KR101820981B1 - Liquid crystal alignment agent containing polyamic acid ester, and liquid crystal alignment film - Google Patents

Abstract

(식 중, X₁ 은 4 가의 유기기이고, Y₁ 은 2 가의 유기기이며, R₁ 은 탄소수 1 ∼ 5 의 알킬기이고, A₁ 및 A₂ 는 각각 독립적으로 수소 원자, 또는 치환기를 가져도 되는 탄소수 1 ∼ 20 의 알킬기, 알케닐기, 알킬기이다)
(조건) 식 (1) 의 X₁, Y₁, A₁, A₂ 중 적어도 1 개가 하기 식 (2) 및 (3) 으로 이루어지는 군에서 선택되는 적어도 1 종류의 구조의 치환기를 갖고 있다.

(식 (2) 및 (3) 의 D₁ 및 D₂ 는 각각 열에 의해 수소 원자로 치환되는 보호기이다. B₁ 은 단결합 또는 2 가의 유기기이다. 단, 식 (3) 중의 에스테르기가 결합하는 원자는 탄소 원자이다)
(B) 성분 : 하기 식 (4) 로 나타내는 반복 단위를 갖는 폴리아믹산.

(식 중, X₂ 는 4 가의 유기기이고, Y₂ 는 2 가의 유기기이며, A₁ 및 A₂ 는 식 (1) 의 것과 동일한 정의이다)A liquid crystal aligning agent characterized by containing the following components (A) and (B).
Component (A): A polyamic acid ester having a repeating unit represented by the following formula (1) and satisfying the following conditions.

(Wherein, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, R ₁ is may have a hydrogen atom, or a substituent in each alkyl group, A ₁ and A ₂ independently of 1 to 5 carbon atoms An alkyl group, an alkenyl group, or an alkyl group having 1 to 20 carbon atoms)
(Condition) At least one of X ₁ , Y ₁ , A ₁ and A ₂ in the formula (1) has at least one substituent of the structure selected from the group consisting of the following formulas (2) and (3).

(In the formulas (2) and (3), D ₁ and D ₂ are each a protecting group substituted by a hydrogen atom by a column, and B ₁ is a single bond or a divalent organic group. Is a carbon atom)
Component (B): Polyamic acid having a repeating unit represented by the following formula (4).

(Wherein, X ₂ is a tetravalent organic group, Y ₂ is a divalent organic group, and A ₁ and A ₂ have the same definitions as in formula (1)

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal aligning agent and a liquid crystal alignment film containing a polyamic acid ester,

The present invention relates to a liquid crystal aligning agent containing a polyamic acid ester and a polyamic acid having thermal deterioration protecting groups, and a liquid crystal alignment film obtained from the liquid crystal aligning agent.

In a liquid crystal display device 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 device. As the liquid crystal alignment film, a polyimide-based liquid crystal alignment film obtained by applying a liquid crystal aligning agent mainly composed of a polyimide precursor such as polyamic acid (polyamic acid) or a soluble polyimide solution to a glass substrate and then firing is mainly used.

From the demand for suppressing the lowering of the contrast of the liquid crystal display element and the reduction of the afterimage phenomenon accompanied by the high definition of the liquid crystal display element, the liquid crystal alignment film is required to exhibit excellent liquid crystal alignability and stable expression of the tilt angle, Characteristics such as suppression of residual image caused by driving, small residual charge when a direct-current voltage is applied, and / or a rapid relaxation of the accumulated residual charge due to a direct-current voltage have become increasingly important.

In the polyimide-based liquid crystal alignment film, various proposals have been made in order to meet such a demand. For example, a liquid crystal aligning agent containing a tertiary amine having a specific structure is used in addition to a polyamic acid or an imide group-containing polyamic acid as a liquid crystal alignment film having a short time until a residual image caused by a DC voltage disappears (See, for example, Patent Document 1) or a liquid crystal aligning agent containing a soluble polyimide in which a specific diamine compound having a pyridine skeleton or the like is used as a raw material (see, for example, Patent Document 2) . It is also possible to use a liquid crystal alignment film having a high voltage holding ratio and a short time until the afterimage caused by the DC voltage disappears as a liquid crystal alignment film containing a compound containing one carboxylic acid group in the molecule in addition to polyamic acid or an imidized polymer thereof, A liquid crystal aligning agent containing a very small amount of a compound selected from the group consisting of a compound containing one carboxylic anhydride group in the molecule and a compound containing one tertiary amino group in the molecule (see, for example, Patent Document 3 ) Has been proposed.

Also disclosed is a liquid crystal alignment film having excellent liquid crystal alignability, high voltage maintaining ratio, low residual image, excellent reliability, and exhibiting a high pretilt angle, and is a liquid crystal alignment film having a tetracarboxylic dianhydride having a specific structure and tetracarboxylic There is known a polyamic acid obtained from an acid dianhydride and a specific diamine compound or a liquid crystal aligning agent containing the imidized polymer (see, for example, Patent Document 4). As a method for suppressing the afterimage due to the AC driving which occurs in the liquid crystal display element of the transversal electric field driving system, there is a method of using a specific liquid crystal alignment film having good liquid crystal alignability and high interaction with liquid crystal molecules Reference 5) has been proposed.

However, in recent years, liquid crystal televisions having a large screen and a large screen have become main subjects, so that the demand for after-images has become stricter, and characteristics capable of enduring long-term use in a severe use environment have been demanded. In addition to this, a liquid crystal alignment film to be used needs to have higher reliability than the conventional ones, and various characteristics of the liquid crystal alignment film are required not only to have good initial characteristics but also to maintain good properties even after long- .

On the other hand, it has been reported that the polyamic acid ester as the polymer component constituting the polyimide-based liquid crystal aligning agent does not cause a decrease in the molecular weight due to the heat treatment at the time of imidation thereof, and thus is excellent in the orientation stability and reliability of the liquid crystal (See Patent Document 6). However, the polyamic acid ester generally has a high volume resistivity and a large residual charge when a direct current voltage is applied. Therefore, a method for improving the characteristics of a polyimide-based liquid crystal aligning agent containing such a polyamic acid ester It was not yet known.

Japanese Patent Application Laid-Open No. 9-316200 Japanese Patent Application Laid-Open No. 10-104633 Japanese Patent Application Laid-Open No. 8-76128 Japanese Patent Application Laid-Open No. 9-138414 Japanese Laid-Open Patent Publication No. 11-38415 Japanese Patent Application Laid-Open No. 2003-26918

The present invention focuses on a liquid crystal aligning agent blended with a polyamic acid ester and a polyamic acid excellent in electrical properties as a method for improving the properties of the liquid crystal aligning agent containing the polyamic acid ester. However, a liquid crystal alignment film obtained from a liquid crystal aligning agent blended with such a polyamic acid ester and a polyamic acid is not satisfactory in terms of liquid crystal alignability and electric characteristics.

That is, a liquid crystal alignment film obtained from a liquid crystal aligning agent containing a polyamic acid ester and a polyamic acid causes a whitening phenomenon, and furthermore, the voltage holding ratio when the film is used at a high temperature, the after- In addition, there arises a problem such as occurrence of residual image due to AC driving.

An object of the present invention is to provide a liquid crystal aligning agent containing a polyamic acid ester and a polyamic acid, which is excellent in both liquid crystal alignability and electrical properties, and which can provide a transparent liquid crystal alignment film free from opacity.

According to the study by the present inventors, the liquid crystal alignment film formed of a liquid crystal aligning agent containing a polyamic acid ester and a polyamic acid was analyzed, and it was confirmed that fine unevenness was formed on the film surface. However, it has been found that the fine irregularities formed on the surface of the film can be remarkably suppressed by using a polyamic acid ester having a specific structure having a functional group substituted by a hydrogen atom by heat as described below, Further, it has been found that when the fine irregularities formed on the film surface are made small, the difficulty of the liquid crystal aligning agent containing the polyamic acid ester and the polyamic acid is solved.

Further, according to the knowledge of the present inventors, the polyamic acid ester having a specific structure having a functional group substituted with a hydrogen atom by the above-mentioned heat has good solubility in an organic solvent even when it is a high molecular weight, and the polyamic acid ester The liquid crystal aligning agent can be made to have a relatively low viscosity even when it is contained at a high concentration in an organic solvent. This makes it possible to easily manufacture a liquid crystal alignment film by, for example, an inkjet method, And it is easy to manufacture.

Thus, the present invention is based on the above findings, and has the following points.

1. A liquid crystal aligning agent which comprises the following components (A) and (B).

Component (A): A polyamic acid ester having a repeating unit represented by the following formula (1) and satisfying any of the following conditions (i) to (iii).

[Chemical Formula 1]

(Wherein, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, R ₁ is may have a hydrogen atom, or a substituent in each alkyl group, A ₁ and A ₂ independently of 1 to 5 carbon atoms An alkyl group, an alkenyl group, or an alkyl group having 1 to 20 carbon atoms)

(I) has at least one kind of monovalent or divalent substituent selected from the group consisting of the following formulas (2) and (3), and X ₁ and Y ₁ in formula (1)

(Ii) a monovalent or divalent substituent of at least one structure selected from the group consisting of A ₁ , A _2, or both of which are represented by the following formulas (2) and (3)

(Ⅲ) formula (1) X _1, Y _1, or both sides have the following formula (2) and (3) group and at least one structure 1 a or a divalent group of the substituents selected from the consisting of, and A ₁ , a has the structure 1 is the group and at least one or a divalent of the substituents selected from the consisting of a _second or both the following equations (2) and (3).

(2)

(In the formulas (2) and (3), D ₁ and D ₂ are each a protecting group substituted by a hydrogen atom by a column, and B ₁ is a single bond or a divalent organic group. Is a carbon atom)

Component (B): Polyamic acid having a repeating unit represented by the following formula (4).

(3)

(Wherein, X ₂ is a tetravalent organic group, Y ₂ is a divalent organic group, and A ₁ and A ₂ have the same definitions as in formula (1)

2. The liquid crystal aligning agent according to 1 above, wherein the content of the component (A) and the content of the component (B) are 1/9 to 9/1 by mass ratio (A / B).

3. The liquid crystal aligning agent according to 1 or 2 above, wherein the total content of the component (A) and the component (B) is 1 to 10 mass% with respect to the organic solvent.

4. The liquid crystal aligning agent according to any one of 1 to 3 above, wherein the protecting group D ₁ is at least one kind of group selected from the group consisting of a tert-butoxycarbonyl group and a 9-fluorenylmethoxycarbonyl group.

5. The liquid crystal aligning agent according to any one of 1 to 4 above, wherein the protecting group D ₂ is a tert-butyl group.

6. The liquid crystal aligning agent according to any one of 1 to 5 above, wherein the component (A) is a polyamic acid ester having a substituent represented by at least one structure selected from the group consisting of the following formulas (5) and (6).

[Chemical Formula 4]

(In the formula (5), B ₂ is a single bond or a divalent organic group, and each of R ₂ , R ₃ and R ₄ independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms)

[Chemical Formula 5]

(In the formula (6), B ₃ is a single bond or a divalent organic group, provided that the atom to which the t-butoxycarbonyl group specified in the formula (6) is bonded is a carbon atom)

7. In the component (A) formula (1) of the polyamic acid ester having a substituent represented by at least one kind of structure selected from the group consisting of structural formula (5) and (6) in the Y ₁ 1-6 The liquid crystal aligning agent described in any one of < 1 >

Wherein the component (A) is a polyamic acid ester having a substituent represented by at least one structure selected from the group consisting of A ₁ or A _{2 in} formula (1) or both of them in formulas (5) and (6) The liquid crystal aligning agent according to any one of 1 to 7 above.

9. The liquid crystal aligning agent according to any one of 1 to 8 above, wherein the component (A) is a polyamic acid ester of the structure represented by the following formula (7) in which Y ₁ in the formula (1)

[Chemical Formula 6]

(Wherein R ₅ is a single bond or a divalent organic group having 1 to 20 carbon atoms, and R ₆ is at least one structure selected from the group consisting of formulas (5) and (6) Lt; / RTI >

10. The liquid crystal aligning agent according to any one of the above items 1 to 9, wherein the component (A) has at least one structure selected from the group consisting of the structure represented by the following formula: wherein Y ₁ in the formula (1)

(7)

11. The liquid crystal display according to any one of the above-mentioned 1 to 10, wherein at least one of X ₁ and X ₂ in the formulas (1) and (4) is independently selected from the group consisting of structures represented by the following formulas: Orientation agent.

[Chemical Formula 8]

12. In the equation (4), Y ₂ is to the liquid crystal alignment according to any one of the at least one of the 1 to 11 selected from the group consisting of structures represented by the following formula.

[Chemical Formula 9]

13. A liquid crystal alignment film obtained by applying and firing the liquid crystal aligning agent according to any one of 1 to 12 above.

14. A liquid crystal alignment film obtained by coating and firing the liquid crystal aligning agent according to any one of 1 to 12 above, and further irradiating with polarized ultraviolet rays.

According to the present invention, it is possible to reduce fine irregularities on the surface of the liquid crystal alignment film to be obtained, to improve the characteristics of the interface between the liquid crystal and the liquid crystal alignment film, such as reduction of the afterimage due to the AC drive, And electrical characteristics such as residual are also improved, thereby providing a liquid crystal aligning agent improved in reliability.

The liquid crystal aligning agent according to the present invention has a comparatively low viscosity even when contained in an organic solvent at a high concentration. For example, a liquid crystal alignment film by an inkjet method can be easily produced, and a liquid crystal alignment film having a large thickness It has an advantage.

In the present invention, by using a polyamic acid ester having a specific structure having a functional group substituted with a hydrogen atom by heat, it is possible to reduce the fine irregularities formed on the surface of such a film and to provide a liquid crystal composition containing a polyamic acid ester and a polyamic acid Whether the difficult point of the alignment agent is solved is not necessarily clear, but it is considered as follows.

That is, in a liquid crystal alignment film formed by removing a solvent from a liquid crystal aligning agent in which a polyamic acid ester and a polyamic acid are dissolved in an organic solvent, a polyamic acid ester having a lower surface free energy than the polyamic acid is localized on the surface, As the mixed acid causes phase separation, an aggregate of polyamic acid is formed in the polyamic acid ester phase, or an aggregate of polyamic acid ester is formed in the polyamic acid phase, so that there are many fine irregularities on the film surface.

On the other hand, in the liquid crystal aligning agent of the present invention, when a solvent is removed from the liquid crystal aligning agent to form a liquid crystal alignment film by using a polyamic acid ester having a specific structure having a functional group substituted with a hydrogen atom by the heat, The phase separation between the amic ester and the polyamic acid is promoted so that the polyamic acid ester is present in the vicinity of the film surface without being mixed with the polyamic acid and the polyamic acid exists in the film and at the substrate interface without being mixed with the polyamic acid ester do.

In this way, the surface of the obtained liquid crystal alignment film is smooth and uneven due to the phase separation of the polyamic acid ester and the polyamic acid, so that the opacity of the film caused by the unevenness is reduced. A liquid crystal alignment film having a smooth surface with no irregularities has excellent properties because a polyamic acid ester having excellent orientation stability and reliability exists on the surface and a polyamic acid having excellent electrical properties exists in the inside of the film and at the electrode interface I think.

On the other hand, since the functional group of the specific structure of the polyamic acid ester is substituted with a hydrogen atom by heating in the subsequent imidization or firing treatment, the functional group is not present in the resulting liquid crystal alignment film, And there is obtained a liquid crystal alignment film having properties equivalent to those in the case of using a polyamic acid ester having no functional group of a specific structure.

≪ Polyamic acid ester and polyamic acid &

The polyamic acid ester and polyamic acid to be used in the present invention are polyimide precursors for obtaining polyimide and are polymers having a site capable of imidization reaction as described below by heating.

[Chemical formula 10]

(11)

The polyamic acid ester and polyamic acid contained in the liquid crystal aligning agent of the present invention have the following formulas (1) and (4), respectively.

[Chemical Formula 12]

In the above formula (1), R ₁ is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 2 carbon atoms. The polyamic acid ester has a higher temperature at which imidization proceeds as the number of carbon atoms in the alkyl group increases. Therefore, R ₁ is particularly preferably a methyl group from the viewpoint of easiness of imidization by heat. In the formulas (1) and (4), A ₁ and A ₂ are each independently a hydrogen atom or an alkyl, alkenyl or alkynyl group having 1 to 20 carbon atoms which may have a substituent. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, t-butyl, hexyl, octyl, decyl, cyclopentyl, cyclohexyl and bicyclohexyl. Examples of the alkenyl group include those wherein at least one CH ₂ -CH ₂ structure existing in the alkyl group is substituted with a CH═CH structure. More specifically, a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, a 2-butenyl group, a 1,3-butadienyl group, a 2-pentenyl group, a 2-hexenyl group, a cyclopropenyl group, , A cyclohexenyl group, and the like. Examples of the alkynyl group include those obtained by substituting at least one CH ₂ -CH ₂ structure existing in the upper alkyl group with a C≡C structure. More specifically, an ethynyl group, 1-propynyl group, 2-propynyl group, .

The above alkyl, alkenyl and alkynyl groups may have a substituent group when the number of carbon atoms is generally from 1 to 20, and may form a cyclic structure by a substituent. The formation of a ring structure by a substituent means that a substituent group or a substituent group and a part of the parent skeleton are bonded to form a ring structure.

Examples of the substituent include a halogen group, a hydroxyl group, a thiol group, a nitro group, an aryl group, an organoxy group, an organotio group, an organosilyl group, an acyl group, an ester group, a thioester group, , An alkenyl group, and an alkynyl group.

Examples of the halogen group as a substituent include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The aryl group which is a substituent includes a phenyl group. These aryl groups may be further substituted with other substituents described above.

The organoxy group as a substituent may represent a structure represented by O-R. These R may be the same or different and are the above-mentioned alkyl, alkenyl, alkynyl, aryl and the like. These R may be further substituted with the aforementioned substituents. Specific examples of the organoxy group include a methoxy group, ethoxy group, propyloxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group and octyloxy group.

The organotio group as a substituent may represent a structure represented by -S-R. Examples of the R include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group. These R may be further substituted with the aforementioned substituents. Specific examples of the organotin group include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a heptylthio group, a heptylthio group and an octylthio group.

The organosilyl group as a substituent may represent a structure represented by -Si- (R) ₃ . These R may be the same or different and are the above-mentioned alkyl, alkenyl, alkynyl, aryl and the like. These R may be further substituted with the aforementioned substituents. Specific examples of the organosilyl group include trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, tripentylsilyl, trihexylsilyl, pentyldimethylsilyl, and hexyldimethylsilyl. .

The acyl group as a substituent may represent a structure represented by -C (O) -R. As R, examples of the alkyl group, alkenyl group, aryl group, and the like can be mentioned. These R may be further substituted with the aforementioned substituents. Specific examples of the acyl group include a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group, and a benzoyl group.

The ester group as a substituent may represent a structure represented by -C (O) O-R or -OC (O) -R. Examples of the R include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group. These R may be further substituted with the aforementioned substituents.

The thioester group as a substituent may represent a structure represented by -C (S) O-R or -OC (S) -R. Examples of the R include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group. These R may be further substituted with the aforementioned substituents.

The phosphoric acid ester group which is a substituent may represent a structure represented by -OP (O) - (OR) ₂ . These R may be the same or different and are the above-mentioned alkyl, alkenyl, alkynyl, aryl and the like. These R may be further substituted with the aforementioned substituents.

The amide group which is a substituent may represent a structure represented by -C (O) NH ₂ or -C (O) NHR, -NHC (O) R, -C (O) N (R) ₂ or -NRC have. These R may be the same or different and are the above-mentioned alkyl, alkenyl, alkynyl, aryl and the like. These R may be further substituted with the aforementioned substituents.

Examples of the aryl group as the substituent include the same aryl groups as described above. These aryl groups may be further substituted with other substituents described above.

Examples of the alkyl group as the substituent include the same alkyl groups mentioned above. These alkyl groups may be further substituted with other substituents described above.

The alkenyl group as a substituent includes the same alkenyl groups as those described above. This alkenyl group may be further substituted with another substituent as described above.

The alkynyl group as a substituent includes the same alkynyl group as mentioned above. These alkynyl groups may be further substituted with other substituents described above.

In general, when introducing a bulky structure, there is a possibility of lowering the reactivity of the amino group and the liquid crystal orientation. Therefore, as A ₁ and A _{2, a} hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent is more preferable, An atom, a methyl group or an ethyl group is particularly preferable.

In the formulas (1) and (4), X ₁ and X ₂ are each independently a tetravalent organic group and Y ₁ And Y < ₂ > are each independently a divalent organic group. X ₁ and X ₂ are tetravalent organic groups and are not particularly limited. In the polyimide precursor, two or more types of X ₁ and X ₂ may be mixed. Specific examples of X ₁ and X ₂ include, independently of each other, X-1 to X-46 shown below. X ₁ , X ₂ , X 3, X 4, X 5, X 6, X 8, X 16, and X ₇ are each independently selected from the monovalent monomers. -19, X-21, X-25, X-26, X-27, X-28 or X-32.

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

In the formulas (1) and (4), Y ₁ and Y ₂ are divalent organic groups and are not particularly limited. Of the polyimide precursors, Y ₁ and Y ₂ may be independently contained in two or more types. Specific examples of Y ₁ and Y ₂ include the following Y-1 to Y-103.

Among them, Y-7, Y-10, Y-11, Y-12, Y-13, and Y-11 are preferred as Y ₁ , in order to obtain good liquid crystal alignability. 21, Y-22, Y-23, Y-25, Y-26, Y-27, Y-41, Y-42, Y-43, Y- More preferred are diamines of Y-61, Y-63, Y-64, Y-71, Y-72, Y-73, Y-74, Y-75 and Y-98. Further, if the want to increase the pre-tilt angle, the side chain chapter chain alkyl group, a polyamic an aromatic ring, an aliphatic ring, a steroid skeleton or a diamine having a combined structure of these acid is preferred to introduce the ester, and roneun Y ₁ Y Y-81, Y-82, Y-83, Y-84, Y-85, Y-86, Y-87, Y-80, , Y-89, Y-90, Y-91, Y-92, Y-93, Y-94, Y-95, Y-96 or Y-97. By adding these diamines in an amount of 1 to 50 mol% of the total diamine, an arbitrary pretilt angle can be expressed.

It is preferable to introduce a diamine having a heteroatom structure, a polycyclic aromatic structure, or a biphenyl skeleton into the polyamic acid, because the residual image due to the accumulation of the DC voltage can be reduced by lowering the volume resistivity of the polyamic acid Y- ₂ , Y-3, Y-23, Y-25, Y-26, Y-27, Y-30, Y-31, Y- More preferably Y-40, Y-40, Y-41, Y-42, Y-44, Y-45, Y-49, Y-50, Y- Among them, Y-31, Y-40, Y-98 and Y-99 are more preferable.

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 22]

(23)

≪ EMI ID =

(25)

(26)

(27)

(28)

[Chemical Formula 29]

Y ₁ in the formula (1) is preferably a structure represented by the following formula (7).

(30)

In the formula (7), R ₅ is a single bond or a divalent organic group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms. The divalent organic group is preferably an alkylene group, an arylene group, or a combination thereof, which may contain an ether bond, an amide bond, an ester bond, a thioester bond or a thioether bond. R ₆ is at least one structure selected from the group consisting of the above formulas (5) and (6). and a is an integer of 1 to 4, preferably 1 or 2.

It is preferable that Y ₁ in the formula (1) in the formula (1) has at least one structure selected from the group consisting of the structures represented by the following formulas.

(31)

It is particularly preferable that Y ₂ in the formula (4) is at least one selected from the structures represented by the following formulas among them.

(32)

<Production method of polyamic acid ester>

The polyamic acid ester represented by the above formula (1) can be obtained by a polycondensation reaction of any of the tetracarboxylic acid derivatives represented by the following formulas (10) to (12) and a diamine compound represented by the formula (13).

(33)

(34)

(Wherein X ₁ , Y ₁ , R ₁ , A ₁ and A ₂ are the same as defined in the formula (1)

The polyamic acid ester represented by the above formula (1) can be synthesized by the following methods (1) to (3) using the above monomers.

(1) Synthesis from polyamic acid

The polyamic acid ester can be synthesized by esterifying a polyamic acid obtained from a tetracarboxylic acid dianhydride and a diamine.

(35)

Specifically, it can be synthesized by reacting the polyamic acid and the esterifying agent in the presence of an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C, for 30 minutes to 24 hours, preferably 1 to 4 hours have.

As the esterifying agent, those which can be easily removed by purification are preferable and N, N-dimethylformamide dimethylacetal, N, N-dimethylformamide diethyl acetal, N, N-dimethylformamide dipropylacetal, N , N-dimethylformamide dineopentylbutylacetal, N, N-dimethylformamide di-t-butyl acetal, 1-methyl-3-p-tolyltriazine, Propyl-3-p-tolyltriazine, and 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride. 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.

As the solvent used in the above-mentioned reaction, N, N-dimethylformamide, N-methyl-2-pyrrolidone and? -Butyrolactone are preferable as the solubility of the polymer. May be used. The concentration in the synthesis is preferably from 1 to 30 mass%, more preferably from 5 to 20 mass%, from the viewpoint that the precipitation of the polymer does not occur well and a high molecular weight product is easily obtained.

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

The polyamic acid ester can be synthesized by a polycondensation reaction of a tetracarboxylic acid diester dichloride with a diamine.

(36)

Specifically, the tetracarboxylic acid diester dichloride and diamine are reacted in the presence of a base and an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C for 30 minutes to 24 hours, For 4 hours.

As the base, pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used, and pyridine is preferable for the reaction to proceed mildly. The added amount of the base is preferably 2 to 4 times the tetracarboxylic acid diester dichloride from the viewpoint of easy removal and high molecular weight.

As the solvent used in the above-mentioned reaction, N-methyl-2-pyrrolidone and? -Butyrolactone are preferable in terms of the solubility of the monomer and the polymer, and they may be used alone or in combination of two or more. The concentration in the synthesis is preferably from 1 to 30 mass%, more preferably from 5 to 20 mass%, from the viewpoint that the precipitation of the polymer does not occur well and a high molecular weight product is easily obtained. In order to prevent the hydrolysis of the tetracarboxylic acid diester dichloride, it is preferable that the solvent used for the synthesis of the polyamic acid ester is dehydrated as much as possible, and it is preferable to prevent the introduction of outside air in a nitrogen atmosphere.

(3) When polyamic acid is synthesized from tetracarboxylic acid diester and diamine

The polyamic acid ester can be synthesized by polycondensation of a tetracarboxylic acid diester and a diamine.

(37)

Specifically, the tetracarboxylic acid diester and the diamine are reacted 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 for 30 minutes to 24 hours, For 15 hours.

Examples of the condensing agent include triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N'- carbonyldiimidazole, dimethoxy- (Benzotriazol-1-yl) -N, N, N ', N'-tetramethyluronium tetrafluoroborate, O- (benzotriazol- (2,3-dihydro-2-thioxo-3-benzoxazolyl) diphenylphosphonate, and the like can be used, for example, by using N, N, N ', N'-tetramethyluronium hexafluorophosphite, . The addition amount of the condensing agent is preferably 2 to 3 times the mole of the tetracarboxylic acid diester.

The base may be a tertiary amine such as pyridine or triethylamine. The amount of the base to be added is an amount that is easy to remove, and the amount of the base is preferably 2 to 4 times the amount of the diamine component from the viewpoint of easily obtaining a high molecular weight product.

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 from 0 to 1.0 times the amount of the diamine component.

Among the methods for synthesizing the above three polyamic acid esters, a polyamic acid ester having a high molecular weight can be obtained, and thus the synthesis method of the above (1) or (2) is particularly preferable.

The polyamic acid ester solution obtained as described above can be precipitated by pouring into a poor solvent while stirring sufficiently. 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.

<Production method of polyamic acid>

The polyamic acid represented by the formula (4) can be obtained by a polycondensation reaction of a tetracarboxylic acid dianhydride represented by the following formula (14) and a diamine compound represented by the formula (15).

(38)

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

The organic solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone or gamma -butyrolactone in terms of the solubility of the monomer and the polymer, May be mixed and used. The concentration of the polymer is preferably from 1 to 30 mass%, more preferably from 5 to 20 mass%, from the viewpoint that precipitation of the polymer does not occur well and a high molecular weight product is easily obtained.

The polyamic acid thus obtained can be recovered by precipitating the polymer by injecting the reaction solution into a poor solvent while sufficiently stirring. It is also possible to obtain a purified polyamic acid powder by conducting precipitation several times, washing with a poor solvent, and then drying at room temperature or by heating. Examples of the poor solvent include, but are not limited to, water, methanol, ethanol, hexane, butyl cellosolve, acetone, and toluene.

&Lt; Polyamic acid ester having a thermal cleavage protecting group >

The polyamic acid ester having a thermally releasable protecting group according to the present invention is a polyamic acid ester having a repeating unit represented by the above formula (1), and also satisfies any of the following conditions (i) to (iii) .

(I) has at least one kind of monovalent or divalent substituent selected from the group consisting of the following formulas (2) and (3), and X ₁ and Y ₁ in formula (1)

(Ii) a monovalent or divalent substituent of at least one structure selected from the group consisting of A ₁ , A _2, or both of which are represented by the following formulas (2) and (3)

(Ⅲ) formula (1) X _1, Y _1, or both sides have the following formula (2) and (3) group and at least one structure 1 a or a divalent group of the substituents selected from the consisting of, and A ₁ , a has the structure 1 is the group and at least one or a divalent of the substituents selected from the consisting of a _second or both the following equations (2) and (3).

[Chemical Formula 39]

In the formula (2), D ₁ is a protecting group for an amino group, and the structure is not particularly limited as long as it is a functional group which is substituted with a hydrogen atom by heating. D ₁ is preferably a structure in which the elimination reaction proceeds efficiently at a firing temperature of 150 ° C. to 300 ° C. in obtaining a liquid crystal alignment film, more preferably a tert-butoxycarbonyl group or a 9-fluorenylmethoxycarbonyl group, Particularly preferred is a butoxycarbonyl group.

In the formula (3), B ₁ is a single bond or a divalent organic group. Preferable examples of the divalent organic group include an alkylene group, an arylene group, or a combination thereof, which may contain an ether bond, an amide bond, an ester bond, a thioester bond or a thioether bond. The atom bonded to the ester group in the formula (3) is carbon.

The monovalent or divalent substituent represented by the formula (2) wherein D ₁ is a tert-butoxycarbonyl group or a 9-fluorenylmethoxycarbonyl group can be obtained by reacting a compound having a primary or secondary amino group represented by the following formula with a compound -tert-butyl in the presence of a base, or a method of reacting a compound having a primary or secondary amino group with chloroformic acid-9-fluorenylmethyl in the presence of a base. And is not particularly limited.

(40)

A compound having a substituent group obtained by the above method is added to a tetracarboxylic acid derivative or a precursor thereof or a diamine compound or a derivative thereof to synthesize a tetracarboxylic acid derivative and / or a diamine having a substituent having a functional group substituted by a hydrogen atom by heat Thus, a polyamic acid ester having a thermal cleavable protecting group of the present invention can be obtained by using a polyamic acid ester as a raw material.

In the formula (3), D ₂ is a protective group of a carboxyl group, and the structure thereof is not particularly limited as long as it is a functional group which is substituted with a hydrogen atom by heating. D ₂ is preferably a structure in which the elimination reaction proceeds efficiently at a firing temperature of 150 ° C. to 300 ° C. at the time of obtaining a liquid crystal alignment layer, more preferably a functional group of the following formulas (D2-1) to (D2-5) The following formula (D2-1) is more preferable.

(41)

, R ₁₀ in the formula (D2-2) is an alkyl group of 1 to 5 carbon atoms, as a specific example may be mentioned methyl (Me) group, ethyl group, propyl, butyl, pentyl, or tert- butyl group.

D ₂ Is a group represented by the formula (D2-1) can be prepared by a method of reacting a carboxyl group and a tert-butyl alcohol represented by the following formula, a method of reacting a chlorocarbonyl compound with tert-butyl alcohol , Or a method in which a carboxyl group is reacted with tert-butyl halide, and any known method is not particularly limited. A compound having a substituent group obtained by the above method is added to a tetracarboxylic acid derivative, a precursor thereof, a diamine compound or a precursor thereof, and a tetracarboxylic acid derivative and / or a diamine having a substituent having a functional group substituted with a hydrogen atom by heat A polyamic acid ester having a thermal cleavable protecting group of the present invention can be obtained by synthesizing these and using them as a raw material for a polyamic acid ester.

(42)

In the structural unit contained in the polyamic acid ester having a thermally removable protecting group of the present invention, the point where at least one kind of substituent selected from the group consisting of the formulas (2) and (3) exists is represented by X ₁ , Y ₁ , A ₁ , and A ₂ . Of these, a structure having at least one substituent selected from the group consisting of the formulas (2) and (3) in the structure of Y ₁ in the formula (1) and a form having at least one substituent selected from the group consisting of A ₁ , A ₂ , The form having at least one kind of substituent selected from the group consisting of the formulas (2) and (3) on both sides is advantageous in terms of easiness in synthesis of monomers to be a raw material of the polyamic acid ester and ease of handling of the monomers .

The polyamic acid ester having a thermal cleavable protecting group of the present invention is represented by the formula (1), and substituents represented by the formulas (2) and (3) are present in any of X ₁ , Y ₁ , A ₁ and A ₂ Or may contain a structural unit which is not present. Equation (2) and (3) as if this is too small, the introduced amount of the substituents shown, since the small effect of suppressing the fine irregularities caused by phase separation of the polyamic acid ester and polyamic acid, X _1, Y _1, A _1, A expression that is present in any location of the _second (2) and the content of the substituents represented by (3) is not less than, preferably not lower than expression (1) 0.05 on the basis of the structural unit represented by, and 0.10 is especially preferred.

In the above definition, for example, the structural unit represented by the formula (1) contained in the polyamic acid ester is preferably selected from the group consisting of the formulas (2) and (3) in X ₁ and Y ₁ of the formula (1) Is a structural unit that has one kind of substituent group, and A ₁ or A ₂ is one kind of substituent selected from the group consisting of formulas (2) and (3) "alone, the formula 2) and (3) is 4.00.

Specific examples of the substituent having a functional group substituted with a hydrogen atom by the heat represented by the formulas (2) and (3) include the following (D-1) to (D-24) .

(43)

(44)

[Chemical Formula 45]

(46)

(47)

Examples of the diamine compound containing a substituent having a functional group substituted with a hydrogen atom by the heat shown by the above-mentioned formulas (2) and (3) include the following diamine compounds of the following formulas (D-25) to But is not limited thereto.

(48)

(49)

(50)

(51)

<Liquid Crystal Aligner>

The liquid crystal aligning agent of the present invention has the form of a solution in which the polyamic acid ester having the thermally releasable protecting group and the polyamic acid are dissolved in the organic solvent. The molecular weight of the polyamic acid ester having a thermal cleavable protecting group is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, and still more preferably 10,000 to 100,000 in terms of weight average molecular weight. The number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and still more preferably 5,000 to 50,000.

On the other hand, the weight average molecular weight of the polyamic acid is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, and still more preferably 10,000 to 100,000. The number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and still more preferably 5,000 to 50,000.

By making the molecular weight of the polyamic acid ester having a thermal cleavable group protective group smaller than that of the polyamic acid, it is possible to further reduce the fine unevenness due to the phase separation. The difference in weight average molecular weight between the polyamic acid ester having a thermal cleavable group and the polyamic acid is preferably 1,000 to 200,000, more preferably 5,000 to 150,000, and particularly preferably 10,000 to 100,000.

In the liquid crystal aligning agent of the present invention, the content ratio (polyamic acid ester / polyamic acid) of the polyamic acid ester and the polyamic acid having a heat-labile protecting group is preferably 1/9 to 9/1 on a mass basis. This ratio is more preferably 2/8, particularly preferably 3/7 to 7/3. When the ratio is within this range, it is possible to provide a liquid crystal aligning agent having both excellent liquid crystal alignability and electrical characteristics.

The liquid crystal aligning agent of the present invention is not particularly limited as long as it has the form of a solution in which a polyamic acid ester having thermal detachable protecting groups and a polyamic acid are dissolved in an organic solvent. For example, a method of mixing powders of a polyamic acid ester and a polyamic acid and dissolving them in an organic solvent, a method of mixing a solution of a polyamic acid ester and a solution of a polyamic acid, a method of mixing a polyamic acid ester solution and a polyamic acid powder , A method of mixing a polyamic acid ester solution and a polyamic acid solution. A polyamic acid ester solution and a polyamic acid solution are more preferable because a homogeneous polyamic acid ester-polyamic acid mixed solution can be obtained even when the two types of solvent in which the polyamic acid ester and the polyamic acid are dissolved are different.

When a polyamic acid ester and / or a polyamic acid having a thermal cleavable protecting group is prepared in an organic solvent, the resulting reaction solution itself may be used, or the reaction solution may be diluted with an appropriate solvent. When a polyamic acid ester having a thermal cleavable protecting group is obtained as a powder, it may be dissolved in an organic solvent to form a solution.

The concentration of the polyamic acid ester and the polyamic acid (sometimes referred to as the polymer in the present invention) in the liquid crystal aligning agent of the present invention can be appropriately changed according to the setting of the thickness of the coating film to be formed. It is preferably 1% by mass or more from the viewpoint of formation of the film, and 10% by mass or less from the viewpoint of the storage stability of the solution.

The organic solvent contained in the liquid crystal aligning agent of the present invention is not particularly limited as long as the polymer component of the amic ester and the polyamic acid having thermal detachable protecting groups are uniformly dissolved. Specific examples thereof include N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methyl- Pyrrolidone, N-vinyl-2-pyrrolidone, dimethylsulfoxide, dimethylsulfone, 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. Further, even a solvent which can not uniformly dissolve the polymer component alone may be mixed with the organic solvent as long as the polymer does not precipitate.

When a silane coupling agent is added to the liquid crystal aligning agent of the present invention, it is preferable to add a polyamic acid ester solution, a polyamic acid solution, or a polyamic acid ester solution and a polyamic acid solution before mixing the polyamic acid ester solution and the polyamic acid solution can do. It may also be added to a polyamic acid ester-polyamic acid mixed solution. The silane coupling agent is added for the purpose of improving the adhesion between the polymer and the substrate. Therefore, as a method of adding the silane coupling agent, it is preferable to add the polymer and the silane coupling agent to the polyamic acid solution, And then mixed with a polyamic acid ester solution. When the added amount of the silane coupling agent is too large, unreacted ones adversely affect liquid crystal alignability. When the silane coupling agent is added in an excessively small amount, the effect on adhesiveness is not exhibited. Therefore, the amount is preferably 0.01 to 5.0 wt% More preferably 0.1 to 1.0% by weight.

The liquid crystal aligning agent of the present invention may contain, in addition to the organic solvent for dissolving the polymer, a solvent for improving the film uniformity when the liquid crystal aligning agent is applied to the substrate. Such a solvent generally uses a solvent having a surface tension lower than that of the organic solvent. Specific examples thereof include ethylcellosolve, butylcellosolve, ethylcarbitol, butylcarbitol, ethylcarbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy- 2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2 Butyl acetate, butyl cellosolve acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactic acid methyl ester, lactic acid ethyl ester, n-propyl lactate, n-butyl lactate, And the like. These solvents may be used in combination of two or more.

The liquid crystal aligning agent of the present invention may contain various additives such as a silane coupling agent and a crosslinking agent. When a silane coupling agent or a crosslinking agent is added, it is preferable to add a poor solvent to the liquid crystal aligning agent in order to prevent precipitation of the polymer. An imidization accelerator may be added in order to efficiently progress the imidization of the polyamic acid ester when the coating film is baked.

Specific examples of the silane coupling agent are given below, but the silane coupling agent usable in the liquid crystal aligning agent of 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-dimethyl-butylidene) 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 ureido-based silane coupling agent such as 3-ureidopropyltriethoxysilane; 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; Carbamate-based silane coupling agents such as triethoxysilylpropylmethyl carbamate and (3-triethoxysilylpropyl) -t-butylcarbamate.

Specific examples of the imidization accelerator of the polyamic acid ester are shown below, but the imidization accelerator which can be used in the liquid crystal aligning agent of the present invention is not limited thereto.

(52)

(53)

In the formulas (B-1) to (B-17), D is independently a tert-butoxycarbonyl group or a 9-fluorenylmethoxycarbonyl group. In addition, in the formulas (B-14) to (B-17), there is a plurality of D's in one formula, which may be the same or different.

The content of the imidization promoting agent is not particularly limited as long as the effect of promoting the heat imidization of the polyamic acid ester can be obtained. It is preferably 0.01 mole or more, more preferably 0.05 mole or more, further preferably 0.1 mole or more, per mole of the amic acid ester moiety of the following formula (16) contained in the polyamic acid ester, . (16), which is contained in the polyamic acid ester of the present invention, may be added to the liquid crystal alignment film in order to minimize the adverse effects of the imidization promoter remaining in the film after firing on various characteristics of the liquid crystal alignment film to a minimum. Is preferably 2 mol or less, more preferably 1 mol or less, and still more preferably 0.5 mol or less based on 1 mol of the amic acid ester moiety of the imidization promoter.

(54)

When an imidization accelerator is added, since imidization may proceed by heating, it is preferable to add it after dilution with a good solvent and a poor solvent.

&Lt; Liquid crystal alignment film &

The liquid crystal alignment film of the present invention is a coating film obtained by applying the liquid crystal aligning agent thus obtained to a substrate, followed by drying and firing, and if necessary, this film surface is subjected to orientation treatment such as rubbing.

The substrate to which the liquid crystal aligning agent of the present invention is applied is not particularly limited as long as it is a substrate having high transparency, and a glass substrate, a silicon nitride substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used. It is preferable to use a substrate on which an ITO electrode or the like for liquid crystal driving is formed from the viewpoint of simplifying the process. In a reflective liquid crystal display element, an opaque material such as a silicon wafer can be used only on a substrate of one side. 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.

The drying and firing steps after the application of the liquid crystal aligning agent of the present invention can be carried out at arbitrary temperature and time. Usually, it is dried at 50 ° C to 120 ° C for 1 minute to 10 minutes and then at 150 ° C to 300 ° C for 5 minutes to 120 minutes in order to sufficiently remove the organic solvent contained therein. The thickness of the coated film after firing is not particularly limited, but if it is too thin, the reliability of the liquid crystal display element may deteriorate, and therefore, it is 5 to 300 nm, preferably 10 to 200 nm.

Examples of the method of orienting the coating film include a rubbing method and a photo-alignment treatment method, and the liquid crystal aligning agent of the present invention is particularly useful when used in a photo-alignment treatment method.

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

The liquid crystal alignment film produced as described above can stably orient liquid crystal molecules in a certain direction.

Example

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

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

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

DA-1: In the above formula (D-25)

BDA: 1,2,3,4-butanetetracarboxylic acid dianhydride

CBDA: 1,2,3,4-Cyclobutane tetracarboxylic acid dianhydride

NMP: N-methyl-2-pyrrolidone

? -BL:? -butyrolactone

BCS: butyl cellosolve

PAE: Polyamic acid ester

PAA: Polyamic acid

DA-2: In the above formula (D-29)

DA-3: In the above formula (D-30)

DA-4: In the formula (D-28)

DA-5: In the above formula (DA-32)

DA-6: n = 5 of the formula (DA-35)

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

DA-8: The following formula (DA-8)

DAH-1: The following formula (DAH-1)

DAH-2: The following formula (DAH-2)

AD-1: The following formula (AD-1)

AD-2: The following formula (AD-2)

AD-3: The following formula (AD-3)

AD-4: The following formula (AD-4)

(55)

[Viscosity]

In the synthesis examples, the viscosity of the polyamic acid ester and the polyamic acid solution was 1.1 ml, a cone rotor TE-1 (1 占 34 ', R24), and a temperature of 25 占 폚, using a E-type viscometer TVE-22H Lt; 0 &gt; C.

[Molecular Weight]

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

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

[Center line average illumination measurement]

The coating film of the liquid crystal aligning agent obtained by spin coating was dried for 5 minutes on a hot plate at a temperature of 80 占 폚 and for 1 hour in a hot air circulating oven at a temperature of 250 占 폚 to form a coating film having a thickness of 100 nm. The film surface of this coating film was observed with an atomic force microscope (AFM), and the center line average roughness (Ra) of the film surface was measured to evaluate the flatness of the film surface.

Measuring device: L-trace probe microscope (manufactured by S-AI Co., Ltd.)

[Voltage maintenance rate]

The liquid crystal aligning agent was spin-coated on a glass substrate having a transparent electrode, dried for 5 minutes on a hot plate at a temperature of 80 占 폚, and baked for 60 minutes in a hot air circulating oven at 250 占 폚 to form a 100 nm- / RTI &gt; This coating film was irradiated with ultraviolet rays of 254 nm through a polarizing plate at 100 mJ / cm 2 to obtain a substrate with a liquid crystal alignment film attached thereto. Two such substrates with liquid crystal alignment films were prepared, spacers having a diameter of 6 占 퐉 were dispersed on the liquid crystal alignment film surface of one of the substrates, and the alignments of the two substrates were anti-parallel. And the periphery was sealed to prepare an empty cell having a cell gap of 6 탆. A liquid crystal (MLC-2041, manufactured by Merck) was injected into the empty cell under vacuum at room temperature, and the injection port was sealed to obtain a liquid crystal cell.

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

A voltage of 4 V was applied for 60 seconds, and the 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 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 Toyota 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.

[AC drive baking of FFS driven liquid crystal cell]

On the glass substrate, an ITO electrode having a film thickness of 50 nm as an electrode was formed as a first layer, silicon nitride having a film thickness of 500 nm as an insulating film was formed on the second layer, and a comb- (FFS) driving electrode having a width of 3 mu m, an electrode pitch of 6 mu m, and an electrode height of 50 nm) was formed on a glass substrate by spin coating to form a liquid crystal alignment agent . Dried on a hot plate at 80 DEG C for 5 minutes and then fired in a hot air circulating oven at 250 DEG C for 60 minutes to form a coating film having a thickness of 100 nm. This coating film was irradiated with ultraviolet rays of 254 nm through a polarizing plate at 100 mJ / cm 2 to obtain a substrate with a liquid crystal alignment film attached thereto. In addition, a coating film was formed on a glass substrate having a columnar spacer having a height of 4 占 퐉, which had no electrode as an opposing substrate, and subjected to alignment treatment.

A sealant was printed on the substrate using the two substrates as a set and the other substrate was adhered with the alignment direction of the liquid crystal alignment film face facing 0 ° and then the sealant was cured to form empty cells Respectively. A liquid crystal MLC-2041 (manufactured by Merck & Co., Inc.) was injected into this empty cell by a vacuum injection method, and the injection port was sealed to obtain an FFS-driven liquid crystal cell.

The V-T characteristic (voltage-transmittance characteristic) of this FFS-driven liquid crystal cell under a temperature of 58 ° C was measured, and then a square wave of ± 4 V / 120 Hz was applied for 4 hours. After 4 hours, the voltage was turned off, and the sample was allowed to stand at a temperature of 58 占 폚 for 60 minutes. Then, the V-T characteristic was measured again to calculate the difference in voltage with a transmittance of 50% before and after the application of the square wave.

[Evaluation of Charge Storage Characteristics]

After the FFS driving liquid crystal cell was placed on the light source, the VT characteristic (voltage-transmittance characteristic) was measured, and then the transmittance (T _a ) in _a state of applying a square wave of ± 1.5 V / 60 Hz was measured. Thereafter, a rectangular wave of ± 1.5 V / 60 Hz was applied for 10 minutes, and 1 V of direct current was superimposed and driven for 30 minutes. The direct current voltage was cut off and the transmittance (T _b ) after 10 minutes of AC driving was measured to calculate the difference in transmittance caused by the voltage remaining in the liquid crystal display element from the difference between T _b and T _a .

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

 (a-1) Synthesis of tetracarboxylic acid dialkyl ester

(56)

1,3-dimethylcyclobutane-1,2,3,4-tetracarboxylic acid dianhydride (compound of the formula (5-1), hereinafter referred to as 1 (1)) was added to a 3 liter (liter) four- (0.981 mol) of methanol and 2200 g (6.87 mol, 10 wt. Times of 1,3-DM-CBDA) of methanol were injected into the reactor and heated to reflux at 65 ° C , And became a homogeneous solution at 30 minutes. The reaction solution was stirred for 4 hours and 30 minutes while heating under reflux. This reaction solution was measured by high performance liquid chromatography (hereinafter abbreviated as HPLC).

After distilling off the solvent from the reaction mixture with an equalizer, 1301 g of ethyl acetate was added and the mixture was heated to 80 캜 and refluxed for 30 minutes. Thereafter, the mixture was cooled for 10 minutes at a rate of 2 to 3 占 폚 until the internal temperature became 25 占 폚, and the mixture was stirred at 25 占 폚 for 30 minutes. The precipitated white crystals were collected by filtration, washed with 141 g of ethyl acetate twice, and dried under reduced pressure to obtain 103.97 g of white crystals.

This crystal was confirmed to be Compound (1-1) (HPLC relative area: 97.5%) (yield: 36.8%) based on the results of 1H NMR analysis and X-ray crystal structure analysis.

(a-2) Synthesis of 1,3-DM-CBDE-C1

(57)

234.15 g (0.81 mol) of the compound (1-1) and 1170.77 g (11.68 ㏖ 5 wt.) Of n - heptane were charged in a 3 L four - necked flask under a nitrogen gas flow. Then, 0.64 g (0.01 mol) And the mixture was heated and stirred at 75 占 폚 under magnetic stirrer stirring. Subsequently, 289.93 g (11.68 mol) of thionyl chloride was added dropwise over 1 hour. Foaming was started immediately after dropping, and after 30 minutes from the end of dropping, the reaction solution became uniform and foaming was stopped. Subsequently, the mixture was stirred at 75 占 폚 for 1 hour and 30 minutes, and then the solvent was distilled off at 40 占 폚 on a water bath using this distributor until the content became 924.42 g. This was heated to 60 DEG C to dissolve the precipitated crystals upon solvent distillation and removal. The insoluble matter was filtered by heating at 60 DEG C, and the filtrate was cooled to 25 DEG C at a rate of 1 DEG C for 10 minutes. Stirring was continued at 25 캜 for 30 minutes, and the precipitated white crystals were taken out by filtration. The crystals were washed with 264.21 g of n-heptane. This was dried under reduced pressure to obtain 226.09 g of white crystals.

Subsequently, 226.09 g of the white crystals obtained above and 452.18 g of n-heptane were poured into a 3 L four-necked flask under a nitrogen gas stream, and the mixture was heated and stirred at 60 ° C to dissolve the crystals. Thereafter, the mixture was cooled and stirred at 25 ° C for 10 minutes at a rate of 1 ° C to precipitate crystals. The mixture was stirred at 25 占 폚 for 1 hour, and the precipitated white crystals were collected by filtration. The crystals were washed with 113.04 g of n-hexane and then dried under reduced pressure to obtain 203.91 g of white crystals. According to the results of &lt; 1 &gt; H NMR analysis, this crystal was found to be a compound (3-1), i.e., dimethyl-1,3-bis (chlorocarbonyl) -1,3-dimethylcyclobutane- 3-DM-CBDE-C1) (HPLC relative area 99.5%) (yield: 77.2%).

(Synthesis Example 1)

The diamine compound (DA-1) was synthesized by the following four-step route.

Step 1: Synthesis of compound (A5)

(58)

(8.81 g, 160 mmol), N, N-dimethylformamide (112 mL) and potassium carbonate (18.5 g, 134 mmol) were placed in a 500 mL eggplant type flask, And a solution of t-butyl bromoacetate (21.9 g, 112 mmol) in N, N-dimethylformamide (80 mL) was added dropwise with stirring for about 1 hour. After completion of dropwise addition, the reaction solution was stirred at room temperature for 20 hours. Thereafter, the solids were removed by filtration, 1 liter of ethyl acetate was added to the filtrate, and the mixture was washed four times with 300 ml of water and once with 300 ml of saturated brine. Thereafter, the organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. Finally, the residual oil was distilled under reduced pressure at 0.6 Torr at 70 占 폚 to obtain t-butyl N-propargylaminoacetate (compound (A5)) as a colorless liquid. The yield was 12.0 g and the yield was 63%.

Step 2: Synthesis of compound (A6)

[Chemical Formula 59]

(12.0 g, 70.9 mmol) and N-propargylaminoacetate (600 mL) were placed in a 1 L eggplant-shaped flask to prepare a solution. While stirring and cooling, 15.5 g , 70.9 mmol) dissolved in dichloromethane (100 mL) was added dropwise for 1 hour. After completion of dropwise addition, the reaction solution was stirred at room temperature for 20 hours. After completion of the reaction, the reaction solution was washed with 300 mL of saturated brine and dried over magnesium sulfate. Thereafter, the solvent was distilled off under reduced pressure to obtain a pale yellow liquid of N-propargyl-Nt-butoxycarbonylaminoacetate t-butyl (Compound (A6)). The yield was 18.0 g and the yield was 94%.

Step 3: Synthesis of compound (A7)

(60)

To a 300 ml four-necked flask was added 2-iodo-4-nitroaniline (22.5 g, 85.4 mmol), bis (triphenylphosphine) palladium dichloride (1.20 g, 1.71 mmol), copper iodide (0.651 g, (43.7 g, 598 mmol) and N, N-dimethylformamide (128 ml) were added to the flask, and while stirring with ice, the N-propargylamino- T-butyl butoxycarbonyl acetate (27.6 g, 102 mmol) was added thereto, followed by stirring at room temperature for 20 hours. After completion of the reaction, 1 liter of ethyl acetate was added, washed with 150 ml of 1 mol / l aqueous ammonium chloride solution three times, once with 150 ml of saturated brine, and dried with magnesium sulfate. Thereafter, the solvent was distilled off under reduced pressure, and the precipitated solid was dissolved in 200 mL of ethyl acetate and recrystallized by adding 1 L of hexane. This solid was collected by filtration and dried under reduced pressure to obtain a yellow solid of 2- {3- (Nt-butoxycarbonyl-Nt-butoxycarbonylmethylamino) -1-propynyl)} 4- A7)). The yield was 23.0 g and the yield was 66%.

Step 4: Reduction of compound (A7)

-1-propynyl)} - 4-nitroaniline (22.0 g, 54.2 mmol) was added to a 500 ml four-necked flask, And ethanol (200 g) were added, the inside of the system was replaced with nitrogen, palladium carbon (2.20 g) was added, the inside of the system was replaced with hydrogen, and the mixture was stirred at 50 ° C for 48 hours. After completion of the reaction, palladium carbon was removed by Celite filtration, and activated carbon was added to the filtrate, followed by stirring at 50 ° C for 30 minutes. Thereafter, the activated carbon was filtered, the organic solvent was distilled off under reduced pressure, and the residual oil was dried under reduced pressure to obtain a diamine compound (DA-1). The yield was 19.8 g and the yield was 96%.

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

(Synthesis Example 2)

4.486 g (22.63 mmol) of 4,4'-diaminodiphenylmethane and 2.147 g (5.658 mmol) of DA-1 were placed in a 300 ml four-necked flask equipped with a stirrer and 121.37 g , 5.16 g (65.19 mmol) of pyridine as a base was added and dissolved by stirring. Next, while 8.8384 g (27.16 mmol) of 1,3DM-CBDE-Cl was added to the diamine solution while stirring, the mixture was allowed to react for 4 hours under water. After 4 hours, 134.86 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 1349 g of water while stirring. The precipitated white precipitate was collected by filtration, washed once with 1349 g of water, once with 1349 g of ethanol, and 3 times with 337 g of ethanol And dried to obtain 11.04 g of a white polyamic acid ester resin powder. The yield was 81.9%. The molecular weight of the polyamic acid ester was Mn = 15,205 and Mw = 30,219.

10.9690 g of the obtained polyamic acid ester resin powder was placed in a 200 ml Erlenmeyer flask, and 98.7394 g of NMP was added thereto. The mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-1).

(Comparative Synthesis Example 1)

8.0132 g (40.35 mmol) of 4,4'-diaminodiphenylmethane was placed in a 300 ml four-necked flask equipped with a stirrer, and 158.1 g of NMP and 7.20 g (91.03 mmol) of pyridine as a base were added, And the mixture was stirred and dissolved. Next, while stirring the diamine solution, 12.3419 g (37.93 mmol) of 1,3DM-CBDE-Cl was added, and the reaction was carried out at a reduced pressure for 4 hours. The resulting polyamic acid ester solution was added to 1757 g of water while stirring. The precipitated white precipitate was collected by filtration, washed once with 1757 g of water, once with 1757 g of ethanol, and three times with 439 g of ethanol And dried to obtain 16.63 g of a white polyamic acid ester resin powder. The yield was 94.6%. The molecular weight of the polyamic acid ester was Mn = 10,180 and Mw = 21,476.

The obtained polyamic acid ester resin powder 14.8252 was placed in a 200 ml Erlenmeyer flask, and 99.3048 g of NMP was added thereto. The mixture was stirred at room temperature for 24 hours to dissolve the polyamic acid ester resin powder (PAE-2).

(Synthesis Example 3)

7.9693 g (40 mmol) of 4,4'-diaminodiphenylamine was added to a 100-ml four-necked flask equipped with a stirrer and a nitrogen-introducing tube, 31.7 g of NMP was added, and dissolved with stirring while nitrogen was being supplied. While stirring the diamine solution, 7.1339 g (36.01 mmol) of BDA was added, and NMP was added thereto so that the solid concentration became 25 mass%, and the mixture was stirred at room temperature for 24 hours to obtain a solution of polyamic acid (PAA-1). The viscosity of this polyamic acid solution at 25 캜 was 2680 mPa s. The molecular weight of the polyamic acid was Mn = 8,176 and Mw = 16,834.

(Synthesis Example 4)

5.9791 g (30.01 mmol) of 4,4'-diaminodiphenylamine and 3.0446 g (20.01 mmol) of 3,5-diaminobenzoic acid were placed in a 100-mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 39.69 g of NMP was added and dissolved by stirring while nitrogen was being supplied. While this diamine solution was stirred, 9.8379 g (49.65 mmol) of BDA was added, and NMP was added thereto so that the solid content concentration became 25 mass%, and the mixture was stirred at room temperature for 24 hours to obtain a polyamic acid solution. The viscosity of this polyamic acid solution at 25 캜 was 8,000 mPa.. The molecular weight of the polyamic acid was Mn = 13,696 and Mw = 28,619.

5.5355 g of the obtained polyamic acid solution was placed in a 50 ml Erlenmeyer flask, 8.3744 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a 10 mass% polyamic acid solution (PAA-2).

(Synthesis Example 5)

3.6652 g (18.39 mmol) of 4,4'-diaminodiphenylamine and 0.6992 g (4.595 mmol) of 3,5-diaminobenzoic acid were placed in a 100-mL four-necked flask equipped with a stirrer and a nitrogen- 39.36 g of NMP was added, and dissolved with stirring while nitrogen was supplied. While this diamine solution was stirred, 4.3326 g (22.09 mmol) of CBDA was added, and NMP was added thereto so that the solid concentration became 15 mass%, and the mixture was stirred at room temperature for 24 hours to obtain a solution of polyamic acid (PAA-3). The viscosity of the polyamic acid solution at 25 캜 was 669 mPa.. The molecular weight of the polyamic acid was Mn = 16,902 and Mw = 34,865.

(Synthesis Example 6)

1.848 g (9.23 mmol) of 4,4'-diaminodiphenyl ether and 2.1025 g (13.82 mmol) of 3,5-diaminobenzoic acid were placed in a 100-mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 39.7 g of NMP was added and dissolved by stirring while nitrogen was being supplied. While this diamine solution was stirred, 4.8162 g (22.08 mmol) of PMDA was added, and NMP was added thereto so that the solid concentration became 15 mass%, and the mixture was stirred at room temperature for 24 hours to obtain a solution of polyamic acid (PAA-4). The viscosity of the polyamic acid solution at 25 캜 was 257 mPa s. The molecular weight of the polyamic acid was Mn = 13,620 and Mw = 28,299.

(Example 1)

1.5289 g of the polyamic acid ester solution (PAE-1) obtained in Synthesis Example 2 and 0.5184 g of the polyamic acid solution (PAA-1) obtained in Synthesis Example 3 were placed in an Erlenmeyer flask, 2.0050 g of NMP and 1.0011 g of BCS were added, Followed by stirring for 30 minutes to obtain a liquid crystal aligning agent (I).

(Example 2)

1.5246 g of the polyamic acid ester solution (PAE-1) obtained in Synthesis Example 2 and 1.4067 g of the polyamic acid solution (PAA-2) obtained in Synthesis Example 4 were placed in an Erlenmeyer flask, 1.0960 g of NMP and 1.0112 g of BCS were added, Followed by stirring for 30 minutes to obtain a liquid crystal aligning agent (II).

(Example 3)

1.5119 g of the polyamic acid ester solution (PAE-1) obtained in Synthesis Example 2 and 1.0074 g of the polyamic acid solution (PAA-3) obtained in Synthesis Example 5 were placed in an Erlenmeyer flask, 1.5183 g of NMP and 1.0313 g of BCS were added, Followed by stirring for 30 minutes to obtain a liquid crystal aligning agent (III).

(Example 4)

1.5018 g of the polyamic acid ester solution (PAE-1) obtained in Synthesis Example 2 and 1.1008 g of the polyamic acid solution (PAA-4) obtained in Synthesis Example 6 were placed in an Erlenmeyer flask, and 1.4859 g of NMP and 1.0214 g of BCS were added, Followed by stirring for 30 minutes to obtain a liquid crystal aligning agent (IV).

(Comparative Example 1)

3.00 g of the polyamic acid ester solution (PAE-2) obtained in Comparative Synthesis Example 1 and 1.021 g of the polyamic acid solution (PAA-1) obtained in Synthesis Example 3 were placed in an Erlenmeyer flask, and 3.99 g of NMP and 2.0128 g of BCS were added, And stirred with a stirrer for 30 minutes to obtain a liquid crystal aligning agent (a).

(Comparative Example 2)

1.5119 g of the polyamic acid ester solution (PAE-2) obtained in Comparative Synthesis Example 1 and 1.4334 g of the polyamic acid solution (PAA-2) obtained in Synthesis Example 4 were charged in an Erlenmeyer flask, 1.0903 g of NMP and 1.0271 g of BCS were added, The mixture was stirred with a stirrer for 30 minutes to obtain a liquid crystal aligning agent (b).

(Comparative Example 3)

3.00 g of the polyamic acid ester solution (PAE-2) obtained in Comparative Synthesis Example 1 and 2.0141 g of the polyamic acid solution (PAA-3) obtained in Synthesis Example 5 were placed in an Erlenmeyer flask, 3.01 g of NMP and 2.0111 g of BCS were added, And stirred with a stirrer for 30 minutes to obtain a liquid crystal aligning agent (c).

(Comparative Example 4)

1.5206 g of the polyamic acid ester solution (PAE-2) obtained in Comparative Synthesis Example 1 and 1.0258 g of the polyamic acid solution (PAA-4) obtained in Synthesis Example 6 were placed in an Erlenmeyer flask, and 1.4838 g of NMP and 1.0418 g of BCS were added, And stirred with a stirrer for 30 minutes to obtain a liquid crystal aligning agent (d).

(Comparative Example 5)

3.1281 g of the polyamic acid ester solution (PAE-1) obtained in Synthesis Example 2 was placed in an Erlenmeyer flask, and 1.0911 g of NMP and 1.0532 g of BCS were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (e).

(Example 5)

The liquid crystal aligning agent (I) obtained in Example 1 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 firing for one hour to form a coating film having a film thickness of 100 nm. The center line average roughness (Ra) was measured for this coating film. The measurement results are shown in Table 1 to be described later.

(Examples 6 to 9 and Comparative Examples 7 to 10)

Except that each of the liquid crystal aligning agents (II) to (IV) and (a) to (d) obtained in Examples 2 to 4 and Comparative Examples 1 to 4 was used, / RTI &gt; The film surface of each coating film was observed with an AFM. The center line average roughness (Ra) was measured for each coating film. The results of these measurements are shown in Table 1 below.

From the results of Examples 5 to 9 and Comparative Examples 7 to 10 shown in Table 1, the liquid crystal aligning agent of the present invention can reduce the fine unevenness caused by the phase separation of the polyamic acid ester and the polyamic acid, It was confirmed that the surface was obtained.

(Example 10)

The liquid crystal aligning agent (I) obtained in Example 1 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 firing for one hour to form a coating film having a film thickness of 100 nm. This coating film was irradiated with ultraviolet rays of 254 nm through a polarizing plate at 100 mJ / cm 2 to obtain a substrate with 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. Then, the two substrates were combined so as to be anti-parallel, And an empty cell having a cell gap of 6 탆 was prepared. A liquid crystal (MLC-2041, manufactured by Merck Co., Ltd.) was injected into the empty cell under vacuum at room temperature, and the injection port was sealed to obtain a liquid crystal cell. For this liquid crystal cell, the voltage holding ratio was measured, 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.

(Examples 11 to 13 and Comparative Examples 11 to 15)

Except that the respective liquid crystal aligning agents (II) to (IV) and (a) to (e) obtained in Examples 2 to 4 and Comparative Examples 1 to 5 were used, Respectively. The voltage holding ratio was measured for each 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.

From the results of Examples 10 to 13 and Comparative Example 15 shown in Table 2, it was confirmed that the liquid crystal aligning agent of the present invention can obtain a liquid crystal alignment film having reliability equal to or higher than that of the liquid crystal aligning agent containing only the polyamic acid ester. From the results of Examples 10 to 13 and Comparative Examples 11 to 14, it can be seen that the liquid crystal aligning agent of the present invention is more reliable than the liquid crystal aligning agent containing polyamic acid ester and polyamic acid which do not contain a low- It was confirmed that a high liquid crystal alignment film was obtained.

(Example 14)

After filtering the liquid crystal aligning agent (I) obtained in Example 1 with a filter of 1.0 mu m, an ITO electrode having a thickness of 50 nm was formed as a first layer on the glass substrate, and a silicon nitride And a FFS driving electrode having a comb-shaped ITO electrode (electrode width: 3 mu m, electrode gap: 6 mu m, electrode height: 50 nm) was formed as a third layer by spin coating. Dried on a hot plate at 80 DEG C for 5 minutes and then fired in a hot air circulating oven at 250 DEG C for 60 minutes to form a coating film having a thickness of 100 nm. This coating film was irradiated with ultraviolet rays of 254 nm through a polarizing plate at 100 mJ / cm 2 to obtain a substrate with a liquid crystal alignment film attached thereto. A coating film was formed on a glass substrate having a columnar spacer having a height of 4 占 퐉, which had no electrode as an opposite substrate, and subjected to orientation treatment.

A sealant was printed on the substrate by using the two substrates as a set and the other substrate was adhered with the alignment direction of the liquid crystal alignment film facing 0 ° so that the sealant was cured to form empty cells Respectively. A liquid crystal MLC-2041 (manufactured by Merck & Co., Inc.) was injected into this empty cell by a vacuum injection method and the injection port was sealed to obtain an FFS-driven liquid crystal cell.

The FFS-driven liquid crystal cell was evaluated for the AC drive bake characteristic and the charge accumulation characteristic. The results are shown in Table 3 below.

(Examples 15 to 17 and Comparative Example 16)

Each of the liquid crystal aligning agents (II) to (IV) and (e) obtained in Examples 2 to 4 and Comparative Example 5 was used to fabricate each FFS driving liquid crystal cell in the same manner as in Example 14. [ Each of the FFS driven liquid crystal cells was evaluated for the AC drive bake characteristic and the charge accumulation characteristic. The results are shown in Table 3 below.

From the results of Examples 14 to 17 and Comparative Example 16 shown in Table 3, it was confirmed that the liquid crystal aligning agent of the present invention obtained a liquid crystal alignment film having a small degree of AC drive baking and a small residual voltage.

(Synthesis Example 7) Synthesis of diamine compound (DA-2)

(Precursor synthesis 1)

(61)

A 1-liter four-necked flask was charged with a gimlet and a 100-ml dropping funnel, and 2-cyano-4-nitroaniline (15 g, 92 mmol) was added thereto. And cooled to 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 the dropwise addition, the mixture was stirred at room temperature for 2 days. After completion of the reaction, hydrochloric acid (2 N, 200 ml) was added, and the mixture was stirred at room temperature for 2 hours. Then, aqueous sodium hydroxide solution (2 N, 250 ml) was added at 10 ° C to make the mixture basic, followed by extraction 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)

(62)

Di-tert-butyl dicarbonate (6.00 g, 27.5 mmol) was added to a 1-liter eggplant-shaped flask to which the above cyano-reduced product (4.60 g, 27.5 mmol) and methylene chloride (900 ml) 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 saline as it was, and dried with magnesium sulfate. The organic layer was concentrated under reduced pressure, and the precipitated solid was recrystallized from ethyl acetate-hexane to obtain a Boc adduct having a yellow solid. The yield was 5.25 g and the yield was 71%.

(Synthesis of DA-2)

(63)

The above Boc adduct (5.0 g, 18.7 mmol) and ethanol (40 ml) were added to a 100 ml eggplant-shaped flask, and the inside of the system was replaced with nitrogen. Then, 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 to dissolve the precipitated white solid, and the catalyst was removed by filtration through Celite. The filtrate was concentrated, and the resulting peach solid was recrystallized from ethyl acetate-hexane to give a pale peach solid. The yield was 3.40 g and the yield was 77%.

¹ H-NMR measurement of the obtained solid confirmed that DA-2 was produced.

(Synthesis Example 8) Synthesis of diamine compound (DA-3)

(Synthesis of N-Boc-Propargylamine)

&Lt; EMI ID =

After adding a solution of propargylamine (25.18 g, 0.448 mol), triethylamine (55.52 g, 0.549 mol) and dichloromethane (400 mL) into a four necked flask, the reaction solution was cooled in a water bath -tert-butyl (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, and 300 ml of a saturated saline solution and 200 ml of dichloromethane were added to the reaction solution. 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)

(65)

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

(Synthesis of DA-3)

(66)

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

(Synthesis Example 9) Synthesis of diamine compound (DA-4)

(67)

P-phenylenediamine (16.2 g, 150 mmol), N, N-dimethylformamide (200 mL) and potassium carbonate (49.8 g, 360 mmol) were placed in a 500 mL eggplant type flask, And a solution of t-butyl bromoacetate (58.5 g, 300 mmol) in N, N-dimethylformamide (100 mL) was added dropwise over 3 hours. Thereafter, the mixture was stirred at room temperature for 20 hours. After the solid in the reaction mixture was removed by filtration, the filtrate was poured into 6 L of water and the crude product of the precipitated diamine compound (D) was recovered. The resulting crude product was dissolved in 100 ml of N, N-dimethylformamide and poured into 2 l of water to precipitate a solid. The solid was washed with methanol and dried under reduced pressure to obtain a pale peach-colored solid diamine compound (DA-4). The yield was 25.1 g and the yield was 50%.

The structure of the diamine compound (D-4) was confirmed by ¹ H NMR.

(Synthesis Example 10) Synthesis of diamine compound (DA-5)

(Synthesis of Nitrozone)

(68)

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 (11.93 g, 117.9 mmol) was added thereto and cooled to -20 占 폚. To this solution was added isobutyl chloroformate (9.99 g, 73.14 mmol) dropwise. 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 opaque. 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 was added 200 ml of ethyl acetate and 200 ml of 1M potassium dihydrogen phosphate aqueous solution to extract. The obtained organic layer was washed once with 1M potassium dihydrogenphosphate aqueous 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 filtrate 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 NMR of the obtained solid was measured. As a result, it was found that the objective nitro chain was obtained (yield: 9.85 g, yield: 54.9%).

(Synthesis of DA-5)

(69)

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 replaced 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 removed from the filtrate. To the obtained concentrate was added 150 ml of toluene, and the mixture was heated to reflux. As a result, a solid precipitated. 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 measurement of the obtained solid confirmed that DA-5 was produced.

(Synthesis Example 11) Synthesis of diamine compound (DA-6)

(Precursor synthesis 1)

(70)

50.00 g (489.3 mmol) of 1,5-diaminopropane, 270.5 g (1.957 mol) of potassium carbonate and 400 g of dimethylsulfoxide were placed in a 2 L four-necked flask, and the mixture was heated and stirred at 100 占 폚. Next, 138.09 g (978.7 mmol) of 4-fluoronitrobenzene and 100 g of dimethyl sulfoxide were added and the mixture was heated and stirred at 100 占 폚 for 4 hours. After 4 hours, the reaction solution was poured into 5 L of water while stirring, and the precipitated yellow solid was collected by filtration. The obtained solid was washed with 3 L of water and 556 g of methanol and dried to obtain a yellow solid (Precursor-1). The yield was 152.71 g. The obtained solid (Precursor-1) was used in the following reaction.

(Synthesis of Precursor 2)

(71)

100 g (290.4 mmol) of the above (Precursor-1), 7.10 g (58.08 mmol) of N, N-dimethylaminopyridine and 800 g of tetrahydrofuran were added to a 2 L four-necked flask, Lt; / RTI &gt; Next, 152.10 g (697.0 mmol) of di tert-butyl adduct was placed in a dropping funnel, and the solution was added dropwise to the solution in a four-necked flask over one hour. After completion of the dropwise addition, the reaction liquid was distilled off with a diverter, to thereby obtain a yellow oily substance. Ethyl acetate was added to the yellow oily substance and 500 ml of a 10 wt% aqueous hydrogen chloride solution was added to the mixture. The obtained organic layer was washed with 500 ml of a 10 wt% aqueous solution of hydrogen chloride and washed twice with 500 ml of water. The obtained organic layer was dried with magnesium sulfate. After removing the drying agent, the solvent was distilled off to obtain a yellow oily substance. The yellow oily substance was allowed to stand overnight, resulting in a yellow solid. 400 g of 2-propanol was added to the solid, followed by washing. The solid was collected by filtration and dried to obtain a yellowish white solid (precursor-2). The yield was 124.32 g. The obtained solid (Precursor-2) was used in the following reaction as it was.

(Synthesis of DA-6)

(72)

100.0 g (183.6 mmol) of the above Precursor-2 and 1500 g of 1,4-dioxane were added to a 2 L four-necked flask. After the reaction vessel was purged with nitrogen, palladium carbon (10.00 g, 10 mass% based on the mass of the nitrile) was added and replaced with nitrogen again. Subsequently, the reaction vessel was purged with hydrogen, and stirred at 20 占 폚 for 24 hours. 800 g of acetonitrile in which a white solid precipitated was added and dissolved. The reaction solution was filtered with a membrane filter (1.0 mu m) to remove palladium carbon. The solvent was removed from the filtrate to give a white solid. To the white solid was added 350 g of 2-propanol and the mixture was stirred for 1 hour. After 1 hour, the solid was filtered, 300 g of 2-propanol was added to the obtained solid, dispersed and washed with an ultrasonic device, followed by filtration and drying to obtain DA-6 as a white solid. The yield was 65.50 g and the yield was 74%. ¹ H-NMR measurement of the obtained solid confirmed that DA-6 was produced.

(Synthesis Example 12) Synthesis of 1,3-bis (4-aminophenetl) urea

(73)

To a four-necked flask under nitrogen purging at room temperature, 2- (4-nitrophenyl) ethylamine hydrochloride

Was added triethylamine (74.90 g, 740 mmol) [A] (52.50 g, 259 mmol), bis (4-nitrophenyl) carbonate [B] (37.53 g, 123 mmol) and THF and 4-N, N-dimethylaminopyridine (3.01 g, 24.7 mmol) were added thereto, and the mixture was stirred with a mechanical stirrer. The reaction was followed by HPLC. After completion of the reaction, the reaction solution was poured into pure water (9 L) and stirred for 30 minutes. Thereafter, filtration was performed, and the filtrate was washed with pure water (1 L) to obtain a crude product of a white solid. The resultant white solid was dispersed and washed with methanol (488 g) using an ultrasonic device, followed by filtration and drying to obtain a dinitro compound [C] as a white solid (Yield 42.3 g, yield 96%).

A mixture of compound [C] (42.32 g, 118 mmol), 5% palladium carbon (4.23 g, 10 wt%) and 1,4-dioxane (2031 g) was replaced with nitrogen, , And the mixture was stirred at room temperature in the presence of hydrogen. The reaction was followed by HPLC. After completion of the reaction, the catalyst was filtered off with celite, and the filtrate was distilled off under reduced pressure to obtain the crude product as a white solid. 2-Propanol (85 g) was added to the crude product, followed by dispersion washing with an ultrasonic device, followed by filtration and drying to obtain 1,3-bis (4-aminophenetyl) urea as white solid g, yield: 91%).

(Synthesis Example 13)

&Lt; EMI ID =

Compound (b) (50.00 g, 229 mmol), pyridine (0.500 g, 0.632 mmol), compound c (63.02, 504 mmol) and acetonitrile (300 g) were added to a 500- The reaction was carried out by heating under reflux. After completion of the reaction, the reaction mixture was cooled to 20 DEG C and then filtered and washed with acetonitrile (100 g) to obtain crude product. Next, 2-propanol (300 g) and distilled water (100 g) were added to the crude product, and the mixture was heated to reflux. Thereafter, the mixture was cooled to 20 캜 and the solid was filtered, washed with 2-propanol (100 g) and dried to obtain a compound (d) (yield: 37.8 g, yield: 37%).

Compound (d) (20.00 g, 44.0 mmol) and thionyl chloride (120.0 g, 1.01 mol) were added to a 500 ml reaction vessel and refluxed under heating. After 30 minutes, the mixture was cooled to 20 ° C, thionyl chloride (120.0 g, 1.01 mol) was added, and the mixture was refluxed for 2 hours. After completion of the reaction, the excess thionyl chloride was distilled off under reduced pressure, and washed with hexane (200 g). Then, dichloromethane (200 g) was added to the crude product at 20 占 폚 and stirred. To the mixture was added a compound (c) (12.1 g, 96.8 mmol), pyridine (13.93 g, 176 mmol), dichloromethane 100 g) was slowly added dropwise. After stirring for 1 hour, a further compound (c) (12.1 g, 96.8 mmol) and pyridine (13.93 g, 176 mmol) were added. After completion of the reaction, the solvent was distilled off and washed with distilled water (144 g) to obtain crude product. Tetrahydrofuran (144 g) was added to the crude product, followed by dispersion washing at 23 ° C, followed by filtration, washing with tetrahydrofuran (130 g), distilled water (170 g) and methanol (150 g) (AD-4) (yield: 17.72 g, yield: 62%).

(Synthesis Example 14)

10.2046 g (39.22 mmol) of 2,4-bis (methoxycarbonyl) cyclobutane-1,3-dicarboxylic acid was added to a 300 ml four-necked flask equipped with a stirrer, 181.2 g of NMP was added, . Subsequently, 8.90 g (87.90 mmol) of triethylamine, 3.8987 g (36.05 mmol) of p-phenylenediamine and 0.9528 g (4.02 mmol) of DA-2 were added and dissolved by stirring. While stirring this solution, 33.74 g (88.01 mmol) of (2,3-dihydroxy-2-thioxo-3-benzoxazoyl) phosphinephosphonate was added and 32 g of NMP was further added, And reacted for 4 hours. The resulting polyamic acid ester solution was added to 1090 g of 2-propanol while stirring, and the precipitated precipitate was collected by filtration, washed with 540 g of 2-propanol five times, and dried to obtain a polyamic acid ester resin powder .

The molecular weight of this polyamic acid ester was Mn = 5210 and Mw = 8755.

2.4495 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 22.1541 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-3).

(Synthesis Example 15)

To a 200 ml four-necked flask equipped with a stirrer was added 1.2736 g (4.51 mmol) of 2,5-bis (methoxycarbonyl) terephthalic acid, 2,4-bis (methoxycarbonyl) cyclobutane- 2.6915 g (10.34 mmol) of the carboxylic acid was added, 73.20 g of NMP was added, and the mixture was dissolved by stirring. Subsequently, 3.34 g (33.01 mmol) of triethylamine, 3.4376 g (12.01 mmol) of 1,3-bis (4-aminophenoxy) propane and 0.7122 g (3.00 mmol) of DA- , And dissolved by stirring. While stirring this solution, 12.65 g (33.0 mmol) of (2,3-dihydroxy-2-thioxo-3-benzoxazoyl) phosphinephosphonate was added, and further 10 g of NMP was added thereto, And reacted for 4 hours. The resulting polyamic acid ester solution was added to 530 g of 2-propanol while stirring, and the precipitated precipitate was collected by filtration, washed with 210 g of 2-propanol five times, and dried to obtain a polyamic acid ester resin powder .

The molecular weight of this polyamic acid ester was Mn = 10281 and Mw = 23163.

2.5429 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 22.9458 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-4).

(Synthesis Example 16)

5.0067 g (25.25 mmol) of 4,4'-diaminodiphenylmethane and 3.0573 g (6.31 mmol) of DA-6 were placed in a 300 ml four-necked flask equipped with a stirrer, and 139 g , 5.57 g (70.36 mmol) of pyridine as a base was added and dissolved by stirring. Next, while stirring the diamine solution, 9.5299 g (29.31 mmol) of 1,3DM-CBDE-Cl was added, and the mixture was allowed to react for 4 hours at a low temperature. The obtained polyamic acid ester solution was added to 1545 g of purified water with stirring. The precipitated white precipitate was collected by filtration, washed once with 1545 g of purified water, once with 1545 g of ethanol, and further with 386 g of ethanol , And dried to obtain a white polyamic acid ester resin powder. The molecular weight of this polyamic acid ester was Mn = 14359 and Mw = 31558.

12.31 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, and 110.79 g of NMP was added and dissolved by stirring at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-5).

(Synthesis Example 17)

5.5958 g (19.83 mmol) of 2,5-bis (methoxycarbonyl) terephthalic acid was placed in a 200 ml four-necked flask equipped with a stirrer, and 68.70 g of NMP was added and dissolved by stirring. Subsequently, 4.01 g (39.63 mmol) of triethylamine, 1.9611 g (16.05 mmol) of 3-aminobenzylamine and 0.9493 g (4.00 mmol) of DA-2 were added and dissolved by stirring. 16.40 g of 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride (15 ± 2 wt% hydrate) Further, 7.72 g of NMP was added thereto and reacted for 4 hours under cooling. The resulting polyamic acid ester solution was added to 633 g of 2-propanol while stirring, and the precipitated precipitate was collected by filtration, washed with 210 g of 2-propanol five times, and dried to obtain a polyamic acid ester resin powder . The molecular weight of this polyamic acid ester was Mn = 5152 and Mw = 8788.

2.5630 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 23.0971 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-6).

(Synthesis Example 18)

1.5163 g (7.65 mmol) of 4,4'-diaminodiphenylmethane and 2.8712 g (7.57 mmol) of DA-1 were placed in a 300 ml four-necked flask equipped with a stirrer and 73.3 g , 2.82 g (35.59 mmol) of pyridine as a base was added and dissolved by stirring. Next, while stirring the diamine solution, 4.8583 g (14.94 mmol) of 1,3DM-CBDE-Cl was added, and the mixture was allowed to react for 4 hours at a low temperature. After 4 hours, 81.44 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 850 g of 2-propanol while stirring, and the precipitated white precipitate was collected by filtration, followed by washing with 170 g of 2-propanol five times and drying to obtain white polyamic acid ester resin powder &Lt; / RTI &gt; The molecular weight of this polyamic acid ester was Mn = 21514 and Mw = 43900.

2.1684 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 19.2226 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-7).

(Synthesis Example 19)

1.7312 g (16.01 mmol) of p-phenylenediamine and 0.9444 g (3.98 mmol) of DA-2 were placed in a 200 ml four-necked flask equipped with a stirrer and a nitrogen introducing tube, 32.47 g of NMP was added, Followed by stirring and dissolving. To this diamine solution, 4.4841 g (20.0 mmol) of 2.3.5-tricarboxycyclopentylacetic acid dianhydride was added while stirring, and further NMP was added so that the solid concentration became 15 mass%, followed by stirring at room temperature for 24 hours. The viscosity of this solution at 25 캜 was 580 mPa s. 23.28 g of NMP was added to this solution to adjust the solid concentration to 10 mass%, 6.04 g (40.5 mmol) of 1-methyl-3-p-tolyltriazole was added, and the mixture was stirred at room temperature for 4 hours. After 4 hours, the reaction solution was added to 286 g of 2-propanol while stirring, and the precipitated precipitate was collected by filtration, washed with 140 g of 2-propanol five times, and dried to obtain a polyamic acid ester resin powder . The molecular weight of this polyamic acid ester was Mn = 16532 and Mw = 50698.

2.2078 g of the obtained polyamic acid ester resin powder was placed in a 50 ml sample tube equipped with a stirrer, 19.7894 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-8).

(Synthesis Example 20)

1.9995 g (13.28 mmol) of 4-amino-N-methylphenethylamine and 0.9379 g (3.35 mmol) of DA-5 were placed in a 300 ml four-necked flask equipped with a stirrer and NMP was maintained at 130.70 g, and 3.80 g (37.54 mmol) of pyridine as a base were added and dissolved by stirring. Then, while stirring the diamine solution, 5.0894 g (15.65 mmol) of 1,3DM-CBDE-Cl was added, and the mixture was allowed to react at a low temperature for 4 hours. The obtained polyamic acid ester solution was added to 688 g of 2-propanol while stirring, and the precipitated white precipitate was collected by filtration, followed by washing with 172 g of 2-propanol five times and drying to obtain white polyamic acid ester resin powder &Lt; / RTI &gt; The molecular weight of this polyamic acid ester was Mn = 7331 and Mw = 14716.

1.9755 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 17.7314 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-9).

(Synthesis Example 21)

0.6005 g (5.55 mmol) of p-phenylenediamine, 0.2334 g (0.694 mmol) of DA-4 and 0.1849 g (0.693 mmol) of DA-3 were placed in a 100 ml four-necked flask equipped with a stirrer under a nitrogen atmosphere. ), 49.80 g of NMP and 1.15 g (14.56 mmol) of pyridine as a base were added and dissolved by stirring. Next, 2.2550 g (6.94 mmol) of 1,3DM-CBDE-Cl was added to the diamine solution while stirring, and the mixture was allowed to react at a low temperature for 4 hours. The obtained polyamic acid ester solution was added to 277 g of water with stirring. The precipitated white precipitate was collected by filtration, washed with 69 g of water five times, and dried to obtain a white polyamic acid ester resin powder. The molecular weight of the polyamic acid ester was Mn = 16919 and Mw = 27982.

2.0204 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 18.1836 g of GBL was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-10).

(Synthesis Example 22)

To a 300 ml four-necked flask equipped with a stirrer were added 2.2570 g (8.00 mmol) of 2,5-bis (methoxycarbonyl) terephthalic acid, 2,4-bis (methoxycarbonyl) cyclobutane- 3.0206 g (11.61 mmol) of the carboxylic acid was added, and 100.35 g of NMP was added and dissolved by stirring. Subsequently, 4.45 g (43.98 mmol) of triethylamine, 3.0934 g (11.98 mmol) of 1,5-bis (4-aminophenoxy) (4.03 mmol) of DA-3, 1.0653 g (4.02 mmol) of DA-3, and dissolved by stirring. While stirring this solution, 16.92 g (44.14 mmol) of (2,3-dihydroxy-2-thioxo-3-benzoxazoyl) phosphinate was added, and further 13.14 g of NMP was added thereto, And reacted for 4 hours. The resulting polyamide acid ester solution was added to 890 g of 2-propanol while stirring, and the precipitated precipitate was collected by filtration, washed with 300 g of 2-propanol five times, and dried to obtain a polyamic acid ester resin powder .

The molecular weight of this polyamic acid ester was Mn = 9170 and Mw = 19990.

1.8720 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, and 16.9543 g of NMP was added thereto. The mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-11).

(Synthesis Example 23)

A 300 ml four-necked flask equipped with a stirrer was charged with 3.02 g (27.93 mmol) of p-phenylenediamine, 173.0 g of NMP and 5.16 g (65.25 mmol) of pyridine as a base, and the mixture was stirred . Next, while stirring the diamine solution, 8.09 g (27.23 mmol) of dimethyl 2,4-bis (chlorocarbonyl) cyclobutane-1,3-dicarboxylate was added and reacted for 2 hours at a low temperature. The obtained polyamic acid ester solution was poured into 1000 g of water, the precipitated white precipitate was collected by filtration, washed with 300 g of 2-propanol five times, and dried to obtain a white polyamic acid ester resin powder. The molecular weight of this polyamic acid ester was Mn = 10820 and Mw = 29197.

The obtained polyamic acid ester resin powder 1.5309 was placed in a 50 ml Erlenmeyer flask, and 13.7781 g of NMP and 16.9279 g of N, N-dimethylformamide were added and dissolved by stirring at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE- .

(Synthesis Example 24)

To a 200 ml four-necked flask equipped with a stirrer were added 1.7779 g (6.30 mmol) of 2,5-bis (methoxycarbonyl) terephthalic acid, 2,4-bis (methoxycarbonyl) cyclobutane- 3.7712 g (14.49 mmol) of the carboxylic acid was added, and 146.71 g of NMP was added and dissolved by stirring. Subsequently, 4.25 g (42.0 mmol) of triethylamine and 5.4239 g (21.0 mmol) of 1,3-bis (4-aminophenoxy) propane were added and dissolved by stirring. While stirring this solution, 16.91 g (44.11 mmol) of (2,3-dihydroxy-2-thioxo-3-benzoxazoyl) phosphinate was added and 25.81 g of NMP was further added thereto And reacted for 4 hours. The resulting polyamic acid ester solution was added to 1224 g of methanol while stirring, and the precipitated precipitate was collected by filtration, washed with 408 g of methanol four times, and dried to obtain a polyamic acid ester resin powder. The molecular weight of this polyamic acid ester was Mn = 15103 and Mw = 32483.

1.0172 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 9.4167 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-13).

(Synthesis Example 25)

A 300 ml four-necked flask equipped with a stirrer was charged with 5.0086 g (25.26 mmol) of 4,4'-diaminodiphenylmethane and 1.8064 g (25.26 mmol) of 1,5-bis (4-aminophenoxy) 6.31 mmol), 272 g of NMP and 5.69 g (71.88 mmol) of pyridine as a base were added and dissolved by stirring. Next, 9.7356 g (29.94 mmol) of 1,3DM-CBDE-Cl was added to the diamine solution while stirring, and the mixture was reacted under the reduced pressure for 4 hours. The obtained polyamic acid ester solution was added to 1436 g of pure water with stirring. The precipitated white precipitate was collected by filtration, washed once with 1,436 g of pure water and once with 1,436 g of ethanol, and further with 386 g of ethanol , And dried to obtain a white polyamic acid ester resin powder. The molecular weight of this polyamic acid ester was Mn = 15205 and Mw = 30219.

11.89 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 107.01 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-14).

(Synthesis Example 26)

3.7141 g (13.16 mmol) of 2,5-bis (methoxycarbonyl) terephthalic acid was placed in a 200 ml four-necked flask equipped with a stirrer, and 72.31 g of NMP was added and dissolved by stirring. Subsequently, 0.71 g (7.01 mmol) of triethylamine and 1.7112 g (14.01 mmol) of 3-aminobenzylamine were added and dissolved by stirring. 11.6258 g of 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride (15 ± 2 wt% hydrate) Further, 12.91 g of NMP was added and reacted under water cooling for 4 hours. The resulting polyamic acid ester solution was added to 616 g of methanol while stirring, and the precipitated precipitate was collected by filtration, washed with 616 g of methanol four times, and dried to obtain a polyamic acid ester resin powder. The molecular weight of this polyamic acid ester was Mn = 7234 and Mw = 15577.

1.1325 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 10.1925 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-15).

(Synthesis Example 27)

In a 300 ml four-necked flask equipped with a stirrer, 7.0100 g (64.82 mmol) of p-phenylenediamine was added, and 108 g of NMP, 324 g of? -BL and 11.55 g of pyridine as a base Mol), and dissolved by stirring. Next, 19.7838 g (60.85 mmol) of 1,3DM-CBDE-Cl was added to the diamine solution while stirring, and the mixture was reacted for 4 hours at a low temperature. The obtained polyamic acid ester solution was added to 1881 g of 2-propanol while stirring, and the precipitated white precipitate was collected by filtration, followed by washing with 940 g of 2-propanol five times and drying to obtain white polyamic acid ester resin powder &Lt; / RTI &gt; The molecular weight of this polyamic acid ester was Mn = 11325 and Mw = 24387.

1.2019 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 10.8171 g of N, N-diethylformamide was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-16).

(Synthesis Example 28)

3.0144 g (20.07 mmol) of 4-amino-N-methylphenethylamine was added to a 300 ml four-necked flask equipped with a stirrer, and 148.88 g of NMP and 4.65 g (46.01 mmol ), And dissolved by stirring. Next, 6.2390 g (19.19 mmol) of 1,3DM-CBDE-Cl was added to the diamine solution while stirring, and the mixture was reacted for 4 hours at a low temperature. The obtained polyamic acid ester solution was added to 784 g of water while stirring, and the precipitated white precipitate was collected by filtration, followed by washing with 784 g of water and 196 g of 2-propanol three times and drying to obtain white polyamic acid To obtain an ester resin powder. The molecular weight of this polyamic acid ester was Mn = 8691 and Mw = 20311.

1.9144 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 17.2026 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-17).

(Synthesis Example 29)

20.0838 g (132.0 mmol) of 3,5-diaminobenzoic acid and 21.3254 g (88.0 mmol) of DA-7 were placed in a 100-ml four-necked flask equipped with a stirrer and a nitrogen introducing tube, 268.48 g of NMP was added, And dissolved with stirring while nitrogen was supplied. 42.4946 g (216.7 mmol) of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride was added while stirring the diamine solution, NMP was added so that the solid content concentration became 20 mass%, and 24 And stirred for a time to obtain a solution of polyamic acid (PAA-5). The viscosity of the polyamic acid solution at 25 캜 was 2156 mPa.. The molecular weight of the polyamic acid was Mn = 18794 and Mw = 63387.

(Synthesis Example 30)

3.5843 g (17.99 mmol) of 4,4'-diaminodiphenylamine and 2.9064 g (12.0 mmol) of DA-7 were placed in a 100-mL four-necked flask equipped with a stirrer and a nitrogen introducing tube, 55.58 g And the mixture was stirred to dissolve while nitrogen was being fed. While this diamine solution was stirred, 5.7653 g (29.40 mmol) of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride was added and NMP was added thereto so that the solid content concentration became 15 mass%, and 24 Lt; / RTI &gt; The viscosity of the obtained polyamic acid solution at 25 캜 was 1269 mPa.. The molecular weight of the polyamic acid was Mn = 15559 and Mw = 43490. Further, 0.0368 g of 3-glycidoxypropylmethyldiethoxysilane was added to this solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyamic acid solution (PAA-6).

(Synthesis Example 31)

In a 100 ml four-necked flask equipped with a stirrer and a nitrogen introduction tube, 1.2133 g (7.97 mmol) of 3,5-diaminobenzoic acid and 6.8216 g (31.98 g) of 4,4'-diaminodiphenyl- mmol), 44.03 g of NMP was added, and dissolved with stirring while nitrogen was being supplied. While stirring the diamine solution, 7.1310 g (36.0 mmol) of BDA was added, and the mixture was stirred at room temperature for 2 hours. Next, 14.62 g of NMP was added, and 0.8713 g (3.99 mmol) of pyromellitic dianhydride was added. Further, NMP was added so that the solid concentration became 18 mass%, and the mixture was stirred at room temperature for 24 hours. The viscosity of the obtained polyamic acid solution at 25 캜 was 577 mPa.. The molecular weight of the polyamic acid was Mn = 12656 and Mw = 28487.

Further, 0.0480 g of 3-glycidoxypropylmethyldiethoxysilane was added to this solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyamic acid solution (PAA-7).

(Synthesis Example 32)

In a 100 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, 3.6541 g (24.02 mmol) of 3,5-diaminobenzoic acid and 4.2931 g (16.00 mmol) of 1,4-bis ), 36.48 g of NMP was added, and dissolved with stirring while nitrogen was supplied. While stirring the diamine solution, 4.7522 g (23.99 mmol) of BDA was added, and the mixture was stirred at room temperature for 2 hours. Next, 36.50 g of NMP was added, and 3.4084 g (15.63 mmol) of pyromellitic dianhydride was added. Further, NMP was added so that the solid concentration became 15 mass%, and the mixture was stirred at room temperature for 24 hours. The viscosity of the obtained polyamic acid solution at 25 캜 was 1166 mPa.. The molecular weight of this polyamic acid was Mn = 19307 and Mw = 42980.

Further, 0.0483 g of 3-glycidoxypropylmethyldiethoxysilane was added to this solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyamic acid solution (PAA-8).

(Synthesis Example 33)

3.6536 g (24.01 mmol) of 3,5-diaminobenzoic acid and 3.8715 g (15.98 mmol) of DA-7 were placed in a 100-mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, and 31.75 g of NMP was added, And dissolved with stirring while nitrogen was supplied. While stirring the diamine solution, 3.9621 g (20.0 mmol) of BDA was added, and the mixture was stirred at room temperature for 2 hours. Next, 25.42 g of NMP was added, and 4.4776 g (19.97 mmol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride was added. Further, NMP was added so that the solid concentration became 20 mass%, and the mixture was stirred at room temperature for 24 hours. The viscosity of the obtained polyamic acid solution at 25 캜 was 417 mPa s. The molecular weight of the polyamic acid was Mn = 13291 and Mw = 54029.

Further, 0.0476 g of 3-glycidoxypropylmethyldiethoxysilane was added to this solution and stirred at room temperature for 24 hours to obtain a polyamic acid solution (PAA-9).

(Synthesis Example 34)

In a 100 ml four-necked flask equipped with a stirrer and a nitrogen-introducing tube, 2.7365 g (17.99 mmol) of 3,5-diaminobenzoic acid and 2.5471 g of 2,2'-dimethyl-4,4'-diaminobiphenyl 12.0 mmol), 27.32 g of NMP was added, and dissolved with stirring while nitrogen was being supplied. 2.2562 g (9.02 mmol) of bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid dianhydride was added while stirring the diamine solution, and the mixture was stirred at 80 ° C for 3 hours. After the reaction solution was cooled to room temperature, 27.32 g of NMP was added, and 4.5715 g (20.96 mmol) of pyromellitic dianhydride was added. Further, NMP was added so that the solid concentration became 15 mass%, and the mixture was stirred at room temperature for 24 hours. The viscosity of the obtained polyamic acid solution at 25 캜 was 2190 mPa.. The molecular weight of this polyamic acid was Mn = 23632 and Mw = 56881.

Further, 0.0360 g of 3-glycidoxypropylmethyldiethoxysilane was added to this solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyamic acid solution (PAA-10).

(Synthesis Example 35)

(40.0 mmol) of 3,5-diaminobenzoic acid was added to a 100-ml four-necked flask equipped with a stirrer and a nitrogen-introducing tube, 65.56 g of NMP was added, and dissolved with stirring while nitrogen was being supplied. While this diamine solution was stirred, 8.5449 g (39.18 mmol) of pyromellitic dianhydride was added, and further NMP was added so that the solid concentration became 15 mass%, followed by stirring at room temperature for 24 hours. The viscosity of the obtained polyamic acid solution at 25 캜 was 523 mPa s. The molecular weight of this polyamic acid was Mn = 20565 and Mw = 47912.

Further, 13.79 g of a 0.3 mass% 3-glycidoxypropylmethyldiethoxysilane NMP solution was added to this solution to obtain a polyamic acid solution (PAA-11).

(Synthesis Example 36)

3.2080 g (16.02 mmol) of 4,4'-diaminodiphenyl ether and 5.8147 (24.0 mmol) of DA-7 were placed in a 100-mL four-necked flask equipped with a stirrer and a nitrogen introducing tube. 60.42 g of NMP And dissolved with stirring while nitrogen was being supplied. 7.7658 g (39.60 mmol) of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride was added while stirring the diamine solution, NMP was added thereto so that the solid concentration became 20 mass%, and the mixture was stirred at room temperature for 24 hours Lt; / RTI &gt; The viscosity of the obtained polyamic acid solution at 25 캜 was 1972 mPa s. The molecular weight of the polyamic acid was Mn = 15159 and Mw = 38251. Further, 0.0504 g of 3-glycidoxypropylmethyldiethoxysilane was added to this solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyamic acid solution (PAA-12).

(Synthesis Example 37)

2.4301 g (15.97 mmol) of 3,5-diaminobenzoic acid and 9.4204 g (24.0 mmol) of DA-8 were placed in a 100-ml four-necked flask equipped with a stirrer and a nitrogen introducing tube, 44.60 g of NMP was added, And dissolved with stirring while nitrogen was supplied. While stirring the diamine solution, 4.7505 g (23.98 mmol) of BDA was added, and the mixture was stirred at room temperature for 2 hours. Next, 44.59 g of NMP was added, and 3.1054 g (15.84 mmol) of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride was added. Further, NMP was added so that the solid concentration became 15 mass%, and the mixture was stirred at room temperature for 24 hours. The viscosity of the obtained polyamic acid solution at 25 캜 was 802 mPa.. The molecular weight of the polyamic acid was Mn = 13261 and Mw = 32578.

Further, 0.0590 g of 3-glycidoxypropylmethyldiethoxysilane was added to this solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyamic acid solution (PAA-13).

(Synthesis Example 38)

3.6504 g (23.69 mmol) of 3,5-diaminobenzoic acid and 3.8718 g (15.98 mmol) of DA-7 were placed in a 100-mL four-necked flask equipped with a stirrer and a nitrogen introducing tube, 68.6 g of NMP was added, And dissolved with stirring while nitrogen was supplied. 11.5387 g (39.21 mmol) of DAH-1 was added while stirring the diamine solution. Further, NMP was added so that the solid concentration became 20 mass%, and the mixture was stirred at room temperature for 24 hours. The viscosity of the obtained polyamic acid solution at 25 캜 was 736 mPa.. The molecular weight of the polyamic acid was Mn = 10091 and Mw = 19511.

Further, 0.0572 g of 3-glycidoxypropylmethyldiethoxysilane was added to this solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyamic acid solution (PAA-14).

(Synthesis Example 39)

To a 100 ml four-necked flask equipped with a stirrer and a nitrogen-introducing tube were charged 3.6603 g (24.06 mmol) of 3,5-diaminobenzoic acid and 4.7740 g (16.0 mmol) of 1,3-bis (4-aminophenetyl) urea ), 28.59 g of NMP was added, and dissolved by stirring while nitrogen was being supplied. While stirring the diamine solution, 2.3782 g (12.0 mmol) of BDA was added, and the mixture was stirred at room temperature for 2 hours. Next, 38.13 g of NMP was added, and 6.0903 g (27.92 mmol) of pyromellitic dianhydride was added. Further, NMP was added so that the solid concentration became 15 mass%, and the mixture was stirred at room temperature for 24 hours. The viscosity of the obtained polyamic acid solution at 25 캜 was 744 mPa.. The molecular weight of the polyamic acid was Mn = 17771 and Mw = 38991.

Further, 0.0505 g of 3-glycidoxypropylmethyldiethoxysilane was added to this solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyamic acid solution (PAA-15).

(Synthesis Example 40)

0.6123 g (4.00 mmol) of 3,5-diaminobenzoic acid and 3.199 g (16.06 mmol) of 4,4-diaminodiphenylamine were placed in a 100-mL four-necked flask equipped with a stirrer and a nitrogen introduction tube. Was added, and dissolved with stirring while nitrogen was being fed. While stirring the diamine solution, 3.1780 g (16.04 mmol) of BDA was added, and the mixture was stirred at room temperature for 2 hours. Next, 8.93 g of NMP was added, and 0.8736 g (4.01 mmol) of pyromellitic dianhydride was added. Further, NMP was added so that the solid concentration became 18 mass%, and the mixture was stirred at room temperature for 24 hours. The viscosity of the obtained polyamic acid solution at 25 캜 was 8100 mPa.. The molecular weight of the polyamic acid was Mn = 22537 and Mw = 72601.

Further, 0.0235 g of 3-glycidoxypropylmethyldiethoxysilane was added to this solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyamic acid solution (PAA-16).

(Synthesis Example 41)

3.6516 g (24.0 mmol) of 3,5-diaminobenzoic acid and 2.4070 g (16.02 mmol) of 4-amino-N-methylphenethylamine were placed in a 100-ml four-necked flask equipped with a stirrer and a nitrogen- , 66.21 g of NMP was added, and dissolved with stirring while nitrogen was supplied. While stirring the diamine solution, 8.5972 g (39.42 mmol) of pyromellitic dianhydride was added. Further, NMP was added so that the solid concentration became 15 mass%, and the mixture was stirred at room temperature for 24 hours. The viscosity of the obtained polyamic acid solution at 25 캜 was 488 mPa.. The molecular weight of the polyamic acid was Mn = 13205 and Mw = 33511.

Further, 0.0438 g of 3-glycidoxypropylmethyldiethoxysilane was added to this solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyamic acid solution (PAA-17).

(Synthesis Example 42)

3.6532 g (24.01 mmol) of 3,5-diaminobenzoic acid and 3.8790 g (16.01 mmol) of DA-7 were placed in a 100-mL four-necked flask equipped with a stirrer and a nitrogen introducing tube, 70.32 g of NMP was added, And dissolved with stirring while nitrogen was supplied. 12.0709 g (39.41 mmol) of DAH-2 was added while stirring the diamine solution. Further, NMP was added so that the solid concentration became 20 mass%, and the mixture was stirred at room temperature for 24 hours. The viscosity of the obtained polyamic acid solution at 25 캜 was 207 mPa.. The molecular weight of the polyamic acid was Mn = 5269 and Mw = 12875.

Further, 0.0586 g of 3-glycidoxypropylmethyldiethoxysilane was added to this solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyamic acid solution (PAA-18).

(Example 18)

3.6139 g of the polyamic acid ester solution (PAE-3) obtained in Synthesis Example 14 and 2.7012 g of the polyamic acid solution (PAA-5) obtained in Synthesis Example 29 were placed in a 50 ml Erlenmeyer flask, 5.7093 g of NMP, 3.01 g of BCS and 0.1284 g of 4- (t-butoxycarbonylamino) pyridine (hereinafter abbreviated as Boc-AP) as an imidization promoter were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (I-1).

(Example 19)

2.4040 g of the polyamic acid ester solution (PAE-4) obtained in Synthesis Example 15 and 2.4687 g of the polyamic acid solution (PAA-6) obtained in Synthesis Example 30 were placed in a 50 ml Erlenmeyer flask and 3.2072 g of NMP, 2.0348 g of BCS and 0.0542 g of Boc-AP as an imidization promoter were added and stirred with a magnetic stirrer for 30 minutes to obtain liquid crystal aligning agent (I-2).

(Example 20)

2.4548 g of the polyamic acid ester solution (PAE-4) obtained in Synthesis Example 15 and 2.0213 g of the polyamic acid solution (PAA-6) obtained in Synthesis Example 31 were placed in a 50 ml Erlenmeyer flask, 2.0116 g of BCS was added, and 0.0415 g of Boc-AP as an imidization accelerator was further added and stirred for 30 minutes by a magnetic stirrer to obtain liquid crystal aligning agent (I-3).

(Example 21)

2.4232 g of the polyamic acid ester solution (PAE-5) obtained in Synthesis Example 16 and 2.4189 g of the polyamic acid solution (PAA-9) obtained in Synthesis Example 33 were placed in a 50 ml Erlenmeyer flask, and 3.2928 g of NMP, 2.0272 g of BCS and 0.0416 g of N-α- (9-fluorenylmethoxycarbonyl) -Nt-butoxycarbonyl-L-histidine (hereinafter abbreviated as Fmoc-His) as an imidization promoter , And the mixture was stirred with a magnetic stirrer for 30 minutes to obtain liquid crystal aligning agent (I-4).

(Example 22)

2.4232 g of the polyamic acid ester solution (PAE-5) obtained in Synthesis Example 16 and 1.8681 g of the polyamic acid solution (PAA-9) obtained in Synthesis Example 33 were placed in a 50 ml Erlenmeyer flask and 3.6548 g of NMP, 2.0158 g of BCS and 0.0372 g of Fmoc-His as an imidization accelerator were added and stirred for 30 minutes by a magnetic stirrer to obtain liquid crystal aligning agent (I-5).

(Example 23)

2.4356 g of the polyamic acid ester solution (PAE-6) obtained in Synthetic Example 17 and 2.5278 g of the polyamic acid solution (PAA-10) obtained in Synthetic Example 34 were placed in a 50 ml Erlenmeyer flask and 3.2644 g of NMP, 2.0366 g of BCS and 0.0550 g of Fmoc-His as an imidization accelerator were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (I-6).

(Example 24)

2.4012 g of the polyamic acid ester solution (PAE-7) obtained in Synthesis Example 18 and 2.4115 g of the polyamic acid solution (PAA-11) obtained in Synthesis Example 35 were placed in a 50 ml Erlenmeyer flask, 2.6514 g of NMP, 2.0052 g of BCS was added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (II-1).

(Example 25)

2.4130 g of the polyamic acid ester solution (PAE-7) obtained in Synthesis Example 18 and 2.4216 g of the polyamic acid solution (PAA-11) obtained in Synthesis Example 35 were placed in a 50 ml Erlenmeyer flask, 2.6780 g of NMP, 2.0198 g of BCS and 0.3062 g of a 20 mass% NMP solution of polyfunctional epoxy compound (AD-1) as a crosslinking agent were added and stirred with a magnetic stirrer for 30 minutes to obtain liquid crystal aligning agent (II-2).

(Example 26)

2.4302 g of the polyamic acid ester solution (PAE-4) obtained in Synthesis Example 15 and 1.8678 g of the polyamic acid solution (PAA-12) obtained in Synthesis Example 36 were placed in a 50 ml Erlenmeyer flask, and 3.8086 g of NMP, 2.0060 g of BCS was added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain liquid crystal aligning agent (II-3).

(Example 27)

2.4144 g of the polyamic acid ester solution (PAE-4) obtained in Synthesis Example 15 and 1.8062 g of the polyamic acid solution (PAA-12) obtained in Synthesis Example 36 were placed in a 50 ml Erlenmeyer flask, 3.8184 g of NMP, 2.0168 g of BCS and 0.040 g of a polyfunctional hydroxyl group-containing compound (AD-2) as a crosslinking agent were added and stirred with a magnetic stirrer for 30 minutes to obtain liquid crystal aligning agent (II-4).

(Example 28)

2.4015 g of the polyamic acid ester solution (PAE-4) obtained in Synthesis Example 15 and 1.8005 g of the polyamic acid solution (PAA-13) obtained in Synthesis Example 37 were placed in a 50 ml Erlenmeyer flask, and 3.8063 g of NMP, 2.0011 g of BCS was added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (II-5).

(Example 29)

2.4120 g of the polyamic acid ester solution (PAE-8) obtained in Synthesis Example 19 and 1.8389 g of the polyamic acid solution (PAA-14) obtained in Synthesis Example 38 were placed in a 50 ml Erlenmeyer flask, and 3.8639 g of NMP, 2.0181 g of BCS was added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (II-6).

(Example 30)

2.4120 g of the polyamic acid ester solution (PAE-8) obtained in Synthesis Example 19 and 1.8389 g of the polyamic acid solution (PAA-14) obtained in Synthesis Example 38 were placed in a 50 ml Erlenmeyer flask, and 3.8639 g of NMP, 2.0181 g of BCS and 0.0318 g of a polyfunctional cyclocarbonate compound (AD-4) as a crosslinking agent were added and stirred with a magnetic stirrer for 30 minutes to obtain liquid crystal aligning agent (II-7).

(Example 31)

1.2268 g of the polyamic acid ester solution (PAE-9) obtained in Synthesis Example 20 and 3.2688 g of the polyamic acid solution (PAA-15) obtained in Synthesis Example 39 were placed in a 50 ml Erlenmeyer flask, 3.6154 g of NMP, 2.0591 g of BCS was added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (II-8).

(Example 32)

2.4236 g of the polyamic acid ester solution (PAE-10) obtained in Synthesis Example 21 and 2.3539 g of the polyamic acid solution (PAA-16) obtained in Synthesis Example 40 were placed in a 50 ml Erlenmeyer flask, 0.3782 g of NMP, 3.0639 g of? -BL and 2.0178 g of BCS were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (II-9).

(Example 33)

4.2045 g of the polyamic acid ester solution (PAE-5) obtained in Synthesis Example 16 and 1.2281 g of the polyamic acid solution (PAA-17) obtained in Synthesis Example 41 were placed in a 50 ml Erlenmeyer flask, 2.6041 g of NMP, 2.0112 g of BCS was added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (II-10).

(Example 34)

2.4195 g of the polyamic acid ester solution (PAE-11) obtained in Synthesis Example 22 and 1.8484 g of the polyamic acid solution (PAA-5) obtained in Synthesis Example 29 were placed in a 50 ml Erlenmeyer flask, 2.0204 g of BCS was added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (II-11).

(Example 35)

2.4176 g of the polyamic acid ester solution (PAE-6) obtained in Synthesis Example 17 and 2.0148 g of the polyamic acid solution (PAA-18) obtained in Synthesis Example 42 were placed in a 50 ml Erlenmeyer flask, 3.8182 g of NMP, 2.0129 g of BCS was added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (II-12).

(Example 36)

2.3987 g of the polyamic acid ester solution (PAE-6) obtained in Synthesis Example 17 and 2.1543 g of the polyamic acid solution (PAA-18) obtained in Synthesis Example 42 were placed in a 50 ml Erlenmeyer flask, and 3.8130 g of NMP, 2.0374 g of BCS and 0.0460 g of polyfunctional oxetane compound (AD-3) as a crosslinking agent were added and stirred for 30 minutes by a magnetic stirrer to obtain liquid crystal aligning agent (I-13).

(Comparative Example 17)

7.2164 g of the polyamic acid ester solution (PAE-12) obtained in Synthesis Example 23 and 2.7470 g of the polyamic acid solution (PAA-5) obtained in Synthesis Example 29 were placed in a 50 ml Erlenmeyer flask, 2.1068 g of NMP, 3.0264 g of BCS and 0.1396 g of Boc-AP as an imidization accelerator were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (a-1).

(Comparative Example 18)

2.4504 g of the polyamic acid ester solution (PAE-13) obtained in Synthesis Example 24 and 2.4805 g of the polyamic acid solution (PAA-6) obtained in Synthesis Example 30 were placed in a 50 ml Erlenmeyer flask, and 3.2447 g of NMP, 2.0226 g of BCS and 0.0547 g of Boc-AP as an imidization promoter were added and stirred for 30 minutes by a magnetic stirrer to obtain a liquid crystal aligning agent (a-2).

(Comparative Example 19)

2.4012 g of the polyamic acid ester solution (PAE-14) obtained in Synthetic Example 25 and 1.8320 g of the polyamic acid solution (PAA-9) obtained in Synthetic Example 33 were placed in a 50 ml Erlenmeyer flask and 3.8172 g of NMP, 2.0195 g of BCS and 0.0433 g of Fmoc-His as an imidization accelerator were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (a-5).

(Comparative Example 20)

2.4017 g of the polyamic acid ester solution (PAE-15) obtained in Synthesis Example 26 and 2.5777 g of the polyamic acid solution (PAA-9) obtained in Synthesis Example 33 were placed in a 50 ml Erlenmeyer flask, and 3.2518 g of NMP, 2.000 g of BCS and 0.0550 g of Fmoc-His as an imidization accelerator were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (a-6).

(Comparative Example 21)

2.4335 g of the polyamic acid ester solution (PAE-2) obtained in Comparative Synthesis Example 1 and 2.4013 g of the polyamic acid solution (PAA-11) obtained in Synthesis Example 35 were placed in a 50 ml Erlenmeyer flask and 2.6238 g , 2.0105 g of BCS was added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (b-1).

(Comparative Example 22)

2.4264 g of the polyamic acid ester solution (PAE-13) obtained in Synthesis Example 24 and 1.8157 g of the polyamic acid solution (PAA-12) obtained in Synthesis Example 36 were placed in a 50 ml Erlenmeyer flask, 3.8352 g of NMP, 2.0448 g of BCS was added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (b-3).

(Comparative Example 23)

1.2049 g of the polyamic acid ester solution (PAE-17) obtained in Synthesis Example 28 and 3.2102 g of the polyamic acid solution (PAA-15) obtained in Synthesis Example 39 were added to a 50 ml Erlenmeyer flask and 3.6342 g of NMP, 2.0694 g of BCS was added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (b-9).

(Comparative Example 24)

2.4025 g of the polyamic acid ester solution (PAE-16) obtained in Synthesis Example 27 and 2.2514 g of the polyamic acid solution (PAA-16) obtained in Synthesis Example 40 were placed in a 50 ml Erlenmeyer flask, and 0.3792 g of NMP, 3.0007 g of? -BL and 2.0015 g of BCS were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (b-10).

(Comparative Example 25)

4.2242 g of the polyamic acid ester solution (PAE-14) obtained in Synthetic Example 25 and 1.2473 g of the polyamic acid solution (PAA-17) obtained in Synthetic Example 41 were placed in a 50 ml Erlenmeyer flask, 2.6481 g of NMP, 2.0664 g of BCS was added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (b-11).

(Comparative Example 26)

2.4260 g of the polyamic acid ester solution (PAE-15) obtained in Synthesis Example 26 and 2.2122 g of the polyamic acid solution (PAA-18) obtained in Synthesis Example 42 were placed in a 50 ml Erlenmeyer flask, 3.8118 g of NMP, 2.0585 g of BCS was added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (b-13).

(Example 37)

The liquid crystal aligning agent (I-1) obtained in Example 18 was filtered with a filter of 1.0 占 퐉 and then spin-coated on a glass substrate with a transparent electrode, followed by drying on a hot plate at 80 占 폚 for 5 minutes, Deg.] C in a warm air circulating oven for 20 minutes to obtain an imidized film having a film thickness of 100 nm. The center line average roughness (Ra) was measured for the imidized film. The measurement results are shown in Table 4 described later.

(Examples 38 to 52 and Comparative Examples 27 to 35)

Each coating film was formed in the same manner as in Example 37 except that the respective liquid crystal aligning agents obtained in Examples 19, 22, 24 to 27, 29 to 36 and Comparative Examples 17 to 19, 21 to 26 were used. The film surface of each coating film was observed with an AFM. The center line average roughness (Ra) was measured for each coating film. The results of these measurements are shown in Table 4 below.

Industrial availability

The liquid crystal aligning agent of the present invention can improve the characteristics of the interface between the liquid crystal and the liquid crystal alignment film such as reduction of the afterimage due to the AC drive through the reduction of the fine irregularities on the surface of the obtained liquid crystal alignment film, Electrical characteristics such as residual DC voltage are also improved. As a result, it is widely useful for TN devices, STN devices, TFT liquid crystal devices, and vertically aligned liquid crystal display devices.

The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2010-058552 filed on March 15, 2010 are hereby incorporated herein by reference, and as a disclosure of the specification of the present invention.

Claims (14)

A liquid crystal aligning agent characterized by containing the following components (A) and (B).
(A): a polyamic acid ester having a repeating unit represented by the following formula (1) and satisfying any of the following conditions (i) to (iii):

(Wherein, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, R ₁ is may have a hydrogen atom, or a substituent in each alkyl group, A ₁ and A ₂ independently of 1 to 5 carbon atoms An alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group)
(I) has at least one kind of monovalent or divalent substituent selected from the group consisting of the following formulas (2) and (3), and X ₁ and Y ₁ in formula (1)
(Ii) a monovalent or divalent substituent of at least one structure selected from the group consisting of A ₁ , A _2, or both of which are represented by the following formulas (2) and (3)
(Ⅲ) formula (1) X _1, Y _1, or both sides have the following formula (2) and (3) group and at least one structure 1 a or a divalent group of the substituents selected from the consisting of, and A ₁ , a has the structure 1 is the group and at least one or a divalent of the substituents selected from the consisting of a _second or both the following equations (2) and (3).

(In the formulas (2) and (3), D ₁ and D ₂ are each a protecting group substituted by a hydrogen atom by a column, and B ₁ is a single bond or a divalent organic group. Is a carbon atom)
Component (B): Polyamic acid having a repeating unit represented by the following formula (4).

(Wherein X ₂ is a tetravalent organic group, Y ₂ is a divalent organic group, and A ₁ and A ₂ have the same definitions as in formula (1) The method according to claim 1,
Wherein the content of the component (A) and the content of the component (B) are 1/9 to 9/1 by mass ratio (A / B). The method according to claim 1,
Wherein the total content of the component (A) and the component (B) is 1 to 10% by mass with respect to the organic solvent. The method according to claim 1,
Wherein the protecting group D ₁ is at least one kind of group selected from the group consisting of a tert-butoxycarbonyl group and a 9-fluorenylmethoxycarbonyl group. The method according to claim 1,
And liquid crystal aligning agent wherein the protecting group D &lt; _{2 &gt;} is a tert-butyl group. The method according to claim 1,
Wherein the component (A) is a polyamic acid ester having a substituent represented by at least one structure selected from the group consisting of the following formulas (5) and (6).

(In the formula (5), B ₂ is a single bond or a divalent organic group, and each of R ₂ , R ₃ and R ₄ is independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms)

(In the formula (6), B ₃ is a single bond or a divalent organic group, provided that the atom to which the t-butoxycarbonyl group in the formula (6) is bonded is a carbon atom) The method according to claim 6,
(A) is a polyamic acid ester having a substituent of at least one structure selected from the group consisting of the formulas (5) and (6) in the structure of Y _{1 in} the formula (1). The method according to claim 6,
Wherein the component (A) is a polyamic acid ester having a substituent of at least one kind selected from the group consisting of A ₁ , A ₂ or both of the groups represented by the formulas (5) and (6) in the formula (1). The method according to claim 6,
(A) is a polyamic acid ester having a structure represented by the following formula (7) in which Y ₁ in the formula (1) is represented by the following formula (7).

(Wherein R ₅ is a single bond or a divalent organic group having 1 to 20 carbon atoms, and R ₆ is at least one structure selected from the group consisting of formulas (5) and (6) Lt; / RTI &gt; The method according to claim 1,
Wherein the component (A) has at least one structure selected from the group consisting of structures represented by the following formulas: Y ₁ in the formula (1).
(7)

The method according to claim 1,
Wherein the liquid crystal aligning agent is at least one selected from the group consisting of structures represented by the following formulas (1) and (4) in which X ₁ and X ₂ each independently represent the following formula:
[Chemical Formula 8]

The method according to claim 1,
A liquid crystal aligning agent according to (4), wherein Y ₂ is at least one kind selected from the group consisting of structures represented by the following formulas.

A liquid crystal alignment film obtained by applying and firing the liquid crystal aligning agent according to any one of claims 1 to 12. A liquid crystal alignment film obtained by coating and firing the liquid crystal aligning agent according to any one of claims 1 to 12 and further irradiating with polarized ultraviolet rays.