KR20150140847A - Diamine, polyimide, liquid crystal aligning agent, and liquid crystal alignment film - Google Patents

Abstract

A diamine compound represented by the following formulas (A) to (F).
[Chemical Formula 18]

Description

DIAMINE, POLYIMIDE, LIQUID CRYSTAL ALIGNING AGENT, AND LIQUID CRYSTAL ALIGNMENT FILM [0002]

The present invention relates to a liquid crystal aligning agent for producing a liquid crystal alignment film, a liquid crystal alignment film obtained from the liquid crystal aligning agent, and a polymer (polymer) and a monomer (monomer) for obtaining the liquid crystal aligning agent. More particularly, the present invention relates to a liquid crystal alignment film which can obtain a liquid crystal alignment film having excellent mechanical strength without rubbing scratches, and which has a high voltage holding ratio at a high temperature and a low ion density, And a polymer and a monomer for obtaining the liquid crystal aligning agent.

In a liquid crystal display element used for a liquid crystal television, a liquid crystal display, or the like, a liquid crystal alignment film for controlling the alignment state of the liquid crystal is usually formed in the element. The liquid crystal alignment film is subjected to various alignment treatments on the surface of the film to impart liquid crystal alignability. Currently, according to the most popular method in industry, a liquid crystal alignment film is produced by performing a so-called rubbing treatment in which a surface of a resin film formed on an electrode substrate is rubbed with a cloth such as a cotton, nylon, or polyester in one direction have. As the resin film, a polyimide film obtained by applying and firing a polyimide precursor such as polyamic acid or a polyimide solution is widely used.

The rubbing treatment of the polyimide film is an industrially useful method which is simple and excellent in productivity. However, when the adhesion and the mechanical strength of the polyimide film formed on the electrode substrate are insufficient, rubbing causes film peeling or scratching due to rubbing.

As a method for suppressing the occurrence of peeling or scratching of the film due to the rubbing, there has been proposed a method using a liquid crystal aligning agent in which a compound containing an epoxy group is added to polyamic acid or polyimide (see Patent Document 1), polyamic acid or polyimide A method of using a liquid crystal aligning agent in which an epoxy compound containing a nitrogen atom is added to a solution (see Patent Documents 2 and 3), a liquid crystal alignment in which a compound containing an epoxy group and a reactive group other than an epoxy group is added to a polyamic acid or polyimide solution (See Patent Document 4) has been proposed.

By adding a cross-linking agent containing a reactive group such as an epoxy group to the polyimide precursor or polyimide, the mechanical strength of the polyimide film is improved. This is because the epoxy group reacts with a polar group such as a carboxylic acid present in the polyimide precursor or polyimide.

Japanese Patent Application Laid-Open No. 9-146100 Japanese Patent Application Laid-Open No. 10-333153 Japanese Patent Application Laid-Open No. 10-46151 Japanese Patent Application Laid-Open No. 2007-11221

Usually, a compound used as a crosslinking agent is a low molecular compound. Therefore, it is sublimated at the time of firing, and the effect is not sufficiently obtained unless an excessive amount is added. In the case of excess addition, the unreacted cross-linking agent remains in the film, which may deteriorate the voltage holding ratio and the ion density when used as a liquid crystal display device, resulting in poor display.

SUMMARY OF THE INVENTION The present invention has been made in view of such circumstances, and it is an object of the present invention to provide a liquid crystal alignment film excellent in mechanical strength without raising scratches even by rubbing treatment, , A liquid crystal aligning agent capable of obtaining a highly reliable liquid crystal alignment film having a low ion density, and a polymer and a monomer for obtaining the liquid crystal aligning agent.

The inventors of the present invention have conducted intensive investigations in order to achieve the above object and as a result have found that the use of a diamine compound and / or a tetracarboxylic acid derivative having a t-butoxycarbonyl group (hereinafter also referred to as a Boc group) It has been found that the object is achieved by a liquid crystal aligning agent containing a polyimide precursor or polyimide. Specifically, the Boc group is removed by heating to produce an aliphatic amine having high reactivity, so that the aliphatic amine becomes a crosslinking point, and a liquid crystal alignment film excellent in mechanical characteristics that does not cause peeling or scratching of the film due to rubbing is obtained, The liquid crystal display device using this liquid crystal alignment film has a high voltage holding ratio and a low ion density even at a high temperature, thereby completing the present invention.

That is, the gist of the present invention is as follows.

1. A liquid crystal aligning agent comprising a polyimide precursor having a substituent having a structure represented by the following formula (1) or an imidized polymer of the polyimide precursor.

(Wherein A is a single bond or a divalent organic group, and R ₁ , R ₂ , and R ₃ are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms)

Wherein the polyimide precursor or the imidized polymer of the polyimide precursor is at least one selected from the group consisting of a diamine compound having a substituent represented by the formula (1) and a tetracarboxylic acid derivative having a substituent represented by the formula (1) The liquid crystal aligning agent according to the above 1, which is obtained by using the liquid crystal aligning agent.

* 3. (1) and / or a tetracarboxylic acid derivative having a substituent represented by the formula (1) in an amount of 2 to 100 mol% based on the total diamine compound and the tetracarboxylic acid derivative, Wherein the liquid crystal aligning agent is an imide polymer of a polyimide precursor or a polyimide precursor thereof.

4. The liquid crystal aligning agent according to any one of 1 to 3 above, wherein the polyimide precursor contains a structural unit represented by the following formula (2).

(Wherein a one, X ₁ is (4 + a) monovalent organic group, Y ₁ is a (2 + b) a monovalent organic group, R ₄ is a hydrogen atom or an alkyl group having a carbon number of 1 ~ 4, Z is the formula (1 A and b each represent an integer of 0 to 4, and a + b > 0)

5. The liquid crystal aligning agent according to any one of 1 to 3 above, wherein the polyimide precursor contains a structural unit represented by the following formula (3).

(2 + c), R ₄ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Z is a structure represented by the above formula (1), wherein X is a tetravalent organic group, Y ₂ is and c is an integer of 1 to 4)

6. The liquid crystal aligning agent according to any one of 1 to 3 above, wherein the polyimide precursor contains a structural unit represented by the following formula (4).

(Note that, X is a tetravalent organic group formula, R ₄ is a hydrogen atom or an alkyl group having from 1 to 4, R ₅ represents a single bond or 1 to 20 carbon atoms of a divalent organic group, Z is the formula (1) And c is an integer of 1 to 4)

7. The liquid crystal aligning agent according to any one of 1 to 3 above, wherein the polyimide precursor contains a structural unit represented by the following formula (5).

(Wherein X is a tetravalent organic group, R ₄ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Z is a structure represented by the formula (1), and c is an integer of 1 to 4)

8. A liquid crystal alignment film obtained by firing the liquid crystal aligning agent according to any one of 1 to 7 above at 150 to 300 占 폚.

9. A polyimide precursor containing a structural unit represented by the following formula (6).

(Note that, X is a tetravalent organic group formula, Y ₂ is (2 + c) is a monovalent organic group, Z is a structure represented by the following formula (1), R ₄ is a hydrogen atom or an alkyl group having from 1 to 4 carbon atoms and c is an integer of 1 to 4)

(Wherein A is a single bond or a divalent organic group, and R ₁ , R ₂ , and R ₃ are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms)

10. A polyimide containing a structural unit represented by the following formula (7).

(Wherein X is a tetravalent organic group, Y ₂ is an organic group represented by the formula (2 + c), Z is a structure represented by the following formula (1), and c is an integer of 1 to 4)

(Wherein A is a single bond or a divalent organic group, and R ₁ , R ₂ , and R ₃ are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms)

11. A polyimide precursor containing a structural unit represented by the following formula (8).

(Wherein X is a tetravalent organic group, Z is a structure represented by the following formula (1), R ₄ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₅ is a divalent organic group having 1 to 20 carbon atoms C is an integer of 1 to 4)

(Wherein A is a single bond or a divalent organic group, and R ₁ , R ₂ , and R ₃ are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms)

12. A polyimide containing a structural unit represented by the following formula (9).

(Wherein X is a tetravalent organic group, Z is a structure represented by the following formula (1), R ₅ is a divalent organic group having 1 to 20 carbon atoms, and c is an integer of 1 to 4)

(Wherein A is a single bond or a divalent organic group, and R ₁ , R ₂ , and R ₃ are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms)

13. A polyimide precursor containing a structural unit represented by the following formula (10).

(Wherein X is a tetravalent organic group, Z is a structure represented by the following formula (1), R ₄ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and c is an integer of 1 to 4)

(Wherein A is a single bond or a divalent organic group, and R ₁ , R ₂ , and R ₃ are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms)

14. A polyimide containing a structural unit represented by the following formula (11).

(Wherein X is a tetravalent organic group and Z is a structure represented by the following formula (1): wherein c is an integer of 1 to 4)

(Wherein A is a single bond or a divalent organic group, and R ₁ , R ₂ , and R ₃ are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms)

15. A diamine compound represented by the following formulas (A) to (F).

According to the liquid crystal aligning agent of the present invention, it is possible to obtain a liquid crystal alignment film excellent in mechanical strength, which does not cause peeling or scratching of the film due to rubbing, even if no crosslinking agent is added. By using this liquid crystal alignment film, even when the liquid crystal aligning ability is given by irradiating polarized radiation, the liquid crystal display device having excellent display characteristics can be obtained because the voltage holding ratio at high temperature is high and the ion density is low.

The liquid crystal aligning agent of the present invention has a high storage stability in a varnish state because the primary or secondary aliphatic amine having high reactivity is protected by a Boc group. The polyimide precursor and the polyimide contained in the liquid crystal aligning agent of the present invention have high solubility in various organic solvents because they have a Boc group as a bulky substituent, An aliphatic amine is produced and an intermolecular crosslinking reaction proceeds to form a polyimide film having excellent mechanical strength.

The diamine compound protected with the Boc group in the present invention can be easily produced by reacting with a tetracarboxylic acid derivative to obtain a polyimide precursor or polyimide having a primary or secondary amino group protected with a Boc group .

The liquid crystal aligning agent of the present invention is characterized by containing a polyimide precursor having a primary or secondary aliphatic amino group protected by a Boc group or an imidized polymer thereof. Here, the primary or secondary aliphatic amino group protected by a Boc group means an aliphatic amino group having -NR ₃ Boc (R ₃ is as defined in the formula (1)).

The polyimide precursor having a primary or secondary aliphatic amino group protected by a Boc group or an imidated polymer thereof is heated at 150 DEG C or higher to decompose the Boc group so that the protective group of the Boc group is released from the reactive primary or secondary aliphatic An amino group is generated. The resulting primary or secondary aliphatic amino group reacts with a functional group existing in the polyimide precursor or the imidized polymer to form intermolecular crosslinking. Examples of the crosslinking reaction include a reaction with a carboxylic acid or ester (the following formula (i)), a reaction with an acid dianhydride produced by a reverse reaction of a polyamic acid (the following formula (ii)), (Iii) below).

The crosslinking reaction proceeds in the course of forming a liquid crystal alignment film from the liquid crystal aligning agent of the present invention, so that the liquid crystal alignment film obtained in the present invention has a high mechanical strength, and a polyimide having no film peeling or scratch due to rubbing It is considered that a film is obtained.

As a method of imparting liquid crystal aligning ability to the liquid crystal alignment film, there is known a photo alignment method in addition to a rubbing method, in which polarized radiation is irradiated to a polyimide film to give a liquid crystal aligning ability. As the photo-alignment method, there have been proposed a photo-isomerization reaction, a photo-crosslinking reaction, and a photo-decomposition reaction.

The liquid crystal aligning agent and the liquid crystal alignment film of the present invention are also useful for the photo alignment method and particularly useful for the photo alignment method using the photo decomposition reaction. In the photo alignment method using a photodegradation reaction, a low molecular weight component is generated by light irradiation. For example, in the photo alignment method using the photolysis reaction of polyimide having a cyclobutane ring in the main chain, low molecular weight components having a maleimide moiety are generated by subjecting to orientation treatment (the following formula (xiii)): . When such a liquid crystal alignment film containing a low molecular weight component is used in a liquid crystal display device, a low molecular weight component is eluted into the liquid crystal, resulting in a decrease in voltage holding ratio and an increase in ion density of the liquid crystal display device, There is a possibility of aggravation.

The liquid crystal aligning agent and the liquid crystal alignment film of the present invention suppress the lower molecular weight of the polyimide precursor and the polyimide by the intermolecular three-dimensional crosslinking formed by the reaction of the above formulas (i) to (iii) The elution of the molecular weight component can be suppressed.

Further, the maleimide produced by the photolysis reaction of the cyclobutane ring can react with the primary or secondary aliphatic amino group generated by heating (the following formula (xiv)). Even in such a crosslinking reaction, the elution of a low molecular weight component into liquid crystal can be suppressed. Even when a liquid crystal alignment film having a liquid crystal aligning ability imparted by a photo alignment method is used for a liquid crystal display device due to the progress of the crosslinking reaction, a liquid crystal display device having a high voltage holding ratio and a low ion density, Is obtained.

On the other hand, when a compound having two or more primary or secondary aliphatic amines is added to a polyimide precursor or polyimide solution, the cross-linking reaction as described above proceeds to form intermolecular crosslinking. However, when a primary or secondary aliphatic amine is added to a polyimide precursor or a polyimide solution, salt formation with a carboxylic acid, progress of an imidation reaction, or ring-opening reaction of an imide ring progresses, , Precipitation and lowering of molecular weight, it is difficult to stably keep the polymer solution for a long period of time. On the other hand, in the liquid crystal aligning agent of the present invention, since the primary or secondary aliphatic amino group is protected by the Boc group, there is no case of reacting with the functional group in the polymer when the liquid crystal aligning agent is stored in the solution state, A liquid crystal aligning agent is obtained.

When a low-molecular cross-linking agent is used, the low-molecular cross-linking agent is sublimated at the time of firing in the process of forming the liquid crystal alignment film, and if not added in an excessive amount, the effect may not be sufficiently obtained. In the case of excess addition, the unreacted cross-linking agent remains in the film, which may deteriorate the voltage holding ratio and the ion density when used as a liquid crystal display device, resulting in poor display. Furthermore, there is a possibility that the sublimed crosslinking agent may contaminate the calcination furnace. On the contrary, since the liquid crystal aligning agent of the present invention contains an aliphatic amine as a crosslinking point in the polymer, the low molecular weight compound remains unreacted in the film, and the sludge does not contaminate the sintering furnace.

As described above, by using the liquid crystal aligning agent of the present invention, it is possible to obtain a liquid crystal alignment film excellent in mechanical strength without peeling or scratching of film due to rubbing, and by using this liquid crystal alignment film, A liquid crystal display element having a high voltage holding ratio and a low ion density can be obtained. Further, the present inventors have found that a liquid crystal aligning agent having excellent storage stability can be obtained by protecting a primary or secondary aliphatic amino group as a crosslinking site with a Boc group.

Hereinafter, the present invention will be described in more detail.

a. [Polyimide precursor and polyimide]

The polyimide precursor in the present invention is a polymer that is polyimide by heating or by the action of a catalyst, and examples thereof include polyamic acid, polyamic acid ester, polyamic acid silyl ester, and polyisoimide. As the polyimide precursor, polyamic acid or polyamic acid ester is particularly preferable from the ease of production and the reaction efficiency of imidization. The polyimide in the present invention is a polymer obtained by imidizing a polyimide precursor.

The liquid crystal aligning agent of the present invention contains a polyimide precursor having a substituent represented by the following formula (1) or an imidized polymer thereof.

Wherein R ₁ , R ₂ and R ₃ are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, Monovalent organic group. Examples of monovalent organic groups include monovalent hydrocarbon groups, hydroxyl groups, thiol groups, phosphate groups, ester groups, carboxyl groups, phosphate groups, thioester groups, amide groups, nitro groups, organoxy groups, organosilyl groups, And an acyl group. As the monovalent organic group, a monovalent hydrocarbon group is preferable in view of the reactivity of the aliphatic amine. Specific examples of the monovalent hydrocarbon group include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, t-butyl group, hexyl group, octyl group and decyl group; A cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; A bicycloalkyl group such as a bicyclohexyl group; An alkenyl group such as vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 1-methyl-2-propenyl group, 1 or 2 or 3-butenyl group and hexenyl group; Aryl groups such as a phenyl group, a xylyl group, a tolyl group, a biphenyl group, and a naphthyl group; And aralkyl groups such as a benzyl group, a phenylethyl group, and a phenylcyclohexyl group.

Some or all of the hydrogen atoms of these monovalent hydrocarbon groups may be replaced with a halogen atom, a hydroxyl group, a thiol group, a phosphate group, an ester group, a carboxyl group, a phosphoric acid group, a thioester group, an amide group, a nitro group, An alkyl group, a cycloalkyl group, a bicycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, a pyrrolyl group, an imidazole group, a pyrazole group, an alkoxycarbonylamino group and the like. These may be cyclic structures. Among them, a pyrrole group, an imidazole group and a pyrazole group are preferable, and a hydrogen atom on a nitrogen atom of a pyrrole group, an imidazole group or a pyrazole group is more preferably substituted with a Boc group.

When R ₁ and R ₂ are bulky structures, the reaction efficiency of the crosslinking reaction is lowered. Therefore, as R ₁ and R ₂ , an alkyl group such as methyl, ethyl, propyl or butyl group or a hydrogen atom is preferable, Do.

When R ₃ is a bulky structure, the reaction efficiency of the crosslinking reaction is lowered. Therefore, R ₃ is preferably an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group or a hydrogen atom, and more preferably a hydrogen atom.

When A is a divalent organic group, its structure is represented by, for example, the following formula (12).

In the formula (12), B is a divalent linking group, and R ₆ and R ₁₆ are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Specific examples of B include, but are not limited to, the following B-1 to B-14.

Specific examples of R ₆ and R ₁₆ in the formula (12) are shown below, but the present invention is not limited thereto. Propylene group, a 1,3-propylene group, a 1,4-butylene group, a 1,2-butylene group, a 1,2-pentyl group, An alkylene group such as a methoxy group, an ethoxy group, an ethoxy group, an ethoxy group, an ethoxy group, an ethoxy group, an isopropoxy group, Cyclobutylene group, 1,2-cyclohexylene group, 1,2-cyclohexylene group, 1,2-cyclopentylene group, 1,2-cyclobutylene group, 1,2-cyclohexylene group, , 2-cyclododecylene, and other cycloalkylene groups; 1,2-ethenylene group, 1,2-ethenylene methylene group, 1-methyl-1,2-ethenylene group, 1,2-ethenylene-1,1-ethylene group , 1,2-ethenylene-1,2-ethylene group, 1,2-ethenylene-1,2-propylene group, 1,2- Butylene group, 1,2-ethenylene-1,2-butylene group, 1,2-ethenylene-1,2-heptylene group, 1,2-ethenylene- An alkenylene group; Ethynylene-1,2-ethylene group, ethynylene-1,2-propylene group, ethynylene-1,3-propylene group, ethynylene-1,1-ethylene group, Butylene group, an ethynylene-1,2-butylene group, an ethynylene-1,2-heptylene group, and an ethynylene-1,2-decylene group; Phenylene group, 1,4-phenylene group, 1,2-naphthylene group, 1,4-naphthylene group, 1,5-naphthylene group, 2,3-naphthylene group Arylene groups such as a thienylene group, a 2,6-naphthylene group, a 3-phenyl-1,2-phenylene group, a 2,2'-diphenylene group and a 2,2'-dinaphtho-1,1'-diyl group; Phenylene methylene group, a 1,2-phenylene methylene group, a 1,3-phenylene methylene group, a 1,4-phenylene methylene group, a 1,2- Phenylene-1,2-propylene group, 1,2-phenylene-1,3-propylene group, 1,2-phenylene-1,4-butylene group, 1,2 1,2-butylene group, 1,2-phenylene-1,2-hexylene group, methylene-1,2-phenylene methylene group, methylene-1,3-phenylene methylene group, methylene- And a bifunctional hydrocarbon group comprising an arylene group such as a 1,4-phenylene methylene group and an alkylene group.

A part or all of the hydrogen atoms of the bivalent hydrocarbon group may be replaced with a halogen atom, a hydroxyl group, a thiol group, a phosphate group, an ester group, a carboxyl group, a phosphoric acid group, a thioester group, an amide group, a nitro group, An acyl group, an alkyl group, a cycloalkyl group, a bicycloalkyl group, an alkenyl group, an aryl group, an aralkyl group and the like. These may be cyclic structures.

When R ₆ and R ₁₆ have a ring structure or alicyclic structure, there is a possibility of lowering the liquid crystal alignability. Therefore, R ₆ and R ₁₆ are each a single bond or an alkylene group, alkenyl group or alkynyl group having 1 to 10 carbon atoms And more preferably an alkylene group having 1 to 10 carbon atoms. It is preferable that either or both of R ₆ and R ₁₆ are single bonds.

In the structures represented by B-1 to B-14, R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. Here, the monovalent hydrocarbon group may be an alkyl group such as methyl group, ethyl group, propyl group, butyl group, t-butyl group, hexyl group, octyl group or decyl group; A cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; A bicycloalkyl group such as a bicyclohexyl group; An alkenyl group such as vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 1-methyl-2-propenyl group, 1 or 2 or 3-butenyl group and hexenyl group; Aryl groups such as a phenyl group, a xylyl group, a tolyl group, a biphenyl group, and a naphthyl group; And aralkyl groups such as a benzyl group, a phenylethyl group, and a phenylcyclohexyl group.

Some or all of the hydrogen atoms of these monovalent hydrocarbon groups may be replaced with a halogen atom, a hydroxyl group, a thiol group, a phosphate group, an ester group, a carboxyl group, a phosphoric acid group, a thioester group, an amide group, a nitro group, An acyl group, an alkyl group, a cycloalkyl group, a bicycloalkyl group, an alkenyl group, an aryl group, an aralkyl group and the like. These may be cyclic structures.

Since bulky structures such as aromatic rings and alicyclic structures may lower the liquid crystal alignability or lower the solubility of the polymer, R ₇ , R ₈ , R ₉ , R ₁₀ , and R ₁₁ may have a methyl group, An alkyl group such as an ethyl group, a propyl group or a butyl group, or a hydrogen atom, and more preferably a hydrogen atom.

As the specific examples of the substituent containing the primary or secondary aliphatic amine protected by the Boc group represented by the formula (1), the following formulas (13) to (18) are particularly preferable.

The liquid crystal aligning agent of the present invention contains a polyimide precursor having a substituent represented by the above formula (1) at the terminal of the polymer or a side chain of the polymer or an imidized polymer thereof. A polyimide precursor having a structural unit represented by the following formula (2) wherein the substituent represented by the formula (1) is introduced into a side chain of the polymer, and a polyimide precursor having a structure represented by the formula It is preferably a hydrogenated polymer.

(Wherein a one, X ₁ is (4 + a) monovalent organic group, Y ₁ is a (2 + b) a monovalent organic group, R ₄ is a hydrogen atom or an alkyl group having a carbon number of 1 ~ 4, Z is the formula (1 A and b each represent an integer of 0 to 4, preferably 0 to 2, and a + b > 0)

As the method for producing the polyimide precursor of the formula (2) and the imidized polymer thereof, a raw material in which a substituent represented by the formula (1) is introduced into a tetracarboxylic acid derivative and a diamine compound which are raw materials of the polyimide precursor . Specifically, it is preferable to use a tetracarboxylic acid derivative represented by the following formulas (19) to (21) and a diamine compound represented by the following formula (22).

In the formulas (19) to (21), R ₄ is an alkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a 2-propyl group, a butyl group, and a t-butyl group. As the polyamic acid ester, the temperature at which the imidization proceeds progressively increases as the number of carbon atoms in the alkyl group increases. Therefore, R ₄ is preferably a methyl group or an ethyl group, particularly preferably a methyl group, from the viewpoint of facilitating imidization by heat . Z is a substituent having the structure represented by the formula (1), and A is an integer of 0 to 4. X ₁ is an organic group of (4 + a).

In the formula (22), Z is a substituent having the structure represented by the formula (1), and b is an integer of 0 to 4. Y ₁ is an organic group of (2 + b).

In the present invention, the tetracarboxylic acid derivative represented by the above formulas (19) to (21) and the tetracarboxylic acid derivative represented by the following formulas (23) to (25) And a diamine compound represented by the following formula (26) are mixed in an arbitrary ratio to prepare a polyimide precursor, whereby a polyimide precursor containing the structural unit represented by the above formula (2) can be produced.

In the above formulas (23) to (25), X and R ₄ are the same as those in the formulas (19) to (21), including preferred examples.

In the formula (26), Y is a divalent organic group.

In the formulas (19) to (21) and the formulas (23) to (25), the structure of X and X ₁ is not particularly limited. Specific examples thereof include the structures shown by the following X-1 to X-46. Two or more of these tetracarboxylic acid derivatives may be used.

In the above equations (19) to (21), the mantissa of X ₁ is changed by a, which is the substitution number of Z. That is, a structure in which a hydrogen atom is eliminated from an arbitrary position of the structure shown by the following X-1 to X-46 by the substitution number of Z is X ₁ .

In the formulas (22) and (26), the structure of Y and Y ₁ is not particularly limited. Specific examples thereof include structures represented by the following Y-1 to Y-100. The diamine compound may be two or more kinds.

However, in the equation (22), the valence of Y ₁ is changed by the substitution number b (b = 0 to 4) of Z. That is, a structure in which a hydrogen atom is removed from an arbitrary position of the structure represented by the following Y-1 to Y-100 by the number of substitution of Z is Y ₁ .

In the present invention, in the above formula (2), the substituent Z may be present in at least one position of the tetracarboxylic acid derivative or the diamine moiety.

It is preferable to use the diamine compound represented by the above formula (22) from the viewpoints of ease of production and ease of handling of the monomers. As the polyimide precursor and polyimide of the present invention, a polyimide precursor containing a structural unit represented by the following formula (3) and a polyimide containing a structural unit represented by the following formula (7) are preferable.

In the formula (3), X is a tetravalent organic group, Y ₂ is an organic group of (2 + c), and R ₄ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Z is a structure represented by the above formula (1). and c is an integer of 1 to 4, preferably 1 to 2.

X, Y ₂ , Z, and c in the formula (7) have the same meanings as those in the formula (3).

The polyimide precursor or polyimide containing the structural units of the formulas (3) and (7) can be obtained by reacting the tetracarboxylic acid derivative represented by the above formulas (23) to (25) and the diamine compound represented by the following formula And mixing the diamine compounds represented by the above formula (26) in an arbitrary ratio and reacting them.

In the formula (27), Y ₂ , Z and c have the same meanings as in the formulas (3) and (7). Specific examples of the structure represented by Y ₂ include the structures represented by Y-1 to Y-100. The diamine compound may be two or more kinds.

However, in the above equation (27), the valence of Y ₂ is changed by the substitution number c of Z. That is, the structure in which the hydrogen atom is removed from any position of the structure represented by Y-1 to Y-100 by the number of substitution of Z is the structure of Y ₂ .

A polyimide precursor or polyimide obtained by using a diamine compound containing an aromatic amino group as a diamine compound containing no bulky side chain such as biphenyl, cyclohexyl, steroid, long chain alkyl group having 10 or more carbon atoms, If used, a liquid crystal alignment film having good liquid crystal alignment properties and excellent mechanical properties can be obtained. The liquid crystal aligning agent of the present invention preferably contains a polyimide precursor containing a structural unit represented by the following formula (4) or a polyimide containing a structural unit represented by the following formula (9).

(Wherein X, R ₄ , Z and c have the same meanings as in the formula (3), and R ₅ is a divalent organic group having a single bond or an aromatic group)

(Wherein X, Z, R ₅ and c have the same meanings as in the formula (4)),

In the present invention, a liquid crystal alignment film having better liquid crystal alignability can be obtained as the linearity of the obtained polymer is higher. Therefore, the diamine compound containing a substituent Z is preferably a compound represented by any of the following formulas (28) to (44) (61) are more preferable. In these formulas, Z represents the structure represented by the formula (1), c represents an integer of 1 to 4, and d and e represent an integer of 1 to 2.

In the present invention, when the polymer main chain is rigid, a polyimide film excellent in mechanical strength can be obtained. Therefore, as the polyimide precursor and polyimide of the present invention, a polyimide precursor containing a structural unit represented by the following formula (5) And polyimide containing a structural unit represented by the formula (11) is more preferable.

(Wherein X, R ₄ , Z and c have the same meanings as in the formula (3)),

(Wherein X, R ₄ , Z and c have the same meanings as in the formula (3)),

b. [Specific diamine compound]

In the present invention, diamine compounds represented by the following formulas (A) to (F) may be mentioned as particularly preferable diamine compounds as raw materials for producing the polyimide precursor.

b1. [Production of specific diamine compound]

The production method of the specific diamine compounds represented by the above formulas (A) to (E) will be described below, but the present invention is not limited thereto.

First, the diamine compound of the formula (A) is prepared by using an intermediate represented by the following formula (iv), for example, by using 2-cyano-4-nitroaniline of the formula (45) .

First, 2-cyano-4-nitroaniline of the formula (45) is dissolved in an organic solvent. Here, the organic solvent to be used is not particularly limited as long as it dissolves 2-cyano-4-nitroaniline and is decomposed by a reducing agent to be added later. However, dehydrated tetrahydrofuran (THF) Do. The obtained 2-cyano-4-nitroaniline solution is cooled to -40 ° C to 70 ° C, preferably -20 ° C to 20 ° C, and then the reducing agent is added while stirring the reaction solution. When the reducing agent is a powder, it is preferably added to the reaction solution as it is, and when the reducing agent is a solution, it is preferably added dropwise. As the reducing agent, borane, borane complex, sodium borohydride, lithium aluminum hydride and the like can be mentioned, and a borane-THF complex is preferable. After the addition of a reducing agent, the reaction solution is cooled while stirring for 30 minutes to 4 hours, preferably 1 to 2 hours. Thereafter, the mixture is stirred at room temperature for 12 to 72 hours, preferably 24 to 48 hours. After completion of the reaction, 1 to 2 M of inorganic acid is added to make the reaction solution acidic. Examples of the inorganic acid include hydrochloric acid, hydrogen fluoride, hydrobromic acid, hydroiodic acid, phosphoric acid, nitric acid, sulfuric acid, boric acid and the like, with hydrochloric acid being more preferred. After the addition of the inorganic acid, the reaction solution is stirred at room temperature for 1 to 2 hours, the reaction solution is cooled to 0 to 10 ° C, and 1 to 2 M of an inorganic alkali aqueous solution is added to make the reaction solution alkaline. Examples of the inorganic alkali aqueous solution include aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate and the like, more preferably an aqueous solution of sodium hydroxide. After making the reaction solution alkaline, an organic solvent is added and extracted.

As the organic solvent to be used for the extraction, a halogen-based organic solvent is preferable, and dichloromethane is more preferable. The obtained organic layer is washed with pure water or saturated saline, and dried with a desiccant. As the drying agent, sodium sulfate and magnesium sulfate are preferable. The obtained organic layer is dried for 4 to 24 hours, preferably 12 to 24 hours. The drying agent is removed, and the solvent is distilled off from the obtained filtrate to obtain a compound represented by the following formula (46). The obtained compound can be used in the next reaction without purification, but it may be purified by various methods. Examples of the purification method include silica gel column chromatography, recrystallization, and washing with an organic solvent. Recrystallization is more preferable because of simplicity of operation and purification efficiency. The organic solvent used for recrystallization may be recrystallized from two or more kinds of mixed solvents regardless of the type thereof, provided that the following formula (46) can be recrystallized.

Next, a method for producing the following formula (47) from the compound represented by the formula (46) will be described.

First, the compound represented by the above-mentioned formula (46) is dissolved in an organic solvent, di-tert-butyl carbonate is added and the reaction is carried out at a reaction temperature of -10 ° C to 40 ° C, preferably 0 ° C to 20 ° C for 12 to 48 hours , Preferably 20 to 40 hours, and reacted. As the organic solvent used in the reaction, dichloromethane and tetrahydrofuran are more preferable as long as the compound of formula (46) dissolves and does not react with di-tert-butyl carbonate. In order to further promote the reaction, an organic base such as triethylamine or pyridine may be added. The addition amount is preferably 1 to 2 mol equivalents to the compound of the formula (46). After completion of the reaction, an organic solvent, pure water or saturated saline solution is added and extracted, and the drying agent is added to the obtained organic layer and dried. The organic solvent used for the extraction is not particularly limited as long as it is not mixed with water, but dichloromethane is preferable. In addition, water or saturated saline may be added to the reaction solution and extracted. As the drying agent, sodium sulfate and magnesium sulfate are preferable. The obtained organic layer is dried for 4 to 24 hours, preferably 12 to 24 hours. The drying agent is removed, and the solvent is distilled off from the obtained filtrate to obtain the compound represented by the formula (47). The obtained compound can be used for the next reaction without purification, and it is preferable to purify it by various methods. Examples of the purification method include silica gel column chromatography, recrystallization, and washing with an organic solvent. Recrystallization is more preferable because of simplicity of operation and purification efficiency. The organic solvent used for recrystallization may be recrystallized from two or more kinds of mixed solvents regardless of the type thereof, provided that the following formula (47) can be recrystallized.

Next, a method for producing the diamine compound represented by the following formula (A) from the compound represented by the formula (47) will be described.

First, the compound represented by the formula (47) is dissolved in an organic solvent. The type of the organic solvent to be used may be any known one. Methanol, ethanol, 2-propanol, tetrahydrofuran and 1,4-dioxane are preferable, and methanol and ethanol are more preferable in order to proceed the reaction more efficiently. After the compound represented by the formula (47) is dissolved in an organic solvent, the interior of the reaction vessel is replaced with nitrogen, and then a catalyst is added to displace the inside of the reaction vessel with hydrogen. Examples of the catalyst include palladium carbon, platinum carbon, platinum oxide and the like, and platinum oxide is more preferable in order to suppress the decomposition reaction of the benzyl position. The reaction mixture is stirred at 0 ° C to 100 ° C, preferably 10 to 60 ° C, for 10 to 48 hours, preferably 15 to 30 hours. After completion of the reaction, the catalyst is removed and the organic solvent is distilled off to obtain the diamine compound of the present invention represented by the above formula (A). If the obtained compound is not purified, the polymerization reaction does not proceed and a polymer having a high molecular weight can not be obtained. Therefore, purification is preferably carried out by various methods. Examples of the purification method include silica gel column chromatography, recrystallization, and washing with an organic solvent. Recrystallization is more preferable because of simplicity of operation and purification efficiency. The organic solvent used for recrystallization may be recrystallized from two or more kinds of mixed solvents regardless of the kind of organic solvent capable of recrystallizing the diamine of the following formula (A).

Hereinafter, the production method of the diamine compounds of the above formulas (B) and (C) is shown, but it is not limited thereto. The diamine compounds of the above formulas (B) and (C) can be produced, for example, by the use of propargylamine of the following formula (48) as a starting material and an intermediate represented by the following formulas (V) do.

The diamines (B) and (C) can be produced by the same method except that the diamines (B) and (C) are produced using the iodide aryls represented by the following formulas (49) and (50), respectively. Further, a compound in which the substitution position of the iodine group in the following formulas (49) and (50) is substituted with a chro- rlo, bromo group, or trifluoromethylsulfonyl group may be used, and from the viewpoint of reactivity, aryl iodide is preferable.

Hereinafter, a method for producing Boc-propargylamine of formula (51) from the above-mentioned propargylamine of formula (48) will be described.

Propargylamine is dissolved in an organic solvent and an organic base is added. The organic solvent used in the reaction is not particularly limited as long as it dissolves propargylamine and does not react with di-tert-butyl dicarbonate added later, but dichloromethane is preferable. The organic base is added for the purpose of improving the nucleophilicity of the amino group, and triethylamine or pyridine is more preferable. The reaction solution is adjusted to -5 ° C to 40 ° C, preferably 0 ° C to 20 ° C, and di-tert-butyl dicarbonate is added dropwise into the reaction solution. If the dropping rate is excessively high, the reaction proceeds rapidly, so the dropping time is preferably 10 minutes to 1 hour. The dropping rate can be changed according to the amount of di-tert-butyl dicarbonate added. After completion of the dropwise addition, the mixture is stirred for 1 to 10 hours, preferably 2 to 4 hours, and then water, saturated saline solution and organic solvent are added to the reaction solution and extracted. The organic solvent used for the extraction is not particularly limited as long as it is not mixed with water, but it is preferable to use the same organic solvent as used for the reaction. The organic layer obtained by extraction is dried with a drying agent. As the drying agent, sodium sulfate or magnesium sulfate is preferable. The obtained organic layer is dried for 4 to 24 hours, preferably 12 to 24 hours. The drying agent is removed, and the solvent is distilled off from the obtained solution to obtain the compound represented by the above formula (51). The obtained compound can be used for the next reaction without purification, and it is preferable to purify it by various methods. Examples of the purification method include silica gel column chromatography, recrystallization, and washing with an organic solvent. Recrystallization is more preferable because of simplicity of operation and purification efficiency. The organic solvent to be used for recrystallization may be recrystallized from two or more kinds of mixed solvents without selecting the kind of the organic solvent as long as it is an organic solvent capable of recrystallizing the following formula (51).

Next, a method for producing a compound represented by the following formula (52) using the compound represented by the formula (51) will be described.

The compound represented by the formula (52) can be produced by subjecting the Boc-propargylamine of the formula (51) and the halogenated aryl represented by the formula (49) to a Sonogashira coupling reaction.

An aryl iodide, a palladium catalyst, a copper catalyst, and a base represented by the above formula (49) are added and dissolved in an organic solvent. As the palladium catalyst, bis (triphenylphosphine) palladium (II) dichloride is preferable, and the addition amount is more preferably 0.05 to 1.0 mol%, preferably 0.1 to 0.5 mol%, relative to the iodine group of the iodide aryl. As the copper catalyst, copper iodide is preferable, and the addition amount thereof is more preferably 0.05 to 1.0 mol%, and more preferably 0.1 to 0.5 mol% with respect to the iodine group of the halogenated aryl. As the base, triethylamine and diethylamine are preferable, and the addition amount thereof is preferably 1 to 3 mol equivalents, more preferably 1 to 2 mol equivalents to the iodine group of iodide aryl. The organic solvent used in the reaction is not particularly limited as long as it dissolves the aryl iodide and does not react with various reagents to be added later, but N, N-dimethylformamide is preferable.

After stirring the reaction solution at 0 ° C to 30 ° C, preferably 0 ° C to 20 ° C, for 5 minutes to 30 minutes, adding the Boc-propargylamine of the formula (51) for 2 to 12 hours, The mixture is stirred for 4 to 10 hours. The amount of Boc-propargylamine to be added is preferably 1 to 2 moles, more preferably 1.20 to 1.50 moles, relative to the iodine group of the aryl iodide.

An organic solvent and an acidic aqueous solution are added to the reaction solution and extracted. The organic solvent used for the extraction is not particularly limited as long as it is not mixed with water, but ethyl acetate, dichloromethane, chloroform, and 1,2-dichloroethane are more preferable. As the acidic aqueous solution, ammonium chloride, hydrochloric acid, acetic acid, or formic acid aqueous solution is preferable. If the acidity is too high, an aqueous solution of ammonium chloride is more preferable since Boc may be desorbed. The concentration of the acidic solution is preferably 0.5 to 2 moles / liter, more preferably 1 to 1.5 moles / liter. The obtained organic layer is washed several times with an acidic aqueous solution and then dried with a drying agent. As the drying agent, sodium sulfate and magnesium sulfate are preferable. The obtained organic layer is dried for 4 to 24 hours, preferably 12 to 24 hours. The drying agent is removed, and the solvent is distilled off from the obtained solution to obtain the compound represented by the above formula (52). The obtained compound can be used for the next reaction without purification, and it is preferable to purify it by various methods. Examples of the purification method include silica gel column chromatography, recrystallization, and washing with an organic solvent. Recrystallization is more preferable because of simplicity of operation and purification efficiency. Regardless of the type of the organic solvent used for recrystallization, recrystallization may be performed with two or more kinds of mixed solvents as long as the formula (52) is an organic solvent capable of recrystallization.

The diamine compound of the present invention represented by the following formula (B) can be produced by hydrogenation of the compound represented by the above formula (52).

The compound represented by the above formula (52) is dissolved in an organic solvent. The organic solvent to be used is not particularly limited as long as it is a known one, but methanol, ethanol, 2-propanol, tetrahydrofuran and 1,4-dioxane are preferable, and methanol , And ethanol is more preferable. After the compound represented by the formula (52) is dissolved in an organic solvent, the inside of the reaction vessel is replaced with nitrogen, and then a catalyst is added to displace the inside of the reaction vessel with hydrogen. Examples of the catalyst include palladium carbon, platinum carbon, platinum oxide and the like. From the reaction efficiency, palladium carbon is more preferable. The reaction mixture is stirred at 0 ° C to 100 ° C, preferably 10 to 60 ° C, for 15 to 72 hours, preferably 24 to 48 hours. After completion of the reaction, the catalyst is removed and the organic solvent is distilled off to obtain the diamine compound of the present invention represented by the above formula (B). If the obtained compound is not purified to a high purity, the polymerization reaction does not proceed and a polymer having a high molecular weight can not be obtained. Therefore, purification is preferably carried out by various methods. Examples of the purification method include silica gel column chromatography, recrystallization, and washing with an organic solvent. Recrystallization is more preferable because of simplicity of operation and purification efficiency. The organic solvent used for recrystallization may be recrystallized with two or more kinds of mixed solvents regardless of the kind of organic solvent capable of recrystallizing the diamine represented by the above formula (B).

Hereinafter, the production method of the diamine compound of the above formulas (D) and (E) is shown, but it is not limited thereto.

The diamine compounds of the formulas (D) and (E) can be obtained by using, for example, 2-amino-4-nitroaniline of the following formula (53) and an amino acid compound of the following formula (Ⅶ). The amino acid compound of the following formula (54) is a compound in which the amino group of the amino acid is protected with Boc. The diamine compounds of the above formulas (D) and (E) can be prepared by using an amino acid compound in which the amino group of glycine and histidine is protected with a Boc group. On the other hand, even in the case of other amino acids, a diamine compound can be produced by the same production method.

The compound represented by the following formula (55) can be prepared by reacting the 2-amino-4-nitroaniline of the formula (53) with the amino acid compound represented by the formula (54).

The amino group at the 1-position of 2-amino-4-nitroaniline degrades nucleophilicity due to the influence of the nitro group present at the 4-position. Therefore, the carboxylic acid of the amino acid compound reacts preferentially with the amino group at the 2-position, so that the compound represented by the formula (55) can be produced. When the amino acid compound is added in excess, it forms an amide bond with the amino group at the 4-position. Therefore, the amount of the amino acid compound to be added is preferably 0.9 to 1.2 times the amount of 2-amino-4-nitroaniline.

The compound represented by the formula (55) can be produced by a condensation reaction of an amino group at 2-position of 2-amino-4-nitroaniline with a carboxylic acid of the amino acid compound of the formula (54). Condensation of an amino group and a carboxylic acid is not particularly limited as long as it is a known method, but in the case of producing the diamine compound of the present invention, a method using a mixed acid anhydride or a method using a condensing agent is more preferable.

The method using a mixed acid anhydride can be carried out, for example, by reacting a carboxylic acid with an acid halide or an acid derivative in an organic solvent in the presence of a base at a temperature of -40 ° C to 40 ° C, preferably -20 ° C to 5 ° C And reacting the obtained mixed acid anhydride with 2-amino-4-nitroaniline in an organic solvent at -40 ° C to 40 ° C, preferably -20 ° C to 5 ° C.

The type of the organic solvent to be used in the reaction is not limited as long as it dissolves the amino acid compound represented by the formula (54) and does not react with each reagent used in the reaction. Examples thereof include dehydrated chloroform, dichloromethane, Tetrahydrofuran is preferable, and tetrahydrofuran is more preferable from solubility in amino acid compounds.

As the base to be used in the reaction, a tertiary amine is preferable, and pyridine, triethylamine, dimethylaminopyridine and N-methylmorpholine are more preferable. The addition amount of the base is preferably 2 to 4 times as much as the amount of 2-amino-4-nitroaniline because it is difficult to remove the base excessively.

As the acid halide and the acid derivative, pivaloyl chloride, tosyl chloride, mesyl chloride, ethyl chloroformate, and isobutyl chloroformate are preferable. The addition amount of the acid halide and the acid derivative is preferably 1.5 to 2 times the molar amount of 2-amino-4-nitroaniline.

A method of using a condensing agent is a method of reacting 2-amino-4-nitroaniline with an amino acid compound in the presence of a condensing agent, a base and an organic solvent at 0 ° C to 150 ° C, preferably 0 ° C to 100 ° C, Hour, preferably 3 to 15 hours.

Examples of the condensing agent include triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3- dimethylaminopropyl) carbodiimide hydrochloride, N, N'-carbonyldiimidazole, dimethoxy- N, N ', N'-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) (2,3-dihydro-2-thioxo-3-benzoxazolyl) diphenylphosphonate, and the like can be used, Can be used. The amount of the condensing agent to be added is preferably 2 to 3 times the amount of the amino acid compound.

As the base, tertiary amines such as pyridine and triethylamine can be used. Amounts of the base are preferably 2 to 4 times as much as the amount of 2-amino-4-nitroaniline, because they are difficult to remove if they are excessively large and small when they are too small. Further, in the method using the condensing agent, the reaction proceeds efficiently by adding Lewis acid as an additive. As the Lewis acid, lithium halides such as lithium chloride and lithium bromide are preferable. The amount of the Lewis acid added is preferably 0 to 1.0 times the molar amount of 2-amino-4-nitroaniline.

In the two kinds of methods, it is preferable that the obtained reaction solution is obtained by removing an precipitate, adding an acidic or basic aqueous solution and an organic solvent, and removing an acid halide or an acid derivative, a condensing agent and a base by extraction. As the acidic aqueous solution, hydrochloric acid, acetic acid, formic acid, or ammonium chloride aqueous solution is preferable. As the base aqueous solution, an aqueous solution of sodium hydroxide, potassium hydroxide, sodium hydrogencarbonate, or potassium carbonate is preferable. The organic solvent to be used for the extraction is not particularly limited as long as it does not precipitate and does not mix with water even if it is added to the reaction solution. However, the organic solvent may be ethyl acetate, dichloromethane, chloroform or 1,2- desirable.

The obtained organic layer is washed with the acidic aqueous solution or the basic aqueous solution several times, and then dried with a drying agent. As the drying agent, sodium sulfate and magnesium sulfate are preferable. The obtained organic layer is dried for 4 to 24 hours, preferably 12 to 24 hours. The drying agent is removed and the solvent is distilled off from the obtained solution to obtain the compound represented by the formula (55). The obtained compound can be used for the next reaction without purification, and it is preferable to purify it by various methods. Examples of the purification method include silica gel column chromatography, recrystallization, and washing with an organic solvent. Recrystallization is more preferable because of simplicity of operation and purification efficiency. The organic solvent used for recrystallization may be recrystallized from two or more kinds of mixed solvents irrespective of the kind of organic solvent capable of recrystallizing the compound represented by the formula (55).

The diamine compound represented by the following formula (56) can be prepared by hydrogenation of the compound represented by the formula (55).

First, the compound represented by the formula (55) is dissolved in an organic solvent. The organic solvent to be used is not particularly limited as long as it is a known one, but methanol, ethanol, 2-propanol, tetrahydrofuran and 1,4-dioxane are preferable, and methanol , And ethanol is more preferable. After the compound represented by the formula (55) is dissolved in an organic solvent, the inside of the reaction vessel is replaced with nitrogen, and then the catalyst is added and the inside of the reaction vessel is replaced with hydrogen. Examples of the catalyst include palladium carbon, platinum carbon, platinum oxide and the like. From the reaction efficiency, palladium carbon is more preferable. The reaction mixture is stirred at 0 ° C to 100 ° C, preferably 10 to 60 ° C, for 15 to 72 hours, preferably 24 to 48 hours. After completion of the reaction, the catalyst is removed and the organic solvent is distilled off to obtain the diamine compound of the present invention represented by the above formula (56). If the obtained compound is not purified to a high purity, the polymerization reaction does not proceed and a polymer having a high molecular weight can not be obtained. Therefore, it is preferable to purify the compound by various methods. Examples of the purification method include silica gel column chromatography, recrystallization, and washing with an organic solvent. Recrystallization is more preferable because of simplicity of operation and purification efficiency. The organic solvent used for recrystallization may be recrystallized from two or more kinds of mixed solvents regardless of the kind of organic solvent that can recrystallize the diamine represented by the following formula (56).

c. [Preparation of polyimide precursor and polyimide]

The polyimide precursor and the polyimide of the present invention can be produced by reacting at least one compound selected from the group consisting of a diamine compound having a substituent represented by the formula (1) and a tetracarboxylic acid derivative having a substituent represented by the formula (1) Also referred to as a specific monomer). Specifically, it is produced by using the tetracarboxylic acid derivative represented by the above formulas (19) to (21) and / or the diamine compound represented by the formula (22). Among them, the specific monomer is preferably a diamine compound having a substituent represented by the above formula (1).

In producing the polyimide precursor and the polyimide of the present invention, the starting monomer may be a tetracarboxylic acid derivative other than the specific monomer (for example, a tetracarboxylic acid derivative represented by the above formulas (23) to (25) ) And / or a diamine compound other than a specific monomer (for example, a diamine compound represented by the above formula (26)) may be used in combination. In this case, the amount of the specific monomer in the raw material monomer is preferably 2 to 100 mol%, more preferably 2 to 60 mol%, still more preferably 2 to 50 mol%, particularly preferably 2 to 30 mol% % to be.

In the present invention, raw material monomers refer to tetracarboxylic acid derivatives and diamine compounds used for producing the polyimide precursor and polyimide of the present invention. However, the tetracarboxylic acid derivative and / or diamine compound used in the present invention contains a specific monomer.

c1. (Preparation of polyamic acid)

Polyamic acid which is a polyimide precursor can be prepared from a tetracarboxylic acid dianhydride and a diamine compound (the following formula (ⅷ)), and the tetracarboxylic acid dianhydride and / or diamine compound contains a specific monomer.

When the polyimide precursor is produced, the tetracarboxylic acid dianhydride and the diamine compound are preferably reacted in the presence of an organic solvent at -20 ° C to 140 ° C, preferably 0 ° C to 50 ° C for 30 minutes to 24 hours, Is reacted for 1 to 12 hours. The solvent used in the production of the polyamic acid of the above formula (III) is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone or? -Butyrolactone from the solubility of the monomer and the polymer, One kind or a mixture of two or more kinds may be used. When the concentration is too high, the polymer tends to precipitate. When the concentration is too low, the molecular weight does not increase. Therefore, the total amount of the tetracarboxylic acid dianhydride and the diamine compound in the reaction liquid is preferably 1 to 30 mass% To 20% by mass is more preferable.

The polyamic acid thus obtained can be used as the liquid crystal aligning agent of the present invention in the reaction solution. When the solvent used in the polymerization is not desired to be contained in the liquid crystal aligning agent, the polymer can be recovered as a solid, Of polyamic acid.

The polymer can be recovered by precipitating the polymer by injecting the reaction solution into a poor solvent while stirring well. After the precipitation is carried out several times, it is washed with a poor solvent and then heated or dried at room temperature to obtain a powder of the purified polyamic acid.

Examples of the poor solvent include, but are not limited to, water, methanol, ethanol, hexane, butyl cellosolve, acetone, and toluene.

c2. (Preparation of polyamic acid ester)

The polyamic acid ester can be produced by a known production method, and specifically, the following methods (a) to (c) are exemplified, but the present invention is not limited thereto.

(a) Production of polyamic acid ester from polyamic acid

The polyamic acid ester of the present invention can be produced by esterifying the above-mentioned polyamic acid of the present invention (the above formula (III)). Concretely, the polyamic acid and the esterifying agent are reacted in the presence of an organic solvent at -20 ° C to 140 ° C, preferably 0 ° C to 50 ° C for 30 minutes to 24 hours, preferably 1 to 4 hours .

The esterifying agent is preferably one which can be easily removed by purification. Examples of the esterifying agent include N, N-dimethylformamide dimethylacetal, N, N-dimethylformamide diethyl acetal, N, N-dimethylformamide dipropyl acetal, N, N-dimethylformamide dineopentylbutyl acetal, N, N-dimethylformamide di-t-butyl acetal, 1-methyl-3-p-tolyltriazine, , 1-propyl-3-p-tolyltriazole, and the like. The addition amount of the esterifying agent is preferably 2 to 6 molar equivalents relative to 1 mol of the repeating unit of the polyamic acid.

The solvent to be used for the production of the polyamic acid ester of the above formula (III) is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone or? -Butyrolactone from the solubility of the monomer and the polymer, These may be used alone or in combination of two or more. The total amount of the polyamic acid and the esterifying agent in the reaction liquid is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass, more preferably from 5 to 20% by mass, Is more preferable.

(b) Production of a polyamic acid ester from an acid chloride and a diamine compound

The polyamic acid ester can be prepared from an acid chloride and a diamine compound (the above formula (x)). In the present invention, the acid chloride and / or the diamine compound contains a specific monomer.

Specifically, the acid chloride and the diamine compound are reacted in the presence of a base and an organic solvent at -20 ° C to 140 ° C, preferably 0 ° C to 50 ° C for 30 minutes to 24 hours, preferably 1 to 4 hours can do. As the base, pyridine, triethylamine, and 4-dimethylaminopyridine can be used, and pyridine is preferable for the reaction to proceed mildly. The amount of the base to be added is preferably 2 to 4 times the amount of the acid chloride, because the amount of the base is too large to remove, and if too small, the molecular weight becomes small.

The solvent used for the production of the polyamic acid ester of the above formula (x) is preferably N-methyl-2-pyrrolidone or? -Butyrolactone from the viewpoint of the solubility of the monomer and the polymer, They may be mixed and used. The total amount of the acid chloride and the diamine compound in the reaction liquid is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass, and more preferably from 5 to 20% by mass, Is more preferable. In order to prevent the hydrolysis of the acid chloride, the solvent used in the production of the polyamic acid ester is preferably dehydrated as much as possible and it is preferable to prevent the introduction of outside air in a nitrogen atmosphere.

(c) Production of polyamic acid ester from dialkyl ester dicarboxylic acid and diamine compound

The polyamic acid ester can be produced by condensing a dialkyl ester dicarboxylic acid and a diamine compound with a condensing agent (formula (xi)). In the present invention, the dialkyl ester dicarboxylic acid and / or diamine compound contains a specific monomer.

Specifically, the dialkyl ester dicarboxylic acid and the diamine compound are reacted in the presence of a condensing agent, a base and an organic solvent at 0 ° C to 140 ° C, preferably 0 ° C to 100 ° C, for 30 minutes to 24 hours, Followed by allowing to react for 15 hours.

Examples of the condensing agent include triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3- dimethylaminopropyl) carbodiimide hydrochloride, N, N'-carbonyldiimidazole, dimethoxy- N, N ', N'-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) (2,3-dihydro-2-thioxo-3-benzooxazolyl) diphenylphosphonate, and the like can be used in combination with a base such as N, N, N ', N'-tetramethyluronium hexafluorophosphite, Can be used. The addition amount of the condensing agent is preferably 2 to 3 times the molar amount of the dialkyl ester dicarboxylic acid.

As the base, tertiary amines such as pyridine and triethylamine can be used. The addition amount of the base is preferably 2 to 4 times the amount of the diamine component, because the amount of the base is too large to remove, and if too small, the molecular weight becomes small.

In addition, in the above reaction, the reaction proceeds efficiently by adding Lewis acid as an additive. As the Lewis acid, lithium halides such as lithium chloride and lithium bromide are preferable. The addition amount of the Lewis acid is preferably 0 to 1.0 times the molar amount of the diamine component.

Among the above-mentioned three methods for producing polyamic acid esters, the production method of (a) and (b) is particularly preferable because a polyamic acid ester having a high molecular weight can be obtained.

The polyamic acid ester solution obtained as described above can be precipitated by pouring into a poor solvent while stirring well. After the precipitation is carried out several times and washed with a poor solvent, the purified polyamic acid ester powder can be obtained at room temperature or by heating and drying.

Examples of the poor solvent include, but are not limited to, water, methanol, ethanol, hexane, butyl cellosolve, acetone, and toluene.

c3. [Molecular Weight]

The ratio of the diamine component used in the polymerization reaction to the tetracarboxylic acid derivative (tetracarboxylic acid dianhydride, acid chloride and dialkyl ester dicarboxylic acid) is 1: 0.7 to 1: 1.2 . The closer the molar ratio is to 1: 1, the larger the molecular weight of the polyimide precursor is. The molecular weight of the polyimide precursor affects the viscosity of the varnish and the physical strength of the polyimide film. If the molecular weight of the polyimide precursor is too large, the varnish coating workability and coating film uniformity may deteriorate. If it is too small, the strength of the obtained polyimide film may be insufficient. Accordingly, the molecular weight of the polyamic acid ester used in the polyimide precursor composition of the present invention is preferably from 2,000 to 500,000, more preferably from 5,000 to 300,000, and still more preferably from 10,000 to 100,000 in terms of weight average molecular weight.

d. [Production of polyimide]

The polyimide of the present invention can be produced by imidizing the polyimide precursor. In the case of producing a polyimide from a polyimide precursor, chemical imidization by adding a catalyst to a solution of the polyamic acid obtained by the reaction of the diamine component and the tetracarboxylic acid dianhydride is simple. The chemical imidization is preferable because the imidization reaction proceeds at a relatively low temperature and the molecular weight of the polymer hardly decreases during the imidization process.

The chemical imidization can be carried out by stirring the polymer to be imidized in the presence of a basic catalyst and an acid anhydride in an organic solvent. As the organic solvent, a solvent used in the above-mentioned polymerization reaction may be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Among them, pyridine is preferred since it has a basicity suitable for proceeding the reaction. As the acid anhydride, acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like can be mentioned. Among them, acetic anhydride is preferable because the purification after completion of the reaction becomes easy.

The temperature at which the imidization reaction is carried out is from -20 占 폚 to 140 占 폚, preferably from 0 占 폚 to 100 占 폚, and the reaction time is from 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 molar times, preferably 2 to 20 molar times, and the amount of the acid anhydride is 1 to 50 molar equivalents, preferably 3 to 30 molar equivalents, of the ammic acid group. The imidization rate of the resulting polymer can be controlled by adjusting the amount of catalyst, temperature, and reaction time. Since the added catalyst remains in the solution after the imidization reaction, it is preferable to recover the imidized polymer obtained by the means described below and redissolve it with an organic solvent to obtain the liquid crystal aligning agent of the present invention.

The polyimide solution obtained as described above can be precipitated by pouring into a poor solvent while stirring well. After the precipitation is carried out several times and washed with a poor solvent, the purified polyamic acid ester powder can be obtained at room temperature or by heating and drying.

Examples of the poor solvent include, but are not limited to, methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene and benzene.

e. [Liquid crystal aligning agent]

The liquid crystal aligning agent of the present invention is a coating liquid for forming a liquid crystal aligning agent in which the polyimide precursor or polyimide obtained as described above is uniformly dissolved in an organic solvent.

e1. [solvent]

As the solvent used as the liquid crystal aligning agent of the present invention, a solvent capable of dissolving a polyimide precursor or polyimide (hereinafter, both solvents) and a solvent for improving the uniformity of a coating film when the liquid crystal aligning agent is applied to the substrate (Hereinafter referred to as " poor solvent "). The positive solvent is not particularly limited as long as it dissolves the polyimide precursor or polyimide. Specific examples thereof include N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methyl- Pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, dimethylsulfone, hexamethylsulfoxide, gamma -butyrolactone, 1,3- Dimethyl-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide, and the like. These may be used alone or in combination of two or more. The solvent may be a solvent that does not dissolve the polymer alone, or may be a solvent that does not precipitate the polymer.

The poor solvent is not particularly limited as long as it has a low surface tension and can improve coating film uniformity. Specific examples thereof include ethylcellosolve, butylcellosolve, ethylcarbitol, butylcarbitol, ethylcarbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy- Propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether Propyl alcohol, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid isoamyl ester, and the like. have. These solvents may be used in combination of two or more.

[Silane coupling agent]

The silane coupling agent is an organosilicon compound having both an organic functional group chemically bonded to an organic material in a molecule and a hydrolyzable group reactive with an inorganic material, and its structure is generally represented by the following formula (57).

Equation (57) of the, Q is the organic functional group, and, R ₁₄ represents a divalent organic group, and R is an alkyl group, W is an alkoxy group represented by OR ₁₅ (where R ₁₅ is an alkyl group), n is 1-3 It is an integer.

The silane coupling agent is added for the purpose of improving adhesion of various inorganic materials used as a substrate of an electronic device to a polymer. The silane coupling agent hydrolyzes alkoxysilane, which is hydrolyzed by heating, to silanol, and forms a hydrogen bond or a covalent bond with a polar group present on the surface of the substrate to impart adhesion.

Specific examples of the silane coupling agent used in the present invention are summarized below, but the present invention is not limited thereto.

Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- Amine-based silane coupling agents such as phenylaminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine and 3-aminopropyldiethoxymethylsilane; Vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, vinylmethyldimethoxysilane, vinyltriacetoxysilane, vinyltriisopropoxysilane, allyltrimethoxysilane, p Vinyl silane coupling agents such as styryltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4 - epoxycyclohexyl) ethyl trimethoxysilane; Methacrylic silane coupling agents such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane. Ring agent; Acrylic silane coupling agents such as 3-acryloxypropyltrimethoxysilane; A ureide-based silane coupling agent such as 3-ureido propyl triethoxysilane; Sulfide-based silane coupling agents such as bis (3- (triethoxysilyl) propyl) disulfide, and bis (3- (triethoxysilyl) propyl) tetrasulfide; Mercapto-based silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane and 3-octanoylthio-1-propyltriethoxysilane; Isocyanate-based silane coupling agents such as 3-isocyanatepropyltriethoxysilane and 3-isocyanatepropyltrimethoxysilane; Aldehyde-based silane coupling agents such as triethoxysilylbutylaldehyde; And carbamate-based silane coupling agents such as triethoxysilylpropylmethyl carbamate and (3-triethoxysilylpropyl) -t-butylcarbamate.

In the silane coupling agent, the organic functional group Q is bonded to the functional group in the polymer and is introduced into the polymer, so that the effect can be further exerted. That is, it is preferable to use the silane coupling agent in accordance with the composition of the polyimide precursor or polyimide to be used.

When a polyimide film is used in an electronic device such as a liquid crystal display device, it is preferable to introduce a silane coupling agent at the end of the polymer in order to improve the adhesion without hindering its characteristics. The polyimide precursor and the polyimide which is an imidation polymer thereof can be obtained by controlling the molar ratio of the tetracarboxylic acid derivative such as tetracarboxylic acid dianhydride, acid chloride and dialkyl ester dicarboxylic acid to the diamine compound, The functional group may be an amine, a carboxylic acid or an ester. Therefore, epoxy silane coupling agents, isocyanate silane coupling agents, aldehyde silane coupling agents, carbamate silane coupling agents and amine silane coupling agents having high reactivity with these functional groups are preferable, and from the viewpoint of reactivity, Based silane coupling agent and an epoxy-based silane coupling agent are particularly preferable.

Further, by modifying the terminal of the polymer with a known functional compound, an arbitrary functional group can be introduced into the polymer. In such a case, it is preferable to add a silane coupling agent having an organic functional group Q which reacts with the introduced functional group.

When the coupling agent is blended, the adhesion can be improved by heating after the addition of the coupling agent to react with the polymer. After the addition of the coupling agent, the reaction may be carried out at 20 to 80 ° C, more preferably 40 to 60 ° C, for 1 to 24 hours.

e3. [Other additives]

Needless to say, various additives such as a crosslinking agent may be used in the liquid crystal aligning agent of the present invention. The polymer contained in the polyimide precursor or polyimide composition of the present invention may be two or more kinds.

e4. [Polymer concentration]

The concentration of the polymer of the liquid crystal aligning agent of the present invention can be appropriately changed depending on the setting of the thickness of the polyimide film to be formed, and is preferably 1 to 10% by mass, more preferably 2 to 8% by mass. If it is less than 1% by mass, it becomes difficult to form a uniform and defect-free coating film. If it is more than 10% by mass, the storage stability of the solution may be deteriorated.

f. [Production method of liquid crystal aligning agent]

The liquid crystal aligning agent of the present invention can be produced by the following method.

When the polymer used is a powder, it is dissolved in the solvent to obtain a polymer solution. At this time, the polymer concentration is preferably 10 to 30% by mass, and particularly preferably 10 to 15% by mass. It may also be heated when the powder of the polymer is dissolved. The heating temperature is preferably 20 to 140 占 폚, particularly preferably 20 to 80 占 폚.

The liquid crystal aligning agent of the present invention can be obtained by adding the solvent and the solvent for improving the uniformity of the coating film to the polymer solution obtained by re-dissolving the polymer or the reaction solution of the polymer, and diluting the solution to a predetermined polymer concentration. In the case of adding a silane coupling agent, it is preferable to add a silane coupling agent before the addition of a solvent for improving the uniformity of the coating film, in order to prevent precipitation of the polymer.

The addition amount of the silane coupling agent is preferably from 0.01 to 5.0% by mass, more preferably from 0.1 to 5.0% by mass, based on the polymer powder, since the amount of the silane coupling agent is too large to adversely affect the liquid crystal alignability in some cases, And more preferably 1.0% by mass.

g. [Liquid Crystal Alignment Layer]

The liquid crystal alignment film of the present invention is obtained as follows. That is, the liquid crystal aligning agent of the present invention can be applied to a substrate, preferably after filtration, followed by drying and firing to form a coating film. The substrate to which the liquid crystal aligning agent of the present invention is applied is not specifically limited as long as it is a substrate having high transparency. A plastic substrate such as a glass substrate, a silicon nitride substrate, an acrylic substrate or a polycarbonate substrate can be used. It is preferable from the viewpoint of process simplification. In the reflection type liquid crystal display element, it is possible to use an opaque material such as a silicon wafer if only one side substrate is used. In this case, a material that reflects light such as aluminum can also be used as the electrode in this case.

Examples of the application method of the liquid crystal aligning agent of the present invention include a spin coating method, a printing method, and an ink jet method. After the liquid crystal aligning agent of the present invention is applied, it is preferably dried and fired. In order to sufficiently remove the organic solvent contained in the liquid crystal aligning agent, it is preferably dried at 50 to 120 ° C for preferably 1 to 10 minutes. Then, it is preferably baked at 150 to 300 占 폚, more preferably at 150 to 250 占 폚. The firing time varies depending on the firing temperature, and is preferably 5 to 120 minutes, and more preferably 5 to 60 minutes.

The liquid crystal aligning agent of the present invention can be obtained by heating a primary or secondary aliphatic amino group protected by a Boc group of a polyimide precursor or an imidation polymer thereof to 150 DEG C or higher as described above, The Boc group is eliminated, resulting in a reactive primary or secondary aliphatic amino group lacking protection of the Boc group. The resulting primary or secondary aliphatic amino group reacts with a polyimide precursor or a functional group present in the imidized polymer to form intermolecular crosslinking. Through such a crosslinking reaction, the liquid crystal alignment film obtained in the present invention has a mechanical strength of So that a polyimide film which does not cause peeling or scratching of the film due to rubbing can be obtained.

The thickness of the liquid crystal alignment film of the present invention is not particularly limited, but if it is too thin, the reliability of the liquid crystal display element may deteriorate. Therefore, it is 5 to 300 nm, preferably 10 to 200 nm. This coating film surface can be used as a liquid crystal alignment film by performing orientation treatment such as rubbing.

Examples of a method for orienting the liquid crystal alignment film of the present invention include a rubbing method and a photo-alignment treatment method.

As a specific example of the photo-alignment treatment method, a method of irradiating the surface of the above-mentioned coating film with polarized radiation in a predetermined direction and, in some cases, a heat treatment at a temperature of 150 to 250 ° C to give a liquid crystal aligning ability . As the radiation, ultraviolet rays and visible rays having a wavelength of 100 to 800 nm can be used. Of these, ultraviolet rays having a wavelength of 100 to 400 nm are preferable, and ultraviolet rays having a wavelength of 200 to 400 nm are particularly preferable. In addition, in order to improve the liquid crystal alignment property, the coated film substrate may be irradiated with radiation while heating at 50 to 250 ° C. The irradiation dose of the radiation is preferably in the range of 1 to 10,000 mJ / cm 2, and particularly preferably in the range of 100 to 5,000 mJ / cm 2.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example

The abbreviations and structures of the compounds used in the present Examples and Comparative Examples are shown below.

CBDA: Cyclobutane tetracarboxylic acid dianhydride

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

p-PDA: p-phenylenediamine

DA-A: diamine of the above formula (A)

DA-B: diamine of formula (B)

DA-D: diamine of the above formula (D)

DA-E: diamine of the above formula (E)

DA-F: diamine of the above formula (F)

DA-H: diamine of the following formula (H)

(Organic solvent)

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellosolve

DMF: N, N-diethylformamide

THF: tetrahydrofuran

? -BL:? -butyrolactone

The measurement methods of ¹ H-NMR, viscosity, molecular weight, and rubbing resistance are shown below.

[ ¹ H-NMR]

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

Solvent: deuterated dimethylsulfoxide (DMSO-d ₆ ) or deuterated chloroform (CDCl ₃ )

Standard material: tetramethylsilane (TMS)

[Viscosity]

In the synthesis examples, the viscosity of the polyamic acid ester and the polyamic acid solution was 1.1 ml of the sample amount, the cone TE-1 (1 ° 34 ', R24), and the temperature of the condenser TE-1 using a E-type viscometer TVE-22H ≪ / RTI >

[Molecular Weight]

The molecular weight of the polyamic acid ester is measured by a GPC (room temperature gel permeation chromatography) apparatus, and the number average molecular weight (hereinafter also referred to as Mn) and the weight average molecular weight (hereinafter also referred to as Mw) as polyethylene glycol or polyethylene oxide equivalent ).

GPC apparatus: manufactured by Shodex Corp. (GPC-101)

Column: manufactured by Shodex Co., Ltd. (serial of KD803, KD805)

Column temperature: 50 ° C

Eluent: N, N- dimethylformamide (lithium bromide as an additive-hydrate (LiBr · H ₂ O) is 30 m㏖ / ℓ, phosphoric acid anhydrous crystal (o- phosphoric acid) is 30 m㏖ / ℓ, tetrahydrofuran ( THF) 10 ml / l)

Flow rate: 1.0 ml / min

Standard sample for calibration curve: TSK standard polyethylene oxide (weight average molecular weight (Mw) of about 900,000, 150,000, 100,000, 30,000) manufactured by Toso Corporation and polyethylene glycol (peak top molecular weight (Mp) of about 12,000, 4,000 , 1,000). In order to avoid duplication of peaks, two samples of samples mixed with four types of 900,000, 100,000, 12,000 and 1,000, and three samples of 150,000, 30,000 and 4,000 were measured.

[Rubbing Resistance of Polyimide Film]

A liquid crystal aligning agent was spin-coated on a glass substrate with a transparent electrode attached thereto, followed by drying on a hot plate at 80 占 폚 for 5 minutes and firing at 230 占 폚 for 20 minutes or 60 minutes to obtain a polyimide film having a thickness of 100 nm Film. After rubbing the polyimide film, the surface state of the polyimide film was observed to evaluate the presence or absence of rubbing scratches, presence or absence of cutting residue of the polyimide film, and peeling of the polyimide film.

[Voltage maintenance rate]

The voltage holding ratio of the liquid crystal cell was measured as follows.

A voltage of 4 V was applied for 60 seconds, and a voltage after 16.67 ms was measured, and the variation from the initial value was calculated as the voltage holding ratio. At the time of measurement, the temperature of the liquid crystal cell was set to 23 deg. C, 60 deg. C, and 90 deg. C, and the measurement was performed at each temperature.

[Ion density]

The ion density of the liquid crystal cell was measured as follows.

The measurement was carried out using a 6254-type liquid crystal physical property evaluation apparatus manufactured by Toyo Technica. 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 the triangular approximation method to obtain the ion density. At the time of measurement, the temperature of the liquid crystal cell was set to 23 캜 and 60 캜, and measurement was performed at each temperature.

≪ Example 1 > Synthesis of DA-A

(Precursor synthesis 1)

2-cyano-4-nitroaniline (15 g, 92 mmol) was added to the 1-liter four-necked flask and the gimlet and a 100 ml dropping funnel were connected. After the inside of the system was replaced with nitrogen, Was added and cooled to 0 < 0 > C. Next, a borane-THF complex (1 M in THF, 100 mL, 100 mmol) was added dropwise from the dropping funnel over 30 minutes. Production of gas was confirmed from the reaction system, and a yellow solid precipitated. After completion of dropwise addition, the mixture was stirred at room temperature for 2 days. After completion of the reaction, an aqueous hydrochloric acid solution (2 N, 200 ml) was added, and the mixture was stirred at room temperature for 2 hours and then basified by adding aqueous sodium hydroxide solution (2 N, 250 ml) at 10 ° C and extracted with dichloromethane . The organic layer was washed with saturated brine (500 ml), dried over magnesium sulfate, concentrated and vacuum-dried to obtain a cyano-reduced product of a yellow solid. The yield was 11.9 g and the yield was 77%.

(Synthesis of Precursor 2)

(6.00 g, 27.5 mmol) and methylene chloride (900 ml) were added to a one-liter eggplant-shaped flask to obtain a solution, and then di-tert-butyl dicarbonate (Boc ₂ O) 27.5 mmol), and the mixture was stirred at room temperature (20 ° C) for 3 days. After completion of the reaction, the reaction solution was washed with saturated brine as it was, and the organic layer was separated and dried with magnesium sulfate. The organic layer was concentrated under reduced pressure, and the precipitated solid was recrystallized from ethyl acetate-hexane (volume ratio: 2/7) to obtain a yellow solid Boc adduct. The yield was 5.25 g and the yield was 71%.

(Synthesis of DA-A)

After adding the above Boc adduct (5.0 g, 18.7 mmol) and ethanol (40 ml) to a 100 ml eggplant type flask, the system was replaced with nitrogen, and platinum oxide (500 mg) . The yellow suspended reaction mixture was stirred at room temperature for 15 hours. After completion of the reaction, ethanol was added, the precipitated white solid was dissolved, and the catalyst was removed by Celite filtration. The filtrate was concentrated, and the resulting pale solid was recrystallized from ethyl acetate-hexane (volume ratio: 1/2) to give a pale peach solid. The yield was 3.40 g and the yield was 77%.

¹ H-NMR of the obtained solid was measured to confirm that it was DA-A.

Example 2 Synthesis of DA-B

(Synthesis of N-Boc-Propargylamine)

(25.18 g, 0.448 mol), triethylamine (55.52 g, 0.549 mol), and dichloromethane (400 mL) were added to a four-necked flask, and while cooling the reaction solution in a water bath Di-tert-butyl carbonate (118.15 g, 0.541 mol) was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was stirred for 2 hours, 300 ml of a saturated aqueous solution of sodium chloride and 200 ml of dichloromethane were added to the reaction solution and extracted. The obtained organic layer was dried with magnesium sulfate. After removing the drying agent, the solvent of the obtained solution was distilled off to obtain a pale yellow oil. Purification by recrystallization (hexane) gave N-Boc-propargylamine as white solid (yield: 47.01 g, yield: 67.6%).

(Synthesis of Nitrozone)

(5.11 g, 19.4 mmol), bis (triphenylphosphine) palladium (II) dichloride (281.7 mg, 0.401 mmol) and copper iodide (160.7 Mg, 0.844 mmol) and diethylamine (30 ml) were added, and the mixture was stirred at room temperature (20 ° C) for 10 minutes. Then, N-Boc-propargylamine (3.72 g, 24.0 mmol) was added, and the mixture was stirred at room temperature (20 ° C) for 4 hours. 200 ml of ethyl acetate and 200 ml of a 1 M ammonium chloride aqueous solution were added and extracted. After the disappearance of the raw material was confirmed by high performance liquid chromatography (HPLC). The obtained organic layer was washed twice with 1M ammonium chloride aqueous solution and dried over anhydrous magnesium sulfate. After the drying agent was removed, the filtrate was concentrated and purified by silica gel column chromatography (effluent: ethyl acetate: hexane = 3: 7 (volume ratio)). The yield was 4.97 g and the yield was 88.0%.

(Synthesis of DA-B)

The above nitroxide (12.45 g, 42.7 mmol) was put in a four-necked flask and suspended in 200 ml of ethanol. The inside of the system was deaerated and purged with nitrogen, and then palladium carbon (1.23 g) was added thereto, followed by hydrogen substitution, followed by stirring at room temperature (20 ° C) for 2 days. Thereafter, palladium carbon was removed by Celite filtration, and the solvent was distilled off. The obtained solid was dissolved in toluene (100 ml), and then hexane (50 ml) was added thereto, followed by recrystallization. The resulting solid was dried under reduced pressure to obtain a pale brown solid (yield: 9.13 g, yield: 80.6%). ¹ H-NMR of the obtained solid was measured to confirm that it was DA-B.

Example 3 Synthesis of DA-D

(Synthesis of Nitrozone)

Boc-glycine (10.17 g, 58.05 mmol) was added to a nitrogen-purged four-necked flask and dissolved in 150 mL of THF. N-Methylmorpholine (N mm) (11.93 g, 117.9 mmol) was added thereto and cooled to -20 占 폚. To this solution was added isobutylchloroformate (9.99 g, 73.14 mmol) dropwise with chloroform. At this time, care was taken so that the temperature of the reaction solution did not exceed 0 캜. After dropwise addition, the mixture was stirred at -20 占 폚 for 10 minutes. At this time, the reaction solution was cloudy. After 10 minutes, 360 ml of a THF solution of 2-amino-4-nitroaniline (8.86 g, 57.86 mmol) was added dropwise from the dropping funnel. After completion of dropwise addition, the mixture was stirred at -20 占 폚 for 1 hour and then at room temperature (20 占 폚) for 18 hours. After 18 hours, the precipitated solid was separated by filtration, and the solvent of the obtained filtrate was distilled off to obtain a concentrate. To this concentrate were added 200 ml of ethyl acetate and 200 ml of 1 M aqueous potassium dihydrogenphosphate solution and extracted. The obtained organic layer was washed once with 1 M aqueous potassium hydrogen phosphate solution, once with saturated brine, twice with saturated aqueous sodium hydrogencarbonate solution and once with saturated brine. The obtained organic layer was dried over anhydrous magnesium sulfate. After removing the drying agent, the solvent was distilled off from the liquid to obtain an orange solid. This solid was suspended in 300 ml of toluene, and the mixture was heated and stirred for 30 minutes. The solid was collected by suction filtration, and the resultant solid was subjected to ¹ H-NMR measurement. As a result, it was confirmed that the objective nitro chain was obtained (yield: 9.85 g, yield: 54.9%).

(Synthesis of DA-D)

To the eggplant-shaped flask was added the nitrile (9.85 g, 31.75 mmol), and 150 ml of ethanol was added. After the reaction vessel was purged with nitrogen, palladium carbon (1.11 g, 10 mass% based on the mass of the nitrrotecane) was added, and the reactor was purged with nitrogen again. Subsequently, the reaction vessel was purged with hydrogen, and stirred at 20 占 폚 for 48 hours. After completion of the reaction, the palladium carbon was removed by Celite filtration, and the solvent was distilled off from the filtrate. To the obtained concentrate was added 150 ml of toluene and heated to reflux, resulting in the precipitation of a solid. The precipitated solid was filtered while hot to obtain a pale purple solid. The yield was 8.05 g and the yield was 90.4%. ¹ H-NMR of the obtained solid was measured to confirm that it was DA-C.

Example 4 Synthesis of DA-E

(Synthesis of Nitrozone)

4-nitroaniline (4.36 g, 28.47 mmol), N-α, im-di-t-butoxycarbonyl-L-histidine (14.61 g, 33.70 mmol) and 4 -N, N-dimethylaminopyridine (4-DMAP) (1.78 g, 14.57 mmol) was added, and DMF (150 mL) was added. After the reaction mixture was purged with nitrogen, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDAP) (6.58 g, 34.32 mmol) was added and stirred at 20 ° C for 18 hours. After completion of the reaction, ethyl acetate and pure water were 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 drying agent, the filtrate was concentrated to obtain an oily compound. To the oily compound was added 150 ml of toluene, and the mixture was stirred with heating, whereby a yellow solid precipitated. The resulting yellow solid was collected by suction filtration and dried under reduced pressure. ^{By 1} H-NMR measurement, it was confirmed that the obtained yellow solid was the intended diamine compound DA-3. Yield: 5.74 g, yield: 41.1%.

(Synthesis of DA-E)

The knitted substance (5.74 g, 11.70 mmol) was added to an eggplant-shaped flask, and 150 ml of ethanol was added thereto. After the reaction vessel was purged with nitrogen, palladium carbon (0.59 g) was added and replaced with nitrogen. Subsequently, the reaction vessel was purged with hydrogen, and stirred at 20 占 폚 for 48 hours. After completion of the reaction, the palladium carbon was removed by Celite filtration, and the solvent was distilled off from the solution. The product was in the form of an oil, but 100 ml of toluene was added, and when an ultrasonic wave was applied, a pale violet solid precipitated. The precipitated solid was dissolved by heating, and then cooled in a water bath to perform recrystallization. The precipitated solid was collected by suction filtration and dried under reduced pressure to give a pale purple solid. The yield was 2.36 g and the yield was 43.8%. The ¹ H-NMR of the obtained solid was measured to confirm that it was DA-D.

Example 5 Preparation of polyamic acid (A-1) solution

1.125 g (10.40 mmol) of p-PDA, 0.689 g (2.596 mmol) of DA-B and 30.62 g of NMP were placed in a 300 ml four-necked flask equipped with a stirrer and a nitrogen- Followed by stirring and dissolving. While stirring the diamine solution, 2.424 g (12.36 mmol) of CBDA was added, and NMP was further added so that the solid concentration became 10% by mass. The mixture was stirred at room temperature for 24 hours to obtain a polyamic acid (A-1) solution . The viscosity of this polyamic acid solution at a temperature of 25 ° C was 138.6 mPa · s. The molecular weight of the polyamic acid was Mn = 16,079 and Mw = 33,544.

Example 6 Preparation of polyamic acid (A-2) solution

1.037 g (9.589 mmol) of p-PDA, 0.671 g (2.394 mmol) of DA-D and 28.37 g of NMP were placed in a 300 ml four-necked flask equipped with a stirrer and a nitrogen- Followed by stirring and dissolving. While stirring the diamine solution, 2.277 g (11.61 mmol) of CBDA was added, and NMP was further added so that the solid concentration became 10% by mass. The mixture was stirred at room temperature for 24 hours to obtain a polyamic acid (A-2) solution . The viscosity of this polyamic acid solution at a temperature of 25 캜 was 146.2 mPa s. The molecular weight of the polyamic acid was Mn = 17,260 and Mw = 34,532.

Example 7 Preparation of a solution of polyamic acid (A-3)

0.951 g (8.794 mmol) of p-PDA, 1.012 g (2.197 mmol) of DA-E and 29.10 g of NMP were placed in a 300 ml four-necked flask equipped with a stirrer and a nitrogen- Followed by stirring and dissolving. While this diamine solution was being stirred, 2.095 g (10.69 mmol) of CBDA was added and NMP was further added to give a solid content concentration of 10% by mass and stirred at room temperature for 24 hours to obtain a polyamic acid (A-3) solution . The viscosity of this polyamic acid solution at a temperature of 25 캜 was 157.3 mPa s. The molecular weight of the polyamic acid was Mn = 20,610 and Mw = 40,640.

<Comparative Synthesis Example 1> Preparation of polyamic acid (B-1) solution

1.621 g (14.99 mmol) of p-PDA and 28.96 g of NMP were added to a 300 ml four-necked flask equipped with a stirrer and a nitrogen-introducing tube, and dissolved with stirring while nitrogen was being supplied. While stirring the diamine solution, 2.87 g (14.74 mmol) of CBDA was added, and NMP was further added so that the solid concentration became 10% by mass. The mixture was stirred at room temperature for 24 hours to obtain a polyamic acid (B-1) solution . The viscosity of this polyamic acid solution at 25 캜 was 152.7 mPa.. The molecular weight of this polyamic acid was Mn = 13,972 and Mw = 30,181.

&Lt; Example 8 > Preparation of liquid crystal aligning agent (A-1)

12.59 g of the polyamic acid (A-1) solution obtained in Example 5 was put in a 50 ml Erlenmeyer flask containing an agitator, and 4.21 g of NMP and 4.19 g of BCS were added thereto. The mixture was stirred for 30 minutes by a magnetic stirrer, (A-1) was obtained.

Example 9 Preparation of liquid crystal aligning agent (A-2)

11.37 g of the polyamic acid (A-2) solution obtained in Example 6 was put in a 50 ml Erlenmeyer flask, and 3.80 g of NMP and 3.79 g of BCS were added. The mixture was stirred with a magnetic stirrer for 30 minutes, (A-2) was obtained.

Example 10 Preparation of liquid crystal aligning agent (A-3)

11.17 g of the polyamic acid (A-3) solution obtained in Example 7 was put in a 50 ml Erlenmeyer flask, and 3.74 g of NMP and 3.76 g of BCS were added and stirred for 30 minutes by a magnetic stirrer to obtain liquid crystal alignment (A-3) was obtained.

&Lt; Comparative Example 1 > Preparation of liquid crystal aligning agent (B-1)

12.98 g of the polyamic acid (B-1) solution obtained in Comparative Synthesis Example 1 was put into a 50 ml Erlenmeyer flask containing an agitator, and 4.42 g of NMP and 4.27 g of BCS were added thereto. The resulting mixture was stirred for 30 minutes by a magnetic stirrer, To obtain an aligning agent (B-1).

&Lt; Example 11 >

The liquid crystal aligning agent (A-1) obtained in Example 8 was filtered with a filter of 1.0 占 퐉, spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at 80 占 폚 for 5 minutes, Followed by baking for 20 minutes to obtain a polyimide film having a thickness of 100 nm. The surface state of the polyimide film was observed after rubbing the polyimide film with a rayon bath (roll diameter 120 mm, rotation speed 1000 rpm, moving speed 20 mm / sec, indentation amount 0.4 mm), scratches by rubbing, No peeling off of the mid film and peeling of the polyimide film were observed.

&Lt; Example 12 >

A polyimide film was prepared and rubbed in the same manner as in Example 11 except that the liquid crystal aligning agent (A-2) obtained in Example 9 was used. As a result of observing the surface state of the polyimide film, scratches by rubbing, cutting residue of the polyimide film, and peeling of the polyimide film were not observed.

&Lt; Example 13 >

A polyimide film was prepared and rubbed in the same manner as in Example 11 except that the liquid crystal aligning agent (A-3) obtained in Example 10 was used. As a result of observing the surface state of the polyimide film, scratches by rubbing, cutting residue of the polyimide film, and peeling of the polyimide film were not observed.

&Lt; Comparative Example 2 &

A polyimide film was prepared and rubbed in the same manner as in Example 11 except that the liquid crystal aligning agent (B-1) obtained in Comparative Example 1 was used. Observation of the surface state of the polyimide film revealed scratches caused by rubbing and scratches on cutting of the polyimide film.

&Lt; Example 14 >

The liquid crystal aligning agent (A-1) obtained in Example 8 was filtered with a filter of 1.0 占 퐉, spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at 80 占 폚 for 5 minutes, Followed by baking for 20 minutes to obtain a polyimide film having a thickness of 100 nm. This polyimide membrane was subjected to ultrasonic irradiation for 1 minute in a rinsing bath (roll diameter 120 mm, rotation speed 1000 rpm, moving speed 20 mm / sec, indentation amount 0.4 mm) and pure water for 1 minute, And then dried at 80 DEG C for 10 minutes to obtain a substrate having a liquid crystal alignment film attached thereto. Two such substrates having liquid crystal alignment films were prepared, spacers having a size of 6 mu m were dispersed on the liquid crystal alignment film surface of one of the substrates, and the two substrates were assembled such that the rubbing directions of the two substrates were twisted from the antiparallel direction by 85 degrees, And the periphery was sealed to prepare an empty cell having a cell gap of 6 탆. A liquid crystal (MLC-2003, manufactured by Merck) was injected into the empty cell by vacuum, and the injection port was sealed to obtain a twisted nematic liquid crystal cell. As a result of observing the alignment state of the liquid crystal cell with a polarizing microscope, it was confirmed that uniform orientation without defects was observed. The voltage holding ratio was measured for this liquid crystal cell and then the ion density was measured. As a result, the voltage holding ratio was found to be 99.3% at 23 ° C, 98.7% at 60 ° C and 94.1% at 90 ° C, Was 10 pC / cm 2 at 23 ° C and 18 pC / cm 2 at 60 ° C.

&Lt; Example 15 >

A twisted nematic liquid crystal cell was produced in the same manner as in Example 14 except that the liquid crystal aligning agent (A-2) obtained in Example 9 was used, and the alignment state of the liquid crystal was confirmed, the voltage holding ratio and the ion density were measured Respectively.

As a result of observing the alignment state of the liquid crystal cell with a polarizing microscope, it was confirmed that uniform orientation without defects was observed. The voltage holding ratio was measured for this liquid crystal cell and then the ion density was measured. As a result, the voltage holding ratio was found to be 99.3% at 23 ° C, 98.8% at 60 ° C and 94.4% at 90 ° C, Was 5 pC / cm 2 at 23 ° C and 11 pC / cm 2 at 60 ° C.

&Lt; Example 16 >

A twisted nematic liquid crystal cell was produced in the same manner as in Example 14 except that the liquid crystal aligning agent (A-3) obtained in Example 10 was used to confirm the alignment state of the liquid crystal, and to measure the voltage holding ratio and ion density Respectively. A liquid crystal (MLC-2003, manufactured by Merck Co.) was vacuum-injected into the empty cell at room temperature, and the injection port was sealed to obtain a twisted nematic liquid crystal cell. As a result of observing the alignment state of the liquid crystal cell with a polarizing microscope, it was confirmed that uniform orientation without defects was observed. The voltage holding ratio was measured for this liquid crystal cell and then the ion density was measured. As a result, the voltage holding ratio was found to be 99.4% at a temperature of 23 占 폚, 99.1% at a temperature of 60 占 폚, 96.7% at a temperature of 90 占 폚, Was 3 pC / cm 2 at 23 ° C and 4 pC / cm 2 at 60 ° C.

&Lt; Comparative Example 3 &

A twisted nematic liquid crystal cell was produced in the same manner as in Example 14 except that the liquid crystal aligning agent (B-1) obtained in Comparative Example 1 was used, and the alignment state of the liquid crystal was confirmed, the voltage holding ratio and the ion density were measured Respectively. As a result of observing the alignment state of the liquid crystal cell with a polarizing microscope, it was confirmed that uniform orientation without defects was observed. As a result of measurement of the ion density, the voltage holding ratio was found to be 99.1% at 23 ° C, 97.4% at 60 ° C and 86.7% at 90 ° C, Cm &lt; 2 &gt; at 23 DEG C and 256 pC / cm &lt; 2 &gt;

Example 17 Synthesis of DA-F

(Precursor synthesis 1)

978.88 g of dichloromethane and 115.13 g (0.528 mol) of di-tert-butyl dicarbonate were added to a 2L four-necked flask, Lt; 0 &gt; C (ice bath). Then, triethylamine (92.58 g, 0.915 mol) was added to the dropping funnel and added dropwise to the slurry solution in the four-necked flask over a period of 30 minutes. After the start of the dropwise addition, the reaction solution was vigorously bubbled to precipitate a white solid. After completion of dropwise addition, stirring was continued for 2 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 drying agent, the solvent was distilled off to obtain a colorless transparent oil. To this oily substance was added 500 ml of hexane and crystallization was carried out at -78 ° C to obtain a white solid. The solid was collected by suction filtration and dried under reduced pressure. ^{By 1} H-NMR measurement, it was confirmed that the obtained white solid was tert-butyl-3-bromopropylcarbamate. The yield was 89.55 g and the yield was 78.3%.

(Synthesis of Precursor 2)

1,5-dihydroxy-4,8-dinitroanthraquinone (14.04 g, 42.52 mmol) was added to a four-necked flask, and 300 g of NMP was added and heated at 80 占 폚 to obtain 1,5- Hydroxy-4,8-dinitroanthraquinone was completely dissolved. To the solution was added potassium carbonate (12.01 g, 86.95 mmol) and potassium iodide (28.77 g, 173.33 mmol) followed by tert-butyl-3-bromopropylcarbamate (30.40 g, 127.7 mmol) And the mixture was heated and stirred at 80 占 폚 for 6 hours. The obtained reaction solution was poured into 500 ml of a 0.5 M aqueous hydrochloric acid solution, and then 500 ml of ethyl acetate was further added and extracted. The obtained organic layer was washed with 0.5 M aqueous hydrochloric acid solution and saturated brine, and dried over anhydrous magnesium sulfate. After the drying agent was removed, the solvent was distilled off, and the residue was purified by silica gel column chromatography (effluent: 1,2-dichloroethane: ethyl acetate = 7: 3 (volume ratio)) to obtain a yellow solid. ^{By 1} H-NMR measurement, it was confirmed that the obtained yellow solid was the above-mentioned nitro. The yield was 3.21 g and the yield was 11.7%.

(Synthesis of DA-F)

(1.48 g, 2.30 mmol) and sodium sulfide tetrahydrate (5.72 g, 23.82 mmol) were added to a four-necked flask, and 50 ml of pure water was added thereto, and the mixture was heated to reflux for 2 hours. After the reaction solution was cooled to room temperature, 50 ml of a 2 mass% aqueous sodium hydroxide solution was added, and the mixture was stirred at 50 캜 for 1 hour. The solid in the reaction solution was collected by suction filtration and washed with pure water. The resulting solid was purified by recrystallization (methanol) to obtain a purple solid. ^It was confirmed that the purple solid obtained by ¹ H NMR was a diamine (F). The yield was 0.15 g and the yield was 11.2%.

Example 18 Synthesis of DA-H

(Precursor synthesis 1)

(500 mg, 128 mmol), bis (triphenylphosphine) palladium (II) dichloride (900 mg, 1.28 mmol), copper iodide (488 mg, 2.56 mmol), diethylamine (32 mL), and THF (165 mL), and the mixture was stirred at room temperature (20 ° C) for 10 minutes. Thereafter, while stirring the solution in the four-necked flask, a THF solution (90 ml) of N-Boc-propargylamine (47.60 g, 307 mmol) was added dropwise over 15 minutes. After completion of dropwise addition, the mixture was stirred at room temperature (20 ° C) for 12 hours. After 12 hours, the reaction solution was poured into 1.28 L of pure water while stirring, and the precipitated black precipitate was collected by suction filtration and washed twice with 50 mL of water. The obtained solid was dried under reduced pressure to obtain a brown solid. This brown solid was purified by recrystallization (toluene) to obtain a yellow solid. ^{By 1} H-NMR measurement, it was confirmed that the obtained yellow solid was the above-mentioned nitro. The yield was 47.09 g and the yield was 83.0%.

(Synthesis of DA-H)

The above nitrosome (47.07 g, 106 mmol) was placed in a 1 L four-necked flask and suspended in 560 mL of ethanol. The inside of the system was degassed and purged with nitrogen, and then palladium carbon (4.71 g) was added thereto, followed by hydrogen substitution, followed by heating and stirring at room temperature (50 ° C) for 8 days. Palladium carbon was removed by Celite filtration, and the solvent was distilled off. The resulting solid was dissolved in 200 ml of 1,2-dichloroethane, and then 70 ml of hexane was added thereto, followed by recrystallization. The obtained solid was dried under reduced pressure to give a gray solid. The yield was 39.54 g and the yield was 87.5%. The ¹ H-NMR of the obtained solid was measured to confirm that it was DA-H.

Example 19 Preparation of polyamic acid (A-4) solution

1.7281 g (16.47 mmol) of p-PDA, 0.9509 g (4.007 mmol) of DA-A and 46.12 g of NMP were placed in a 100 ml four-necked flask equipped with a stirrer and a nitrogen- Followed by stirring and dissolving. While stirring the diamine solution, 3.8093 g (19.43 mmol) of CBDA was added, and NMP was further added so that the solid content concentration became 10 mass%, followed by stirring at room temperature for 24 hours to obtain a polyamic acid (A-4) solution . The viscosity of this polyamic acid solution at a temperature of 25 ° C was 149 mPa · s. The molecular weight of this polyamic acid was Mn = 18,136 and Mw = 37,265.

Example 20 Preparation of polyamic acid (A-5) solution

0.8665 g (8.013 mmol) of p-PDA, 0.8442 g (1.998 mmol) of DA-H and 25.31 g of NMP were placed in a 100 ml four-necked flask equipped with a stirrer and a nitrogen- Followed by stirring and dissolving. While this diamine solution was stirred, 1.9047 g (9.713 mmol) of CBDA was added, and NMP was further added so that the solid content concentration became 10 mass%, and the mixture was stirred at room temperature for 24 hours to obtain a polyamic acid (A-5) solution . The viscosity of this polyamic acid solution at 25 캜 was 254.7 mPa.. The molecular weight of the polyamic acid was Mn = 27,447 and Mw = 59,038.

Example 21 Preparation of polyamic acid ester resin (C-1)

A 300 ml four-necked flask equipped with a stirrer was charged with 2.00 g (18.50 mmol) of p-PDA, 1.2269 g (4.624 mmol) of DA-D, 167.67 g of NMP, 4.21 g (53.26 mmol) of triethylamine were added and dissolved by stirring. Next, while stirring the diamine solution, 7.216 g (22.19 mmol) of 1,3 DM-CBDE-Cl was added, and the mixture was allowed to react for 4 hours under water. The obtained polyamic acid ester solution was added to 882 g of water with stirring, and the precipitated white precipitate was collected by filtration. Subsequently, this was washed once with 889 g of water, once with 882 g of ethanol and three times with 221 g of ethanol, and dried to obtain 7.22 g of a white polyamic acid ester resin powder (C-1). The yield was 81.8%. The molecular weight of the polyamic acid ester was Mn = 20,469 and Mw = 40,025.

Example 22 Preparation of polyamic acid ester resin (C-2)

A 300 ml four-necked flask equipped with a stirrer was charged with 2.00 g (18.50 mmol) of p-PDA, 1.2961 g (4.624 mmol) of DA-B, 168.98 g of NMP, 4.21 g (53.26 mmol) of triethylamine were added and dissolved by stirring. Next, while stirring the diamine solution, 7.216 g (22.19 mmol) of 1,3 DM-CBDE-Cl was added, and the mixture was allowed to react for 4 hours under water. The obtained polyamic acid ester solution was added to 889 g of water while stirring, and the precipitated white precipitate was collected by filtration. Subsequently, this was washed once with 889 g of water, once with 889 g of ethanol, and three times with 222 g of ethanol, followed by drying to obtain 7.79 g of a white polyamic acid ester resin powder (C-2). The yield was 87.6%. The molecular weight of the polyamic acid ester was Mn = 20,886 and Mw = 45,830.

Example 23 Preparation of polyamic acid ester resin (C-3)

In a 300 ml four-necked flask equipped with a stirrer, 1.50 g (13.87 mmol) of p-PDA, 1.597 g (3.468 mmol) of DA-E, 65.26 g of NMP, 3.13 g (39.53 mmol) of p-toluenesulfonic acid were added and dissolved by stirring. Next, while stirring the diamine solution, 5.3556 g (16.47 mmol) of 1,3 DM-CBDE-Cl was added, and the mixture was reacted for 4 hours at a low temperature. After 4 hours, 72.51 g of NMP was added to the reaction solution, and the mixture was stirred at room temperature (20 ° C) for 15 minutes. The resulting polyamic acid ester solution was added to 725 g of water with stirring, and the precipitated white precipitate was collected by filtration. Subsequently, this was washed once with 725 g of water, once with 725 g of ethanol and three times with 181 g of ethanol, followed by drying to obtain 3.76 g of a white polyamic acid ester resin powder (C-3). The yield was 51.8%. The molecular weight of the polyamic acid ester was Mn = 20,525 and Mw = 43,395.

Example 24 Preparation of polyamic acid ester resin (C-4)

In a 300 ml four-necked flask equipped with a stirrer, 2.50 g (23.11 mmol) of p-PDA, 1.3715 g (5.80 mmol) of DA-A, 97.16 g of NMP, 5.21 g (65.89 mmol) were added and dissolved by stirring. Next, while stirring the diamine solution, 8.926 g (27.45 mmol) of 1,3 DM-CBDE-Cl) was added, and the reaction was carried out at a low temperature for 4 hours. After 4 hours, 107.95 g of NMP was added to the reaction solution, and the mixture was stirred at room temperature (20 DEG C) for 15 minutes. The obtained polyamic acid ester solution was added to 1080 g of water while stirring, and the precipitated white precipitate was collected by filtration. Subsequently, this was washed once with 1080 g of water, once with 1080 g of ethanol and three times with 270 g of ethanol, and dried to obtain 9.17 g of a white polyamic acid ester resin powder (C-4). The yield was 85.2%. The molecular weight of the polyamic acid ester was Mn = 17,573 and Mw = 37,258.

Example 25 Preparation of polyamic acid ester resin (C-5)

In a 300 ml four-necked flask equipped with a stirrer, 1,420 g (13.13 mmol) of p-PDA, 1.3872 g (3.283 mmol) of DA-H, 59.54 g of NMP, 2.87 g (36.24 mmol) was added and dissolved by stirring. Then, while stirring the diamine solution, 4.9099 g (15.10 mmol) of 1,3 DM-CBDE-Cl was added, and the reaction was carried out for 4 hours under the following conditions. After 4 hours, 66.15 g of NMP was added to the reaction solution, and the mixture was stirred at room temperature (20 ° C) for 15 minutes. The obtained polyamic acid ester solution was added to 662 g of water with stirring, and the precipitated white precipitate was collected by filtration. Subsequently, this was washed once with 662 g of water, once with 662 g of ethanol, and three times with 165 g of ethanol, followed by drying to obtain 5.11 g of a white polyamic acid ester resin powder (C-5). The yield was 77.3%. The molecular weight of the polyamic acid ester was Mn = 14,724 and Mw = 27,150.

&Lt; Comparative Synthesis Example 2 > Preparation of polyamic acid ester resin (D-1)

0.699 g (64.64 mmol) of p-PDA, 427.1 g of NMP, and 11.65 g (147.38 mmol) of pyridine as a base were put in a 50 ml four-necked flask equipped with a stirrer, and stirred . Then, while stirring the diamine solution, 19.9657 g (61.41 mmol) of 1,3 DM-CBDE-Cl was added, and the mixture was reacted for 4 hours at a low temperature. The obtained polyamic acid ester solution was added to 2248 g of water with stirring, and the precipitated white precipitate was collected by filtration. Subsequently, this was washed once with 2248 g of water, once with 2248 g of ethanol and three times with 562 g of ethanol, and dried to obtain 22.10 g of a white polyamic acid ester resin (D-1) powder. The yield was 98.4%. The molecular weight of the polyamic acid ester was Mn = 16,813 and Mw = 38,585.

Example 26 Preparation of liquid crystal aligning agent (A-4)

6.18 g of the polyamic acid (A-4) solution obtained in Example 19 was put in a 50 ml Erlenmeyer flask containing an agitator, and 1.60 g of NMP and 1.99 g of BCS were added and stirred with a magnetic stirrer for 30 minutes, (A-4) was obtained.

Example 27 Preparation of liquid crystal aligning agent (A-5)

5.87 g of the polyamic acid (A-5) solution obtained in Example 20 was added to a 50 ml Erlenmeyer flask containing an agitator, and 1.15 g of NMP and 1.76 g of BCS were added and stirred for 30 minutes using a magnetic stirrer to obtain liquid crystal alignment (A-5) was obtained.

Example 28 Preparation of liquid crystal aligning agent (C-1)

1.65 g of the polyamic acid ester resin powder obtained in Example 21 was taken in an Erlenmeyer flask, and 14.95 g of? -BL was added and dissolved by stirring at room temperature for 24 hours. 5.43 g of? -BL and 5.55 g of BCS were added to this solution, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (C-1).

Example 29: Preparation of liquid crystal aligning agent (C-2)

0.733 g of the polyamic acid ester resin powder obtained in Example 22 was taken in an Erlenmeyer flask and 6.60 g of? -BL was added and dissolved by stirring at room temperature for 24 hours. 2.48 g of? -BL and 2.45 g of BCS were added to this solution, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (C-2).

&Lt; Example 30 > Preparation of liquid crystal aligning agent (C-3)

0.907 g of the polyamic acid ester resin powder obtained in Example 23 was taken in an Erlenmeyer flask, and 8.18 g of? BL was added and dissolved by stirring at room temperature for 24 hours. 3.06 g of? -BL and 3.04 g of BCS were added to this solution, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (C-3).

Example 31 Preparation of liquid crystal aligning agent (C-4)

0.802 g of the polyamic acid ester resin powder obtained in Example 24 was taken in an Erlenmeyer flask, and 7.23 g of? BL was added and dissolved by stirring at room temperature for 24 hours. 2.78 g of? -BL and 2.68 g of BCS were added to this solution, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (C-4).

Example 32 Preparation of liquid crystal aligning agent (C-5)

0.755 g of the polyamic acid ester resin powder obtained in Example 25 was taken in an Erlenmeyer flask and 7.57 g of? BL was added and dissolved by stirring at room temperature for 24 hours. 2.65 g of? -BL and 2.55 g of BCS were added to this solution, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (C-5).

&Lt; Comparative Example 4 > Preparation of liquid crystal aligning agent (D-1)

1.02 g of the polyamic acid ester resin powder obtained in Comparative Synthesis Example 2 was taken in an Erlenmeyer flask and 9.21 g of DMF was added and dissolved by stirring at room temperature for 24 hours. 3.29 g of? -BL and 3.39 g of BCS were added to this solution, and the mixture was stirred for 30 minutes by a magnetic stirrer to obtain a liquid crystal aligning agent (D-1).

&Lt; Example 33 >

A polyimide film was prepared and rubbed in the same manner as in Example 11 except that the liquid crystal aligning agent (A-4) obtained in Example 26 was used. As a result of observing the surface state of the polyimide film, scratches due to rubbing were observed, but it was milder than that of Comparative Example 2. [ No peeling off of the polyimide film and peeling of the polyimide film were observed.

&Lt; Example 34 >

A polyimide film was prepared and rubbed in the same manner as in Example 11 except that the liquid crystal aligning agent (A-5) obtained in Example 27 was used. As a result of observing the surface state of the polyimide film, scratches by rubbing, cutting residue of the polyimide film, and peeling of the polyimide film were not observed.

&Lt; Example 35 >

The liquid crystal aligning agent (C-1) obtained in Example 28 was filtered with a filter of 1.0 占 퐉 and then spin-coated on a glass substrate with a transparent electrode attached thereto. The substrate was dried on a hot plate at 80 占 폚 for 5 minutes, To obtain a polyimide film having a thickness of 100 nm. The surface state of the polyimide film was observed after rubbing the polyimide film with a rayon bath (roll diameter 120 mm, rotation speed 1000 rpm, moving speed 20 mm / sec, indentation amount 0.4 mm), scratches by rubbing, No peeling off of the mid film and peeling of the polyimide film were observed.

&Lt; Example 36 >

A polyimide film was prepared and rubbed in the same manner as in Example 35 except that the liquid crystal aligning agent (C-2) obtained in Example 29 was used. As a result of observing the surface state of the polyimide film, scratches by rubbing, cutting residue of the polyimide film, and peeling of the polyimide film were not observed.

&Lt; Example 37 >

A polyimide film was prepared and rubbed in the same manner as in Example 35 except that the liquid crystal aligning agent (C-3) obtained in Example 30 was used. As a result of observing the surface state of the polyimide film, scratches due to rubbing and cutting debris of the polyimide film were observed, but the results were milder than those of Comparative Example 5 described later. No peeling of the polyimide was observed.

&Lt; Example 38 >

A polyimide film was prepared and rubbed in the same manner as in Example 35 except that the liquid crystal aligning agent (C-4) obtained in Example 31 was used. As a result of observing the surface state of the polyimide film, scratches due to rubbing were observed, but it was milder than the result of Comparative Example 5 described later. No peeling off of the polyimide film and peeling of the polyimide film were observed.

&Lt; Example 39 >

A polyimide film was prepared and rubbed in the same manner as in Example 35 except that the liquid crystal aligning agent (C-5) obtained in Example 32 was used. As a result of observing the surface state of the polyimide film, scratches by rubbing, cutting residue of the polyimide film, and peeling of the polyimide film were not observed.

&Lt; Comparative Example 5 &

A polyimide film was prepared and rubbed in the same manner as in Example 35 except that the liquid crystal aligning agent (D-1) obtained in Comparative Example 4 was used. As a result of observing the surface state of the polyimide film, scratches due to rubbing, cutting debris of the polyimide film, and peeling of the polyimide film were observed.

&Lt; Example 40 >

A twisted nematic liquid crystal cell was produced in the same manner as in Example 14 except that the liquid crystal aligning agent (A-4) obtained in Example 26 was used, and the alignment state of the liquid crystal was confirmed, the voltage holding ratio and the ion density were measured Respectively. As a result of observing the alignment state of the liquid crystal cell with a polarizing microscope, it was confirmed that uniform orientation without defects was observed. The voltage holding ratio was measured for this liquid crystal cell, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 1 described later.

&Lt; Example 41 >

A twisted nematic liquid crystal cell was produced in the same manner as in Example 14 except that the liquid crystal aligning agent (A-5) obtained in Example 27 was used, and the alignment state of the liquid crystal was confirmed, the voltage holding ratio and the ion density were measured Respectively. As a result of observing the alignment state of the liquid crystal cell with a polarizing microscope, it was confirmed that uniform orientation without defects was observed. The voltage holding ratio was measured for this liquid crystal cell, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 1 described later.

&Lt; Example 42 >

The liquid crystal aligning agent (C-1) obtained in Example 28 was filtered with a filter of 1.0 占 퐉 and then spin-coated on a glass substrate with a transparent electrode attached thereto. The substrate was dried on a hot plate at 80 占 폚 for 5 minutes, To obtain a polyimide film having a thickness of 100 nm. This polyimide membrane was subjected to ultrasonic irradiation for 1 minute in a rinsing bath (roll diameter 120 mm, rotation speed 1000 rpm, moving speed 20 mm / sec, indentation amount 0.4 mm) and pure water for 1 minute, And then dried at 80 DEG C for 10 minutes to obtain a substrate having a liquid crystal alignment film attached thereto. Two such substrates having liquid crystal alignment films were prepared, spacers having a size of 6 mu m were dispersed on the liquid crystal alignment film surface of one of the substrates, and the two substrates were assembled such that the rubbing directions of the two substrates were twisted from the antiparallel direction by 85 degrees, And the periphery was sealed to prepare an empty cell having a cell gap of 6 탆. A liquid crystal (MLC-2003, manufactured by Merck Co.) was vacuum-injected into the empty cell at room temperature, and the injection port was sealed to obtain a twisted nematic liquid crystal cell. As a result of observing the alignment state of the liquid crystal cell with a polarizing microscope, it was confirmed that uniform orientation without defects was observed. The voltage holding ratio was measured for this liquid crystal cell, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 1 described later.

&Lt; Example 43 >

A twisted nematic liquid crystal cell was produced in the same manner as in Example 42 except that the liquid crystal aligning agent (C-2) obtained in Example 29 was used, and the alignment state of the liquid crystal, the voltage holding ratio and the ion density were measured Respectively. As a result of observing the alignment state of the liquid crystal cell with a polarizing microscope, it was confirmed that uniform orientation without defects was observed. The voltage holding ratio was measured for this liquid crystal cell, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 1 described later.

&Lt; Example 44 >

A twisted nematic liquid crystal cell was produced in the same manner as in Example 42 except that the liquid crystal aligning agent (C-3) obtained in Example 30 was used to confirm the alignment state of the liquid crystal, measure the voltage holding ratio and ion density Respectively. As a result of observing the alignment state of the liquid crystal cell with a polarizing microscope, it was confirmed that uniform orientation without defects was observed. The voltage holding ratio was measured for this liquid crystal cell, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 1 described later.

&Lt; Example 45 >

A twisted nematic liquid crystal cell was produced in the same manner as in Example 42 except that the liquid crystal aligning agent (C-4) obtained in Example 31 was used to confirm the alignment state of the liquid crystal, and to measure the voltage holding ratio and ion density Respectively. As a result of observing the alignment state of the liquid crystal cell with a polarizing microscope, it was confirmed that uniform orientation without defects was observed. The voltage holding ratio was measured for this liquid crystal cell, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 1 described later.

&Lt; Example 46 >

A twisted nematic liquid crystal cell was produced in the same manner as in Example 42 except that the liquid crystal aligning agent (C-5) obtained in Example 32 was used to confirm the alignment state of the liquid crystal, measurement of the voltage holding ratio and ion density Respectively. As a result of observing the alignment state of the liquid crystal cell with a polarizing microscope, it was confirmed that uniform orientation without defects was observed. The voltage holding ratio was measured for this liquid crystal cell, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 1 described later.

&Lt; Comparative Example 6 >

A twisted nematic liquid crystal cell was produced in the same manner as in Example 42 except that the liquid crystal aligning agent (D-1) obtained in Comparative Example 4 was used, and the alignment state of the liquid crystal was confirmed, the voltage holding ratio and the ion density were measured Respectively. As a result of observing the alignment state of the liquid crystal cell with a polarizing microscope, it was confirmed that uniform orientation without defects was observed. The voltage holding ratio was measured for this liquid crystal cell, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 1 described later.

Table 1 shows the results of measurement of voltage holding ratio and ion density in Examples 14 to 16, Examples 40 to 46, Comparative Examples 3 and 6.

&Lt; Example 47 >

The liquid crystal aligning agent (A-1) obtained in Example 8 was filtered with a filter of 1.0 占 퐉, spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at 80 占 폚 for 5 minutes, Followed by baking for 20 minutes to obtain a polyimide film having a thickness of 100 nm. Ultraviolet rays of 254 nm were irradiated at 1.0 J / cm 2 through the polarizing plate to the coated film surface to obtain a substrate having a liquid crystal alignment film attached thereto. Two such substrates having the liquid crystal alignment film attached thereto were prepared, spacers having a size of 6 mu m were dispersed on the liquid crystal alignment film surface of one of the substrates, and the two substrates were combined in such a manner that the alignment directions of the two substrates were twisted by 85 degrees from parallel. And the periphery was sealed to prepare an empty cell having a cell gap of 6 탆. A liquid crystal (MLC-2003, manufactured by Merck Co.) was vacuum-injected into the empty cell at room temperature, and the injection port was sealed to obtain a twisted nematic liquid crystal cell. As a result of observing the alignment state of the liquid crystal cell with a polarizing microscope, it was confirmed that uniform orientation without defects was observed. The voltage holding ratio was measured for this liquid crystal cell, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 described later.

&Lt; Example 48 >

A twisted nematic liquid crystal cell was produced in the same manner as in Example 47 except that the liquid crystal aligning agent (A-2) obtained in Example 9 was used, and the alignment state of the liquid crystal was confirmed, the voltage holding ratio and the ion density were measured Respectively. As a result of observing the alignment state of the liquid crystal cell with a polarizing microscope, it was confirmed that uniform orientation without defects was observed. The voltage holding ratio was measured for this liquid crystal cell, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 described later.

&Lt; Example 49 >

A twisted nematic liquid crystal cell was produced in the same manner as in Example 47 except that the liquid crystal aligning agent (A-3) obtained in Example 10 was used to confirm the alignment state of the liquid crystal, and to measure the voltage holding ratio and ion density Respectively. As a result of observing the alignment state of the liquid crystal cell with a polarizing microscope, it was confirmed that uniform orientation without defects was observed. The voltage holding ratio was measured for this liquid crystal cell, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 described later.

&Lt; Example 50 >

A twisted nematic liquid crystal cell was produced in the same manner as in Example 47 except that the liquid crystal aligning agent (A-4) obtained in Example 26 was used to confirm the alignment state of the liquid crystal, and to measure the voltage holding ratio and ion density Respectively. As a result of observing the alignment state of the liquid crystal cell with a polarizing microscope, it was confirmed that uniform orientation without defects was observed. The voltage holding ratio was measured for this liquid crystal cell, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 described later.

&Lt; Example 51 >

A twisted nematic liquid crystal cell was produced in the same manner as in Example 47 except that the liquid crystal aligning agent (A-5) obtained in Example 27 was used, and the alignment state of the liquid crystal was confirmed, the voltage holding ratio and the ion density were measured Respectively. As a result of observing the alignment state of the liquid crystal cell with a polarizing microscope, it was confirmed that uniform orientation without defects was observed. The voltage holding ratio was measured for this liquid crystal cell, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 described later.

&Lt; Comparative Example 7 &

A twisted nematic liquid crystal cell was produced in the same manner as in Example 47 except that the liquid crystal aligning agent (B-1) obtained in Comparative Example 1 was used to confirm the alignment state of the liquid crystal, measure the voltage holding ratio and ion density Respectively. As a result of observing the alignment state of the liquid crystal cell with a polarizing microscope, it was confirmed that uniform orientation without defects was observed. The voltage holding ratio was measured for this liquid crystal cell, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 described later.

&Lt; Example 52 >

The liquid crystal aligning agent (C-1) obtained in Example 28 was filtered with a filter of 1.0 占 퐉 and then spin-coated on a glass substrate with a transparent electrode attached thereto. The substrate was dried on a hot plate at 80 占 폚 for 5 minutes, To obtain a polyimide film having a thickness of 100 nm. Ultraviolet rays of 254 nm were irradiated at 1.0 J / cm 2 through the polarizing plate to the coated film surface to obtain a substrate having a liquid crystal alignment film attached thereto. Two such substrates having the liquid crystal alignment film attached thereto were prepared, spacers having a size of 6 mu m were dispersed on the liquid crystal alignment film surface of one of the substrates, and the two substrates were combined in such a manner that the alignment directions of the two substrates were twisted by 85 degrees from parallel. And the periphery was sealed to prepare an empty cell having a cell gap of 4 탆. A liquid crystal (MLC-2003, manufactured by Merck Co.) was vacuum-injected into the empty cell at room temperature, and the injection port was sealed to obtain a twisted nematic liquid crystal cell. As a result of observing the alignment state of the liquid crystal cell with a polarizing microscope, it was confirmed that uniform orientation without defects was observed. The voltage holding ratio was measured for this liquid crystal cell, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 described later.

&Lt; Example 53 >

A twisted nematic liquid crystal cell was produced in the same manner as in Example 52 except that the liquid crystal aligning agent (C-2) obtained in Example 29 was used, and the alignment state of the liquid crystal was confirmed, the voltage holding ratio and the ion density were measured Respectively. As a result of observing the alignment state of the liquid crystal cell with a polarizing microscope, it was confirmed that uniform orientation without defects was observed. The voltage holding ratio was measured for this liquid crystal cell, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 described later.

<Example 54>

A twisted nematic liquid crystal cell was produced in the same manner as in Example 52 except that the liquid crystal aligning agent (C-3) obtained in Example 30 was used, and the alignment state of the liquid crystal was confirmed, the voltage holding ratio and the ion density were measured Respectively. As a result of observing the alignment state of the liquid crystal cell with a polarizing microscope, it was confirmed that uniform orientation without defects was observed. The voltage holding ratio was measured for this liquid crystal cell, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 described later.

&Lt; Example 55 >

A twisted nematic liquid crystal cell was produced in the same manner as in Example 52 except that the liquid crystal aligning agent (C-4) obtained in Example 31 was used, and the alignment state of the liquid crystal was confirmed, the voltage holding ratio and the ion density were measured Respectively. As a result of observing the alignment state of the liquid crystal cell with a polarizing microscope, it was confirmed that uniform orientation without defects was observed. The voltage holding ratio was measured for this liquid crystal cell, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 described later.

&Lt; Example 56 >

A twisted nematic liquid crystal cell was produced in the same manner as in Example 52 except that the liquid crystal aligning agent (C-5) obtained in Example 32 was used, and the alignment state of the liquid crystal was confirmed, the voltage holding ratio and the ion density were measured Respectively. As a result of observing the alignment state of the liquid crystal cell with a polarizing microscope, it was confirmed that uniform orientation without defects was observed. The voltage holding ratio was measured for this liquid crystal cell, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 described later.

&Lt; Comparative Example 8 >

A twisted nematic liquid crystal cell was produced in the same manner as in Example 52 except that the liquid crystal aligning agent (D-1) obtained in Comparative Example 4 was used, and the alignment state of the liquid crystal was confirmed, the voltage holding ratio and the ion density were measured Respectively. As a result of observing the alignment state of the liquid crystal cell with a polarizing microscope, it was confirmed that uniform orientation without defects was observed. The voltage holding ratio was measured for this liquid crystal cell, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 described later.

Table 2 shows the results of measurement of voltage holding ratio and ion density in Examples 47 to 56 and Comparative Examples 7 to 8.

Example 57 Preparation of polyamic acid ester resin (E-1)

In a 300 ml four-necked flask equipped with a stirrer, 1.50 g (13.87 mmol) of p-PDA, 0.4090 g (1.541 mmol) of DA-B, 107.47 g of NMP, 2.82 g (35.67 mmol) was added and dissolved by stirring. Next, while stirring the diamine solution, 4.83 g (14.86 mmol) of 1,3 DMCBDE-Cl was added and reacted for 4 hours under water cooling. The obtained polyamic acid ester solution was added to 566 g of water while stirring, and the precipitated white precipitate was collected by filtration. Subsequently, this was washed once with 566 g of water, once with 566 g of ethanol and three times with 141 g of ethanol, and dried to obtain 4.92 g of a white polyamic acid ester resin (E-1) powder. The yield was 87.0%. The molecular weight of the polyamic acid ester was Mn = 17,828 and Mw = 31,832.

&Lt; Example 58 >

1.02 g of the polyamic acid ester resin powder obtained in Synthesis Example 57 was placed in an Erlenmeyer flask and further 9.18 g of? BL was added and dissolved by stirring at room temperature for 24 hours. To this solution was added 1.03 g of a 1.0 mass% γ-butyl lactone solution of 3-glycidoxypropylmethyldiethoxysilane (abbreviated as GPS hereinafter) as a silane coupling agent, and the mixture was heated and stirred at 50 ° C. for 24 hours. To the obtained solution, 2.41 g of? -Bz and 3.41 g of BCS were added and stirred for 30 minutes by a magnetic stirrer to prepare a polyamic acid ester solution.

To 5.75 g of the above-mentioned polyamic acid ester solution, 0.0906 g (0.02 mmol) of N-α, N-ω1 and N-ω2-tri-t-butoxycarbonyl-L-arginine (hereinafter abbreviated as Boc-Arg) (0.1 mol equivalent based on 1 mol of the amic ester group) was added and stirred at room temperature for 30 minutes to completely dissolve Boc-Arg to obtain the liquid crystal aligning agent (E-1a) of the present invention.

&Lt; Comparative Example 9 &

1.04 g of the polyamic acid ester resin powder obtained in Comparative Synthesis Example 2 was placed in an Erlenmeyer flask, and further 9.35 g of DMF was added and dissolved by stirring at room temperature for 24 hours. To this solution was added 1.07 g of a 1.0 mass% gamma -butyllactone solution of GPS as a silane coupling agent, and the mixture was heated and stirred at 50 DEG C for 24 hours. 2.71 g of? -BL and 3.06 g of BCS were added to the obtained solution, and the mixture was stirred with a magnetic stirrer for 30 minutes to prepare a polyamic acid ester solution.

To 5.42 g of the above-mentioned polyamic acid ester solution was added 0.0775 g of Boc-Arg as an imidization accelerator (0.1 mol equivalent based on 1 mol of the amic ester group), and the mixture was stirred at room temperature for 30 minutes to completely dissolve Boc-Arg, Thereby obtaining a liquid crystal aligning agent (D-1a).

<Example 59>

The liquid crystal aligning agent (E-1a) obtained in Example 58 was filtered with a filter of 1.0 占 퐉, spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at 80 占 폚 for 5 minutes, Followed by baking for 20 minutes to obtain a polyimide film having a thickness of 100 nm. Ultraviolet rays of 254 nm were irradiated at 1.0 J / cm 2 through the polarizing plate to the coated film surface to obtain a substrate having a liquid crystal alignment film attached thereto. Two such substrates having the liquid crystal alignment film attached thereto were prepared, spacers having a size of 4 mu m were dispersed on the liquid crystal alignment film surface of one of the substrates, and the two substrates were combined in such a manner that the alignment directions of the two substrates were twisted by 85 degrees from parallel. And the periphery was sealed to prepare an empty cell having a cell gap of 4 탆. A liquid crystal (MLC-2041, manufactured by Merck) was vacuum-injected into the empty cell at room temperature, and the injection port was sealed to obtain a twisted nematic liquid crystal cell. As a result of observing the alignment state of the liquid crystal cell with a polarizing microscope, it was confirmed that uniform orientation without defects was observed. The voltage holding ratio was measured for this liquid crystal cell and then the ion density was measured. As a result, the voltage holding ratio was found to be 99.4% at a temperature of 23 占 폚, 98.6% at a temperature of 60 占 폚, 95.3% at a temperature of 90 占 폚, Was 85 pC / cm &lt; 2 &gt; at 23 DEG C and 507 pC / cm &lt; 2 &gt;

&Lt; Comparative Example 10 &

A twisted nematic liquid crystal cell was produced in the same manner as in Example 59 except that the liquid crystal aligning agent (D-1a) obtained in Comparative Example 9 was used. As a result of observing the alignment state of the liquid crystal cell with a polarizing microscope, it was confirmed that uniform orientation without defects was observed. The voltage holding ratio was measured for this liquid crystal cell and then the ion density was measured. As a result, the voltage holding ratio was found to be 99.2% at 23 ° C, 98.1% at 60 ° C and 94.9% at 90 ° C, Was 159 pC / cm 2 at 23 ° C and 644 pC / cm 2 at 60 ° C.

From the above results, it was confirmed that the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention becomes a liquid crystal alignment film excellent in mechanical strength without rubbing scratches due to rubbing treatment, even if no crosslinking agent or the like is added.

It has also been confirmed that the liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention is a liquid crystal display element having a high voltage holding ratio at a high temperature and a low ion density and excellent reliability.

Even when the liquid crystal alignment film of the present invention is irradiated with polarized ultraviolet light and subjected to a light distribution treatment to impart a liquid crystal aligning ability, the liquid crystal display device having a liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention, It has been confirmed that the liquid crystal display device is excellent in reliability with a high retention ratio and low ion density.

From the comparison between Example 59 and Comparative Example 10, it was confirmed that even when the silane coupling agent and other additives were added to the liquid crystal aligning agent of the present invention, the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention had a high voltage holding ratio , It was confirmed that a liquid crystal display element excellent in reliability with a low ion density can be obtained.

By using the liquid crystal aligning agent of the present invention, it is possible to obtain a liquid crystal alignment film excellent in mechanical strength and hardly causing rubbing scratches due to rubbing treatment, and when the liquid crystal alignment film is used, a liquid crystal display element with less display defects can be obtained. Further, by using the liquid crystal alignment film of the present invention, the liquid crystal aligning agent of the present invention can provide a liquid crystal display device having a high voltage maintaining ratio, a low ion density and an excellent reliability even at high temperature, It can be preferably used as a liquid crystal alignment film which is a member of a device.

The polyimide precursor and the polyimide of the present invention contain a primary or secondary aliphatic amine protected by a Boc group and allow the intermolecular crosslinking reaction to proceed by eliminating the Boc group at the time of firing to provide a polyimide film having excellent mechanical strength The polyimide film can be preferably used for a protective film or for use in an electronic device, particularly as a liquid crystal alignment film.

The diamine compound of the present invention has a structure containing a primary or secondary aliphatic amine protected with a Boc group and is optimal as a raw material for obtaining the polyimide precursor and polyimide of the present invention and a liquid crystal alignment film using the same.

The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2008-278317 filed on October 29, 2008 are hereby incorporated herein by reference as the disclosure of the present specification.

Claims (1)

A diamine compound represented by the following formulas (A) to (F).
[Chemical Formula 18]