KR101864913B1 - Liquid crystal aligning agent, and liquid crystal alignment film produced using same - Google Patents

Abstract

(X₁ 은 4 가의 유기기이고, Y₁ 은 2 가의 유기기이며, R₁ 은 수소 원자, 또는 탄소수 1 ∼ 5 의 알킬기이다.)
[화학식 2]
R₂-SO₂-OR₃ (2)
(R₂ 및 R₃ 은 각각 독립적으로 치환기를 가져도 되는 탄소수 1 ∼ 30 의 1 가의 유기기이고, R₂ 와 R₃ 이 서로 결합하여 고리 구조를 형성해도 된다.)A liquid crystal alignment film for obtaining a liquid crystal display element having a fast relaxation rate of a residual charge due to a direct current voltage and a liquid crystal alignment agent for obtaining a liquid crystal alignment film.
At least one kind of polymer selected from the group consisting of a polyimide precursor having a structural unit represented by the formula (1) and an imidization polymer of the polyimide precursor, a sulfonic acid ester represented by the formula (2) Wherein the liquid crystal aligning agent is a liquid crystal aligning agent.
[Chemical Formula 1]

(Wherein X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, and R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)
(2)
R ₂ -SO ₂ -OR ₃ (2)
(R ₂ and R ₃ are each independently a monovalent organic group of 1 to 30 carbon atoms which may have a substituent, and R ₂ and R ₃ may be bonded to each other to form a cyclic structure.)

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal alignment agent and a liquid crystal alignment film using the liquid crystal alignment agent,

The present invention relates to a liquid crystal aligning agent for producing a liquid crystal alignment film, and a liquid crystal alignment film obtained from the liquid crystal aligning agent. Specifically disclosed is a liquid crystal alignment film in which a liquid crystal display element having a fast relaxation rate of a residual charge due to a direct current voltage is obtained and a liquid crystal aligning agent for obtaining a liquid crystal alignment film.

In a liquid crystal display element used for a liquid crystal television, a liquid crystal display, or the like, a liquid crystal alignment film for controlling the alignment state of the liquid crystal is usually formed in the element. As the liquid crystal alignment layer, a liquid crystal alignment layer mainly composed of a solution of a polyimide precursor such as polyamic acid (polyamic acid) or a soluble polyimide is coated on a glass substrate or the like, and a polyimide-based liquid crystal alignment layer .

In order to suppress the decrease in the contrast of the liquid crystal display element and to reduce the afterimage phenomenon, the liquid crystal alignment layer has excellent liquid crystal alignability and a stable pretilt angle, It has become increasingly important to suppress the afterimage caused by the driving, to reduce the residual charge when the direct-current voltage is applied, and / or to rapidly relax the accumulated residual charge due to the direct-current voltage.

In the polyimide-based liquid crystal alignment film, various proposals have been made in order to answer 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), a liquid crystal aligning agent containing a soluble polyimide using a specific diamine compound having a pyridine skeleton or the like as a raw material (see, for example, Patent Document 2) .

In addition, as a liquid crystal alignment film having a high voltage holding ratio and a short time until the after-image caused by the DC voltage disappears, a liquid crystal alignment film containing a compound containing one carboxylic acid group in the molecule, (See, for example, Patent Document 3) which uses a liquid crystal aligning agent containing a very small amount of a compound containing one carboxylic acid anhydride group and a compound containing one tertiary amino group in the molecule have.

Japanese Patent Application Laid-Open No. 9-316200 Japanese Patent Application Laid-Open No. 10-104633 Japanese Patent Application Laid-Open No. 8-76128

As described above, various methods for suppressing the afterimage of the liquid crystal display have been studied. However, in recent years, a large-sized, high-precision liquid crystal television has become a main body, and the demand for after-images has become stricter, and characteristics that can withstand long-term use in a severe use environment have been demanded. The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid crystal alignment film capable of producing a liquid crystal display element having a fast relaxation time of residual charges due to a direct current voltage and a liquid crystal aligning agent for obtaining the alignment film have.

According to the study of the present inventors, it has been found that a liquid crystal alignment film formed of a liquid crystal aligning agent containing a specific amount of a specific sulfonate ester together with a polyimide precursor and / or an imidized polymer of the polyimide precursor does not inhibit other characteristics, It is possible to obtain a new liquid crystal display device that can advance the relaxation time of the residual charges due to the above-mentioned problems.

The present invention is based on this finding, and has the following points.

1. A polyimide precursor composition comprising at least one polymer selected from the group consisting of a polyimide precursor having a structural unit represented by the following formula (1) and an imidized polymer of the polyimide precursor, a sulfonate ester represented by the following formula (2) A liquid crystal aligning agent characterized by containing a solvent.

[Chemical Formula 1]

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

(2)

R ₂ -SO ₂ -OR ₃ (2)

(In the formula (2), R ₂ and R ₃ are each independently a monovalent organic group having 1 to 30 carbon atoms which may have a substituent, and R ₂ and R ₃ may bond to each other to form a cyclic structure.)

2. The liquid crystal aligning agent according to 1 above, wherein the content of the sulfonic acid ester is 0.01 part by mass to 30 parts by mass with respect to 100 parts by mass of the polymer.

3. The liquid crystal aligning agent according to 1 or 2, wherein R ₂ is a methyl group which may have a substituent.

4. The liquid crystal aligning agent according to any one of items 1 to 3, wherein R ₃ is a methyl group.

5. The liquid crystal aligning agent according to 1 or 2, wherein the sulfonic acid ester is methyl trifluoromethanesulfonate or ethyl trifluoromethanesulfonate.

6. The liquid crystal aligning agent according to any one of items 1 to 5, wherein the polymer has a weight average molecular weight of 5,000 to 300,000.

7. The liquid crystal aligning agent according to any one of 1 to 6 above, wherein the content of the polymer is 0.5% by mass to 20% by mass with respect to the organic solvent.

(8) A liquid crystal alignment film obtained by applying and firing the liquid crystal aligning agent according to any one of (1) to (7) above.

9. A liquid crystal alignment film obtained by irradiating polarized radiation to a film obtained by applying and firing the liquid crystal aligning agent according to any one of 1 to 7 above.

10. A liquid crystal display element comprising the liquid crystal alignment film according to 8 or 9 above.

The liquid crystal alignment film formed of the liquid crystal aligning agent containing a specific amount of the specific sulfonic acid ester together with the imidized polymer of the polyimide precursor and / or the polyimide precursor thereof according to the present invention is effective in reducing the residual charge due to the direct current voltage of the liquid crystal display element The time can be shortened, and excellent liquid crystal alignability and stable pretilt angle can be exhibited, and an excellent liquid crystal display element can be provided.

The mechanism by which the above-mentioned effect is obtained by the liquid crystal aligning agent of the present invention is not necessarily clear, but is generally considered as follows. When the sulfonate ester of the formula (2) contained in the liquid crystal aligning agent of the present invention is present, the polyimide precursor of the liquid crystal aligning agent and / or the imide polymer of the polyimide precursor react with the carboxyl group or the amino group, Anion represented by the following formula (3) is produced.

(3)

R ₂ -SO ₂ -O ^- (3)

When the anion represented by the formula (3) is present in the liquid crystal alignment film formed by baking the coating film of the liquid crystal aligning agent, the resistivity of the obtained liquid crystal alignment film is lowered and the residual charge due to the direct current voltage of the liquid crystal display element is relaxed It is considered that the effect of improving the speed is expressed.

<Polyimide precursor>

The polyimide precursor used in the present invention is a polymer having a site capable of imidization reaction as described below by heating or reacting with an imidation catalyst. In the formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably 1 to 2 carbon atoms.

[Chemical Formula 4]

The imidized polymer used in the present invention is a polymer obtained by heating or reacting the polyimide precursor with an imidization catalyst.

The polyimide precursor contained in the liquid crystal aligning agent of the present invention is a polymer having a structural unit represented by the following formula (1).

[Chemical Formula 5]

In the formula (1), R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably 1 to 2 carbon atoms. When R ₁ is an alkyl group, the temperature at which the imidization proceeds progressively increases as the number of carbon atoms in the alkyl group increases. Therefore, from the viewpoint of easiness of imidization by heat, R ₁ is particularly preferably a hydrogen atom or a methyl group. In formula (1), A ₁ and A ₂ each independently represent a hydrogen atom or an alkyl, alkenyl or alkynyl group having 1 to 10 carbon atoms which may have a substituent. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a hexyl group, an octyl group, a decyl group, a cyclopentyl group, a cyclohexyl group and a bicyclohexyl group. As the alkenyl group, one having at least one CH-CH structure present in the alkyl group may be substituted with a C = C structure. More specifically, examples thereof include 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 wherein at least one CH ₂ -CH ₂ structure present in the alkyl group is substituted with a C≡C structure. More specifically, an ethynyl group, 1-propynyl group, 2-propynyl group, .

The alkyl group, alkenyl group and alkynyl group as described above may have a substituent as a whole when the carbon number is 1 to 10 as a whole, or 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) bond 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 organothio group, an organosilyl group, an acyl group, an ester group, a thioester group, An alkyl 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.

As the aryl group as a substituent, a phenyl group can be mentioned. 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 which is a substituent may represent a structure represented by -S-R. As R, examples of the alkyl group, alkenyl group, alkynyl group, aryl group and the like can be mentioned. These R may be further substituted with the aforementioned substituents. Specific examples of the organotitanium group include methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, heptylthio group and 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 a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a tripentylsilyl group, a trihexylsilyl group, a pentyldimethylsilyl group, a hexyldimethylsilyl group, .

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 may 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. As R, examples of the alkyl group, alkenyl group, alkynyl group, aryl group and the like can be mentioned. 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. As R, examples of the alkyl group, alkenyl group, alkynyl group, aryl group and the like can be mentioned. These R may be further substituted with the aforementioned substituents.

As the phosphoric acid ester group which is a substituent, it 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.

Examples of the amide group which is a substituent group include -C (O) NH ₂ or a group represented by -C (O) NHR, -NHC (O) R, -C (O) N (R) ₂ or -NRC Structure. 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 those 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.

Examples of the alkenyl group as the substituent include the same alkenyl groups as those described above. This alkenyl group may be further substituted with another substituent as described above.

Examples of the alkynyl group as the substituent include the same alkynyl groups 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 that the reactivity of the amino group and the liquid crystal orientation may be lowered. 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 And a hydrogen atom, a methyl group or an ethyl group is particularly preferable.

In the formula (1), X ₁ is a tetravalent organic group and Y ₁ is a divalent organic group. X ₁ is a tetravalent organic group and is not particularly limited. In the polyimide precursor, two or more types of X ₁ may be mixed. Specific examples of X ₁ include X-1 to X-46 shown below. Among these, from the availability of the monomers, X ₁ is X-1, X-2, X-3, X-4, X-5, X-6, X-8, X-16, X-19, X- 21, X-25, X-26, X-27, X-28 or X-32.

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

In the formula (1), Y ₁ is a divalent organic group and is not particularly limited. In the polyimide precursor, two or more types of Y ₁ may be mixed. Specific examples of Y ₁ include the following Y-1 to Y-113.

Among them, Y-7, Y-10, Y-11, Y-12, Y, and Y are preferable as Y _{1 in} the case of introducing diamine having high linearity into the polyamic acid ester in order to obtain good liquid crystal alignability. -13, Y-21, Y-22, Y-23, Y-25, Y-26, Y-27, Y-41, Y-42, Y-43, Y-44, , Y-61, Y-61, Y-63, Y-64, Y-71, Y-72, Y-73, Y-74, Y-75, More preferably a diamine of Y-102, Y-103, Y-0104, Y-105, Y-106, Y-107, Y-108, Y-109 or Y-110.

In order to increase the pretilt angle, it is preferable to introduce a diamine having a long-chain alkyl group, an aromatic ring, an aliphatic ring, a steroid skeleton, or a combination thereof in the side chain into the polyamic acid ester. roneun _{1, Y-76, Y-} 77, Y-78, Y-79, Y-80, Y-81, Y-82, Y-83, Y-84, Y-85, Y-86, Y-87 , Diamine of Y-88, Y-89, Y-90, Y-91, Y-92, Y-93, Y-94, Y-95, Y-96 or Y-97 is more preferable. By adding these diamines in an amount of 1 to 50 mol% of the total diamine, an arbitrary pretilt angle can be expressed.

By lowering the volume resistivity of the polyimide precursor, the charge relaxation rate due to the accumulation of the direct-current voltage can be made faster, so that the diamine having a heteroatom, a polycyclic aromatic structure, or a biphenyl skeleton can be added to the polyamic acid introducing desirable to and roneun Y ₁ in this case, Y-19, Y-23 , Y-25, Y-26, Y-27, Y-30, Y-31, Y-32, Y-33, Y Y-50, Y-51, Y-61, Y-45, Y-45, Y-35, Y-36, Y-40, Y-41, Y-42, , Y-111, Y-112, or Y-113 are more preferable.

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 22]

(23)

&Lt; EMI ID =

(25)

(26)

(27)

(28)

<Sulfonic Acid Ester>

The sulfonic acid ester contained in the liquid crystal aligning agent of the present invention is represented by the following formula (2).

[Chemical Formula 29]

R ₂ -SO ₂ -OR ₃ (2)

In the formula (2), R ₂ and R ₃ each independently represent a monovalent organic group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms, which may have a substituent. The organic group may be selected from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, and an aryl group, and R ₂ and R ₃ may form a ring structure.

Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a hexyl group, an octyl group, a decyl group, a cyclopentyl group, a cyclohexyl group and a bicyclohexyl group. Examples of the alkenyl group include those wherein at least one CH-CH structure present in the alkyl group is substituted with a C = C structure, and more specifically, a vinyl group, allyl group, 1-propenyl group, 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-hexenyl, cyclopropenyl, cyclopentenyl, cyclohexenyl and the like. Examples of the alkynyl group include those wherein at least one CH ₂ -CH ₂ structure present in the alkyl group is substituted with a C≡C structure. More specifically, an ethynyl group, 1-propynyl group, 2-propynyl group, . Examples of the aryl group include a phenyl group, an a-naphthyl group, a p-naphthyl group, an o-biphenylyl group, an m- Anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group and 9-phenanthryl group.

The alkyl group, alkenyl group, alkynyl group, and aryl group may have a substituent group as a whole when the carbon number is 1 to 20 as a whole, or may form a ring structure by a substituent group. 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 organoxy group, an organotio group, an organosilyl group, an acyl group, an ester group, a thioester group, a phosphate ester group, an amide 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 organoxy group which is a substituent group may represent a structure represented by -O-R such as an alkoxy group, an alkenyloxy group, an aryloxy group and the like. As R, examples of the alkyl group, alkenyl group, aryl group, and the like may be mentioned. These R may be further substituted with the aforementioned substituents. Specific examples of the alkyloxy group include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, lauryloxy And the like.

Examples of the organotio group as a substituent include a structure represented by -S-R such as an alkylthio group, an alkenylthio group, an arylthio group and the like. As R, examples of the alkyl group, alkenyl group, aryl group, and the like may be mentioned. These R may be further substituted with the aforementioned substituents. Specific examples of alkylthio groups include methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, heptylthio group, octylthio group, nonylthio group, decylthio group, And the like.

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

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 may 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. As R, examples of the alkyl group, alkenyl group, aryl group, and the like may be mentioned. 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. As R, examples of the alkyl group, alkenyl group, aryl group, and the like may be mentioned. These R may be further substituted with the aforementioned substituents.

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

Examples of the amide group which is a substituent include a structure represented by -C (O) NH ₂ , -C (O) NHR, -NHC (O) R, -C (O) N (R) ₂ or -NRC Lt; / RTI &gt; These R may be the same or different and may be exemplified by the above-mentioned alkyl group, aryl group 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 those 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.

Examples of the alkenyl group as the substituent include the same alkenyl groups as those described above. This alkenyl group may be further substituted with another substituent as described above.

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

In the formula (2), R ₂ is preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group, which may have a substituent, and more preferably a phenyl group, An alkyl group having 1 to 4 carbon atoms which may have a substituent, more preferably a methyl group which may have a substituent.

The substituent that may be substituted with R ₂ in the above formula (2) is preferably an electron-withdrawing group because the stability of the anion produced from the sulfonate ester can be enhanced. Specific examples of the electron-withdrawing group include a nitro group, a cyano group, a halogen atom, a hydroxyl group, an alkoxy group and the like, more preferably a halogen atom, still more preferably a fluorine atom.

R ₃ in the formula (2) is preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group because the effect can be obtained with a small addition amount by decreasing the molecular weight of the sulfonic ester similarly to the above, Preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group.

Specific preferred examples of the sulfonic acid ester used in the present invention include methyl trifluoromethanesulfonate, ethyl trifluoromethanesulfonate, methyl p-toluenesulfonate, methyl methanesulfonate, 2,2,2-trifluoroethyl methanesulfonate , Methanesulfonic acid 2-methoxyethyl, and propanesultone. Among them, methyl trifluoromethanesulfonate and ethyl trifluoromethanesulfonate are more preferable.

If the content of the sulfonic acid ester in the liquid crystal aligning agent of the present invention is too small, the effect is not exhibited. Even if the content is excessively large, the other properties may be adversely affected. Therefore, the polyimide precursor of the liquid crystal aligning agent and / More preferably 0.1 part by mass to 10 parts by mass, and still more preferably 0.1 part by mass to 5 parts by mass with respect to 100 parts by mass of the polymer composed of the imidized polymer of the polyimide precursor .

<Production method of polyamic acid ester>

When the polyimide precursor of the present invention is a polyamic acid ester, the polyamic acid ester can be obtained by reacting any of the tetracarboxylic acid derivatives represented by the following formulas (4) to (6) with a diamine compound represented by the formula (7) Can be obtained.

(30)

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

The polyimide precursor represented by the above formula (1) can be synthesized by the following methods (1) to (3) using the above-mentioned monomers.

(1) Synthesis with polyamic acid

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

Concretely, the polyamic acid and the esterifying agent are reacted in the presence of an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C for 30 minutes to 24 hours, preferably 1 to 4 hours .

The esterification agent is preferably one which can be easily removed by purification. Examples of the esterification agent include N, N-dimethylformamide dimethylacetal, N, N-dimethylformamide diethyl acetal, N, N-dimethylformamide dipropyl acetal, N, N-dimethylformamide dineopentylbutyl acetal, N, N-dimethylformamide di-t-butyl acetal, 1-methyl-3-p-tolyltriazine, , 1-propyl-3-p-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.

The solvent to be used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone or gamma -butyrolactone in the solubility of the polymer, May be used. The concentration at the time of 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 the high molecular weight material is easily obtained.

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

Polyamic acid esters can be synthesized from tetracarboxylic acid diester dichloride and diamine.

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, but pyridine is preferable for the reaction to proceed mildly. The amount of the base to be added 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 reaction, N-methyl-2-pyrrolidone or? -Butyrolactone is preferable as the solubility of the monomer and the polymer, and these solvents may be used alone or in combination. The concentration of the polymer 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 the high molecular weight material 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 ambient air from being mixed in the nitrogen atmosphere.

(3) When synthesized by tetracarboxylic acid diester and diamine

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

Specifically, the tetracarboxylic acid diester and 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, preferably 3 To &lt; / RTI &gt; 15 hours.

Examples of the condensing agent include triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3- dimethylaminopropyl) carbodiimide hydrochloride, N, N'-carbonyldiimidazole, dimethoxy- N, N ', N'-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) 1-yl) -N, N, N ', N'-tetramethyluronium hexafluorophosphate and (2,3-dihydro-2-thioxo-3-benzoxazolyl) . The amount of the condensing agent to be added is preferably 2 to 3 times the mole of the tetracarboxylic acid diester.

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

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, the synthesis method of the above (1) or (2) is particularly preferable because a high molecular weight polyamic acid ester can be obtained.

The solution of the polyamic acid ester thus obtained can be precipitated by pouring into a poor solvent while stirring well. After several times of precipitation and washing 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>

When the polyimide precursor used in the present invention is a polyamic acid, the polyamic acid can be obtained by reacting the tetracarboxylic acid dianhydride represented by the formula (4) with the diamine compound represented by the formula (7).

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 to be used in the reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone or gamma -butyrolactone as the solubility of the monomer and the polymer, May be mixed and used. The concentration of the polymer is preferably from 1 to 30% by mass, and more preferably from 5 to 20% by mass from the viewpoint that the precipitation of the polymer does not occur well and the high molecular weight material 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 stirring well. 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.

<Production method of polyimide>

The polyimide used in the present invention can be prepared by imidizing a polyimide precursor comprising the polyamic acid ester and / or polyamic acid. In the case of producing polyimide by a polyamic acid ester, chemical imidization by adding a basic catalyst to a polyamic acid solution obtained by dissolving the polyamic acid ester solution or polyamic acid ester resin powder in an organic solvent is simple. The chemical imidization is preferable because the imidization reaction proceeds at a relatively low temperature and the molecular weight of the polymer does not decrease during the imidization process.

The chemical imidization can be carried out by stirring the polyamic acid ester to be imidized in an organic solvent in the presence of a basic catalyst. As the organic solvent, a solvent used in the above-mentioned polymerization reaction may be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Among them, triethylamine is preferred because it has sufficient basicity to proceed the reaction.

The temperature at which the imidization reaction is carried out is -20 占 폚 to 140 占 폚, preferably 0 占 폚 to 100 占 폚, and the reaction time is 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles per mole of the amic ester group. The imidization rate of the resulting polymer can be controlled by adjusting the amount of catalyst, temperature, and reaction time. Since the added catalyst remains in the solution after the imidization reaction, it is preferable that the imidized polymer obtained is recovered by the means described below and redissolved in an organic solvent to obtain the liquid crystal aligning agent of the present invention.

When a polyimide is produced from polyamic acid, chemical imidization by adding a catalyst to a solution of the polyamic acid obtained by the reaction of the diamine component and the tetracarboxylic acid dianhydride is simple. The chemical imidization is preferable because the imidization reaction proceeds at a relatively low temperature and the molecular weight of the polymer does not decrease during the imidization process.

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

The temperature at which the imidization reaction is carried out is -20 占 폚 to 140 占 폚, preferably 0 占 폚 to 100 占 폚, and the reaction time is 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 molar equivalents, preferably 2 to 20 molar equivalents, and the amount of the acid anhydride is 1 to 50 molar equivalents, preferably 3 to 30 molar equivalents, of the atomic acid group. The imidization rate of the resulting polymer can be controlled by controlling the amount of catalyst, the temperature, and the reaction time.

Since the added catalyst remains in the solution after the imidization reaction of the polyamic acid ester or polyamic acid, the imidized polymer thus obtained is recovered and redissolved in an organic solvent, It is preferable to use an orientation agent.

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

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

<Liquid Crystal Aligner>

The liquid crystal aligning agent of the present invention comprises at least one polymer selected from the group consisting of a polyimide precursor represented by the formula (1) and an imidized polymer of the polyimide precursor, a sulfonate ester represented by the formula (2) , And an organic solvent. The polymer contained in the liquid crystal aligning agent of the present invention is preferably a polyimide precursor comprising a polyamic acid ester and / or a polyamic acid in view of solubility in an organic solvent. Two or more kinds of polymers may be used in the present invention.

The weight average molecular weight of the polymer contained in the liquid crystal aligning agent of the present invention is preferably from 5,000 to 300,000, more preferably from 10,000 to 200,000. The number average molecular weight is preferably 2,500 to 150,000, more preferably 5,000 to 100,000. The liquid crystal aligning agent of the present invention is preferably in the form of a solution in which the polymer and the sulfonic acid ester are dissolved in an organic solvent.

The content (concentration) of the polymer and the sulfonic acid ester in the liquid crystal aligning agent of the present invention can be appropriately changed depending on the setting of the thickness of the polyimide film to be formed, but from the viewpoint of forming a uniform and defect- With respect to the organic solvent, the content of the polymer component is preferably 0.5% by mass or more, more preferably 20% by mass or less, and more preferably 1 to 15% by mass from the viewpoint of the storage stability of the solution. In this case, it is also possible to prepare a polymer-rich solution in advance and to dilute the liquid-crystal aligning agent from such a concentrated solution. The concentration of the concentrated solution of the polymer component is preferably 10 to 30% by mass, more preferably 10 to 15% by mass. The polymer component powder may be dissolved in an organic solvent to prepare a solution. The heating temperature is preferably 20 占 폚 to 150 占 폚, and particularly preferably 20 占 폚 to 80 占 폚.

The organic solvent contained in the liquid crystal aligning agent of the present invention is not particularly limited as long as the polymer and the sulfonic acid ester are uniformly dissolved. Specific examples thereof include N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methyl- , N-methylcaprolactam, 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethylsulfoxide, dimethylsulfone,? -Butyrolactone, 1,3-dimethyl- imidazolidinone, 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.

The liquid crystal aligning agent of the present invention may contain, in addition to the organic solvent for dissolving the polymer and the sulfonate ester, a solvent for improving the uniformity of the coating film when the liquid crystal aligning agent is applied to the substrate. Solvents having a lower surface tension than those of the organic solvents are generally used for such solvents. Specific examples thereof include ethyl cellosolve, butyl cellosolve, butyl cellosolve acetate, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1- 2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol- Lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid isoamyl ester, lactic acid ethyl ester-2-acetate, dipropylene glycol, 2- (2- ethoxypropoxy) propanol, Esters and the like. These solvents may be used in combination of two or more.

The liquid crystal aligning agent of the present invention preferably contains two or more kinds of organic solvents selected from the group consisting of N-methyl-2-pyrrolidone,? -Butyrolactone, and butyl cellosolve, Pyrrolidone and butyl cellosolve, and it is particularly preferable to contain N-methyl-2-pyrrolidone,? -Butyrolactone and butyl cellosolve.

The sulfonic acid ester is added to the concentrated solution or diluted solution of the polymer and stirred at 0 ° C to 100 ° C, preferably 20 ° C to 50 ° C to prepare a liquid crystal aligning agent. The stirring time is preferably 1 hour to 48 hours, more preferably 1 to 14 hours.

The liquid crystal aligning agent of the present invention may contain various additives such as a silane coupling agent and a crosslinking agent. The silane coupling agent is added for the purpose of improving adhesion between the substrate to which the liquid crystal aligning agent is applied and the liquid crystal alignment film formed thereon.

&Lt; Liquid crystal alignment film &

The liquid crystal alignment film of the present invention is a film obtained by applying the liquid crystal aligning agent to a substrate, followed by drying and firing. 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. A plastic substrate such as a glass substrate, a silicon nitride substrate, an acrylic substrate or a polycarbonate substrate can be used. It is preferable from the viewpoint of simplification of the process. In the reflection type liquid crystal display device, if it is only one substrate, it may be opaque such as a silicon wafer. In this case, a material that reflects light such as aluminum may 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 to 120 ° C for 1 to 10 minutes to sufficiently remove the contained organic solvent, and then baked at 150 to 300 ° C for 5 to 120 minutes. 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. Therefore, it is 5 to 300 nm, preferably 10 to 200 nm.

Examples of a method for aligning the obtained liquid crystal alignment film include a rubbing method and an optical alignment treatment method.

Specific examples of the photo-alignment treatment method include a method of irradiating the surface of the above-mentioned coating film with radiation deflected in a predetermined direction and, if necessary, further heating treatment at a temperature of 150 to 250 ° C to give a liquid crystal aligning ability . As the radiation, ultraviolet rays and visible rays having a wavelength of 100 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. Further, in order to improve the liquid crystal alignment property, the coated film substrate may be irradiated with radiation while heating at 50 to 250 ° C. The irradiation dose of the radiation is preferably 1 to 10,000 mJ / cm 2, and particularly preferably 100 to 5,000 mJ / cm 2. The liquid crystal alignment film thus produced 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

NMP: N-methyl-2-pyrrolidone

GBL: gamma butyrolactone

BCS: butyl cellosolve

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

(31)

(32)

[Viscosity]

In the synthesis examples, the viscosity of the polyamic acid ester and the polyamic acid solution was 1.1 ml in a sample amount, the cone rotor TE-1 (1 ° 34 ', R24), The temperature was measured at 25 캜.

[Molecular Weight]

The molecular weight of the polyamic acid ester is measured by a GPC (room temperature gel permeation chromatography) apparatus, and the number average molecular weight (hereinafter also referred to as Mn) and the weight average molecular weight (hereinafter also referred to as Mw) of polyethylene glycol and 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: 30 mmol / l of lithium bromide-hydrate (LiBr 占 O 2O), 30 mmol / l of phosphoric anhydride crystal (o-phosphoric acid), 30 ml of tetrahydrofuran (THF ) &Lt; / RTI &gt; 10 ml / l)

Flow rate: 1.0 ml / min

Standard sample for preparing a 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 top molecular weight (Mp) 4,000, 1,000). In order to avoid peaks overlapping, two samples of samples mixed with four types of 900,000, 100,000, 12,000 and 1,000 and three samples of 150,000, 30,000 and 4,000 were separately measured.

[Production of FFS-driven liquid crystal cell]

On the glass substrate, an ITO electrode having a thickness of 50 nm was used as an electrode in the first layer, silicon nitride having a thickness of 500 nm was used as an insulating film in the second layer, and a comb-like ITO electrode (electrode width: (Hereinafter referred to as &quot; FFS &quot;) driving electrode having a thickness 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 Respectively. 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 surface was irradiated with polarized ultraviolet rays or rubbed to obtain a substrate having a liquid crystal alignment film attached thereto. A coating film was similarly formed on a glass substrate having a columnar spacer having a height of 4 占 퐉, on which no electrode was formed as a counter substrate, and the alignment treatment was carried out.

The two substrates were set as one set, a sealant was printed on the substrate, and another substrate was bonded to the liquid crystal alignment film so that the alignment direction of the liquid crystal alignment film face was 0 °, and then the sealant was cured A blank cell was prepared. A liquid crystal MLC-2041 (manufactured by Merck & Co., Inc.) was injected into this vacant cell by a reduced pressure injection method and the injection port was sealed to obtain an FFS-driven liquid crystal cell.

[Charge relaxation characteristics]

The liquid crystal cell was placed on a light source, and the transmittance (Ta) of the liquid crystal cell in a state where a V-T characteristic (voltage-transmittance characteristic) was measured and then a square wave of ± 1.5 V / 60 Hz was applied was measured. Thereafter, a rectangular wave of ± 1.5 V / 60 Hz was applied for 10 minutes, and 2 V of direct current was superimposed and driven for 120 minutes. The transmittance (Tb) of the liquid crystal cell was measured when the DC voltage was turned off and again driven with a square wave of ± 1.5 V / 60 Hz for 0 minute, 5 minutes, 10 minutes, 20 minutes and 60 minutes, The difference in transmittance caused by the voltage remaining in the liquid crystal display element was calculated from the difference (T) between the initial transmittance (Tb) and the initial transmittance (Ta).

(Synthesis Example 1)

5.89 g (30.0 mmol) of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride was added to a 100-ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, 64.08 g of NMP was added And stirred while nitrogen was supplied. Next, 3.04 g (28.1 mmol) of p-phenylenediamine (hereinafter also referred to as p-PDA) was added while stirring the solution in the reaction vessel, NMP was further added so that the solid content concentration became 10 mass% Followed by stirring at room temperature for 24 hours to obtain a solution of polyamic acid (PAA-1). The viscosity of this polyamic acid solution at 25 캜 was 171 mPa.. The molecular weight of the polyamic acid was Mn = 12373 and Mw = 28957.

(Synthesis Example 2)

3.65 g (24.0 mmol) of 3,5-diaminobenzoic acid and 1.46 g (6.0 mmol) of DA-4 were placed in a 100 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, 55.74 g was added, and dissolved with stirring while nitrogen was being supplied. 5.83 g (29.7 mmol) of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride was added while stirring the diamine solution, NMP was further added so that the solid concentration became 15% by mass, Followed by stirring for 24 hours to obtain a solution of polyamic acid (PAA-2). The viscosity of this polyamic acid solution at 25 캜 was 264 mPa s. The molecular weight of this polyamic acid was Mn = 11630 and Mw = 30056.

(Synthesis Example 3)

20.08 g (132 mmol) of 3,5-diaminobenzoic acid and 21.33 g (88.0 mmol) of DA-4 were taken in a 100 ml four-necked flask equipped with a stirrer and a nitrogen introduction tube, and NMP 268.48 g was added and dissolved by stirring while nitrogen was being supplied. 42.49 g (217 mmol) of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride was added while stirring the diamine solution, NMP was further added so that the solid content concentration became 20% by mass, Followed by stirring for 24 hours to obtain a solution of polyamic acid (PAA-3). 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 4)

3.65 g (24.0 mmol) of 3,5-diaminobenzoic acid was added to a 100-ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, 8.99 g of NMP was added, . Next, 1.46 g (6.01 mmol) of DA-4 was taken, and 15.75 g of GBL was added and dissolved by stirring while nitrogen was being fed. While stirring the diamine solution, 4.16 g (21.0 mmol) of 1,2,3,4-butanetetracarboxylic acid dianhydride was added, and the mixture was stirred for 2 hours under water-cooling. Then, 11.18 g of GBL was added, and 1.96 g (9.0 mmol) of pyromellitic dianhydride was added. GBL was further added so that the solid content 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 1904 mPa.. The molecular weight of the polyamic acid was Mn = 8509 and Mw = 16774.

Further, 0.03 g of 3-glycidoxypropylmethyldiethoxysilane was added to this solution and stirred at room temperature for 24 hours to obtain a polyamic acid solution (PAA-4).

(Synthesis Example 5)

2.60 g (24.0 mmol) of m-phenylenediamine and 1.45 g (6.0 mmol) of DA-4 were taken in a 100 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, and 53.69 g And the mixture was stirred to dissolve while nitrogen was being fed. While stirring the diamine solution, 6.41 g (39.4 mmol) of pyromellitic dianhydride was added, and NMP was further added so that the solid concentration became 15 mass%. The mixture was stirred at room temperature for 24 hours to obtain polyamic acid (PAA-5) &Lt; / RTI &gt; The viscosity of the polyamic acid solution at 25 캜 was 208 mPa.. The molecular weight of this polyamic acid was Mn = 10671 and Mw = 22829.

(Synthesis Example 6)

4.81 g (24.0 mmol) of 4,4'-diaminodiphenyl ether and 1.56 g (6.0 mmol) of DA-5 were taken in a 100 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube And 61.85 g of NMP were added and dissolved by stirring while nitrogen was being supplied. 5.37 g (29.4 mmol) of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride was added while stirring the diamine solution, NMP was further added so that the solid content concentration became 15 mass% Followed by stirring for 24 hours to obtain a solution of polyamic acid (PAA-6). The viscosity of the polyamic acid solution at 25 캜 was 799 mPa s. The molecular weight of the polyamic acid was Mn = 12569 and Mw = 27653.

(Synthesis Example 7)

In a 100 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, 3.65 g (24.0 mmol) of 3,5-diaminobenzoic acid and 0.66 g (6.0 mmol) of 2,6-diaminopyridine were added, , 51.67 g of NMP was added, and dissolved by stirring while nitrogen was being supplied. 5.83 g (29.7 mmol) of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride was added while stirring the diamine solution, NMP was further added so that the solid concentration became 15% by mass, And stirred for 24 hours to obtain a solution of polyamic acid (PAA-7). The viscosity of this polyamic acid solution at 25 캜 was 60 mPa.. The molecular weight of the polyamic acid was Mn = 5090 and Mw = 7824.

(Synthesis Example 8)

0.65 g (6.0 mmol) of m-phenylenediamine and 1.57 g (4.0 mol) of DA-6 were placed in a 100 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, 35.29 g of NMP And dissolved with stirring while nitrogen was being supplied. While stirring the diamine solution, 2.14 g (9.8 mmol) of pyromellitic dianhydride was added, and NMP was further added so that the solid concentration became 10% by mass. The mixture was stirred at room temperature for 24 hours to obtain polyamic acid (PAA-8) &Lt; / RTI &gt; The viscosity of this polyamic acid solution at 25 캜 was 219 mPa.. The molecular weight of the polyamic acid was Mn = 15827 and Mw = 36626.

(Synthesis Example 9)

In a 100 ml four-necked flask equipped with a stirrer and a nitrogen-introducing tube, 0.31 g (2.0 mmol) of 3,5-diaminobenzoic acid and 0.81 (1.5 mmol) of 1,4- g (3.0 mmol) of NMP, 33.70 g of NMP was added, and dissolved with stirring while nitrogen was being supplied. While this diamine solution was stirred, 0.97 g (5.0 mmol) of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride was added, NMP was further added so that the solid content concentration became 10 mass% And stirred for 24 hours to obtain a solution of polyamic acid (PAA-9). The viscosity of this polyamic acid solution at a temperature of 25 캜 was 375 mPa s. The molecular weight of this polyamic acid was Mn = 14398 and Mw = 35294.

(Synthesis Example 10)

1.51 g (14.0 mmol) of m-phenylenediamine and 0.84 g (3.5 mol) of DA-4 were placed in a 300 ml four-necked flask equipped with a stirrer, 115.36 g of NMP, Was added 3.16 g (40.0 mmol) and dissolved by stirring. Next, while stirring the diamine solution, 4.95 g (16.7 mmol) of dimethyl 1,3-bis (chlorocarbonyl) cyclobutane-2,4-dicarboxylate was added and reacted for 4 hours under water cooling. The obtained polyamic acid ester solution was added to 607 g of water while stirring, and the precipitated precipitate was collected by filtration, washed once with 607 g of water, once with 607 g of ethanol, and three times with 125 g of ethanol And dried to obtain a polyamic acid ester resin powder.

The molecular weight of this polyamic acid ester was Mn = 5967 and Mw = 12346.

2.75 g of the obtained polyamic acid ester resin powder was placed in a 100 mL Erlenmeyer flask, 24.79 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-1).

(Synthesis Example 11)

2.01 g (13.2 mmol) of 3,5-diaminobenzoic acid and 0.80 g (3.3 mol) of DA-4 were placed in a 300 ml four-necked flask equipped with a stirrer, 120.31 g of NMP, 2.99 g (37.9 mmol) of pyridine was added and dissolved by stirring. Then, 4.69 g (15.8 mmol) of dimethyl 1,3-bis (chlorocarbonyl) cyclobutane-2,4-dicarboxylate was added to the diamine solution while stirring, and the mixture was allowed to react for 4 hours under water cooling. The obtained polyamic acid ester solution was added to 633 g of water with stirring. The precipitated precipitate was collected by filtration, washed once with 633 g of water, once with 633 g of ethanol, and three times with 130 g of ethanol And dried to obtain a polyamic acid ester resin powder.

The molecular weight of this polyamic acid ester was Mn = 6757 and Mw = 11827.

2.72 g of the obtained polyamic acid ester resin powder was placed in a 100 mL Erlenmeyer flask, 24.46 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-2).

(Synthesis Example 12)

2.01 g (18.6 mmol) of p-phenylenediamine and 1.12 g (4.6 mmol) of DA-4 were placed in a 300 ml four-necked flask equipped with a stirrer. 164.36 g of NMP and 4.21 g (53.3 mmol) of pyridine as a base were added and dissolved by stirring. Next, 7.22 g (22.2 mmol) of 1,3DM-CBDE-Cl was added to the diamine solution while stirring, and the mixture was reacted under water-cooling for 4 hours. The obtained polyamic acid ester solution was added to 865 g of water while stirring, and the precipitated white precipitate was collected by filtration, followed by once with 865 g of water, once with 865 g of ethanol, and 3 Washed twice, and dried to obtain a white polyamic acid ester resin powder. The molecular weight of this polyamic acid ester was Mn = 14692 and Mw = 31251.

2.14 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 20.35 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 13)

5.40 g (27.0 mmol) of 4,4'-diaminodiphenyl ether and 0.73 g (3.0 mmol) of DA-4 were taken in a 100 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube , 65.23 g of NMP was added, and dissolved with stirring while nitrogen was being supplied. While this diamine solution was stirred, 6.66 g (29.7 mmol) of 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride was added, and further NMP And the mixture was stirred at room temperature for 24 hours to obtain a polyamic acid solution. The viscosity of the polyamic acid solution at 25 캜 was 233 mPa..

Next, 25.52 g of the polyamic acid solution was taken in a 100 ml eggplant-shaped flask, and 37.53 g of NMP was added to obtain a solid concentration of 6% by mass. 16.93 g of acetic anhydride and 7.91 g of pyridine were added to this polyamic acid solution, and the mixture was stirred at 50 占 폚 for 3 hours. The obtained reaction solution was poured into 306 g of methanol while stirring. The precipitated white precipitate was collected by filtration, washed with 306 g of ethanol twice, 100 g of ethanol three times, and dried to obtain white polyimide resin Powder was obtained. The imidization ratio of the polyimide resin was 98%. The molecular weight of this polyimide resin was Mn = 10539 and Mw = 21428.

2.32 g of the obtained polyimide resin powder was placed in a 50 ml Erlenmeyer flask, 20.92 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyimide solution (SPI-1).

(Synthesis Example 14)

2.09 g (13.7 mmol) of 3,5-diaminobenzoic acid, 1.51 g (6.2 mmol) of DA-4, and 10.7 g (6.2 mmol) of DA-7 were placed in a 100 ml four-necked flask equipped with a stirrer and a nitrogen- (5.0 mmol) of NMP, and 41.22 g of NMP were added and dissolved by stirring at 40 占 폚. Then, while stirring the diamine solution, 4.79 g (24.4 mmol) of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride was added and reacted at 40 DEG C for 24 hours to obtain a polyamic acid solution (PAA -10). The molecular weight of this polyamic acid was Mn = 15400 and Mw = 52600.

(Synthesis Example 15)

1.07 g (7.0 mmol) of 3,5-diaminobenzoic acid and 1.70 g (7.0 mmol) of DA-4 were added to a 100 ml four-necked flask equipped with a stirrer and a nitrogen introduction tube, (6.0 mmol) of NMP, 27.37 g of NMP, and dissolved by stirring at 80 占 폚. While stirring the diamine solution, 3.75 g (15.0 mmol) of bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid dianhydride was added and reacted at 80 ° C for 5 hours. After 5 hours, 0.95 g (4.8 mmol) of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride and 12.93 g of NMP were added and reacted at 40 DEG C for 6 hours to obtain a polyamic acid solution .

NMP was added to 20.0 g of the polyamic acid solution to dilute it to 6 mass%, 4.04 g of acetic anhydride and 1.25 g of pyridine were added as an imidation catalyst, and the reaction was carried out at 100 占 폚 for 3 hours. This reaction solution was added to 330 g of methanol while stirring, and the precipitated precipitate was collected by filtration, washed twice with 150 g of methanol, and dried to obtain a polyimide resin powder. The imidization rate of this polyimide was 80%. The molecular weight of this polyimide was Mn = 19100 and Mw = 61600.

5.02 g of the obtained polyimide resin powder was placed in a 100 mL Erlenmeyer flask, and 33.60 g of NMP was added. The mixture was stirred at room temperature for 24 hours to dissolve the polyimide resin powder (SPI-2).

(Synthesis Example 16)

In a 100 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, 4,4'-diaminodiphenyl-N-methylamine was added to a solution of 0.43 (2.0 mmol) and 1,3-bis Phenoxy) propane (2.07 g, 8.0 mol), 37.68 g of NMP was added, and the mixture was stirred to dissolve while nitrogen was being fed. To this diamine solution, 2.05 g (9.4 mmol) of pyromellitic dianhydride was added while stirring, and NMP was further added so as to have a solid content concentration of 10 mass%. The mixture was stirred at room temperature for 24 hours to obtain polyamic acid (PAA-11) &Lt; / RTI &gt; The viscosity of the polyamic acid solution at 25 캜 was 214 mPa.. The molecular weight of this polyamic acid was Mn = 17227 and Mw = 44964.

(Synthesis Example 17)

2.81 g (26.0 mmol) of p-phenylenediamine and 1.10 g (2.89 mmol) of DA-1 were placed in a 300 ml four-necked flask equipped with a stirrer, 155.97 g and 5.16 g (65.18 mmol) of pyridine as a base were added and dissolved by stirring. Next, 8.83 g (27.2 mmol) of dimethyl 1,3-bis (chlorocarbonyl) cyclobutane-2,4-dicarboxylate was added to the diamine solution while stirring, and the mixture was reacted under water-cooling for 4 hours. After 4 hours, 0.75 g (8.3 mmol) of acryloyl chloride was added and the reaction was carried out for 30 minutes under water-cooling. The obtained polyamic acid ester solution was added to 905 g of 2-propanol while stirring, and the precipitated precipitate was collected by filtration, washed with 448 g of 2-propanol five times, and dried to obtain polyamic acid ester resin powder .

The molecular weight of this polyamic acid ester was Mn = 15623 and Mw = 30510.

10.10 g of the obtained polyamic acid ester resin powder was taken in a 100 ml Erlenmeyer flask, and 91.06 g of GBL was added and dissolved by stirring at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-4).

(Synthesis Example 18)

2.03 g (18.8 mmol) of p-PDA and 1.23 g (4.6 mmol) of DA-3 were placed in a 300 ml four-necked flask equipped with a stirrer, and 167.80 g of NMP and pyridine 4.21 g (53.3 mmol) was added and dissolved by stirring. Next, while stirring the diamine solution, 7.22 g (22.2 mmol) of dimethyl 1,3-bis (chlorocarbonyl) cyclobutane-2,4-dicarboxylate was added and reacted for 4 hours under water-cooling. The resulting polyamic acid ester solution was added to 885 g of water with stirring, and the precipitated white precipitate was filtered out. The filtrate was then washed once with 885 g of water, once with 885 g of ethanol, and with 220 g of ethanol Washed three times, and dried to obtain a white polyamic acid ester resin powder. The molecular weight of this polyamic acid ester was Mn = 14116 and Mw = 27044.

7.26 g of the obtained polyamic acid ester resin powder was placed in a 100 ml Erlenmeyer flask, and 65.35 g of GBL was added and dissolved by stirring at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-5).

(Synthesis Example 19)

19.47 g (180 mmol) of p-phenylenediamine and 4.47 g (18.8 mmol) of DA-2 were taken in a 1 L four-necked flask equipped with a stirrer and a nitrogen inlet tube, And the mixture was stirred to dissolve while nitrogen was being fed. While stirring the diamine solution, 38.04 g (194 mmol) of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride was added, NMP was further added so that the solid concentration became 10% by mass, And stirred for 24 hours to obtain a solution of polyamic acid (PAA-12). The viscosity of this polyamic acid solution at 25 캜 was 462 mPa s. The molecular weight of this polyamic acid was Mn = 16976 and Mw = 43749.

(Synthesis Example 20)

3.65 g (24.0 mmol) of 3,5-diaminobenzoic acid was added to a 100-ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, 18.82 g of NMP was added, . Next, 3.88 g (16.0 mmol) of DA-4 was taken, 18.81 g of GBL was added, and dissolved with stirring while nitrogen was being fed. 5.43 g (27.6 mmol) of 1,2,3,4-butanetetracarboxylic acid dianhydride was added to the diamine solution while stirring, and the mixture was stirred for 2 hours under water-cooling. Next, 4.71 g of GBL was added and 2.74 g (12.2 mmol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride was added. GBL was further added so that the solid concentration became 25 mass%, and the mixture was stirred at room temperature for 24 hours. The viscosity of the obtained polyamic acid solution at 25 캜 was 2142 mPa s. The molecular weight of this polyamic acid was Mn = 6509 and Mw = 11481.

Further, 0.05 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 21)

4.00 g (37.0 mmol) of p-phenylenediamine and 1.56 g (4.11 mol) of DA-4 were placed in a 300 ml four-necked flask equipped with a stirrer, and 76.32 g of NMP and 228.03 g, 92.6 mmol) of 2,4,6-trimethylpyridine as a base, and dissolved by stirring. Next, 12.56 g (38.6 mmol) of dimethyl 1,3-bis (chlorocarbonyl) cyclobutane-2,4-dicarboxylate was added to the diamine solution while stirring, and the mixture was reacted under water-cooling for 4 hours. After stirring for 4 hours, 0.878 g (4.93 mmol) of isonicotinic acid chloride was added, and the obtained polyamic acid ester solution was added to 1335 g of ethanol while stirring. The precipitated precipitate was collected by filtration, and then 661 g of ethanol , And dried to obtain a polyamic acid ester resin powder.

The molecular weight of this polyamic acid ester was Mn = 14983 and Mw = 34387.

3.45 g of the obtained polyamic acid ester resin powder was placed in a 100 ml Erlenmeyer flask, and 30.94 g of GBL was added and dissolved by stirring at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-6).

(Synthesis Example 22)

3.09 g (28.6 mmol) of p-phenylenediamine and 1.21 g (3.18 mol) of DA-4 were placed in a 300 ml four-necked flask equipped with a stirrer, 58.81 g of NMP and 176.42 g, and 5.67 g (71.7 mmol) of pyridine as a base were added and dissolved by stirring. Then, 9.72 g (29.9 mmol) of dimethyl 1,3-bis (chlorocarbonyl) cyclobutane-2,4-dicarboxylate was added to the diamine solution while stirring, and the mixture was reacted under water-cooling for 4 hours. The obtained polyamic acid ester solution was added to 1018 g of ethanol while stirring, and the precipitated precipitate was collected by filtration, washed with 504 g of ethanol five times, and dried to obtain a polyamic acid ester resin powder.

The molecular weight of this polyamic acid ester was Mn = 16701 and Mw = 33541.

0.40 g of the obtained polyamic acid ester resin powder was placed in a 100 ml Erlenmeyer flask, and 3.60 g of GBL was added and dissolved by stirring at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-7).

(Example 1)

An agitator was placed in a 50 ml Erlenmeyer flask, 6.12 g of the polyamic acid solution (PAA-1) obtained in Synthesis Example 1, 0.0639 g of methyl trifluoromethanesulfonate was added, and the mixture was stirred at room temperature for 4 hours. Next, 1.76 g of NMP and 1.96 g of BCS were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (A-1).

(Example 2)

6.23 g of the polyamic acid solution (PAA-2) obtained in Synthesis Example 2 was added to a 50 ml Erlenmeyer flask, 0.0770 g of methyl trifluoromethanesulfonate was added, and the mixture was stirred at room temperature for 4 hours to obtain a polyamic acid solution PAA-2S). Next, 2.25 g of a polyamic acid solution (PAA-2S) was taken in another 50 ml Erlenmeyer flask equipped with a stirrer, 2.57 g of NMP and 1.23 g of BCS were added and stirred with a magnetic stirrer for 30 minutes, (A-2) was obtained.

(Example 3)

4.53 g of the polyamic acid solution (PAA-3) obtained in Synthesis Example 3 was put in a 50 ml Erlenmeyer flask, 0.1470 g of methyl trifluoromethanesulfonate was added, and the mixture was stirred at room temperature for 4 hours to obtain a polyamic acid solution PAA-3S). Next, 1.64 g of a polyamic acid solution (PAA-3S) was taken in another 50 ml Erlenmeyer flask equipped with a stirrer, 3.24 g of NMP and 1.23 g of BCS were added and stirred with a magnetic stirrer for 30 minutes, (A-3) was obtained.

(Example 4)

4.82 g of the polyamic acid solution (PAA-4) obtained in Synthesis Example 4 was put in a 50 ml Erlenmeyer flask, and 0.0754 g of methyl trifluoromethanesulfonate was added. After stirring at room temperature for 4 hours, a polyamic acid solution PAA-4S1). Next, 2.61 g of a polyamic acid solution (PAA-4S1), 2.21 g of NMP and 1.19 g of BCS were added to another 50 ml Erlenmeyer flask equipped with a stirrer and stirred with a magnetic stirrer for 30 minutes, (A-4) was obtained.

(Example 5)

4.82 g of the polyamic acid solution (PAA-4) obtained in Synthetic Example 4 was put in a 50 ml Erlenmeyer flask, and 0.0359 g of methyl trifluoromethanesulfonate was added. After stirring at room temperature for 4 hours, a polyamic acid solution PAA-4S2). Then, 2.61 g of a polyamic acid solution (PAA-4S2) was taken in another 50 ml Erlenmeyer flask containing the stirrer, 2.22 g of NMP and 1.21 g of BCS were added and stirred with a magnetic stirrer for 30 minutes, (A-5) was obtained.

(Example 6)

7.27 g of the polyamic acid solution (PAA-5) obtained in Synthesis Example 5 was put in a 50 ml Erlenmeyer flask, and 0.0856 g of methyl p-toluenesulfonate was added. The mixture was stirred at room temperature for 4 hours to obtain a polyamic acid solution (PAA -5S). Next, 2.61 g of a polyamic acid solution (PAA-5S), 2.20 g of NMP and 1.23 g of BCS were added to another 50 ml Erlenmeyer flask equipped with a stirrer and stirred with a magnetic stirrer for 30 minutes, (A-6) was obtained.

(Example 7)

6.88 g of the polyamic acid solution (PAA-6) obtained in Synthetic Example 6 was put in a 50 ml Erlenmeyer flask, and 0.0553 g of methyl methanesulfonate was added and stirred at room temperature for 4 hours to obtain a polyamic acid solution (PAA-6S ). Next, 2.46 g of a polyamic acid solution (PAA-6S) was taken in another 50 ml Erlenmeyer flask equipped with a stirrer, 2.34 g of NMP and 1.24 g of BCS were added and stirred with a magnetic stirrer for 30 minutes, (A-7) was obtained.

(Example 8)

6.50 g of the polyamic acid solution (PAA-7) obtained in Synthesis Example 7 was added to a 50 ml Erlenmeyer flask, 0.0836 g of methyl trifluoromethanesulfonate was added, and the mixture was stirred at room temperature for 4 hours to obtain a polyamic acid solution PAA-7S1). Next, 2.33 g of a polyamic acid solution (PAA-7S1) was taken in another 50 ml Erlenmeyer flask containing a stirrer, 2.55 g of NMP and 1.20 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes, (A-8) was obtained.

(Example 9)

6.48 g of the polyamic acid solution (PAA-7) obtained in Synthetic Example 7 was added to a 50 ml Erlenmeyer flask, 0.0462 g of methanesulfonic acid 2,2,2-trifluoroethyl was added, and the mixture was stirred at room temperature for 4 hours To obtain a polyamic acid solution (PAA-7S2). Next, 2.34 g of a polyamic acid solution (PAA-7S2) was taken in another 50 ml Erlenmeyer flask equipped with a stirrer, 2.48 g of NMP and 1.24 g of BCS were added and stirred with a magnetic stirrer for 30 minutes, (A-9) was obtained.

(Example 10)

10.52 g of the polyamic acid solution (PAA-8) obtained in Synthetic Example 8 was added to a 50 ml Erlenmeyer flask, and 0.2204 g of 2-methoxyethyl methanesulfonate was added and stirred at room temperature for 4 hours to obtain a polyamic acid solution (PAA-8S). Next, 3.77 g of a polyamic acid solution (PAA-8S) was taken in another 50 ml Erlenmeyer flask equipped with a stirrer, 1.07 g of NMP and 1.22 g of BCS were added and stirred with a magnetic stirrer for 30 minutes, (A-10) was obtained.

(Example 11)

9.87 g of the polyamic acid solution (PAA-9) obtained in Synthesis Example 9 was put in a 50 ml Erlenmeyer flask, and 0.1875 g of methyl trifluoromethanesulfonate was added. The mixture was stirred at room temperature for 4 hours to obtain a polyamic acid solution PAA-9S). Next, 3.57 g of a polyamic acid solution (PAA-9S) was taken in another 50 ml Erlenmeyer flask equipped with a stirrer, 1.25 g of NMP and 1.22 g of BCS were added and stirred with a magnetic stirrer for 30 minutes, (A-11) was obtained.

(Example 12)

10.01 g of the polyamic acid ester solution (PAE-1) obtained in Synthesis Example 10 was put in a 50 ml Erlenmeyer flask, and 0.0671 g of propanesultone was added and stirred at room temperature for 4 hours to obtain a polyamic acid ester solution (PAE- 1S). Subsequently, 3.63 g of a polyamic acid ester solution (PAE-1S) was taken in another 50 ml Erlenmeyer flask equipped with a stirrer, 1.20 g of NMP and 1.21 g of BCS were added and stirred with a magnetic stirrer for 30 minutes, To thereby obtain an aligning agent (A-12).

(Example 13)

10.31 g of the polyamic acid ester solution (PAE-2) obtained in Synthetic Example 11 was put in a 50 ml Erlenmeyer flask, and 0.0813 g of methyl trifluoromethanesulfonate was added. The mixture was stirred at room temperature for 4 hours to obtain a polyamic acid ester Solution (PAE-2S). Next, 3.62 g of a polyamic acid ester solution (PAE-2S) was taken in another 50 ml Erlenmeyer flask equipped with a stirrer, 1.23 g of NMP and 1.21 g of BCS were added and stirred with a magnetic stirrer for 30 minutes, (A-13) was obtained.

(Example 14)

 10.32 g of the polyimide solution (SPI-1) obtained in Synthetic Example 13 was added to a 50 ml Erlenmeyer flask, and 0.0352 g of methyl trifluoromethanesulfonate was added and stirred at room temperature for 4 hours to obtain a polyimide solution ( SPI-1S). Next, 3.61 g of a polyimide solution (SPI-1S) was taken in another 50 ml Erlenmeyer flask containing the stirrer, 1.22 g of NMP and 1.20 g of BCS were added and stirred with a magnetic stirrer for 30 minutes, (A-14) was obtained.

(Example 15)

5.28 g of the polyamic acid solution (PAA-10) obtained in Synthetic Example 14 was added to a 50 ml Erlenmeyer flask, 0.0813 g of methyl trifluoromethanesulfonate was added, and the mixture was stirred at room temperature for 4 hours to obtain a polyamic acid solution PAA-10S). Next, 1.85 g of a polyamic acid solution (PAA-10S) was taken in another 50 ml Erlenmeyer flask equipped with a stirrer, 3.00 g of NMP and 1.21 g of BCS were added and stirred with a magnetic stirrer for 30 minutes, (A-15) was obtained.

(Example 16)

3.74 g of the polyimide solution (SPI-2) obtained in Synthesis Example 15 was added to a 50 ml Erlenmeyer flask, 0.0539 g of methyl trifluoromethanesulfonate was added and the mixture was stirred at room temperature for 4 hours to obtain a polyimide solution ( SPI-2S). Then, 0.32 g of NMP and 4.05 g of BCS were added and stirred for 30 minutes by a magnetic stirrer to obtain a liquid crystal aligning agent (A-16).

(Example 17)

9.91 g of the polyamic acid ester solution (PAE-3) obtained in Synthesis Example 12 was put in a 50 ml Erlenmeyer flask, and 0.0909 g of methyl trifluoromethanesulfonate was added and stirred at room temperature for 4 hours to obtain a polyamic acid ester Solution (PAE-3S). Next, 3.60 g of a polyamic acid ester solution (PAE-3S) was taken in another 50 ml Erlenmeyer flask equipped with a stirrer, 1.23 g of NMP and 1.22 g of BCS were added and stirred with a magnetic stirrer for 30 minutes, (A-17) was obtained.

(Example 18)

10.10 g of the polyamic acid solution (PAA-11) obtained in Synthesis Example 16 was added to a 50 ml Erlenmeyer flask, and 0.0619 g of methyl trifluoromethanesulfonate was added. The mixture was stirred at room temperature for 4 hours to obtain a polyamic acid solution PAA-11S). Next, 3.69 g of a polyamic acid solution (PAA-11S) was taken in another 50 ml Erlenmeyer flask containing the stirrer, 1.12 g of NMP and 1.22 g of BCS were added and stirred with a magnetic stirrer for 30 minutes, (A-18) was obtained.

(Example 19)

2.24 g of the polyamic acid solution (PAA-12) obtained in Synthetic Example 19, 2.48 g of the polyamic acid solution (PAA-2S) obtained in Example 2, 3.33 g of NMP, and 20.0 ml of BCS And the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (A-19).

(Example 20)

2.41 g of the polyamic acid ester solution (PAE-5) obtained in Synthesis Example 18, 1.93 g of the polyamic acid solution (PAA-3S1) obtained in Example 4, 0.43 g of NMP and 0.45 g of GBL (Hereinafter abbreviated as Fmoc-His) as an imidization accelerator, 3.27 g of BCS, and 2.00 g of BCS. (0.0844 g) was added and stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal aligning agent (A-20).

(Example 21)

30.70 g of the polyamic acid solution (PAA-13) obtained in Synthetic Example 20 was put in a 50 ml Erlenmeyer flask, 0.9011 g of methyl trifluoromethanesulfonate was added, and the mixture was stirred at room temperature for 4 hours to obtain a polyamic acid solution PAA-13S). Next, 2.02 g of a polyamic acid solution (PAA-13S) was taken in another 50 ml Erlenmeyer flask equipped with a stirrer, 4.68 g of NMP and 1.66 g of BCS were added and stirred with a magnetic stirrer for 30 minutes, (A-21) was obtained.

(Example 22)

3.36 g of the polyamic acid ester solution (PAE-4) obtained in Synthesis Example 17, 2.24 g of the polyamic acid solution (PAA-13S) obtained in Example 21, 1.37 g of NMP and 1.36 g of GBL , 2.81 g of BCS, and 0.1146 g of Fmoc-His as an imidization accelerator were further added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (A-22).

(Example 30)

4.00 g of the polyamic acid ester solution (PAE-6) obtained in Synthetic Example 21 was put in a 50 ml Erlenmeyer flask, and 0.019 g of methyl trifluoromethanesulfonate was added, followed by stirring at room temperature for 4 hours. Next, 2.41 g of GBL, 1.61 g of BCS, and 0.1478 g of Fmoc-His were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (A-23).

(Example 31)

4.00 g of the polyamic acid ester solution (PAE-6) obtained in Synthetic Example 21 was put in a 50 ml Erlenmeyer flask, 0.0205 g of ethyl trifluoromethanesulfonate was added, and the mixture was stirred at room temperature for 4 hours. Next, 2.41 g of GBL, 1.61 g of BCS and 0.1425 g of Fmoc-His were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (A-24).

(Comparative Example 1)

4.66 g of the polyamic acid solution (PAA-1) obtained in Synthesis Example 1, 1.58 g of NMP and 1.57 g of BCS were added to a 20 ml sample tube containing the stirrer and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (B -1).

(Comparative Example 2)

2.46 g of the polyamic acid solution (PAA-2) obtained in Synthesis Example 2, 2.34 g of NMP and 1.21 g of BCS were added to a 20 ml sample tube into which a stirrer was placed and stirred for 30 minutes by a magnetic stirrer to obtain a liquid crystal aligning agent (B -2).

(Comparative Example 3)

3.67 g of the polyamic acid solution (PAA-11) obtained in Synthesis Example 16, 1.15 g of NMP and 1.21 g of BCS were added to a 20-ml sample tube into which a stirrer was placed and stirred for 30 minutes by a magnetic stirrer to obtain a liquid crystal aligning agent (B -3).

(Comparative Example 4)

3.61 g of the soluble polyimide solution (SPI-1) obtained in Synthesis Example 13, 1.22 g of NMP and 1.22 g of BCS were added to a 20 ml sample tube into which a stirrer was inserted and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent B-4).

(Comparative Example 5)

3.15 g of the polyamic acid solution (PAA-12) obtained in Synthesis Example 19, 3.46 g of the polyamic acid solution (PAA-2) obtained in Synthesis Example 2, 4.62 g of NMP and BCS 2.81 g, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (B-5).

(Comparative Example 6)

3.37 g of the polyamic acid ester solution (PAE-5) obtained in Synthesis Example 18, 2.69 g of the polyamic acid solution (PAA-4) obtained in Synthesis Example 3, 0.61 g of NMP and 0.45 g of GBL And 2.83 g of BCS. The mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal aligning agent (B-6).

(Comparative Example 7)

3.37 g of the polyamic acid ester solution (PAE-4) obtained in Synthetic Example 17, 2.25 g of the polyamic acid solution (PAA-13) obtained in Synthetic Example 20, 1.39 g of NMP and 1.25 g of GBL And 2.80 g of BCS, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (B-7).

(Comparative Example 15)

4.00 g of the polyamic acid ester solution (PAE-7) obtained in Synthesis Example 22 was put in a 50 ml Erlenmeyer flask, 2.41 g of GBL, 1.60 g of BCS and 0.1416 g of Fmoc-His were added, Followed by stirring for 30 minutes to obtain a liquid crystal aligning agent (B-8).

(Example 23)

The liquid crystal aligning agent (A-1) obtained in Example 1 was filtered with a filter having a size of 1.0 mu m and then an ITO electrode having a thickness of 50 nm as a first layer and an ITO electrode having a thickness of 500 Nm silicon nitride as the third layer and a comb-shaped ITO electrode (electrode width: 3 mu m, electrode gap: 6 mu m, electrode height: 50 nm) . Dried on a hot plate at 80 DEG C for 5 minutes, and then fired in a hot air circulating oven at 230 DEG C for 30 minutes to form a coating film having a film thickness of 100 nm. Ultraviolet rays of 254 nm were irradiated at 1000 mJ / cm 2 through the polarizing plate to the coated film surface to obtain a substrate with a liquid crystal alignment film attached. A coating film was similarly formed on a glass substrate having a columnar spacer having a height of 4 占 퐉, on which no electrode was formed as a counter substrate, and the alignment treatment was carried out.

The two substrates were set as one set, a sealant was printed on the substrate, and another substrate was bonded to the liquid crystal alignment film so that the alignment direction of the liquid crystal alignment film face was 0 °, and then the sealant was cured Free cell was prepared. A liquid crystal MLC-2041 (manufactured by Merck & Co., Inc.) was injected into this vacant cell by a reduced pressure injection method and the injection port was sealed to obtain an FFS-driven liquid crystal cell.

As a result of evaluating the charge relaxation characteristics for this FFS-driven liquid crystal cell, ΔT at 0 minute, 5 minutes, 10 minutes, 20 minutes, and 60 minutes after AC driving were 34%, 0%, 0%, 0%, and 0% .

(Example 24)

The liquid crystal aligning agent (A-7) obtained in Example 7 was used, and instead of light irradiation, rubbing treatment was performed under the conditions of a roller rotation speed of 700 rpm, a stage moving speed of 10 mm / s, and a rubbing impregnation pressure of 0.3 mm An FFS-driven liquid crystal cell was produced in the same manner as in Example 23. [ As a result of evaluating the charge relaxation characteristics of this FFS-driven liquid crystal cell, ΔT at 0 minutes, 5 minutes, 10 minutes, 20 minutes, and 60 minutes after AC driving were 3%, 2%, 2%, 1%, and 0% .

(Example 25)

The liquid crystal aligning agent (A-14) obtained in Example 14 was used and subjected to rubbing under the conditions of a roller rotation speed of 700 rpm, a stage moving speed of 10 mm / s, and a rubbing impregnation pressure of 0.3 mm instead of light irradiation An FFS-driven liquid crystal cell was produced in the same manner as in Example 23. [ As a result of evaluating the charge relaxation characteristics of this FFS-driven liquid crystal cell, ΔT at 0 minute, 5 minutes, 10 minutes, 20 minutes, and 60 minutes after AC driving were 32%, 0%, 0%, 0%, and 0% .

(Example 26)

An FFS-driving liquid crystal cell was produced in the same manner as in Example 23 except that the liquid crystal aligning agent (A-18) obtained in Example 18 was used and irradiated with polarized ultraviolet rays of 100 mJ / cm 2. As a result of evaluating the charge relaxation characteristics for the FFS-driven liquid crystal cell, ΔT at 0 minute, 5 minutes, 10 minutes, 20 minutes, and 60 minutes after AC driving were 27%, 1%, 1%, 1%, and 0% .

(Example 27)

An FFS-driving liquid crystal cell was produced in the same manner as in Example 23 except that the liquid crystal aligning agent (A-19) obtained in Example 19 was used and irradiated with polarized ultraviolet rays of 750 mJ / cm 2. As a result of evaluating the charge relaxation characteristics for this FFS-driven liquid crystal cell, ΔT at 0 minute, 5 minutes, 10 minutes, 20 minutes, and 60 minutes after AC driving were 31%, 0%, 0%, 0%, and 0% .

(Example 28)

An FFS-driving liquid crystal cell was produced in the same manner as in Example 23 except that the liquid crystal aligning agent (A-20) obtained in Example 20 was used and irradiated with polarized ultraviolet rays of 500 mJ / cm 2. The charge relaxation characteristics of the FFS-driven liquid crystal cell were evaluated. As a result, ΔT at 0 minute, 5 minutes, 10 minutes, 20 minutes, and 60 minutes after AC driving were 29%, 0%, 0%, 0%, and 0% .

(Example 29)

An FFS-driven liquid crystal cell was produced in the same manner as in Example 23 except that the liquid crystal aligning agent (A-22) obtained in Example 22 was used and irradiated with polarized ultraviolet light of 500 mJ / cm 2. As a result of evaluating the charge relaxation characteristics of the FFS-driven liquid crystal cell, ΔT at 0 minute, 5 minutes, 10 minutes, 20 minutes, and 60 minutes after AC driving were 36%, 0%, 0%, 0%, and 0% .

(Example 32)

An FFS-driving liquid crystal cell was produced in the same manner as in Example 23 except that the liquid crystal aligning agent (A-23) obtained in Example 30 was used and irradiated with polarized ultraviolet rays of 500 mJ / cm 2. As a result of evaluating the charge relaxation characteristics for this FFS-driven liquid crystal cell, ΔT at 0 minute, 5 minutes, 10 minutes, 20 minutes, and 60 minutes after AC driving were 30%, 0%, 0%, 0%, and 0% .

(Example 33)

An FFS-driven liquid crystal cell was produced in the same manner as in Example 23 except that the liquid crystal aligning agent (A-24) obtained in Example 31 was used and irradiated with polarized ultraviolet rays of 500 mJ / cm 2. The charge relaxation characteristics of the FFS-driven liquid crystal cell were evaluated. As a result, ΔT at 0 minute, 5 minutes, 10 minutes, 20 minutes, and 60 minutes after AC driving were 29%, 0%, 0%, 0%, and 0% .

(Comparative Example 8)

An FFS-driving liquid crystal cell was produced in the same manner as in Example 23 except that the liquid crystal aligning agent (B-1) obtained in Comparative Example 1 was used. As a result of evaluating the charge relaxation characteristics for this FFS-driven liquid crystal cell, ΔT at 0 minutes, 5 minutes, 10 minutes, 20 minutes, and 60 minutes after AC driving were 36%, 9%, 4%, 2%, and 1% .

(Comparative Example 9)

The liquid crystal aligning agent (B-2) obtained in Comparative Example 2 was used, and in place of light irradiation, rubbing treatment was performed under the conditions of a roller rotation speed of 700 rpm, a stage moving speed of 10 mm / s, and a rubbing impregnation pressure of 0.3 mm An FFS-driven liquid crystal cell was produced in the same manner as in Example 23. [ As a result of evaluating the charge relaxation characteristics for the FFS-driven liquid crystal cell, ΔT at 0 minutes, 5 minutes, 10 minutes, 20 minutes, and 60 minutes after AC driving were 4%, 3%, 2%, 2%, and 1% .

(Comparative Example 10)

The liquid crystal aligning agent (B-3) obtained in Comparative Example 3 was used and subjected to rubbing under the conditions of a roller rotation speed of 700 rpm, a stage moving speed of 10 mm / s, and a rubbing impregnation pressure of 0.3 mm instead of light irradiation An FFS-driven liquid crystal cell was produced in the same manner as in Example 23. [ As a result of evaluating the charge relaxation characteristics of this FFS-driven liquid crystal cell, ΔT at 0 minute, 5 minutes, 10 minutes, 20 minutes, and 60 minutes after AC driving were 30%, 1%, 1%, 1%, and 0% .

(Comparative Example 11)

An FFS-driven liquid crystal cell was produced in the same manner as in Example 23 except that the liquid crystal aligning agent (B-4) obtained in Comparative Example 4 was used and irradiated with polarized ultraviolet rays of 100 mJ / cm 2. As a result of evaluating the charge relaxation characteristics with respect to this FFS-driven liquid crystal cell, ΔT at 0 minute, 5 minutes, 10 minutes, 20 minutes, and 60 minutes after AC driving were 22%, 6%, 2%, 1%, and 0% .

(Comparative Example 12)

An FFS-driving liquid crystal cell was produced in the same manner as in Example 23 except that the liquid crystal aligning agent (B-5) obtained in Comparative Example 5 was used and irradiated with polarized ultraviolet rays of 750 mJ / cm 2. As a result of evaluating the charge relaxation characteristics of this FFS-driven liquid crystal cell, ΔT at 0 minute, 5 minutes, 10 minutes, 20 minutes, and 60 minutes after AC driving were 28%, 5%, 5%, 5%, and 4% .

(Comparative Example 13)

An FFS-driving liquid crystal cell was produced in the same manner as in Example 23 except that the liquid crystal aligning agent (B-6) obtained in Comparative Example 6 was used and irradiated with polarized ultraviolet rays of 500 mJ / cm 2. As a result of evaluating the charge relaxation characteristics of this FFS-driven liquid crystal cell, ΔT at 0 minutes, 5 minutes, 10 minutes, 20 minutes, and 60 minutes after AC driving were 31%, 8%, 7%, 7%, and 4% .

(Comparative Example 14)

An FFS-driven liquid crystal cell was produced in the same manner as in Example 23 except that the liquid crystal aligning agent (B-7) obtained in Comparative Example 7 was used and irradiated with polarized ultraviolet rays of 500 mJ / cm 2. As a result of evaluating the charge relaxation characteristics for this FFS-driven liquid crystal cell, ΔT at 0 minutes, 5 minutes, 10 minutes, 20 minutes, and 60 minutes after AC driving were 38%, 3%, 3%, 3%, and 1% .

(Comparative Example 16)

An FFS-driven liquid crystal cell was produced in the same manner as in Example 23 except that the liquid crystal aligning agent (B-8) obtained in Comparative Example 15 was used and irradiated with polarized ultraviolet rays of 500 mJ / cm 2. As a result of evaluating the charge relaxation characteristics for the FFS-driven liquid crystal cell, ΔT at 0 minute, 5 minutes, 10 minutes, 20 minutes, and 60 minutes after AC driving were 29%, 5%, 2%, 1%, and 0% .

Industrial availability

The liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention can speed up the relaxation rate of the residual electric charge in the liquid crystal display element accumulated by the direct current voltage. 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, drawings and summary of Japanese Patent Application No. 2011-078688 filed on March 31, 2011 are hereby incorporated herein by reference and the disclosure of the specification of the present invention.

Claims (11)

At least one polymer selected from the group consisting of a polyimide precursor having a repeating unit represented by the following formula (1) and an imidization polymer of the polyimide precursor, a sulfonate ester represented by the following formula (2) And a liquid crystal alignment agent.
[Chemical Formula 1]

(In the formula (1), X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and A ₁ and A ₂ are each independently A hydrogen atom, or an alkyl, alkenyl or alkynyl group having 1 to 10 carbon atoms which may have a substituent).
(2)
R ₂ -SO ₂ -OR ₃ (2)
(In the formula (2), R ₂ and R ₃ are each independently a monovalent organic group having 1 to 30 carbon atoms which may have a substituent, and R ₂ and R ₃ may bond to each other to form a cyclic structure.) The method according to claim 1,
Wherein the content of the sulfonic acid ester is 0.01 part by mass to 30 parts by mass with respect to 100 parts by mass of the polymer. The method according to claim 1,
And R ₂ is a methyl group which may have a substituent. The method according to claim 1,
And R ₃ is a methyl group. The method according to claim 1,
Wherein the sulfonic acid ester is trifluoromethanesulfonic acid methyl ester or trifluoromethanesulfonic acid ethyl ester. The method according to claim 1,
Wherein the polymer has a weight average molecular weight of 5,000 to 300,000. The method according to claim 1,
And the content of the polymer is 0.5% by mass to 20% by mass with respect to the organic solvent. A liquid crystal alignment film obtained by applying and firing the liquid crystal aligning agent according to any one of claims 1 to 7. A liquid crystal alignment film obtained by irradiating polarized radiation to a film obtained by applying and firing the liquid crystal aligning agent according to any one of claims 1 to 7. 9. A liquid crystal display element comprising the liquid crystal alignment film according to claim 8. A liquid crystal display element comprising the liquid crystal alignment film according to claim 9.