JP2001002780A - Diamine compound having silphenylene residue and polyamide, polyamic acid, polyimide, liquid crystal orienting agent and liquid crystal display element produced by using the compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new diamine compound containing a specific silphenylene residue, having excellent solubility in solvents and orientation uniformity of a polymer chain by rubbing, and useful as a liquid crystal orienting agent. SOLUTION: A diamine compound containing a silphenylene group expressed by formula I (R1 to R4 are each a 1-6C alkyl or phenyl; X1 and X2 are each an ether bond, or the like; (m) is 2-20), e.g. a compound of formula II. The compound of formula I can be produced by reacting a silphenylene compound of formula III with an alkenyl compound of formula IV in the presence of a hydrosilylation catalyst (e.g. platinum) preferably in a solvent (e.g. hexane) at 40-100 deg.C in an inert gas atmosphere (e.g. argon) and reducing the nitro group of the produced dinitro compound at -100 to +150 deg.C preferably in a solvent (e.g. an alcohol).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel diamine compound having a silphenylene residue, a polyamide derived from the compound, a polyamic acid, a polyimide obtained by imidizing the polyamic acid, and a liquid crystal alignment using the same. The present invention relates to a processing agent and a liquid crystal display device.

The polyamide of the present invention has excellent solubility in a solvent, can be fired at a low temperature during film formation, and has excellent alignment of polymer chains by rubbing, and exhibits a uniform liquid crystal alignment. Useful as an alignment treatment agent for devices,
Further, the polyamic acid and polyimide of the present invention are excellent in the alignment of the polymer chains by rubbing, and are useful as an alignment treatment agent for a liquid crystal display device exhibiting uniform liquid crystal alignment.

[0003]

2. Description of the Related Art A liquid crystal display element is a display element utilizing electro-optical change of liquid crystal, and is small and light in terms of a device.
Attention has been paid to characteristics such as low power consumption, and in recent years, display devices for various displays have been remarkably developed. Above all, using nematic liquid crystal having positive dielectric anisotropy, liquid crystal molecules are arranged parallel to the substrate at each interface of a pair of electrode substrates facing each other, and the orientation directions of the liquid crystal molecules are orthogonal to each other. A twisted nematic (TN type) field effect type liquid crystal display element combining both substrates is a typical example thereof.

In such a TN type liquid crystal display device, it is necessary to uniformly align the major axis direction of the liquid crystal molecules parallel to the substrate surface, and to align the liquid crystal molecules at a constant tilt alignment angle with respect to the substrate. In the case of a liquid crystal device using a ferroelectric liquid crystal or an antiferroelectric liquid crystal, the layer directions are aligned,
It is important that the long axis direction of the liquid crystal molecules be uniformly aligned on the substrate surface. A typical method of aligning liquid crystal molecules in this way is to apply an organic coating on the substrate surface, rub the surface with a cloth such as cotton, nylon, polyester, etc. in a certain direction, and to align the liquid crystal molecules in the rubbing direction. Method is used. Examples of the organic film include polyvinyl alcohol, polyoxyethylene, polyamide, and polyimide. Among them, polyimide is most commonly used in terms of chemical stability, thermal stability, and the like. A typical example of polyimide used for such a liquid crystal alignment film is disclosed in JP-A-61-47932.

[0005]

The liquid crystal alignment film is generally formed by applying a liquid crystal alignment treatment agent obtained by dissolving a polymer in a solvent onto a substrate by spin coating or printing. . As the solvent used at that time, a poor solvent is added together with the aprotic polar solvent to improve the coatability on the substrate. However, polymers such as soluble polyimides and polyamides do not always have sufficient solubility in a solvent, and the viscosity of the polymer solution becomes unstable, or the polymer is precipitated by the addition of a poor solvent. was there.

The liquid crystal alignment treatment agent applied on the substrate is dried and baked, and then subjected to a rubbing treatment.
The firing temperature used at this time is preferably firing at a lower temperature from the viewpoint of heat resistance of members such as color filters. Further, from the viewpoint of weight reduction, a liquid crystal display element using a substrate having low heat resistance such as a plastic substrate has been studied.

[0007] Soluble polyimide or polyamide can be heated and dried at a relatively low temperature of, for example, about 100 ° C to 200 ° C to form a polyimide film or polyamide film on a substrate. However, when a polyimide precursor solution is applied on a substrate and then dehydrated and closed by heating and baking to form a polyimide film, generally, 200
High-temperature baking at a temperature of at least 250C, preferably about 250C to 300C is required, and baking at a higher temperature is particularly important for obtaining more stable liquid crystal alignment. Therefore, application to a substrate having low heat resistance such as a plastic substrate has been difficult.

Further, although the mechanism of the liquid crystal alignment by the rubbing method is not always clear, the grooves formed on the alignment film surface by the rubbing, the polymer chains of the alignment film in which anisotropy is induced in the rubbing direction, and the liquid crystal molecules. It is considered that the liquid crystal molecules are aligned by the anisotropic interaction of. Grooves generated by rubbing align liquid crystal molecules in the direction of the grooves, but if the grooves are too large or uneven, they may become rubbing scratches and reduce the uniformity of liquid crystal alignment, resulting in a liquid crystal display with high contrast. This is not preferable in manufacturing an element. On the other hand, when inducing the anisotropy of the polymer chains by rubbing, it is not easy to uniformly align the polymer chains in the rubbing direction by the conventional method of rubbing a liquid crystal alignment film, and in particular, to avoid rubbing scratches. When the rubbing treatment is weak, the uniformity of the alignment of the polymer chains is remarkably low, so that there is a problem that the uniformity of the liquid crystal alignment is reduced.

That is, in the conventional liquid crystal alignment film, the alignment uniformity of the polymer chains by the rubbing treatment is not always sufficient. From the viewpoint of achieving a liquid crystal display element having high uniformity of liquid crystal alignment and high contrast, rubbing is not preferable. It is an important issue to further improve the uniformity of the orientation of the polymer chains by the method. Japanese Patent Application Laid-Open Nos. 11-65854 and 11-658 disclose polymers having a high orientation uniformity of polymer chains.
As described in Japanese Patent No. 55-55, these polymers did not always have sufficient solubility in a solvent.

The present invention relates to a novel diamine, and a polyamide, a polyamic acid and a polyimide using the same. When this polyamide is used, the polymer is excellent in solubility in a solvent, can be fired at a low temperature, and can be rubbed. It is intended to provide a liquid crystal alignment treatment agent capable of forming a liquid crystal alignment film having excellent chain alignment uniformity and high liquid crystal alignment uniformity. Further, when polyamic acid and / or polyimide is used, high rubbing due to rubbing occurs. It is an object of the present invention to provide a liquid crystal alignment treatment agent which is capable of forming a liquid crystal alignment film having excellent molecular chain alignment uniformity and high liquid crystal alignment uniformity.

[0011]

SUMMARY OF THE INVENTION The present invention relates to a polyamide, a polyamic acid or a polyimide useful as a liquid crystal alignment treatment agent, and a raw material compound thereof.
As a result of intensive studies on the solubility in a solvent and the uniformity of orientation of the polymer chains by rubbing, novel polyamides, polyamide sans and polyimide resins were found, and the present invention was completed. That is, the present invention provides the following general formula (I)

[0012]

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(Wherein, R ^{1 to} R ⁴ are an alkyl group or phenyl group having 1 to 6 carbon atoms, X ¹ and X ² are ether bonds,
An ester bond or an amide bond, m is an integer of 2 to 20. A diamine compound having a silphenylene residue represented by the following general formula (II):

[0014]

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(Wherein, R ^{1 to} R ⁴ are an alkyl group or phenyl group having 1 to 6 carbon atoms, X ¹ and X ² are ether bonds,
An ester bond or an amide bond, A ¹ is a divalent organic group constituting a dicarboxylic acid, and m is an integer of 2 to 20. )
Containing at least 5 mol% of a repeating unit represented by
Polyamide having a weight average molecular weight of at least 2,000, or the following general formula (III)

[0016]

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(Wherein, R ^{1 to} R ⁴ are an alkyl group or phenyl group having 1 to 6 carbon atoms, A ² is a tetravalent organic group constituting tetracarboxylic acid, and m is an integer of 2 to 20). The present invention relates to a polyamic acid containing at least 5 mol% of the repeating unit represented by the formula (1) and having a weight average molecular weight of at least 2,000, and a polyimide derived from the polyamic acid.

Further, the present invention relates to a liquid crystal alignment treatment agent used for forming a liquid crystal alignment film formed by rubbing after coating and firing on a substrate with a transparent electrode, wherein the liquid crystal alignment treatment agent has the general formula A liquid crystal alignment treatment agent comprising a polyamide solution having a silphenylene residue having a weight average molecular weight of at least 2,000, containing at least 5 mol% of the repeating unit represented by (II), and the liquid crystal A liquid crystal element characterized by using a liquid crystal alignment film formed using an alignment treatment agent, and the liquid crystal alignment treatment agent contains at least 5 mol% of a repeating unit represented by the general formula (III). A polyamic acid solution having a weight average molecular weight of at least 2,000 and / or a polyimide solution derived from the polyamic acid. Agents, and to a liquid crystal element characterized by using a liquid crystal alignment film formed by using the liquid crystal aligning agent.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION In the above general formulas (I) and (II), the alkyl group having 1 to 6 carbon atoms represented by R ^{1 to} R ⁴ is a methyl group, an ethyl group, a propyl group, an iso-propyl group. Groups, a butyl group, a sec-butyl group, a t-butyl group, a pentyl group, a hexyl group and the like can be exemplified, and a methyl group is most preferred in view of availability of raw material compounds and ease of synthesis. In the bonds represented by X ¹ and X ² in the general formulas (I) and (II), an ether bond is a case where X ¹ and X ² are an oxygen atom or a sulfur atom. X ¹ is a group represented by —OC (＝ O) — and X ² is a group represented by —C (＝ O) O—, or X ¹ is —C (＝ O) O—. And X ² is a group represented by —OC (＝ O) —, and the amide bond means that X ¹ is —N (—H) C
(= O) - in a group represented and X ² is -C (= O)
N (-H) - it is a group represented by or X ¹ is -C (= O) N (-H ) - a group represented by and X ²
Is a group represented by -N (-H) C (= O)-.

The diamine compound of the present invention represented by the general formula (I) can be produced, for example, by the following method. That is, the following general formula (IV)

[0021]

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(Wherein, R ^{1 to} R ⁴ are an alkyl group having 1 to 6 carbon atoms or a phenyl group); and a general formula (V):

[0023]

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(Wherein X is an ether bond, an ester bond or an amide bond, and m is an integer of 2 to 20) in the presence of a hydrosilylation catalyst. )

[0025]

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(Wherein, R ^{1 to} R ⁴ are alkyl or phenyl groups having 1 to 6 carbon atoms, X ¹ and X ² are ether bonds,
An ester bond or an amide bond, m is an integer of 2 to 20. After obtaining the dinitro compound represented by the formula (1), the diamine compound represented by the formula (I) can be produced by reducing the nitro group of the compound by a commonly used reaction.

The hydrosilylation catalyst used herein includes platinum, platinum-carbon, chloroplatinic acid, platinum-1,3-divinyltetramethyldisiloxane complex, di (cyanophenyl) platinum dichloride and dicyclopentadienyl platinum. Most commonly, a platinum-based catalyst such as dichloride is used, but other metal complexes containing palladium and rhodium can also be used. For example, (Ph ₃ P) ₄
Pd, (Ph ₃ P) ₂ PdCl ₂ , (PhCN) ₂ PdCl ₂ ,
(Ph ₃ P) ₃ RhCl, (Ph ₂ PH) ₂ RhCl, (Ph
₃ P) ₂ (CO) RhCl and _{[(C 2 H 5) 3} P] 2 (CO) R
hCl or the like can be used as a catalyst. The amount of the catalyst used is usually about 1/100 to 1/5000 equivalents to the alkenyl compound represented by the general formula (V).

This reaction is preferably carried out in a solvent. As the solvent, hexane, benzene, toluene, acetone, chloroform, dichloromethane, trichloroethylene, tetrahydrofuran and the like can be used. The reaction is usually carried out in a temperature range of 40 ° C. to 100 ° C., and preferably in an atmosphere of an inert gas such as argon or nitrogen.

The above-mentioned reduction reaction of the nitro group can easily proceed by reacting with a generally used known reducing agent. However, in a hydrogen gas atmosphere, a catalytic reaction using a metal such as nickel, platinum, palladium or rhodium as a catalyst is carried out. By performing the reduction, the dinitro compound represented by the general formula (I) of the present invention can be synthesized with a high yield from the dinitro compound represented by the general formula (VI). It is desirable to carry out each reaction in a solvent, and any solvent may be used as long as it does not participate in the reaction, and examples thereof include alcohol, tetrahydrofuran, dimethoxyethane, dioxane, benzene, and toluene. The reaction temperature is -100 ° C to 150 ° C, preferably -50 ° C to 100 ° C.
It can be performed in the range of ° C.

Some of the silphenylene compounds represented by the general formula (IV) are commercially available, and those not commercially available can be easily synthesized by known methods. The alkenyl compound represented by the general formula (V) is
For example, the following general formula (VII)

[0031]

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(Wherein Y ¹ is a halogen atom other than fluorine, a tosyloxy group, a hydroxyl group, a carboxyl group or an amino group, and m is an integer of 2 to 20), and a compound represented by the following general formula ( VIII)

[0033]

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(Wherein, Y ² is a hydroxyl group, a thiol group, a carboxyl group or an amino group) in a suitable combination and reacted. That is, for those X of alkenyl compound represented by the general formula (V) is an ether bond, a halogen atom or a tosyloxy group Y ¹ is other than fluorine of the above formula (VII) Compound And a compound represented by formula (VIII) wherein Y ² is a hydroxyl group or a thiol group, and the mixture is subjected to an etherification reaction by a usual method to easily produce the compound. Further, among the alkenyl compounds represented by the general formula (V), those in which X is an ester bond include those in which Y ¹ is a hydroxyl group in the compounds represented by the general formula (VII) and A compound represented by the formula (VIII) wherein Y ² is a carboxyl group is mixed, or a compound represented by the formula (VII) wherein Y ¹ is a carboxyl group and It can be easily produced by mixing the compound represented by (VIII) with a compound in which Y ² is a hydroxyl group and performing a condensation reaction by a usual method.

Further, among the alkenyl compounds represented by the general formula (V), those in which X is an amide bond, those in which Y ¹ is an amino group among the compounds represented by the general formula (VII) And a compound of the formula (VIII) wherein Y ² is a carboxyl group, or a compound of the formula (VII) wherein Y ¹ is a carboxyl group And the general formula (VII
It can be easily produced by mixing a compound represented by I) wherein Y ² is an amino group and conducting a condensation reaction by an ordinary method.

Some of the dinitro compounds represented by the general formula (VI) wherein X ¹ and X ² are ester bonds or amide bonds can be separately synthesized from the following starting compounds. is there. That is, the following general formula (IX)

[0037]

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(Wherein, R ^{1 to} R ⁴ are an alkyl group having 1 to 6 carbon atoms or a phenyl group, and m is an integer of 2 to 20).
And a compound represented by the general formula (VIII), wherein Y ² is a hydroxyl group or an amino group, and subjected to a condensation reaction by a conventional method to obtain a compound represented by the general formula (VI) A part of the dinitro compounds represented by the formulas in which X ¹ and X ² are ester bonds or amide bonds can be synthesized.

The compound represented by the general formula (IX) used herein is, for example, a silphenylene compound represented by the general formula (IV) and a compound represented by the following general formula (X)

[0040]

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Wherein R is a lower alkyl group and m is 2 to 2
It is an integer of 0. With an alkenyl compound represented by the formula (XI):

[0042]

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Wherein R ^{1 to} R ⁴ are an alkyl group or phenyl group having 1 to 6 carbon atoms, R is a lower alkyl group, and m is 2 to
It is an integer of 20. )), And then can be produced by hydrolyzing the ester site of the compound by a commonly used reaction.

In the general formulas (X) and (XI), R
Examples of the lower alkyl group represented by are a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a t-butyl group, a pentyl group and a hexyl group.

The thus obtained general formula (I)
The present invention comprising a diamine compound having a silphenylene residue of the present invention represented by the following formula (hereinafter, referred to as the diamine compound of the present invention) as a monomer and containing at least 5 mol% of the repeating unit represented by the general formula (II). (Hereinafter, referred to as the polyamide of the present invention), or the polyamic acid of the present invention containing at least 5 mol% of the repeating unit represented by the general formula (III) (hereinafter, referred to as the polyamic acid of the present invention), and Polyimide derived from polyamic acid (hereinafter, referred to as polyimide of the present invention) can be produced. The polyamide of the present invention comprises a diamine compound of the present invention and the following general formula (XII)

[0046]

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(Wherein, A ³ is a divalent organic group constituting a diamine) and a diamine compound of the present invention are mixed at least 5 mol%. Further, the following general formula (XIII)

[0048]

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Wherein A ¹ is a dicarboxylic acid
Is a valence organic group. Can be synthesized by mixing the dicarboxylic acid compound represented by the formula (1) in an equimolar amount with respect to the total molar amount of the above diamine compound, and performing a polycondensation reaction by an ordinary method. Further, in the above reaction, the diamine compound of the present invention and the diamine compound of the general formula (XII) were used without using the diamine compound represented by the general formula (XII).
The polycondensation reaction may be performed by mixing equimolar amounts of the dicarboxylic acid compound represented by I).

When the above monomers are used, the polycondensation reaction is desirably carried out in the presence of a condensing agent. Triphenyl phosphite, tritoluyl phosphite, tri (chlorophenyl) phosphite, phenyl dichlorophosphite, dichlorophosphite Diphenyl phosphate, triphenylphosphine / hexachloroethane, diphenyl (2,3-hydro-2-thioxo-3-benzothiazolyl) phosphonate, (C ₃ H ₇ ) ₃ P (O) O, POCl ₃ , SOCl
₂ , an organic base such as pyridine, 4- (dimethylamino) pyridine, triethylamine, N, N-dimethylaniline, or imidazole is added to a condensing agent such as ₂ , SiCl ₄ , (CH ₃ ) ₂ SiCl ₂ as necessary. Thereby, the reaction proceeds suitably. This reaction is preferably performed in an organic solvent, and hexane, tetrahydrofuran, dioxane, dimethoxyethane, benzene, toluene, pyridine, chloroform, dichloroethane, dimethylformamide, N,
N-dimethylacetamide, N, N-dimethylsulfoxide, N-methylpyrrolidone, hexamethylphosphoramide and the like are preferably used. Further, when the solubility of the polyamide obtained by this condensation reaction is low, the reaction suitably proceeds by adding an inorganic base such as calcium chloride, lithium chloride or lithium bromide. The reaction temperature in the condensation reaction is preferably in the range of usually room temperature to about 200 ° C.

The diamine compound represented by the general formula (XII) includes 1,4-phenylenediamine, 1,3-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, and 4,4 ′ -Diaminobiphenyl, 3,3'-dimethyl-4,4'-
Diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 2,2-bis (4-aminophenyl) propane, 4,4 '-Diaminodiphenyl sulfone, 4,
4'-diaminobenzophenone, 1,4-bis (4-aminophenyl) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) diphenylsulfone, 2,2 -Bis [4- (4-aminophenoxy) phenyl] propane, bis (4-aminocyclohexyl) methane, bis (4-aminophenyl) adipate, bis (3-aminophenyl) adipate, bis (4-aminophenyl) pimelate , Bis (4-aminophenyl) suberate, bis (4-aminophenyl) azelate, bis (4-aminophenyl) sebacate, ethylenediamine, 1,3-diaminopropane, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, hepta Methylene diamine, octamethylene diamine, nonamethylene diamine,
Decamethylenediamine and dodecamethylenediamine can be exemplified.

Specific examples of the dicarboxylic acid compound represented by the general formula (XIII) include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, and 2,6-anthracene dicarboxylic acid. Acid, 1,6-anthracenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid,
Oxalic acid, fumaric acid, maleic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid and 1,10-decanedicarboxylic acid Can be mentioned.

Further, the polyamide of the present invention is obtained by reacting the dicarboxylic acid compound represented by the general formula (XIII) with thionyl chloride, thionyl bromide or the like to form an acid halide, and then diamine compound of the present invention or It can also be produced by a polycondensation reaction with a mixture of the diamine compound of the present invention and the diamine compound represented by the general formula (XII). Since hydrogen halide is generated in this case, the reaction suitably proceeds when the reaction is carried out in the presence of an organic base such as triethylamine, N, N-dimethylaniline or pyridine as a scavenger.

In this case, it is preferable to carry out the reaction at a relatively low temperature of 0 ° C. to about room temperature in order to suppress a side reaction. These reactions are preferably performed in an organic solvent, and include hexane, tetrahydrofuran, dioxane, dimethoxyethane, benzene, toluene, pyridine, chloroform, dichloroethane, N, N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, Methyl phosphoramide and the like are preferably used. When the solubility of the obtained amide is low,
The reaction suitably proceeds by adding the same inorganic base as described above.

Further, the following monomers derived from the diamine compound of the present invention and the diamine compound represented by the above general formula (XII), that is, the following monomers represented by the following general formula (XIV)

[0056]

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(Wherein R ^{1 to} R ⁴ are alkyl or phenyl groups having 1 to 6 carbon atoms, X ¹ and X ² are ether bonds,
An ester bond or an amide bond, Y ³ is a triorganosilyl group, an acetyl group or a substituted acetyl group, and m is 2 to 2
It is an integer of 0. ) And the following general formula (XV)

[0058]

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Wherein A ³ is a divalent organic group constituting a diamine, Y ³ is a triorganosilyl group, an acetyl group or a substituted acetyl group, and a compound represented by the above general formula (XIII) Or a polycondensation reaction by mixing the dicarboxylic acid compound represented by the general formula (XII) with the dicarboxylic acid compound represented by the general formula (XIII). The following general formula (XVI) derived from the dicarboxylic acid compound represented by the formula:

[0060]

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(In the formula, A ¹ is a dicarboxylic acid 2
A valent organic group, Y ^4, is a lower alkyl group, a phenyl group or a substituted phenyl group. In the same manner as described above, the desired polyamide of the present invention can also be produced by mixing the compound represented by the formula (1) with the above and conducting a polycondensation reaction.

Here, the general formulas (XIV) and (XV)
Among the substituents represented by Y ³ , triorganosilyl groups include trimethylsilyl, triethylsilyl,
Examples of the phenyldimethylsilyl group and t-butyldimethylsilyl group include trifluoroacetyl group, bromoacetyl group, dibromoacetyl group, and phenylacetyl group.

On the other hand, among the substituents represented by Y ⁴ in the above general formula (XVI), lower alkyl groups include methyl, ethyl, propyl, iso-propyl, butyl, sec
A -butyl group, a t-butyl group, a pentyl group and a hexyl group; and the substituted phenyl group include a chlorophenyl group and a nitrophenyl group.

Formulas (XIV), (XV) and (XVI)
In the case of performing a polycondensation reaction using each of the monomer compounds represented by the above, the desired polyamide can be obtained by reacting in the presence of the above-described condensing agent in an organic solvent, if necessary. The desired polyamide of the present invention can be produced by mixing predetermined amounts of the respective monomers, adding a catalyst as needed, and raising the temperature to a temperature at which the monomers melt under normal pressure or reduced pressure. Examples of the catalyst used here include sulfuric acid, nitric acid, tosylic acid, lithium hydroxide, potassium hydroxide, sodium hydroxide, calcium hydroxide, aluminum chloride, tributylaluminum, titanium chloride, tributyltitanium, and lead acetate.

On the other hand, it is essential that the polyamic acid of the present invention contains at least 5 mol% of the diamine compound of the present invention represented by the general formula (XII), but its production method is particularly limited. Not something. In general, the following general formula (XVII)

[0066]

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(Wherein A ² is a tetravalent organic group constituting a tetracarboxylic acid). The molar ratio of tetracarboxylic dianhydride or its derivative represented by the following formula and diamine is 0.50.
The polyamic acid can be obtained by reaction polymerization in an organic solvent in the range of from 2.0 to 2.0, preferably from 0.9 to 1.10. The polymerization reaction temperature of the tetracarboxylic dianhydride or a derivative thereof and the diamine can be any temperature of -20 to 150C, but is particularly preferably in the range of -5 to 100C.

Specific examples of the organic solvent used in the polymerization reaction include N, N-dimethylformamide,
Examples thereof include N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylphosphoramide, butyllactone, and the like. These may be used alone or as a mixture. Further, even if the solvent does not dissolve the polyamic acid, the solvent may be used in addition to the above solvent within a range where a homogeneous solution can be obtained.

Specific examples of the tetracarboxylic dianhydride represented by the general formula (XVII) include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,2 5,6-anthracenetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 3,3 ′, 4,4'-
Benzophenonetetracarboxylic dianhydride, bis (3,
4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride,
2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis (3,4-dicarboxyphenyl) propane dianhydride Anhydride, bis (3,4-dicarboxyphenyl)
Dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, 2,3,5,6
-Pyridinetetracarboxylic dianhydride, 2,6-bis (3,4-dicarboxyphenoxy) pyridine dianhydride, cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride Anhydride and 3,4-dicarboxy 1,
2,3,4-tetrahydro-1-naphthalene succinic acid tetracarboxylic dianhydride and the like can be mentioned.

The derivatives of the tetracarboxylic dianhydride represented by the general formula (XVII) include tetracarboxylic acids, tetracarboxylic acid chlorides and tetracarboxylic acid esters.

It is essential that the polyamic acid of the present invention contains at least 5 mol% of the diamine compound of the present invention, and other diamine components are not particularly limited. Specific examples thereof include 1,4-phenylenediamine, 1,
3-phenylenediamine, 2,5-diaminotoluene,
2,6-diaminotoluene, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'- Diaminodiphenylmethane, 4,
4'-diaminodiphenyl ether, 2,2-bis (4
-Aminophenyl) propane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminobenzophenone,
1,4-bis (4-aminophenyl) benzene, 1,4
-Bis (4-aminophenoxy) benzene, 4,4'-
Bis (4-aminophenoxy) diphenyl sulfone,
2,2-bis [4- (4-aminophenoxy) phenyl] propane, bis (4-aminocyclohexyl) methane, bis (4-aminophenyl) adipate, bis (3
-Aminophenyl) adipate, bis (4-aminophenyl) pimelate, bis (4-aminophenyl) suberate, bis (4-aminophenyl) azeleate, bis (4-aminophenyl) sebacate, ethylenediamine, 1,3-diaminopropane , Tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, and the like.

Further, in order to convert the polyamic acid into a polyimide, a method of dehydration and ring closure by heating or a method of chemically dehydration and ring closure with a catalyst can be used. The heat dehydration ring closure temperature can be selected from any temperature of 150 to 450 ° C., preferably 170 to 350 ° C., and the time depends on the reaction temperature, but is 30 seconds to 10 hours, preferably 5 minutes to 5 hours. Time is appropriate. In the case of chemically dehydrating ring closure, a known method can be employed.

In the polyamide, polyamic acid and polyimide of the present invention obtained by the above-described production method, the molar ratio of the repeating units represented by the general formulas (II) and (III) is 10 mol% to 100 mol, respectively. It is preferable that it is in the range of mol% in terms of solubility and orientation of the polymer chain by rubbing. The polyamide and the polyamic acid of the present invention have a weight average molecular weight of at least 2,000, preferably 2,000 to 300,
000, more preferably 5,000 to 100,000, in terms of stability of liquid crystal alignment, workability, and the like. The molecular weight is measured by a known method such as gel permeation chromatography, osmotic pressure method, light scattering method, and viscosity method.

When the polyamide or polyamic acid of the present invention is used as a liquid crystal aligning agent, the polyamide solution, polyamic acid solution or polyimide solution obtained by the above condensation reaction can be used as it is. Also,
Once the polyamide, polyamic acid or polyimide is isolated from the obtained polyamide solution, polyamic acid solution or polyimide solution, it can be used by redissolving it in an appropriate solvent. The solvent to be re-dissolved is not particularly limited as long as it dissolves the obtained polyamide, polyamic acid or polyimide.
N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, hexamethylphosphoramide, γ-butyrolactone, tetrahydrofuran, pyridine, chloroform, dichloromethane, chlorobenzene, dichlorobenzene, phenol, p-chloro Phenol, anisole, cresol and the like. Further, in this case, a part of the polyamic acid is converted to a polyimide to prepare a mixed solution of the polyamic acid and the polyimide, which can be used as a liquid crystal alignment treatment agent.

For the purpose of improving the coating property on the substrate, a solvent which does not dissolve the polyamide or the polyamic acid alone may be added to the above solvent as long as the solubility is not impaired. Examples thereof include butyl cellosolve, ethyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, toluene and xylene. Further, additives such as a silane coupling agent can be used as appropriate for the purpose of increasing the adhesion to the substrate.

In preparing a liquid crystal alignment film from the liquid crystal alignment treatment agent of the present invention obtained as described above, the polyamide solution, polyamic acid solution or polyimide acid solution obtained as described above is spin-coated. In general, a polyamide film, a polyamic acid film, and a polyimide film are formed by applying the film onto a substrate such as a glass, a wafer, or a plastic using a method such as a transfer printing method, and subjecting the resultant to a heat treatment. The heat treatment temperature is 50 ° C to 4 ° C.
Any temperature of 50 ° C., preferably 80 ° C. to 350 ° C. can be selected. In the case of forming a liquid crystal alignment film for obtaining the effect of the present invention, in the case of polyamide, generally 80 ° C. to 200 ° C. Relatively low heating temperatures can be employed. Although the thickness of the coating film is not particularly limited, it is suitably set in the range of 100 to 3000 ° for use as a normal liquid crystal alignment film. Next, this coating film is subjected to an alignment treatment such as a rubbing treatment, and can be used as a liquid crystal alignment film.

The rubbing treatment can be performed by bringing a roller wrapped with a cloth of cotton, nylon, polyester or the like into contact with the substrate at a constant pressing pressure, and further moving the roller or the substrate at a constant speed. At this time, the rollers are generally rotated, but need not be rotated. It has been reported that the rubbing strength is represented by a rubbing degree (mm) defined by the following equation.

[0078]

L = N · M {(2πrn / 60V) −1} (1)

In the equation (1), N is the number of rubbings, M is the pushing amount (mm), and r is the radius of the rubbing roller (m).
m) and n are roller rotation speeds (rpm), and V is a stage moving speed (mm / sec). The rubbing degree that can be used in the present invention is not particularly limited, but is preferably 500 mm or less from the viewpoint of the adhesion of the coating film.

It is known that the rubbing treatment causes the polymer chains to be oriented in the rubbing direction. The effect of the orientation of the polymer chains is generally due to the birefringence of the coating film induced after the rubbing treatment. It can be evaluated by measuring the phase difference and the deviation angle between the rubbing direction and the slow axis.

The birefringence retardation depends on the refractive index anisotropy of the polymer unit structure, the rubbing degree, the film thickness in which anisotropic orientation is induced, and the like. It is considered that the polymer chains tend to be oriented, and furthermore, the deviation angle between the slow axis and the rubbing direction is such that the smaller the size, the higher the uniformity of orientation of the polymer chains in the rubbing direction. Conceivable. In order to obtain the effect of the present invention, the magnitude of the birefringence phase difference, the rubbing degree is 10 to 100 mm
When the rubbing degree is 100 mm or more, it is preferably 1.0 nm or more, and the misalignment angle between the rubbing direction and the slow axis is 1.0 ° or less, more preferably 0.5 ° or less. is there.

As described above, by using the liquid crystal alignment film in which the polymer chains are uniformly aligned in one direction by rubbing, the liquid crystal molecules can be uniformly aligned and the liquid crystal element of the present invention can be adjusted. As the liquid crystal, a ferroelectric liquid crystal or an antiferroelectric liquid crystal can be used in addition to a commonly used nematic liquid crystal. Hereinafter, the present invention will be described in more detail by reference examples, examples, and comparative examples. However, it goes without saying that the present invention is not limited to these.

[0083]

[Example] Reference Example 1

[0084]

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Under an argon atmosphere, di (cyanophenyl)
5 mg of platinum dichloride was dispersed in 20 ml of dry tetrahydrofuran (hereinafter abbreviated as THF),
2.00 ml of 4-bis (dimethylsilyl) benzene
(8.97 mmol) and 4.00 ml (18.0 mmol) of methyl 10-undecanoate were added, and the mixture was stirred at 60 ° C. for 12 hours. After distilling off the solvent, silica gel column chromatography (developing solvent: diethyl ether /
After purification by hexane = 1/10 vol.), 3.19 g of the compound represented by the above structural formula (1) was obtained as a white solid (yield: 60.2%). The structure is ¹ H-
Confirmed by NMR and IR spectra.

¹ H-NMR δ (CDCl ₃ , ppm): 0.24 (s, 12H), 1.1-1.
4 (m, 32H), 2.30 (t, 4H), 3.66 (s, 6H), 7.47 (s, 4H) .IRν (KBr disk, cm ^-1 ): 3059 (w), 2919 (s), 2851 ( m), 1740
(s, C = O), 1470 (m), 1431 (m), 1381 (w), 1312 (w), 1252 (m, Si-
C), 1186 (m), 1171 (m), 1136 (m), 876 (m), 841 (m), 829 (m), 80
2 (m), 781 (m), 766 (m), 710 (w), 671 (w), 503 (w), 467 (w). 3.11 g (5.26 mmol) of compound (1) in 10 ml of methanol Then, 0.5 g (12.5 mmol) of sodium hydroxide and 1 ml of water were added thereto, and the mixture was stirred at reflux temperature. After about 1 hour, a precipitate was formed and the solution was solidified, and 5 ml of water was added. After stirring at reflux temperature for 3 hours, the solution was poured into 100 ml of water. Next, a 1N aqueous hydrochloric acid solution was added, and the mixture was stirred at room temperature for 2 hours. The resulting white precipitate was collected by filtration, washed sufficiently with water, and dried. The obtained crude product is subjected to silica gel column chromatography (developing solvent: chloroform / methanol = 100 / 1vo).
l.), 2.26 g of the compound represented by the above structural formula (2) was obtained as a white powder (yield: 76.
3%). The structure was confirmed by ¹ H-NMR and IR spectra.

¹ H-NMR δ (CDCl ₃ , ppm): 0.21 (s, 12H), 0.70
(m, 4H), 1.16-1.30 (m, 28H), 1.47 (m, 4H), 2.17 (t, 4H, J = 7.4
Hz), 7.46 (s, 4H), 11.93 (bs, 2H) .IRν (KBr disk, cm ^-1 ): 3046 (w), 2920 (s), 2853 (m), 2683
(b, acid OH), 1715 (s, C = O), 1470 (w), 1427 (w), 1408 (w), 13
14 (w), 1287 (w), 1252 (m, Si-C), 1225 (w), 1198 (w), 1134
(w), 939 (w), 878 (w), 837 (m), 797 (w), 666 (w), 502 (w).

[0088]

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Under an argon atmosphere, 0.300 g (0.533 mmol) of the compound (2) obtained in Reference Example 1, 0.148 g (1.066 mmol) of p-nitrophenol,
0.280 g of triphenylphosphine (1.066 mm
ol) was dissolved in 10 ml of dry THF and cooled to 0 ° C. To this solution is added diethyl azodicarboxylate 0.1.
168 ml (1.066 mmol) was added dropwise, and the mixture was returned to room temperature and stirred for 3 hours. After evaporating the solvent, the residue was purified by silica gel column chromatography (developing solvent: diethyl ether / hexane = 1/10 vol.) To obtain 0.260 g of a compound represented by the above structural formula (3) as a white solid. (Yield: 60.6%). The structure is ¹
Confirmed by 1 H-NMR and IR spectrum.

¹ H-NMR δ (CDCl ₃ , ppm): 0.24 (s, 12H), 0.74
(m, 4H), 1.20-1.40 (m, 28H), 1.75 (m, 4H), 2.59 (t, 4H, J = 7.5
Hz), 7.27 (d, 4H, J = 9.0Hz), 7.48 (s, 4H), 8.26 (d, 4H, J = 9.0H
z) .IRν (KBr disk, cm ^-1 ): 2924 (s), 2854 (s), 1768 (s, C = O), 16
14 (w), 1593 (m), 1525 (m), 1491 (m), 1346 (m), 1248 (m, Si-
C), 1209 (s), 1134 (s), 1111 (s), 837 (m).

1.78 g (2.21 mmol) of the dinitro compound (3) obtained by the above method was added to 40 m of THF.
and ethanol in a mixed solvent of 10 ml. To this, 0.25 g of 5% Pd-carbon powder was added. The solution was cooled to −78 ° C., degassed under reduced pressure, replaced with hydrogen gas, and then stirred in a hydrogen gas atmosphere at room temperature for 12 hours. Next, the reaction solution was filtered through celite, the filtrate was concentrated, and then purified by silica gel column chromatography (developing solvent: chloroform / ethyl acetate = 40/1 vol.), Which was represented by the above structural formula (4). Compound 1.
60 g was obtained as a light brown solid (yield: 96.6%).
In addition, the structure is ¹ H-NMR and IR spectrum,
And elemental analysis.

¹ H-NMR δ (CDCl ₃ , ppm): 0.24 (s, 12H), 0.73
(m, 4H), 1.20-1.40 (m, 28H), 1.72 (m, 4H), 2.50 (t, 4H, J = 7.0
Hz), 3.40 (bs, 4H), 6.65 (d, 4H, J = 8.8 Hz), 6.85 (d, 4H, J = 8.8
Hz), 7.48 (s, 4H) .IRν (KBr disk, cm ^-1 ): 3400 (w, NH), 3320 (w, NH), 2935
(w), 2895 (w), 1768 (s, C = O), 1630 (w), 1614 (w), 1595 (m), 15
10 (m), 1470 (m), 1340 (m), 1248 (m, Si-C), 1200 (s), 1134
. (s), 1112 (s ), 835 (m), 790 (m), 775 (w) Elemental analysis (molecular _{formula: C 44 H 68 N 2 O} 4 Si 2, molecular weight: 745.2
0): Elemental analysis result: Calculated value; C: 70.91%, H: 9.22%, N: 3.76%. Observed value: C: 70.63%, H: 8.96%, N: 3.66%.

[0093]

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Under an argon atmosphere, 1.00 g (1.34 mmol) of the diamine compound (4) obtained in Example 1 was treated with N-methylpyrrolidone (hereinafter abbreviated as NMP) 1.34.
and cooled to -78 ° C. To this solution was added adipic acid chloride (0.20 ml, 1.
The reaction temperature was gradually raised to room temperature by adding an NMP solution of 34 mmol), and the mixture was further stirred at room temperature for 18 hours. Next, NMP was added to the reaction solution to dilute it twice, and then the solution was poured into 500 ml of methanol with stirring. The resulting precipitate was collected by filtration, dried under reduced pressure at 60 ° C. overnight,
0.84 g of the polyamide represented by A-1 was obtained. The number-average molecular weight and weight-average molecular weight of PA-1 determined by gel permeation chromatography were 3.5, respectively.
They were 1 × 10 ³ and 6.13 × 10 ³ . FIG. 1 shows the IR spectrum of PA-1. Example 3

[0095]

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The diamine compound (4) obtained in Example 1
10.0 g (13.4 mmol) and 2.57 g of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (1
3.1 mmol) in 71.2 g of NMP at room temperature
The reaction was carried out for a time to obtain a polyamic acid PAA-1. PAA-1 determined by gel permeation chromatography
Has a number average molecular weight and a weight average molecular weight of 2.5
They were 0 × 10 ⁴ and 5.34 × 10 ⁴ . PAA-1
Is shown in FIG. Example 4

[0097]

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The diamine compound (4) obtained in Example 1
10.0 g (13.4 mmol) and 2.86 g (13.1 mmol) of pyromellitic dianhydride were added to NMP 72.9.
g for 10 hours at room temperature.
-2 was obtained. The number average molecular weight and weight average molecular weight of PAA-2 determined by gel permeation chromatography were 2.44 × 10 ⁴ and 4.22 × 10 ⁴ , respectively. FIG. 3 shows the IR spectrum of PAA-2. Reference example 2

[0099]

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8.00 g of 4-nitrophenol (57.
5 mmol), 5.0 ml of 3-bromopropene (59 m
mol) and potassium carbonate 7.95 g (57.5 mm
ol) were dispersed in 50 ml of acetone, and 14
Stirred for hours. After filtering the generated salt, ethanol /
Recrystallization purification was performed at -20 ° C using hexane mixed solvent.
Then, 150 ml of toluene was further added and distilled off under reduced pressure.
Excess 3-bromopropene was removed. As a result, the above structure
4. 4-allyloxynitrobenzene represented by the formula (5)
86 g was obtained as a light brown liquid (yield: 56.9%).
The structure is ¹Confirmed by H-NMR spectrum
Was.¹ H-NMRδ (CDCl_Three, ppm): 4.64 (d, 2H), 5.40 (m, 2H), 6.10 (m, 1
H), 6.97 (d, 2H), 8.20 (d, 2H).

[0101]

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Under an argon atmosphere, 3.181 g (16.36 mmol) of 1,4-bis (dimethylsilyl) benzene and 5.864 g of the compound (5) obtained in Reference Example 2 (3
2.73 mmol) was dissolved in 10 ml of THF, and 0.2 ml of a 30% by weight xylene solution of a platinum-1,3-divinyltetramethyldisiloxane complex was added to this solution.
For 4 hours. After distilling off the solvent, silica gel column chromatography (developing solvent: diethyl ether /
After purification by hexane = 1/4 vol.), 7.138 g of the compound represented by the above structural formula (6) was obtained as a pale yellow solid (yield: 78.9%). The structure is ¹ H
-Confirmed by NMR and IR spectra.

¹ H-NMRδ (CDCl3, ppm): 0.31 (s, 12H), 0.90
(m, 4H), 1.90 (m, 4H), 3.97 (t, 4H), 6.88 (d, 4H), 7.50 (s, 4
H), 8.17 (d, 4H) .IRν (KBr disk, cm ^-1 ): 3086 (w), 3044 (w), 2938 (m), 2880
(w), 1607 (m), 1591 (s), 1507 (s), 1331 (s), 1265 (s), 1250
(s), 1177 (m), 1111 (m), 891 (m), 847 (m), 802 (m), 772 (m), 75
4 (m), 656 (m), 505 (m).

6.542 g (11.83 mmol) of the dinitro compound (6) obtained by the above method was added to THF 6
It was dissolved in a mixed solvent of 0 ml and ethanol 60 ml. To this, 0.25 g of 5% Pd-carbon powder was added. The solution was cooled to −78 ° C., degassed under reduced pressure, replaced with hydrogen gas, and then stirred in a hydrogen gas atmosphere at room temperature for 12 hours. Next, the reaction solution was filtered through Celite, the filtrate was concentrated, and then purified by silica gel column chromatography (developing solvent: diethyl ether).
5.82 g of the compound represented by the above structural formula (7) was obtained as an orange solid (yield: 99.9%). The structure is
^It was confirmed by ¹ H-NMR and IR spectra, and elemental analysis.

¹ H-NMR δ (CDCl ₃ , ppm): 0.29 (s, 12H), 0.85
(m, 4H), 1.77 (m, 4H), 3.82 (t, 4H, J = 6.8Hz), 6.62 (t, 4H, J =
8.8Hz), 6.70 (d, 4H, J = 8.8Hz), 7.50 (s, 4H) .IRν (KBr disk, cm ^-1 ): 3399 (w, NH), 3322 (w, NH), 2944
(w), 2897 (w), 1626 (w), 1512 (s), 1472 (m), 1331 (s), 1236
(s), 1177 (w), 1134 (m), 1019 (m), 841 (m), 791 (m), 774 (m), 5
01 (w). Elemental analysis result (molecular formula: C ₂₈ H ₄₀ N ₂ O ₂ Si ₂ , molecular weight: 492.8)
1): Calculated value; C: 68.24%, H: 8.18%, N: 5.68%. Actual value: C: 68.28%, H: 8.51%, N: 5.28%.

[0106]

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In an argon atmosphere, 0.600 g (1.218 mmol) of the diamine compound (7) obtained in Example 5 was obtained.
l) was dissolved in 2.0 ml of dry NMP and cooled to -78 ° C. To this solution was added an NMP solution of adipic acid chloride (0.177 ml, 1.218 mmol) adjusted to the same concentration, the reaction temperature was gradually raised to room temperature, and the mixture was further stirred at room temperature for 18 hours. Next, NMP was added to the reaction solution to dilute it twice, and then the solution was poured into 500 ml of methanol with stirring. The resulting precipitate was collected by filtration and dried under reduced pressure at 60 ° C. overnight to obtain 0.55 g of a polyamide represented by the above structural formula PA-2. The number average molecular weight and the weight average molecular weight of PA-2 determined by gel permeation chromatography were 6.58 × 10 ³ and 1.41 ×, respectively.
It was 10 ⁴ . FIG. 4 shows the IR spectrum of PA-2. Example 7

[0108]

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The diamine compound (7) obtained in Example 5
10.0 g (20.3 mmol) and 4.34 g (19.9 mmol) of pyromellitic dianhydride were added to NMP81.3.
g for 10 hours at room temperature.
-4 was obtained. The number average molecular weight and weight average molecular weight of PAA-3 determined by gel permeation chromatography were 3.82 × 10 ⁴ and 6.34 × 10 ⁴ , respectively. FIG. 5 shows the IR spectrum of PAA-3.

Examples 8 to 9 Polyamide PAs obtained in Examples 2 and 6
1. PA-2 was converted to NMP and butyl cellosolve (hereinafter referred to as BC
), And the mixture was stirred at room temperature to obtain a colorless and transparent solution. This solution did not show any precipitation or change in viscosity even after storage at 23 ° C. for 5 months.

This solution was spin-coated on a glass substrate, dried at 80 ° C. for 5 minutes, and then subjected to heat treatment at 180 ° C. for 1 hour. I got it.

The obtained spin-coated film was subjected to a rubbing treatment using a rayon cloth under the conditions shown in Table 1, and the uniformity of the orientation of the polymer chains was measured by a high-sensitivity automatic birefringence measuring device manufactured by Oak Manufacturing Co., Ltd. (Hereinafter abbreviated as Δnd) and the deviation between the slow axis and the rubbing direction were evaluated at nine different points on the substrate. Table 2 shows Δnd and the shift angle of the slow axis with respect to the rubbing degree. At any rubbing degree, a large Δnd was obtained, and the deviation angle of the slow axis (average absolute value) was extremely small, so that it was confirmed that the alignment uniformity of the polymer chains in the rubbing direction was high. Was.

[0113]

[Table 1] Table 1 Rubbing conditions ─────────────────────────────── Rubbing conditions Roller Stage movement Pressing amount (Rubbing degree: mm) Number of rotations (rpm) Speed (mm / sec) (mm) 条件 Condition 1 ( 46.6) 300 20 0.5 Condition 2 (114.6) 500 15 0.55 Condition 3 (263.2) 700 10 0.6 ───────────────────────────── ──

[0114]

[Table 2] Table 2 Size of birefringence phase difference and shift angle of slow axis from rubbing direction ─────────────────────────── ──────── Example Rubbing degree Δnd (nm) Slow axis shift angle (°) (Polyamito) (mm) Maximum value Minimum value Average value Maximum value Minimum value Average value ─────── ──────────────────────────── Example 8 46.6 3.51 2.59 3.17 0.2 -0.2 0.1 (PA-1) 114.6 4.31 3.44 3.93 0.2- 0.2 0.1 263.2 5.25 4.41 4.98 0.3 -0.2 0.1 例 Example 9 46.6 1.56 1.04 1.28 1.3 -0.9 0.4 (PA-2) 114.6 1.96 1.24 1.62 0.4 -0.6 0.3 263.2 2.35 1.51 1.99 0.7 -0.5 0.2 ─────────────────────── ────────────

Further, the rubbed polyamide film-coated substrate was combined with a 50 μm spacer so that the rubbing directions were antiparallel, and then a liquid crystal (Merck ZLI-2293) was injected to prepare a liquid crystal cell. . When the alignment state of the liquid crystal in these liquid crystal cells was observed with a polarizing microscope, no defect was observed, and it was confirmed that uniform liquid crystal alignment was obtained. Also,
When the tilt orientation angle was measured by the crystal rotation method, PA-
1 and PA-2 were 0.7 ° and 0.4 °, respectively, and it was confirmed that a uniform tilt orientation angle was obtained in both polyamide films.

Examples 10 to 12 The polyamic acid solutions PAA1 to PAA3 obtained in Examples 3, 4 and 7 were mixed with NMP and BC in a mixed solvent (weight ratio of 4: 1) to give a solid content of 5% by weight. Dilution. These solutions were spin-coated on a glass substrate,
After drying at 0 ° C. for 5 minutes, heat treatment was performed at 250 ° C. for 1 hour to convert to polyimides PI-1 to PI-3, thereby obtaining a uniform polyimide film having a thickness of 1000 °. Polyimide P
6 to 8 show IR spectra of I-1 to PI-3.

Using the rayon cloth, Δnd and the shift between the slow axis and the rubbing direction of the obtained spin-coated film were evaluated at nine different points on the substrate in the same manner as in Example 8. Table 3 shows Δnd and the shift angle of the slow axis with respect to the rubbing degree. At any rubbing degree, a large Δnd was obtained, and the deviation angle of the slow axis (average absolute value) was extremely small, so that it was confirmed that the alignment uniformity of the polymer chains in the rubbing direction was high. Was.

[0118]

[Table 3] Table 3 Size of birefringence phase difference and shift angle of slow axis from rubbing direction ─────────────────────────── ──────── Example Rubbing degree Δnd (nm) Slow axis shift angle (°) (Polyamito) (mm) Maximum value Minimum value Average value Maximum value Minimum value Average value ─────── ──────────────────────────── Example 10 46.6 1.39 0.82 1.17 1.5 -1.5 0.6 (PI-1) 114.6 2.18 1.48 1.90 0.7- 0.5 0.3 263.2 2.14 1.65 1.85 0.7 -0.8 0.4 例 Example 11 46.6 2.29 1.80 1.99 0.3 -0.3 0.1 (PI-2) 114.6 2.97 1.81 2.36 0.2 -0.3 0.1 263.2 3.40 2.15 2.63 0.1 -0.2 0.1 ─────────────────────── ──────────── Example 12 46.6 2.39 1.63 1.98 0.4 -0.2 0 .1 (PI-3) 114.6 2.72 2.00 2.35 0.2 -0.2 0.1 263.2 2.38 1.80 2.14 0.2 -0.2 0.1 ─────────────────────────── ────────

Further, injection was performed in the same manner as in Example 8 to fabricate liquid crystal cells, and the alignment state of the liquid crystal in these liquid crystal cells was observed with a polarizing microscope. Was obtained. When the tilt orientation angle was measured by the crystal rotation method, each of PI-1, PI-2, and PI-3 was 2.0 °,
It was 1.9 ° and 3.8 °, and it was confirmed that a uniform tilt orientation angle was obtained in both polyimide films.

Comparative Example 1 Polyamide PA-3 obtained by using bis (4-aminophenyl) adipate instead of the silphenylene-containing diamine of polyamide PA-1 obtained in Example 2 was polymerized by the following method.

That is, 2.261 g (6.884 mmol) of bis (4-aminophenyl) adipate was weighed,
After making a 1 mol / l NMP solution, the solution was cooled to -78 ° C with stirring under an argon atmosphere and solidified.
Here, 1.000 ml (6.884 m) of adipic acid chloride in an equimolar amount to bis (4-aminophenyl) adipate was added.
mol) was added, and the reaction temperature was slowly raised to room temperature. Stirring was resumed with the temperature rise, and after 30 minutes, halved with NMP.
Diluted to molarity. The reaction solution was poured into about 100 times the amount of methanol with stirring, and the resulting fibrous precipitate was collected by filtration, dried at 60 ° C. under reduced pressure overnight, and treated with polyamide PA-3.
2.881 g was obtained.

The number-average molecular weight and weight-average molecular weight of the obtained PA-3 were measured by gel permeation chromatography and found to be 5.11 × 10 ³ , respectively.
8.97 × 10 ⁴ . This PA-3 was mixed with a mixed solvent of NMP and BC (weight ratio 4: 1) at a solid content of 5 watts.
The mixture was stirred at room temperature so as to obtain a t%, but did not dissolve in this mixed solvent.

Comparative Example 2 Equimolar amounts of isophthalic acid chloride and diaminodiphenyl ether were placed in a nitrogen stream at −78 ° C. in NMP (concentration: 1 mol).
(l / l) and stirred at room temperature. This solution was poured into methanol with stirring, and the resulting precipitate was separated by filtration and dried. This operation was repeated to obtain a polyamide powder PA-4. When the number average molecular weight and weight average molecular weight of the obtained polyamide were measured by gel permeation chromatography, each was 1.40 × 10
⁴ , 2.90 × 10 ⁴ .

PA-4 was dissolved in a mixed solvent of NMP and BC (weight ratio: 4: 1) so as to have a solid content of 5 wt%. This solution is spin-coated on a glass substrate,
For 5 minutes and then at 180 ° C. for 60 minutes to produce a uniform polyamide film having a thickness of 1000 °.

With respect to Δnd and the deviation angle between the slow axis and the rubbing direction when the polyamide film was subjected to the rubbing treatment,
Table 4 shows the measurement results obtained by changing the rubbing degree in the same manner as in Example 8. Since Δnd was small and the shift angle of the slow axis (average absolute value) was large at any rubbing degree, it was found that the uniformity of orientation of the polymer chains in the rubbing direction was low.

[0126]

[Table 4] Table 4 Size of birefringence phase difference and shift angle of slow axis from rubbing direction ─────────────────────────── ──── Degree of rubbing Δnd (nm) Deviation angle of slow axis (°) (mm) Maximum value Minimum value Average value Maximum value Minimum value Average value ──────────────── ─────────────── 46.6 0.45 0.38 0.42 1.8 -3.0 1.9 149.1 1.03 0.81 0.95 -0.6 -0.9 0.8 307.0 1.06 0.69 0.94 -0.5 -1.0 0.7 ───────── ──────────────────────

Comparative Example 3 Pyromellitic dianhydride and diaminodiphenyl ether were reacted in NMP to polymerize a polyimide precursor PAA-4. This solution was diluted with a mixed solvent of NMP and BC (weight ratio: 4: 1) to prepare a solution having a solid content of 5% by weight. When the number average molecular weight and weight average molecular weight of the obtained polyamic acid were measured by gel permeation chromatography, they were 1.97 × 10 ⁴ and 9.6, respectively.
It was 2 × 10 ⁴ . This PAA-4 solution was spin-coated on a glass substrate and dried at 120 ° C. for 5 minutes.
Heat treatment was performed at 250 ° C. for 1 hour to convert the polyimide into PI-4, thereby obtaining a uniform polyimide film having a thickness of 1000 °.

Regarding Δnd and the deviation angle between the slow axis and the rubbing direction when the polyimide film was subjected to the rubbing treatment,
Table 5 shows the measurement results obtained by changing the rubbing degree in the same manner as in Example 8. Since Δnd was small and the shift angle of the slow axis (average absolute value) was large at any rubbing degree, it was found that the uniformity of orientation of the polymer chains in the rubbing direction was low.

[0129]

[Table 5] Table 5 Size of birefringence phase difference and deviation angle of slow axis from rubbing direction ─────────────────────────── ──── Degree of rubbing Δnd (nm) Deviation angle of slow axis (°) (mm) Maximum value Minimum value Average value Maximum value Minimum value Average value ──────────────── ─────────────── 37.3 0.39 0.24 0.30 -0.2 -1.8 1.1 74.6 0.79 0.54 0.60 0.0 -2.2 1.2 307.0 0.79 0.49 0.64 -0.1 -2.0 1.0 ───────── ──────────────────────

[0130]

The polyamide using the diamine compound having a silphenylene residue of the present invention has excellent solubility in a solvent and can be fired at a low temperature during film formation. The liquid crystal alignment film using the polyamide is obtained by rubbing. It has excellent polymer chain alignment and shows uniform liquid crystal alignment. Also, the polyamic acid and / or polyimide using the diamine of the present invention is excellent in the alignment of the polymer chains by rubbing, and exhibits the same liquid crystal alignment as the polyamide.

[Brief description of the drawings]

FIG. 1 shows IR of polyamide PA-1 obtained in Example 2.
Spectrum.

FIG. 2 shows I of polyamide PAA-1 obtained in Example 3.
R spectrum.

FIG. 3 shows I of polyamide PAA-2 obtained in Example 4.
R spectrum.

FIG. 4 shows IR of polyamide PA-2 obtained in Example 6.
Spectrum.

FIG. 5 shows I of polyamide PAA-3 obtained in Example 7.
R spectrum.

FIG. 6 shows I of polyamide PI-1 obtained in Example 10.
R spectrum.

FIG. 7 shows I of polyamide PI-2 obtained in Example 11.
R spectrum.

FIG. 8 shows I of polyamide PI-3 obtained in Example 12.
R spectrum.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takayasu Nihira 722-1, Tsuboi-cho, Funabashi-shi, Chiba Nissan Chemical Industry Co., Ltd. (72) Inventor Hiroshi Nagase 1-9-2 Minamidai, Sagamihara City, Kanagawa Prefecture (72) Eiichi Akiyama 2786-4-211 Tsuruma, Yamato City, Kanagawa Prefecture F-term (reference) 2H090 HB08Y HB09Y HC05 HC20 HD14 JB13 KA05 KA08 KA14 KA15 MB01 4H049 VN01 VP02 VP10 VQ35 VQ37 VQ77 VR24 VU24 VU25 VW02 4J001 DA01 DB01 DB04 DC03 DC05 DC06 DC10 DC14 DC15 EC02 EB02 EB04 EB04 EB05 EB06 EB07 EB07 EB07 EB07 EB07 EB07 EB08 EC54 EC65 EC66 EC67 EC68 EC70 EC75 EE27A GA13 JA17 JA20 JB01 JB50 JC08 4J043 PA02 PA04 PC145 PC146 QB26 QB31 RA34 SA05 SB02 TA14 TA22 TB01 UA022 UA032 UA042 UA122 UA132 UA141 UA252 UA262 UA362 UB011 UB022 UB121 UB122 UB152 UB161 UB221 UB321 ZA09 ZB23

Claims (8)

[Claims] 1. A compound represented by the following general formula (I) (Wherein, R ^{1 to} R ⁴ are an alkyl group or a phenyl group having 1 to 6 carbon atoms, X ¹ and X ² are an ether bond, an ester bond or an amide bond, and m is an integer of 2 to 20). Diamine compound having a silphenylene residue. 2. The following general formula (II): (Wherein, R ^{1 to} R ⁴ are an alkyl group or phenyl group having 1 to 6 carbon atoms, X ¹ and X ² are an ether bond, an ester bond or an amide bond, and A ¹ is a divalent organic group constituting a dicarboxylic acid , M is an integer of 2 to 20), and has a weight average molecular weight of 2,000 or more. 3. The following general formula (III): In the formula, R ^{1 to} R ⁴ are an alkyl group or a phenyl group having 1 to 6 carbon atoms, A ² is a tetravalent organic group constituting a tetracarboxylic acid, and m is an integer of 2 to 20. A) a polyamic acid containing at least 5 mol% of the repeating unit represented by the formula (1) and having a weight average molecular weight of at least 2,000. 4. A polyimide derived from a polyamic acid containing at least 5 mol% of the repeating unit represented by the general formula (III) and having a weight average molecular weight of at least 2,000. 5. A polyamide solution according to claim 2, wherein the liquid crystal alignment treatment agent is used for forming a liquid crystal alignment film formed by applying, baking, and rubbing a substrate with a transparent electrode. A liquid crystal alignment treatment agent, characterized in that: 6. A liquid crystal device comprising a liquid crystal alignment film formed using the liquid crystal alignment treatment agent according to claim 5. 7. The polyamic acid according to claim 3, wherein the liquid crystal alignment treatment agent is used for forming a liquid crystal alignment film, which is formed by rubbing after coating and baking on a substrate with a transparent electrode. 5. A liquid crystal alignment treating agent, which is a solution and / or the polyimide solution according to claim 4, which is derived from the polyamic acid. 8. A liquid crystal device comprising a liquid crystal alignment film formed using the liquid crystal alignment treatment agent according to claim 7.