KR20130109018A - Liquid crystal aligning agent containing thermally cleavable group-containing compound, and liquid crystal alignment film - Google Patents

Abstract

The mechanical strength of the obtained liquid crystal aligning film is large, while being excellent in the tolerance to a rubbing process, excellent in the point of liquid crystal orientation, especially electrical characteristics, such as voltage retention and ion density at the time of high temperature, and providing a high pretilt angle The liquid crystal aligning agent which can form the highly reliable liquid crystal aligning film to be provided is provided.
Protected by a polyimide precursor obtained by reacting a diamine compound with a tetracarboxylic acid derivative, and / or a polyimide obtained by imidating the polyimide precursor, and a heat leaving group substituted with hydrogen by heating at 80 to 300 ° C. It is characterized by containing the compound which has an amic acid or an amic acid ester structure which has an amino group.

Description

Liquid crystal aligning agent and liquid crystal aligning film containing a heat leaving group-containing compound TECHNICAL FIELD [LIQUID CRYSTAL ALIGNING AGENT CONTAINING THERMALLY CLEAVABLE GROUP-CONTAINING COMPOUND, AND LIQUID CRYSTAL ALIGNMENT FILM}

The present invention has a high mechanical strength, excellent resistance to rubbing treatment, excellent liquid crystal alignment properties, in particular, electrical properties such as voltage retention and ion density at high temperatures, and also provides high pretilt angles. The liquid crystal aligning agent which can form the highly reliable liquid crystal aligning film, the liquid crystal aligning film obtained from this liquid crystal aligning agent, and a liquid crystal display element.

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, as a main component, and bakes is mainly used, have.

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

In the polyimide-based liquid crystal aligning agent, various proposals have been made in order to meet the above requirements. For example, the soluble polyimide which used the specific diamine compound which has a liquid crystal aligning agent (refer patent document 1) containing a tertiary amine of a specific structure, a pyridine skeleton, etc. in addition to a polyamic acid or an imide group containing polyamic acid for a raw material. Liquid crystal aligning agent containing the (refer patent document 2), etc. are proposed.

Moreover, in addition to a polyamic acid, its imidation polymer, etc., the compound containing one carboxylic acid group in a molecule | numerator, the compound containing one carboxylic acid anhydride group in a molecule | numerator, and the compound containing one tertiary amino group in a molecule | numerator Polyamic acid obtained from a liquid crystal aligning agent (see Patent Literature 3) containing a very small amount of a compound selected from the above, a tetracarboxylic dianhydride having a specific structure and a tetracarboxylic dianhydride having a cyclobutane, and a specific diamine compound, or the like The liquid crystal aligning agent (refer patent document 4) containing a drawing polymer is known.

Moreover, it selects from the imidation polymer of the liquid crystal aligning agent (refer patent document 5), polyamic acid, and polyamic acid which contain an imide group containing monomer or an amic acid site containing monomer which have a specific structure with polyamic acid or polyimide. The liquid crystal aligning agent (refer patent document 6) containing the at least 1 sort (s) of polymer which becomes, and at least 1 sort (s) of compound chosen from an amic acid compound and an imide compound is proposed.

Japanese Patent Laid-Open No. 9-316200 Japanese Unexamined Patent Publication No. 10-104633 Japanese Patent Laid-Open No. 8-76128 Japanese Patent Application Laid-Open No. 9-138414 Japanese Patent Laid-Open No. 6-110061 Japanese Patent Laid-Open No. 9-269491

However, in recent years, a larger screen and a high-definition liquid crystal television have become main subjects, and the demand for liquid crystal display elements has become increasingly strict, so that the liquid crystal alignment film closely related to the characteristics of the liquid crystal display element can also be obtained. More excellent high reliability properties are required, better high properties are required, not only good initial properties but also high reliability for maintaining good properties even after long-term exposure at high temperatures.

The present invention has a high mechanical strength of the obtained liquid crystal alignment film, excellent resistance to rubbing treatment, and excellent liquid crystal alignment properties, in particular, electrical properties such as voltage retention and ion density at high temperature, and high. It aims at providing the liquid crystal aligning agent which can form the highly reliable liquid crystal aligning film which gives a pretilt angle.

MEANS TO SOLVE THE PROBLEM This inventor carried out earnest research in order to achieve the said objective, and, as a result, the polyimide precursor obtained by making the diamine compound and tetracarboxylic acid derivative which are components of the conventional liquid crystal aligning agent react, and / or its polyimide In addition to the polyimide which imidated the precursor, the compound which has the amino group protected by the heat leaving group substituted with hydrogen by heating, and has an amic acid or an amic acid ester structure (henceforth a heat leaving group containing compound) It discovered that the said objective can be achieved by the liquid crystal aligning agent which made it contain.

Compound which has an amino group protected by the heat leaving group substituted with hydrogen by the heating added in such a liquid crystal aligning agent, and has an amic acid or an amic acid ester structure (henceforth a heat leaving group containing compound) is this application Although it is a novel compound of non-patent literature before application, when such a heat leaving group-containing compound is added to a liquid crystal aligning agent, the mechanical strength of a film | membrane is large, it is excellent in resistance to a rubbing process, and liquid crystal aligning property, especially the voltage in high temperature It was found that a liquid crystal alignment film having high reliability, which is excellent in electrical characteristics such as retention rate and ion density, and which gives a high pretilt angle, can be formed.

Thus, the present invention has the following points.

1. Protected by a polyimide precursor obtained by reacting a diamine compound and a tetracarboxylic acid derivative, and / or a polyimide obtained by imidating the polyimide precursor and a heat leaving group substituted with hydrogen by heating at 80 to 300 ° C. The compound which has the amic acid or amic acid ester structure which has a given amino group is contained, The liquid crystal aligning agent characterized by the above-mentioned.

2. The said liquid crystal aligning agent of 1 whose said polyimide precursor has a repeating unit represented by following formula (7).

[Formula 1]

(Wherein X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, R ₆ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. A ₁ and A ₂ are each independently a hydrogen atom or a substituent; Alkyl group, alkenyl group or alkynyl group having 1 to 10 carbon atoms)

3. Amic acid or amic acid ester in which the said polyimide precursor and the said polyimide contain 0.5-15 mass% in liquid crystal aligning agent in those total amounts, and have the amino group protected by the heat-leaving group substituted by hydrogen by heating. The liquid crystal as described in said 1 or 2 in which the compound which has a structure contains 0.5-50 mol% with respect to the polyimide precursor which has a repeating unit represented by said Formula (7), and 1 unit of repeating units of the imidation polymer of this polyimide precursor. Aligning agent.

4. Liquid crystal aligning agent in any one of said 1-3 whose compound which has said amic acid or amic acid ester structure is compound represented by following formula (1).

(2)

(In formula, X is a tetravalent organic group, R <_1> is a hydrogen atom or a C1-C5 alkyl group, Z is a structure represented by following formula (2).)

(3)

(In formula, Z <_1> is a single bond or a C1-C30 divalent organic group. R <_2> and R <_3> respectively independently represents a hydrogen atom or a C1-C30 alkyl group and alkenyl group which may have a substituent. , an alkynyl group, an aryl group, or a combination thereof, and form a ring structure. R ₄ is an alkyl group having 1 to 30 carbon atoms which may have a hydrogen atom or a substituent. D ₁ is the thermal desorption group)

5. Liquid crystal aligning agent in any one of said 1-4 whose said heat leaving group is tert-butoxycarbonyl group or 9-fluorenyl methoxycarbonyl group.

6. Liquid crystal aligning agent in any one of said 1-5 which is any selected from group which X consists of structure represented by following formula.

[Formula 4]

7. The liquid crystal aligning film which carried out the orientation process of the film obtained by apply | coating and baking the liquid crystal aligning agent in any one of said 1-6.

8. Liquid crystal aligning film of said 7 whose said orientation process is rubbing process or irradiation process of polarized radiation.

9. Liquid crystal display element provided with liquid crystal aligning film of said 7 or 8.

10. The compound which has an amic acid or an amic acid ester structure represented by following formula (1).

[Chemical Formula 5]

(In formula, X is a tetravalent organic group, R <_1> is a hydrogen atom or a C1-C5 alkyl group, and Z is a structure represented by following formula (2).)

[Formula 6]

(In formula, Z <_1> is a single bond or a C1-C30 divalent organic group. R <_2> and R <_3> respectively independently represents a hydrogen atom or a C1-C30 alkyl group and alkenyl group which may have a substituent. , an alkynyl group, an aryl group, or a combination thereof, and form a ring structure. R ₄ is an alkyl group having 1 to 30 carbon atoms which may have a hydrogen atom or a substituent. D ₁ is the thermal desorption group)

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

[Formula 7]

(Wherein X, Z ₁ , R ₂ , R ₃ , R ₄ , and D ₁ are the same definitions as those of the formulas (1) and (2), and R ₅ is an alkyl group having 1 to 5 carbon atoms)

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

[Formula 8]

(Wherein X and R ₅ are the same as defined in the formulas (1) and (3))

13. The molar ratio of (tetracarboxylic dianhydride / monoamine) to tetracarboxylic dianhydride represented by following formula (6) and the monoamine compound represented by said formula (4) reacts with 1/2 to 1/3 The compound as described in said 10 obtained by making it.

[Chemical Formula 9]

(Wherein X is the same definition as that of formula (1) above)

14. The molar ratio of (tetracarboxylic dianhydride / monoamine) to tetracarboxylic dianhydride represented by said formula (6) and monoamine compound represented by said formula (4) reacts with 1/2 to 1/3 And the compound according to the above 10 obtained by further esterifying a carboxyl group with an esterifying agent.

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

[Formula 10]

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

According to this invention, while the mechanical strength of the liquid crystal aligning film obtained is large, it is excellent in the tolerance to a rubbing process, and is excellent in the point of liquid crystal orientation, especially electrical characteristics, such as voltage retention and ion density at the time of high temperature, The liquid crystal aligning agent which can form the highly reliable liquid crystal aligning film which gives a high pretilt angle is provided.

While the liquid crystal aligning agent of this invention can form the liquid crystal aligning film of the said outstanding characteristic, it is excellent also in the storage stability over the long term at the time of preserving before using a liquid crystal aligning agent.

Moreover, the compound which has an amino group protected by the heat leaving group contained in the liquid crystal aligning agent of this invention, and has an amic acid or an amic acid ester structure is a novel compound, Such a novel compound is also provided.

The mechanism of why the liquid crystal aligning agent of the present invention has such excellent characteristics is not necessarily clear, but is estimated as follows.

When the heat leaving group containing compound contained in the liquid crystal aligning agent of this invention apply | coats a liquid crystal aligning agent to a board | substrate surface, and bakes to form a liquid crystal aligning film, a heat leaving group is decomposed | disassembled at the temperature in the process of baking , Primary or secondary amines are highly reactive. This generated primary or secondary amine promotes the imidization reaction of the polymer of the polyimide precursor and / or polyimide, which is a main component contained in the liquid crystal aligning agent, induces a high imidization ratio and crosslinks between the polymers. It causes reaction and gives a big mechanical strength with respect to the liquid crystal aligning film obtained from a liquid crystal aligning agent. An increase in mechanical strength brings about an improvement in rubbing resistance and stability of liquid crystal properties at high temperatures.

In addition, since a heat-desorption group containing compound has the same amic acid or amic acid ester structure as the polymer of the polyimide precursor and / or polyimide which the skeletal structure which the main component contains in a liquid crystal aligning agent, this is a liquid crystal aligning agent. When added in the middle, rather than inhibiting liquid crystal alignment, the liquid crystal alignment is improved on the contrary, and as a result, liquid crystal properties such as voltage retention, ion density, and pretilt angle are improved.

In addition, since the heat leaving group has no decomposition | disassembly of the heat leaving group until the high temperature is loaded, the heat leaving group does not adversely affect the storage stability of the liquid crystal aligning agent containing this.

According to this invention, while the mechanical strength of the liquid crystal aligning film obtained is large, it is excellent in the tolerance to a rubbing process, and is excellent in the point of liquid crystal orientation, especially electrical characteristics, such as voltage retention and ion density at the time of high temperature, The liquid crystal aligning agent which can form the highly reliable liquid crystal aligning film which gives a high pretilt angle is provided.

<Thermal leaving group containing compound>

The heat leaving group containing compound added to a liquid crystal aligning agent in this invention is a compound which has the amino group protected by the heat leaving group, and has an amic acid or an amic acid ester structure, The compound has a temperature of 80-300 degreeC Preferably, the heat leaving group is decomposed and replaced with a hydrogen atom at 100 to 250 ° C, particularly preferably 150 to 230 ° C. Thereby, a liquid crystal aligning agent is apply | coated to the board | substrate of a liquid crystal display element, and a heat leaving group is detached at 150-300 degreeC which is the normal temperature at the time of baking, and is substituted by hydrogen.

The heat leaving group-containing compound used in the present invention is preferably represented by the following general formula (1).

[Formula 11]

In formula, X is a tetravalent organic group, R <_1> is a hydrogen atom or a C1-C5 alkyl group, and Z is a structure represented by following formula (2).

[Chemical Formula 12]

In formula, Z <_1> is a single bond or a C1-C30 divalent organic group, R <_2> and R <_3> respectively independently represents a hydrogen atom or a C1-C30 alkyl group, alkenyl group, An alkynyl group, an aryl group, or a combination thereof, may form a ring structure, R ₄ is a C 1-30 alkyl group which may have a hydrogen atom or a substituent, and D ₁ Is a protecting group of an amino group which is substituted with a hydrogen atom by heating.

In said Formula (1), R <_1> is a hydrogen atom or a C1-C5 alkyl group. In the case where R ₁ has a bulky structure, when used as a liquid crystal alignment film, since there is a possibility that the alignment of the liquid crystal may be inhibited, as R ₁ , a hydrogen atom, a methyl group, or an ethyl group is more preferable, and a hydrogen atom or a methyl group is particularly preferred. desirable.

In said Formula (1), X is a tetravalent organic group, The structure is not specifically limited. When the specific example of X is shown, X-1 to X-46 shown below are mentioned. Among them, X-1, X-2, X-3, X-4, X-5, X-6, X-8, X-16, X-19, X-21, X-25, X-26 , X-27, X-28 or X-32 are preferred.

[Chemical Formula 13]

In said Formula (2), R <_2> and R <_3> is a C1-C30 alkyl group, alkenyl group, alkynyl group, an aryl group, or a combination thereof which may each independently have a hydrogen atom or a substituent, and is ring structure You may form.

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 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 and the like. As the alkynyl group, there may be mentioned that the substitution of one or more CH ₂ -CH ₂ structures present in the alkyl group of the structure with C≡C, more specifically, ethynyl group, 1-propynyl group, 2-propynyl group Can be mentioned. As an aryl group, a phenyl group, (alpha)-naphthyl group, (beta) -naphthyl group, o-biphenylyl group, m-biphenylyl group, p-biphenylyl group, 1- antolyl group, 2-antholyl group, 9-anthol, for example And a aryl group, 1-phenantholyl group, 2-phenantholyl group, 3-phenantholyl group, 4-phenanthtolyl group, 9-phenanthtolyl group, and the like.

Said alkyl group, alkenyl group, alkynyl group, and aryl group may have a substituent as a whole as C1-C20, and may form ring structure by a substituent. 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 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, Alkenyl group and alkynyl group are mentioned.

As a halogen group which is a substituent, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.

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, propioxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, lauryloxy group and the like. 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 lauryl tea. Ogi 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 octyldimethylsilyl group And decyldimethylsilyl group.

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.

The substituent of the amide group, -C (O) NH _2, or -C (O) NHR, -NHC ( O) R, -C (O) N (R) represented by the structure _2, -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.

In said formula (2), R <_4> is a C1-C30 alkyl group which may have a hydrogen atom or a substituent. As a specific example of an alkyl group and a substituent, the thing similar to the alkyl group and substituent mentioned above is mentioned.

In the formula (2), Z ₁ is a single bond or a divalent organic group having 1 to 30 carbon atoms. When Z <_1> is a C1-C30 bivalent organic group, it is preferable that it is a divalent organic group represented by following formula (8).

[Formula 14]

(Formula (8) in, B ₁ and B ₂ are each respectively independently a single bond, or a divalent linking group is provided that at least either one of B ₁ and B ₂ is a divalent linking group. R ₈ and R ₉ independently Is an alkylene group having 1 to 20 carbon atoms, an alkenylene group, an alkynylene group, an arylene group, or a combination thereof) which may have a single bond or a substituent)

Represents a specific example of the B ₁ and B ₂ in the following, the invention is not limited to this.

[Formula 15]

In said B-5-B-8, B-10, B-11, R <^10> and R <^11> is a hydrogen atom or the alkyl group which may have a substituent, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof, and is a ring You may form a structure. Specific examples of the alkyl group, alkenyl group, alkynyl group, aryl group, and substituent include the same ones described above.

If R ¹⁰ and R ¹¹ are bulky structures such as an aromatic ring or alicyclic structure, when used as a liquid crystal aligning film, there is a possibility that the liquid crystal alignment property may be reduced, and alkyl groups such as methyl group, ethyl group, propyl group and butyl group, or A hydrogen atom is preferable and a hydrogen atom is more preferable.

In formula (8), when R <_8> and R <_9> is a C1-C20 alkylene group, an alkenylene group, an alkynylene group, an arylene group, or a combination thereof, although the specific example is given to the following, it is not limited to this. .

As said alkylene group, the structure remove | excluding one hydrogen atom from the alkyl group is mentioned. More specifically, methylene group, 1,1-ethylene group, 1,2-ethylene group, 1,2-propylene group, 1,3-propylene group, 1,4-butylene group, 1,2-butylene group, 1,2-pentylene group, 1,2-hexylene group, 1,2-nonylene group, 1,2-dodecylene group, 2,3-butylene group, 2,4-pentylene group, 1,2-cyclopropylene Group, 1,2-cyclobutylene group, 1,3-cyclobutylene group, 1,2-cyclopentylene group, 1,2-cyclohexylene group, 1,2-cyclononylene group, 1,2-cyclododecylene And the like can be mentioned. As an alkenylene group, the structure remove | excluding one hydrogen atom from an alkenyl group is mentioned. More specifically, 1,1-ethenylene group, 1,2-ethenylene group, 1,2-ethenylene methylene group, 1-methyl-1,2-ethenylene group, 1,2-ethenylene-1 , 1-ethylene group, 1,2-ethenylene-1,2-ethylene group, 1,2-ethenylene-1,2-propylene group, 1,2-ethenylene-1,3-propylene group, 1, 2-ethenylene-1,4-butylene group, 1,2-ethenylene-1,2-butylene group, 1,2-ethenylene-1,2-heptylene group, 1,2-ethenylene-1,2 -A decylene group, etc. are mentioned. As an alkynylene group, the structure remove | excluding one hydrogen atom from an alkynyl group is mentioned. More specifically, ethynylene group, ethynylene methylene group, ethynylene-1,1-ethylene group, ethynylene-1,2-ethylene group, ethynylene-1,2-propylene group, ethynylene-1,3 -Propylene group, ethynylene-1,4-butylene group, ethynylene-1,2-butylene group, ethynylene-1,2-heptylene group, ethynylene-1,2-decylene group, etc. are mentioned. As an arylene group, the structure remove | excluding one hydrogen atom from the aryl group is mentioned. More specifically, 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1,2-naphthylene group, 1,4-naphthylene group, 1,5-naphthylene group, 2,3-naphthylene group, 2,6-naphthylene group, 3-phenyl-1,2-phenylene group, 2,2'- diphenylene group, etc. are mentioned.

Said alkylene group, alkenylene group, alkynylene group, arylene group, and the group which combined these may have a substituent as long as carbon number is 1-20, and may form ring structure by a substituent. The formation of a ring structure by a substituent means that a substituent group or a substituent group and a part of the parent skeleton are bonded to form a ring structure.

As an example of this substituent, the same thing as the above-mentioned is mentioned.

R ₈ and R ₉ is, if the carbon number is less when used as a liquid crystal orientation film, since it liquid crystal orientation is favorable, and an alkynyl group having 1 to 5 carbon atoms alkylene group, a C 1 -C 5 alkenylene group, a group having 1 to 5 carbon atoms in the alkenylene Groups are preferred. Moreover, it is preferable that both or one of R <_8> and R <_9> is a single bond.

In Formula (2), as long as D <_1> is a protecting group of an amino group and it is a functional group substituted by a hydrogen atom by heating, the structure will not be specifically limited. From the viewpoint of the storage stability of the liquid crystal aligning agent of the present invention, it is preferable that this protecting group D ₁ is not detached at room temperature, preferably it is a protecting group which is deprotected at 80 ° C or higher heat, and more preferably at 100 ° C or higher. It is a protecting group which is deprotected from heat. Moreover, it is preferable that it is a protecting group deprotected by the heat of 300 degrees C or less from a viewpoint of the efficiency which promotes the thermal imidation of a polyamic acid ester, and a crosslinking reaction with a polyimide precursor or a polyimide, More preferably, it is 250 degrees C or less. It is a protecting group which is deprotected by the heat of, More preferably, it is a protecting group which is deprotected by the heat of 200 degrees C or less. As the structure of the D ₁ as described above, is preferably an ester represented by the following formula.

[Chemical Formula 16]

(In formula, R <_11> is a C1-C22 hydrocarbon.)

Specific examples of the ester group represented by the formula (9) include a methoxycarbonyl group, trifluoromethoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, tert-butoxycarbonyl group, sec-butoxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, 9-fluorenyl methoxycarbonyl group, etc. are mentioned. Among these, the structure in which a desorption reaction advances efficiently at 150 degreeC-300 degreeC which is the baking temperature at the time of obtaining a liquid crystal aligning film is preferable, a tert-butoxycarbonyl group or 9-fluorenyl methoxycarbonyl group is more preferable, and tert- Butoxycarbonyl groups are particularly preferred.

Although the structure of D-1-D-24 is mentioned as a preferable specific example of the structure shown by Formula (2) below, it is not limited to this.

[Chemical Formula 17]

[Chemical Formula 18]

Moreover, although the following structures are mentioned as a compound of this invention, it is not limited to this.

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 22]

(23)

&Lt; EMI ID =

(25)

(26)

(27)

(28)

[Formula 29]

(30)

[Synthesis method of the compound of the present invention]

The compound of this invention is a bischlorocarbonyl compound represented by following formula (3), the tetracarboxylic-acid derivative represented by following formula (5), or the tetracarboxylic dianhydride represented by following formula (6), and a following formula It can synthesize | combine by making it react by various methods using the monoamine compound represented by (4) as a raw material. Although the method of (i)-(iii) is mentioned specifically, it is not limited to this.

(31)

(Wherein R ₅ is an alkyl group having 1 to 5 carbon atoms, X, Z ₁ , R ₂ , R ₃ , R ₄ and D ₁ are the same as defined in formulas (1) and (2), respectively)

The bischlorocarbonyl compound of the said Formula (3) reacts the tetracarboxylic dianhydride of the said Formula (6) with the alcohol represented by R <_5> OH, for example, after making it the tetracarboxylic-acid dialkyl ester, It can obtain by converting a carboxyl group into a chlorocarbonyl group by an agent.

The tetracarboxylic-acid derivative of the said Formula (5) can be obtained by making the tetracarboxylic dianhydride of the said Formula (6), and the alcohol represented by R <_5> OH react, for example.

The monoamine compound of the said Formula (4) has the method of making the compound which has a primary or secondary amino group represented by a following formula, and di-tert- butyl bicarbonate react in presence of a base, or has a primary or secondary amino group Although it is obtained by the method of making a compound react with chloroformate-9-fluorenylmethyl in presence of a base, if it is a well-known method, it will not specifically limit.

(32)

The compound having a substituent obtained by the above method is added to a nitro compound, a monoamine compound, a diamine compound or a derivative thereof, and further, if necessary, reduction of the nitro group or introduction of an amino group can be carried out to provide a mono-desorption protecting group. An amine compound is obtained.

Although the method of following (i)-(iii) is mentioned as a synthesis | combining method of the compound of this invention, it is not limited to this.

(i) Synthesis from Bischlorocarbonyl Compound and Monoamine Compound

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

Specifically, the bischlorocarbonyl compound and the monoamine compound are in the presence of a base and an organic solvent at -20 ° C to 80 ° C, preferably 0 ° C to 50 ° C, for 30 minutes to 24 hours, preferably 1 to 4 hours. It can synthesize | combine by making time react.

As the base, pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used, but pyridine is preferable for the reaction to proceed mildly.

It is preferable that the addition amount of a base is 2-4 times mole with respect to a bischlorocarbonyl compound from the point which is easy quantity of removal.

(ii) Synthesis from Tetracarboxylic Acid Derivative and Monoamine Compound

The compound of this invention can be synthesize | combined by dehydrating and condensing the tetracarboxylic-acid derivative represented by the said Formula (5) and the monoamine compound represented by the said Formula (4).

Specifically, the tetracarboxylic acid derivative and the monoamine compound are mixed at 0 ° C. to 80 ° C., preferably 0 ° C. to 50 ° C., in the presence of a condensing agent, a base, and an organic solvent, for 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 the tetracarboxylic-acid derivative.

As the base, tertiary amines such as pyridine and triethylamine can be used. Since the addition amount of a base is the quantity which is easy to remove, 2-4 times mole is preferable with respect to a diamine component. 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. As for the addition amount of a Lewis acid, 0-1.0 times mole is preferable with respect to a monoamine compound.

(iii) Synthesis from tetracarboxylic dianhydride and monoamine compound

The compound of this invention can be synthesize | combined by making tetracarboxylic dianhydride represented by the said Formula (6), and the monoamine compound represented by the said Formula (4) react.

Specifically, tetracarboxylic dianhydride and a monoamine compound are present in the presence of an organic solvent at -20 ° C to 80 ° C, preferably at 0 ° C to 50 ° C, for 30 minutes to 24 hours, preferably for 1 to 12 hours. It can synthesize | combine by making it react. The solvent used for the above reaction is N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, in terms of solubility of tetracarboxylic dianhydride, monoamine compound, and product. N, N-dimethylacetamide, tetrahydrofuran, chloroform, etc. are mentioned, N-methyl-2-pyrrolidone, N, N- dimethylformamide, or tetrahydrofuran is preferable, These are 1 type or 2 You may mix and use types or more. 1-30 mass% is preferable, and, as for the density | concentration at the time of synthesis | combination, 5-20 mass% is more preferable.

Moreover, the compound of this invention whose R <_1> of said Formula (1) is a C1-C5 alkyl group adds various esterifying agents to the reaction solution of tetracarboxylic dianhydride and a monoamine compound, and esterifies a carboxyl group. It can synthesize | combine by implementing.

Specifically, the tetracarboxylic dianhydride, the monoamine compound, and the esterifying agent are -20 ° C to 80 ° C, preferably 0 ° C to 50 ° C, for 30 minutes to 24 hours, preferably in the presence of an organic solvent. It can synthesize | combine by making it react for 1 to 4 hours.

As an esterification agent, what can be easily removed by refinement | purification is preferable, and N, N- dimethylformamide dimethyl acetal, N, N- dimethylformamide diethyl acetal, N, N- dimethylformamide dipropyl acetal, N , N-dimethylformamidedienepentylbutylacetal, N, N-dimethylformamidedi-t-butylacetal, 1-methyl-3-p-tolyltriagen, 1-ethyl-3-p-tolyltriagen, 1-propyl-3-p-tolyltriazene, 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride, etc. are mentioned. As for the addition amount of an esterifying agent, 2-6 mol equivalent is preferable with respect to 1 mol of tetracarboxylic dianhydride.

The solvent used for reaction of said (i)-(iii) is N-methyl- 2-pyrrolidone, (gamma) -butyrolactone, and N, N- dimethylformamide from the viewpoint of the solubility of the monomer and the product used for synthesis | combination. , N, N-dimethylacetamide, tetrahydrofuran, chloroform, and the like, and N-methyl-2-pyrrolidone, N, N-dimethylformamide, or tetrahydrofuran are preferable, and these are one kind or You may mix and use 2 or more types. 1-30 mass% is preferable, and, as for the density | concentration at the time of synthesis | combination, 5-20 mass% is more preferable. In addition, when using a bischlorocarbonyl compound, in order to prevent the hydrolysis of a bischlorocarbonyl compound, it is preferable that the solvent used at the time of synthesis is dehydrated as much as possible, and mixing of outside air in nitrogen atmosphere is prevented. It is desirable to prevent.

The reaction solution obtained by the reaction of said (i)-(iii) can be used also as a composition of this invention as it is. In particular, in the case of obtaining the compound of the present invention, wherein R ₁ in formula (1) is a hydrogen atom, it is a reaction of an acid anhydride and an amine. do not include. Therefore, as for the compound of this invention as mentioned above, it is especially preferable to use a reaction solution as it is as a composition of this invention.

Moreover, the compound of this invention can be precipitated by inject | pouring into the poor solvent, stirring well the reaction solution obtained by the reaction of said (i)-(iii). Precipitation is carried out several times, followed by washing with a poor solvent, followed by normal temperature or heat drying to obtain a purified powder of the compound of the present invention. Although the poor solvent is not specifically limited, Water, methanol, ethanol, hexane, etc. are mentioned. When the purity of the obtained compound is low, when the film obtained from the composition is used for an electronic material, the electrical properties may be deteriorated, and therefore, it is preferable to purify by various methods. Examples of the purification method include silica gel column chromatography, recrystallization, washing with an organic solvent, and the like. Recrystallization is more preferable in view of ease of operation and high purification efficiency. As long as the organic solvent used for recrystallization is an organic solvent which can recrystallize the compound of this invention, you may recrystallize with two or more types of mixed solvents, without selecting the kind.

<Polyimide Precursor and Polyimide>

The polyimide precursor contained in the liquid crystal aligning agent of this invention is a polymer which has the site | part which enables the imidation reaction shown below by heating.

(33)

The polyimide precursor used for this invention has a structure represented by following formula (7).

(34)

In said formula, R <_6> is a hydrogen atom or a C1-C5, Preferably it is a 1-2 alkyl group. A ₁ and A ₂ are each independently a hydrogen atom or an alkyl group having 1 to 10, preferably 1 to 5, carbon atoms which may have 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. Said alkyl group may have a substituent and may form ring structure by a substituent. 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 halogen group, hydroxyl group, thiol group, nitro group, aryl group, organooxy group, organothio group, organosilyl group, acyl group, ester group, thioester group, phosphate ester group, amide group, alkyl group, Alkenyl group and alkynyl group are mentioned.

In a polyimide precursor, when a bulky structure is generally introduced, there is a possibility that the reactivity of the amino group and the liquid crystal alignment property may be lowered. As A ₁ and A ₂ , C 1 to C 1 which may have a hydrogen atom or a substituent may be used. The alkyl group of 5 is more preferable, and a hydrogen atom, a methyl group, or an ethyl group is especially preferable.

In the formula (7), X ₁ is a tetravalent organic group, and Y ₁ is a divalent organic group. Two or more types of X <_1> may be mixed in a polyimide precursor. When the specific example is shown, in the structure represented by Formula (2) which is a preferable compound of the above-mentioned heat leaving group, the same X-1 to X-46 as what was described as an example of X are mentioned.

In addition, in Formula (7), Y <_1> is a divalent organic group, It does not specifically limit, 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-97 in.

Especially, in order to acquire favorable liquid-crystal orientation, it is preferable to introduce diamine with a high linearity into a polyimide precursor or a polyimide, As Y <_1> , 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- The diamine of 46, Y-48, Y-61, Y-63, Y-64, Y-71, Y-72, Y-73, Y-74, Y-75, Y-98 is more preferable. In addition, when it is desired to increase the pretilt angle, it is preferable to introduce a diamine having a long chain alkyl group, an aromatic ring, an aliphatic ring, a steroid skeleton, or a combination thereof in the side chain to a polyimide precursor or a polyimide. As Y ₁ , Y-76, Y-77, Y-78, Y-79, Y-80, Y-81, Y-82, Y-83, Y-84, Y-85, Y-86, More preferred are diamines of Y-87, Y-88, Y-89, Y-90, Y-91, Y-92, Y-93, Y-94, Y-95, Y-96, or Y-97. . Arbitrary pretilt angles can be expressed by adding 1-50 mol% of these diamines.

(35)

(36)

[Formula 37]

(38)

[Chemical Formula 39]

[Formula 40]

(41)

(42)

(43)

(44)

[Chemical Formula 45]

(46)

[Formula 47]

&Lt; Process for producing polyimide precursor &gt;

In this invention, a polyamic acid ester and a polyamic acid are mentioned as a polyimide precursor. Among them, polyamic acid ester can be obtained by reaction of any of the tetracarboxylic acid derivatives represented by the following formulas (10) to (12) with the diamine compound represented by the formula (13).

(48)

(49)

(In formula, X <_1> , Y <_1> , R <_6> , A <_1> and A <_2> are respectively the same as the definition in said Formula (7).

The polyamic acid ester represented by said formula (1) can be synthesize | combined by the method (1)-(3) shown below using the said monomer.

(1) Synthesis from polyamic acid

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

(50)

Specifically, the polyamic acid and the esterifying agent can be synthesized by reacting 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 4 hours. have.

As an esterification agent, what can be easily removed by refinement | purification is preferable, and N, N- dimethylformamide dimethyl acetal, N, N- dimethylformamide diethyl acetal, N, N- dimethylformamide dipropyl acetal, N , N-dimethylformamidedienepentylbutylacetal, N, N-dimethylformamidedi-t-butylacetal, 1-methyl-3-p-tolyltriagen, 1-ethyl-3-p-tolyltriagen, 1-propyl-3-p-tolyltriazene, 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride, etc. are mentioned. 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 above 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. You may mix and use. 1-30 mass% is preferable, and, as for the density | concentration at the time of a synthesis | combination from a viewpoint that a precipitation of a polymer does not occur easily and a high molecular weight body is easy to obtain, 5-20 mass% is more preferable.

(2) When synthesize | combining by reaction of tetracarboxylic-acid diester dichloride and diamine A polyamic acid ester can be synthesize | combined from tetracarboxylic-acid diester dichloride and diamine.

(51)

Specifically, tetracarboxylic acid diester dichloride and diamine are present in the presence of a base and 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 4 hours. It can synthesize | combine by making time react.

As the base, pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used, but pyridine is preferable for the reaction to proceed mildly. It is preferable that the addition amount of a base is the quantity which is easy to remove, and is 2-4 times mole with respect to tetracarboxylic-acid diester dichloride from a viewpoint that a high molecular weight body is easy to obtain.

As for the solvent used for the said reaction, N-methyl- 2-pyrrolidone or (gamma) -butyrolactone is preferable at the solubility of a monomer and a polymer, These may be used 1 type or in mixture of 2 or more types. 1-30 mass% is preferable, and, as for the polymer concentration at the time of synthesis | combination from a viewpoint that a precipitation of a polymer does not occur easily and a high molecular weight body is easy to be obtained, 5-20 mass% is more preferable. 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 from tetracarboxylic acid diester and diamine

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

(52)

Specifically, tetracarboxylic acid diester and diamine are used in the presence of a condensing agent, a base, and an organic solvent at 0 ° C to 150 ° C, preferably 0 ° C to 100 ° C, for 30 minutes to 24 hours, preferably 3 to 15 hours. It can synthesize | combine by making time react.

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 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 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 described above can be precipitated by injecting it into a poor solvent while stirring well. Precipitation is carried out several times, followed by washing with a poor solvent, followed by normal temperature or heat drying to obtain a purified polyamic acid ester powder. Although the poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene, etc. are mentioned.

The weight average molecular weight of polyamic acid ester becomes like this. Preferably it is 5,000-300,000, More preferably, it is 10,000-200,000. The number average molecular weight is preferably 2,500 to 150,000, and more preferably 5,000 to 100,000.

On the other hand, when a polyimide precursor is a polyamic acid, a polyamic acid can be obtained by reaction of the tetracarboxylic dianhydride represented by following formula (12) and the diamine compound represented by Formula (13).

(53)

(In the formula, X₁, Y₁, A₁ and A ₂ is as defined in each of the 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 for 1 to 12 hours. Can be synthesized.

The organic solvent used for the above 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 or two. You may mix and use types or more. 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 hardly occurs 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. In addition, the precipitate can be subjected to several times, and after washing with a poor solvent, the powder of purified polyamic acid can be obtained by normal temperature or heat drying. Although the poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene, etc. are mentioned.

The weight average molecular weight of a polyamic acid becomes like this. Preferably it is 10,000-300,000, More preferably, it is 20,000-200,000. The number average molecular weight is preferably 2,500 to 15,000, and more preferably 5,000 to 100,000.

<Polyimide>

Thermal imidization or chemical imidation is generally preferred for the imidization reaction for dehydrating and closing the polyimide precursor, but chemical imidization in which the imidation reaction proceeds at a relatively low temperature is preferred because the molecular weight decrease of the resulting polyimide does not occur well.

Chemical imidation can be performed by stirring a polyimide precursor in presence of a basic catalyst and an acid anhydride in an organic solvent. The reaction temperature at this time is -20 ~ 250 ℃, preferably 0 ~ 180 ℃, the reaction time can be carried out for 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 polyimide precursor, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol times of the polyimide precursor. If the amount of the basic catalyst or the acid anhydride is small, the reaction does not proceed sufficiently. If the amount is too high, it is difficult to completely remove the reaction after completion of the reaction.

Pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. are mentioned as a basic catalyst used for imidation. Especially, pyridine is preferable because it has a basicity suitable for advancing reaction.

Moreover, as an acid anhydride, acetic anhydride, trimellitic anhydride, a pyromellitic anhydride, etc. are mentioned, Especially, when acetic anhydride is used, since refinement | purification after completion | finish of reaction becomes easy, it is preferable. As an organic solvent, the solvent used at the time of the polyamic-acid polymerization reaction mentioned above can be used. The imidation ratio by chemical imidation can be controlled by adjusting catalyst amount, reaction temperature, and reaction time.

In the polyimide solution thus obtained, since the added catalyst remains in the solution, in order to use the liquid crystal aligning agent of the present invention, the polyimide solution is added to the stirred poor solvent, and the polyimide is recovered by precipitation. It is preferable to use. Although it does not specifically limit as a poor solvent used for precipitation recovery of a polyimide, methanol, acetone, hexane, a butyl cellosol part, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, etc. can be illustrated. The polyimide precipitated by adding to the poor solvent can be collected by filtration, washing, and recovered, followed by normal temperature or heat drying under normal pressure or reduced pressure to obtain a powder. If this powder is further melt | dissolved in a good solvent, and the operation to reprecipitate is repeated 2-10 times, a polyimide can also be refine | purified. When impurities cannot be completely removed by one precipitation recovery operation, it is preferable to repeat this purification step. As the poor solvent at the time of carrying out the refining process, for example, alcohols, ketones, hydrocarbons or the like are mixed or sequentially used, so that the efficiency of purification is further improved.

The imidation ratio of the polyimide contained in the liquid crystal aligning agent of this invention is not specifically limited. What is necessary is just to set it to arbitrary values in consideration of the solubility of a polyimide. Although the molecular weight of the polyimide contained in the liquid crystal aligning agent of this invention is not specifically limited, When the molecular weight of a polyimide is too small, the intensity | strength of the coating film obtained may become inadequate, On the contrary, when the molecular weight of a polyimide is too large, it will manufacture The viscosity of a liquid crystal aligning agent may become high too much, and the workability at the time of coating film formation, and the uniformity of a coating film may worsen. Therefore, as for the weight average molecular weight of the polyimide used for the liquid crystal aligning agent of this invention, 2,000-500,000 are preferable, More preferably, it is 5,000-300,000.

<Liquid Crystal Aligner>

The liquid crystal aligning agent of this invention is a form of the solution which the said polyimide precursor and / or polyimide melt | dissolved in the organic solvent. As long as it has such a form, when synthesize | combining polyimide precursors, such as a polyamic acid ester and / or a polyamic acid, in an organic solvent, the reaction solution itself may be sufficient, and also dilute this reaction solution with an appropriate solvent. It may be one. In addition, when a polyimide precursor and / or polyimide is obtained as a powder, it may be made to melt | dissolve this in the organic solvent and set it as the solution.

Although content (concentration) of the polyimide precursor and / or polyimide (henceforth a polymer) 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, it is uniform In the point of forming a coating film without a defect, the polymer content is preferably 0.5% by mass or more with respect to the organic solvent, and preferably 15% by mass or less in terms of storage stability of the solution, and more preferably 1 to 10% by mass. to be.

In addition to a polymer, the above-mentioned heat leaving group containing compound is added to the liquid crystal aligning agent of this invention. The thermal leaving group-containing compound is preferably added in an amount of 0.5 to 50 mol% based on 1 unit of the repeating unit of the imidized polymer of the polyimide precursor and the polyimide precursor.

The content of the heat leaving group-containing compound is more preferably 1 to 30 mol%, particularly preferably 5 to 20 mol%. When the content is excessively small, the imidization reaction or crosslinking reaction of the polyimide precursor becomes insufficient, and when the content is excessively large, it is not preferable because it may adversely affect the liquid crystal alignment.

The said organic solvent contained in the liquid crystal aligning agent of this invention will not be specifically limited if a polymer melt | dissolves 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 uniformly, as long as it is a range in which a polymer does not precipitate, you may mix with said organic solvent.

In addition to the organic solvent for dissolving a polymer, 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. In general, a solvent having a lower surface tension than that of the organic solvent is used. 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.

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. Although the specific example of a silane coupling agent is given to the following, it is not limited to this.

3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3- Amine silane coupling agents such as phenylaminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, and 3-aminopropyldiethoxymethylsilane; Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, vinylmethyldimethoxysilane, vinyltriacetoxysilane, vinyltriisopropoxysilane, allyltrimethoxysilane, p Vinyl silane coupling agents such as -styryl trimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4 Epoxy silane coupling agents such as epoxycyclohexyl) ethyltrimethoxysilane; Methacrylic silane couplers, such as 3-methacryloxypropyl methyldimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropylmethyl diethoxysilane, and 3-methacryloxypropyl triethoxysilane Ring agent; Acrylic silane coupling agents, such as 3-acryloxypropyl trimethoxysilane; Ureido-based silane coupling agents such as 3-ureidopropyltriethoxysilane; Sulfide silane coupling agents such as bis (3- (triethoxysilyl) propyl) disulfide and bis (3- (triethoxysilyl) propyl) tetrasulfide; Mercapto-based silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-octanoylthio-1-propyltriethoxysilane; Isocyanate type silane coupling agents, such as 3-isocyanate propyl triethoxysilane and 3-isocyanate propyl trimethoxysilane; Aldehyde-based silane coupling agents such as triethoxysilylbutyl aldehyde; Carbamate type silane coupling agents, such as triethoxy silyl propyl methyl carbamate and (3-triethoxy silyl propyl) -t-butyl carbamate.

When the addition amount of the said silane coupling agent is too large, unreacted thing may adversely affect liquid crystal orientation, and when too small, the effect on adhesiveness does not appear, 0.01-5.0 weight% is preferable with respect to solid content of a polymer, 0.1-1.0 weight% is more preferable.

When adding the said silane coupling agent, in order to prevent precipitation of a polymer, it is preferable to add before adding the solvent for improving said coating film uniformity.

You may add the imidation promoter, in order to advance imidation of polyamic acid ester efficiently, when baking a coating film.

In the liquid crystal aligning agent of this invention, in addition to the above, if it is a range in which the effect of this invention is not impaired, the dielectric or electrically conductive substance for the purpose of changing electrical characteristics, such as a dielectric constant and electroconductivity of polymers other than a polymer and a liquid crystal aligning film, and a liquid crystal aligning film You may add a crosslinking | crosslinked compound etc. for the purpose of raising the hardness and the density of a film | membrane at the time of setting it as it.

After apply | coating and baking on a board | substrate, the liquid crystal aligning agent of this invention can be used as an orientation process by a rubbing process, light irradiation, etc., or a vertical alignment use etc. can be used as a liquid crystal aligning film without an orientation process. In this case, the substrate to be used is not particularly limited as long as it is a substrate having high transparency, and a glass substrate, a plastic substrate such as an acrylic substrate, a polycarbonate substrate, or the like can be used, and a substrate having an ITO electrode or the like for liquid crystal driving is used. It is preferable in view of the simplification of the process. In the reflective liquid crystal display element, only one substrate can be used as an opaque substance such as a silicon wafer, and as the electrode in this case, a material that reflects light such as aluminum can be used.

Although the coating method of a liquid crystal aligning agent is not specifically limited, Industrially, the method of performing by screen printing, offset printing, flexographic printing, an inkjet, etc. is common. Other coating methods include dips, roll coaters, slit coaters, spinners, and the like, which may be used depending on the purpose.

Baking of the board | substrate which apply | coated the liquid crystal aligning agent can be performed at the arbitrary temperature of temperature 100-350 degreeC, Preferably it is temperature 150-300 degreeC, More preferably, it is temperature 180-250 degreeC. Although the conversion rate to polyimide changes with the baking temperature, the polyimide precursor contained in a liquid crystal aligning agent does not necessarily need to imidize 100%. Therefore, although baking time can be set to arbitrary time, since a display defect may generate | occur | produce when the baking time is too short, it is preferably 5 to 60 minutes, More preferably, it is 10 to 40 minutes.

In this baking process, the thermally leaving group containing compound contained in the liquid crystal aligning agent of this invention decomposes a thermally leaving group, and produces | generates highly reactive primary or secondary amine. This generated primary or secondary amine promotes the imidization reaction of the polymer of the polyimide precursor and / or polyimide, which is a main component contained in the liquid crystal aligning agent, induces a high imidization ratio and crosslinks between the polymers. It causes reaction and gives a big mechanical strength with respect to the liquid crystal aligning film obtained from a liquid crystal aligning agent. An increase in mechanical strength brings about an improvement in rubbing resistance and stability of liquid crystal properties at high temperatures.

When the thickness of the coating film after baking is too thick, it becomes disadvantageous in terms of the power consumption of a liquid crystal display element, When too thin, the reliability of a liquid crystal display element may fall, Preferably it is 5-300 nm, More preferably, it is 10 -100 nm. When making a liquid crystal align horizontally or diagonally, the coating film after baking is processed by rubbing or polarized ultraviolet irradiation.

In the liquid crystal display element of the present invention, a substrate on which a liquid crystal alignment film is formed from the liquid crystal aligning agent of the present invention is obtained by the above-mentioned technique, and a liquid crystal cell is produced by a known method to form a liquid crystal display element.

If an example of liquid crystal cell manufacture is given, a pair of board | substrate with which the liquid crystal aligning film was formed is prepared, a spacer is spread | dispersed on the liquid crystal aligning film of a single side board | substrate, so that a liquid crystal aligning film surface may become inner side, and the other one board | substrate is bonded together ( And a method of injecting and sealing the liquid crystal under reduced pressure, or dropping the liquid crystal onto the liquid crystal alignment film surface on which the spacer is dispersed, and then bonding the substrate to perform sealing. The thickness of the spacer at this time becomes like this. Preferably it is 1-30 micrometers, More preferably, it is 2-10 micrometers.

Example

Although an Example is given to the following and this invention is demonstrated in more detail, this invention is not limited to these. 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

CBDE-Cl: Dimethyl 2,4-bis (chlorocarbonyl) cyclobutane-1,3-dicarboxylate

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

PMDA: pyromellitic dianhydride

NMP: N-methyl-2-pyrrolidone

GBL:? -Butyrolactone

BCS: butyl cellosolve

PAE: Polyamic Acid Ester

PAA: Polyamic Acid

[ ¹ H NMR]

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

Solvent: Deuterated dimethyl sulfoxide (DMSO-d ₆ ), Deuterated chloroform (CDCl ₃ )

Standard material: tetramethylsilane (TMS)

[Viscosity]

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

[Molecular Weight]

In addition, the molecular weight of a polyamic acid ester is measured by the 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 polyethylene glycol 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 (lithium bromide as an additive-hydrate (LiBr · H ₂ O) is 30 m㏖ / ℓ, phosphoric acid anhydrous crystal (o- phosphoric acid) is 30 m㏖ / ℓ, tetrahydrofuran ( THF) is 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, 4,000, by Polymer Laboratories 1,000). The measurement measured separately two 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.

[FT-IR measurement]

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

Measuring method: ATR method

[Rubber Resistance of Liquid Crystal Alignment Film]

The liquid crystal aligning agent was spin-coated on the glass substrate in which the transparent electrode was formed, it dried for 5 minutes on the hotplate of temperature 80 degreeC, and baked at the temperature of 230 degreeC for 20 minutes, and formed the imidized film of 100 nm in film thickness. After performing a rubbing process to this coating film, the surface state of the film | membrane was observed, and the presence or absence of rubbing damage, the presence of cutting debris, and the peeling of the film were evaluated.

[Liquid crystal alignment property]

The liquid crystal aligning agent was spin-coated on the glass substrate in which the transparent electrode was formed, the coating film of thickness 100nm is formed after drying for 5 minutes on a hotplate of 80 degreeC, and baking for 20 minutes in 230 degreeC hot air circulation type oven. I was. The rubbing process or the photo-alignment process was performed to this coating film surface, and the board | substrate with a liquid crystal aligning film was obtained. Two substrates having such a liquid crystal alignment film were prepared, and 6 μm spacers were scattered on the liquid crystal alignment film surface of one substrate, and the two substrates were combined so that the orientations were antiparallel, and the surroundings were sealed leaving a liquid crystal injection hole. , The empty cell having a cell gap of 6 μm was prepared. A liquid crystal (MLC-2041, manufactured by Merck Co., Ltd.) was vacuum-injected into the empty cell at room temperature, and the injection port was sealed to obtain a liquid crystal cell. Using this liquid crystal cell, the liquid crystal orientation was observed with the polarization microscope, and the liquid crystal orientation was evaluated on the following references | standards.

<Evaluation Criteria>

(Circle): No flow orientation is observed and there is no light leakage under cross nicol.

(Triangle | delta): A flow orientation is observed slightly and light leakage is observed under cross nicol.

X: Flow orientation is observed in the whole cell.

[Voltage retention rate]

The measurement of the voltage retention of the said liquid crystal cell was performed as follows.

The change from the initial value was calculated as the voltage retention by applying a voltage of 4 V for 60 Hz and measuring the voltage after 16.67 ms. At the time of a measurement, the temperature of the liquid crystal cell was 23 degreeC, 60 degreeC, and 90 degreeC, and it measured at each temperature.

[Ion density]

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

It measured using the 6254 type liquid crystal physical property evaluation apparatus manufactured by Toyo Technica. A triangular wave of 10 V and 0.01 Hz was applied, and the area corresponding to the ion density of the obtained waveform was calculated by the triangular approximation method to obtain an ion density. At the time of a measurement, the temperature of the liquid crystal cell was 23 degreeC and 60 degreeC, and it measured at each temperature.

[Measurement of Pretilt Angle]

The measurement of the pretilt angle of the said liquid crystal cell was measured using AxoScan by Axometrics.

(Synthesis Example 1)

The diamine compound (DA-1) was synthesize | combined by the four steps of path | route shown below.

First Step: Synthesis of Compound (A5)

[Formula 54]

Into a 500 mL eggplant flask were placed propargylamine (8.81 g, 160 mmol), N, N-dimethylformamide (112 mL) and potassium carbonate (18.5 g, 134 mmol) in that order, at 0 ° C. The solution obtained by dissolving t-butyl bromoacetic acid (21.9 g, 112 mmol) in N, N-dimethylformamide (80 mL) was added dropwise while stirring for about 1 hour. After completion of the dropwise addition, the reaction solution was stirred at room temperature for 20 hours. Thereafter, the solid was removed by filtration, 1 L of ethyl acetate was added to the filtrate, and washed four times with 300 ml of water and once with 300 ml of saturated saline. Thereafter, the organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. Finally, the remaining oily substance was distilled under reduced pressure at 0.6 Torr and 70 degreeC, and N-propargyl amino acetate t-butyl (compound (A5)) which was a colorless liquid was obtained. The yield was 12.0 g and the yield was 63%.

Second Step: Synthesis of Compound (A6)

(55)

N-propargylaminoacetic acid t-butyl (12.0 g, 70.9 mmol) and dichloromethane (600 ml) were put into a 1 L branched flask to make a solution. Dit-butyl dicarbonate (15.5 g) was stirred and cooled with ice. , 70.9 mmol) dissolved in dichloromethane (100 mL) was added dropwise for 1 hour. After completion of the dropwise addition, the reaction solution was stirred at room temperature for 20 hours. After the reaction was completed, the reaction solution was washed with 300 ml of saturated brine and dried over magnesium sulfate. Thereafter, the solvent was distilled off under reduced pressure to obtain N-propargyl-N-t-butoxycarbonylaminoacetate t-butyl (compound (A6)) as a pale yellow liquid. The yield was 18.0 g and the yield was 94%.

Third Step: Synthesis of Compound (A7)

(56)

In a 300 mL four-necked flask, 2-iodine-4-nitroaniline (22.5 g, 85.4 mmol), bis (triphenylphosphine) palladium dichloride (1.20 g, 1.71 mmol), copper iodide (0.651 g, 3.42 mmol) was added to the mixture, followed by nitrogen substitution. Then, diethylamine (43.7 g, 598 mmol) and N, N-dimethylformamide (128 ml) were added thereto, and the N-propargylamino-Nt was cooled with ice cooling. -Butoxycarbonyl acetate t-butyl (27.6 g, 102 mmol) was added, and it stirred at room temperature for 20 hours. After completion of the reaction, 1 L of ethyl acetate was added, washed three times with 150 ml of a 1 mol / L aqueous ammonium chloride solution and once with 150 ml of saturated brine, and dried over magnesium sulfate. Thereafter, the solvent was distilled off under reduced pressure to dissolve the precipitated solid in 200 ml of ethyl acetate, and recrystallization was performed by adding 1 L of hexane. The solid was collected by filtration and dried under reduced pressure to thereby yield 2- {3- (Nt-butoxycarbonyl-Nt-butoxycarbonylmethylamino) -1-propynyl)}-4-nitroaniline (compound) as a yellow solid. (A7)) was obtained. The yield was 23.0 g and the yield was 66%.

Fourth Step: Reduction of Compound (A7)

In a 500 mL four-necked flask, the 2- {3- (Nt-butoxycarbonyl-Nt-butoxycarbonylmethylamino) -1-propynyl)}-4-nitroaniline (22.0 g, 54.2 mmol) , And ethanol (200 g) were added, the inside of the system was replaced with nitrogen, then palladium carbon (2.20 g) was added, the inside of the system was replaced with hydrogen, and the mixture was stirred at 50 ° C. for 48 hours. After completion | finish of reaction, palladium carbon was removed by Celite filtration, activated carbon was added to the filtrate, and it stirred at 50 degreeC for 30 minutes. Thereafter, the activated carbon was filtered, the organic solvent was distilled off under reduced pressure, and the remaining oily substance was dried under reduced pressure to obtain a diamine compound (DA-1). The yield was 19.8 g and the yield was 96%.

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

(57)

(Synthesis Example 2)

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

a-1: synthesis of tetracarboxylic acid dialkyl ester

(58)

1,3-dimethylcyclobutane-1,2,3,4-tetracarboxylic dianhydride (compound of formula (5-1), below 1,3-) in a 3 L four-necked flask under nitrogen stream 220 g (0.981 mol) and 2200 g (6.87 mol, 10 wt times with respect to 1,3-DM-CBDA) of methanol (abbreviated as DM-CBDA) were injected and heated to reflux at 65 DEG C for 30 minutes. It became a homogeneous solution. The reaction solution was stirred under heating reflux for 4 hours 30 minutes. This reaction solution was measured by high performance liquid chromatography (hereinafter abbreviated as HPLC). The analysis of this measurement result is mentioned later.

The solvent was distilled off from this reaction liquid by the evaporator, 1301 g of ethyl acetate was added, it heated to 80 degreeC, and it refluxed for 30 minutes. Then, it cooled until internal temperature became 25 degreeC by the speed | rate of 2-3 degreeC in 10 minutes, and stirred at 25 degreeC as it is for 30 minutes. The precipitated white crystals were taken out by filtration, and the crystals were washed twice with 141 g of ethyl acetate, and then dried under reduced pressure to obtain 103.97 g of white crystals.

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

[Chemical Formula 59]

a-2: Synthesis of 1,3-DM-CBDE-C1

(60)

234.15 g (0.81 mol) of compound (1-1) and 1170.77 g (11.68 mol. 5 wt times) of n-heptane were injected into a 3-liter four-necked flask under nitrogen stream, and then 0.64 g (0.01 mol) of pyridine Was added and heated and stirred to 75 ° C under magnetic stirrer stirring. Then, 289.93 g (11.68 mol) of thionyl chlorides were dripped over 1 hour. Foaming started immediately after dripping, and 30 minutes after completion | finish of dripping, the reaction solution became uniform and foaming was stopped. Then, after stirring at 75 degreeC as it is for 1 hour and 30 minutes, the solvent was distilled off with the evaporator until the content became 924.42g in 40 degreeC of water bath. The insolubles were filtered by heating this to 60 degreeC, dissolving the crystal | crystallization which precipitated at the time of solvent distillation, and performing thermal filtration at 60 degreeC, and then filtering a filtrate to 25 degreeC for 10 minutes by 1 degreeC. Cooled at rate. After stirring at 25 degreeC for 30 minutes as it was, the precipitated white crystals were taken out by filtration and washed with 264.21 g of n-heptane. By drying under reduced pressure, 226.09 g of white crystals were obtained.

Subsequently, 226.09 g of the white crystals obtained above and 452.18 g of n-heptane obtained above were poured into a 3 L four-necked flask under nitrogen stream, and it heated and stirred at 60 degreeC, and dissolved the crystal | crystallization. Thereafter, the mixture was cooled and stirred at a rate of 1 ° C. for 10 minutes to 25 ° C. to precipitate crystals. After stirring at 25 degreeC as it is for 1 hour, the precipitated white crystal | crystallization was taken out by filtration, this crystal was wash | cleaned with 113.04g of n-hexane, and 203.91g of white crystal | crystallization was obtained by drying under reduced pressure. This crystal was analyzed by ¹ H NMR analysis to obtain Compound (3-1), that is, dimethyl-1,3-bis (chlorocarbonyl) -1,3-dimethylcyclobutane-2,4-dicarboxylate ( Hereinafter, it was confirmed that it is 1,3-DM-CBDE-C1) (HPLC relative area 99.5%) (yield 77.2%).

(Synthesis Example 3)

A 3-liter four-necked flask with a stirring device was placed in a nitrogen atmosphere, 10.9293 g (0.101 mol) of p-phenylenediamine and 10.8177 g (0.0285 mol) of diamine (DA-1) were added, and NMP 472 g, a base. As a pyridine, 23.12 g (0.292 mol) was added, followed by stirring to dissolve. Next, 39.6013 g (0.122 mol) of 1,3DM-CBDE-Cl was added, stirring this diamine solution, and it was made to react for 4 hours under water cooling. NMP2101g was added to the obtained solution of the polyamic acid ester, and it stirred for 30 minutes, and the polyamic acid ester solution which obtained 5 wt% of solid content concentration was obtained. The polyamic acid ester solution was added to 5247 g of water while stirring, and the precipitated white precipitate was collected by filtration, then, once with 5247 g of water, once with 5247 g of ethanol, and three times with 1312 g of ethanol. 45.90 g of white polyamic acid ester resin powders were obtained by washing and drying. The yield was 87.7%. Moreover, the molecular weight of this polyamic acid ester was Mn = 16,556 and Mw = 35,901.

35.99 g of the obtained polyamic acid ester resin powder was placed in a 300 ml Erlenmeyer flask, 230.85 g of GBL was added, and stirred at room temperature for 24 hours to dissolve to obtain a polyamic acid ester solution (PAE-1).

(Synthesis Example 4)

A 300 ml four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, 10.532 g (53.12 mmol) of 4,4'-diaminodiphenylmethane was added, 197.63 g of NMP and 9.00 g (113.8 m) of pyridine as a base. Mol), and stirred and dissolved. Next, 15.4194g (47.42 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 2196 g of water while stirring, and the precipitated white precipitate was collected by filtration and then, once with 2196 g of water, once with 2196 g of ethanol, and with 549 g of ethanol. 20.37 g of white polyamic acid ester resin powders were obtained by washing three times and drying. The yield was 92.8%. Moreover, the molecular weight of this polyamic acid ester was Mn = 11,659 and Mw = 25,571.

3.9648 g of the obtained polyamic acid ester resin powder was placed in a 100 ml Erlenmeyer flask, NMP 35.7135 g was added, and stirred at room temperature for 24 hours to dissolve to obtain a polyamic acid ester solution (PAE-2).

(Synthesis Example 5)

5.8936 g (30.05 mmol) of CBDA was put into a 100 mL four-necked flask with a stirring apparatus and a nitrogen inlet tube, and then 56.11 g of NMP was added, followed by stirring while sending nitrogen to form a slurry. . While stirring this slurry liquid, 3.0196g (27.92 mmol) of p-PDAs were added, NMP was further added so that solid content concentration might be 10 mass%, and it stirred at room temperature for 24 hours, and made of polyamic acid (PAA-1) A solution was obtained. The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 136.5 mPa * s. Moreover, the molecular weight of this polyamic acid was Mn = 13,391 and Mw = 32,745.

Example 1 Synthesis of Compound (1-a)

(61)

Below, compound (1-a) was synthesize | combined in the route of 4 steps.

First step: synthesis of the precursor (1-a1)

[Formula 62]

18.78 g (92.68 mmol) of 2- (4-nitrophenyl) ethylamine hydrochloride were put into a 300 mL four neck flask, and then 152 ml of toluene and 9.847 g (97.31 mmol) of triethylamine were added thereto. It stirred at C (ice bath). 21.24 g (97.31 mmol) of di-tert-butyl dicarbonate was dripped at the dripping funnel over the solution in a four neck flask over 30 minutes. After completion of dropwise addition, the mixture was stirred at room temperature (20 ° C) for 8 hours. After the reaction was completed, 500 ml of pure water was added to the reaction solution and extracted. The obtained organic layer was washed twice with pure water and dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was distilled off to obtain a white solid. 100 mL of hexane and 20 mL of ethyl acetate were added to this white solid, and recrystallization was performed. The precipitated solid was collected by suction filtration and dried under reduced pressure. ^It was confirmed that the white solid obtained from ¹ H NMR was the precursor (1-a1). The yield was 20.92 g and the yield was 85%.

Second Step: Synthesis of Precursor (1-a2)

(63)

20.90 g (78.49 mmol) of precursor (1-a1) was put into the 500 mL eggplant flask, and 200 mL of tetrahydrofuran was added. After nitrogen substitution of the reaction vessel, 2.09 g of palladium carbon was added to carry out nitrogen substitution. The reaction vessel was hydrogen substituted and stirred at 20 ° C. for 19 hours. After the reaction was completed, palladium carbon was removed by celite filtration, and the solvent was removed from the filtrate to obtain a white solid. The obtained solid was dissolved in 20 ml of acetate esters, 140 ml of hexane was added, and recrystallization was performed. The precipitated solid was collected by suction filtration and dried under reduced pressure. ^It was confirmed that the white solid obtained from ¹ H NMR was a precursor (1-a2). The yield was 16.54 g and the yield was 89%.

Third Step: Synthesis of Compound (1-a)

A 100 ml four-necked flask was placed in a nitrogen atmosphere, and 5.00 g (15.38 mmol) of 1,3DM-CBDE-Cl was added thereto, followed by 25 ml of tetrahydrofuran (dehydration) and 2.68 g (33.83 mmol) of pyridine. ) Was added and stirred to obtain an acid chloride solution. Next, 7.45 g (31.53 mmol) of precursor (1-a2) was put into the 100 mL Erlenmeyer flask, and 15 mL of tetrahydrofuran (dehydration) was then added, and it was set as the monoamine solution. This monoamine solution was moved to the dropping funnel, and the monoamine solution was dripped over 15 minutes in the four neck flask. After dripping, it stirred for 20 hours. After 20 hours, the reaction solution was poured into 200 ml of water, and 100 ml of chloroform was added for extraction. The obtained organic layer was washed twice with pure water and dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was distilled off to obtain a white solid. The obtained solid was dissolved in 30 ml of tetrahydrofuran, 100 ml of diisopropyl ether was added, and recrystallization was performed. The precipitated solid was collected by suction filtration and dried under reduced pressure. ^It was confirmed that the white solid obtained from ¹ H NMR was compound (1-a). The yield was 8.38 g and the yield was 75%.

Example 2 Synthesis of Compound (1-b)

&Lt; EMI ID =

Below, compound (1-b) was synthesize | combined by the route of 3 steps.

First step: synthesis of the precursor (1-b1)

(65)

A nitrogen-substituted 100 mL four-necked flask was charged with 8.95 g (44.30 mmol) of 4-bromonitrobenzene, 0.311 g (0.44 mmol) of bis (triphenylphosphine) palladium (II) dichloride, and 0.169 copper iodide. 5.38 g (53.16 mmol) was put in g (0.89 mmol) and triethylamine, 30 ml of tetrahydrofuran was added, and it stirred at room temperature (20 degreeC) for 10 minutes. Next, 8.25 g (53.16 mmol) of N- (tert-butoxycarbonyl) propargylamine was put into a 100 mL Erlenmeyer flask, and 15 mL of tetrahydrofuran was added and dissolved. This solution was transferred to the dropping funnel, and it was dripped at the solution in a four neck flask over 5 minutes. After dripping, it stirred at 60 degreeC for 3 hours. After 3 hours, the reaction solution was poured into 250 ml of pure water to precipitate a solid. After the precipitated solid was collected by suction filtration, the obtained solid was dissolved in 40 ml of toluene, and 25 ml of hexane was added and recrystallized. The precipitated solid was collected by suction filtration and dried under reduced pressure. ^It was confirmed that the brown solid obtained from ¹ H NMR was the precursor (1-b1). The yield was 7.66 g and the yield was 62.5%.

Second Step: Synthesis of Precursor (1-b2)

[Formula 66]

12.87 g (46.58 mmol) of precursors (1-b1) were placed in a 500 mL eggplant flask, and 130 mL of methanol was added thereto. After nitrogen substitution of the reaction vessel, 1.28 g of palladium carbon was added to carry out nitrogen substitution. The reaction vessel was hydrogen substituted and heated and stirred at 50 ° C. for 24 hours. After completion | finish of reaction, palladium carbon was removed by Celite filtration, the solvent was removed from the filtrate, and the brown candy compound was obtained. The obtained candy compound was purified by silica gel column chromatography (ethyl acetate: hexane = 50: 50) to obtain a brown candy compound. ^It was confirmed that the brown candy compound obtained from ¹ H NMR was a precursor (1-b2). The yield was 4.42 g and the yield was 37.9%.

Third Step: Synthesis of Compound (1-b)

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

Example 3 Synthesis of Compound (1-c)

(67)

Below, compound (1-c) was synthesize | combined in three steps of pathways.

First step: synthesis of the precursor (1-c1)

(68)

50.42 g (0.230 mol) of 3-bromopropylamine hydrobromide was added to a 2-liter four-neck flask, 672 g of dichloromethane and 56.28 g (0.258 mol) of di-tert-butyl dicarbonate were added thereto, and the temperature was 0 ° C (ice bath). Stirred at. 60.86 g (0.471 mol) of N, N- diisopropylethylamines were put into the dripping funnel, and it was dripped at the slurry solution in a four neck flask over 30 minutes. After the start of dropwise addition, the reaction solution foamed violently to precipitate a white solid. After completion of the dropwise addition, the mixture was stirred for 3 hours. After the reaction was completed, 500 ml of pure water was added to the reaction solution and extracted. The obtained organic layer was washed twice with pure water and dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was distilled off to obtain a colorless transparent oil. 500 mL of hexane was added to this oily substance, and it crystallized at -78 degreeC, and obtained white solid. The solid was collected by suction filtration and dried under reduced pressure. ^It was confirmed that the white solid obtained from ¹ H NMR was tert-butyl-3-bromopropylcarbamate, i.e., precursor (1-c1). The yield was 42.99 g and the yield was 78.5%.

Second Step: Synthesis of Precursor (1-c2)

[Formula 69]

40.00 g (0.168 mol) of precursors (1-c1) and 32.86 g (0.238 mol) of potassium carbonate were put into the 1 L four neck flask, 481g of DMF was added, and it stirred at 60 degreeC for 7 hours. After 7 hours, the obtained reaction solution was added to 3 L of pure water with stirring, and 1 L of acetate ester was added for extraction. The obtained organic layer was washed with pure water twice with 500 ml of an aqueous 1 M sodium hydroxide solution, and dried over anhydrous magnesium sulfate. After removing a desiccant, the solvent was distilled off and the yellow solid was obtained. The obtained solid was dissolved in 200 ml of acetate ester, and 1 liter of hexane was added while stirring to precipitate a solid. The obtained solid was collected by suction filtration and dried under reduced pressure. ^It was confirmed that the yellow solid obtained from ¹ H NMR was a precursor (1-c2). The yield was 35.49 g and the yield was 71.3%.

Third Step: Synthesis of Precursor (1-c3)

(70)

30.04 g (0.102 mol) of precursor (1-c2) was put into the 500 mL eggplant flask, and 170 g of ethanol was added. After nitrogen substitution of the reaction vessel, 3.11 g of palladium carbon was added to carry out nitrogen substitution. The reaction vessel was hydrogen substituted and stirred at 20 ° C. for 48 hours. After completion of the reaction, palladium carbon was removed by celite filtration, and the solvent was removed from the filtrate to obtain a solid. The obtained solid was melt | dissolved in 100 ml of acetate esters, 400 ml of hexane was added stirring, and white solid precipitated further by cooling to -50 degreeC. The precipitated solid was collected by suction filtration and dried under reduced pressure. ^It was confirmed that the yellow solid obtained from ¹ H NMR was a precursor (1-c3). The yield was 26.64 g and the yield was 97.7%.

Fourth Step: Synthesis of Compound (1-c)

A 300 ml four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, 12.26 g (46.0 mmol) of the precursor (1-c3) was added thereto, 241 g of NMP was added, and 5.31 g (67.1 mmol) of pyridine was added as a base. It was stirred and dissolved. Next, 7.43g (22.9 mol) of 1,3DM-CBDE-Cl was added, stirring this monoamine solution, and it was made to react for 4 hours under water cooling. The obtained reaction solution was poured into 1800 g of water while stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 1800 g of water, once with 1800 g of ethanol, and three times with 540 g of ethanol. To give a white solid. The obtained white solid was dissolved in ethyl acetate, and hexane was added to recrystallize. The precipitated solid was collected by suction filtration and dried under reduced pressure. ^It was confirmed that the yellow solid obtained from ¹ H NMR was the precursor (1-c). The yield was 15.23 g and the yield was 84.4%.

Example 4 Synthesis of Compound (1-d)

(71)

A 300 ml four-necked flask with a stirring device was placed in a nitrogen atmosphere, 1.87 g (6.63 mmol) of 2,5-bis (methoxycarbonyl) terephthalic acid and 1.10 g (13.9 mmol) of pyridine were added thereto, followed by dehydration. 40 ml of tetrahydrofuran was added, and it heated and refluxed. Thionyl chloride 1.54g (12.9 mmol) was added to this solution, and it heated and refluxed for 1 hour. After 1 hour, 3.13 g (19.56 mmol) of the precursor (1-a2) was added to the reaction solution, and the mixture was further heated to reflux for 2 hours. The obtained reaction solution was thrown into 500 g of water while stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 500 g of water, once with 500 g of methanol and three times with 240 g of methanol. Thus, a white solid was obtained. The obtained white solid was put into a 200 ml eggplant flask, and 100 ml of ethyl acetate was added and stirred by heating. The remaining solid was collected by suction filtration and dried under reduced pressure. ^It was confirmed that the white solid obtained from ¹ H NMR was compound (1-d). The yield was 1.97 g and the yield was 41.4%.

Example 5 Synthesis of Compound (1-j)

(72)

A 30 ml four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, 1.04 g (4.42 mmol) of the precursor (1-a2) was added, 20 g of NMP was added, and 0.58 g (7.43 mmol) of pyridine was added as a base. It was stirred and dissolved. Next, 0.658 g (2.22 mol) of CBDE-Cl was added, stirring this monoamine solution, and it was made to react under water cooling for 2 hours. The obtained reaction solution was poured into 200 g of water while stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 200 g of water, once with 200 g of ethanol, and three times with 100 g of ethanol. To give a white solid. The obtained white solid was put into a 50 ml eggplant flask, 30 ml of ethyl acetate was added, and it stirred for 30 minutes by heating at 80 degreeC. After 30 minutes, the remaining solid was collected by suction filtration and dried under reduced pressure. ^It was confirmed that the white solid obtained from ¹ H NMR was the precursor (1-j). The yield was 0.42 g and the yield was 27.3%.

Example 6 Synthesis of Compound (1-k)

(73)

A 30 ml four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, 1.06 g (3.99 mmol) of the precursor (1-c3) was added, 20 g of NMP was added, and 0.58 g (7.43 mmol) of pyridine as a base. It was stirred and dissolved. Next, 0.658 g (1.99 mol) of CBDE-Cl were added, stirring this monoamine solution, and it was made to react under water cooling for 2 hours. The obtained reaction solution was poured into 200 g of water while stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 200 g of water, once with 200 g of ethanol, and three times with 100 g of ethanol. Thus, a white solid was obtained. The obtained white solid was put into a 50 ml eggplant flask, 30 ml of ethyl acetate was added, and it stirred for 30 minutes by heating at 80 degreeC. After 30 minutes, the remaining solid was collected by suction filtration and dried under reduced pressure. ^It was confirmed that the white solid obtained from ¹ H NMR was a precursor (1-k). The yield was 0.58 g and the yield was 38.4%.

Example 7 Synthesis of Compound (1-i)

&Lt; EMI ID =

A 50 ml two-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, 0.62 g (2.20 mmol) of 2,5-bis (methoxycarbonyl) terephthalic acid and 0.38 g (4.80 mmol) of pyridine were added thereto, followed by dehydration. 20 ml of tetrahydrofuran was added and heated to reflux. 0.55 g (4.62 mmol) of thionyl chlorides were added to this solution, and the mixture was heated to reflux for 1 hour. After 1 hour, 1.23 g (4.62 mmol) of the precursor (1-c3) was added to the reaction solution, and the mixture was further heated to reflux for 2 hours. The obtained reaction solution was poured into 200 g of water while stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 100 g of water, once with 100 g of ethanol, and three times with 50 g of ethanol. To give a pale yellow solid. The obtained pale yellow solid was put into a 50 mL eggplant flask, 20 mL of ethyl acetate was added, and it stirred with heat. The remaining solid was collected by suction filtration and dried under reduced pressure. ^It was confirmed that the white solid obtained from ¹ H NMR was compound (1-i). The yield was 0.57 g and the yield was 33.1%.

Example 8 Preparation of Solution Containing Compound (1-e)

(75)

2.37 g (10.03 mmol) of precursors (1-a2) were placed in a 50 ml four-necked flask with a stirring apparatus and a nitrogen inlet tube, followed by adding 9.40 g of NMP, followed by stirring while sending nitrogen. And monoamine solution. While stirring this monoamine solution, 0.98g (5.00 mmol) added CBDA, NMP was further added so that solid content concentration might be 20 mass%, and it stirred at room temperature for 24 hours, and prepared the compound (1-e) containing solution. Got it.

A part of the obtained solution was added with 1-methyl-3-p-tolyltriazene and methyl esterification of carboxylic acid resulted in the same compound as (1-j) obtained in Example 5 from ¹ H NMR. It confirmed that it was obtained. From this, it was confirmed that (1-e) is contained in the said solution.

Example 9 Preparation of Solution Containing Compound (1-f)

[Formula 76]

2.37 g (10.03 mmol) of precursors (1-a2) were placed in a 50 ml four-necked flask with a stirring device and a nitrogen inlet tube, followed by adding 9.62 g of NMP, followed by stirring while sending nitrogen. And monoamine solution. While stirring this monoamine solution, 1.09g (5.00 mmol) PMDA was added, Furthermore, NMP was added so that solid content concentration might be 20 mass%, and it stirred at room temperature for 24 hours, and the compound (1-f) containing solution was added. Got it.

To a part of the obtained solution, methyl esterification of carboxylic acid by addition of 1-methyl-3-p-tolyltriagen showed the same compound as (1-d) obtained in Example 4 from ¹ H NMR. It confirmed that it was obtained. From this, it was confirmed that (1-f) is contained in the said solution.

Example 10 Preparation of Solution Containing Compound (1-g)

[Formula 77]

2.66 g (9.99 mmol) of precursors (1-c3) were placed in a 50 ml four-necked flask with a stirring device and a nitrogen inlet tube, followed by addition of 10.19 g of NMP, followed by stirring while sending nitrogen. And monoamine solution. While stirring this monoamine solution, 1.09 g (5.00 mmol) CBDA was added, Furthermore, NMP was added so that solid content concentration might be 20 mass%, and it stirred at room temperature for 24 hours, and the compound (1-g) containing solution was added. Got it.

When 1-methyl-3-p-tolyltriagen was added to a part of the obtained solution and methyl esterification of carboxylic acid was carried out, the same compound as (1-k) obtained in Example 6 from ¹ H NMR was obtained. It confirmed that it was obtained. From this, it was confirmed that (1-g) is contained in the said solution.

Example 11 Preparation of Solution containing Compound (1-h)

(78)

3.99 g (15.0 mmol) of precursor (1-c3) were put into a 50 ml four-necked flask with a stirring device and a nitrogen inlet tube, followed by addition of 16.91 g of NMP, followed by stirring while sending nitrogen. And monoamine solution. While stirring this monoamine solution, 1.64g (7.52 mmol) PMDA was added, Furthermore, NMP was added so that solid content concentration might be 20 mass%, and it stirred at room temperature for 24 hours, and prepared the compound (1-h) containing solution. Got it.

When 1-methyl-3-p-tolyltriagen was added to a part of the obtained solution and methyl esterification of carboxylic acid was carried out, the same compound as (1-i) obtained in Example 7 from ¹ H NMR was obtained. It confirmed that it was obtained. From this, it was confirmed that (1-h) is contained in the said solution.

(Example 12)

44.3382 g of polyamic acid ester solution (PAE-1) obtained in Synthesis Example 3 was placed in a 100 ml Erlenmeyer flask, then 19.6930 g of GBL and 16.0839 g of BCS were added to obtain a dilute solution of polyamic acid ester.

5.02 g of the solution was placed in a 20 ml sample tube containing a stirrer, and then 0.0645 g (0.1 mol equivalent to 1 mol of the repeating unit of the polyamic acid ester) was added to the compound (1-a) obtained in Example 1, followed by room temperature. It stirred for 30 minutes, and the compound (1-a) was dissolved completely, and the liquid crystal aligning agent (A1-1) was obtained.

(Example 13)

A liquid crystal aligning agent (A1) was prepared in the same manner as in Example 12 except for using the compound (1-c) obtained in Example 3 instead of the compound (1-a) with respect to 1 mol of the repeating unit of the polyamic acid ester. -2) was obtained.

(Example 14)

Instead of compound (1-a), the compound (1-e) -containing solution obtained in Example 8 was added so that compound (1-e) was 0.1 molar equivalent to 1 mole of the repeating unit of the polyamic acid ester. In the same manner as in Example 12, a liquid crystal aligning agent (A1-3) was obtained.

(Example 15)

Instead of compound (1-a), the compound (1-f) -containing solution obtained in Example 9 was added so that compound (1-f) was 0.1 molar equivalent to 1 mole of the repeating unit of the polyamic acid ester. In the same manner as in Example 12, a liquid crystal aligning agent (A1-4) was obtained.

(Example 16)

Instead of compound (1-a), the compound (1-g) -containing solution obtained in Example 10 was added so that compound (1-g) was 0.1 molar equivalent to 1 mole of the repeating unit of the polyamic acid ester. In the same manner as in Example 12, a liquid crystal aligning agent (A1-5) was obtained.

(Example 17)

Instead of compound (1-a), the compound (1-h) -containing solution obtained in Example 11 was added so that compound (1-h) was 0.1 molar equivalent to 1 mole of the repeating unit of the polyamic acid ester. In the same manner as in Example 12, a liquid crystal aligning agent (A1-6) was obtained.

(Example 18)

4.4560g of polyamic acid ester solution (PAE-2) obtained by the synthesis example 4 was put into the 20 ml sample tube which put the stirrer, Then, 1.4837g and 1.5021g of NMP are added, and the compound obtained by Example 1 further 0.1023g (0.2 mol equivalent to 1 mol of repeating units of polyamic acid ester) is added, and it stirred for 30 minutes at room temperature, dissolves a compound (1-a) completely, and a liquid crystal aligning agent (A2-1) )

(Example 19)

A liquid crystal aligning agent (A2) was prepared in the same manner as in Example 18 except for using the compound (1-d) obtained in Example 4 with respect to 1 mol of the repeating unit of the polyamic acid ester instead of the compound (1-a). -2) was obtained.

(Example 20)

Instead of compound (1-a), the compound (1-e) -containing solution obtained in Example 8 was added so that compound (1-e) was 0.2 molar equivalent to 1 mole of the repeating unit of the polyamic acid ester. In the same manner as in Example 18, a liquid crystal aligning agent (A2-3) was obtained.

(Example 21)

Instead of compound (1-a), the compound (1-f) -containing solution obtained in Example 9 was added so that compound (1-f) was 0.2 molar equivalent to 1 mole of the repeating unit of the polyamic acid ester. And the liquid crystal aligning agent (A2-4) was obtained like Example 18.

(Example 22)

4.4156g of polyamic-acid solution (PAA-1) obtained by the synthesis example 5 was put into the 20 mL sample tube which put the stirrer, Then, 1.3409g and 1.4426g of NMP are added, and the compound obtained in Example 1 ( 0.2113 g (0.2 molar equivalent with respect to 1 mol of repeating units of a polyamic acid) is added, and it stirred at room temperature for 30 minutes, the compound (1-a) is dissolved completely and a liquid crystal aligning agent (A3-1) is added. Got it.

(Example 23)

The liquid crystal aligning agent (A3-) was carried out similarly to Example 22 except having used the compound (1-d) obtained in Example 4 with respect to 1 mol of repeating units of a polyamic acid instead of compound (1-a). 2) was obtained.

(Example 24)

Instead of compound (1-a), the compound (1-e) -containing solution obtained in Example 8 was added so that compound (1-e) was 0.2 molar equivalent to 1 mole of the repeating unit of the polyamic acid, In the same manner as in Example 22, a liquid crystal aligning agent (A3-3) was obtained.

(Example 25)

Instead of compound (1-a), the compound (1-f) -containing solution obtained in Example 9 was added so that compound (1-f) was 0.2 molar equivalent to 1 mole of the repeating unit of the polyamic acid. In the same manner as in Example 22, a liquid crystal aligning agent (A3-4) was obtained.

(Comparative Example 1)

2.7692g of polyamic acid ester solution (PAE-1) obtained by the synthesis example 3 was put into the 20 mL sample tube which put the stirrer, Then, 1.2308g of GBL and 1.012g of BCS are added, and it stirred at room temperature for 30 minutes, and liquid crystal An aligning agent (B1-1) was obtained.

(Comparative Example 2)

4.3431g of polyamic acid ester solution (PAE-2) obtained by the synthesis example 4 was put into the 20 ml sample tube which put the stirrer, Then, 1.4722g of NMP and 1.4589g of BCS are added, and it stirred at room temperature for 30 minutes, and liquid-crystal An aligning agent (B2-1) was obtained.

(Comparative Example 3)

4.7100 g of polyamic acid ester solution (PAE-2) obtained in the synthesis example 4 was put into the 20 mL sample tube which put the stirrer, Then, 1.5935 g of NMP and 1.5892 g of BCS are added, and the precursor obtained in Example 1 further 0.0985g (0.4 mol equivalent per 1 mol of repeating units of polyamic acid ester) was added (1-a2), and it stirred at room temperature for 30 minutes, and obtained the liquid crystal aligning agent (B2-2).

(Comparative Example 4)

3.9775g of polyamic-acid solution (PAA-1) obtained by the synthesis example 5 was put into the 20 mL sample tube which put the stirrer, Then, 1.2069g and 1.2953g of NMP are added, and it stirred at room temperature for 30 minutes, and aligns liquid crystal The agent (B3-1) was obtained.

(Comparative Example 5)

4.3645g of the polyamic-acid solution (PAA-1) obtained by the synthesis example 5 was put into the 20 mL sample tube which put the stirrer, Then, 1.3462g of NMP and 1.4297g of BCS are added, and the precursor obtained in Example 1 ( 0.1357g (0.4 mol equivalent per 1 mol of repeating units of polyamic acid) was added, and it stirred at room temperature for 30 minutes, and obtained the liquid crystal aligning agent (B3-2).

(Example 26)

After filtering the liquid crystal aligning agent (A1-1) obtained in Example 12 with a 1.0 micrometer membrane filter, spin-coating on a glass substrate and drying for 5 minutes on a hotplate of 80 degreeC, for 10 minutes at 230 degreeC It baked and the imidized film | membrane of 100 nm of film thickness was obtained. This coating film was cut out, the FT-IR spectrum was measured by the ATR method, and the imidation ratio was computed. The results are shown in Table 1.

(Examples 27 to 31)

The imidized film was produced by operation similar to Example 26 using the liquid crystal aligning agent (A1-2)-(A1-6) obtained in Examples 13-17, and measuring an FT-IR spectrum and measuring imidation ratio Calculated. The results are shown in Table 1.

(Comparative Example 6)

The imidized film was produced like Example 26 using the liquid crystal aligning agent (B1-1) obtained by the comparative example 1, the FT-IR spectrum was measured and the imidation ratio was computed. The results are shown in Table 1.

In the result of Examples 26-31 and the comparative example 6, it was confirmed that the compound of this invention accelerates the imidation reaction of polyamic acid ester.

(Example 32)

After filtering the liquid crystal aligning agent (A2-1) obtained in Example 18 with a 1.0 micrometer membrane filter, spin-coating on a glass substrate and drying for 5 minutes on a hotplate of 80 degreeC, after 10 minutes at 20 degreeC It baked and the imidized film | membrane of 100 nm of film thickness was obtained. This coating film was cut out, the FT-IR spectrum was measured by the ATR method, and the imidation ratio was computed. The results are shown in Table 2.

(Examples 33 to 35)

Using the liquid crystal aligning agent (A2-2)-(A2-4) of this invention obtained in Examples 19-21, the imidized film was produced like Example 32, the FT-IR spectrum was measured, and The dehydration rate was calculated. The results are shown in Table 2.

(Comparative Examples 7 to 8)

The imidized film was produced like Example 32 using the liquid crystal aligning agent (B2-1) and (B2-2) obtained in the comparative examples 2 and 3, respectively, and measuring FT-IR spectrum, The rate of fire was calculated. The results are shown in Table 2.

In the result of Examples 32-35 and the comparative example 7, it was confirmed that the compound of this invention accelerates the imidation reaction of polyamic acid ester. Moreover, in the result of Example 34, 35 and the comparative example 8, it was confirmed that the reaction product of tetracarboxylic dianhydride and precursor (1-a2) accelerates the imidation reaction of polyamic acid ester.

(Example 36)

After filtering the liquid crystal aligning agent (A3-1) obtained in Example 22 with the membrane filter of 1.0 microm, spin-coating on the glass substrate with a transparent electrode, and drying for 5 minutes on a hotplate of 80 degreeC, It baked for 20 minutes at 230 degreeC, and obtained the imidized film with a film thickness of 100 nm. After rubbing this polyimide membrane with a rayon cloth (roll diameter 120mm, rotation speed 1000rpm, movement speed 20mm / sec, indentation amount 0.4mm), when the surface state of the polyimide membrane was observed, the flaw by rubbing and polyei Cutting chips of the mid film and peeling of the polyimide film were not observed.

(Example 37)

Except having used the liquid crystal aligning agent (A3-2) obtained in Example 23, the polyimide membrane was produced like Example 36, and the rubbing process was performed. As a result of observing the surface state of the polyimide membrane, the scratch by rubbing, the cutting chips of the polyimide membrane, and the peeling of the polyimide membrane were not observed.

(Example 38)

Except having used the liquid crystal aligning agent (A3-3) obtained in Example 24, the polyimide membrane was produced like Example 36, and the rubbing process was performed. As a result of observing the surface state of the polyimide membrane, the scratch by rubbing, the cutting chips of the polyimide membrane, and the peeling of the polyimide membrane were not observed.

(Example 39)

Except having used the liquid crystal aligning agent (A3-4) obtained in Example 25, the polyimide membrane was produced like Example 36, and the rubbing process was performed. As a result of observing the surface state of the polyimide membrane, the scratch by rubbing, the cutting chips of the polyimide membrane, and the peeling of the polyimide membrane were not observed.

(Comparative Example 9)

Except having used the liquid crystal aligning agent (B3-1) obtained by the comparative example 4, the polyimide membrane was produced like Example 36, and the rubbing process was performed. As a result of observing the surface state of the polyimide film, scratches due to rubbing and cutting chips of the polyimide film were observed.

(Comparative Example 10)

Except having used the liquid crystal aligning agent (B3-2) obtained by the comparative example 5, the polyimide membrane was produced like Example 36, and the rubbing process was performed. As a result of observing the surface state of the polyimide film, scratches due to rubbing and cutting chips of the polyimide film were observed.

As a result of Examples 36-39 and the comparative example 9, it was confirmed that the imidation film excellent in the mechanical strength which is hard to be damaged by rubbing is obtained by apply | coating and baking the polyamic-acid solution which added the compound of this invention. Moreover, in the result of Example 38, 39 and the comparative example 10, it was confirmed that the reaction product of tetracarboxylic dianhydride and precursor (1-a2) improves the mechanical strength of the imidation film obtained.

(Example 40)

After filtering the liquid crystal aligning agent (A2-1) obtained in Example 18 with the 1.0 micrometer membrane filter, it spin-coated on the glass substrate with a transparent electrode, dried for 5 minutes on the hotplate of temperature 80 degreeC, and temperature An imidized film having a film thickness of 100 nm was formed through baking at 230 ° C. for 20 minutes. The coating film was rubbed with a rayon cloth (roll diameter 120 mm, rotational speed 300 rpm, moving speed 20 mm / sec, indentation amount 0.4 mm), ultrasonically irradiated with pure water for 1 minute, and washed with water blow to remove water droplets. After removing, it dried for 10 minutes at 80 degreeC, and obtained the board | substrate with a liquid crystal aligning film.

After preparing two board | substrates with such a liquid crystal aligning film, spread | dispersing a 6 micrometers spacer on the liquid crystal aligning film surface of one board | substrate, combining so that the rubbing direction of two board | substrates may become antiparallel, and sealing around the liquid crystal inlet opening Thus, a empty cell having a cell gap of 6 µm was produced. A liquid crystal (MLC-2041, manufactured by Merck Co., Ltd.) was vacuum-injected into the empty cell at room temperature, and the liquid crystal cell with which the injection port was sealed was observed for liquid crystal alignment, pretilt angle measurement, voltage retention measurement, and ion density measurement. The results are shown in Tables 3 and 4 described later.

(Example 41)

A liquid crystal cell was produced in the same manner as in Example 40 except that the liquid crystal aligning agent (A2-2) obtained in Example 19 was used. This liquid crystal cell was observed for liquid crystal alignment, pretilt angle measurement, voltage retention measurement and ion density measurement. The results are shown in Tables 3 and 4 described later.

(Example 42)

A liquid crystal cell was produced in the same manner as in Example 40 except that the liquid crystal aligning agent (A3-1) obtained in Example 22 was used. The liquid crystal cell orientation was observed, the pretilt angle measurement, the voltage retention measurement, and the ion density measurement were performed about this liquid crystal cell. The results are shown in Table 3 and Table 4.

(Example 43)

A liquid crystal cell was produced in the same manner as in Example 40 except that the liquid crystal aligning agent (A3-2) obtained in Example 23 was used. About this liquid crystal cell, observation of liquid crystal alignability, pretilt angle measurement, voltage retention measurement, and ion density measurement were performed. The results are shown in Table 3 and Table 4.

(Comparative Example 11)

Using the liquid crystal aligning agent (B2-1) obtained in the comparative example 2, the liquid crystal cell was produced like Example 40 except having set baking time to 1 hour. About this liquid crystal cell, observation of liquid crystal alignability, pretilt angle measurement, voltage retention measurement, and ion density measurement were performed. The results are shown in Table 3 and Table 4.

(Comparative Example 12)

A liquid crystal cell was produced in the same manner as in Example 40 except that the liquid crystal aligning agent (B3-1) obtained in Comparative Example 4 was used. About this liquid crystal cell, observation of liquid crystal alignability, pretilt angle measurement, voltage retention measurement, and ion density measurement were performed. The results are shown in Table 3 and Table 4.

In the results of Examples 40 to 43 and Comparative Examples 11 and 12, it was confirmed that a liquid crystal display device having good liquid crystal alignment property was obtained by using the liquid crystal alignment film of the present invention. Moreover, it was confirmed that a pretilt angle becomes high by using the liquid crystal aligning film of this invention.

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

(Example 44)

After filtering the liquid crystal aligning agent (A3-1) obtained in Example 22 with a 1.0 micrometer membrane filter, it spin-coated on the glass substrate with a transparent electrode, dried for 5 minutes on the hotplate of temperature 80 degreeC, and temperature An imidized film having a film thickness of 100 nm was formed through baking at 230 ° C. for 20 minutes. 1 J / 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.

After preparing two board | substrates with which this liquid crystal aligning film was formed, spread | dispersing a 6 micrometers spacer on the liquid crystal aligning film surface of one board | substrate, combining so that the orientation of two board | substrates may be antiparallel, sealing around the liquid crystal leaving the injection hole, Empty cells with a cell gap of 6 μm were prepared. A liquid crystal (MLC-2041, manufactured by Merck Co., Ltd.) was vacuum-injected into the empty cell at room temperature, and the liquid crystal cell orientation, the voltage retention measurement, and the ion density measurement were performed on the liquid crystal cell in which the injection port was sealed. The results are shown in Table 5 described later.

(Example 45)

A liquid crystal cell was produced in the same manner as in Example 44 except that the liquid crystal aligning agent (A3-2) obtained in Example 23 was used. About this liquid crystal cell, observation of liquid crystal alignability, pretilt angle measurement, voltage retention measurement, and ion density measurement were performed. The results are shown in Table 5.

(Comparative Example 13)

A liquid crystal cell was produced in the same manner as in Example 44 except that the liquid crystal aligning agent (B3-1) obtained in Comparative Example 4 was used. About this liquid crystal cell, observation of liquid crystal alignability, pretilt angle measurement, voltage retention measurement, and ion density measurement were performed. The results are shown in Table 5.

As a result of Examples 44 and 45 and Comparative Example 13, by using the liquid crystal aligning film of this invention, it showed the liquid crystal aligning property also in photo-alignment, the liquid crystal display element which was excellent in the reliability which was high in voltage retention and low ion density even at high temperature. Was obtained.

Industrial availability

According to the liquid crystal aligning agent of this invention, while being excellent in mechanical strength, being excellent in resistance to a rubbing process, it is excellent in the point of liquid crystal orientation, especially electrical characteristics, such as voltage retention and ion density at the time of high temperature, The highly reliable liquid crystal aligning film which gives a high pretilt angle can be formed. As a result, it is widely useful for TN devices, STN devices, TFT liquid crystal devices, and vertically aligned liquid crystal display devices.

In addition, the JP Patent application 2010-123471, the claim, and all the content of the abstract for which it applied on May 28, 2010 are referred here, and it introduces as an indication of the specification of this invention.

Claims (17)

Protected by a polyimide precursor obtained by reacting a diamine compound with a tetracarboxylic acid derivative, and / or a polyimide obtained by imidating the polyimide precursor, and a heat leaving group substituted with hydrogen by heating at 80 to 300 ° C. A compound containing an amic acid or an amic acid ester structure which has an amino group is contained, The liquid crystal aligning agent characterized by the above-mentioned. The method of claim 1,
The said polyimide precursor has a liquid crystal aligning agent which has a repeating unit represented by following formula (7).
[Formula 1]

(Wherein X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, R ₆ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. A ₁ and A ₂ are each independently a hydrogen atom or a substituent) An alkyl group, alkenyl group or alkynyl group having 1 to 10 carbon atoms) 3. The method according to claim 1 or 2,
Amic acid or amic acid ester in which the said polyimide precursor and the said polyimide contain 0.5-15 mass% in liquid crystal aligning agent in those total amounts, and also has the amino group protected by the heat-leaving group substituted by hydrogen by heating. The liquid crystal aligning agent in which the compound which has a structure contains 0.5-50 mol% with respect to the polyimide precursor which has a repeating unit represented by said Formula (7), and 1 unit of repeating units of the imidation polymer of this polyimide precursor. The method according to any one of claims 1 to 3,
The liquid crystal aligning agent whose compound which has the said amic acid or an amic acid ester structure is a compound represented by following formula (1).
(2)

(In formula, X is a tetravalent organic group, R <_1> is a hydrogen atom or a C1-C5 alkyl group, Z is a structure represented by following formula (2).)
(3)

(In formula, Z <_1> is a single bond or a C1-C30 divalent organic group. R <_2> and R <_3> respectively independently represents a hydrogen atom or a C1-C30 alkyl group and alkenyl group which may have a substituent. , an alkynyl group, an aryl group, or a combination thereof, and form a ring structure. R ₄ is an alkyl group having 1 to 30 carbon atoms which may have a hydrogen atom or a substituent. D ₁ is the thermal desorption group) The method according to any one of claims 1 to 4,
The said heat leaving group is a tert-butoxycarbonyl group or 9-fluorenyl methoxycarbonyl group, The liquid crystal aligning agent. 6. The method according to any one of claims 1 to 5,
Liquid crystal aligning agent whose said X is either selected from the group which consists of a structure represented by a following formula.
[Chemical Formula 4]

The liquid crystal aligning film which carried out the orientation process of the film | membrane obtained by apply | coating and baking the liquid crystal aligning agent in any one of Claims 1-6. The method of claim 7, wherein
The liquid crystal aligning film whose said orientation process is a rubbing process or the irradiation process of the polarized radiation. The liquid crystal display element provided with the liquid crystal aligning film of Claim 7 or 8. The compound which has an amic acid or an amic acid ester structure represented by following formula (1).
[Chemical Formula 5]

(In formula, X is a tetravalent organic group, R <_1> is a hydrogen atom or a C1-C5 alkyl group, and Z is a structure represented by following formula (2).)
[Chemical Formula 6]

(In formula, Z <_1> is a single bond or a C1-C30 divalent organic group. R <_2> and R <_3> respectively independently represents a hydrogen atom or a C1-C30 alkyl group and alkenyl group which may have a substituent. , an alkynyl group, an aryl group, or a combination thereof, and form a ring structure. R ₄ is an alkyl group having 1 to 30 carbon atoms which may have a hydrogen atom or a substituent. D ₁ is the thermal desorption group) 11. The method of claim 10,
The bischlorocarbonyl compound represented by following formula (3) and the monoamine compound represented by following formula (4) are made to react by molar ratio of (chlorocarbonyl compound / monoamine) in 1/2 to 1/3 in presence of a base. Obtained compound.
(7)

(Wherein X, Z ₁ , R ₂ , R ₃ , R ₄ , and D ₁ are the same definitions as those of the formulas (1) and (2), and R ₅ is an alkyl group having 1 to 5 carbon atoms) 11. The method of claim 10,
The tetracarboxylic acid derivative represented by the following formula (5) and the monoamine compound represented by the formula (4) according to claim 11 are contained in a molar ratio of (tetracarboxylic acid derivative / monoamine) in the presence of a condensing agent. Compound obtained by reacting with 1/3.
[Chemical Formula 8]

(Wherein X and R ₅ are the same as defined in the formulas (1) and (3)) 11. The method of claim 10,
The molar ratio of (tetracarboxylic dianhydride / monoamine) to the tetracarboxylic dianhydride represented by following formula (6) and the monoamine compound represented by Formula (4) of Claim 11 is 1 / 2-1 / Compound obtained by reacting with 3.
[Chemical Formula 9]

(Wherein X is the same definition as that of formula (1) above) 11. The method of claim 10,
The molar ratio of tetracarboxylic dianhydride represented by Formula (6) of Claim 13 and the monoamine compound represented by Formula (4) of Claim 11 to (tetracarboxylic dianhydride / monoamine) is 1 / A compound obtained by reacting with 2 to 1/3 and further esterifying a carboxyl group with an esterifying agent. 15. The method according to any one of claims 10 to 14,
X is any one selected from the group which consists of a structure represented by a following formula.
[Formula 10]

16. The method according to any one of claims 10 to 15,
The said R <_1> is a C1-C5 alkyl group. Compound which is any one of following formula (1-a)-(1-o)
(11)

[Chemical Formula 12]

[Chemical Formula 13]