherein, X ₁ , Y ₁ , A ₁ and A ₂ are each the same as defined in the above formula (7).)

Specifically, the tetracarboxylic dianhydride and the diamine can be reacted in the presence of an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C, for 30 minutes to 24 hours, preferably. It is synthesized for 1 to 12 hours.

The organic solvent used in the above reaction is N,N-dimethylformamide, N-methyl-2-pyrrolidone or γ-butyrolactone in terms of solubility of the monomer and the polymer. It is preferable to use one type or a mixture of two or more types. The concentration of the polymer is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass, from the viewpoint that the polymer is difficult to precipitate and the high molecular weight body is easily obtained.

The obtained polylysine is obtained by injecting the reaction solution into a poor solvent while stirring, and the polymer is precipitated and recovered. Further, it is precipitated several times, washed with a poor solvent, and then dried at room temperature or by heating to obtain a purified powder of polylysine. The poor solvent is not particularly limited, and examples thereof include water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene, and the like.

The weight average molecular weight of the polyamic acid is preferably from 10,000 to 300,000, more preferably from 20,000 to 200,000. Further, the number average molecular weight is preferably from 2,500 to 15,000, more preferably from 5,000 to 100,000.

<polyimine]

The hydrazine imidization reaction which dehydrates the polyimine precursor is generally a thermal hydrazine imidization or a chemical hydrazine imidization, and the chemical hydrazine imidization at the lower temperature is carried out. It is preferred because it does not easily cause a decrease in the molecular weight of the polyimine.

The chemical hydrazine imidization is carried out by stirring a polyimide precursor in an organic solvent in the presence of a basic catalyst and an acid anhydride. The reaction temperature at this time is -20 to 250 ° C, preferably 0 to 180 ° C, and the reaction time is 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 times moles, preferably 2 to 20 times moles of the polyimide precursor, and the amount of the acid anhydride is 1 to 50 times moles of the polyimide precursor. Good for 3 to 30 times Mo. When the amount of the basic catalyst or acid anhydride is small, the reaction cannot be sufficiently carried out, and if it is too large, it is difficult to completely remove the reaction after completion of the reaction.

Examples of the basic catalyst used in the ruthenium imidization include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferred because it has moderate alkalinity during the reaction.

Further, examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, acetic anhydride is preferred because it is easily purified after completion of the reaction. As the organic solvent, a solvent used in the polymerization of the above polyamic acid can be used. The imidization ratio of the chemical hydrazine imidization can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.

The polyimine solution obtained in this manner is left in the solution because the added catalyst remains. In order to be used in the liquid crystal alignment agent of the present invention, the polyimine solution is put into a poor solvent which is being stirred, and precipitated. It is preferred to recycle the polyimine. The poor solvent used in the precipitation recovery of the polyimine is not particularly limited, and examples thereof include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, and ethanol. , toluene, benzene, etc. The polyimine precipitated by the introduction of a poor solvent is recovered by filtration, washed, and then dried at room temperature or under reduced pressure to form a powder. The powder is further dissolved in a good solvent, and the reprecipitation operation is repeated 2 to 10 times to purify the polyimine. It is preferable to repeat this purification step when the impurities cannot be completely removed by the single precipitation recovery operation. In order to repeat the lean solvent in the purification step, it is preferred to mix three or more kinds of poor solvents such as alcohols, ketones, and hydrocarbons, or to use the above-mentioned solvent in order, thereby further improving the efficiency of purification.

The ruthenium imidization ratio of the polyimine contained in the liquid crystal alignment agent of the present invention is not particularly limited. Any value can be set in consideration of the solubility of polyimine. The molecular weight of the polyimine contained in the liquid crystal alignment agent of the present invention is not particularly limited. However, if the molecular weight of the polyimide is too small, the strength of the obtained coating film may be insufficient. When the molecular weight of the imine is too large, the viscosity of the liquid crystal alignment agent to be produced is too high, and the workability at the time of formation of a coating film and the uniformity of a coating film may worsen. Therefore, the polyiminoimine used in the liquid crystal alignment agent of the present invention has a weight average molecular weight of preferably 2,000 to 500,000, more preferably 5,000 to 300,000.

<Liquid alignment agent>

The liquid crystal alignment agent of the present invention is in the form of a solution in which the polyimine precursor and/or polyimine is dissolved in an organic solvent. In the case of having such a form, for example, in the case of synthesizing a polyamidene precursor such as polyglycolate and/or polyglycolic acid in an organic solvent, it may be directly the obtained reaction solution or may be used. This reaction solution was diluted with a suitable solvent. Further, when the obtained polyimine precursor and/or polyimine are powders, it is preferred to dissolve the mixture in an organic solvent to form a solution.

The content (concentration) of the polyimine precursor and/or polyimine (hereinafter referred to as polymer) in the liquid crystal alignment agent of the present invention can be appropriately set according to the thickness of the polyimide film to be formed. In the case of a coating film having uniform strokes and no defects, the polymer content is preferably 0.5% by mass or more based on the organic solvent, and from the viewpoint of storage stability of the solution, It is preferably 15% by mass or less, more preferably 1% to 10% by mass.

In the liquid crystal alignment agent of the present invention, in addition to the polymer, the above-mentioned compound containing a thermally dissociable group may be added. The compound containing a thermally dissociable group may preferably be added in an amount of from 0.5 to 50 mol% per 1 unit of the repeating unit of the above-mentioned polyimine precursor and the quinone imidized polymer of the polyimine precursor.

The content of the compound containing a thermally dissociable group is more preferably from 1 to 30 mol%, particularly preferably from 5 to 20 mol%. When the content is too small, the ruthenium imidization reaction or the crosslinking reaction of the polyimide precursor is insufficient, and when the content is too large, the liquid crystal alignment may be adversely affected.

The organic solvent contained in the liquid crystal alignment agent of the present invention is not particularly limited as long as it is uniformly soluble in the polymer. Specific examples thereof include N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone. , N-ethyl-2-pyrrolidone, N-methyl caprolactam, 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyl hydrazine, dimethyl hydrazine, γ - Butyrolactone, 1,3-dimethyl-tetrahydroimidazolidone, 3-methoxy-N,N-dimethylpropane decylamine, and the like. These may be used alone or in combination of two or more. Further, even if it is a solvent which cannot be uniformly dissolved by the addition of the polymer alone, it may be mixed in the above organic solvent in the range where the polymer does not precipitate.

The liquid crystal alignment agent of the present invention may contain, in addition to the organic solvent for dissolving the polymer, a solvent for improving the uniformity of the coating film when the liquid crystal alignment agent is applied to the substrate. As the solvent, generally, a solvent having a lower surface tension than the above organic solvent can be used. Specific examples thereof include ethyl cellosolve, butyl cellosolve, butyl cellosolve acetate, 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 II Acetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propane Alcohol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, and the like. These solvents may be used in combination of two or more kinds.

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

3-aminopropyltriethoxydecane, 3-(2-aminoethyl)aminopropyltrimethoxydecane, 3-(2-aminoethyl)aminopropylmethyldimethoxy Baseline, 3-aminopropyltrimethoxydecane, 3-phenylaminopropyltrimethoxydecane, 3-triethoxydecyl-N-(1,3-dimethyl-butylene) An amine decane coupling agent such as propylamine or 3-aminopropyldiethoxymethyl decane; vinyl trimethoxy decane, vinyl triethoxy decane, vinyl ginseng (2-methoxy phenyl) Oxy) decane, vinyl methyl dimethoxy decane, vinyl triethoxy decane, vinyl triisopropoxy decane, allyl trimethoxy decane, p-styryl trimethoxy decane Vinyl decane coupling agent; 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropylmethyldi An epoxy decane coupling agent such as ethoxy decane, 3-glycidoxypropylmethyldimethoxy decane or 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane; -methacryloxypropylmethyldimethoxydecane, 3-methylpropenyloxy a methacrylic decane coupling agent such as propyltrimethoxydecane, 3-methacryloxypropylmethyldiethoxydecane, 3-methylpropenyloxypropyltriethoxydecane; Acrylic decane coupling agent such as 3-acryloxypropyltrimethoxydecane; urea-based decane coupling agent such as 3-ureidopropyltriethoxysilane; bis(3-(triethoxydecane) a sulfide-based decane coupling agent such as propyl)disulfide or bis(3-(triethoxydecyl)propyl)tetrasulfide; 3-hydrothiopropylmethyldimethoxydecane a hydrogenthio-based decane coupling agent such as 3-hydrothiopropyltrimethoxydecane or 3-octydecylthio-1-propyltriethoxydecane; 3-isocyanatepropyltriethoxydecane, 3 - an isocyanate decane coupling agent such as isocyanate propyl trimethoxy decane; an aldehyde decane coupling agent such as triethoxy decyl butyl aldehyde; and triethoxy decyl propyl methyl urethane; A urethane-based decane coupling agent such as 3-triethoxydecylpropyl)-t-butylcarbamate.

When the amount of the decane coupling agent added is too large, the unreacted one may adversely affect the liquid crystal alignment property, and if it is too small, the adhesion property may not be exhibited, and the solid content of the polymer is 0.01 to 5.0. The weight % is preferably from 0.1 to 1.0% by weight.

When the above decane coupling agent is added, in order to prevent precipitation of the polymer, it is preferred to add it before adding the solvent for improving the uniformity of the coating film.

When the coating film is fired, a ruthenium-imiding accelerator may be added in order to more efficiently carry out the imidization of the polyamidite.

In addition to the above, the liquid crystal alignment agent of the present invention can be added with a polymer other than a polymer, and a dielectric property such as a dielectric constant or conductivity of a liquid crystal alignment film, in addition to the effects of the present invention. A dielectric material or a conductive material for the purpose of changing the properties, or a cross-linking compound or the like for the purpose of improving the film hardness or density when the liquid crystal alignment film is formed.

The liquid crystal alignment agent of the present invention can be used as a liquid crystal alignment film after being applied and fired on a substrate, subjected to alignment treatment by polishing treatment or light irradiation, or in an alignment treatment such as vertical alignment. In this case, the substrate to be used is not particularly limited, and a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used. From the viewpoint of simplifying the process, the system is used. It is preferable to use a substrate on which an ITO electrode or the like for driving a liquid crystal is formed. Further, in the reflective liquid crystal display device, an opaque substance such as a germanium wafer can be used on the substrate on one side, and a material such as aluminum which can reflect light can be used as the electrode.

The coating method of the liquid crystal alignment agent is not particularly limited, and industrially, a method such as screen printing, lithography, flexographic printing, or inkjet printing is generally applied. Other coating methods include an immersion, a roll coater, a slit coater, a rotator, etc., and these methods can be used depending on the purpose.

The firing of the substrate to which the liquid crystal alignment agent has been applied can be carried out at any temperature of from 100 to 350 ° C, preferably from 150 to 300 ° C, more preferably from 180 to 250 ° C. The polyimine precursor contained in the liquid crystal alignment agent changes the conversion ratio of the polyimine to the polypyrimidine according to the firing temperature, but the liquid crystal alignment agent does not necessarily have to be 100% ruthenium. Therefore, the firing time can be set at any time. However, if the firing time is too short, the display failure may occur due to the influence of the residual solvent. Therefore, it is preferably 5 to 60 minutes, more preferably 10 to 40 minutes. .

In the calcination process, the thermally dissociable group-containing compound contained in the liquid crystal alignment agent of the present invention is decomposed as described above, and a highly reactive first- or second-order amine is produced. The resulting amine of the first or second grade promotes the ruthenium imidization reaction of the polyimine precursor and/or the polymer of the polyimine contained in the liquid crystal alignment agent, and has a ruthenium imine. At the same time, the crosslinking reaction occurs between the polymers, and the liquid crystal alignment film obtained by the liquid crystal alignment agent can be imparted with a large mechanical strength. An increase in mechanical strength leads to an improvement in the polishing resistance and a stability in the liquid crystal properties at a high temperature.

When the thickness of the coating film after firing is too thick, it is disadvantageous to the power consuming surface of the liquid crystal display element. If it is too thin, the reliability of the liquid crystal display element is lowered. Therefore, it is preferably 5 to 300 nm, more preferably 10 to 100 nm. . When the liquid crystal is aligned horizontally or obliquely, the coating film after firing is subjected to treatment such as polishing or polarized ultraviolet irradiation.

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

For example, a pair of substrates in which a liquid crystal alignment film is formed may be prepared, and a spacer may be spread on a liquid crystal alignment film of a single substrate so that the liquid crystal alignment film surface is inside. Another single-piece substrate is a method in which a liquid crystal is injected under reduced pressure and then sealed, or a method in which a liquid crystal is dropped on a liquid crystal alignment film surface on which a spacer is dispersed, and a substrate is bonded and sealed. The thickness of the spacer at this time is preferably from 1 to 30 μm, more preferably from 2 to 10 μm.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto. The methods for measuring the codes and the respective characteristics of the compounds used in the examples and the comparative examples are as follows.

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

CBDE-C1: dimethyl 2,4-bis(chlorocarbonyl)cyclobutane-1,3-dicarboxylate

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

PMDA: pyromellitic dianhydride

NMP: N-methyl-2-pyrrolidone

GBL: γ-butyrolactone

BCS: butyl cellosolve

PAE: Polyamidomate

PAA: Polylysine

[ ¹ HNMR]

Device: Fourier transform type superconducting nuclear magnetic resonance device (FT-NMR) INOVA-400 (manufactured by Varian) 400 MHz

Solvent: dihydrogen dimethyl hydrazine (DMSO-d ₆ ), heavy hydrogen chloroform (CDCl ₃ )

Reference material: tetramethyl decane (TMS)

[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 rotor TE-1 (1°). 34'; R24), temperature 25 ° C for measurement.

[molecular weight]

Further, the molecular weight of the polyglycolate is measured by a GPC (normal temperature colloidal permeation chromatography) apparatus, and the number average molecular weight (hereinafter referred to as Mn) and the weight average are calculated in terms of polyethylene glycol and polyethylene oxide. Molecular weight (hereinafter 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 (additives, lithium bromide-hydrate (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 the production of calibration lines: TSK standard polyethylene oxide (weight average molecular weight (Mw) of about 900,000, 150,000, 100,000, 30,000) made by TOSOH (Tosoh Corporation), and polyethylene glycol (peak of Polyethylene Laboratories) The top molecular weight (Mp) is about 12,000, 4,000, 1,000). At the time of measurement, in order to avoid overlapping of peaks, two samples of four types of samples of 900,000, 100,000, 12,000, and 1,000 and a sample of three types of 150,000, 30,000, and 4,000 were mixed, respectively.

[FT-IR measurement]

Device: NICOLET5700 (manufactured by Thermo ELECTRON) Smart Orbit Accessory

Determination method: ATR method

[Grinding resistance of liquid crystal alignment film]

The liquid crystal alignment agent was spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at a temperature of 80 ° C for 5 minutes, and baked at a temperature of 230 ° C for 20 minutes to form a ruthenium imidized film having a thickness of 100 nm. After the coating film was subjected to a rubbing treatment, the surface state of the film was observed, and the presence or absence of the scratch, the presence or absence of the chip shavings, and the presence or absence of peeling of the film were evaluated.

[Liquid alignment]

The liquid crystal alignment agent was spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at a temperature of 80 ° C for 5 minutes, and fired in a hot air circulating oven at 230 ° C for 20 minutes to form a film thickness of 100 nm. Coating film. A polishing treatment or a photoalignment treatment is applied to the surface of the coating film to obtain a substrate with a liquid crystal alignment film. Two substrates having such a liquid crystal alignment film were prepared, and a spacer of 6 μm was spread on the liquid crystal alignment film surface of one of the substrates, so that the alignment of the two substrates was reversed, and the liquid crystal injection port was left, and the periphery was sealed. An empty unit cell having a cell gap of 6 μm was produced. Liquid crystal (MLC-2041, manufactured by Merck) was vacuum-injected at room temperature in this empty cell, and the injection port was sealed to be a liquid crystal cell. Using this liquid crystal cell, the liquid crystal alignment property was observed by a polarizing 顕 micromirror, and the liquid crystal alignment property was evaluated on the basis of the following.

<Evaluation criteria>

○: No flow alignment was observed, and no light leakage was observed under crossed nibble.

△: Flow alignment was slightly observed, and light leakage was observed under crossed nibble.

×: Flow alignment was observed in the entire cell.

[Voltage retention rate]

The measurement of the voltage holding ratio of the liquid crystal cell described above was carried out in the following manner.

The voltage of 4 V was applied between 60 μs, and the voltage after 16.67 ms was measured to calculate the fluctuation from the initial value as the voltage holding ratio. At the time of measurement, the temperature of the liquid crystal cell was 23 ° C, 60 ° C, and 90 ° C, and the measurement was performed at each temperature.

[ion density]

The measurement of the ion density of the liquid crystal cell described above was carried out in the following manner.

The measurement was carried out using a 6254 liquid crystal physical property evaluation apparatus manufactured by TOYO Corporation. A triangular wave of 10 V and 0.01 Hz was applied, and the area corresponding to the ion density of the obtained waveform was calculated by a triangle approximation as the ion density. At the time of measurement, the temperature of the liquid crystal cell was 23 ° C and 60 ° C, and the measurement was performed at each temperature.

[Measurement of pretilt angle]

The measurement of the pretilt angle of the above liquid crystal cell was carried out using AxoScan manufactured by Axometrics.

(Synthesis Example 1)

The diamine compound (DA-1) was synthesized in a four-stage process as shown below.

Stage 1: Synthesis of Compound (A5)

Propargylamine (8.81 g, 160 mmol), N,N-dimethylformamide (112 mL), potassium carbonate (18.5 g, 134 mmol) were placed in a 500 mL eggplant flask. The temperature was 0 ° C, and the tamborine bromoacetate (21.9 g, 112 mmol) was dissolved in N,N-dimethylformamide (80 mL) with stirring for about 1 hour. Solution. After the completion of the dropwise addition, the reaction solution was allowed to stand at room temperature and stirred for 20 hours. Thereafter, the solid matter was removed by filtration, and 1 L of ethyl acetate was added to the filtrate, washed four times with 300 mL of water, and once with 300 mL of saturated saline. Then, the organic layer was dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. Finally, the residual oil was distilled under reduced pressure at 0.6 Torr at 70 ° C to give N-propargylamino acetic acid t-butyl ester (compound (A5)) as a colorless liquid. The yield was 12.0 g and the yield was 63%.

Stage 2: Synthesis of Compound (A6)

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

Stage 3: Synthesis of Compound (A7)

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

Stage 4: Reduction of Compound (A7)

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

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

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

(Synthesis Example 2) Synthesis of dimethyl 1,3-bis(chlorocarbonyl)-1,3-dimethylcyclobutane-2,4-dicarboxylate (1,3DMCBDE-Cl) A-1: Synthesis of dialkyl tetracarboxylate

In a nitrogen gas stream, 1,3-dimethylcyclobutane-1,2,3,4-tetracarboxylic dianhydride (compound of formula (5-1), below, was placed in a 3 L four-necked flask. 1,3-DM-CBDA for short, 220g (0.981mol) and methanol 2200g (6.87mol, 10wt times for 1,3-DM-CBDA), heated and refluxed at 65 ° C, after 30 minutes A homogeneous solution. The reaction solution was stirred directly under reflux with heating for 4 hours and 30 minutes. This reaction solution was measured by high speed liquid chromatography (hereinafter referred to as HPLC). The analysis of the measurement results is as follows.

After the solvent was distilled off from the reaction liquid in an evaporator, 1301 g of ethyl acetate was added, and the mixture was heated to 80 ° C, and refluxed for 30 minutes. Then, the internal temperature was cooled to 25 ° C at a rate of 2 to 3 ° C per 10 minutes, and stirred at 25 ° C for 30 minutes. The precipitated white crystals were taken out by filtration, and the crystals were washed twice with 141 g of ethyl acetate.

The crystal was analyzed by ¹ H NMR analysis and X-ray crystal structure, and was confirmed to be Compound (1-1) (HPLC relative area: 97.5%) (yield: 36.8%).

¹ H NMR (DMSO-d6, δ ppm); 12.82 (s, 2H), 3.60 (s, 6H), 3.39 (s, 2H), 1.40 (s, 6H).

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

Into a three-liter four-necked flask, 234.15 g (0.81 mol) of compound (1-1) and 1170.77 g (11.68 mol. 5 wt.) of n-heptane were placed in a nitrogen gas stream, and then 0.64 g of pyridine (0.01 mol) was added. ), the electromagnetic stirrer is heated and stirred to 75 ° C under stirring. Next, 289.93 g (11.68 mol) of sulfite dichloride was added dropwise over 1 hour. The foaming started immediately after the dropping, and the reaction solution became uniform after 30 minutes from the end of the dropping, and the foaming was stopped. Then, after stirring at 75 ° C for 1 hour and 30 minutes, the solvent was distilled off in a water bath at 40 ° C to make the content amount 924.42 g. This was heated to 60 ° C to dissolve the crystals precipitated when the solvent was distilled off, and filtered while hot at 60 ° C. After filtering the insoluble matter, the filtrate was cooled to 25 ° C at a rate of 1 ° C per 10 minutes. After stirring directly at 25 ° C for 30 minutes, the precipitated white crystals were taken out by filtration, and the crystals were washed with n-heptane 264.21 g. This was dried under reduced pressure to give 226.09 g of white crystal.

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

¹ H NMR (CDCl 3 , δ ppm): 3.78 (s, 6H), 3.72 (s, 2H), 1.69 (s, 6H).

(Synthesis Example 3)

A 3 L four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, and 10.293 g (0.101 mol) of p-phenylenediamine, 10.78177 g (0.0285 mol) of diamine (DA-1), and 472 g of NMP were added as a base. Pyridine 23.12 g (0.292 mol) was stirred and dissolved. Next, 1,3DM-CBDE-C1 39.6013 g (0.122 mol) was added to the diamine solution while stirring, and the mixture was reacted for 4 hours under water cooling. Into the obtained polyphthalate solution, 2101 g of NMP was added, and the mixture was stirred for 30 minutes to obtain a polyglycolate solution having a solid content concentration of 5 wt%. The polyglycolate solution was poured into 5247 g of water while stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 5247 g of water, once with 5247 g of ethanol, and washed with 1312 g of ethanol. Three times, 45.90 g of a white polyphthalate resin powder was obtained by drying. The yield was 87.7%. Further, the molecular weight of the polyglycolate was Mn = 16,556 and Mw = 35,901.

35.99 g of the obtained polyphthalate resin powder was placed in a 300 ml Erlenmeyer flask, and 230.85 g of GBL was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-1).

(Synthesis Example 4)

A 3 L four-necked flask equipped with a stirrer was placed under a nitrogen atmosphere, and 10.532 g (53.12 mmol) of 4,4'-diaminodiphenylmethane was placed, and 19.63 g of NMP was added, and 9.00 g (113.8 mmol) of pyridine as a base was added. ) and dissolve it. Next, 1,3DM-CBDE-Cl 15.4194 g (47.42 mmol) was added while stirring the diamine solution, and the mixture was reacted for 4 hours under water cooling. The obtained solution of the polyglycolate was poured into 2196 g of water while stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 2196 g of water, once with 2196 g of ethanol, and washed with 549 g of ethanol. The powder was dried three times and dried to give a white polyphthalate resin powder of 20.37 g. The yield was 92.8%. Further, the molecular weight of the polyglycolate was Mn = 11,659 and Mw = 25,571.

3.9648 g of the obtained polyphthalate resin powder was placed in a 100 ml Erlenmeyer flask, and 35.7135 g of NMP was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-2).

(Synthesis Example 5)

CBDA 5.8936 g (30.05 mmol) was placed in a 100 mL four-necked flask equipped with a stirring apparatus and a nitrogen gas introduction tube, and then, 56.11 g of NMP was added thereto, and the mixture was stirred while stirring with nitrogen gas to obtain a slurry. While stirring the slurry, 3.0196 g (27.92 mmol) of p-PDA was added thereto, and NMP was added thereto to have a solid content concentration of 10% by mass, and the mixture was stirred at room temperature for 24 hours to obtain a solution of polyamine acid (PAA-1). The polyamic acid solution had a viscosity of 136.5 mPa ‧ at a temperature of 25 ° C. Further, the molecular weight of the polyamic acid was Mn = 13,391 and Mw = 32,745.

(Example 1) Synthesis of Compound (1-a)

Hereinafter, the compound (1-a) was synthesized in a four-stage process.

Stage 1: Synthesis of precursor (1-a1)

In a 300 ml four-necked flask, 18.78 g (92.68 mmol) of 2-(4-nitrophenyl)ethylamine hydrochloride was placed, followed by 152 ml of toluene and 9.847 g (97.31 mmol) of triethylamine. Stir at 0 ° C (ice bath). 21.24 g (97.31 mmol) of di-tert-butyl dicarbonate was placed in the dropping funnel, and it was dropped into the solution in the four-necked flask over 30 minutes. After the completion of the dropwise addition, the mixture was stirred at room temperature (20 ° C) for 8 hours. After completion of the reaction, 500 ml of pure water was added to the reaction solution and extracted. The obtained organic layer was washed twice with pure water and dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was distilled off to obtain a white solid. To the white solid, 100 ml of hexane and 20 ml of ethyl acetate were added to carry out recrystallization. The precipitated solid was vacuum filtered and dried under reduced pressure. The obtained white solid was confirmed to be a precursor (1-a1) by ¹ H NMR. The yield was 20.92 g and the yield was 85%.

_{^{1 H NMR (400MHz, CDCl 3}} , δppm): 1.43 (s, 9H), 2.92 (t, J = 6.8Hz, 2H), 3.41 (q, J = 6.8Hz, 2H), 4.56 (bs, 1H), 7.35 (d, J = 8.8 Hz, 2H), 8.16 (d, J = 8.8 Hz, 2H).

Stage 2: Synthesis of precursor (1-a2)

In a 500 ml eggplant type flask, 20.90 g (78.49 mmol) of the precursor (1-a1) was placed, and 200 ml of tetrahydrofuran was added. After the reaction vessel was replaced with nitrogen, 2.09 g of palladium carbon was added and replaced with nitrogen. The reaction vessel was replaced with hydrogen and stirred at 20 ° C for 19 hours. After completion of the reaction, the palladium carbon was removed by filtration through diatomaceous earth, and the solvent was removed from the filtrate to obtain a white solid. The obtained solid was dissolved in 20 ml of an acetate, and 140 ml of hexane was added thereto to carry out recrystallization. The precipitated solid was collected by vacuum filtration and dried under reduced pressure. The white solid obtained was confirmed to be the precursor (1-a2) by ¹ H NMR. The yield was 16.54 g and the yield was 89%.

_{^{1 H NMR (400MHz, CDCl 3}} , δppm): 1.43 (s, 9H), 2.67 (t, J = 6.8Hz, 2H), 3.31 (q, J = 6.8Hz, 2H), 3.59 (bs, 2H), 4.52 (bs, 1H), 6.64 (d, J = 8.0 Hz, 2H), 6.97 (d, J = 8.0 Hz, 2H).

Stage 3: Synthesis of Compound (1-a)

A 100 ml four-necked flask was placed under a nitrogen atmosphere, and 1,3DM-CBDE-Cl 5.00 g (15.38 mmol) was placed therein, followed by the addition of 25 ml of tetrahydrofuran (dehydrated) and 2.68 g (33.83 mmol) of pyridine, followed by stirring to obtain an acid chloride. Compound solution. Next, 7.45 g (31.53 mmol) of the precursor (1-a2) was placed in a 100 ml Erlenmeyer flask, and then 15 ml of tetrahydrofuran (dehydrated) was added to obtain a monoamine solution. The monoamine solution was transferred to a dropping funnel, and the monoamine solution was dropped into a four-necked flask over 15 minutes. After dropping, it was stirred for 20 hours. After 20 hours, the reaction solution was poured into 200 ml of water, and extraction was carried out by adding 100 ml of chloroform. The obtained organic layer was washed twice with pure water and dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was distilled off to obtain a white solid. The obtained solid was dissolved in 30 ml of tetrahydrofuran, and 100 ml of diisopropyl ether was added thereto to carry out recrystallization. The precipitated solid was collected by vacuum filtration and dried under reduced pressure. The white solid obtained was confirmed to be the compound (1-a) by ¹ H NMR. The yield was 8.38 g and the yield was 75%.

_{^{1 H NMR (400MHz, CDCl 3}} , δppm): 1.43 (s, 18H), 1.58 (s, 6H), 2.78 (t, J = 6.8Hz, 4H), 3.53 (m, 4H), 3.84 (s, 6H ), 4.10 (s, 2H), 4.55 (bs, 2H), 7.18 (d, J = 8.0 Hz, 4H), 7.45 (d, J = 8.0 Hz, 4H), 8.62 (s, 2H).

(Example 2) Synthesis of Compound (1-b)

Hereinafter, the compound (1-b) was synthesized in a three-stage process.

Stage 1: Synthesis of precursor (1-b1)

In a 100 ml four-necked flask substituted with nitrogen, 8.95 g (44.30 mmol) of 4-bromonitrobenzene, 0.311 g (0.44 mmol) of bis(triphenylphosphine)palladium(II) dichloride, and copper iodide were placed. 0.169 g (0.89 mmol) and triethylamine 5.38 g (53.16 mmol) were added to 30 ml of tetrahydrofuran, and stirred at room temperature (20 ° C) for 10 minutes. Next, 8.25 g (53.16 mmol) of N-(tert-butoxycarbonyl)propargylamine was placed in a 100 ml Erlenmeyer flask, and 15 ml of tetrahydrofuran was added thereto and dissolved. This solution was transferred to a dropping funnel, and it took 5 minutes to drip the solution in the four-necked flask. After the dropwise addition, the mixture was stirred under heating at 60 ° C for 3 hours. After 3 hours, the reaction solution was poured into 250 ml of pure water to precipitate a solid. The solid which precipitated was collected by vacuum filtration, and the obtained solid was dissolved in 40 ml of toluene, and 25 ml of hexane was added to carry out recrystallization. The precipitated solid was collected by vacuum filtration and dried under reduced pressure. The obtained brown solid was confirmed to be the precursor (1-b1) by ¹ H NMR. The yield was 7.66 g and the yield was 62.5%.

_{^{1 H NMR (400MHz, CDCl 3}} , δppm): 1.43 (s, 9H), 4.20 (s, 2H), 4.82 (bs, 1H), 7.56 (d, J = 8.0Hz, 2H), 8.18 (d, J =8.0Hz, 2H).

Stage 2: Synthesis of precursor (1-b2)

A precursor (1-b1) of 12.87 g (46.58 mmol) was placed in a 500 ml eggplant type flask, and 130 ml of methanol was added. After the reaction vessel was replaced with nitrogen, 1.28 g of palladium carbon was added and replaced with nitrogen. The reaction vessel was replaced with hydrogen and stirred with heating at 50 ° C for 24 hours. After completion of the reaction, the palladium carbon was removed by filtration through diatomaceous earth, and the solvent was removed from the filtrate to obtain a brown sugary compound. The obtained saccharide compound was purified by silica gel column chromatography (ethyl acetate: hexane = 50:50) to obtain a brown sugary compound. The obtained brownish sugary compound was confirmed to be the precursor (1-b2) by ¹ H NMR. The yield was 4.42 g and the yield was 37.9%.

_{^{1 H NMR (400MHz, CDCl 3}} , δppm): 1.43 (s, 9H), 1.75 (quin, J = 6.8Hz, 2H), 2.55 (t, J = 6.8Hz, 2H), 3.16 (q, J = 6.8 Hz, 2H), 3.59 (bs, 2H), 4.56 (bs, 1H), 6.67 (d, J = 8.0 Hz, 2H), 6.96 (d, J = 8.0 Hz, 2H).

Stage 3: Synthesis of Compound (1-b)

A 100 ml four-necked flask was placed under a nitrogen atmosphere, and 1,3DM-CBDE-C1 2.40 g (15.38 mmol) was added thereto, followed by the addition of tetrahydrofuran (dehydrated) 10 ml, pyridine 1.29 g (16.24 mmol), and stirred to obtain an acidic chloride solution. . Next, 4.07 g (16.24 mmol) of the precursor (1-b2) was placed in a 50 ml Erlenmeyer flask, and then 10 ml of tetrahydrofuran (dehydrated) was added as a monoamine solution. The monoamine solution was transferred to a dropping funnel, and the monoamine solution was dropped into a four-necked flask over 5 minutes. After dripping, it was stirred for 3 hours. After 20 hours, the reaction solution was poured into 60 ml of water, and 40 ml of chloroform was added thereto for extraction. The obtained organic layer was washed twice with pure water and dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was distilled off to obtain a white solid. The obtained solid was purified by silica gel column chromatography (ethyl acetate:hexane = 1:1) to afford white solid. The white solid obtained was confirmed to be the compound (1-b) by ¹ H NMR. The yield was 3.72 g and the yield was 66.9%.

^{1 H NMR (400MHz, DMSO-} d6, δppm): 1.43 (s, 18H), 1.58 (s, 6H), 1.67 (quin, J = 6.8Hz, 4H), 2.55 (m, 4H), 2.97 (q, J = 6.8 Hz, 4H), 3, 59 (s, 6H), 3.62 (s, 2H), 6.86 (t, J = 6.8 Hz, 2H), 7.16 (d, J = 8.0 Hz, 4H), 7.45 ( d, J = 8.0 Hz, 4H), 9.43 (s, 2H).

(Example 3) Synthesis of Compound (1-c)

Hereinafter, the compound (1-c) was synthesized in a three-stage process.

Stage 1: Synthesis of precursor (1-c1)

50.42 g (0.230 mol) of 3-bromopropylamine hydrobromide was placed in a 2-L four-necked flask, and 672 g of dichloromethane and 56.28 g (0.258 mol) of di-tert-butyl dicarbonate were added. Stir at 0 ° C (ice bath). 60.86 g (0.471 mol) of N,N-indolediisopropylethylamine was placed in the dropping funnel, and the mixture was dropped into a slurry solution in a four-necked flask for 30 minutes. After the start of the dropping, the reaction solution was vigorously foamed, and a white solid precipitated. After the completion of the dropwise addition, the mixture was stirred for 3 hours. After completion of the reaction, 500 ml of pure water was added to the reaction solution to carry out extraction. The obtained organic layer was washed twice with pure water and dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was distilled off to obtain a colorless transparent oil. 500 ml of hexane was added to the oily substance, which was crystallized at -78 ° C to give a white solid. The solid was collected by vacuum and dried under reduced pressure. The white solid obtained was confirmed to be tert-butyl-3-bromopropylcarbamate, i.e., the precursor (1-cl), by ¹ H NMR. The yield was 42.99 g and the yield was 78.5%.

_{^{1 H NMR (400MHz, CDCl 3}} , δppm): 1.44 (s, 9H), 2.05 (quin, J = 6.4Hz, 2H), 3.27 (q, J = 6.4Hz, 2H), 3.45 (t, J = 6.4 Hz, 2H), 4.69 (bs, 1H).

Stage 2: Synthesis of precursor (1-c2)

Into a 1 L four-necked flask, 40.00 g (0.168 mol) of a precursor (1-c1) and 32.86 g (0.238 mol) of potassium carbonate were placed, and 481 g of DMF was added thereto, and the mixture was stirred under heating at 60 ° C for 7 hours. After 7 hours, the obtained reaction solution was poured into 3 L of pure water with stirring, and 1 L of acetate was added thereto for extraction. The obtained organic layer was washed twice with pure water, washed with 500 ml of 1M aqueous sodium hydroxide, and dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was distilled off to obtain a yellow solid. The obtained solid was dissolved in 200 ml of an acetate, and 1 L of hexane was added thereto with stirring to precipitate a solid. The resulting solid was vacuum filtered and dried under reduced pressure. The yellow solid obtained was confirmed to be the precursor (1-c2) by ¹ H NMR. The yield was 35.49 g and the yield was 71.3%.

_{^{1 H NMR (400MHz, CDCl 3}} , δppm): 1.44 (s, 9H), 2.03 (quin, J = 6.4Hz, 2H), 3.34 (q, J = 6.4Hz, 2H), 4.12 (t, J = 6.4 Hz, 2H), 4.72 (bs, 1H), 6.95 (d, 8.0 Hz, 2H), 8.20 (d, 8.0 Hz, 2H).

Stage 3: Synthesis of precursor (1-c3)

A precursor (1-c2) 30.04 g (0.102 mol) was placed in a 500 ml eggplant type flask, and 170 g of ethanol was added. After the reaction vessel was replaced with nitrogen, 3.11 g of palladium carbon was added and replaced with nitrogen. The reaction vessel was replaced with hydrogen and stirred at 20 ° C for 48 hours. After completion of the reaction, the palladium carbon was removed by filtration through diatomaceous earth, and the solvent was removed from the filtrate to obtain a solid. The obtained solid was dissolved in 100 ml of an acetate, and 400 ml of hexane was added thereto with stirring, and a white solid was precipitated by further cooling to -50 °C. The precipitated solid was collected by vacuum filtration and dried under reduced pressure. The obtained yellow solid was confirmed to be a precursor (1-c3) by ¹ H NMR. The yield was 26.64 g and the yield was 97.7%.

_{^{1 H NMR (400MHz, CDCl 3}} , δppm): 1.44 (s, 9H), 1.93 (quin, J = 6.4Hz, 2H), 3.32 (q, J = 6.4Hz, 2H), 3.44 (bs, 2H), 3.94 (t, J = 6.4 Hz, 2H), 4.85 (bs, 1H), 6.63 (d, 8.0 Hz, 2H), 6.73 (d, 8.0 Hz, 2H).

Stage 4: Synthesis of Compound (1-c)

A 3 L four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, and 12.26 g (46.0 mmol) of the precursor (1-c3) was placed, and 241 g of NMP and 5.31 g (67.1 mmol) of pyridine as a base were added and stirred. Dissolved. Next, 7.43 g (22.9 mol) of 1,3DM-CBDE-Cl was added while stirring the monoamine solution, and the mixture was reacted for 4 hours under water cooling. The obtained reaction solution was poured into 1800 g of water while stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 1800 g of water, once with 1800 g of ethanol, and washed with 540 g of ethanol three times. White solid. The obtained white solid was dissolved in ethyl acetate, and hexane was added to carry out recrystallization. The precipitated solid was collected by vacuum filtration and dried under reduced pressure. The obtained yellow solid was confirmed to be the precursor (1-c) by ¹ H NMR. The yield was 15.23 g and the yield was 84.4%.

_{^{1 H NMR (400MHz, CDCl 3}} δppm): 1.44 (s, 18H), 1.58 (s, 6H), 1.97 (quin, J = 6.4Hz, 4H), 3.31 (q, J = 6.4Hz, 4H), 3.85 (s, 6H), 3.99 (t, J = 6.4 Hz, 4H), 4.80 (bs, 2H), 6.85 (d, 8.0 Hz, 4H), 7.42 (d, 8.0 Hz, 4H), 8.50 (s, 2H) ).

(Example 4) Synthesis of Compound (1-d)

A 3 L four-necked flask equipped with a stirring apparatus was placed under a nitrogen atmosphere, and 1.87 g (6.63 mmol) of 2,5-bis(methoxycarbonyl)terephthalic acid and 1.10 g (13.9 mmol) of pyridine were placed, and dehydrated tetrahydrofuran was added thereto. 40 ml, heated to reflux. 1.54 g (12.9 mmol) of sulfite dichloride was added to the solution, and the mixture was heated under reflux for 1 hour. After 1 hour, 3.13 g (19.56 mmol) of the precursor (1-a2) was placed in the reaction solution, followed by heating under reflux for 2 hours. The obtained reaction solution was poured into 500 g of water while stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 500 g of water, once with 500 g of methanol, and washed with 240 g of methanol three times. White solid. The obtained white solid was placed in a 200 ml eggplant type flask, and 100 ml of ethyl acetate was added thereto, followed by heating and stirring. The residual solid was collected by vacuum and dried under reduced pressure. The white solid obtained was confirmed to be the compound (1-d) by ¹ H NMR. The yield was 1.97 g and the yield was 41.4%.

^{1 H NMR (400MHz, DMSO-} d6 δppm): 1.38 (s, 18H), 2.67 (t, J = 8.0Hz, 4H), 3.13 (q J = 8.0Hz, 4H), 3.81 (s, 6H), 6.89 (t, J = 5.6 Hz, 2H), 7.18 (d, 8.8 Hz, 4H), 7.42 (d, 8.8 Hz, 4H), 8.03 (s, 2H), 10.56 (s, 2H).

(Example 5) Synthesis of Compound (1-j)

A 30 ml four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, and 1.04 g (4.42 mmol) of the precursor (1-a2) was placed, and 20 g of NMP and 0.58 g (7.43 mmol) of pyridine as a base were added and stirred to dissolve. Next, 0.68 g (2.22 mol) of CBDE-C1 was added while stirring the monoamine solution, and the mixture was reacted for 2 hours under water cooling. The obtained reaction solution was poured into 200 g of water while stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 200 g of water, once with 200 g of ethanol, and washed with 100 g of ethanol three times. White solid. The obtained white solid was placed in a 50 ml eggplant type flask, and 30 ml of ethyl acetate was added thereto, and the mixture was stirred under heating at 80 ° C for 30 minutes. After 30 minutes, the residual solid was collected by vacuum and dried under reduced pressure. The obtained white solid was confirmed to be a precursor (1-j) by ¹ H NMR. The yield was 0.42 g and the yield was 27.3%.

^{1 H NMR (400MHz, DMSO-} d6 δppm): 1.33 (s, 18H), 1.58 (s, 6H), 2.59 (t, J = 7.2Hz, 4H), 3.06 (q, J = 7.2Hz, 4H), 3.47 (s, 6H), 3.56 to 3.63 (m, 2H), 3.86 to 3.91 (m, 2H), 6.83 (t, J = 5.6 Hz, 4H), 7.08 (d, 8.4 Hz, 4H), 7.43 (d) , 8.4 Hz, 4H), 10.10 (s, 2H).

(Example 6) Synthesis of Compound (1-k)

A 30 ml four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, and 1.06 g (3.99 mmol) of the precursor (1-c3) was placed, and 20 g of NMP and 0.58 g (7.43 mmol) of pyridine as a base were added and stirred to dissolve. Next, 0.658 g (1.99 mol) of CBDE-C1 was added while stirring the monoamine solution, and the mixture was reacted for 2 hours under water cooling. The obtained reaction solution was poured into 200 g of water while stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 200 g of water, once with 200 g of ethanol, and washed with 100 g of ethanol three times. White solid. The obtained white solid was placed in a 50 ml eggplant type flask, and 30 ml of ethyl acetate was added thereto, and the mixture was stirred under heating at 80 ° C for 30 minutes. After 30 minutes, the residual solid was collected by vacuum and dried under reduced pressure. The obtained white solid was confirmed to be a precursor (1-k) by ¹ H NMR. The yield was 0.58 g and the yield was 38.4%.

^{1 H (400MHz, DMSO-d6} δppm) NMR: 1.44 (s, 18H), 1.79 (quin, J = 6.4Hz, 4H), 3.06 (q, J = 6.4Hz, 4H), 3.60 (s, 6H), 3.59 to 3.66 (m, 2H), 3.86 to 3.96 (m, 6H), 6.86 (d, 8.0 Hz, 4H), 6.90 (t, J = 6.4 Hz, 2H), 7.46 (d, 8.0 Hz, 4H), 10.06(s, 2H).

(Example 7) Synthesis of Compound (1-i)

A 50 ml two-necked flask equipped with a stirring apparatus was placed under a nitrogen atmosphere, and 0.62 g (2.20 mmol) of 2,5-bis(methoxycarbonyl)terephthalic acid and 0.38 g (4.80 mmol) of pyridine were placed, and 20 ml of dehydrated tetrahydrofuran was added thereto. Heat and reflux. To the solution was added 0.55 g (4.62 mmol) of sulfoxide dichloride, and the mixture was heated under reflux for 1 hour. After 1 hour, 1.23 g (4.62 mmol) of the precursor (1-c3) was placed in the reaction solution, followed by heating under reflux for 2 hours. The obtained reaction solution was poured into 200 g of water while stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 100 g of water, once with 100 g of ethanol, and washed three times with 50 g of ethanol to obtain three times. Light yellow solid. The obtained pale yellow solid was placed in a 50 ml eggplant type flask, and 20 ml of ethyl acetate was added thereto, followed by heating and stirring. The residual solid was collected by vacuum and dried under reduced pressure. The white solid obtained was confirmed to be the compound (1-i) by ¹ H NMR. The yield was 0.57 g and the yield was 33.1%.

^{1 H NMR (400MHz, DMSO-} d6 δppm): 1.38 (s, 18H), 1.83 (quin, J = 6.4Hz, 4H), 3.08 (q J = 6.4Hz, 4H), 3.81 (s, 6H), 3.96 (t, J = 6.4 Hz, 4H), 6.86 to 7.00 (m, 6H), 7.58 (d, 7.2 Hz, 4H), 8.02 (s, 2H), 10.47 (s, 2H).

(Example 8) Preparation of solution containing compound (1-e)

In a 50 mL four-necked flask equipped with a stirring device and a nitrogen gas introduction tube, 2.37 g (10.03 mmol) of the precursor (1-a2) was placed, and then 9.40 g of NMP was added, followed by stirring with nitrogen gas to obtain a monoamine solution. . While stirring the monoamine solution, 0.98 g (5.00 mmol) of CBDA was added, and further NMP was added to adjust the solid content concentration to 20% by mass, and the mixture was stirred at room temperature for 24 hours to obtain a solution containing the compound (1-e).

To a part of the obtained solution, 1-methyl-3-p-tolyltriazene was added to carry out methyl esterification of the carboxylic acid, and it was confirmed by ¹ H NMR to obtain (1-j obtained in Example 5). ) the same compound. From this, it was confirmed that (1-e) was contained in the above solution.

(Example 9) Preparation of solution containing compound (1-f)

In a 50 mL four-necked flask equipped with a stirring device and a nitrogen gas introduction tube, 2.37 g (10.03 mmol) of the precursor (1-a2) was placed, followed by the addition of 9.62 g of NMP, and stirred while feeding nitrogen gas to be a monoamine. Solution. While stirring the monoamine solution, 1.09 g (5.00 mmol) of PMDA was added, and further NMP was added to adjust the solid content concentration to 20% by mass, and the mixture was stirred at room temperature for 24 hours to obtain a solution containing the compound (1-f).

To a part of the obtained solution, 1-methyl-3-p-tolyltriazene was added, and methylation of the carboxylic acid was carried out, and it was confirmed by ¹ H NMR to obtain (1-d) obtained in Example 4. ) the same compound. From this, it was confirmed that the above solution contained (1-f).

(Example 10) Preparation of a solution containing a compound (1-g)

Into a 50 mL four-necked flask equipped with a stirring device and a nitrogen gas introduction tube, 2.66 g (9.99 mmol) of the precursor (1-c3) was placed, and then 10.19 g of NMP was added thereto, and the mixture was stirred while being fed with nitrogen gas to be a monoamine. Solution. While stirring the monoamine solution, 1.09 g (5.00 mmol) of CBDA was added, and further NMP was added to adjust the solid content concentration to 20% by mass, and the mixture was stirred at room temperature for 24 hours to obtain a solution containing the compound (1-g).

To a part of the obtained solution, 1-methyl-3-p-tolyltriazene was added, and methylation of the carboxylic acid was carried out, and it was confirmed by ¹ H NMR that (1) obtained in Example 6 was obtained. k) the same compound. From this, it was confirmed that the above solution contained (1-g).

(Example 11) Preparation of solution containing compound (1-h)

In a 50 mL four-necked flask equipped with a stirring device and a nitrogen gas introduction tube, 3.99 g (15.0 mmol) of the precursor (1-c3) was placed, followed by the addition of 16.91 g of NMP, and stirred while feeding nitrogen gas to be a monoamine. Solution. While stirring the monoamine solution, 1.64 g (7.52 mmol) of PMDA was added, and further NMP was added to adjust the solid content concentration to 20% by mass, and the mixture was stirred at room temperature for 24 hours to obtain a solution containing the compound (1-h).

To a part of the obtained solution, 1-methyl-3-p-tolyltriazene was added, and methylation of the carboxylic acid was carried out, and it was confirmed by ¹ H NMR that (1) obtained in Example 7 was obtained. i) the same compound. From this, it was confirmed that the above solution contained (1-h).

(Embodiment 12)

Into a 100 ml Erlenmeyer flask, 44.3382 g of the polyamidate solution (PAE-1) obtained in Synthesis Example 3 was placed, followed by the addition of GBL 19.6930 g and BCS 16.0839 g to obtain a diluted solution of polyglycolate.

Into a 20 ml sample tube into which a stir bar was placed, 5.02 g of the above solution was injected, followed by the addition of 0.0645 g of the compound (1-a) obtained in Example 1 (for the repeating unit of the polyamidomate 1 mol) The mixture was stirred at room temperature for 30 minutes to completely dissolve the compound (1-a) to obtain a liquid crystal alignment agent (A1-1).

(Example 13)

The compound and Example 12 were used except that the compound (1-c) obtained in Example 3 was used instead of the compound (1-a) in an amount of 0.1 mol per equivalent of the repeating unit of the polyphthalate. The liquid crystal alignment agent (A1-2) was obtained in the same manner.

(Example 14)

The solution containing the compound (1-e) obtained in Example 8 was added in place of the compound (1-a), except that the compound (1-e) was 0.1 molar equivalent to the repeating unit of the polyphthalate. The liquid crystal alignment agent (A1-3) was obtained in the same manner as in Example 12 except for the above.

(Example 15)

The compound (1-f)-containing solution obtained in Example 9 was added in place of the compound (1-a), except that the compound (1-f) was 0.1 molar equivalent to the repeating unit of the polyphthalate. The liquid crystal alignment agent (A1-4) was obtained in the same manner as in Example 12 except for the above.

(Embodiment 16)

The compound (1-g) solution obtained in Example 10 was added in place of the compound (1-a), except that the compound (1-g) was 0.1 molar equivalent to the repeating unit of the polyphthalate. The liquid crystal alignment agent (A1-5) was obtained in the same manner as in Example 12 except for the above.

(Example 17)

The compound (1-h)-containing solution obtained in Example 11 was added in place of the compound (1-a), except that the compound (1-h) was 0.1 mole equivalent to the repeating unit of the polyphthalate. The liquid crystal alignment agent (A1-6) was obtained in the same manner as in Example 12 except for the above.

(Embodiment 18)

In a 20 ml sample tube to which a stirrer was placed, 4.4560 g of the polyamidomate solution (PAE-2) obtained in Synthesis Example 4 was placed, followed by addition of 1.4837 g of NMP and 1.5021 g of BCS, followed by the addition of Example 1. 0.1023 g of the compound (1-a) (0.2 mol equivalent for the repeating unit of polyphthalamide), and stirred at room temperature for 30 minutes to completely dissolve the compound (1-a) to obtain a liquid crystal. Orienting agent (A2-1).

(Embodiment 19)

The compound and Example 18 were used except that the compound (1-d) obtained in Example 4 was used instead of the compound (1-a) in an amount of 0.2 mol per equivalent of the repeating unit of the polyphthalate. The liquid crystal alignment agent (A2-2) was obtained in the same manner.

(Embodiment 20)

The solution containing the compound (1-e) obtained in Example 8 was added in place of the compound (1-a), except that the compound (1-e) was 0.2 molar equivalent to the repeating unit of the polyphthalate. The liquid crystal alignment agent (A2-3) was obtained in the same manner as in Example 18 except for the above.

(Example 21)

The compound (1-f)-containing solution obtained in Example 9 was added in place of the compound (1-a), except that the compound (1-f) was 0.2 molar equivalent to the repeating unit of the polyphthalate. The liquid crystal alignment agent (A2-4) was obtained in the same manner as in Example 18 except for the above.

(Example 22)

In a 20 ml sample tube to which a stir bar was placed, 4.4156 g of the polyaminic acid solution (PAA-1) obtained in Synthesis Example 5 was placed, and then NMP 1.3409 g and BCS 1.4426 g were added, and the obtained Example 1 was added. Compound (1-a): 0.2113 g (0.2 mol equivalent of repeating unit of poly-proline), stirred at room temperature for 30 minutes to completely dissolve compound (1-a) to obtain liquid crystal alignment agent (A3-1).

(Example 23)

The same procedure as in Example 22 except that the compound (1-d) obtained in Example 4 was used instead of the compound (1-a) in an amount of 0.2 mol per equivalent of the repeating unit of poly-proline. The liquid crystal alignment agent (A3-2) was obtained.

(Example 24)

The solution containing the compound (1-e) obtained in Example 8 was added in place of the compound (1-a) except that the compound (1-e) was 0.2 molar equivalent to the repeating unit of poly-proline. The liquid crystal alignment agent (A3-3) was obtained in the same manner as in Example 22 except for the above.

(Embodiment 25)

The addition of the compound (1-f) solution obtained in Example 9 except that the compound (1-f) is 0.2 molar equivalent of the repeating unit of poly-proline. 22 was carried out in the same manner to obtain a liquid crystal alignment agent (A3-4).

(Comparative Example 1)

Into a 20 ml sample tube in which a stirrer was placed, 2.7692 g of the polyamidomate solution (PAE-1) obtained in Synthesis Example 3 was placed, followed by addition of GBL 1.2308 g, BCS 1.012 g, and stirring at room temperature for 30 minutes. A liquid crystal alignment agent (B1-1) was obtained.

(Comparative Example 2)

Into a 20 ml sample tube in which a stirrer was placed, 4.3431 g of a polyamidomate solution (PAE-2) obtained in Synthesis Example 4 was placed, followed by addition of N722 1.4722 g, BCS 1.4589 g, and stirring at room temperature for 30 minutes. A liquid crystal alignment agent (B2-1) was obtained.

(Comparative Example 3)

Into a 20 ml sample tube in which a stir bar was placed, 4.7100 g of the polyamidomate solution (PAE-2) obtained in Synthesis Example 4 was placed, followed by NMR 1.5935 g, BCS 1.5892 g, and the addition of Example 1 was added. The precursor (1-a2) was 0.0985 g (0.4 mol equivalent for the repeating unit of polyphthalamide), and the mixture was stirred at room temperature for 30 minutes to obtain a liquid crystal alignment agent (B2-2).

(Comparative Example 4)

In a 20 ml sample tube to which a stir bar was placed, 3.9775 g of the polyaminic acid solution (PAA-1) obtained in Synthesis Example 5 was placed, and then NMP 1.2069 g and BCS 1.2953 g were added, and the mixture was stirred at room temperature for 30 minutes. A liquid crystal alignment agent (B3-1) was obtained.

(Comparative Example 5)

Into a 20 ml sample tube into which a stir bar was placed, 4.3645 g of the polyaminic acid solution (PAA-1) obtained in Synthesis Example 5 was placed, followed by addition of NMP 1.3462 g, BCS 1.4297 g, and addition of Example 1 before addition. 0.1357 g of the precursor (1-a2) (0.4 mol equivalent of repeating unit of polyproline) was stirred at room temperature for 30 minutes to obtain a liquid crystal alignment agent (B3-2).

(Example 26)

The liquid crystal alignment agent (A1-1) obtained in Example 12 was filtered through a 1.0 μm membrane filter, and then spin-coated on a glass substrate, dried on a hot plate at a temperature of 80 ° C for 5 minutes, and then fired at 230 ° C. After 10 minutes, a ruthenium imidized film having a film thickness of 100 nm was obtained. The coating film was taken, and the FT-IR spectrum was measured by the ATR method, and the ruthenium iodide ratio was calculated. The results are shown in Table 1.

(Examples 27 to 31)

Using the liquid crystal alignment agents (A1-2) to (A1-6) obtained in Examples 13 to 17, a ruthenium imidized film was produced in the same manner as in Example 26, and the FT-IR spectrum was measured, and 醯 was calculated. The rate of imidization. The results are shown in Table 1.

(Comparative Example 6)

Using the liquid crystal alignment agent (B1-1) obtained in Comparative Example 1, a ruthenium imidized film was produced in the same manner as in Example 26, and the FT-IR spectrum was measured, and the oxime imidization ratio was calculated. The results are shown in Table 1.

From the results of Examples 26 to 31 and Comparative Example 6, it was confirmed that the compound of the present invention can promote the ruthenium imidization reaction of the polyphthalate.

(Example 32)

The liquid crystal alignment agent (A2-1) obtained in Example 18 was filtered through a membrane filter of 1.0 μm, and then spin-coated on a glass substrate, dried on a hot plate at 80 ° C for 5 minutes, and then fired at 230 ° C. After 10 minutes, a ruthenium imidized film having a film thickness of 100 nm was obtained. The coating film was taken, and the FT-IR spectrum was measured by the ATR method, and the ruthenium iodide ratio was calculated. The results are shown in Table 2.

(Examples 33 to 35)

Using the liquid crystal alignment agents (A2-2) to (A2-4) of the present invention obtained in Examples 19 to 21, a ruthenium imidized film was produced in the same manner as in Example 32, and the FT-IR spectrum was measured. The yield of hydrazine imidation was calculated. The results are shown in Table 2.

(Comparative Examples 7 to 8)

Using the liquid crystal alignment agents (B2-1) and (B2-2) obtained in Comparative Examples 2 and 3, a ruthenium imidized film was produced in the same manner as in Example 32, and the FT-IR spectrum was measured, and 醯 was calculated. The rate of imidization. The results are shown in Table 2.

From the results of Examples 32 to 35 and Comparative Example 7, it was confirmed that the compound of the present invention can promote the ruthenium imidization reaction of the polyphthalate. Further, from the results of Examples 34 and 35 and Comparative Example 8, it was confirmed that the reaction product of the tetracarboxylic dianhydride and the precursor (1-a2) promoted the ruthenium imidization reaction of the polyphthalate.

(Example 36)

The liquid crystal alignment agent (A3-1) obtained in Example 22 was filtered through a 1.0 μm membrane filter, and then spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at a temperature of 80 ° C for 5 minutes. The film was fired at 230 ° C for 20 minutes to obtain a ruthenium imidized film having a film thickness of 100 nm. The polyimine film was polished with a rayon cloth (roll diameter: 120 mm, number of revolutions: 1000 rpm, moving speed: 20 mm/sec, and extrusion amount: 0.4 mm), and the surface state of the polyimide film was observed. No result was observed. Damage caused by grinding, chipping of the polyimide film and peeling of the polyimide film.

(Example 37)

A polyimide film was produced in the same manner as in Example 36 except that the liquid crystal alignment agent (A3-2) obtained in Example 23 was used, and subjected to a polishing treatment. The surface state of the polyimide film was observed, and as a result, no damage due to grinding, chipping of the polyimide film, and peeling of the polyimide film were observed.

(Example 38)

A polyimide film was produced in the same manner as in Example 36 except that the liquid crystal alignment agent (A3-3) obtained in Example 24 was used, and subjected to a polishing treatment. The surface state of the polyimide film was observed, and as a result, no damage due to grinding, chipping of the polyimide film, and peeling of the polyimide film were observed.

(Example 39)

A polyimine film was produced in the same manner as in Example 36 except that the liquid crystal alignment agent (A3-4) obtained in Example 25 was used, and subjected to a polishing treatment. The surface state of the polyimide film was observed, and as a result, no damage due to grinding, chipping of the polyimide film, and peeling of the polyimide film were observed.

(Comparative Example 9)

A polyimide film was produced in the same manner as in Example 36 except that the liquid crystal alignment agent (B3-1) obtained in Comparative Example 4 was used, and a polishing treatment was applied. The surface state of the polyimide film was observed, and as a result, damage due to grinding or chipping of the polyimide film was observed.

(Comparative Example 10)

A polyimide film was produced in the same manner as in Example 36 except that the liquid crystal alignment agent (B3-2) obtained in Comparative Example 5 was used, and a polishing treatment was carried out. The surface state of the polyimide film was observed, and as a result, damage due to grinding or chipping of the polyimide film was observed.

From the results of Examples 36 to 39 and Comparative Example 9, it was confirmed that the polyamic acid solution prepared by adding the compound of the present invention was applied and baked, whereby it was found that it was difficult to be damaged by polishing and the mechanical strength was excellent. The oxime imidization film. Further, from the results of Examples 38 and 39 and Comparative Example 10, it was confirmed that the reaction product of the tetracarboxylic dianhydride and the precursor (1-a2) can improve the mechanical strength of the obtained ruthenium imidized film.

(Embodiment 40)

The liquid crystal alignment agent (A2-1) obtained in Example 18 was filtered through a 1.0 μm membrane filter, and then spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at a temperature of 80 ° C for 5 minutes. The film was baked at a temperature of 230 ° C for 20 minutes to form a ruthenium imidized film having a film thickness of 100 nm. The coating film was ground with a rayon cloth (roller diameter: 120 mm, number of revolutions: 300 rpm, moving speed: 20 mm/sec, and extrusion amount: 0.4 mm), and after being ultrasonicated for 1 minute in pure water, it was washed and removed by air flow. After the water drop, it was dried at 80 ° C for 10 minutes to obtain a substrate with a liquid crystal alignment film.

Two substrates having such a liquid crystal alignment film were prepared, and a spacer of 6 μm was spread on the liquid crystal alignment film surface of one substrate, and then the polishing directions of the two substrates were combined in antiparallel to leave a liquid crystal injection port to seal the periphery. The cell gap is an empty cell of 6 μm. Liquid crystal (MLC-2041, manufactured by Merck) was vacuum-injected at room temperature to seal the injection port to form a liquid crystal cell, and the liquid crystal cell was observed for liquid crystal alignment, pretilt angle measurement, and voltage. Retention rate measurement and ion density measurement. The results are shown in Tables 3 and 4 which will be described later.

(Example 41)

A liquid crystal cell was produced in the same manner as in Example 40 except that the liquid crystal alignment agent (A2-2) obtained in Example 19 was used. With respect to this liquid crystal cell, observation of liquid crystal alignment, measurement of pretilt angle, measurement of voltage holding ratio, and measurement of ion density were performed. The results are shown in Tables 3 and 4 which will be described later.

(Example 42)

A liquid crystal cell was produced in the same manner as in Example 40 except that the liquid crystal alignment agent (A3-1) obtained in Example 22 was used. With respect to this liquid crystal cell, observation of liquid crystal alignment, measurement of pretilt angle, measurement of voltage holding ratio, and measurement of ion density were performed. The results are shown in Tables 3 and 4.

(Example 43)

A liquid crystal cell was produced in the same manner as in Example 40 except that the liquid crystal alignment agent (A3-2) obtained in Example 23 was used. With respect to this liquid crystal cell, observation of liquid crystal alignment, measurement of pretilt angle, measurement of voltage holding ratio, and measurement of ion density were performed. The results are shown in Tables 3 and 4.

(Comparative Example 11)

A liquid crystal cell was produced in the same manner as in Example 40 except that the liquid crystal alignment agent (B2-1) obtained in Comparative Example 2 was used and the baking time was set to 1 hour. With respect to this liquid crystal cell, observation of liquid crystal alignment, measurement of pretilt angle, measurement of voltage holding ratio, and measurement of ion density were performed. The results are shown in Tables 3 and 4.

(Comparative Example 12)

A liquid crystal cell was produced in the same manner as in Example 40 except that the liquid crystal alignment agent (B3-1) obtained in Comparative Example 4 was used. With respect to this liquid crystal cell, observation of liquid crystal alignment, measurement of pretilt angle, measurement of voltage holding ratio, and measurement of ion density were performed. The results are shown in Tables 3 and 4.

From the results of Examples 40 to 43 and Comparative Examples 11 and 12, it was confirmed that the liquid crystal display element having good liquid crystal alignment property can be obtained by using the liquid crystal alignment film of the present invention. Further, it was confirmed that the pretilt angle was increased by using the liquid crystal alignment film of the present invention.

From the results of Examples 40 to 43 and Comparative Examples 11 and 12, it was confirmed that the liquid crystal display element having a high voltage holding ratio and a low ion density can be obtained even at a high temperature by using the liquid crystal alignment film of the present invention.

(Example 44)

The liquid crystal alignment agent (A3-1) obtained in Example 22 was filtered through a 1.0 μm membrane filter, and then spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at a temperature of 80 ° C for 5 minutes. The film was baked at a temperature of 230 ° C for 20 minutes to form a ruthenium imidized film having a film thickness of 100 nm. The coating film surface was irradiated with ultraviolet rays of 254 nm at 1 J/cm ² through a polarizing plate to obtain a substrate with a liquid crystal alignment film.

Two substrates having such a liquid crystal alignment film were prepared, and a spacer of 6 μm was spread on the liquid crystal alignment film surface of a substrate, and then the two substrates were combined in antiparallel to each other, leaving a liquid crystal injection port to seal the periphery to form a crystal. The cell gap is an empty cell of 6 μm. On the empty cell, liquid crystal (MLC-2041, manufactured by Merck) was vacuum-injected at a normal temperature to seal the injection port to form a liquid crystal cell, and the liquid crystal cell was observed for liquid crystal alignment and voltage retention. Ion density determination. The results are shown in Table 5 below.

(Example 45)

A liquid crystal cell was produced in the same manner as in Example 44 except that the liquid crystal alignment agent (A3-2) obtained in Example 23 was used. With respect to this liquid crystal cell, observation of liquid crystal alignment, measurement of voltage holding ratio, and measurement of ion density were performed. The results are shown in Table 5.

(Comparative Example 13)

A liquid crystal cell was produced in the same manner as in Example 44, except that the liquid crystal alignment agent (B3-1) obtained in Comparative Example 4 was used. With respect to this liquid crystal cell, observation of liquid crystal alignment, measurement of voltage holding ratio, and measurement of ion density were performed. The results are shown in Table 5.

From the results of Examples 44 and 45 and Comparative Example 13, it was confirmed that by using the liquid crystal alignment film of the present invention, it is possible to exhibit good liquid crystal alignment even in the light alignment, and the voltage retention rate even at a high temperature. A liquid crystal display element having high reliability and low ion density and excellent reliability.

[Industrial availability]

According to the liquid crystal alignment agent of the present invention, it is excellent in mechanical strength, excellent in resistance to polishing treatment, and excellent in liquid crystal alignment properties, particularly electrical properties such as voltage retention or ion density at high temperatures. Further, it is possible to impart a highly reliable liquid crystal alignment film having a high pretilt angle. As a result, it can be widely applied to TN elements, STN elements, TFT liquid crystal elements, and even vertical alignment type liquid crystal display elements.

In addition, the entire disclosure of Japanese Patent Application No. 2010-123471, the entire disclosure of which is hereby incorporated by reference in its entirety in its entirety in

Claims (16)

A liquid crystal alignment agent characterized by comprising: a polyimine precursor obtained by reacting a diamine compound with a tetracarboxylic acid derivative; and/or a polyimide which is imidized by imidating the polyimine precursor And a compound having a structure of a proline or a guanamine ester which has an amine group protected by a heat dissociable group which is substituted by hydrogen at a temperature of 80 to 300 ° C, and has the aforementioned proline or glutamate The compound of the structure is a compound represented by the following formula (1), (wherein X is a tetravalent organic group; R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; and Z is a structure represented by the following formula (2)) (wherein Z ₁ is a single bond or a divalent organic group having 1 to 30 carbon atoms; and R ₂ and R ₃ are each independently a hydrogen atom or an alkyl group or an alkenyl group having 1 to 30 carbon atoms which may have a substituent; An alkynyl group, an aryl group or a combination thereof may also form a ring structure; R ₄ is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms which may have a substituent; D ₁ is a thermally dissociable group). The liquid crystal alignment agent according to claim 1, wherein the polyimine precursor has a repeating unit represented by the following formula (7). (wherein X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group; R ₆ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; and A ₁ and A ₂ are each independently a hydrogen atom or may have The alkyl group, alkenyl group or alkynyl group having 1 to 10 carbon atoms of the substituent. The liquid crystal alignment agent according to claim 1 or 2, wherein the content of the polyimine precursor and the polyimine is 0.5 to 15% by mass based on the total amount of the liquid crystal alignment agent. Further, for a repeating unit having a polyimine precursor having a repeating unit represented by the above formula (7) and a quinone imidized polymer of the polyimine precursor, the unit has a heating unit The compound of the guanamine or glutamate structure which can be substituted with the amine group protected by the thermally dissociable group of hydrogen contains 0.5 to 50 mol%. The liquid crystal alignment agent according to claim 1 or 2, wherein the thermally dissociable group is a tert-butoxycarbonyl group or a 9-fluorenylmethoxycarbonyl group. The liquid crystal alignment agent according to claim 1 or 2, wherein the X system is selected from the group consisting of the structures represented by the following formulas, A liquid crystal alignment film obtained by subjecting a film obtained by baking the liquid crystal alignment agent according to any one of claims 1 to 5 to an alignment treatment. The liquid crystal alignment film according to claim 6, wherein the alignment treatment is a polishing treatment or an irradiation treatment of polarized radiation. A liquid crystal display element comprising the liquid crystal alignment film according to claim 6 or 7. a compound having a structure of a proline or a guanamine represented by the following formula (1), (wherein X is a tetravalent organic group; R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; and Z is a structure represented by the following formula (2)) (wherein Z ₁ is a single bond or a divalent organic group having 1 to 30 carbon atoms; and R ₂ and R ₃ are each independently a hydrogen atom or an alkyl group or an alkenyl group having 1 to 30 carbon atoms which may have a substituent; An alkynyl group, an aryl group or a combination thereof may also form a ring structure; R ₄ is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms which may have a substituent; D ₁ is a thermally dissociable group). The compound of the above formula (9), wherein the bischlorocarbonyl compound represented by the following formula (3) and the monoamine compound represented by the following formula (4) are used as a (chlorocarbonyl compound/ Monoamine) has a molar ratio of 1/2 to 1/3, (wherein, X, Z ₁ , R ₂ , R ₃ , R ₄ and D ₁ are the same as those of the above formulae (1) and (2); and R ₅ is an alkyl group having 1 to 5 carbon atoms). The compound of claim 9, which is a tetracarboxylic acid derivative represented by the following formula (5) and a monoamine compound represented by the formula (4) as recited in claim 10, in a condensing agent. In the presence of (tetracarboxylic acid derivative / monoamine) molar ratio of 1/2 to 1/3 reaction, (wherein X and R ₅ are the same as defined in the above formulae (1) and (3)). The compound of claim 9, which is a tetracarboxylic dianhydride represented by the following formula (6) and a monoamine compound represented by the formula (4) described in claim 10, The molar ratio of dianhydride/monoamine is 1/2~1/3 reaction. (In the formula, the X system is synonymous with the above formula (1)). The compound of the formula (9), wherein the tetracarboxylic acid dihydrate represented by the formula (6) in the claim 12 and the monoamine compound represented by the formula (4) in the claim 10 are obtained. It is obtained by reacting a molar ratio of (tetracarboxylic dianhydride/monoamine) to 1/2 to 1/3, and esterifying the carboxyl group with an esterifying agent. The compound according to any one of claims 9 to 13, wherein the X is selected from the group consisting of the structures represented by the following formulas, The compound according to claim 9, wherein the above R ₁ is an alkyl group having 1 to 5 carbon atoms. Any of the following compounds of the formula (1-a) to (1-o),