KR20140037834A - 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.)The liquid crystal aligning agent for obtaining the liquid crystal aligning film and liquid crystal aligning film from which the liquid crystal display element of which the relaxation rate of residual charge by DC voltage is quick is obtained is provided.
At least 1 type of polymer chosen from the group which consists of a polyimide precursor which has a structural unit represented by Formula (1), and the imidation polymer of this polyimide precursor, the sulfonic acid ester represented by Formula (2), and an organic solvent are contained The liquid crystal aligning agent characterized by the above-mentioned.
[Chemical Formula 1]

(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> is a C1-C30 monovalent organic group which may respectively independently have a substituent, and R <_2> and R <_3> may combine with each other and form a ring structure.)

Description

Liquid crystal aligning agent and liquid crystal aligning film using the same {LIQUID CRYSTAL ALIGNING AGENT, AND LIQUID CRYSTAL ALIGNMENT FILM PRODUCED USING SAME}

This invention relates to the liquid crystal aligning agent for manufacturing a liquid crystal aligning film, and the liquid crystal aligning film obtained from this liquid crystal aligning agent. In detail, it is providing the liquid crystal aligning film from which the liquid crystal display element with a quick relaxation rate of residual charge by DC voltage is obtained, and a liquid crystal aligning agent for obtaining a liquid crystal aligning film.

In the liquid crystal display element used for a liquid crystal television, a liquid crystal display, etc., the liquid crystal aligning film for controlling the arrangement state of a liquid crystal is formed in an element normally. As a liquid crystal aligning film, the polyimide-type liquid crystal aligning film which apply | coated and baked the liquid crystal aligning agent which mainly uses the solution of polyimide precursors, such as a polyamic acid (polyamic acid), and a soluble polyimide, etc. as a main component is mainly used heretofore. It is becoming.

With the high precision of a liquid crystal display element, from the request | requirement of suppression of the contrast fall of a liquid crystal display element, or reduction of an afterimage phenomenon, in a liquid crystal aligning film, in addition to the expression of the outstanding liquid-crystal orientation and stable pretilt angle, high voltage retention and alternating current The characteristics of suppression of an afterimage generated by driving, low residual charge when a direct current voltage is applied, and / or rapid relaxation of accumulated residual charge by a direct current voltage are becoming increasingly important.

In the polyimide-based liquid crystal aligning film, various proposals have been made in order to answer the above requirements. For example, in addition to polyamic acid and imide group containing polyamic acid, the liquid crystal aligning agent containing the tertiary amine of a specific structure was used as a liquid crystal aligning film with a short time until the afterimage which generate | occur | produces by DC voltage disappears. The thing (for example, refer patent document 1), the thing using the liquid crystal aligning agent containing the soluble polyimide which used the specific diamine compound which has a pyridine skeleton etc. as a raw material (for example, refer patent document 2), etc. It is.

Moreover, the compound and molecule | numerator which contain one carboxylic acid group in a molecule | numerator in addition to a polyamic acid, its imidation polymer, etc. as a liquid crystal aligning film with a high voltage retention and a short time until the afterimage which generate | occur | produced by DC voltage disappears. The use of the liquid crystal aligning agent which contains the minimum amount of the compound chosen from the compound containing one carboxylic anhydride group in the compound, and the compound containing one tertiary amino group in a molecule | numerator (for example, refer patent document 3) is proposed have.

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

Thus, various methods of suppressing the afterimage of a liquid crystal display are examined. However, in recent years, large screen and high-definition liquid crystal televisions have become main subjects, and demand for afterimages has become more stringent, and properties that can withstand long-term use in harsh use environments have been demanded. This invention is made | formed by the said situation, The objective is to provide the liquid crystal aligning film which can manufacture the liquid crystal display element with which the relaxation time of residual charge by DC voltage is quick, and the liquid crystal aligning agent for obtaining this alignment film. have.

According to the research of the present inventors, the liquid crystal aligning film formed from the liquid crystal aligning agent containing a specific amount of a specific sulfonic acid ester with the polyimide precursor and / or the imidation polymer of the polyimide precursor does not impair other characteristics, New knowledge has been obtained that a liquid crystal display device having an earlier relaxation time of residual charges can be obtained.

This invention is based on this knowledge and has the following summary.

1. At least 1 sort (s) of polymer chosen from the group which consists of the polyimide precursor which has a structural unit represented by following formula (1), and the imidation polymer of this polyimide precursor, the sulfonic acid ester represented by following formula (2), and organic A solvent is contained, The liquid crystal aligning agent characterized by the above-mentioned.

[Formula 1]

(In formula (1), X <_1> is a tetravalent organic group, Y <_1> is a divalent organic group, R <_1> is a hydrogen atom or a C1-C5 alkyl group, A <_1> and A <_2> are respectively independently A hydrogen atom or a C1-C10 alkyl group, alkenyl group, or alkynyl group which may have a substituent.)

(2)

R ₂ -SO ₂ -OR ₃ (2)

(In Formula (2), R <_2> and R <_3> is a C1-C30 monovalent organic group which may respectively independently have a substituent, and R <_2> and R <_3> may combine with each other and form a ring structure.)

2. Liquid crystal aligning agent of said 1 whose content of said sulfonic acid ester is 0.01 mass part-30 mass parts with respect to 100 mass parts of said polymers.

3. Liquid crystal aligning agent of said 1 or 2 whose R <_2> is methyl group which may have substituent.

4. Liquid crystal aligning agent in any one of said 1-3 whose R <_3> is methyl group.

5. Liquid crystal aligning agent of said 1 or 2 whose said sulfonic acid ester is methyl trifluoromethanesulfonic acid or ethyl trifluoromethanesulfonic acid.

6. Liquid crystal aligning agent in any one of said 1-5 whose weight average molecular weights of said polymer are 5,000-300,000.

7. Liquid crystal aligning agent in any one of said 1-6 whose content of said polymer is 0.5 mass%-20 mass% with respect to organic solvent.

8. Liquid crystal aligning film obtained by apply | coating and baking liquid crystal aligning agent in any one of said 1-7.

9. Liquid crystal aligning film obtained by irradiating polarized radiation to the film obtained by apply | coating and baking the liquid crystal aligning agent in any one of said 1-7.

10. The liquid crystal display element provided with the liquid crystal aligning film of said 8 or 9.

The liquid crystal aligning film formed from the liquid crystal aligning agent containing a specific amount of a specific sulfonic acid ester with the polyimide precursor and / or the imidation polymer of the polyimide precursor by this invention is the relaxation of the residual electric charge by the direct current voltage of a liquid crystal display element. Time can be advanced and excellent liquid crystal display element is provided with the outstanding liquid-crystal orientation, the expression of a stable pretilt angle, etc.

The mechanism by which the said effect is acquired by the liquid crystal aligning agent of this invention is not necessarily clear, but is generally considered as follows. When the sulfonic acid ester of the said Formula (2) contained in the liquid crystal aligning agent of this invention exists, it reacts with the carboxyl group which the polyimide precursor of a liquid crystal aligning agent, and / or the imidation polymer of this polyimide precursor has, or an amino group, An anion represented by the following formula (3) is produced.

(3)

^{_{R 2 -SO 2 -O - (3}} )

When the anion represented by this formula (3) exists in the liquid crystal aligning film formed by baking the coating film of a liquid crystal aligning agent, the specific resistance of the liquid crystal aligning film obtained falls and also the relaxation of the residual electric charge by the direct current voltage of a liquid crystal display element. It is thought that the effect of improving speed is expressed.

<Polyimide precursor>

The polyimide precursor used for this invention is a polymer which has the site | part which enables the imidation reaction shown below by heating or reacting with an imidation catalyst. In the following formulae, 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]

Moreover, the imidation polymer used for this invention is a polymer obtained by making the said polyimide precursor heat or react with an imidation catalyst.

The polyimide precursor which the liquid crystal aligning agent of this invention contains is a polymer which has a structural unit represented by following formula (1).

[Chemical Formula 5]

In said Formula (1), R <_1> is a hydrogen atom or a C1-C5, Preferably it is an alkyl group of 1-2. When R <_1> is an alkyl group, the temperature at which imidation advances becomes high as carbon number in an alkyl group increases. Therefore, R ₁ is particularly preferably a hydrogen atom or a methyl group from the viewpoint of ease of heat imidation. In Formula (1), A <_1> and A <_2> are a C1-C10 alkyl group, an alkenyl group, or an alkynyl group which may respectively independently have a hydrogen atom or a substituent. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, t-butyl group, hexyl group, octyl group, decyl group, cyclopentyl group, cyclohexyl group and bicyclohexyl group. As an alkenyl group, what substituted one or more CH-CH structures which exist in the said alkyl group by C = C structure is mentioned. 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, .

Said alkyl group, alkenyl group, and alkynyl group may have a substituent as a whole as long as it is C1-C10, and may form a ring structure by a substituent further. In addition, forming a ring structure by a substituent means that a substituent or part of a substituent and a parent skeleton couple | bonds and becomes a ring structure.

Examples of the substituent include a halogen group, a hydroxyl group, a thiol group, a nitro group, an aryl group, an organooxy group, an organothio group, an organosilyl group, an acyl group, an ester group, a thioester group, a phosphate ester group, an amide group, Alkyl group, alkenyl group, and alkynyl group are mentioned.

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

A phenyl group is mentioned as an aryl group which is a substituent. The other substituent mentioned above may further substitute by this aryl group.

As an organooxy group which is a substituent, the structure represented by O-R can be shown. This R may be same or different and can illustrate an alkyl group, an alkenyl group, an alkynyl group, an aryl group, etc. which were mentioned above. The substituent mentioned above may further substitute by such R. Specific examples of the organooxy group include a methoxy group, ethoxy group, propyloxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group and the like.

As an organothio group which is a substituent, the structure represented by -S-R can be shown. As said R, the alkyl group, alkenyl group, alkynyl group, aryl group, etc. which were mentioned above can be illustrated. The substituent mentioned above may further substitute by such R. Specific examples of the organothio group include methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, heptylthio group, octylthio group and the like.

As an organosilyl group which is a substituent, the structure represented by -Si- (R) ₃ can be shown. This R may be same or different and can illustrate an alkyl group, an alkenyl group, an alkynyl group, an aryl group, etc. which were mentioned above. The substituent mentioned above may further substitute by such R. Specific examples of the organosilyl group include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tributylsilyl group, tripentylsilyl group, trihexylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, and the like. Can be mentioned.

As an acyl group which is a substituent, the structure represented by -C (O) -R can be shown. As this R, the alkyl group, alkenyl group, aryl group, etc. which were mentioned above can be illustrated. The substituent mentioned above may further substitute by such R. Specific examples of the acyl group include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, benzoyl group and the like.

As ester group which is a substituent, the structure represented by -C (O) O-R or -OC (O) -R can be shown. As said R, the alkyl group, alkenyl group, alkynyl group, aryl group, etc. which were mentioned above can be illustrated. The substituent mentioned above may further substitute by such R.

As a thioester group which is a substituent, the structure represented by -C (S) O-R or -OC (S) -R can be shown. As said R, the alkyl group, alkenyl group, alkynyl group, aryl group, etc. which were mentioned above can be illustrated. The substituent mentioned above may further substitute by such R.

As a phosphate ester group which is a substituent, the structure represented by -OP (O)-(OR) ₂ can be shown. This R may be same or different and can illustrate an alkyl group, an alkenyl group, an alkynyl group, an aryl group, etc. which were mentioned above. The substituent mentioned above may further substitute by such R.

Substituent of the amide group include, -C (O) NH _2, or, -C (O) NHR, -NHC (O) R, -C (O) N (R) 2, -NRC (O) represented by R The structure can be represented. This R may be same or different and can illustrate an alkyl group, an alkenyl group, an alkynyl group, an aryl group, etc. which were mentioned above. The substituent mentioned above may further substitute by such R.

As an aryl group which is a substituent, the thing similar to the aryl group mentioned above is mentioned. The other substituent mentioned above may further substitute by this aryl group.

As an alkyl group which is a substituent, the thing similar to the alkyl group mentioned above is mentioned. The other substituent mentioned above may further substitute by this alkyl group.

As an alkenyl group which is a substituent, the same thing as the alkenyl group mentioned above is mentioned. The other substituent mentioned above may further substitute by this alkenyl group.

As an alkynyl group which is a substituent, the thing similar to the alkynyl group mentioned above is mentioned. The other substituent mentioned above may further substitute by this alkynyl group.

In general, when a bulky structure is introduced, the reactivity and liquid crystal alignment of the amino group may be lowered. As A ₁ and A ₂ , a C 1-5 alkyl group which may have a hydrogen atom or 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. Two or more types of X <_1> may be mixed in a polyimide precursor. When the specific example of X <_1> is shown, X-1 to X-46 shown below are mentioned. Among them, in the availability of the monomer, X ₁ is X-1, X-2, X-3, X-4, X-5, X-6, X-8, X-16, X-19, X- Preference is given to 21, X-25, X-26, X-27, X-28 or X-32.

[Chemical Formula 6]

[Formula 7]

[Formula 8]

[Chemical Formula 9]

In addition, in Formula (1), Y <_1> is a divalent organic group and it is not specifically limited. Two or more types of Y <_1> may be mixed in a polyimide precursor. Represents a specific example of Y ₁ can be given to the Y-1 ~ Y-113 in.

Among these, in order to obtain a good liquid crystal alignment property, it is preferable that the polyamic acid introduced into the ester with a high linearity and a diamine, and roneun Y ₁ in this case, Y-7, Y-10 , Y-11, Y-12, Y -13, Y-21, Y-22, Y-23, Y-25, Y-26, Y-27, Y-41, Y-42, Y-43, Y-44, Y-45, Y-46 , Y-48, Y-61, Y-63, Y-64, Y-71, Y-72, Y-73, Y-74, Y-75, Y-98, Y-100, Y-101, Y More preferred are diamines of -102, Y-103, Y-0104, Y-105, Y-106, Y-107, Y-108, Y-109, or Y-110.

When the pretilt angle is to be increased, 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 to the polyamic acid ester, and in that case, Y ₁ is Y-76, Y-77, Y-78, Y-79, Y-80, Y-81, Y-82, Y-83, Y-84, Y-85, Y-86, Y-87 , Diamines of Y-88, Y-89, Y-90, Y-91, Y-92, Y-93, Y-94, Y-95, Y-96, or Y-97 are more preferable. By adding 1-50 mol% of these diamines, arbitrary pretilt angles can be expressed.

By lowering the volume resistivity of the polyimide precursor, the rate of relaxation of charge due to the accumulation of direct current voltage can be made faster, so that a diamine having a hetero atom, 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 -34, Y-35, Y-36, Y-40, Y-41, Y-42, Y-44, Y-45, Y-49, Y-50, Y-51, Y-61, Y-110 , Y-111, Y-112, or Y-113 are more preferable.

[Formula 10]

[Formula 11]

[Chemical Formula 12]

[Chemical Formula 13]

[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 this invention is represented by following formula (2).

[Chemical Formula 29]

R ₂ -SO ₂ -OR ₃ (2)

In said Formula (2), R <_2> and R <_3> is C1-C30, Preferably it is 1-20, More preferably, it is a monovalent organic group of 1-10, respectively which may have a substituent. This organic group is selected from the group which consists of an alkyl group, an alkenyl group, an alkynyl group, and an aryl group, and may form ring structure with R <_2> and R <_3> .

Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, t-butyl group, hexyl group, octyl group, decyl group, cyclopentyl group, cyclohexyl group and bicyclohexyl group. As an alkenyl group, what substituted one or more CH-CH structures which exist in the said alkyl group by C = C structure is mentioned, More specifically, a vinyl group, an allyl group, 1-propenyl group, isopropenyl group, 2-butenyl group, 1,3-butadienyl group, 2-pentenyl group, 2-hexenyl group, cyclopropenyl group, cyclopentenyl group, cyclohexenyl group, etc. are mentioned. 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, . As an aryl group, a phenyl group, (alpha)-naphthyl group, (beta) -naphthyl group, o-biphenylyl group, m-biphenylyl group, p-biphenylyl group, 1- anthryl group, 2- anthryl group, 9, for example -Anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, and the like.

Said alkyl group, alkenyl group, alkynyl group, and aryl group may have a substituent as a whole as long as it is C1-C20, and may form a ring structure by a substituent further. In addition, forming a ring structure by a substituent means that a substituent or part of a substituent and a parent skeleton couple | bond together and becomes a ring structure.

Examples of this substituent include a halogen group, hydroxyl group, thiol group, nitro group, organooxy group, organothio group, organosylyl group, acyl group, ester group, thioester group, phosphate ester group, amide group, aryl group, alkyl group And alkenyl groups and alkynyl groups.

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

As an organooxy group which is a substituent, the structure represented by -O-R, such as an alkoxy group, an alkenyloxy group, an aryloxy group, can be shown. As this R, the alkyl group, alkenyl group, aryl group, etc. which were mentioned above can be illustrated. The substituent mentioned above may further substitute by such R. Specific examples of the alkyloxy group include a methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group and lauryloxy group Etc. can be mentioned.

As an organothio group which is a substituent, the structure represented by -S-R, such as an alkylthio group, an alkenylthio group, an arylthio group, can be shown. As this R, the alkyl group, alkenyl group, aryl group, etc. which were mentioned above can be illustrated. The substituent mentioned above may further substitute by such R. Specific examples of the alkylthio group include methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, heptylthio group, octylthio group, nonylthio group, decylthio group, and Uryl thio group etc. are mentioned.

As an organosilyl group which is a substituent, the structure represented by -Si- (R) ₃ can be shown. This R may be same or different and can illustrate an alkyl group, an aryl group, etc. which were mentioned above. The substituent mentioned above may further substitute by such R. Specific examples of the alkylsilyl group include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tributylsilyl group, tripentylsilyl group, trihexylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group and octyldimethyl Silyl group, decyldimethylsilyl group, and the like.

As an acyl group which is a substituent, the structure represented by -C (O) -R can be shown. As this R, the alkyl group, alkenyl group, aryl group, etc. which were mentioned above can be illustrated. The substituent mentioned above may further substitute by such R. Specific examples of the acyl group include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, benzoyl group and the like.

As ester group which is a substituent, the structure represented by -C (O) O-R or -OC (O) -R can be shown. As this R, the alkyl group, alkenyl group, aryl group, etc. which were mentioned above can be illustrated. The substituent mentioned above may further substitute by such R.

As a thioester group which is a substituent, the structure represented by -C (S) O-R or -OC (S) -R can be shown. As this R, the alkyl group, alkenyl group, aryl group, etc. which were mentioned above can be illustrated. The substituent mentioned above may further substitute by such R.

As a phosphate ester group which is a substituent, the structure represented by -OP (O)-(OR) ₂ can be shown. This R may be same or different and can illustrate an alkyl group, an aryl group, etc. which were mentioned above. The substituent mentioned above may further substitute by such R.

As an amide group which is a substituent, a structure represented by -C (O) NH ₂ , -C (O) NHR, -NHC (O) R, -C (O) N (R) ₂ , or -NRC (O) R Can be represented. This R may be same or different and can illustrate an alkyl group, an aryl group, etc. which were mentioned above. The substituent mentioned above may further substitute by such R.

As an aryl group which is a substituent, the thing similar to the aryl group mentioned above is mentioned. The other substituent mentioned above may further substitute by this aryl group.

As an alkyl group which is a substituent, the thing similar to the alkyl group mentioned above is mentioned. The other substituent mentioned above may further substitute by this alkyl group.

As an alkenyl group which is a substituent, the same thing as the alkenyl group mentioned above is mentioned. The other substituent mentioned above may further substitute by this alkenyl group.

As an alkynyl group which is a substituent, the thing similar to the alkynyl group mentioned above is mentioned. The other substituent mentioned above may further substitute by this alkynyl group.

Since the effect is acquired by a small addition amount by making molecular weight of sulfonic acid ester small, it is preferable that R <_2> is a C1-C4 alkyl group which may have a substituent, or a phenyl group in said Formula (2), More preferably, It is a C1-C4 alkyl group which may have a substituent, More preferably, it is a methyl group which may have a substituent.

As a substituent which may be substituted by R <_2> in said Formula (2), it is preferable that it is an electron withdrawing group from the reason that the stability of the anion produced | generated from sulfonic acid ester can be improved. As a specific example of an electron withdrawing group, a nitro group, a cyano group, a halogen atom, a hydroxyl group, an alkoxy group etc. are mentioned, More preferably, a halogen atom, More preferably, a fluorine atom is mentioned.

In addition, R ₃ in the formula (2) is preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group, because the effect is obtained at a small amount by adding the molecular weight of the sulfonic acid ester as described above. Preferably it is a C1-C4 alkyl group, More preferably, it is a methyl group.

As a preferable specific example of the sulfonic acid ester used for this invention, methyl trifluoromethanesulfonic acid, ethyl trifluoromethanesulfonic acid, methyl p-toluenesulfonic acid, methyl methanesulfonic acid, methanesulfonic acid 2,2,2- trifluoroethyl And methanesulfonic acid 2-methoxyethyl and propanesultone. Especially, methyl trifluoromethane sulfonate or ethyl trifluoromethane sulfonate is more preferable.

When content of the sulfonic acid ester in the liquid crystal aligning agent of this invention is too small, an effect will not be expressed, and even if too much, there is a possibility that it may adversely affect another characteristic, The polyimide precursor of a liquid crystal aligning agent, and / or its 0.01 mass part-30 mass parts are preferable with respect to 100 mass parts of polymers which consist of an imidation polymer of a polyimide precursor, More preferably, they are 0.1 mass part-10 mass parts, More preferably, they are 0.1 mass part-5 mass parts. .

<Production method of polyamic acid ester>

In the case where the polyimide precursor of the present invention is a polyamic acid ester, the polyamic acid ester is reacted with any of the tetracarboxylic acid derivatives represented by the following formulas (4) to (6) with the diamine compound represented by the formula (7). You can get it.

(30)

(In formula, X <_1> , Y <_1> , R <_1> , A <_1> and A <_2> are the same as the definition in said Formula (1), respectively.)

The polyimide precursor represented by the said Formula (1) can be synthesize | combined by the method of (1)-(3) shown below using the said monomer.

(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 used for the reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or γ-butyrolactone in terms of solubility of the polymer, and these may be used alone or in combination of two or more thereof. You may use it. 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 in order 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.

The solvent used for the said reaction has preferable N-methyl- 2-pyrrolidone or (gamma) -butyrolactone by the solubility of a monomer and a polymer, These may be used 1 type or in mixture of 2 or more types. 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. Moreover, in order to prevent the hydrolysis of tetracarboxylic-acid diester dichloride, it is preferable that the solvent used for the synthesis | combination of a polyamic acid ester is dehydrated as much as possible, and it is preferable to prevent mixing of external air in nitrogen atmosphere.

(3) When synthesized with tetracarboxylic acid diester and diamine

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

Specifically, tetracarboxylic acid diester and diamine 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, 30 minutes to 24 hours, preferably 3 It can synthesize | combine by making it react for 15 hours.

Examples of the condensing agent include triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3- dimethylaminopropyl) carbodiimide hydrochloride, N, N'-carbonyldiimidazole, dimethoxy- N, N ', N'-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) 1-yl) -N, N, N ', N'-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2-thioxo-3-benzoxazolyl) . It is preferable that the addition amount of a condensing agent is 2-3 times mole with respect to tetracarboxylic-acid diester.

As the base, tertiary amines such as pyridine and 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.

Since the high molecular weight polyamic acid ester is obtained among the synthesis | combining method of said three polyamic acid ester, the synthesis method of said (1) or said (2) is especially preferable.

The solution of the polyamic acid ester obtained as mentioned above can deposit a polymer by inject | pouring into a poor solvent, 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. Although the poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene, etc. are mentioned.

<Production method of polyamic acid>

When the polyimide precursor used for this invention is a polyamic acid, this polyamic acid can be obtained by reaction of the tetracarboxylic dianhydride represented by the said Formula (4), and the diamine compound represented by the said Formula (7).

Specifically, tetracarboxylic dianhydride and diamine are reacted in the presence of an organic solvent at −20 ° C. to 150 ° C., preferably at 0 ° C. to 50 ° C. for 30 minutes to 24 hours, preferably 1 to 12 hours. It can synthesize | combine by making it.

The organic solvent used for the reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or γ-butyrolactone in terms of solubility of the monomer and the polymer, and these are one kind or two or more kinds. You may mix and use these. The concentration of the polymer is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, from the viewpoint that the precipitation of the polymer does not occur easily and the high molecular weight is easily obtained.

The polyamic acid obtained as described above can be recovered by depositing a polymer by injecting the reaction solution into a poor solvent while stirring the reaction solution 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. Although the poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene, etc. are mentioned.

<Production method of polyimide>

The polyimide used for this invention can be manufactured by imidating the polyimide precursor which consists of the said polyamic acid ester and / or polyamic acid. When manufacturing a polyimide with polyamic acid ester, chemical imidation which adds a basic catalyst to the polyamic acid solution obtained by melt | dissolving the said polyamic acid ester solution or polyamic acid ester resin powder in an organic solvent is easy. Chemical imidation is preferable since the imidation reaction advances at a comparatively low temperature, and the molecular weight fall of a polymer does not occur easily in the process of imidation.

Chemical imidation can be performed by stirring the polyamic acid ester to make it imidate in basic catalyst presence in an organic solvent. As an organic solvent, the solvent used at the time of the polymerization reaction mentioned above can 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 the time of performing an imidation reaction is -20 degreeC-140 degreeC, Preferably it is 0 degreeC-100 degreeC, and reaction time can be implemented in 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 etc. remain | survived in the solution after imidation reaction, it is preferable to collect | recover the obtained imidation polymer by means of the below-mentioned means, to redissolve | dissolve in an organic solvent, and to make it the liquid crystal aligning agent of this invention.

When producing a polyimide from a polyamic acid, chemical imidation which adds a catalyst to the solution of the said polyamic acid obtained by reaction of a diamine component and tetracarboxylic dianhydride is easy. Chemical imidation is preferable since the imidation reaction advances at a comparatively low temperature, and the molecular weight fall of a polymer does not occur easily in the process of imidation.

Chemical imidation can be performed by stirring the polymer to make it imidate in presence of a basic catalyst and an acid anhydride in an organic solvent. As an organic solvent, the solvent used at the time of the polymerization reaction mentioned above can 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. Moreover, acetic anhydride, trimellitic anhydride, a pyromellitic dianhydride, etc. are mentioned as an acid anhydride, Especially, since acetic anhydride is used, since refinement | purification after completion | finish of reaction becomes easy, it is preferable.

The temperature at the time of performing an imidation reaction is -20 degreeC-140 degreeC, Preferably it is 0 degreeC-100 degreeC, and reaction time can be implemented in 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times, of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol times of the amic 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 mentioned above can deposit a polymer by inject | pouring into a poor solvent, 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.

Although the said poor solvent is not specifically limited, Methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, etc. are mentioned.

<Liquid Crystal Aligner>

The liquid crystal aligning agent of this invention is at least 1 sort (s) of polymer chosen from the group which consists of the polyimide precursor represented by said Formula (1), and the imidation polymer of this polyimide precursor, and sulfonic acid ester represented by said Formula (2). And organic solvents. As a polymer contained in the liquid crystal aligning agent of this invention, the polyimide precursor which consists of a polyamic acid ester and / or a polyamic acid is preferable at the point of the solubility with respect to an organic solvent. Moreover, two or more types may be sufficient as the polymer used for this invention.

The weight average molecular weight of the polymer contained in the liquid crystal aligning agent of this invention becomes like this. Preferably it is 5,000-300,000, More preferably, it is 10,000-200,000. In addition, the number average molecular weight is preferably 2,500 to 150,000, and more preferably 5,000 to 100,000. It is preferable that the liquid crystal aligning agent of this invention is a form of the solution which the said polymer and sulfonic acid ester melt | dissolved in the organic solvent.

Although content (concentration) of the polymer and sulfonic acid ester in the liquid crystal aligning agent of this invention can be changed suitably also according to the setting of the thickness of the polyimide film to form, in the point which forms a uniform and defect-free coating film, 0.5 mass% or more is preferable with respect to an organic solvent, 20 mass% or less is preferable at the point of storage stability of a solution, More preferably, it is 1-15 mass%. In this case, in the case of preparing a concentrated solution of the polymer in advance and using the concentrated solution as the liquid crystal aligning agent, it may be diluted. 10-30 mass% is preferable, and, as for the density | concentration of the rich solution of such a polymer component, 10-15 mass% is more preferable. Moreover, you may heat, when melt | dissolving the powder of a polymer component in an organic solvent and manufacturing a solution. 20 to 150 degreeC is preferable and 20 to 80 degreeC of heating temperature is especially preferable.

The said organic solvent which the liquid crystal aligning agent of this invention contains will not be specifically limited if a polymer and sulfonic acid ester dissolve uniformly. Specific examples thereof include N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone , N-methylcaprolactam, 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyl sulfoxide, dimethyl sulfone, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, 3-meth And oxy-N, N-dimethylpropanamide. These may be used alone or in combination of two or more. Moreover, if individual, even if it is a solvent which cannot melt | dissolve a polymer component uniformly, as long as it is a range in which a polymer does not precipitate, you may mix with said organic solvent.

The liquid crystal aligning agent of this invention may contain the solvent for improving the coating film uniformity at the time of apply | coating a liquid crystal aligning agent to a board | substrate other than the organic solvent for dissolving a polymer and sulfonic acid ester. As such a solvent, a solvent having a lower surface tension is generally used than the organic solvent. Specific examples thereof include ethyl cellosolve, butyl cellosolve, butyl cellosolve acetate, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, and 1-e. Methoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol- 1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, isoamyl lactate Ester etc. are mentioned. These solvents may be used in combination of two or more.

It is preferable that the liquid crystal aligning agent of this invention contains 2 or more types of organic solvents chosen from the group which consists of N-methyl- 2-pyrrolidone, (gamma) -butyrolactone, and butyl cellosolve, and N-methyl It is more preferable to contain 2-pyrrolidone and butyl cellosolve, and it is particularly preferable to contain N-methyl-2-pyrrolidone, γ-butyrolactone and butyl cellosolve.

Sulfonic acid ester is added to the concentrated solution or dilution solution of the said polymer, and it can stir at 0 degreeC-100 degreeC, Preferably it is 20 degreeC-50 degreeC, and can prepare a liquid crystal aligning agent. 1 hour-48 hours are preferable and, as for stirring time, 1 to 14 hours are more preferable.

The liquid crystal aligning agent of this invention may contain various additives, such as a silane coupling agent and a crosslinking agent. A silane coupling agent is added in order to improve the adhesiveness of the board | substrate with which a liquid crystal aligning agent is apply | coated, and the liquid crystal aligning film formed there.

<Liquid crystal aligning film>

The liquid crystal aligning film of this invention is a film | membrane obtained by apply | coating the said liquid crystal aligning agent to a board | substrate, and drying and baking. As a board | substrate which apply | coats the liquid crystal aligning agent of this invention, if it is a board | substrate with high transparency, it will not specifically limit, Plastic substrates, such as a glass substrate, a silicon nitride substrate, an acryl substrate, a polycarbonate substrate, etc. can be used, The ITO electrode for liquid crystal drive It is preferable to use a substrate on which the back is formed from the viewpoint of simplification of the process. In the reflective liquid crystal display element, only an opaque one such as a silicon wafer can be used as long as it is a substrate on one side, and in this case, a material that reflects light such as aluminum can also be used.

As a coating method of the liquid crystal aligning agent of this invention, a spin coat method, the printing method, the inkjet method, etc. are mentioned. The drying after apply | coating the liquid crystal aligning agent of this invention, and the baking process can select 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.

As a method of orientation-processing the obtained liquid crystal aligning film, the rubbing method, the photo-alignment processing method, etc. are mentioned.

As a specific example of the photo-alignment processing method, the radiation which deflected to the said coating film surface in the fixed direction is irradiated, and if necessary, further heat-processes at the temperature of 150-250 degreeC, and provides a liquid-crystal orientation capability. Can be mentioned. As the radiation, ultraviolet rays and visible rays having a wavelength of 100 nm to 800 nm can be used. Among these, the ultraviolet-ray which has a wavelength of 100 nm-400 nm is preferable, and what has a wavelength of 200 nm-400 nm is especially preferable. Moreover, in order to improve the liquid-crystal orientation, you may irradiate a radiation, heating a coating film substrate at 50-250 degreeC. 1-10,000 mJ / cm <2> is preferable and, as for the irradiation amount of the said radiation, 100-5,000 mJ / cm <2> is especially preferable. The liquid crystal aligning film manufactured as mentioned above can align a liquid crystal molecule stably in a fixed direction.

Example

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

Below, the symbol of the compound used by the present Example and the comparative example and the measuring method of each characteristic are as follows.

1,3DMCBDE-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 ： Formula (DAH-1)

(31)

(32)

[Viscosity]

In the synthesis example, the viscosity of the polyamic acid ester and the polyamic acid solution was 1.1 ml of sample volume, cone rotor TE-1 (1 ° 34 ', R24), using an E-type viscometer TVE-22H (manufactured by Toki Kogyo Co., Ltd.), It measured at the temperature of 25 degreeC.

[Molecular Weight]

In addition, the molecular weight of a polyamic acid ester is measured by GPC (room temperature gel permeation chromatography) apparatus, and it is also called a number average molecular weight (henceforth Mn) and a weight average molecular weight (henceforth Mw) as a polyethyleneglycol and polyethylene oxide conversion value. ) Was calculated.

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

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

Column temperature: 50 ° C

Eluent: N, N-dimethylformamide (as additive, lithium bromide-hydrate (LiBr.H2O) is 30 mmol / l, phosphoric acid and anhydrous crystals (o-phosphate) is 30 mmol / l, tetrahydrofuran (THF A) 10 ml / l)

Flow rate: 1.0 ml / min

Standard sample for calibration curve preparation: TSK standard polyethylene oxide (weight average molecular weight (Mw) about 900,000, 150,000, 100,000, 30,000) by Tosoh Corporation, and polyethylene glycol (peak top molecular weight (Mp) about 12,000, by Polymer Laboratories) 4,000, 1,000). The measurement measured separately 2 samples of the sample which mixed four types, 900,000, 100,000, 12,000, 1,000, and the sample which mixed three types, 150,000, 30,000, and 4,000, in order to avoid that a peak overlaps.

[Production of FFS Drive Liquid Crystal Cell]

On the glass substrate, an ITO electrode having a film thickness of 50 nm as an electrode on the first layer, a silicon nitride having a film thickness of 500 nm as an insulating film on the second layer, and a comb-shaped ITO electrode as an electrode on the third layer Fringe Field Switching (Fringe Field Switching: hereinafter referred to as FFS) having an electrode width of 3 mu m, an electrode spacing of 6 mu m, and an electrode height of 50 nm The liquid crystal aligning agent was apply | coated. After drying for 5 minutes on a 80 degreeC hotplate, baking was performed for 60 minutes by the 250 degreeC hot air circulation type oven, and the coating film of 100 nm of film thickness was formed. Irradiation of a polarizing ultraviolet-ray or rubbing process was performed to this coating film surface, and the board | substrate with a liquid crystal aligning film was obtained. Moreover, the coating film was similarly formed and the orientation process was performed also to the glass substrate which has the columnar spacer of 4 micrometers in height where an electrode is not formed as an opposing board | substrate.

The said two board | substrates are set as one set, the sealing compound is printed on a board | substrate, and the other one board | substrate is bonded so that the orientation direction which a liquid crystal aligning film surface may face may be 0 degree, and the sealing compound is hardened, An empty cell was prepared. Liquid crystal MLC-2041 (made by Merck) was injected into this empty cell by the pressure reduction injection method, the injection hole was sealed, and the FFS drive liquid crystal cell was obtained.

[Charge Relaxation Characteristics]

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

(Synthesis Example 1)

To a 100 ml four-necked flask with a stirring device and a nitrogen inlet tube, 5.89 g (30.0 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was added, and 64.08 g of NMP was added. It stirred, sending nitrogen. Next, 3.04 g (28.1 mmol) of p-phenylenediamine (henceforth p-PDA) is added, stirring a liquid in a reaction container, NMP is further added so that solid content concentration may be 10 mass%, It stirred at room temperature for 24 hours and obtained the solution of polyamic acid (PAA-1). The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 171 mPa * s. Moreover, the molecular weight of this 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 taken in a 100 ml four-necked flask with a stirring device and a nitrogen inlet tube, and NMP was 55.74g was added, and it stirred for dissolving sending nitrogen. 5.83 g (29.7 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride are added, stirring this diamine solution, Furthermore, NMP is added so that solid content concentration may be 15 mass%, and it is room temperature. It stirred for 24 hours and obtained the solution of polyamic acid (PAA-2). The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 264 mPa * s. Moreover, the molecular weight of this polyamic acid was Mn = 11630 and Mw = 30056.

(Synthesis Example 3)

To a 100 ml four-necked flask with a stirring device and a nitrogen inlet tube, 20.08 g (132 mmol) of 3,5-diaminobenzoic acid and 21.33 g (88.0 mmol) of DA-4 were taken, and NMP 268.48g was added, and it stirred, sending nitrogen and dissolved. 42.49 g (217 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydrides are added, stirring this diamine solution, Furthermore, NMP is added so that solid content concentration may be 20 mass%, and it is room temperature. It stirred for 24 hours and obtained the solution of polyamic acid (PAA-3). The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 2156 mPa * s. Moreover, the molecular weight of this 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 stirring device and a nitrogen inlet tube, and 8.99 g of NMP was added, followed by stirring while dissolving nitrogen to dissolve. I was. Next, 1.46 g (6.01 mmol) of DA-4 were taken, 15.75 g of GBL was added, and it stirred and sent dissolving nitrogen. 4.16g (21.0 mmol) of 1,2,3,4- butanetetracarboxylic dianhydrides were added, stirring this diamine solution, and it stirred under water cooling for 2 hours. Next, 11.18g of GBL was added and 1.96g (9.0 mmol) of pyromellitic dianhydride was added. Furthermore, GBL was added so that solid content concentration might be 20 mass%, and it stirred at room temperature for 24 hours. The viscosity in the temperature of 25 degreeC of the obtained polyamic-acid solution was 1904 mPa * s. Moreover, the molecular weight of this polyamic acid was Mn = 8509 and Mw = 16774.

Furthermore, 0.03g of 3-glycidoxy propylmethyl diethoxysilane was added to this solution, and it stirred at room temperature for 24 hours, and obtained the polyamic-acid solution (PAA-4).

(Synthesis Example 5)

To a 100 ml four-necked flask with a stirring device and a nitrogen inlet tube, 2.60 g (24.0 mmol) and 1.45 g (6.0 mmol) of DA-4 were taken, and NMP 53.69 g. It was added and dissolved while sending nitrogen. 6.41g (39.4 mmol) of pyromellitic dianhydrides are added stirring this diamine solution, Furthermore, NMP is added so that solid content concentration may be 15 mass%, and it stirred at room temperature for 24 hours, and polyamic acid (PAA-5) Solution was obtained. The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 208 mPa * s. Moreover, the molecular weight of this polyamic acid was Mn = 10671 and Mw = 22829.

(Synthesis Example 6)

To a 100 ml four-necked flask with a stirring device and a nitrogen inlet tube, 4.81 g (24.0 mmol) of 4,4'-diaminodiphenyl ether and 1.56 g (6.0 mmol) of DA-5 were taken. 61.85g of NMP (s) were added, and it stirred for dissolving sending nitrogen. 5.77 g (29.4 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride are added, stirring this diamine solution, NMP is further added so that solid content concentration may be 15 mass%, and it is room temperature. It stirred for 24 hours and obtained the solution of polyamic acid (PAA-6). The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 799 mPa * s. Moreover, the molecular weight of this polyamic acid was Mn = 12569 and Mw = 27653.

(Synthesis Example 7)

In a 100 ml four-necked flask with a stirring device 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 It was taken, and 51.67g of NMP was added, it stirred, sending nitrogen and dissolved. 5.83 g (29.7 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride are added, stirring this diamine solution, Furthermore, NMP is added so that solid content concentration may be 15 mass%, and it is room temperature. It stirred for 24 hours and obtained the solution of polyamic acid (PAA-7). The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 60 mPa * s. Moreover, the molecular weight of this polyamic acid was Mn = 5090 and Mw = 7824.

(Synthesis Example 8)

To a 100 ml four-necked flask with a stirring device and a nitrogen inlet tube, 0.65 g (6.0 mmol) of m-phenylenediamine and 1.57 g (4.0 mol) of DA-6 were added, and 35.29 g of NMP was added. The solution was dissolved by sending nitrogen. 2.14 g (9.8 mmol) of pyromellitic dianhydrides are added stirring this diamine solution, Furthermore, NMP is added so that solid content concentration may be 10 mass%, and it stirred at room temperature for 24 hours, and polyamic acid (PAA-8) Solution was obtained. The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 219 mPa * s. Moreover, the molecular weight of this polyamic acid was Mn = 15827 and Mw = 36626.

(Synthesis Example 9)

In a 100 ml four-necked flask with a stirring device and a nitrogen inlet tube, 0.31 g (2.0 mmol) of 3,5-diaminobenzoic acid and 0.81 of 1,4-bis (4-aminophenyl) piperazine g (3.0 mmol) was added, 33.70 g of NMP was added, and it stirred and sent dissolving nitrogen. 0.97g (5.0 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydrides are added stirring this diamine solution, Furthermore, NMP is added so that solid content concentration may be 10 mass%, and it is room temperature. It stirred for 24 hours and obtained the solution of polyamic acid (PAA-9). The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 375 mPa * s. Moreover, the molecular weight of this polyamic acid was Mn = 14398 and Mw = 35294.

(Synthesis Example 10)

A 300 ml four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, 1.51 g (14.0 mmol) of m-phenylenediamine and 0.84 g (3.5 mol) of DA-4 were added. 3.16 g (40.0 mmol) was added, and it stirred and dissolved. Next, 4.95g (16.7 mmol) of dimethyl 1, 3-bis (chlorocarbonyl) cyclobutane-2, 4- dicarboxylates were added, stirring this diamine solution, and it was made to react for 4 hours under water cooling. The obtained polyamic acid ester solution was thrown into 607 g of water while stirring, and the precipitate deposited was collected by filtration, and then washed once with 607 g of water, once with 607 g of ethanol, and three times with 125 g of ethanol. And polyamic acid ester resin powder was obtained by drying.

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 taken into a 100 ml Erlenmeyer flask, 24.79 g of NMP was added, and stirred at room temperature for 24 hours to dissolve to obtain a polyamic acid ester solution (PAE-1).

(Synthesis Example 11)

A 300 ml four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, 2.01 g (13.2 mmol) of 3,5-diaminobenzoic acid and 0.80 g (3.3 mol) of DA-4 were added, and NMP was 120.31 g and a base. As a pyridine, 2.99 g (37.9 mmol) was added, followed by stirring to dissolve it. Next, 4.69g (15.8 mmol) of dimethyl 1, 3-bis (chlorocarbonyl) cyclobutane-2, 4- dicarboxylate was added, stirring this diamine solution, and it was made to react under water cooling for 4 hours. The obtained polyamic acid ester solution was thrown into 633 g of water while stirring, and the precipitate deposited was collected by filtration, and then washed once with 633 g of water, once with 633 g of ethanol, and three times with 130 g of ethanol. And polyamic acid ester resin powder was obtained by drying.

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 taken into a 100 ml Erlenmeyer flask, 24.46 g of NMP was added, and stirred at room temperature for 24 hours to dissolve, thereby obtaining a polyamic acid ester solution (PAE-2).

(Synthesis Example 12)

A 300 ml four-necked flask with a stirring device was placed in a nitrogen atmosphere, and 2.01 g (18.6 mmol) of p-phenylenediamine and 1.12 g (4.6 mmol) of DA-4 were added thereto. 4.21 g (53.3 mmol) of pyridine was added as 164.36g of NMP and a base, and it stirred and dissolved. Next, 7.22g (22.2 mmol) was added 1,3DM-CBDE-Cl, stirring this diamine solution, and it was made to react for 4 hours under water cooling. The solution of the obtained polyamic acid ester was thrown into 865 g of water while stirring, and the precipitated white precipitate was collected by filtration, and then, once with 865 g of water, once with 865 g of ethanol, 3 with 180 g of ethanol. It wash | cleaned once and dried and the white polyamic acid ester resin powder was obtained. 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 taken into a 50 ml Erlenmeyer flask, 20.35 g of NMP was added, and stirred at room temperature for 24 hours to dissolve to obtain a polyamic acid ester solution (PAE-3).

(Synthesis Example 13)

To a 100 ml four-necked flask with a stirring device and a nitrogen inlet tube, 5.40 g (27.0 mmol) of 4,4'-diaminodiphenyl ether and 0.73 g (3.0 mmol) of DA-4 were taken. 65.23g of NMP (s) were added, and it stirred for dissolving sending nitrogen. While stirring this diamine solution, 6.66g (29.7 mmol) of 1, 3- dimethyl- 1,2,3, 4- cyclobutane tetracarboxylic dianhydrides are added, and NMP so that solid content concentration may be 15 mass% further. Was added and stirred at room temperature for 24 hours to obtain a polyamic acid solution. The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 233 mPa * s.

Next, 25.52g of said polyamic-acid solutions were taken to the 100 mL eggplant flask, 37.53g of NMP (s) were added, and solid content concentration was 6 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 ° C for 3 hours. The obtained reaction solution was thrown into 306 g of methanol with stirring, and the precipitated white precipitate was collected by filtration, then washed twice with 306 g of ethanol, three times with 100 g of ethanol and dried to obtain a white polyimide resin. A powder was obtained. The imidation ratio of this polyimide resin was 98%. Moreover, the molecular weight of this polyimide resin was Mn = 10539 and Mw = 21428.

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

(Synthesis Example 14)

In a 100 mL four-necked flask with a stirring device and a nitrogen introduction tube, 2.09 g (13.7 mmol) of 3,5-diaminobenzoic acid, 1.51 g (6.2 mmol) of DA-4, DA-7 1.90 g (5.0 mmol) and 41.22g of NMP were added, and it stirred at 40 degreeC and dissolved. Next, while stirring this diamine solution, 4.79g (24.4 mmol) is added to 1,2,3,4-cyclobutane tetracarboxylic dianhydride, it is made to react at 40 degreeC for 24 hours, and a polyamic-acid solution (PAA -10) was obtained. The molecular weight of this polyamic acid was Mn = 15400 and Mw = 52600.

(Synthesis Example 15)

In a 100 ml four-necked flask with a stirring device and a nitrogen introduction tube, 1.07 g (7.0 mmol) of 3,5-diaminobenzoic acid, 1.70 g (7.0 mmol) of DA-4, DA-8 2.61g (6.0 mmol) and 27.37g of NMP were added, and it stirred at 80 degreeC and dissolved. While stirring this diamine solution, 3.75g (15.0 mmol) of bicyclo [3.3.0] octane-2,4,6,8- tetracarboxylic dianhydride was added, and it was made to react at 80 degreeC for 5 hours. After 5 hours, 0.95 g (4.8 mmol) and 12.93 g of NMP were added to 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and it reacted at 40 degreeC for 6 hours, and the polyamic-acid solution was obtained. .

After adding NMP to 20.0 g of this polyamic-acid solution, and diluting to 6 mass%, 4.04 g of acetic anhydride and 1.25 g of pyridine were added as an imidation catalyst, and it was made to react at 100 degreeC for 3 hours. The reaction solution was poured into 330 g of methanol with stirring, and the precipitate deposited was collected by filtration, washed twice with 150 g of methanol, and dried to obtain a polyimide resin powder. The imidation ratio 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 taken into a 100 mL Erlenmeyer flask, 33.60 g of NMP was added, and stirred at room temperature for 24 hours to dissolve to obtain a polyimide solution (SPI-2).

(Synthesis Example 16)

In a 100 ml four-necked flask with a stirring device and a nitrogen inlet tube, 4,4'-diaminodiphenyl-N-methylamine was added to 0.43 (2.0 mmol) and 1,3-bis (4-amino 2.07g (8.0mol) of phenoxy) propanes were taken, 37.68g of NMP (s) were added, and it stirred, sending nitrogen, and dissolved. While stirring this diamine solution, 2.05 g (9.4 mmol) of pyromellitic dianhydrides are added, NMP is further added so that solid content concentration may be 10 mass%, and it stirred at room temperature for 24 hours, and polyamic acid (PAA-11) Solution was obtained. The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 214 mPa * s. Moreover, the molecular weight of this polyamic acid was Mn = 17227 and Mw = 44964.

(Synthesis Example 17)

A 300 ml four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, 2.81 g (26.0 mmol) of p-phenylenediamine and 1.10 g (2.89 mmol) of DA-1 were added, and 51.99 g of NMP was added to GBL. 5.16 g (65.18 mmol) of pyridine was added as 155.97g and a base, and it stirred and dissolved. Next, 8.83g (27.2 mmol) of dimethyl 1, 3-bis (chlorocarbonyl) cyclobutane-2, 4- dicarboxylates were added, stirring this diamine solution, and it was made to react under water cooling for 4 hours. After 4 hours, 0.75 g (8.3 mmol) of acryloyl chloride was added and reacted for 30 minutes under water cooling. The obtained polyamic acid ester solution was thrown into 905 g of 2-propanol while stirring, and the precipitate deposited was collected by filtration, washed 5 times with 448 g of 2-propanol, and dried to thereby dry the polyamic acid ester resin powder. Got it.

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 into a 100 ml Erlenmeyer flask, 91.06 g of GBL was added, and stirred at room temperature for 24 hours to dissolve to obtain a polyamic acid ester solution (PAE-4).

Synthesis Example 18

A 300 ml four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, 2.03 g (18.8 mmol) of p-PDA and 1.23 g (4.6 mmol) of DA-3 were added. 4.21 g (53.3 mmol) was added, and it stirred and dissolved. Next, 7.22g (22.2 mmol) of dimethyl 1, 3-bis (chlorocarbonyl) cyclobutane-2, 4- dicarboxylate was added, stirring this diamine solution, and it was made to react under water cooling for 4 hours. The solution of the obtained polyamic acid ester was poured into 885 g of water while stirring, and the precipitated white precipitate was collected by filtration, then, once with 885 g of water, once with 885 g of ethanol, and 220 g of ethanol. It washed three times and dried, and obtained 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 taken into a 100 ml Erlenmeyer flask, 65.35 g of GBL was added, and stirred at room temperature for 24 hours to dissolve to obtain a polyamic acid ester solution (PAE-5).

Synthesis Example 19

To a 1 L four-necked flask equipped with a stirring device and a nitrogen inlet tube, 19.47 g (180 mmol) of p-phenylenediamine and 4.47 g (18.8 mmol) of DA-2 were taken, and NMP 502.03 g. It was added and dissolved while sending nitrogen. 38.04 g (194 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydrides are added while stirring this diamine solution, NMP is further added so that solid content concentration may be 10 mass%, and it is room temperature. It stirred for 24 hours and obtained the solution of polyamic acid (PAA-12). The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 462 mPa * s. Moreover, 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 with a stirring apparatus and a nitrogen inlet tube, 18.82 g of NMP was added thereto, and stirred to dissolve while sending nitrogen. I was. Next, 3.88 g (16.0 mmol) of DA-4 were taken, and 18.81 g of GBL was added, and it stirred and sent dissolving nitrogen. 5.47g (27.6 mmol) was added for 1,2,3,4- butane tetracarboxylic dianhydride, stirring this diamine solution, and it stirred under water cooling for 2 hours. Next, 4.71g of GBL was added and 2.74g (12.2 mmol) of 1,2,4,5-cyclohexane tetracarboxylic dianhydride was added. Furthermore, GBL was added so that solid content concentration might be 25 mass%, and it stirred at room temperature for 24 hours. The viscosity in the temperature of 25 degreeC of the obtained polyamic-acid solution was 2142 mPa * s. Moreover, the molecular weight of this polyamic acid was Mn = 6509 and Mw = 11481.

Furthermore, 0.05g of 3-glycidoxy propylmethyl diethoxysilane was added to this solution, and it stirred at room temperature for 24 hours, and obtained the polyamic-acid solution (PAA-13).

(Synthesis Example 21)

A 300 ml four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, 4.00 g (37.0 mmol) of p-phenylenediamine and 1.56 g (4.11 mol) of DA-4 were added, NMP was 76.32 g and GBL was 228.03. 11.2 g (92.7 mmol) of 2,4,6-trimethylpyridine was added as g and base, and it stirred and dissolved. Next, 12.56 g (38.6 mmol) of dimethyl 1,3-bis (chlorocarbonyl) cyclobutane-2,4-dicarboxylate was added while stirring this diamine solution, and it 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, and the precipitate deposited was collected by filtration and then 661 g of ethanol. It washed with 5 times and dried, and obtained 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 taken into a 100 ml Erlenmeyer flask, 30.94 g of GBL was added, and stirred at room temperature for 24 hours to dissolve to obtain a polyamic acid ester solution (PAE-6).

(Synthesis Example 22)

A 300 ml four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, 3.09 g (28.6 mmol) of p-phenylenediamine and 1.21 g (3.18 mol) of DA-4 were added, NMP was 58.81 g and GBL was 176.42. 5.67 g (71.7 mmol) of pyridine was added as g and base, and it stirred and dissolved. Next, 9.72g (29.9 mmol) of dimethyl 1, 3-bis (chlorocarbonyl) cyclobutane-2, 4- dicarboxylate was added, stirring this diamine solution, and it was made to react under water cooling for 4 hours. The obtained polyamic acid ester solution was thrown into 1018 g of ethanol while stirring, the precipitate precipitate was collected by filtration, washed five times with 504 g of ethanol 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 taken in a 100 ml Erlenmeyer flask, 3.60 g of GBL was added, and stirred at room temperature for 24 hours to dissolve to obtain a polyamic acid ester solution (PAE-7).

(Example 1)

A stirrer was put into a 50 ml Erlenmeyer flask, 6.12g of polyamic-acid solutions (PAA-1) obtained by the synthesis example 1 were added, 0.0639g of methyl trifluoromethanesulfonic acid was added, and it stirred at room temperature for 4 hours. Next, 1.76 g of NMP and 1.96 g of BCS were added, and it stirred for 30 minutes with the magnetic stirrer, and obtained the liquid crystal aligning agent (A-1).

(Example 2)

The stirrer was put into a 50 mL Erlenmeyer flask, 6.23g of polyamic-acid solutions (PAA-2) obtained by the synthesis example 2 were added, 0.0770g of methyl trifluoromethanesulfonic acid was added, and it stirred at room temperature for 4 hours, and the polyamic-acid solution ( PAA-2S) was obtained. Next, 2.25 g of polyamic-acid solution (PAA-2S) was taken to another 50 mL Erlenmeyer flask containing a stirrer, 2.57 g of NMP and 1.23 g of BCS were added, followed by stirring for 30 minutes with a magnetic stirrer to align the liquid crystal. The agent (A-2) was obtained.

(Example 3)

The stirrer was put into a 50 ml Erlenmeyer flask, 4.53g of polyamic-acid solutions (PAA-3) obtained by the synthesis example 3 were taken, 0.1470g of methyl trifluoromethanesulfonic acid was added, and it stirred at room temperature for 4 hours, and the polyamic-acid solution ( PAA-3S) was obtained. Next, 1.64 g of polyamic-acid solutions (PAA-3S) were taken to another 50 mL Erlenmeyer flask containing a stirrer, 3.24 g of NMP and 1.23 g of BCS were added, followed by stirring for 30 minutes with a magnetic stirrer to align the liquid crystal. The agent (A-3) was obtained.

(Example 4)

The stirrer was put into a 50 ml Erlenmeyer flask, 4.82g of polyamic-acid solutions (PAA-4) obtained by the synthesis example 4 were added, 0.0754g of methyl trifluoromethanesulfonic acid was added, and it stirred at room temperature for 4 hours, and the polyamic-acid solution ( PAA-4S1) was obtained. Next, 2.61 g of polyamic-acid solutions (PAA-4S1) were taken to another 50 mL Erlenmeyer flask containing a stirrer, 2.21 g of NMP and 1.19 g of BCS were added, followed by stirring for 30 minutes with a magnetic stirrer to align the liquid crystal. The agent (A-4) was obtained.

(Example 5)

The stirrer was put into a 50 mL Erlenmeyer flask, 4.82g of polyamic-acid solutions (PAA-4) obtained by the synthesis example 4 were added, 0.0359g of methyl trifluoromethanesulfonic acid was added, it stirred at room temperature for 4 hours, and the polyamic-acid solution ( PAA-4S2) was obtained. Next, to another 50 ml Erlenmeyer flask containing a stirrer, 2.61 g of a polyamic acid solution (PAA-4S2) was taken, 2.22 g of NMP and 1.21 g of BCS were added, followed by stirring with a magnetic stirrer for 30 minutes to align the liquid crystal. The (A-5) was obtained.

(Example 6)

The stirrer was put into a 50 ml Erlenmeyer flask, 7.27g of polyamic-acid solutions (PAA-5) obtained by the synthesis example 5 were added, 0.0856g of methyl p-toluenesulfonic acid was added, it stirred at room temperature for 4 hours, and the polyamic-acid solution (PAA -5S) was obtained. Next, 2.61 g of polyamic-acid solutions (PAA-5S) were taken to another 50 mL Erlenmeyer flask containing a stirrer, 2.20 g of NMP and 1.23 g of BCS were added, followed by stirring with a magnetic stirrer for 30 minutes to align the liquid crystal. The (A-6) was obtained.

(Example 7)

The stirrer was put into a 50 ml Erlenmeyer flask, 6.88g of polyamic-acid solutions (PAA-6) obtained by the synthesis example 6 were added, 0.0553g of methyl methanesulfonates were added, it stirred at room temperature for 4 hours, and the polyamic-acid solution (PAA-6S ) Next, 2.46 g of polyamic-acid solutions (PAA-6S) were taken to another 50 mL Erlenmeyer flask containing a stirrer, 2.34 g of NMP and 1.24 g of BCS were added, followed by stirring for 30 minutes with a magnetic stirrer to align the liquid crystal. The (A-7) was obtained.

(Example 8)

The stirrer was put into a 50 ml Erlenmeyer flask, 6.50g of polyamic-acid solutions (PAA-7) obtained by the synthesis example 7 were added, 0.0836g of methyl trifluoromethanesulfonic acid was added, it stirred at room temperature for 4 hours, and the polyamic-acid solution ( PAA-7S1) was obtained. Next, 2.33 g of polyamic-acid solutions (PAA-7S1) were taken into another 50 mL Erlenmeyer flask containing a stirrer, 2.55 g of NMP and 1.20 g of BCS were added, followed by stirring for 30 minutes with a magnetic stirrer to align the liquid crystal. The (A-8) was obtained.

(Example 9)

The stirrer was put into a 50 ml Erlenmeyer flask, 6.48g of polyamic-acid solutions (PAA-7) obtained by the synthesis example 7 were added, 0.0462g of methanesulfonic acid 2,2, 2- trifluoroethyls were added, and it stirred at room temperature for 4 hours. To obtain a polyamic acid solution (PAA-7S2). Next, 2.34 g of polyamic-acid solutions (PAA-7S2) were taken into another 50 mL Erlenmeyer flask containing a stirrer, 2.48 g of NMP and 1.24 g of BCS were added, followed by stirring with a magnetic stirrer for 30 minutes to align the liquid crystal. The (A-9) was obtained.

(Example 10)

A stirrer was put into a 50 mL Erlenmeyer flask, 10.52 g of polyamic acid solution (PAA-8) obtained in Synthesis Example 8 was taken, 0.2204 g of methanesulfonic acid 2-methoxyethyl was added, and the mixture was stirred at room temperature for 4 hours to give a polyamic acid solution. (PAA-8S) was obtained. Next, 3.77 g of polyamic-acid solution (PAA-8S) was taken to another 50 mL Erlenmeyer flask containing a stirrer, 1.07 g of NMP and 1.22 g of BCS were added, followed by stirring with a magnetic stirrer for 30 minutes to align the liquid crystal. The agent (A-10) was obtained.

(Example 11)

A stirrer was put into a 50 mL Erlenmeyer flask, 9.87g of polyamic acid solution (PAA-9) obtained in Synthesis Example 9 was added, 0.1875 g of methyl trifluoromethanesulfonate was added thereto, and stirred at room temperature for 4 hours to give a polyamic acid solution ( PAA-9S) was obtained. Next, 3.57 g of polyamic-acid solution (PAA-9S) was taken to another 50 mL Erlenmeyer flask containing a stirrer, 1.25 g of NMP and 1.22 g of BCS were added, followed by stirring for 30 minutes with a magnetic stirrer to align the liquid crystal. The agent (A-11) was obtained.

(Example 12)

A stirrer was put into a 50 mL Erlenmeyer flask, 10.01 g of the polyamic acid ester solution (PAE-1) obtained in Synthesis Example 10 was added, 0.0671 g of propanesultone was added, and the mixture was stirred at room temperature for 4 hours to give a polyamic acid ester solution (PAE- 1S) was obtained. Next, 3.63 g of polyamic acid ester solution (PAE-1S) was taken to another 50 ml Erlenmeyer flask containing a stirrer, 1.20 g of NMP and 1.21 g of BCS were added, followed by stirring for 30 minutes with a magnetic stirrer to give a liquid crystal. An aligning agent (A-12) was obtained.

(Example 13)

A stirrer was put into a 50 mL Erlenmeyer flask, 10.31 g of the polyamic acid ester solution (PAE-2) obtained in Synthesis Example 11 was added, 0.0813 g of methyl trifluoromethanesulfonic acid was added, and the mixture was stirred at room temperature for 4 hours to carry out a polyamic acid ester. A solution (PAE-2S) was obtained. Next, 3.62 g of polyamic acid ester solution (PAE-2S) was taken to another 50 mL Erlenmeyer flask containing a stirrer, 1.23 g of NMP and 1.21 g of BCS were added, followed by stirring for 30 minutes with a magnetic stirrer to give a liquid crystal. An aligning agent (A-13) was obtained.

(Example 14)

 A stirrer was put into a 50 mL Erlenmeyer flask, 10.32 g of the polyimide solution (SPI-1) obtained in Synthesis Example 13 was added, 0.0352 g of methyl trifluoromethanesulfonate was added, and the mixture was stirred at room temperature for 4 hours to give a polyimide solution ( SPI-1S). Next, 3.61 g of polyimide solutions (SPI-1S) were taken to another 50 mL Erlenmeyer flask containing a stirrer, 1.22 g of NMP and 1.20 g of BCS were added, followed by stirring for 30 minutes with a magnetic stirrer to align the liquid crystal. The agent (A-14) was obtained.

(Example 15)

The stirrer was put into a 50 ml Erlenmeyer flask, 5.28g of polyamic-acid solutions (PAA-10) obtained by the synthesis example 14 were added, 0.0813g of methyl trifluoromethanesulfonic acid was added, it stirred at room temperature for 4 hours, and the polyamic-acid solution ( PAA-10S) was obtained. Next, 1.85 g of polyamic-acid solutions (PAA-10S) were taken to another 50 mL Erlenmeyer flask containing a stirrer, 3.00 g of NMP and 1.21 g of BCS were added, followed by stirring for 30 minutes with a magnetic stirrer to align the liquid crystal. The (A-15) was obtained.

(Example 16)

A stirrer was put into a 50 mL Erlenmeyer flask, 3.74g of polyimide solutions (SPI-2) obtained in Synthesis Example 15 were added, 0.0539 g of methyl trifluoromethanesulfonate was added thereto, and stirred at room temperature for 4 hours to give a polyimide solution ( SPI-2S). Next, 0.32g of NMP and 4.05g of BCS were added, and it stirred for 30 minutes with the magnetic stirrer, and obtained the liquid crystal aligning agent (A-16).

(Example 17)

A stirrer was put into a 50 mL Erlenmeyer flask, 9.91g of polyamic acid ester solution (PAE-3) obtained in the synthesis example 12 was added, 0.0909g of methyl trifluoromethanesulfonic acid was added, and it stirred at room temperature for 4 hours, and polyamic acid ester A solution (PAE-3S) was obtained. Next, 3.60 g of polyamic acid ester solution (PAE-3S) was taken to another 50 mL Erlenmeyer flask containing a stirrer, 1.23 g of NMP and 1.22 g of BCS were added, and the mixture was stirred for 30 minutes with a magnetic stirrer to give a liquid crystal. An aligning agent (A-17) was obtained.

(Example 18)

A stirrer was put into a 50 ml Erlenmeyer flask, 10.10 g of the polyamic acid solution (PAA-11) obtained in the synthesis example 16 was taken, 0.0619 g of methyl trifluoromethanesulfonic acid was added, and it stirred at room temperature for 4 hours, and the polyamic acid solution ( PAA-11S) was obtained. Next, 3.69 g of polyamic-acid solutions (PAA-11S) were taken to another 50 mL Erlenmeyer flask containing a stirrer, 1.12 g of NMP and 1.22 g of BCS were added, followed by stirring with a magnetic stirrer for 30 minutes to align the liquid crystal. The agent (A-18) was obtained.

(Example 19)

In a 20 ml sample tube containing a stirrer, 2.24 g of polyamic acid solution (PAA-12) obtained in Synthesis Example 19, 2.48 g of polyamic acid solution (PAA-2S) obtained in Example 2, 3.33 g of NMP, and BCS 2.00g was added, and it stirred for 30 minutes with the magnetic stirrer, and obtained the liquid crystal aligning agent (A-19).

(Example 20)

In a 20 ml sample tube containing a stirrer, 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 GBL 3.27 g of BCS, 2.00 g of BCS, and further N-α- (9-fluorenylmethoxycarbonyl) -Nt-butoxycarbonyl-L-histidine (hereinafter abbreviated as Fmoc-His) as an imidation promoter 0.0844g was added, and it stirred for 30 minutes with the magnetic stirrer, and obtained the liquid crystal aligning agent (A-20).

(Example 21)

A stirrer was put into a 50 ml Erlenmeyer flask, 30.70 g of the polyamic acid solution (PAA-13) obtained in Synthesis Example 20 was taken, 0.9011 g of methyl trifluoromethanesulfonic acid was added, and the mixture was stirred at room temperature for 4 hours to give a polyamic acid solution ( PAA-13S) was obtained. Next, 2.02 g of polyamic-acid solutions (PAA-13S) were taken for another 50 mL Erlenmeyer flask containing a stirrer, 4.68 g of NMP and 1.66 g of BCS were added, and the mixture was stirred for 30 minutes with a magnetic stirrer to align the liquid crystal. The (A-21) was obtained.

(Example 22)

To a 20 ml sample tube containing a stirrer, 2.36 g of a polyamic acid solution (PAA-13S) obtained in 3.36 g of the polyamic acid ester solution (PAE-4) obtained in Synthesis Example 17, Example 21, 1.37 g of NMP, and GBL 0.122g of Fmoc-His was added as 4.22g and 2.81g and BCS as an imidation promoter, and it stirred for 30 minutes with the magnetic stirrer, and obtained the liquid crystal aligning agent (A-22).

(Example 30)

A stirrer was put into a 50 mL Erlenmeyer flask, 4.00g of polyamic acid ester solution (PAE-6) obtained in the synthesis example 21 was added, 0.019g of methyl trifluoromethanesulfonic acid was added, and it stirred at room temperature for 4 hours. Next, 2.461g of GBL, 1.61g of BCS, and 0.1478g of Fmoc-His were added, and it stirred for 30 minutes with the magnetic stirrer, and obtained the liquid crystal aligning agent (A-23).

(Example 31)

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

(Comparative Example 1)

4.66 g of 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 a stirrer, and stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal aligning agent (B -1) was obtained.

(Comparative Example 2)

2.46 g of 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 containing a stirrer, and stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal aligning agent (B -2) was obtained.

(Comparative Example 3)

3.67 g of 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 containing a stirrer, and stirred with a magnetic stirrer for 30 minutes to form a liquid crystal aligning agent (B -3) was obtained.

(Comparative Example 4)

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

(Comparative Example 5)

In a 20 ml sample tube containing a stirrer, 3.46 g of polyamic acid solution (PAA-12) obtained in Synthesis Example 19, 3.46 g of polyamic acid solution (PAA-2) obtained in Synthesis Example 2, 4.62 g of NMP, and BCS 2.81g was added, and it stirred for 30 minutes with the magnetic stirrer, and obtained the liquid crystal aligning agent (B-5).

(Comparative Example 6)

To a 20 ml sample tube containing a stirrer, 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 GBL 4.56g and 2.83g of BCS were added, and it stirred for 30 minutes with the magnetic stirrer, and obtained the liquid crystal aligning agent (B-6).

(Comparative Example 7)

In a 20 ml sample tube containing a stirrer, 3.37 g of the polyamic acid ester solution (PAE-4) obtained in Synthesis Example 17, 2.25 g of the polyamic acid solution (PAA-13) obtained in Synthesis Example 20, 1.39 g of NMP, and GBL 4.25g and 2.80g of BCS were added, and it stirred for 30 minutes with the magnetic stirrer, and obtained the liquid crystal aligning agent (B-7).

(Comparative Example 15)

A stirrer was put into a 50 ml Erlenmeyer flask, 4.00 g of the polyamic acid ester solution (PAE-7) obtained in the synthesis example 22 was taken, 2.41 g of GBL, 1.60 g of BCS, and 0.1416 g of Fmoc-His were added, and the magnetic stirrer was added. In addition, it stirred for 30 minutes and obtained the liquid crystal aligning agent (B-8).

(Example 23)

After filtering the liquid crystal aligning agent (A-1) obtained in Example 1 with a 1.0 micrometer filter, the ITO electrode of 50 nm of film thickness as a 1st layer was used as an insulating film as a 2nd layer on a glass substrate on a glass substrate. Spin coating is carried out on the glass substrate in which the FFS drive electrode in which nm nanometer silicon nitride has a comb-shaped ITO electrode (electrode width: 3 micrometers, electrode space | interval: 6 micrometers, electrode height: 50 nm) is formed as a 3rd layer. It was applied by application. After drying for 5 minutes on an 80 degreeC hotplate, baking was performed for 30 minutes by the 230 degreeC hot air circulation type oven, and the coating film with a film thickness of 100 nm was formed. 1000 mJ / cm <2> of 254 nm ultraviolet-rays were irradiated to this coating film surface through the polarizing plate, and the board | substrate with a liquid crystal aligning film was obtained. Moreover, the coating film was similarly formed and the orientation process was performed also to the glass substrate which has the columnar spacer of 4 micrometers in height where an electrode is not formed as an opposing board | substrate.

The said two board | substrates are set as one set, the sealing compound is printed on a board | substrate, and the other one board | substrate is bonded so that the orientation direction which a liquid crystal aligning film surface may face may be 0 degree, and the sealing compound is hardened, A blank cell was prepared. Liquid crystal MLC-2041 (made by Merck) was injected into this empty cell by the pressure reduction injection method, the injection hole was sealed, and the FFS drive liquid crystal cell was obtained.

When the charge relaxation characteristic was evaluated about this FFS drive liquid crystal cell, ΔT after 0 minutes, 5 minutes, 10 minutes, 20 minutes, and 60 minutes of AC drive was 34%, 0%, 0%, 0%, and 0%, respectively. .

(Example 24)

Using the liquid crystal aligning agent (A-7) obtained in Example 7, the rubbing process was performed on condition of roller rotation speed 700rpm, stage movement speed 10mm / s, and rubbing cloth indentation pressure 0.3mm instead of light irradiation. A FFS driving liquid crystal cell was produced in the same manner as in Example 23 except the above. When the charge relaxation characteristic was evaluated about this FFS drive liquid crystal cell, (DELTA) T after 0 minutes, 5 minutes, 10 minutes, 20 minutes, and 60 minutes of AC drive was 3%, 2%, 2%, 1%, and 0%, respectively. .

(Example 25)

Using the liquid crystal aligning agent (A-14) obtained in Example 14, the rubbing process was performed on condition of roller rotation speed 700 rpm, stage movement speed 10 mm / s, and rubbing cloth indentation pressure 0.3 mm instead of light irradiation. A FFS driving liquid crystal cell was produced in the same manner as in Example 23 except the above. When the charge relaxation characteristic was evaluated about this FFS drive liquid crystal cell, (DELTA) T after 0 minutes, 5 minutes, 10 minutes, 20 minutes, and 60 minutes of AC drive was 32%, 0%, 0%, 0%, and 0%, respectively. .

(Example 26)

Using the liquid crystal aligning agent (A-18) obtained in Example 18, the FFS drive liquid crystal cell was produced by the same method as Example 23 except having irradiated the polarized ultraviolet-ray of 100 mJ / cm <2>. When the charge relaxation characteristic was evaluated about this FFS drive liquid crystal cell, (DELTA) T after 0 minutes, 5 minutes, 10 minutes, 20 minutes, and 60 minutes of AC drive was 27%, 1%, 1%, 1%, and 0%, respectively. .

(Example 27)

Using the liquid crystal aligning agent (A-19) obtained in Example 19, the FFS drive liquid crystal cell was produced by the same method as Example 23 except having irradiated the polarized ultraviolet-ray of 750 mJ / cm <2>. When the charge relaxation characteristic was evaluated about this FFS drive liquid crystal cell, (DELTA) T after 0 minutes, 5 minutes, 10 minutes, 20 minutes, and 60 minutes of AC drive was 31%, 0%, 0%, 0%, and 0%, respectively. .

(Example 28)

Using the liquid crystal aligning agent (A-20) obtained in Example 20, the FFS drive liquid crystal cell was produced by the method similar to Example 23 except having irradiated the polarized ultraviolet-ray of 500 mJ / cm <2>. When the charge relaxation characteristic was evaluated about this FFS drive liquid crystal cell, (DELTA) T after 0 minutes, 5 minutes, 10 minutes, 20 minutes, and 60 minutes of AC drive was 29%, 0%, 0%, 0%, and 0%, respectively. .

(Example 29)

A FFS driving liquid crystal cell was produced in the same manner as in Example 23 except that the polarized ultraviolet ray of 500 mJ / cm 2 was irradiated using the liquid crystal aligning agent (A-22) obtained in Example 22. When the charge relaxation characteristic was evaluated about this FFS drive liquid crystal cell, (DELTA) T after 0 minutes, 5 minutes, 10 minutes, 20 minutes, and 60 minutes of AC drive was 36%, 0%, 0%, 0%, and 0%, respectively. .

(Example 32)

Using the liquid crystal aligning agent (A-23) obtained in Example 30, the FFS drive liquid crystal cell was produced by the same method as Example 23 except having irradiated the polarized ultraviolet-ray of 500 mJ / cm <2>. When the charge relaxation characteristic was evaluated about this FFS drive liquid crystal cell, (DELTA) T after 0 minutes, 5 minutes, 10 minutes, 20 minutes, and 60 minutes of AC drive was 30%, 0%, 0%, 0%, and 0%, respectively. .

(Example 33)

Using the liquid crystal aligning agent (A-24) obtained in Example 31, the FFS drive liquid crystal cell was produced by the same method as Example 23 except having irradiated the polarized ultraviolet-ray of 500 mJ / cm <2>. When the charge relaxation characteristic was evaluated about this FFS drive liquid crystal cell, (DELTA) T after 0 minutes, 5 minutes, 10 minutes, 20 minutes, and 60 minutes of AC drive was 29%, 0%, 0%, 0%, and 0%, respectively. .

(Comparative Example 8)

The FFS drive liquid crystal cell was produced by the method similar to Example 23 using the liquid crystal aligning agent (B-1) obtained in the comparative example 1. When the charge relaxation characteristic was evaluated about this FFS drive liquid crystal cell, (DELTA) T after 0 minutes, 5 minutes, 10 minutes, 20 minutes, and 60 minutes of AC drive was 36%, 9%, 4%, 2%, and 1%, respectively. .

(Comparative Example 9)

Using the liquid crystal aligning agent (B-2) obtained by the comparative example 2, instead of light irradiation, the rubbing process was performed on condition of roller rotation speed 700 rpm, stage movement speed 10 mm / s, and rubbing cloth indentation pressure of 0.3 mm. A FFS driving liquid crystal cell was produced in the same manner as in Example 23 except the above. When the charge relaxation characteristic was evaluated about this FFS drive liquid crystal cell, (DELTA) T after 0 minutes, 5 minutes, 10 minutes, 20 minutes, and 60 minutes of AC drive was 4%, 3%, 2%, 2%, and 1%, respectively. .

(Comparative Example 10)

Using the liquid crystal aligning agent (B-3) obtained by the comparative example 3, the rubbing process was performed on condition of roller rotation speed 700rpm, stage movement speed 10mm / s, and rubbing cloth indentation pressure 0.3mm instead of light irradiation. A FFS driving liquid crystal cell was produced in the same manner as in Example 23 except the above. When the charge relaxation characteristic was evaluated about this FFS drive liquid crystal cell, (DELTA) T after 0 minutes, 5 minutes, 10 minutes, 20 minutes, and 60 minutes of AC drive was 30%, 1%, 1%, 1%, and 0%, respectively. .

(Comparative Example 11)

Using the liquid crystal aligning agent (B-4) obtained in the comparative example 4, the FFS drive liquid crystal cell was produced by the method similar to Example 23 except having irradiated the polarized ultraviolet-ray of 100 mJ / cm <2>. When the charge relaxation characteristic was evaluated about this FFS drive liquid crystal cell, (DELTA) T after 0 minutes, 5 minutes, 10 minutes, 20 minutes, and 60 minutes of AC drive was 22%, 6%, 2%, 1%, and 0%, respectively. .

(Comparative Example 12)

Using the liquid crystal aligning agent (B-5) obtained in the comparative example 5, the FFS drive liquid crystal cell was produced by the method similar to Example 23 except having irradiated the polarized ultraviolet-ray of 750 mJ / cm <2>. When the charge relaxation characteristic was evaluated about this FFS drive liquid crystal cell, (DELTA) T after 0 minutes, 5 minutes, 10 minutes, 20 minutes, and 60 minutes of AC drive was 28%, 5%, 5%, 5%, and 4%, respectively. .

(Comparative Example 13)

Using the liquid crystal aligning agent (B-6) obtained in the comparative example 6, the FFS drive liquid crystal cell was produced by the method similar to Example 23 except having irradiated the polarized ultraviolet-ray of 500 mJ / cm <2>. When the charge relaxation characteristic was evaluated about this FFS drive liquid crystal cell, (DELTA) T after 0 minutes, 5 minutes, 10 minutes, 20 minutes, and 60 minutes of AC drive was 31%, 8%, 7%, 7%, and 4%, respectively. .

(Comparative Example 14)

Using the liquid crystal aligning agent (B-7) obtained in the comparative example 7, the FFS drive liquid crystal cell was produced by the same method as Example 23 except having irradiated the polarized ultraviolet-ray of 500 mJ / cm <2>. When the charge relaxation characteristic was evaluated about this FFS drive liquid crystal cell, (DELTA) T after 0 minutes, 5 minutes, 10 minutes, 20 minutes, and 60 minutes of AC drive was 38%, 3%, 3%, 3%, and 1%, respectively. .

(Comparative Example 16)

Using the liquid crystal aligning agent (B-8) obtained in the comparative example 15, the FFS drive liquid crystal cell was produced by the same method as Example 23 except having irradiated the polarized ultraviolet-ray of 500 mJ / cm <2>. When the charge relaxation characteristic was evaluated about this FFS drive liquid crystal cell, (DELTA) T after 0 minutes, 5 minutes, 10 minutes, 20 minutes, and 60 minutes of AC drive was 29%, 5%, 2%, 1%, and 0%, respectively. .

Industrial availability

The liquid crystal aligning film obtained from the liquid crystal aligning agent of this invention can speed up the relaxation rate of the residual electric charge in the liquid crystal display element accumulated by DC voltage. As a result, it is widely useful for a TN element, an STN element, a TFT liquid crystal element, and also a liquid crystal display element of a vertical alignment type.

In addition, all the content of JP Patent application 2011-078688, a claim, drawing, and the abstract for which it applied on March 31, 2011 is referred here, and it takes in as an indication of the specification of this invention.

Claims (10)

Contains at least 1 sort (s) of polymer chosen from the group which consists of a polyimide precursor which has a repeating unit represented by following formula (1), and the imidation polymer of this polyimide precursor, sulfonic acid ester represented by following formula (2), and an organic solvent. The liquid crystal aligning agent characterized by the above-mentioned.
[Chemical Formula 1]

(In formula (1), X <_1> is a tetravalent organic group, Y <_1> is a divalent organic group, R <_1> is a hydrogen atom or a C1-C5 alkyl group, A <_1> and A <_2> are respectively independently A hydrogen atom or a C1-C10 alkyl group, alkenyl group, or alkynyl group which may have a substituent.)
(32)
R ₂ -SO ₂ -OR ₃ (2)
(In Formula (2), R <_2> and R <_3> is a C1-C30 monovalent organic group which may respectively independently have a substituent, and R <_2> and R <_3> may combine with each other and form a ring structure.) The method of claim 1,
The liquid crystal aligning agent whose content of the said sulfonic acid ester is 0.01 mass part-30 mass parts with respect to 100 mass parts of said polymers. 3. The method according to claim 1 or 2,
The liquid crystal aligning agent whose R <_2> is the methyl group which may have a substituent. The method according to any one of claims 1 to 3,
Liquid crystal aligning agent whose R <_3> is a methyl group. 3. The method according to claim 1 or 2,
The said sulfonic acid ester is methyl trifluoromethane sulfonate or ethyl trifluoromethane sulfonate. 6. The method according to any one of claims 1 to 5,
The liquid crystal aligning agent whose weight average molecular weights of the said polymer are 5,000-300,000. 7. The method according to any one of claims 1 to 6,
The liquid crystal aligning agent whose content of the said polymer is 0.5 mass%-20 mass% with respect to an organic solvent. The liquid crystal aligning film obtained by apply | coating and baking the liquid crystal aligning agent in any one of Claims 1-7. The liquid crystal aligning film obtained by irradiating the polarized radiation to the film obtained by apply | coating and baking the liquid crystal aligning agent in any one of Claims 1-7. The liquid crystal display element provided with the liquid crystal aligning film of Claim 8 or 9.