KR20110046257A - Liquid crystal aligning agent, liquid crystal display element, and compound and polymer contained therein - Google Patents

Abstract

PURPOSE: A liquid crystal alignment material is provided to form a liquid crystal alignment film without the deterioration of display quality even when lights are on for a long time. CONSTITUTION: A liquid crystal alignment material includes at least one polymer selected from the group consisting of polyamic acids and polyimide. The polymer has a structure of chemical formula (A0) at a part inside molecule. In formula, X is a divalent group selected from chemical formulas (X-1)-(X-4); RI is hydrogen atom or C1-4 alkyl group; m is 1 or 2; and n is 0 or 1. In (X-1) and (X-2), RII is hydrogen atom, C1-4 alkyl group, carboxylic acid group or C2-5 carboxylic alkyl group.

Description

Liquid crystal aligning agent, liquid crystal display device, and compound and polymer contained therein {LIQUID CRYSTAL ALIGNING AGENT, LIQUID CRYSTAL DISPLAY DEVICE, AND COMPOUND AND POLYMERS CONTAINED THEREIN}

The present invention relates to a liquid crystal aligning agent and a liquid crystal display element. In more detail, even if it drives continuously for a long time, the fall of display quality, such as an electrical property deterioration and a liquid-crystal orientation defect, hardly arises, and it provides favorable printability in the liquid saving coating process in a liquid crystal display element manufacturing process. It is related with the liquid crystal aligning agent which can be used, and the display quality, and it is related with the liquid crystal display element which a display quality does not deteriorate even if it drives continuously for a long time.

Currently, as a liquid crystal display element, the liquid crystal aligning film is formed in the surface of the board | substrate with which the transparent conductive film is formed, it is set as a board | substrate for liquid crystal display elements, the two sheets are opposed, and the nematic type which has positive dielectric anisotropy in the clearance gap. A TN type liquid crystal display element having a so-called TN type liquid crystal cell in which a layer of liquid crystal is formed to form a sandwich structure cell and the long axis of the liquid crystal molecules is continuously twisted by 90 ° from one substrate to the other substrate is It is known (patent document 1). Moreover, STN (Super Twisted Nematic) type liquid crystal display element (Patent Document 2) which can realize a high contrast ratio compared with TN type liquid crystal display element, or IPS (In-Plane Switching) type which has little visual dependence. Liquid crystal display device (Patent Document 3), optical compensation band (OCB) type liquid crystal display device (Patent Document 4) excellent in high-speed response of video screen while having low visual dependence, and nematic type having negative dielectric anisotropy VA (Vertical Alignment) type liquid crystal display elements (patent document 5) etc. which use a liquid crystal are developed.

As a material of the liquid crystal aligning film in these liquid crystal display elements, polyamic acid, polyimide, polyamide, polyester, etc. are known conventionally, and especially polyamic acid and polyimide have heat resistance, affinity with a liquid crystal, mechanical strength, etc. It is excellent and is used for many liquid crystal display elements (patent documents 6-11).

In recent years, examination of display quality improvement, low power consumption, etc. which begin with high definition of a liquid crystal display element is advanced, and the use range of a liquid crystal display element is expanded. In particular, the use as a liquid crystal television instead of a CRT television has been expanded. In connection with this, the liquid crystal display element which is superior to the conventional in electrical characteristics, is higher in display quality, and which can continuously drive for a long time is calculated | required.

However, in the liquid crystal display element provided with the liquid crystal aligning film formed from the polyamic acid or polyimide conventionally known, the liquid crystal aligning film deteriorates by heat or light in continuous lighting for a long time, and the deterioration of an electrical property and the orientation of liquid crystal molecules are bad. It has been pointed out that a problem that significantly lowers the display quality such as

Therefore, even when it illuminates continuously for a long time, development of the liquid crystal aligning film which does not deteriorate the display quality, such as deterioration of an electrical property and orientation defect of a liquid crystal molecule, is desired.

On the other hand, in recent years, in order to use a liquid crystal aligning agent effectively in the liquid crystal aligning agent application process, the attempt to reduce the liquid amount of the liquid crystal aligning agent used at the time of printing is made. However, with a conventional aligning agent, when there is little liquid amount at the time of application | coating, the solvent in a liquid crystal aligning agent will evaporate during application | coating, the density | concentration of an aligning agent will rise, and abnormality like coating failure and precipitation of a resin component will arise. It was a problem. Then, in order to maintain the application quality, while achieving the liquid saving of a liquid crystal aligning agent, the liquid crystal aligning agent which shows the outstanding printability even with a small liquid amount is desired.

Japanese Patent Application Laid-open No. Hei 6-138457 Japanese Patent Laid-Open No. 5-19231 Japanese Patent Application Laid-Open No. 11-24109 Japanese Patent Application Laid-open No. Hei 8-327822 Japanese Patent Application Laid-Open No. 5-113561 Japanese Patent Application Laid-open No. Hei 4-153622 Japanese Laid-Open Patent Publication No. 60-107020 Japanese Laid-Open Patent Publication No. 56-91277 US Patent No. 5,928,733 Japanese Patent Application Laid-Open No. 11-258605 Japanese Laid-open Patent Publication No. 62-165628 Japanese Patent Laid-Open No. 6-222366 Japanese Patent Application Laid-open No. Hei 6-281937 Japanese Patent Application Laid-Open No. 5-107544 Japanese Laid-Open Patent Publication No. 2010-97188

This invention is made | formed in view of the said situation, The objective can form the liquid crystal aligning film which does not deteriorate the display quality, such as deterioration of an electrical property or the orientation defect of a liquid crystal molecule, even when it illuminates continuously for a long time, The present invention also relates to a liquid crystal aligning agent excellent in printability and a liquid crystal display element which does not deteriorate in display quality even when continuously driven for a long time even when printing is performed in a small liquid amount.

Further objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the above objects and advantages of the present invention, firstly,

Polyester polymer of at least one selected from the acid, and the group consisting of polyimide are achieved by a liquid crystal aligning agent containing a (where this polymer, having a structure represented by the following formula (A ⁰⁾ on at least part in the molecule).

(Wherein (A ^0), X is the formula (X-1) ~ (X -4):

(In formula (X-1) and (X-2), R ^II is a hydrogen atom, a C1-C4 alkyl group, a carboxyl group, or a C2-C5 carboxyalkyl group.)

Is a divalent group represented by any of which R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, m is 1 or 2, and n is 0 or 1)

The above object and advantages of the present invention, secondly,

It is achieved by the liquid crystal display element provided with the liquid crystal aligning film formed from said liquid crystal aligning agent.

The liquid crystal aligning agent of this invention can form the liquid crystal aligning film which does not deteriorate the display quality, such as deterioration of an electrical property or the orientation defect of a liquid crystal molecule, even if it carries out continuous drive for a long time, and performed printing by a small liquid amount. Even if it shows excellent printability.

The liquid crystal display element of this invention provided with the liquid crystal aligning film formed from such a liquid crystal aligning agent can display high quality, and even if it drive | operates for a long time, display performance does not deteriorate. Therefore, the liquid crystal display element of the present invention can be effectively applied to various devices, for example, a clock, a portable game, a word processor, a notebook personal computer, a car navigation system, a camcorder, a portable information terminal, a digital camera, a portable device. It can be used suitably for display apparatuses, such as a telephone, various monitors, and a liquid crystal television.

(Form to carry out invention)

Hereinafter, the present invention will be described in detail.

Liquid crystal aligning agent of the present invention, at least one kind of polymer, provided that said polymer is selected from the group consisting of a polyamic acid and a polyimide-containing one having a structure represented by the above formula (A ⁰⁾ on at least part in the molecule. Such a polymer is called "specific polymer" in the present invention. In particular the polymer structure represented by the above formula (A ⁰⁾ is, may be present in the main chain of the polymer, may be present in the side chain of the polymer, or may be present in the main chain and side chains both in the polymer.

Examples of X in the formula (A ^0), is preferably a divalent group represented by any of the formulas (X-1) ~ (X -3). In the above formula (X-1) and as the alkyl group having a carbon number of from 1 to 4 of R ^Ⅱ in the (X-2), for example, methyl group, ethyl group, n- propyl group, isopropyl group, n- butyl group Can be. As a C2-C5 carboxyalkyl group, a carboxymethyl group, 2-carboxyethyl group, 3-carboxy-n-propyl group, 4-carboxy-n-butyl group etc. are mentioned, for example. Formula Examples of R ^Ⅱ in the (X-1) and (X-2), a hydrogen atom, a methyl group, an ethyl group, an isopropyl group or a carboxyl group it is preferred, more preferably a hydrogen atom, a methyl group or a carboxyl group, especially carboxyl It is preferable that it is a group.

As a C1-C4 alkyl group of R <^I> , it is preferable that they are a C1-C2 alkyl group, ie, a methyl group or an ethyl group. As R ^I , a hydrogen atom is preferable.

M and n in the formula (A ⁰⁾ is, or m is n is 0 or 1 as the first, or preferably m is n is 0, a 2.

As the content of the structure represented by the above formula (A ⁰⁾ in the polymer, which it is desirable 0.00005~ 0.0035 mol / g, more preferably from 0.00025 to 0.0025 mol / g.

Polyamic acid having a structure represented by the formula (A ⁰ ) in at least part of the molecule is, for example

And a tetracarboxylic acid dianhydride comprising a compound having a structure and two carboxylic acid anhydride represented by the above formula (A ^0), by reacting with a diamine, or, or

And tetracarboxylic acid dianhydride, can be obtained by reacting a diamine and containing a compound having a structure and two amino groups represented by the above formula (A ^0),

G. Poly, for example, polyimide having a structure represented by the formula (A ⁰⁾ on at least part in the molecule can be obtained by dehydration ring-closure of the polyamic acid obtained as described above.

As the specific polymer contained in the liquid crystal aligning agent of the present invention, a tetracarboxylic acid dianhydride and the above formula (A ⁰⁾ as shown the structure and 2 by reacting the diamine and comprising a compound having two amino groups obtained polyamic acid and the art poly It is preferable that it is at least 1 sort (s) of polymer chosen from the group which consists of polyimide formed by dehydrating ring-closure of amic acid.

Hereinafter, the polyamic acid and polyimide which are preferable specific polymers in this invention are demonstrated in order.

<Polyamic acid>

As described above, the preferred polycarboxylic acid in the present invention can be obtained by reacting a diamine and containing a compound having the tetracarboxylic acid dianhydride, structure and two amino groups represented by the above formula (A ^0).

[Tetracarboxylic dianhydride]

As tetracarboxylic dianhydride used for synthesize | combining the polyamic acid in this invention, aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, etc. are mentioned, for example. As these specific examples, As an aliphatic tetracarboxylic dianhydride, For example, butanetetracarboxylic dianhydride etc .;

As alicyclic tetracarboxylic dianhydride, For example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5- tricarboxy cyclopentyl acetic dianhydride, 1,3,3a, 4, 5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4 , 5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3- Oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3 -Furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornan-2: 3,5: 6-2 anhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-2 anhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3 , 5,8,10-tetraon and the like;

As aromatic tetracarboxylic dianhydride, a pyromellitic dianhydride etc. are mentioned, respectively, for example,

The tetracarboxylic dianhydride described in patent document 15 (Japanese Unexamined-Japanese-Patent No. 2010-97188) can be used.

As tetracarboxylic dianhydride used for synthesize | combining the said polyamic acid, it is preferable to contain alicyclic tetracarboxylic dianhydride among these, and especially contains 2,3,5- tricarboxy cyclopentyl acetic dianhydride. It is preferable.

As tetracarboxylic dianhydride used for synthesize | combining the said polyamic acid, it is preferable to contain 2,3, 5- tricarboxylic cyclopentyl acetic dianhydride 10 mol% or more with respect to the total tetracarboxylic dianhydride, It is more preferable to contain 20 mol% or more.

As tetracarboxylic dianhydride used for synthesize | combining the said polyamic acid, what consists only of 2,3,5- tricarboxylic cyclopentyl acetic acid dianhydride, or

1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3- Most preferably, at least one selected from the group consisting of furanyl) -naphtho [1,2-c] furan-1,3-dione and only 2,3,5-tricarboxycyclopentylacetic acid dianhydride.

Diamine used to synthesize the preferred polyamic acid in the liquid crystal aligning agent of the present invention, the above formula (A ⁰⁾ structure and 2 (hereinafter referred to as "compound (A)"), compounds having one amino group represented by It is to include.

As a compound (A), following formula (A):

(Same as defined as in formula (A) of, X, R ^I, m and n are, respectively, the formula (A ⁰⁾⁾

It is preferable that it is a compound represented, and following formula (A-1)-(A-17) especially:

It is preferable to use at least 1 sort (s) chosen from the group which consists of compounds represented by each of the.

Such a compound (A) can be synthesize | combined by combining suitably the method of organic chemistry. For example, the following formula (A ⁰ -1):

(In formula (A ^0-1 ), X, R ^I , m and n have the same meanings as those in the formula (A ⁰ ), respectively.)

After reacting the compound represented by and halogenated dinitrobenzene to obtain a dinitro body which is an intermediate, the nitro group of the intermediate can be easily synthesized by using a suitable reducing system.

As a compound (A) used by this invention, the compound represented by each of said Formula (A-1)-(A-4) and (A-7)-(A-16) is preferable. Among them, at least one selected from the group consisting of compounds represented by each of (A-1) to (A-4) and (A-9) to (A-16), in particular, the formulas (A-1) to Use of at least one selected from the group consisting of compounds represented by each of (A-4) and (A-14) to (A-16) is preferable in that the light resistance of the formed liquid crystal alignment film can be further improved. ,

Printability of the liquid crystal aligning agent obtained when using at least 1 sort (s) chosen from the group which consists of a compound represented by said Formula (A-3), (A-4), and (A-7)-(A-10), respectively. It is preferable at the point which can make it more favorable.

As the diamine used for synthesizing the preferred polyamic acid in the present invention, only the compound (A) may be used alone, or the compound (A) and other diamines may be used in combination.

As other diamine which can be used here, an aliphatic diamine, alicyclic diamine, aromatic diamine, diamino organosiloxane, etc. are mentioned, for example. As these specific examples, As an aliphatic diamine, For example, 1, 1- metha xylylenediamine, 1, 3- propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, etc .;

As alicyclic diamine, For example, 1, 4- diamino cyclohexane, 4, 4'- methylenebis (cyclohexylamine), 1, 3-bis (aminomethyl) cyclohexane, etc .;

As aromatic diamine, for example, p-phenylenediamine, 4,4'- diaminodiphenylmethane, 4,4'- diaminodiphenyl sulfide, 1,5- diaminonaphthalene, 2,2'-dimethyl -4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,7-diaminofluorene, 4,4'-diamino Diphenylether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy Phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-(p-phenylenediisopropylidene) bisaniline, 4,4'-(m- Phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4 -Diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3 , 6-diaminocarbazole, N-phenyl-3,6- Aminocarbazole, N, N'-bis (4-aminophenyl) -benzidine, N, N'-bis (4-aminophenyl) -N, N'-dimethylbenzidine, dodecaneoxy-2,4-diamino Benzene, pentadecaneoxy-2,4-diaminobenzene, hexadecaneoxy-2,4-diaminobenzene, octadecaneoxy-2,4-diaminobenzene, dodecaneoxy-2,5-diaminobenzene, Pentadecaneoxy-2,5-diaminobenzene, hexadecaneoxy-2,5-diaminobenzene, octadecaneoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, chole Stenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestanyl, 3 , 5-diaminobenzoic acid cholesteryl, 3,5-diaminobenzoic acid ranostanyl, 2,5-diaminobenzoic acid, N, N'-bis- (4-aminophenyl) -piperazine, the following formula (D -One):

Compounds represented by these;

Examples of the diaminoorganosiloxanes include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and the like, and at least one diamine selected from these (hereinafter, "other specific diamines"). Can be used),

The diamine described in patent document 15 (Unexamined-Japanese-Patent No. 2010-97188) can be used with or instead of these.

As other diamines used in the present invention, it is preferable to use other specific diamines, and in particular, 3,5-diaminobenzoic acid, cholestanyloxy-2,4-diaminobenzene and 3,5-diaminobenzoic acid It is preferable to use at least 1 sort (s) chosen from the group which consists of cholestanyl.

It is preferable that the diamine used in order to synthesize | combine the polyamic acid contained preferably in the liquid crystal aligning agent of this invention contains a compound (A) 1 mol% or more with respect to all diamine, and it contains 5 mol% or more. More preferably, it is especially preferable to contain 10-90 mol%. Moreover, it is preferable that the diamine used for synthesize | combining preferable polyamic acid contains other specific diamine as mentioned above in addition to a compound (A). As the usage ratio of other specific diamine in this case, it is preferable that it is 30 mol% or more with respect to all diamine, It is more preferable that it is 50 mol% or more, It is preferable that it is especially 80 mol% or more.

It is preferable that the diamine used in order to synthesize | combine the polyamic acid contained preferably in the liquid crystal aligning agent of this invention consists only of a compound (A), or consists of a compound (A) and other specific diamine.

[Synthesis of Polyamic Acid]

The polyamic acid contained in the liquid crystal aligning agent of this invention is obtained by making tetracarboxylic dianhydride and the diamine containing a compound (A) react.

The use ratio of tetracarboxylic dianhydride and diamine to be used for the polyamic acid synthesis reaction is preferably such that the acid anhydride group of tetracarboxylic dianhydride is 0.2 to 2 equivalents to 1 equivalent of the amino group of the diamine. Preferably it is the ratio used as 0.3-1.2 equivalent.

The synthesis reaction of the polyamic acid is preferably in an organic solvent, preferably -20 ° C to 150 ° C, more preferably under a temperature condition of 0 to 100 ° C, preferably 0.1 to 24 hours, more preferably Is carried out for 0.5 to 12 hours.

As an organic solvent which can be used at the time of synthesis | combination of a polyamic acid, a non-protic polar solvent, a phenol and its derivatives, alcohol, a ketone, ester, an ether, a halogenated hydrocarbon, hydrocarbon, etc. are mentioned, for example. Examples of the aprotic polar solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, and tetramethylurea. , Hexamethylphosphortriamide and the like;

As said phenol derivative, For example, m-cresol, xylenol, a halogenated phenol etc .;

As said alcohol, For example, methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1, 4- butanediol, triethylene glycol, ethylene glycol monomethyl ether, etc .;

As said ketone, For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc .;

As said ester, For example, ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, diethyl oxalate, diethyl malonate, etc .;

Examples of the ethers include diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, Ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetra Hydrofuran and the like;

Examples of the halogenated hydrocarbons include dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene and the like;

As said hydrocarbon, hexane, heptane, octane, benzene, toluene, xylene, isoamyl propionate, isoamyl isobutylate, diisopentyl ether, etc. are mentioned, for example.

Among these organic solvents, at least one selected from the group consisting of aprotic polar solvents and phenols and derivatives thereof (first group of organic solvents), or at least one type and alcohols selected from the first group of organic solvents, Preference is given to using mixtures with at least one member selected from the group consisting of ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons (organic solvents of the second group). In the latter case, the use ratio of the organic solvent of the second group is preferably 50% by weight or less, and more preferably 40% by weight or less with respect to the total of the organic solvent of the first group and the organic solvent of the second group. Furthermore, it is preferable that it is 30 weight% or less.

As described above, a reaction solution obtained by dissolving polyamic acid is obtained.

This reaction solution may be used as it is for preparation of a liquid crystal aligning agent, may be provided to preparation of a liquid crystal aligning agent after isolating the polyamic acid contained in a reaction solution, or after refine | purifying the isolated polyamic acid, preparation of a liquid crystal aligning agent You may provide to.

When polyamic acid is dehydrated and closed, and it is set as polyimide, the said reaction solution may be used for a dehydration ring-closure reaction as it is, may be used for dehydration ring-closure reaction after isolating the polyamic acid contained in the reaction solution, or the isolated polyamic acid After purification, the dehydration ring-closure reaction may be used.

Isolation of polyamic acid is carried out by pouring the reaction solution in a large amount of poor solvent to obtain a precipitate, and drying the precipitate under reduced pressure, or by distilling off the solvent in the reaction solution with an evaporator under reduced pressure. I can do it. Further, the polyamic acid is again dissolved in an organic solvent, and then precipitated with a poor solvent, or the polyamic acid is dissolved in an organic solvent again, and after washing the solution, the organic solvent in the solution is reduced in pressure with an evaporator. Polyamic acid can be refine | purified by the method of performing the distillation process once or several times.

<Polyimide>

The polyimide which can be contained in the liquid crystal aligning agent of this invention can be obtained by dehydrating and ring-closing and imidating the polyamic acid obtained by the above.

As tetracarboxylic dianhydride used for the synthesis | combination of the preferable polyimide in this invention, the compound similar to tetracarboxylic dianhydride used for the synthesis | combination of polyamic acid mentioned above is mentioned. The kind of preferable tetracarboxylic dianhydride and its preferable use ratio are also the same as that of polyamic acid.

As diamine used in order to synthesize | combine the preferable polyimide in this invention, the diamine of the same kind as the diamine used for the synthesis | combination of said polyamic acid is mentioned. That is, the diamine used for the synthesis | combination of the polyimide contained in the liquid crystal aligning agent of this invention contains a compound (A), may use only a compound (A), and may use a compound (A) and other diamine together good.

It is preferable that the diamine used in order to synthesize | combine the polyamic acid contained preferably in the liquid crystal aligning agent of this invention contains a compound (A) 1 mol% or more with respect to all diamine, and contains 1-50 mol% It is more preferable, and it is preferable to contain 5-40 mol% especially. Moreover, it is preferable that the diamine used for synthesize | combining preferable polyamic acid contains other specific diamine as mentioned above in addition to a compound (A). As the usage ratio of other specific diamine in this case, it is preferable that it is 30 mol% or more with respect to all diamine, It is more preferable that it is 50 mol% or more, It is preferable that it is especially 80 mol% or more.

It is preferable that the diamine used in order to synthesize | combine the polyamic acid preferably contained in the liquid crystal aligning agent of this invention consists of a compound (A) and other specific diamine.

The polyimide preferably contained in the liquid crystal aligning agent of the present invention may be a complete imide obtained by dehydrating and ring-closing all the acid structures of the polyamic acid as a raw material. The partial imide which the structure coexists may be sufficient. It is preferable that the imidation ratio of the polyimide contained in the liquid crystal aligning agent of this invention preferably is 30% or more, It is more preferable that it is 40% or more, It is especially preferable that it is 50 to 80%. The said imidation ratio shows the ratio which the number of the number of the imide ring structures to the sum of the number of the dark acid structures of a polyimide, and the number of imide ring structures occupies as a percentage. At this time, a part of the imide ring may be an isoimide ring.

The dehydration ring closure of the polyamic acid is preferably heated by (i) a method of heating the polyamic acid, or (ii) the polyamic acid is dissolved in an organic solvent, and a dehydrating agent and a dehydration ring closure catalyst are added to the solution, if necessary. It is done by the method.

The reaction temperature in the method of heating the polyamic acid of said (i) becomes like this. Preferably it is 50-200 degreeC, More preferably, it is 60-170 degreeC. When reaction temperature is less than 50 degreeC, dehydration ring-closure reaction does not fully advance, but when reaction temperature exceeds 200 degreeC, the molecular weight of the polyimide obtained may fall. The reaction time is preferably 1.0 to 24 hours, more preferably 1.0 to 12 hours.

On the other hand, in the method of adding a dehydrating agent and a dehydrating ring-closure catalyst to the solution of the polyamic acid of said (ii), acid anhydrides, such as acetic anhydride, a propionic anhydride, a trifluoroacetic anhydride, can be used as a dehydrating agent, for example. Although the use ratio of a dehydrating agent depends on a desired imidation ratio, it is preferable to set it as 0.01-20 mol with respect to 1 mol of dark acid structures of polyamic acid. As the dehydration ring closure catalyst, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used, for example. However, it is not limited to these. It is preferable to make the use rate of a dehydration ring-closure catalyst into 0.01-10 mol with respect to 1 mol of dehydrating agents to be used. The imidation ratio can be raised so that the use rate of the said dehydrating agent and dehydration ring closure agent is large. As an organic solvent used for a dehydration ring-closure reaction, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid is mentioned. The reaction temperature of the dehydration ring-closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

The polyimide obtained in the said method (i) may be provided as it is to preparation of a liquid crystal aligning agent, or may be provided to preparation of a liquid crystal aligning agent after refine | purifying the polyimide obtained. On the other hand, in the said method (ii), the reaction solution containing a polyimide is obtained. This reaction solution may be provided as it is to preparation of a liquid crystal aligning agent as it is, may be provided to preparation of a liquid crystal aligning agent after removing a dehydrating agent and a dehydration ring-closure catalyst from a reaction solution, and after isolation of a polyimide to preparation of a liquid crystal aligning agent You may provide, or after refine | purifying an isolated polyimide, you may provide for preparation of a liquid crystal aligning agent. In order to remove a dehydrating agent and a dehydration ring-closure catalyst from a reaction solution, methods, such as solvent substitution, can be applied, for example. Isolation and purification of a polyimide can be performed by performing the same operation as the above as an isolation | purification and purification method of polyamic acid.

Terminal Modified Polymer

The polyamic acid and polyimide contained in the liquid crystal aligning agent of this invention may be a terminal modified polymer in which molecular weight was adjusted, respectively. By using the polymer of terminal modification type, the application | coating characteristic of a liquid crystal aligning agent, etc. can further be improved, without the effect of this invention being impaired. Such terminal-modified polymer can be performed by adding a suitable molecular weight regulator to a polymerization reaction system when synthesize | combining a polyamic acid. As a molecular weight modifier, an acid monoanhydride, a monoamine compound, a monoisocyanate compound, etc. are mentioned, for example.

As said acid monoanhydride, maleic anhydride, a phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n- tetradecyl succinic anhydride, n-hexadecyl succinic anhydride, etc. are mentioned, for example. have. Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n- Eicosylamine, etc. are mentioned. As said monoisocyanate compound, phenyl isocyanate, naphthyl isocyanate, etc. are mentioned, for example.

The use ratio of the molecular weight modifier is preferably 20 parts by weight or less, more preferably 10 parts by weight or less based on 100 parts by weight of the total amount of tetracarboxylic dianhydride and diamine used when synthesizing the polyamic acid.

Solution viscosity

When the polyamic acid and polyimide obtained as mentioned above are each made into the solution of 10 weight% of concentration, it is preferable to have a solution viscosity of 20-800 mPa * s, and it is more preferable to have a solution viscosity of 30-500 mPa * s. Do.

The solution viscosity (mPa * s) of the said polymer is 10 weight% of the density | concentration prepared using the quantity solvent of the said polymer (for example, (gamma) -butyrolactone, N-methyl- 2-pyrrolidone, etc.). About a polymer solution, it is the value measured at 25 degreeC using the E-type rotational viscometer.

<Other additives>

Although the liquid crystal aligning film of this invention contains the above-mentioned specific polymer as an essential component, you may contain other components as needed. Examples of such other components include other polymers, compounds having at least one epoxy group in the molecule (hereinafter referred to as "epoxy compound"), functional silane compounds, and the like.

[Other polymers]

The other polymer can be used for improving solution properties and electrical properties. Such other polymers are polyamic acids (hereinafter referred to as "other polyamic acids") obtained by reacting a tetracarboxylic acid dianhydride with a diamine containing no compound (A) with a polymer other than a specific polymer. Polyimide formed by dehydrating and closing polyamic acid (hereinafter referred to as "other polyimide"), polyamic acid ester, polyester, polyamide, polysiloxane, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide) Derivatives, poly (meth) acrylates, and the like. Among these, other polyamic acid or other polyimide is preferable.

As a usage ratio of other polymer, it is 85 weight% or less, More preferably, it is 50 weight% or less with respect to the sum total of a polymer (it says the sum total of said specific polymer and other polymers, the same below), More preferably, Preferably it is 40 weight% or less, It is especially preferable that it is 30 weight% or less, and it is especially preferable not to use other polymer.

[Epoxy Compound]

It is preferable that it is a compound which has at least 2 epoxy group in a molecule | numerator as said epoxy compound, For example, ethylene glycol diglycidyl ether, polyethyleneglycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol di Glycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylol propane triglycidyl ether, 2,2-dibromoneopentylglycol diglycidyl ether, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycid) Dilaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl-benzylamine, N, N-di Glycidyl-aminomethylcyclohexane, N, N- diglycidyl cyclohexylamine, etc. are mentioned as a preferable thing. .

The blending ratio of these epoxy compounds is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight with respect to 100 parts by weight in total of the polymer.

[Functional silane compound]

As said functional silane compound, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 2-aminopropyl trimethoxysilane, 2-aminopropyl triethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxy Silane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimeth Methoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecan, 10-triethoxysilyl-1,4,7-triazadecan, 9-trimethoxysilyl-3 , 6-diazanyl acetate, 9-trimethoxysilyl-3,6-diazanyl acetate, 9-triethoxysilyl-3,6-diazanyl acetate, 9-trimeth Methyl sisyl-3,6-diazanonanoic acid, 9-triethoxysilyl-3,6-methyl diazanonanate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltri Ethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 2- Glycidoxy ethyl trimethoxysilane, 2-glycidoxy ethyl triethoxysilane, 3-glycidoxy propyl trimethoxysilane, 3-glycidoxy propyl triethoxysilane, etc. are mentioned.

The compounding ratio of these functional silane containing compounds becomes like this. Preferably it is 2 weight part or less with respect to a total of 100 weight part of polymers, More preferably, it is 0.2 weight part or less.

<Liquid crystal aligning agent>

The liquid crystal aligning agent of this invention is melt | dissolved and contained in the organic solvent, Preferably the specific polymer mentioned above and other additives mix | blended arbitrarily as needed are comprised.

As an organic solvent which can be used for the liquid crystal aligning agent of this invention, for example, N-methyl- 2-pyrrolidone, (gamma) -butyrolactone, (gamma) -butyrolactam, N, N- dimethylformamide, N, N -Dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, ethylene glycol methyl ether, Ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl Ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate , Diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, di-isopentyl ether, ethylene carbonate, propylene carbonate, and the like. These may be used alone or in combination of two or more thereof.

Although solid content concentration (the ratio which the total weight of components other than the solvent of a liquid crystal aligning agent occupies in the total weight of a liquid crystal aligning agent) in the liquid crystal aligning agent of this invention is selected suitably in consideration of viscosity, volatility, etc., Preferably It is the range of 1-10 weight%. That is, the liquid crystal aligning agent of this invention is apply | coated to the surface of a board | substrate as mentioned later, Preferably, the coating film used as a liquid crystal aligning film is formed by heating, but when solid content concentration is less than 1 weight%, the film thickness of this coating film is too small. When it becomes impossible to obtain a favorable liquid crystal aligning film, and when solid content concentration exceeds 10 weight%, the film thickness of a coating film becomes excessive and a favorable liquid crystal aligning film cannot be obtained, Furthermore, the viscosity of a liquid crystal aligning agent increases and application | coating characteristics become Will fall.

The range of especially preferable solid content concentration changes with the method used when apply | coating a liquid crystal aligning agent to a board | substrate. For example, in the case of a spinner method, the range of 1.5 to 4.5 weight% of solid content concentration is especially preferable. In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by weight, and the solution viscosity is in the range of 12 to 50 mPa · s. When using the inkjet method, it is especially preferable to make solid content concentration into the range of 1 to 5 weight%, and to make solution viscosity into the range of 3-15 mPa * s.

The temperature at the time of preparing the liquid crystal aligning agent of this invention becomes like this. Preferably it is 10 degreeC-50 degreeC, More preferably, it is 20 degreeC-30 degreeC.

<Liquid crystal display element>

The liquid crystal display element of this invention is equipped with the liquid crystal aligning film formed from the above-mentioned liquid crystal aligning agent of this invention.

The liquid crystal display element of this invention can be manufactured by the process of the following (1)-(3), for example. In the step (1), the substrate used differs depending on the desired operation mode. Processes (2) and (3) are common in each operation mode.

(1) First, the liquid crystal aligning agent of this invention is apply | coated on a board | substrate, and then a coating film is formed on a board | substrate by heating a coating surface.

(1-1) When manufacturing a TN type, STN type, or VA type liquid crystal display element, two board | substrates with which the patterned transparent conductive film is formed are made into a pair, on this transparent conductive film formation surface, this invention The liquid crystal aligning agent is preferably applied by an offset printing method, a spin coating method or an inkjet printing method, respectively, and then each coating surface is heated to form a coating film. Here, as a board | substrate, For example, glass, such as a plot glass and a soda glass; A transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and poly (alicyclic olefin) can be used. As the transparent conductive film formed on one surface of the substrate, an NESA film (registered trademark of PPG Co., Ltd.) made of tin oxide (SnO ₂ ), an ITO film made of indium tin oxide (In ₂ O ₃ -SnO ₂ ), or the like can be used. It is possible to obtain a patterned transparent conductive film, for example, by forming a patternless transparent conductive film and then forming a pattern by photo etching, or by using a mask having a desired pattern when forming the transparent conductive film. can do. At the time of coating of the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional silane compound, a functional titanium compound, and the like are previously added to the surface on which the coating film should be formed on the substrate surface. Pretreatment to apply may be performed.

After application of the liquid crystal aligning agent, preheating (prebaking) is preferably performed for the purpose of preventing the liquid flow of the applied alignment agent. Prebaking temperature becomes like this. Preferably it is 30-200 degreeC, More preferably, it is 40-150 degreeC, Especially preferably, it is 40-100 degreeC. Prebaking time becomes like this. Preferably it is 0.25-10 minutes, More preferably, it is 0.5-5 minutes. Thereafter, the solvent is completely removed and a firing (postbaking) step is performed for the purpose of thermally imidating the polyamic acid as necessary. This baking (post-baking) temperature becomes like this. Preferably it is 80-300 degreeC, More preferably, it is 120-250 degreeC. Post-baking time becomes like this. Preferably it is 5-200 minutes, More preferably, it is 10-100 minutes. Thus, the film thickness of the film formed becomes like this. Preferably it is 0.001-1 micrometer, More preferably, it is 0.005-0.5 micrometer.

(1-2) On the other hand, when manufacturing an IPS type | mold liquid crystal display element, this invention is carried out on the electrically conductive film formation surface of the board | substrate in which the transparent conductive film patterned by the comb-tooth shape is formed, and the one surface of the opposing board | substrate in which the electrically conductive film is not formed. The liquid crystal aligning agent of preferably is apply | coated by an offset printing method, a spin coating method, or the inkjet printing method, respectively, and then each coating surface is heated, and a coating film is formed.

The material of the board | substrate and transparent conductive film used at this time, the patterning method of a transparent conductive film, the pretreatment of a board | substrate, and the heating method after apply | coating a liquid crystal aligning agent are the same as said (1-1).

Preferable film thickness of the coating film formed is the same as that of said (1-1).

(2) When the liquid crystal display element manufactured by the method of this invention is a VA type liquid crystal display element, the coating film formed as mentioned above can be used as a liquid crystal aligning film as it is, but if desired, the rubbing process described next You may provide for use after performing this.

On the other hand, when manufacturing liquid crystal display elements other than VA type, a rubbing process is given to the coating film formed as mentioned above, and it is set as a liquid crystal aligning film.

The rubbing treatment can be performed by rubbing in a predetermined direction with a roll wound with a cloth made of fibers such as nylon, rayon, cotton and the like on the coating film surface formed as described above. Thereby, the orientation ability of a liquid crystal molecule is provided to a coating film, and it becomes a liquid crystal aligning film.

Moreover, about the liquid crystal aligning film formed as mentioned above, liquid crystal as described, for example in patent document 12 (Unexamined-Japanese-Patent No. 6-222366) and patent document 13 (Japanese Unexamined-Japanese-Patent No. 6-281937). The resist film is applied to a part of the surface of the liquid crystal alignment film as a treatment for changing the pretilt angle of a part of the liquid crystal alignment film by irradiating a part of the alignment film with ultraviolet rays or as described in Patent Document 14 (Japanese Patent Laid-Open No. Hei 5-107544). After forming, the rubbing treatment is performed in a different direction from the preceding rubbing treatment, and then the resist film is removed to improve the field of view characteristics of the liquid crystal display device obtained by allowing the liquid crystal alignment film to have different liquid crystal alignment capabilities for each region. It is possible.

(3) The liquid crystal cell is manufactured by preparing two board | substrates with a liquid crystal aligning film as mentioned above, and arrange | positioning a liquid crystal between two board | substrates which oppose. Here, when the rubbing process is performed with respect to a coating film, two board | substrates are mutually arrange | positioned so that the rubbing direction in each coating film may mutually become a predetermined angle, for example, orthogonal or antiparallel.

The following two methods are mentioned, for example in manufacturing a liquid crystal cell.

The first method is a conventionally known method. First, two substrates are disposed to face each other so as to face each liquid crystal alignment film, and the peripheral portions of the two substrates are bonded together using a sealing agent, and the cells partitioned by the substrate surface and the sealing agent. After the liquid crystal is injected and filled into the gap, the liquid crystal cell can be manufactured by sealing the injection hole.

The second method is a method called an ODF (One Drop Fill) method. An ultraviolet-ray curable sealing compound is apply | coated to predetermined | prescribed place on one board | substrate among two board | substrates with which the liquid crystal aligning film was formed, and a liquid crystal is dripped further on the liquid crystal aligning film surface, and then the other is made so that a liquid crystal aligning film may oppose. A liquid crystal cell can be manufactured by bonding a board | substrate, then irradiating an ultraviolet light to the whole surface of a board | substrate, and hardening a sealing compound.

Even in the case of any of the methods, the liquid crystal cell produced as described above is subsequently heated to a temperature at which the used liquid crystal takes an isotropic phase, and then slowly cooled to room temperature, thereby adjusting the flow orientation during liquid crystal filling. It is desirable to remove.

And the liquid crystal display element of this invention can be obtained by bonding a polarizing plate to the outer surface of a liquid crystal cell.

Here, as a sealing agent, the epoxy resin etc. which contain the hardening agent and the aluminum oxide sphere as a spacer can be used, for example.

As said liquid crystal, a nematic liquid crystal, a smectic liquid crystal, etc. can be used, for example, a nematic liquid crystal is preferable among these. In the case of a VA type liquid crystal cell, a nematic liquid crystal having negative dielectric anisotropy is preferable, for example, a dicyano benzene liquid crystal, a pyridazine liquid crystal, a siphon base liquid crystal, a subfamily clock liquid crystal, a biphenyl liquid crystal, or a phenylcyclohexane System liquid crystal etc. are used. In the case of a TN type liquid crystal cell or an STN type liquid crystal cell, a nematic liquid crystal having positive dielectric anisotropy is preferable, for example, a biphenyl type liquid crystal, a phenylcyclohexane type liquid crystal, an ester liquid crystal, a terphenyl type liquid crystal, or a biphenyl. Cyclohexane-based liquid crystals, pyrimidine-based liquid crystals, dioxane-based liquid crystals, bicyclooctane-based liquid crystals, cuban-based liquid crystals and the like are used. For these liquid crystals, For example, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonaate, cholesteryl carbonate; Chiral agents such as those sold under the trade names C-15 and CB-15 (manufactured by Merck); Strong dielectric liquid crystals such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate may be further added and used.

As a polarizing plate bonded to the outer surface of a liquid crystal cell, the polarizing plate which consists of a polarizing plate which sandwiched the polyvinyl alcohol, and absorbed iodine, and sandwiched the polarizing film called "H film" with the cellulose acetate protective film, or the H film itself is mentioned. Can be.

(Example)

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not restrict | limited to these Examples. The solution viscosity of the polymer in the following synthesis examples, and the imidation ratio of the polyimide were evaluated by the following method.

[Solution Viscosity of Polymer]

The solution viscosity (mPa * s) of a polymer was measured at 25 degreeC using the E-type rotational viscometer about the N-methylpyrrolidone solution adjusted to the polymer concentration of 10 weight%, respectively.

[Imidation Rate of Polyimide]

In the imidation ratio of the polymer, a small amount of the solution of the polyimide obtained in each synthesis example was added to pure water, the resulting precipitate was collected, dried under reduced pressure at room temperature, and then dissolved in deuterated dimethyl sulfoxide. It calculated | required by following formula (1) from the ¹ H-NMR spectrum measured at room temperature using tetramethylsilane as a reference substance.

Imidation ratio (%) = (1-A ¹ / A ² × α) × 100 (1)

(In Formula (1), A <^1> is the peak area derived from the proton of the NH group which shows around 10 ppm of chemical shifts, A <^2> is the peak area derived from other protons, and (alpha) is a precursor (polyamic acid) of a polymer. It is number ratio of other protons to one proton of NH group.)

Synthesis Example of Compound (A)

Synthesis Example S-1

According to following Reaction Formula 1, the compound (compound (A-1)) represented by said formula (A-1) was synthesize | combined.

In a 3,000 mL flask, 186.1 g (1.00 mole) of 2,4-dinitrofluorobenzene, 152.0 g (1.10 mole) of potassium carbonate and 1,000 mL of dimethylsulfoxide were mixed, and 148.5 mL (1.50 mole) of piperidine ) Was added and the reaction was carried out at 80 ° C. under stirring for 1 hour. After the completion of the reaction, the organic layer obtained by adding 4,000 mL of ethyl acetate to the reaction mixture was washed four times with 1,000 mL of ion-exchanged water, dehydrated with magnesium sulfate, and then magnesium sulfate was removed by filtration. 231.1 g (0.92 mol) of compounds (A-1-a) were obtained by recrystallizing the solid obtained by removing a solvent from the filtrate under reduced pressure from 500 mL of ethanol.

Next, 226.1 g (0.90 mol) of the compound (A-1-a) obtained above, 21.8 g of palladium carbon (Pd / C), 2,000 mL of ethanol and 1,000 mL of tetrahydrofuran were added in a 5,000 mL three-neck flask under a nitrogen atmosphere. Mixed. Here, 220 mL of hydrazine monohydrate was slowly added while paying attention to the temperature so that the temperature of the reaction system did not reach 40 ° C, and then the reaction was carried out under nitrogen for 1 hour at 25 ° C, followed by 4 hours at 70 ° C. After completion of the reaction, the catalyst was removed from the reaction mixture by celite filtration, and then the solvent was removed from the filtrate under reduced pressure to obtain a solid. The solution obtained by dissolving the obtained solid in 4,000 mL of ethyl acetate was washed four times with 1,000 mL of ion-exchanged water, dehydrated with magnesium sulfate, and then magnesium sulfate was removed by filtration. 99.5 g (0.52 mol) of compound (A-1) were obtained by recrystallizing the solid obtained by removing a solvent from the filtrate under reduced pressure from the mixed solvent which consists of 50 mL of ethyl acetate and 400 mL of hexane.

Synthesis Example S-2

According to the following Reaction Formula 2, the compound (compound (A-3)) represented by the formula (A-3) was synthesized.

In a 3,000 mL flask, 193.7 g (1.50 mol) of isonipecotic acid, 186.1 g (1.00 mol) of 2,4-dinitrofluorobenzene, 167.1 g (1.10 mol) cesium fluoride, and dimethyl sulfoxide 1,000 The mL was mixed and reacted at 25 degreeC under stirring for 12 hours. After completion of the reaction, the organic layer obtained by adding 3,000 mL of ethyl acetate to the reaction mixture was washed four times with 1,000 mL of ion-exchanged water, dehydrated with magnesium sulfate, and then magnesium sulfate was removed by filtration. 224.4 g (0.76 mol) of Compound (A-3-a) was obtained by recrystallizing the solid obtained by removing a solvent from the filtrate under reduced pressure from 1,000 mL of ethyl acetate.

Subsequently, 221.4 g (0.75 mol) of Compound (A-3-a), 18.7 g of palladium carbon (Pd / C), 1,200 mL of ethanol and 1,200 mL of tetrahydrofuran were added in a 5,000 mL three-neck flask under nitrogen atmosphere. After mixing, 185 mL of hydrazine monohydrate was slowly added thereto, paying attention to the temperature so that the temperature of the reaction system did not reach 40 ° C, and then the reaction was carried out at 25 ° C for 1 hour, then at 70 ° C for 1.5 hours, under stirring. After completion of the reaction, the catalyst was removed from the reaction mixture by celite filtration, and then the solvent was removed from the filtrate under reduced pressure to obtain a solid. The obtained solid is purified by column chromatography (filler: silica gel (manufactured by Merck, product name "Silica gel 60"), developing solvent: mixed solvent consisting of chloroform and ethanol (chloroform: ethanol = 20: 1 (volume ratio))), By removing the solvent from the residue, 35.3 g (0.15 mol) of compound (A-3) was obtained.

Synthesis Example S-3

According to Reaction Scheme 3 below, a compound (compound (A-12)) represented by Formula (A-12) was synthesized.

In a 3,000 mL flask, 186.1 g (1.00 mol) of 2,4-dinitrofluorobenzene, 152.0 g (1.10 mol) of potassium carbonate, 204.6 mL (1.50 mol) of 3,5-dimethylpiperidine and 1,000 dimethyl sulfoxide The mL was mixed and reacted under stirring at 80 degreeC for 5 hours. After the completion of the reaction, the organic layer obtained by adding 4,000 mL of ethyl acetate to the reaction mixture was washed four times with 1,000 mL of ion-exchanged water, dehydrated with magnesium sulfate, and then magnesium sulfate was removed by filtration. The solid obtained by removing the solvent from the filtrate under reduced pressure was recrystallized from 500 mL of ethanol to obtain 262.5 g (0.94 mol) of compound (A-12-a).

Subsequently, 251.4 g (0.90 mol) of the compound (A-12-a) obtained above, 21.8 g of palladium carbon (Pd / C), 2,000 mL of ethanol and 1,000 mL of tetrahydrofuran were added in a 5,000 mL three-neck flask under a nitrogen atmosphere. After mixing, 220 mL of hydrazine monohydrate was added slowly, paying attention to temperature so that the temperature of a reaction system may not reach 40 degreeC, and then reaction was performed at 25 degreeC for 1 hour, then 70 degreeC for 4 hours, and stirring. After completion of the reaction, the catalyst was removed from the reaction mixture by celite filtration, and then the solvent was removed from the filtrate under reduced pressure to obtain a solid. The solution obtained by dissolving the obtained solid in 4,000 mL of ethyl acetate was washed four times with 1,000 mL of ion-exchanged water, dehydrated with magnesium sulfate, and then magnesium sulfate was removed by filtration. 142.6 g (0.65 mol) of Compound (A-12) was obtained by recrystallizing the solid obtained by removing a solvent from the filtrate under reduced pressure from the mixed solvent which consists of 80 mL of ethyl acetate and 400 mL of hexane.

Synthesis Example S-4

According to following Reaction Formula 4, the compound (compound (A-14)) represented by said formula (A-14) was synthesize | combined.

In a 3,000 mL flask, 202.6 g (1.0 mole) of 2,4-dinitrochlorobenzene, 120.2 g (1.2 mole) of 1-methylpiperazine, 92.4 g (1.1 mole) of sodium hydrogen carbonate, and 1,000 mL of ethanol were mixed, The reaction was carried out at 25 ° C. under stirring for 12 hours. After completion of the reaction, the organic layer obtained by adding 3,000 mL of ethyl acetate to the reaction mixture was washed four times with 1,000 mL of ion-exchanged water, dehydrated with magnesium sulfate, and then magnesium sulfate was removed by filtration. The solvent was removed from the filtrate under reduced pressure to obtain 242.3 g (0.91 mol) of compound (A-14-a).

Next, 239.6 g (0.90 mol) of the compound (A-14-a) obtained above, 21.8 g of palladium carbon (Pd / C), 1,350 mL of ethanol, and 1,350 mL of tetrahydrofuran were added in a 5,000 mL three-neck flask in a nitrogen atmosphere. After mixing, 220 mL of hydrazine monohydrate was added slowly, paying attention to temperature so that the temperature of a reaction system may not reach 40 degreeC, and then reaction was performed at 25 degreeC for 1 hour, then 70 degreeC for 4 hours, and stirring. After completion of the reaction, the catalyst was removed from the reaction mixture by celite filtration, and then the solvent was removed from the filtrate under reduced pressure to obtain a solid. The resulting solid was dissolved in 4,000 mL of ethyl acetate, and the resulting solution was washed four times with 1,000 mL of ion-exchanged water, dehydrated with magnesium sulfate, and then the magnesium sulfate was removed by filtration. The solvent was removed from the filtrate under reduced pressure to obtain a solid. Got it. The obtained solid is purified by column chromatography (filler: silica gel (manufactured by Merck, product name "Silica gel 60"), developing solvent: mixed solvent consisting of chloroform and ethanol (chloroform: ethanol = 20: 1 (volume ratio))), By removing the solvent from the residue, 169.2 g (0.82 mol) of compound (A-14) was obtained.

Synthesis Example S-5

Scheme 5:

According to the above, a compound (Compound (A-16)) represented by Formula (A-16) was synthesized.

In a 3,000 mL flask, 202.6 g (1.0 mole) of 2,4-dinitrochlorobenzene, 104.5 g (1.2 mole) of morpholine, 92.4 g (1.1 mole) of sodium hydrogen carbonate and 1,000 mL of ethanol are mixed and at 25 ° C. The reaction was carried out under stirring for 12 hours. After completion of the reaction, the organic layer obtained by adding 3,000 mL of ethyl acetate to the reaction mixture was washed four times with 1,000 mL of ion-exchanged water, dehydrated with magnesium sulfate, and then magnesium sulfate was removed by filtration. The solvent was removed from the filtrate under reduced pressure to obtain 220.3 g (0.87 mol) of compound (A-16-a).

Subsequently, 202.6 g (0.80 mol) of the compound (A-16-a) obtained above, 20.0 g of palladium carbon (Pd / C), 1,200 mL of ethanol, and 1,200 mL of tetrahydrofuran were added in a 5,000 mL three-necked flask under a nitrogen atmosphere. After mixing, 187 mL of hydrazine monohydrate was added slowly, paying attention to temperature so that the temperature of a reaction system might not reach 40 degreeC, and then it reacted at 25 degreeC for 1 hour, then at 70 degreeC for 3.5 hours, and stirring. After completion of the reaction, the catalyst was removed from the reaction mixture by celite filtration, and then the solvent was removed from the filtrate under reduced pressure to obtain a solid. The obtained solid is purified by column chromatography (filler: silica gel (manufactured by Merck, product name "Silica gel 60"), developing solvent: mixed solvent consisting of chloroform and ethanol (chloroform: ethanol = 20: 1 (volume ratio))), 146.87 g (0.76 mol) of Compound (A-16) were obtained by removing a solvent from this residue.

Synthesis of Polymer

Synthesis Examples 1-11

To N-methyl-2-pyrrolidone, diamine and tetracarboxylic dianhydride in the amounts shown in the first table were added in this order to prepare a solution having a monomer concentration of 20% by weight and reacting at 60 ° C for 4 hours. The solution containing polyamic acid (PA-1) (PA-11)-was obtained, respectively. A small amount of each solution was aliquoted, and the solution viscosity measured by adding N-methyl-2-pyrrolidone as a solution having a polyamic acid concentration of 10% by weight is shown in the first table.

Each half of these polyamic acid solutions was ensured and used in Examples 17 to 28 and Comparative Examples 5 to 8, respectively.

Pyridine and acetic anhydride are added to the remaining half of each of the polyamic acid solutions so as to have the molar ratios described in Table 1 with respect to 1 mole of the acid units contained in the polyamic acid, respectively, and then heated to 110 ° C for 4 hours of dehydration ring closure reaction. Done. After the dehydration ring closure reaction, the solvent in the system was substituted with fresh N-methyl-2-pyrrolidone (pyridine and acetic anhydride used in the dehydration ring closure reaction in this operation were removed to the outside of the system. Solutions containing 16% by weight of 1) to (PI-11), respectively, were obtained. The imidation ratio of each polyimide and each solution contained in these polyimide solutions were fractionated, and the solution viscosity measured as the N-methyl- 2-pyrrolidone solution of 10 weight% of polyimide density | concentration was 1st, respectively. Shown in the table.

These polyimide solutions were used in subsequent Examples 1-16 and 28 and Comparative Examples 1-4, respectively.

Synthesis Examples 12-17

To N-methyl-2-pyrrolidone, diamine and tetracarboxylic dianhydride in the amounts shown in the first table were added in this order to prepare a solution having a monomer concentration of 20% by weight, and reaction at 60 ° C for 4 hours. The solution containing polyamic acid (PA-12)-(PA-17) was obtained, respectively. A small amount of each solution was aliquoted, and the solution viscosity measured by adding N-methyl-2-pyrrolidone as a solution having a polyamic acid concentration of 10% by weight is shown in the first table.

These polyamic acid solutions were used in subsequent Examples 29-35, respectively.

Synthesis Examples 18 and 19

To N-methyl-2-pyrrolidone, diamine and tetracarboxylic dianhydride in the amounts shown in the first table were added in this order to prepare a solution having a monomer concentration of 20% by weight, and reaction at 60 ° C for 4 hours. The solution containing polyamic acid (PA-18) and (PA-19) was obtained, respectively. Each solution was aliquoted a little, and the solution viscosity measured by adding N-methyl- 2-pyrrolidone as a solution of 10 weight% of polyamic acid concentration is shown in the 1st table | surface.

Pyridine and acetic anhydride were added to each of the polyamic acid solutions so as to have a molar ratio as described in Table 1 with respect to 1 mole of the dark acid unit contained in the polyamic acid, respectively, and then heated to 110 ° C to perform a dehydration ring closure reaction for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was solvent-substituted with fresh N-methyl-2-pyrrolidone to obtain a solution containing 16 wt% of polyimide (PI-18) and (PI-19), respectively. The imidation ratio of each polyimide and each solution contained in these polyimide solutions were fractionated, and the solution viscosity measured as the N-methyl- 2-pyrrolidone solution of 10 weight% of polyimide density | concentration was 1st, respectively. Shown in the table.

These polyimide solutions were used in the following Example 36 and the comparative example 9, respectively.

In addition, in the 1st table | surface, the abbreviation of diamine and tetracarboxylic anhydride has the following meanings, respectively.

<Diamine>

A-1, A-3, A-12, A-14 and A-16: Compounds (A-1), (A-3) and (A) synthesized in Synthesis Examples S-1 to S-5, respectively. -12), (A-14) and (A-16)

d-1: 3,5-diaminobenzoic acid

d-2: cholestanyloxy-2,4-diaminobenzene

d-3: 3,5-diaminobenzoic acid cholestanyl

d-4: p-phenylenediamine

d-5: 4,4'-diaminodiphenylmethane

d-6: N, N'-bis (4-aminophenyl) piperazine

d-7: compound represented by the above formula (D-1)

<Tetracarboxylic dianhydride>

t-1: 2,3,5-tricarboxycyclopentyl acetic acid dianhydride

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

t-3: 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c Furan-1,3-dione

<Preparation and evaluation of liquid crystal aligning agent>

Example 1

(I) Preparation of liquid crystal aligning agent

(1) Preparation of liquid crystal aligning agent for printability evaluation

N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) were added to the solution containing 100 weight part of polyimide (PI-1) obtained by the said synthesis example 1, and a solvent composition is NMP: BC It was set as the solution of = 70: 30 (weight ratio) and solid content concentration 6.5weight%. The liquid crystal aligning agent for printability evaluation was prepared by filtering this solution using the filter of 1 micrometer of pore diameters.

(2) Preparation of liquid crystal aligning agent for liquid crystal display element manufacture

In the preparation of the liquid crystal aligning agent for evaluating printability, the liquid crystal aligning agent for liquid crystal display element manufacture was prepared like the above except having made solid content concentration of the solution before filtration into 4.0 weight%.

(II) Evaluation of the liquid crystal aligning agent

The two types of alignment agents prepared above were evaluated by the following methods, respectively. The evaluation result was shown to the 2nd table | surface.

(1) evaluation of printability

About the liquid crystal aligning agent for evaluation of the printability prepared above, the liquid crystal aligning agent dropping quantity to an anis roll was carried out on the conditions of 15 drops (about 0.15 g) reciprocating using a liquid crystal aligning film printing machine (made by Nippon Shin-Shin Insatsu Co., Ltd.). And the transparent electrode surface of the glass substrate with a transparent electrode which consists of an ITO film | membrane. The liquid crystal aligning agent dropping amount described above is less strict than the dropping amount (30 drops of reciprocation, about 0.3 g) usually employed in a printer of the same type, and is a more stringent printing condition. The board | substrate after apply | coating a liquid crystal aligning agent was heated (prebaked) at 80 degreeC for 1 minute, and after removing a solvent, it heated at 180 degreeC for 10 minutes (postbaking), and formed the coating film of 600 kPa of average film thicknesses. The coating film was observed under a microscope with a magnification of 20 times to investigate the presence of unevenness and coating unevenness, and both cases were observed as coating property "good", and when either was observed as coating property "bad" Evaluated. In addition, among things evaluated as applicability "good", applicability "very good" was made about the thing with especially favorable linearity of the outer end of a coating film.

About the coating film formed above, the film thickness in the center of a board | substrate and the film thickness in the position which deviated to 15 mm center from the outer end of a coating film were measured using a stylus type thickness meter (made by KLA-Tencor), respectively. The film thickness difference between them was examined. When this film thickness difference is 50 GPa or less, it can be said that film thickness uniformity is favorable. Moreover, when the said film thickness difference is 25 micrometers or less, it can be said that film thickness uniformity is very favorable.

(2) Production of Vertically Aligned Liquid Crystal Display Element

On the transparent conductive film which consists of an ITO film formed on one surface of the glass substrate of thickness 1mm, the liquid crystal aligning agent for liquid crystal display element manufacture prepared above was apply | coated with a spinner, prebaking for 1 minute at 80 degreeC on a hotplate, Subsequently, by post-baking at 220 degreeC for 15 minutes, the coating film (liquid crystal aligning film) of 800 micrometers of average film thickness was formed. This operation was repeated and two (pair) board | substrates which have a liquid crystal aligning film were manufactured.

After apply | coating the aluminum oxide sphere containing epoxy resin adhesive of diameter 3.5micrometer to the outer edge of the surface which has one liquid crystal aligning film among these pairs of board | substrates, it overlaps and crimps | bonds so that a liquid crystal aligning film surface may face, and an adhesive agent Hardened. Subsequently, after filling a negative type liquid crystal (MLC-6608 by Merck Co., Ltd.) between a pair of board | substrates from a liquid crystal injection port, a liquid crystal injection port is sealed with acrylic photocuring adhesive agent, and a polarizing plate is bonded to both surfaces of the outer side of a board | substrate. , The liquid crystal display element of the vertical alignment type was manufactured.

(3) evaluation of light resistance

To the liquid crystal display device manufactured above, after applying a voltage of 5 V at 70 ° C. with an application time of 60 microseconds and a span of 167 milliseconds, a voltage retention rate of 167 milliseconds after the release of the application was manufactured by Toyo Technica Co., Ltd. It measured by "VHR-1". The numerical value at this time was made into the initial voltage holding ratio (VHR _BF ).

Subsequently, 5,000 hours of light irradiation was performed with respect to the liquid crystal cell after the initial voltage retention measurement using the weather meter which uses carbon arc as a light source.

About the liquid crystal cell after light irradiation, the voltage holding ratio was measured again by the same method as the above. The numerical value at this time was made into voltage retention (VHR _AF ) after light irradiation.

From the VHR _BF and VHR _AF measured above, the change rate of the voltage holding ratio before and behind light irradiation was calculated | required. These values were shown to the 2nd table | surface, respectively. When the said rate of change was less than 5.0%, light resistance was considered "good", and when the said rate of change was 5.0% or more, light resistance was evaluated as "defect".

Examples 2 to 35 and Comparative Examples 1 to 8

As a solution containing a polymer, using the solution containing the polymer shown in the 2nd table, respectively, and describing in the 2nd table, in the preparation of a liquid crystal aligning agent, after adding NMP and BC to a polymer solution, the 2nd table The liquid crystal aligning agent was prepared and evaluated similarly to Example 1 except having added the epoxy compound of the kind and quantity specifically described to the above. The evaluation result was also shown in the 2nd table | surface. In addition, in Examples 28-35, two types of polymer solutions of the kind and quantity described in the 2nd table were mixed and used.

In addition, abbreviated-name of an epoxy compound is the following meanings, respectively in a 2nd table | surface.

G-1: N, N, N'N'-tetraglycidyl-4,4'-diaminodiphenylmethane

G-2: N, N, N'N'-tetraglycidyl-m-xylenediamine

Example 36 and Comparative Example 9

(I) Preparation of liquid crystal aligning agent

As the solution containing the polymer, NMP and BC were added to the polymer solution using the solution containing the polymer shown in Table 3, respectively, except that an epoxy compound of the kind and amount specifically described in Table 3 was further added. And the liquid crystal aligning agent for printability evaluation, and the liquid crystal aligning agent for liquid crystal display element manufacture were prepared like Example 1, respectively.

(II) Evaluation of the liquid crystal aligning agent

(1) evaluation of printability

The printability was evaluated like Example 1 using the liquid crystal aligning agent for printability evaluation prepared above. The evaluation results are shown in Table 3.

(2) Fabrication of TN type liquid crystal display element

On the transparent conductive film which consists of an ITO film formed on one surface of the glass substrate of thickness 1mm, the liquid crystal aligning agent for liquid crystal display element manufacture prepared above was apply | coated with a spinner, prebaking for 1 minute at 80 degreeC on a hotplate, Subsequently, it post-baked at 220 degreeC for 15 minutes, and formed the coating film with an average film thickness of 800 Pa. About this coating film, the rubbing process was performed on the conditions of a roll rotation speed of 400 rpm, a stage movement speed of 3 cm / sec, and a hair pressing indentation length of 0.4 mm using the rubbing machine which has the roll which wound the rayon cloth. Subsequently, the board | substrate which has the coating film after this rubbing process was ultrasonically cleaned for 1 minute in ultrapure water, and dried for 10 minutes in a 100 degreeC clean oven, and the liquid crystal aligning film was formed on the transparent electrode surface of a glass substrate. This operation was repeated and two (pair) board | substrates which have a liquid crystal aligning film were manufactured.

After apply | coating the aluminum oxide sphere containing epoxy resin adhesive of diameter 3.5micrometer to the outer edge of the surface which has one liquid crystal aligning film among these pairs of board | substrates, it overlapped and crimped | bonded so that the liquid crystal aligning film surface could face and hardened the adhesive agent. Subsequently, after filling a positive type liquid crystal (MLC-6221 made by Merck Co., Ltd.) between a pair of board | substrates from a liquid crystal inlet, the liquid crystal inlet is sealed with acrylic photocuring adhesive, and a polarizing plate is bonded to both surfaces of the outer side of a board | substrate. And TN liquid crystal display elements were manufactured.

(3) evaluation of light resistance

About the liquid crystal display element manufactured above, light resistance was evaluated like Example 1. The evaluation results are shown in Table 3.

Claims (8)

A liquid crystal aligning agent comprising at least one polymer selected from the group consisting of polyamic acid and polyimide, provided that at least part of the polymer has a structure represented by the following formula (A ⁰ ) in the molecule:

Wherein (A ^0), X is the formula (X-1) ~ (X -4):

(In formula (X-1) and (X-2), R ^II is a hydrogen atom, a C1-C4 alkyl group, a carboxyl group, or a C2-C5 carboxyalkyl group.)
Is a divalent group represented by any of which R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, m is 1 or 2, and n is 0 or 1. The method of claim 1,
The polymer is tetracarboxylic dianhydride and
Formula (A):

(Same as defined as in formula (A) of, X, R ^I, m and n are, respectively, the formula (A ⁰⁾⁾
Diamine containing a compound represented by
The liquid crystal aligning agent which is at least 1 sort (s) of polymer chosen from the group which consists of polyamic acid obtained by making it react and polyimide formed by dehydrating and ring-closing the said polyamic acid. The method of claim 2,
The liquid crystal aligning agent of bivalent group in which X in said Formula (A) is represented by any of said Formula (X-1)-(X-3). The method according to claim 2 or 3,
The liquid crystal aligning agent whose R <^II> in said Formula (X-1) and (X-2) is a hydrogen atom or a carboxyl group. The liquid crystal aligning film formed from the liquid crystal aligning agent of any one of Claims 1-3 is provided. The liquid crystal display element characterized by the above-mentioned. Tetracarboxylic dianhydride
To the diamine containing the compound represented by said Formula (A) of Claim 2
Polyamic acid obtained by making it react. Tetracarboxylic dianhydride
To the diamine containing the compound represented by said Formula (A) of Claim 2
Polyimide formed by dehydrating and ring-closing polyamic acid obtained by reaction. Compound represented by the following formula (A):

(Wherein (A) of, X, R ^I, m and n are, each being the same meaning as in the formula (A ⁰⁾ as defined in claim 1).