KR102073458B1 - Diamine compound, polyamic acid, polyimide, and liquid crystal aligning agent - Google Patents

Abstract

(식 중, X¹ 은 -CO- 또는 -CONH- 를 나타내고, X² 는 탄소수 1 ∼ 5 의 알킬렌기 또는 질소 원자를 함유하는 비방향족 복소 고리를 나타내고, X³ 은 탄소수 1 ∼ 5 의 알킬기로 치환되어 있어도 되는, 질소 원자를 2 개 함유하는 5 원자 고리 또는 6 원자 고리의 방향족 복소 고리를 나타낸다)It is used as a raw material of polyamic acid and / or polyimide which comprises a liquid-crystal aligning agent which can obtain a liquid crystal aligning film which has a high voltage retention and quick relaxation of the residual electric charge accumulate | stored by a direct current voltage, even after long time exposure to high temperature. Possible novel diamine compounds are provided.
The liquid-crystal aligning agent containing the novel diamine compound shown by Formula [1], and the polyamic acid and / or polyimide obtained using this diamine compound.
[Formula 1]

(In formula, X <^1> represents -CO- or -CONH-, X <^2> represents the C1-5 alkylene group or the non-aromatic heterocycle containing a nitrogen atom, X <^3> represents a C1-C5 alkyl group A 5-membered ring or a 6-membered aromatic heterocyclic ring containing two nitrogen atoms which may be substituted)

Description

Diamine compound, polyamic acid, polyimide and liquid crystal aligning agent {DIAMINE COMPOUND, POLYAMIC ACID, POLYIMIDE, AND LIQUID CRYSTAL ALIGNING AGENT}

This invention relates to the novel diamine compound useful as a raw material of the polymer used for a liquid crystal aligning film, the polyamic acid and polyimide obtained using it, and a liquid-crystal aligning agent. Furthermore, it is related with the liquid crystal display element which has a liquid crystal aligning film obtained from the said liquid-crystal aligning agent.

Currently, as a liquid crystal aligning film of a liquid crystal display element, what is called poly which baked and apply | coated and baked the liquid-crystal aligning agent (also called liquid crystal aligning agent) which uses the solution of polyimide precursors, such as polyamic acid, and soluble polyimide as a main component, etc. in a glass substrate. The mid type liquid crystal aligning film is mainly used.

A liquid crystal aligning film is used for the purpose of controlling the alignment state of a liquid crystal. However, with high definition of the liquid crystal display element, there is a high voltage retention even in the liquid crystal aligning film to be used, or the residual when the direct current voltage is applied to the liquid crystal aligning film to be used from the request such as suppression of contrast reduction of the liquid crystal display element or reduction of afterimage phenomenon. It has become increasingly important that the characteristics of low charge and / or rapid relaxation of residual charge accumulated by DC voltage are fast.

In the liquid crystal aligning film of a polyimide system, the time until the afterimage generated by DC voltage disappears is short, and the liquid crystal aligning agent containing the tertiary amine of a specific structure is added to a polyamic acid or an imide group containing polyamic acid. The thing used (for example, refer patent document 1), the thing using the liquid crystal aligning agent containing the soluble polyimide which used the specific diamine compound which has a pyridine skeleton etc. as a raw material (for example, refer patent document 2), etc. are known. . In addition, the voltage retention is high, and the time until the afterimage generated by the direct current voltage disappears is short, and in addition to the polyamic acid or the imidized polymer, the compound containing one carboxylic acid group in the molecule, one in the molecule It is known to use a liquid crystal aligning agent containing a very small amount of a compound containing a carboxylic acid anhydride group and a compound selected from a compound containing one tertiary amine group in a molecule (see Patent Document 3, for example).

However, in recent years, large-screen and high-definition liquid crystal televisions have been widely put to practical use, and the liquid crystal display device in such a use has a higher demand for afterimages than the display use mainly displaying characters and still images. There is a demand for properties that are strict and that can withstand long-term use in harsh use environments. Therefore, the liquid crystal aligning film used needs to be more reliable than the conventional one, and also the electrical property of a liquid crystal aligning film is not only favorable in initial stage property but it is calculated | required to maintain a favorable characteristic even after exposing for a long time under high temperature, for example. have.

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

An object of the present invention is to provide a polyamic acid and / or a polyamic acid that forms a liquid crystal alignment treatment agent capable of obtaining a liquid crystal alignment film that has a high voltage retention and has a rapid relaxation of residual charge accumulated by DC voltage even after long time exposure at high temperature. It is providing the diamine compound which can be used as a raw material of a mead (henceforth a polymer).

Moreover, the objective of this invention is a liquid-crystal aligning agent which can obtain the liquid crystal aligning film which has a high voltage retention and quick relaxation of the residual electric charge accumulate | stored by DC voltage, even after long-term exposure under high temperature, and long-term use in a severe use environment. An object of the present invention is to provide a highly reliable liquid crystal display element that can withstand.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching so that the said objective may be achieved, the present inventors found out the diamine compound which has a specific novel structure, and the liquid-crystal aligning agent containing the polymer obtained using this diamine compound achieves the said objective. I found out. This invention is based on this knowledge and has the following summary.

(1) The diamine compound of following formula [1].

[Formula 1]

(In formula, X <^1> represents -CO- and -CONH-, X <^2> represents a C1-C5 alkylene group or the non-aromatic heterocycle containing a nitrogen atom, X <^3> represents a C1-C5 alkyl group An aromatic heterocyclic ring of 5 or 6 membered rings containing two nitrogen atoms, which may be substituted by

(2) The diamine compound according to the above (1), wherein the aromatic hetero ring is an imidazole ring, a pyrazine ring, or a pyrimidine ring.

(3) The diamine compound according to the above (1) or (2), wherein the non-aromatic heterocycle containing the nitrogen atom is a piperazine ring.

(4) The polyimide which imidated the polyamic acid obtained by making the diamine component containing the diamine compound in any one of said (1)-(3), and the tetracarboxylic dianhydride component react, or its polyamic acid.

(5) The polyimide which imidated the polyamic acid as described in said (4) or 1-80 mol% of diamine compounds in any one of said (1)-(3) is contained in the said diamine component. .

(6) The polyimide which imidated the polyamic acid as described in said (4) in which the diamine compound containing a carboxyl group is contained in the said diamine component, or its polyamic acid.

(7) The polyamide according to the above (6), wherein 0.01 to 99 mol of the diamine compound having a carboxyl group is contained in the molecule with respect to 1 mol of the diamine according to any one of the above (1) to (3) in the diamine component. Polyimide which imidated acid or its polyamic acid.

(8) The polyimide which imidated the polyamic acid or its polyamic acid as described in said (6) or (7) whose diamine compound which has a carboxyl group in the said molecule is diamine represented by following formula [2].

[Formula 2]

(In formula [2], X <^5> is an organic group which has a C6-C30 aromatic ring, n is an integer of 1-4.)

(9) The liquid-crystal aligning agent containing at least one of the polyamic acid in any one of said (4)-(8), and the polyimide which imidated this polyamic acid, and a solvent.

(10) The liquid-crystal aligning agent as described in said (9) whose 5-80 mass% in the said solvent is a poor solvent.

(11) The liquid crystal aligning film obtained from the liquid-crystal aligning agent as described in said (9) or (10).

The liquid crystal display element which has a liquid crystal aligning film as described in said (11).

 The diamine compound of this invention is a novel diamine which contains in a side chain the specific structure containing the five-membered ring or the six-membered aromatic heterocyclic ring containing two nitrogen atoms (henceforth a specific diamine compound). It can be obtained by a relatively simple method. Since the aromatic heterocycle of the 5-membered ring or 6-membered ring containing two nitrogen atoms in this specific diamine compound functions as an electron hopping site by the conjugated structure, the polyamic acid using the specific diamine compound, and // Or the liquid crystal aligning film obtained from the polyimide polymer which imidated the polyamic acid can promote the movement of the electric charge in a liquid crystal aligning film, The voltage retention is high, and the residual electric charge accumulate | stores by DC voltage, even after long time exposure under high temperature. May have the property of fast relaxation.

Thereby, the liquid crystal display element which has the liquid-crystal aligning film obtained from the liquid-crystal aligning agent containing the polyamic acid and / or polyimide polymer using the diamine compound of this invention becomes excellent in reliability, and it is suitable for the liquid crystal television etc. which are large screen and high definition. Can be used.

<Specific diamine compound>

The specific diamine compound of this invention is shown by following formula [1].

[Formula 3]

In formula, X <^1> represents -CO- or -CONH-, X <^2> represents a C1-C5 alkylene group or the non-aromatic heterocyclic ring containing a nitrogen atom, X <^3> represents a C1-C5 alkyl group The aromatic heterocyclic ring of the 5-membered ring or 6-membered ring which may be substituted and contains two nitrogen atoms is shown.

The bonding position of two amino groups (-NH ₂ ) in Formula [1] is not limited. Specifically, with respect to the side chain linking group (X ¹ ), 2, 3 positions, 2, 4 positions, 2, 5 positions, 2, 6 positions, 3, 4 positions, 3, The position of 5 is mentioned. Among these, in view of the reactivity in synthesizing the polyamic acid and the ease in synthesizing the diamine compound, the binding positions of the two amino groups are 2, 4, 2, 5, 3, 5 The position of is particularly preferred.

In formula [1], X <^1> is -CO- or -CONH-.

In formula [1], X <^2> is a non-aromatic heterocycle containing a C1-C5 alkylene group or nitrogen atom.

When X <^2> is a C1-C5 alkylene group, the alkylene group may be linear or may be branched. Especially as for carbon number of an alkylene group, 1-3 are preferable.

Moreover, when X <^2> is a non-aromatic heterocycle containing a nitrogen atom, a pyrrolidin ring, a piperidine ring, a piperazine ring, a pyrazolidine ring, a quinuclidin ring, an imidazolidine ring Can be mentioned. In particular, when a non-aromatic heterocyclic ring is a 5-membered ring or a 6-membered ring, since favorable orientation is obtained when it is set as a liquid crystal aligning film, it is preferable. Moreover, when a non-aromatic heterocyclic ring contains two nitrogen atoms, when it is set as a liquid crystal display element, it adsorbs the ionic impurity in a liquid crystal in a liquid crystal aligning film interface, and a liquid crystal display element maintains favorable electrical characteristics, and is preferable. Do. From the above viewpoints, the piperazine ring is particularly preferable as the non-aromatic heterocycle containing a nitrogen atom.

When X ² is bonded to a nitrogen atom in X ³ or an atom adjacent to the nitrogen atom, preferably a carbon atom, X ² exhibits an effect of speeding up the relaxation of the residual charge accumulated by the DC voltage in the liquid crystal display device. It is preferable because it is easy.

In formula [1], X <^3> is the 5-membered ring or 6-membered aromatic heterocyclic ring containing two nitrogen atoms which may be substituted by the C1-C5 alkyl group. Examples of the five-membered or six-membered aromatic heterocyclic ring containing two nitrogen atoms include imidazole ring, pyrazole ring, pyrazine ring, pyrimidine ring and pyridazine ring, but among these, imidazole Preference is given to rings, pyrazine rings, or pyrimidine rings. When the aromatic heterocyclic ring in X ³ is substituted with an alkyl group, the alkyl group preferably has 1 to 3 carbon atoms.

Preferable specific combinations of X ¹ , X ² , and X ³ in the formula [1] are as shown in Tables 1 and 2 below.

<The synthesis method of a specific diamine compound>

Although the method of manufacturing the specific diamine compound shown by Formula [1] of this invention is not specifically limited, The following method is mentioned as a preferable method.

[Formula 4]

The specific diamine compound of this invention is obtained by synthesize | combining the dinitro compound represented by Formula [3], and further reducing the nitro group which a dinitro compound has, and converting into an amino group. There is no restriction | limiting in particular in the method of reducing a dinitro compound, Usually, palladium-carbon, platinum oxide, Raney nickel, platinum black, rhodium-alumina, platinum sulfide carbon etc. are used as a catalyst, ethyl acetate, toluene, tetrahydrofuran And solvents such as dioxane and alcohols, may be carried out by hydrogen gas, hydrazine, hydrogen chloride, or the like. Formula [3] in the X ^1, X ^2, and X ³ have the same meanings as defined in formula (1).

Represented by the formula [3] dinitro compound is, for dinitrobenzene can be obtained with such a method of bonding a -X ² -X ³ via the X ^1, for example, X ¹ is an amide bond (-CONH- ), A method of reacting dinitrobenzene acid chloride with an amino compound containing X ² and X ³ in the presence of alkali. Moreover, when X <^1> is a reverse amide bond (-HNCO-), the method of making amino group containing nitrobenzene and the acid chloride containing X <^2> and X <^3> react in alkali presence is mentioned.

As said dinitro benzene acid chloride, 3, 5- dinitro benzoic acid chloride, 3, 5- dinitro benzoic acid, 2, 4- dinitro benzoic acid chloride, 3, 5- dinitro benzyl chloride, 2, 4- di Examples of nitrobenzyl chloride or amino group-containing nitrobenzene include 2,4-dinitroaniline, 3,5-dinitroaniline, 2,6-dinitroaniline, and the like. In consideration of the availability of the raw materials and the point of the reaction, one or more kinds can be selected and used.

<Polymer>

The polymer of this invention is a polyimide obtained by dehydrating and ring-closing the polyamic acid obtained by reaction of the diamine component containing a specific diamine compound, and tetracarboxylic dianhydride, and this polyamic acid. Both these polyamic acids and polyimides are useful as a polymer for obtaining a liquid crystal aligning film.

In the liquid crystal aligning film obtained using the polymer of the present invention, the higher the content ratio of the specific diamine compound in the diamine component, the higher the voltage retention, and the residual accumulated by DC voltage even after long-term exposure at high temperature. The relaxation of charges is faster.

It is preferable that 1 mol% or more of a diamine component is a specific diamine compound for the purpose of improving said characteristic. Furthermore, it is preferable that 5 mol% or more of a diamine component is a specific diamine compound, More preferably, it is 10 mol% or more.

Although 100 mol% of a diamine component may be a specific diamine compound, 80 mol% or less of a diamine component is preferable from a viewpoint of the uniform applicability at the time of apply | coating a liquid-crystal aligning agent, More preferably, 40 mol% or less to be.

<Diamine compound which has a carboxyl group in a molecule>

In this invention, when the diamine compound which has a carboxyl group in a molecule | numerator is used with a specific diamine compound as a diamine component, the aromatic heterocyclic ring which has two nitrogen atoms which the said specific diamine compound has has a diamine compound which has a carboxyl group in a molecule | numerator. The charge transfer occurs between the carboxyl group possessed by the carboxyl group and the electrostatic interaction such as salt formation or hydrogen bonding, thereby forming an aromatic heterocyclic ring. Therefore, the charge moved to the nitrogen-containing aromatic heterocyclic moiety can efficiently move in the molecule and between the molecules of the copolymer, and as a result, the liquid crystal alignment treatment agent obtained in this case has a high voltage retention when the liquid crystal alignment film is obtained as a liquid crystal alignment film. Moreover, even after long time exposure under high temperature, the effect of relaxation of the residual electric charge accumulate | stored by DC voltage is quicker.

Although the diamine compound which has a carboxyl group in a molecule | numerator is not specifically limited about the specific structure, The compound represented by Formula [2] is preferable.

[Formula 5]

In formula [2], X <^5> is an organic group which has a C6-C30 aromatic ring, and n is an integer of 1-4.

When formula [2] is shown concretely, the structure of following formula [3]-[7] is mentioned.

[Formula 6]

The formula [3], m1 is an integer from 1-4, formula [4] of, X ⁶ represents a single _{bond, -CH 2 -, -C 2 H} 4 -, -C (CH 3) 2 -, -CF _2- , -C (CF ₃ ) _2- , -O-, -CO-, -NH-, -N (CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH _2- , -COO-, -OCO-, -CON (CH ₃ )-or -N (CH ₃ ) CO-, m2 and m3 are each an integer of 0 to 4, and m2 + m3 is an integer of 1 to 4 a represents the formula [5] of, and m4 and m5 are each an integer of 1 to 5, the formula [6] wherein X ⁷ is a straight-chain or branched alkyl group having a carbon number of 1 to 5 and m6 is an integer from 1 to 5 , In formula [7], X ⁸ is a single bond, -CH _2- , -C ₂ H _4- , -C (CH ₃ ) _2- , -CF _2- , -C (CF ₃ ) _2- , -O -, -CO-, -NH-, -N (CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH _2- , -COO-, -OCO-, -CON (CH ₃ )-Or -N (CH ₃ ) CO- and m7 represents an integer of 1 to 4.

Formula [3] to expression in the structure of [7], preferably the formula [3], m1 is an integer from 1 to structural formula [4] of, X ⁶ is a single bond in the _2, -CH 2 -, -C ₂ H _4- , -C (CH ₃ ) _2- , -O-, -CO-, -NH-, -N (CH ₃ )-, -CONH-, -NHCO-, -COO-, or- OCO- is, m2 and m3 is an integer with the structure of Figure 1, equation [7] of, X ⁸ is a single _{bond, -CH 2 -, -O-, -CO-} , -NH-, -CONH-, -NHCO- , -CH ₂ O-, -OCH2-, -COO-, or -OCO-, and m7 is a structure which is an integer of 1-2.

As a specific example of the diamine compound shown by Formula [3]-Formula [7], the compound of following formula [8]-formula [18] is mentioned.

[Formula 7]

[Formula 8]

In formula [17], X ⁹ is a single bond, -CH _2- , -O-, -CO-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCH _2- , -COO -Or -OCO-, and in formula [18], X ¹⁰ is a single bond, -CH _2- , -O-, -CO-, -NH-, -CONH-, -NHCO-, -CH ₂ O- , -OCH _2- , -COO-, or -OCO-.

[Other Diamine Compounds]

In this invention, in addition to the specific diamine compound and the diamine compound which has a carboxyl group in the said molecule, the other diamine compound can be used together as a diamine component, unless the effect of this invention is impaired. The specific example is given to the following.

p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m-phenyl Rendiamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl Alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3, 3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-ratio Phenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobi Phenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'- Diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodipe Ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4 ' -Sulfonyldianiline, 3,3'-sulfonyldianiline, bis (4-aminophenyl) silane, bis (3-aminophenyl) silane, dimethyl-bis (4-aminophenyl) silane, dimethyl-bis (3-amino Phenyl) silane, 4,4'-thiodaniline, 3,3'-thiodaniline, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-dia Minodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl) amine, N-methyl (3,3 ＇-Diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl (2,2'-diaminodiphenyl) amine, N-methyl (2,3'- Diaminodiphenyl) amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2'- Diaminobenzo Paddy, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diamino Naphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis (4-aminophenyl) ethane, 1,2-bis (3-aminophenyl) Ethane, 1,3-bis (4-aminophenyl) propane, 1,3-bis (3-aminophenyl) propane, 1,4-bis (4-aminophenyl) butane, 1,4-bis (3-amino Phenyl) butane, bis (3,5-diethyl-4-aminophenyl) methane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (4-aminobenzyl) benzene, 1,3-bis (4-aminophenoxy) benzene , 4,4 '-[1,4-phenylenebis (methylene)] dianiline, 4,4'-[1,3-phenylenebis (methylene)] dianiline, 3,4 '-[1,4 -Phenylenebis (methylene)] dianiline, 3,4 '-[1,3-phenylenebis (methylene)] dianiline, 3,3 VII- [1,4-phenylenebis (methylene)] dianiline, 3,3 '-[1,3-phenylenebis (methylene)] dianiline, 1,4-phenylenebis [(4-aminophenyl ) Methanone], 1,4-phenylenebis [(3-aminophenyl) methanone], 1,3-phenylenebis [(4-aminophenyl) methanone], 1,3-phenylenebis [( 3-aminophenyl) methanone], 1,4-phenylenebis (4-aminobenzoate), 1,4-phenylenebis (3-aminobenzoate), 1,3-phenylenebis (4-amino Benzoate), 1,3-phenylenebis (3-aminobenzoate), bis (4-aminophenyl) terephthalate, bis (3-aminophenyl) terephthalate, bis (4-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, N, N '-(1,4-phenylene) bis (4-aminobenzamide), N, N'-(1,3-phenylene) bis (4-aminobenz Amide), N, N '-(1,4-phenylene) bis (3-aminobenzamide), N, N'-(1,3-phenylene) bis (3-aminobenzamide), N, N VIII-bis (4-aminophenyl) terephthalamide, N, NV-bis (3- Minophenyl) terephthalamide, N, N'-bis (4-aminophenyl) isophthalamide, N, N'-bis (3-aminophenyl) isophthalamide, 9,10-bis (4-aminophenyl) anthracene , 4,4'-bis (4-aminophenoxy) diphenylsulfone, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane, 2,2'-bis [4- (4- Aminophenoxy) phenyl] hexafluoropropane, 2,2'-bis (4-aminophenyl) hexafluoropropane, 2,2'-bis (3-aminophenyl) hexafluoropropane, 2,2'- Bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2′-bis (4-aminophenyl) propane, 2,2′-bis (3-aminophenyl) propane, 2,2′-bis ( 3-amino-4-methylphenyl) propane, 1,3-bis (4-aminophenoxy) propane, 1,3-bis (3-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) Butane, 1,4-bis (3-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,5-bis (3-aminophenoxy) pentane, 1,6-bis ( 4-aminophenoxy) hexane, 1,6-bis ( 3-aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) heptane, 1,7- (3-aminophenoxy) heptane, 1,8-bis (4-aminophenoxy) octane, 1 , 8-bis (3-aminophenoxy) octane, 1,9-bis (4-aminophenoxy) nonane, 1,9-bis (3-aminophenoxy) nonane, 1,10- (4-aminophenoxy Decane, 1,10- (3-aminophenoxy) decane, 1,11- (4-aminophenoxy) undecane, 1,11- (3-aminophenoxy) undecane, 1,12- ( 4-aminophenoxy) dodecane, 1,12- (3-aminophenoxy) dodecane. Bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1, 6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1, 12-diaminododecane, etc. are mentioned.

Moreover, the diamine compound which has an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, and the cyclic substituent which consists of them as a diamine side chain is mentioned. As a specific example of this diamine compound, the diamine compound shown by following formula [DA1]-a formula [DA26] is mentioned.

[Formula 9]

R <^1> is a C1-C22 alkyl group or a fluorine-containing alkyl group in a formula [DA1]-a formula [DA5].

[Formula 10]

Formula [DA6] ~ formula [DA9] of, R ² is -COO-, -OCO-, -CONH-, -NHCO-, -CH 2 - represents, -O-, -CO-, or -NH-, R <^3> represents a C1-C22 alkyl group or a fluorine-containing alkyl group.

[Formula 11]

Formula [DA10] and formula [DA11] of, R ⁴ is _{-O-, -OCH 2 -, -CH 2} O-, -COOCH 2 -, or represents a -CH ₂ OCO-, R ⁵ is more than a carbon number of 1 22 The following alkyl groups, alkoxy groups, fluorine-containing alkyl groups or fluorine-containing alkoxy groups.

[Formula 12]

Formula [DA12] ~ formula [DA14] of, R ⁶ is -COO-, -OCO-, -CONH-, -NHCO-, -COOCH 2 -, -CH 2 OCO-, -CH 2 O-, -OCH 2 -Or -CH ₂ -is represented, and R ⁷ is an alkyl group, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group having 1 to 22 carbon atoms.

[Formula 13]

In formula [DA15] and formula [DA16], R <^8> is -COO-, -OCO-, -CONH-, -NHCO-, -COOCH _2- , -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -, -CH _2- , -O- or -NH-, R ⁹ represents a fluorine group, cyano group, trifluoromethane group, nitro group, azo group, formyl group, acetyl group, acetoxy group, or hydroxyl group to be.

[Formula 14]

[Formula 15]

[Formula 16]

In addition, diamino siloxane etc. which are shown by following formula [DA27] are mentioned.

[Formula 17]

(M is an integer of 1-10 in a formula [DA27].)

Another diamine compound can also be used 1 type or in mixture of 2 or more types according to the characteristics, such as liquid crystal alignability, voltage retention characteristic, and stored charge, when it sets as a liquid crystal aligning film.

<Tetracarboxylic dianhydride>

In order to obtain the polyamic acid of this invention, the tetracarboxylic dianhydride reacted with a diamine component is not specifically limited. The preferable specific example is given to the following.

Pyromellitic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic Acid dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,5,6-anthracene tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyltetracar Acid dianhydride, 2,3,3 ', 4-biphenyltetracarboxylic acid dianhydride, bis (3,4-dicarboxyphenyl) ether, 3,3', 4,4'-benzophenonetetracarboxylic Acid dianhydride, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1, 3,3,3-hexafluoro-2,2-bis (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) di Phenylsilane, 2,3,4,5-pyridinetetracarboxylic dianhydride, 2,6-bis (3,4-dicarboxyphenyl) pyridine, 3,3 ', 4,4'-diphenylsulfontetracar complex Acid dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, oxydiphthaltetracar Acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetra Carboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane Tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cycloheptane tetracarboxylic dianhydride, 2,3 , 4,5-tetrahydrofurantetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexyl succinic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,4-dicarboxy -1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, bicyclo [3,3,0] octane-2,4,6,8-tetraca Acid dianhydride, bicyclo [4,3,0] nonane-2,4,7,9-tetracarboxylic dianhydride, bicyclo [4,4,0] decane-2,4,7,9- Tetracarboxylic dianhydride, bicyclo [4,4,0] decane-2,4,8,10-tetracarboxylic dianhydride, tricyclo [6.3.0.0 <2,6>] undecane-3, 5,9,11-tetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2 , 3,4-tetrahydrinaphthalene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2] octo-7-ene-2,3,5,6-tetracarboxylic dianhydride , 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexane-1,2-dicarboxylic dianhydride, tetracyclo [6,2,1,1,0,2, 7] dodeca-4,5,9,10-tetracarboxylic dianhydride, 3,5,6-tricarboxynorbornane-2: 3,5: 6 dicarboxylic dianhydride, 1,2, 4, 5- cyclohexane tetracarboxylic dianhydride etc. are mentioned.

Tetracarboxylic dianhydride can be used together with one type or two types or more according to the characteristics, such as liquid crystal alignability, voltage retention characteristic, and stored charge, when it is set as a liquid crystal aligning film.

When obtaining the polyamic acid of this invention by reaction of tetracarboxylic dianhydride and a diamine component, a well-known synthetic method can be used. Generally, it is the method of making tetracarboxylic dianhydride and a diamine component react in an organic solvent. The reaction between the tetracarboxylic dianhydride and the diamine component is advantageous in that it proceeds relatively easily in an organic solvent and no by-products are generated.

As an organic solvent used for reaction of tetracarboxylic dianhydride and a diamine component, if the produced polyamic acid melt | dissolves, it will not specifically limit. The specific example is given to the following.

N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methyl caprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl iso amyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cello Solv, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate , Propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, die Len glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate mono Propyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butylbutyl Latex, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, Methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol hair Ethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid, Butyl 3-methoxy propionate, diglyme, 4-hydroxy-4-methyl- 2-pentanone, etc. are mentioned. These may be used independently, or may mix and use them. Moreover, even if it is a solvent which does not dissolve a polyamic acid, you may mix and use it with the said solvent in the range which does not precipitate the produced polyamic acid.

In addition, since water in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the produced polyamic acid, the organic solvent is preferably dehydrated and dried as much as possible.

When making tetracarboxylic dianhydride and a diamine component react in an organic solvent, the solution which disperse | distributed or dissolved the diamine component in the organic solvent is stirred, and tetracarboxylic dianhydride is disperse | distributed or dissolved in an organic solvent, and added. Conversely, the method of adding a diamine component to the solution which disperse | distributed or dissolved tetracarboxylic dianhydride in the organic solvent, the method of adding the tetracarboxylic dianhydride and a diamine component alternately, etc. are mentioned among these, You may use either method. Moreover, when tetracarboxylic dianhydride or a diamine component consists of multiple types of compounds, it may be made to react in the state mixed previously, may be made to react individually one by one, and the low molecular weight reacted individually may be mixed-reacted, and a high molecular weight body may be made. You may make it.

The polymerization temperature at that time can select arbitrary temperature of -20 degreeC-150 degreeC, Preferably it is the range of -5 degreeC-100 degreeC. In addition, although the reaction can be carried out at an arbitrary concentration, if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring becomes difficult, therefore, tetracarboxyl The total concentration in the reaction solution of the acid dianhydride and the diamine component is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The reaction initial stage can be performed in high concentration | density, and can add an organic solvent after that.

In the polymerization reaction of polyamic acid, it is preferable that ratio of the total number-of-moles of tetracarboxylic dianhydride and the total number-of-moles of a diamine component is 0.8-1.2. As in the normal polymerization reaction, the closer the molar ratio is to 1.0, the higher the molecular weight of the polyamic acid produced.

The polyimide of this invention is a polyimide obtained by dehydrating and ring-closing said polyamic acid, and is useful as a polymer for obtaining a liquid crystal aligning film.

In the polyimide of the present invention, the dehydration ring closure rate (imidization rate) of the amic acid group is not necessarily 100%, and can be arbitrarily adjusted according to the use or the purpose.

As a method of imidating polyamic acid, thermal imidation which heats the solution of polyamic acid as it is, and catalyst imidation which adds a catalyst to the solution of polyamic acid are mentioned.

The temperature at the time of thermally imidating a polyamic acid in a solution is 100 degreeC-400 degreeC, Preferably it is 120 degreeC-250 degreeC, It is more preferable to carry out, removing water produced | generated by the imidation reaction out of system. .

Catalytic imidization of polyamic acid can be performed by adding a basic catalyst and an acid anhydride to the solution of polyamic acid, and stirring at -20 degreeC-250 degreeC, Preferably it is 0 degreeC-180 degreeC. The amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times, of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, and preferably 3 to 30 mol times, of the amic acid group. Pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. are mentioned as a basic catalyst, Especially, pyridine is preferable because it has moderate basicity for advancing reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like, and among these, acetic anhydride is preferred since the purification after completion of the reaction becomes easy. The imidation ratio by catalyst imidation can be controlled by adjusting catalyst amount, reaction temperature, and reaction time.

When recovering the produced polyamic acid or polyimide from the reaction solution of polyamic acid or polyimide, the reaction solution may be poured into a poor solvent and precipitated. Examples of the poor solvent used for the precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene and water. The polymer precipitated by being poured into the poor solvent can be recovered by filtration and then dried by normal temperature or heating under normal pressure or reduced pressure. Moreover, if the polymer which precipitated and collect | recovered is redissolved in an organic solvent and the operation of reprecipitation recovery is repeated 2-10 times, impurities in a polymer can be reduced. Examples of the poor solvent include alcohols, ketones, hydrocarbons, and the like, and the use of three or more poor solvents selected from these is preferable because the efficiency of purification is further increased.

When the molecular weight of the polyamic acid and the polyimide contained in the liquid-crystal aligning agent of this invention considers the intensity | strength of the coating film obtained from it, the workability at the time of coating film formation, and the uniformity of a coating film, the GPC (Gel Permeation Chromatography) method It is preferable to set it as 5,000-1,000,000 in the weight average molecular weight measured by, More preferably, it is 10,000-150,000.

<Liquid crystal aligning agent>

The liquid-crystal aligning agent of this invention is a coating liquid for forming a liquid crystal aligning film, and is a solution which the polymer component for forming a polymer film melt | dissolved in the solvent. Here, the said polymer component contains at least 1 sort (s) of polymer of the polymer of this invention mentioned above. In that case, 1 mass%-20 mass% are preferable in a liquid-crystal aligning agent, More preferably, it is 3 mass%-15 mass%, Especially preferably, it is 3-10 mass%.

In the present invention, all of the polymer components may be polymers of the present invention, or may contain other polymers within the scope of the present invention as long as the effects of the present invention are not impaired. When a polymer component contains another polymer, the content is preferably 0.05 to 4 parts by mass, more preferably 0.1 to 3 parts by mass with respect to 1 part by mass of the polymer of the present invention.

The said other polymer is polyimide which imidated the polyamic acid obtained by using diamine compounds other than the said specific diamine compound, or its polyamic acid as a diamine component made to react with tetracarboxylic dianhydride component, for example. Etc. can be mentioned.

The solvent used by the liquid-crystal aligning agent of this invention has preferable organic solvent in which a high molecular component is dissolved, and the specific example is given to the following.

N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methyl caprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone Don, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl Isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4-methyl-2-pentanone and the like. These may be used independently, or may mix and use them.

The liquid-crystal aligning agent of this invention may contain the component of that excepting the above. Examples thereof include a solvent and a compound which improves the film thickness uniformity and surface smoothness when the liquid crystal aligning agent is applied, and a compound which improves the adhesion between the liquid crystal aligning film and the substrate.

As a solvent which improves the uniformity and surface smoothness of a film thickness, the poor solvent with little solubility to the high molecular component in a liquid-crystal aligning agent is mentioned. The following are mentioned as a specific example of a poor solvent.

For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl Carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol Monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl Ether, dipropylene glycol monoprop Fill ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, di Isobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1-hexanol, n-hexane, n-pentane, n-octane, diethyl ether , Methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-methoxy Ethyl propionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl, 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-part Oxy-2-propane Ol, 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 And solvents having low surface tension such as 2- (2-ethoxypropoxy) propanol, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid isoamyl ester, and the like. have.

One type of these poor solvents may be used, and two or more types may be mixed and used for them. When using the above poor solvent, it is preferable that the poor solvent is 5-80 mass% of the whole solvent contained in a liquid-crystal aligning agent, More preferably, it is 20-60 mass%.

As a compound which improves the uniformity and surface smoothness of a film thickness, a fluorochemical surfactant, silicone type surfactant, nonionic surfactant, etc. are mentioned.

More specifically, for example, F-Top EF301, EF303, EF352 (manufactured by Tochem Products), Megapak F171, F173, R-30 (manufactured by Dainippon Ink, Inc.), fluoride FC430, FC431 (manufactured by Sumitomo 3M) ), Asahi Guard AG710, Saflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.), etc. are mentioned. The use ratio of these surfactants becomes like this. Preferably it is 0.01-2 mass parts with respect to 100 mass parts of the polymer component contained in a liquid-crystal aligning agent, More preferably, it is 0.01-1 mass part.

As a specific example of the compound which improves the adhesiveness of a liquid crystal aligning film and a board | substrate, the functional silane containing compound, epoxy group containing compound, etc. which are shown next are mentioned.

For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3 -Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxy Carbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetri Amines, 10-trimethoxysilyl-1,4,7-triazadecan, 10-triethoxysilyl-1,4,7-triazadecan, 9-trimethoxysilyl-3,6-diazanyl Acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phen -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3- Aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neo Pentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6 Tetraglycidyl-2,4-hexanediol, N, N, N ', N',-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylamino Methyl) cyclohexane, N, N, N ', N',-tetraglycidyl-4,4'- diamino diphenylmethane, etc. are mentioned.

When using the compound which improves adhesiveness with a board | substrate, it is preferable that the usage-amount is 0.1-30 mass parts with respect to 100 mass parts of the polymer component contained in a liquid-crystal aligning agent, More preferably, it is 1-20 mass parts. If the amount of use is less than 0.1 part by mass, the effect of improving the adhesiveness cannot be expected. If the amount is more than 30 parts by mass, the alignment of the liquid crystal may deteriorate.

When the liquid-crystal aligning agent of this invention is a range which does not impair the effect of this invention other than the above, in order to change electrical characteristics, such as dielectric constant and electroconductivity of a liquid crystal aligning film, when it sets it as a dielectric material, a conductive material, and also a liquid crystal aligning film, You may add the crosslinkable compound for the purpose of raising the hardness and the density of the film | membrane.

<Liquid crystal aligning film, liquid crystal display element>

After apply | coating and baking on a board | substrate, the liquid-crystal aligning agent of this invention can be used as a liquid-crystal aligning film, without performing an orientation process in a rubbing process, light irradiation, etc., or a vertical alignment use. Under the present circumstances, it will not specifically limit, if it is a board | substrate with high transparency as a board | substrate to be used, A plastic board | substrate, such as a glass substrate, an acryl substrate, a polycarbonate board | substrate, etc. can be used. In addition, it is preferable to use a substrate on which an ITO electrode or the like for driving the liquid crystal is formed in view of the simplification of the process. In the reflective liquid crystal display element, only a substrate on one side may be used as an opaque one such as a silicon wafer, and the electrode in this case may also use a material that reflects light such as aluminum.

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, and may be used according to the purpose.

Baking after apply | coating a liquid-crystal aligning agent on a board | substrate can be performed at 50 degreeC-300 degreeC, Preferably it is 80 degreeC-250 degreeC by heating means, such as a hotplate, and can evaporate a solvent and can form a coating film. . When the thickness of the coating film formed after baking is too thick, it becomes disadvantageous in terms of the power consumption of a liquid crystal display element, and when too thin, the reliability of a liquid crystal display element may fall, Preferably it is 5-300 nm, More preferably, 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.

After obtaining the board | substrate with which the liquid-crystal aligning film was formed from the liquid-crystal aligning agent of this invention by said method, the liquid crystal display element of this invention produces a liquid crystal cell by a well-known method, and sets it as a liquid crystal display element.

As an example of liquid crystal cell preparation, a pair of board | substrates with which the liquid crystal aligning film was formed is prepared, a spacer is spread | dispersed on the liquid crystal aligning film of one board | substrate, so that a liquid crystal aligning film surface may become inward, the other board | substrate is bonded together, and a liquid crystal The method of injecting and sealing under reduced pressure, or the method of carrying out sealing by bonding a board | substrate together after dropping a liquid crystal on the liquid crystal aligning film surface which spread | dispersed a spacer, etc. can be illustrated. The thickness of the spacer at this time becomes like this. Preferably it is 1-30 micrometers, More preferably, it is 2-10 micrometers.

As mentioned above, the liquid crystal display element produced using the liquid-crystal aligning agent of this invention becomes excellent in reliability, and can be used suitably for a large screen high definition liquid crystal television etc.

Example

Although an Example and a comparative example are given to the following and this invention is demonstrated in more detail, the interpretation of this invention is not limited to these Examples.

Synthesis of Diamine Compound

<Example 1>

Synthesis of Diamine Compound (4)

[Formula 18]

A solution of tetrahydrofuran (1000 g) of compound (2) (57.00 g, 455 mmol), and triethylamine (46.08 g, 455 mmol) was cooled to 10 ° C. or less, and compound (1) (100.00 g, 434 mmol) Tetrahydrofuran (500 g) solution) was added dropwise while paying attention to exotherm. After completion of the dropwise addition, the reaction temperature was raised to 23 ° C. and the reaction was carried out again. After confirming completion of the reaction by HPLC (high-speed liquid chromatography), the reaction solution was poured into distilled water (9 L), and then the precipitated solid was filtered and washed with water, then dispersed and washed with 2-propanol (200 g) to obtain a compound ( 3) was obtained (amount: 120.6 g, a yield: 89%).

Then, a mixture of compound (3) (100.00 g, 313 mmol), 5% palladiumcarbon (functional, 10.00 g, 10 wt%), and N, N-dimethylformamide (2000 g) was added in the presence of hydrogen, 23 It stirred at ° C. After completion | finish of reaction, after nitrogen-substituting, activated carbon (10.00g) was added and it stirred at 23 degreeC for 1 hour. Thereafter, the catalyst and the activated carbon were removed by filtration, and the liquid was distilled off to obtain crude crystals. 2-propanol (300 g) was added to this crude crystal, and it stirred at 23 degreeC for 30 minutes. Filtration and drying were performed and the diamine compound (4) was obtained (amount: 76.3 g, a yield: 94%).

<Example 2>

Synthesis of Diamine Compound (7)

[Formula 19]

A tetrahydrofuran (500 g) solution of compound (5) (24.00 g, 195 mmol), and triethylamine (19.72 g, 195 mmol) is cooled to 10 ° C. or less, and compound (1) (42.80 g, 186 mmol) Tetrahydrofuran (142 g) solution was added dropwise while paying attention to exotherm. After completion of the dropwise addition, the reaction temperature was raised to 23 ° C. and the reaction was carried out again. After confirming completion of the reaction by HPLC, the reaction solution was poured into distilled water (3.9 L), and the precipitated solid was filtered and washed with water, then dispersed and washed with 2-propanol (240 g) to obtain Compound (6). : 51.3 g, yield: 87%).

Then a mixture of compound (6) (45.00 g, 142 mmol), 5% palladiumcarbon (water, 4.5 g, 10 wt%), and 1,4-dioxane (675 g) / DMF (200 g) was added. In the presence of hydrogen, the mixture was stirred at 70 ° C. After completion | finish of reaction, after nitrogen-substituting, activated carbon (4.5g) was added and it stirred at 70 degreeC for 1 hour. Thereafter, the catalyst and the activated carbon were removed by filtration, and the liquid was distilled off to obtain crude crystals. The diamine compound (7) was obtained by dispersion-washing the obtained crude substance with 2-propanol (100g) (gain: 33.7g, yield: 92%).

<Example 3>

Synthesis of Diamine Compound (10)

[Formula 20]

A solution of tetrahydrofuran (332 g) of compound (8) (24.00 g, 146 mmol), and triethylamine (14.79 g, 146 mmol) was cooled to 10 ° C. or less, and compound (1) (32.10 g, 139 mmol) Tetrahydrofuran (100 g) solution was added dropwise while paying attention to the exotherm. After completion of the dropwise addition, the reaction temperature was raised to 23 ° C. and the reaction was carried out again. After confirming completion of the reaction by HPLC, the reaction solution was poured into distilled water (3.9 L), and then the precipitated solid was filtered and washed with water, then dispersed and washed with 2-propanol (200 g) to obtain Compound (9). : 47.6 g, yield: 95%).

Subsequently, a mixture of compound (9) (40.00 g, 112 mmol), 5% palladium carbon (functional product, 4.0 g, 10 wt%), and DMF (800 g) was stirred at 70 ° C. in the presence of hydrogen. After completion | finish of reaction, after filtering a catalyst with celite, the solvent was distilled off with the evaporator and the crude material was obtained. The obtained crude substance was disperse-washed with 2-propanol (12g), and the diamine compound (10) was obtained (amount: 1.7 g, yield: 68%).

<Synthesis example 1>

Synthesis of Diamine Compound (13)

[Formula 21]

A tetrahydrofuran (150 g) solution of compound (11) (15.22 g, 142 mmol), and triethylamine (15.09 g, 149 mmol) is cooled to 10 ° C. or less, and compound (1) (31.1 g, 135 mmol) Tetrahydrofuran (50 g) solution) was added dropwise while paying attention to exotherm. After completion of the dropwise addition, the reaction temperature was raised to 23 ° C. and the reaction was carried out again. After confirming completion | finish of reaction by HPLC, after pouring a reaction liquid in distilled water (1L), the precipitated solid was filtered and washed with water. Thereafter, the solid was dispersed and washed with ethanol (300 g) to obtain compound (12) (gain: 36.92 g, yield: 90%).

Subsequently, a mixture of compound (12) (36.00 g, 119 mmol), 5% palladiumcarbon (functional, 3.6 g, 10 wt%), and 1,4-dioxane (300 g) was then heated at 60 ° C. in the presence of hydrogen. Stirred at. After completion | finish of reaction, after filtering a catalyst with celite, the solvent was distilled off with the evaporator and the crude material was obtained. The obtained crude substance was recrystallized with methanol (200g), and the diamine compound (13) was obtained (amount: 21.5 g, a yield: 72%).

<Synthesis example 2>

Synthesis of Diamine Compound (16)

[Formula 22]

A solution of tetrahydrofuran (230 g) of compound (14) (23.45 g, 190 mmol), and triethylamine (19.23 g, 277 mmol) was cooled to 10 ° C. or lower, and compound (1) (41.68 g, 180 Mmol) of tetrahydrofuran (110 g) was added dropwise while paying attention to exotherm. After completion of the dropwise addition, the reaction temperature was raised to 23 ° C. and the reaction was carried out again. After confirming completion | finish of reaction by HPLC (high-speed liquid chromatography), after pouring a reaction liquid in distilled water (1.5 L), the precipitated solid was filtered and washed with water. Thereafter, the solid was dispersed and washed with ethanol (380 g) to obtain compound (15) (gain: 50.82 g, yield: 89%).

Subsequently, a mixture of compound (15) (48.00 g, 151 mmol), 5% palladiumcarbon (functional, 4.8 g, 10 wt%), and 1,4-dioxane (490 g) was then heated at 60 ° C. in the presence of hydrogen. Stirred at. After completion | finish of reaction, after filtering a catalyst with celite, the solvent was distilled off with the evaporator and the crude material was obtained. The obtained crude substance was disperse-washed with ethanol (300g), and the diamine compound (16) was obtained (gain: 27.20g, yield: 70%).

[Synthesis of polyamic acid and polyimide]

The symbol of compounds, such as tetracarboxylic dianhydride used below, was shown.

(Tetracarboxylic dianhydride)

CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride

BODA: Bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride

[Formula 23]

(Diamine compound)

DBA: 3,5-diaminobenzoic acid

p-PDA: p-phenylenediamine

AP18: 1,3-diamino-4-octadecyloxybenzene

PCH7DAB: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene

[Formula 24]

(Organic solvent)

NMP: N-methyl-2-pyrrolidone

BCS: Butyl Cellosolve

<Measurement of Molecular Weight of Polyimide>

The molecular weight of the polyimide in a synthesis example is as follows using the Showa Denko-made normal-temperature gel permeation chromatography (GPC) apparatus (GPC-101), the Shodex company column (KD-803, KD-805). It was measured by.

Column temperature: 50 ℃

Eluent: N, N'-dimethylformamide (as additive, lithium bromide monohydrate (LiBr.H ₂ O) is 30 mmol / l, phosphoric acid and anhydrous crystals (o-phosphate) is 30 mmol / l, tetrahydrofuran (THF) 10 ml / l)

Flow rate: 1.0 ml / min

Standard sample for calibration curve preparation: TSK standard polyethylene oxide (molecular weight about 900,000, 150,000, 100,000, 30,000) by Tosoh Corporation, and polyethylene glycol (molecular weight about 12,000, 4,000, 1,000) by Polymer Laboratories.

<Measurement of imidation ratio>

The imidation ratio of the polyimide in a synthesis example was measured as follows.

20 mg of polyimide powder was placed in an NMR sample tube (NMR sampling tube standard φ 5 manufactured by Kusano Scientific Co., Ltd.), 0.53 mL of deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS (tetramethylsilane) mixture) was added, and ultrasonic waves were added. Added and completely dissolved. 500 MHz of proton NMR was measured for this solution by the NMR measuring machine (JNW-ECA500) by the Japan Electronic Datum company. The imidation ratio determines the proton derived from the structure which does not change before and after imidation as a reference proton, and the peak integration value derived from the peak integration value of this proton and the NH group of the amic acid appearing around 9.5-10.0 ppm. It calculated | required by the following formula using

Imidation ratio (%) = (1-α * x / y) × 100

In the above formula, x is the proton peak integrated value derived from the NH group of the amic acid, y is the peak integrated value of the reference proton, and α is the NH of the amic acid when the polyamic acid (imidization ratio is 0%). The ratio of the number of reference protons to one proton.

<Example 4>

NDA was obtained with BODA (3.24 g, 13.0 mmol), p-PDA (0.65 g, 6.01 mmol), PCH7DAB (3.30 g, 8.67 mmol), and the diamine compound (4) obtained in Example 1 (0.68 g, 2.62 mmol). After mixing in (14.5 g) and reacting at 80 ° C. for 5 hours, CBDA (0.85 g, 4.34 mmol) and NMP (11.9 g) were added and reacted at 40 ° C. for 6 hours to give a polyamic acid solution (A) ( Concentration: 24.8 mass%) was obtained. The number average molecular weight of this polyamic acid was 22,800, and the weight average molecular weight was 53,900.

<Example 5>

NMP was added to the polyamic acid solution (A) obtained in Example 4 (20.0 g), and the polyamic acid concentration was diluted to 6 mass%, followed by acetic anhydride (2.65 g) and pyridine ( 2.07 g) was added and reacted at 80 degreeC for 2 hours. This reaction solution was poured into methanol (350 mL), and the obtained precipitate was separated by filtration. Methanol wash | cleaned this deposit, it dried under reduced pressure at 100 degreeC, and the polyimide powder (B) was obtained. The imidation ratio of this polyimide was 40%, the number average molecular weight was 18,800 and the weight average molecular weight was 49,500.

<Example 6>

BODA (3.25 g, 13.0 mmol), DBA (0.52 g, 3.42 mmol), PCH7DAB (3.30 g, 8.67 mmol), and the diamine compound (4) obtained in Example 1 (1.36 g, 5.24 mmol) were prepared by NMP (15.5). g), the mixture was reacted at 80 ° C for 5 hours, and then CBDA (0.85 g, 4.34 mmol) and NMP (12.7 g) were added thereto, and reacted at 40 ° C for 6 hours to give a polyamic acid solution (C) (concentration: 24.8 mass%) was obtained. The number average molecular weight of this polyamic acid was 24,100, and the weight average molecular weight was 55,500.

<Example 7>

NMP was added to the polyamic acid solution (C) obtained in Example 6 (20.1 g), and the polyamic acid concentration was diluted to 6 mass%, followed by acetic anhydride (2.66 g) and pyridine ( 2.07 g) was added and reacted at 80 degreeC for 2 hours. This reaction solution was poured into methanol (350 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (D). The imidation ratio of this polyimide was 40%, the number average molecular weight was 19,900 and the weight average molecular weight was 51,500.

<Example 8>

BODA (3.15 g, 12.6 mmol), p-PDA (1.01 g, 9.34 mmol), AP18 (1.25 g, 3.32 mmol), and the diamine compound (7) obtained in Example 2 (1.10 g, 4.28 mmol) were prepared by NMP ( 8.35 g), the mixture was reacted at 80 ° C for 5 hours, CBDA (0.85 g, 4.34 mmol) and NMP (6.83 g) were added, and the mixture was reacted at 40 ° C for 6 hours to obtain a polyamic acid solution. The number average molecular weight of this polyamic acid was 21,500, and the weight average molecular weight was 52,400.

NMP was added to the obtained polyamic acid solution (20.0 g), and the polyamic acid concentration was diluted to 6 mass%, followed by addition of acetic anhydride (2.65 g) and pyridine (2.07 g) as an imidization catalyst, followed by 80 It was made to react at 2 degreeC. This reaction solution was poured into methanol (350 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (E). The imidation ratio of the polyimide was 40%, the number average molecular weight was 18,100 and the weight average molecular weight was 48,700.

<Example 9>

BODA (3.22 g, 12.9 mmol), DBA (0.79 g, 5.19 mmol), PCH7DAB (3.22 g, 8.46 mmol), and the diamine compound (7) obtained in Example 2 (0.92 g, 3.58 mmol) were purified by NMP (13.5 g). ), The mixture was allowed to react at 80 ° C for 5 hours, and then CBDA (0.85 g, 4.34 mmol) and NMP (11.0 g) were added, and the mixture was reacted at 40 ° C for 6 hours to obtain a polyamic acid solution. The number average molecular weight of this polyamic acid was 23,700, and the weight average molecular weight was 54,000.

NMP was added to the obtained polyamic acid solution (20.1 g), and the polyamic acid concentration was diluted to 6 mass%, followed by addition of acetic anhydride (2.65 g) and pyridine (2.07 g) as an imidization catalyst, followed by 80 It was made to react at 2 degreeC. This reaction solution was poured into methanol (350 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (F). The imidation ratio of this polyimide was 40%, the number average molecular weight was 19,900 and the weight average molecular weight was 49,800.

<Example 10>

BODA (2.97 g, 11.9 mmol), p-PDA (0.70 g, 6.47 mmol), PCH7DAB (3.06 g, 8.04 mmol), and the diamine compound (10) obtained in Example 3 (0.51 g, 1.71 mmol) were prepared by NMP ( 12.6 g), reacted at 80 ° C for 5 hours, and then CBDA (0.85 g, 4.34 mmol) and NMP (10.3 g) were added, and reacted at 40 ° C for 6 hours to give a polyamic acid solution (G) (concentration : 26.1 mass%) was obtained. The number average molecular weight of this polyamic acid was 21,200, and the weight average molecular weight was 52,100.

<Example 11>

NMP was added to the polyamic acid solution (G) obtained in Example 10, and the polyamic acid concentration was diluted to 6 mass%, followed by acetic anhydride (2.67 g), and pyridine ( 2.05 g) was added and reacted at 80 degreeC for 2 hours. This reaction solution was poured into methanol (360 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (H). The imidation ratio of this polyimide was 40%, the number average molecular weight was 18,100 and the weight average molecular weight was 48,500.

<Synthesis example 3>

NDA was obtained from BODA (3.22 g, 12.9 mmol), p-PDA (0.65 g, 6.00 mmol), PCH7DAB (3.26 g, 8.57 mmol), and the diamine compound (13) obtained in Synthesis Example 1 (0.62 g, 2.56 mmol). After mixing in (15.2 g) and reacting at 80 ° C. for 5 hours, CBDA (0.84 g, 4.28 mmol) and NMP (11.1 g) were added and reacted at 40 ° C. for 6 hours to give a polyamic acid solution (I) ( Concentration: 24.6 mass%) was obtained. The number average molecular weight of this polyamic acid was 22,100, and the weight average molecular weight was 53,200.

<Synthesis example 4>

NMP was added to the polyamic acid solution (I) obtained in Synthesis Example 3 (20.1 g), and the polyamic acid concentration was diluted to 6 mass%, followed by acetic anhydride (2.68 g) and pyridine ( 2.04 g) was added and reacted at 80 degreeC for 2 hours. This reaction solution was poured into methanol (350 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (J). The imidation ratio of this polyimide was 41%, the number average molecular weight was 18,400 and the weight average molecular weight was 49,100.

<Synthesis example 5>

BODA (3.29 g, 13.2 mmol), p-PDA (0.67 g, 6.14 mmol), PCH7DAB (3.34 g, 8.77 mmol), and the diamine compound (16) (0.68 g, 2.79 mmol) obtained in Synthesis Example 2 were prepared by NMP ( 15.0 g), reacted at 80 ° C for 5 hours, and then CBDA (0.86 g, 4.39 mmol) and NMP (11.5 g) were added, and reacted at 40 ° C for 6 hours to give a polyamic acid solution (K) (concentration). : 25.0 mass%) was obtained. The number average molecular weight of this polyamic acid was 22,600, and the weight average molecular weight was 54,900.

<Synthesis example 6>

NMP was added to the polyamic acid solution (K) obtained in Synthesis Example 5 (20.0 g), and the polyamic acid concentration was diluted to 6 mass%, followed by acetic anhydride (2.65 g) and pyridine ( 2.08 g) was added and reacted at 80 degreeC for 2 hours. This reaction solution was poured into methanol (320 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (L). The imidation ratio of this polyimide was 40%, the number average molecular weight was 18,900 and the weight average molecular weight was 49,200.

The reaction conditions (mol of each component) and imidation ratio of Examples 4-11 and Synthesis Examples 3-6 (synthesis | combination of a polyamic acid and a polyimide) are shown in Table 3 and Table 4 together.

[Preparation and Evaluation of Liquid-crystal Orientation Processing Agent]

<Example 12>

NMP (10.2g) and BCS (20.0g) were added to the polyamic-acid solution [A] obtained in Example 4, and (10.0g), and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent [1]. Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, and it was confirmed that a polymer component is melt | dissolving uniformly.

[Production of Liquid Crystal Cells]

The liquid-crystal aligning agent [1] obtained above was spin-coated to the ITO surface of the board | substrate with which the 3 cm x 4 cm (vertical x horizontal) ITO electrode was formed, and baked at 80 degreeC for 5 minutes in 210 degreeC hot-air circulation type oven for 1 hour. Was carried out to produce a polyimide coating film having a film thickness of 100 nm.

The board | substrate with which this liquid crystal aligning film was formed was subjected to the rubbing process on the conditions of rotation speed 300rpm, roll advancing speed 20mm / sec, and a press amount 0.3mm with the rubbing apparatus of roll diameter 120mm and rayon cloth, and the board | substrate with a liquid crystal aligning film formed Got.

Two board | substrates with this liquid crystal aligning film were prepared, and after spread | dispersing a 6 micrometers bead spacer on the surface of this liquid crystal aligning film, the sealing compound was printed from on. After attaching the other one board | substrate which prepared, the liquid crystal aligning film surface was made inside, and a rubbing direction reversed, it pasted, the sealing compound was hardened and the empty cell was produced. Liquid crystal MLC-6608 (made by Merck Japan) was injected into this empty cell by the pressure reduction injection method, and the nematic liquid crystal cell of antiparallel orientation was obtained.

[Evaluation of Voltage Retention Rate]

The voltage of 4 V was applied to the liquid crystal cell obtained above at 60 degreeC, the voltage after 16.67 ms and after 1667 ms was measured, and it calculated as voltage retention (%) how much voltage was hold | maintained. . The results are shown in Table 5.

[Evaluation of Mitigation of Residual Charge]

DC voltage 10V was applied to the liquid crystal cell after voltage retention measurement for 30 minutes, and short-circuited for 1 second, and the electric potential generate | occur | produced in the liquid crystal cell was measured for 1800 second. And the residual electric charge (V) after 50 second and 1000 second was measured. In addition, the Toyo Technica Corporation 6254 type liquid crystal physical property evaluation apparatus was used for the measurement. The results are shown in Table 6.

[Evaluation after High Temperature Neglect]

After leaving the liquid crystal cell after residual charge measurement for 7 days in the high temperature tank set to 100 degreeC, the voltage retention and the residual charge were measured. The results are shown in Tables 5 and 6 described later.

About the liquid-crystal aligning agent obtained in the following Examples 13-19 and Comparative Examples 1-4, a liquid crystal cell was produced using these liquid-crystal aligning agents similarly to Example 12, and evaluation of each liquid crystal cell was further performed. Was carried out. The results are summarized in Tables 5 and 6.

<Example 13>

NMP (36.3g) was added to the polyimide powder [B] (5.1g) obtained in Example 5, and it stirred for 40 hours and was made to melt | dissolve at 70 degreeC. NMP (18.1g) and BCS (25.6g) were added to this solution, and the liquid-crystal aligning agent [2] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, and it was confirmed that a polymer component is melt | dissolving uniformly.

<Example 14>

NMP (10.2g) and BCS (20.0g) were added to the polyamic-acid solution [C] (10.0g) obtained in Example 6, and the liquid-crystal aligning agent [3] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, and it was confirmed that a polymer component is melt | dissolving uniformly.

<Example 15>

NMP (30.3g) is added to the polyimide powder [D] (5.0g) obtained in Example 7, and it stirred for 40 hours and was made to melt | dissolve at 70 degreeC. NMP (14.8g) and BCS (33.8g) were added to this solution, and the liquid-crystal aligning agent [4] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, and it was confirmed that a polymer component is melt | dissolving uniformly.

<Example 16>

NMP (33.0g) is added to the polyimide powder [E] (5.1g) obtained in Example 8, and it stirred for 40 hours and was made to melt | dissolve at 70 degreeC. NMP (17.1g) and BCS (29.8g) were added to this solution, and the liquid-crystal aligning agent [5] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, and it was confirmed that a polymer component is melt | dissolving uniformly.

<Example 17>

NMP (34.5g) was added to the polyimide powder [F] (5.2g) obtained in Example 9, and it stirred for 40 hours and was made to melt | dissolve at 70 degreeC. NMP (16.5g) and BCS (30.3g) were added to this solution, and the liquid-crystal aligning agent [6] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, and it was confirmed that a polymer component is melt | dissolving uniformly.

<Example 18>

NMP (15.6g) and BCS (17.1g) were added to the polyamic-acid solution [G] (10.0g) obtained in Example 10, and the liquid-crystal aligning agent [7] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, and it was confirmed that a polymer component is melt | dissolving uniformly.

<Example 19>

NMP (35.5g) was added to the polyimide powder [H] (5.0g) obtained in Example 11, and it stirred for 40 hours and was made to melt | dissolve at 70 degreeC. NMP (17.8g) and BCS (25.1g) were added to this solution, and the liquid-crystal aligning agent [8] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, and it was confirmed that a polymer component is melt | dissolving uniformly.

<Comparative Example 1>

NMP (18.8g) and BCS (12.2g) were added to the polyamic-acid solution [I] (10.0g) obtained by the synthesis example 3, and the liquid-crystal aligning agent [9] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, and it was confirmed that a polymer component is melt | dissolving uniformly.

<Comparative Example 2>

NMP (38.6g) is added to the polyimide powder [J] (4.7g) obtained by the synthesis example 4, and it stirred for 40 hours and was made to melt | dissolve at 70 degreeC. NMP (19.4g) and BCS (15.8g) were added to this solution, and the liquid-crystal aligning agent [10] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, and it was confirmed that a polymer component is melt | dissolving uniformly.

<Comparative Example 3>

NMP (17.5g) and BCS (15.3g) were added to the polyamic-acid solution [K] (10.4g) obtained in the synthesis example 5, and the liquid-crystal aligning agent [11] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, and it was confirmed that a polymer component is melt | dissolving uniformly.

<Comparative Example 4>

NMP (34.5g) was added to the polyimide powder [L] (4.5g) obtained in the synthesis example 6, and it stirred for 40 hours and was made to melt | dissolve at 70 degreeC. NMP (17.2g) and BCS (18.8g) were added to this solution, and the liquid-crystal aligning agent [12] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, and it was confirmed that a polymer component is melt | dissolving uniformly.

Industrial availability

When the liquid-crystal aligning agent containing the diamine compound of this invention is set as a liquid crystal aligning film, even if it has high voltage retention and after exposing for a long time under high temperature, the liquid crystal aligning film which is quick in relaxation of the charge accumulated by a DC voltage is obtained. Furthermore, the liquid crystal display element with high reliability which can endure long-term use in a severe use environment can be provided. As a result, it is useful for a TN element, an STN element, a TFT liquid crystal element, and furthermore, a liquid crystal display element of a vertical alignment type or a horizontal alignment type (IPS).

In addition, the JP Patent application 2009-170396, the claim, and all the content of the abstract for which it applied on July 21, 2009 are referred here, and it takes in as an indication of the specification of this invention.

Claims (10)

The diamine compound represented by following formula (4), formula (7), or formula (10).

The polyimide which imidated the polyamic acid obtained by making the diamine component containing the diamine compound of Claim 1, and tetracarboxylic dianhydride component react, or the polyamic acid. The method of claim 2,
The polyimide which imidated the polyamic acid or its polyamic acid which 1-80 mol% of said diamine compounds contain in the said diamine component. The method of claim 2,
The polyimide which imidated the polyamic acid or its polyamic acid in which the diamine compound containing a carboxyl group is contained in the said diamine component. The method of claim 4, wherein
The polyimide which imidated the polyamic acid or its polyamic acid which contains 0.01-99 mol of diamine compounds which have a carboxyl group in a molecule | numerator with respect to 1 mol of the said diamine compound in the said diamine component. The method of claim 4, wherein
The polyimide which imidated the polyamic acid or its polyamic acid whose diamine compound which has a carboxyl group in the said molecule is represented by following formula [2].

(In formula [2], X <^5> is an organic group which has a C6-C30 aromatic ring, n is an integer of 1-4.) The liquid-crystal aligning agent containing at least one of the polyamic acid as described in any one of Claims 2-6, and the polyimide which imidated this polyamic acid, and a solvent. The method of claim 7, wherein
The liquid-crystal aligning agent whose 5-80 mass% in the said solvent is a poor solvent. The liquid crystal aligning film obtained from the liquid-crystal aligning agent of Claim 7. The liquid crystal display element which has a liquid crystal aligning film of Claim 9.