KR20080028318A - Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display device - Google Patents

Abstract

A liquid crystal aligning agent is provided to ensure good printability, and form liquid crystal aligning films capable of reducing charge-up ions while maintaining a voltage holding ratio. A liquid crystal aligning agent includes a compound represented by the following formula 1, wherein each of R1-R8 is independently a hydrogen atom, alkyl group, or alkoxy group, each of R9-R12 is independently a hydrogen atom, aromatic group, or aliphatic group, A is a hydrogen atom or aliphatic group, and n is an integer of 1-100. A liquid crystal display device has a liquid crystal aligning film obtained from the liquid crystal aligning agent.

Description

Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element {LIQUID CRYSTAL ALIGNING AGENT, LIQUID CRYSTAL ALIGNMENT FILM AND LIQUID CRYSTAL DISPLAY DEVICE}

This invention relates to a liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element. In more detail, it is related with the liquid crystal aligning agent which provides the liquid crystal aligning film which has a favorable electrical characteristic, and printability, the said liquid crystal aligning film, and the liquid crystal display element containing the same.

Currently, as a liquid crystal display element, the liquid crystal aligning film containing polyamic acid, polyimide, etc. is formed in the surface of the board | substrate with which the transparent conductive film is provided, and it is set as a board | substrate for liquid crystal display elements, and two of these are opposingly arranged and positive in the clearance gap is carried out. A so-called TN (Twisted Nematic) type in which a layer of a nematic liquid crystal having dielectric anisotropy is formed to form a sandwich cell and the long axis of the liquid crystal molecules is continuously twisted 90 degrees from one substrate to the other substrate. TN type liquid crystal display elements having a liquid crystal cell are known. In addition, STN (Super Twisted Nematic) type liquid crystal display elements and vertically oriented liquid crystal display elements have been developed that have higher contrast and less visual dependence than TN type liquid crystal display elements. This STN type liquid crystal display element uses a blend of nematic liquid crystals with a chiral agent, an optically active substance, as a liquid crystal, and the birefringence generated when the major axis of the liquid crystal molecules is continuously twisted over 180 degrees between the substrates. To use the effect. About these, as described in the following nonpatent literature 1 and patent document 1, the vertically-aligned liquid crystal display element called MVA system which forms a processus | protrusion on ITO and controls the orientation direction of a liquid crystal was proposed. The liquid crystal display element of MVA system is excellent in a viewing angle, contrast, etc., and is excellent also in a manufacturing process aspect, such as not having to perform a rubbing process in formation of a liquid crystal aligning film. As a liquid crystal aligning film suitable for TN, STN, and MVA system, performance, such as afterimage erasing time of a liquid crystal display element, is calculated | required. Moreover, as an aligning agent used for formation of these liquid crystal aligning films, the outstanding printability in offset printing is calculated | required.

[Non-Patent Document 1] "Liquid Crystal" Vol. 3, No. 2, 117 (1999)

[Patent Document 1] Japanese Patent Application Laid-Open No. 11-258605

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object thereof is to provide a liquid crystal aligning film which maintains a voltage retention and at the same time reduces accumulated charges, and has a more excellent printability, the liquid crystal aligning film and a liquid crystal using the same. It is to provide a display element.

Still other 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 are, firstly,

It is achieved by the liquid crystal aligning agent containing the compound represented by following General formula (1, hereafter may be called a specific compound).

(Wherein, R ₁ to R ₈ are each independently a hydrogen atom, an alkyl group or an alkoxy group, R ₉ to R ₁₂ are each independently a hydrogen atom, an aromatic group or an aliphatic group, A is a hydrogen atom or an aliphatic group, n is an integer from 1 to 100)

In Formula 1, R ₁ to R ₈ are each independently a hydrogen atom, an alkyl group of 1 to 6 carbon atoms or an alkoxy group of 1 to 6 carbon atoms, R ₉ to R ₁₂ are all hydrogen atoms, A is a hydrogen atom, Compounds in which n is an integer from 1 to 100 are preferred compounds.

In Formula 1, R ₁ to R ₈ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, R ₉ and R ₁₁ are aromatic groups, and R ₁₀ and R ₁₂ are hydrogen Another preferred compound is a compound which is an atom or an aliphatic group, A is a hydrogen atom or an aliphatic group and n is an integer from 1 to 100.

In Formula 1, R ₁ to R ₈ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, R ₉ and R ₁₁ are aromatic groups, and R ₁₀ and R ₁₂ A compound in which is an aliphatic group containing hydrogen or an epoxy group, A is an aliphatic group containing a hydrogen atom or an epoxy group, and n is an integer of 1 to 100 is a more preferable compound.

According to the present invention, the above objects and advantages of the present invention are second,

In Formula 1, R ₁ to R ₈ are each independently a hydrogen atom, an alkyl group of 1 to 6 carbon atoms or an alkoxy group of 1 to 6 carbon atoms, R ₉ to R ₁₂ are all hydrogen atoms, A is a hydrogen atom, To the liquid crystal aligning agent containing polyamic acid polymer (Hereinafter, it may be called a specific polyamic acid polymer.) obtained by reaction of the said preferable compound whose n is an integer of 1-100 with tetracarboxylic dianhydride. Is achieved.

In addition, the liquid crystal aligning agent of the present invention may be a polyamic acid comprising a polyamic acid including a repeating unit represented by the following Formula 1a, and at least one of the specific compound and the specific polyamic acid polymer. It may contain at least one polymer selected from the group consisting of meads.

(Wherein P ¹ is a tetravalent organic group and Q ¹ is a divalent organic group)

(Wherein P ² is a tetravalent organic group and Q ² is a divalent organic group)

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The liquid crystal aligning agent of the present invention is preferably constituted by dissolving at least one of a specific compound and a specific polyamic acid polymer, and at least one polymer selected from polyamic acid and polyimide in an organic solvent.

[Specific Compounds]

In formula (1), R ₁ to R ₈ are each independently a hydrogen atom, an alkyl group or an alkoxy group. The alkyl group and the alkoxyl group are preferably an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms. As an alkyl group contained in such an alkyl group and an alkoxy group, for example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, 2-methyl- propyl group, 3-methyl-propyl group, n-pentyl group and n-hexyl group. R ₉ to R ₁₂ are each independently a hydrogen atom, an aromatic group or an aliphatic group. The aliphatic group containing a hydrogen atom, a phenyl group, a naphthyl group, a C1-C4 aliphatic group, or an epoxy group is preferable, and a methyl group, an ethyl group, a propyl group, a butyl group, and a glycidyl group are mentioned specifically ,. A is preferably an aliphatic group containing a hydrogen atom or an aliphatic group having 1 to 4 carbon atoms or an epoxy group, and examples thereof include methyl group, ethyl group, propyl group, butyl group and glycidyl group. In addition, n is an integer of 1-100.

Especially preferably, R <_1> -R <_8> is hydrogen, R <_9> -R <_12> is respectively independently a hydrogen atom, a methyl group, an ethyl group, a phenyl group, and a glycidyl group, and A is a hydrogen atom or a glycidyl group.

The following compounds are mentioned as a specific compound.

In the said specific compound, when all of R <_9> -R <_12> are hydrogen atoms, it can react with an acid dianhydride, and can obtain a specific polyamic-acid polymer. In synthesizing the polymer of this specific polyamic acid, as an acid dianhydride, as a preferable thing, for example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5- Dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, cis-3,7-dibutylcycloocta-1,5-diene-1,2,5, 6-tetracarboxylic dianhydride, 3,5,6-tricarbonyl-2-carboxynorbornane-2: 3,5: 6- dianhydride, 1,3,3a, 4,5,9b-hexa Hydro-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 anhydride, 3,5,6-tricarboxy-2-carboxyno Vor I-2: 3,5: 6-dianhydride, 4,9- dioxa-tricyclo "5.3.1.0 ^2,6 'undecane -3,5,8,10- tetrahydro-one, pyromellitic dianhydride, etc. Can be mentioned. These acid dianhydrides can be used individually or in combination of 2 or more types.

In addition, at this time, in addition to the said specific compound which has a diamine structure, another diamine compound can be used together. As other preferred diamine compounds, for example, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 2,2'-dimethyl-4,4'- Diaminobiphenyl, 1,5-diaminonaphthalene, 2,7-diaminofluorene, 9,9-dimethyl-2,7-diaminofluorene, 4,4'-diaminodiphenylether, 2, 2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluor Lopropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-(p-phenylenediisopropylidene) bisaniline, 4,4'-(m-phenylenediisopropylidene) Bisaniline, 1,4-cyclohexanediamine, 4,4'-methylenebis (cyclohexylamine), 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- Aminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N'-di (4-aminophenyl) -benzidine, N, N'- Di (4-aminophenyl) -N, N'-dimethyl-benzidine and the like. These other diamine compounds can be used individually or in combination of 2 or more types.

[Polyamic acid]

Tetracarboxylic dianhydride

In this invention, as a tetracarboxylic dianhydride used for the synthesis | combination of the said polyamic acid other than the said specific polyamic acid polymer, alicyclic tetracarboxylic dianhydride is preferable. As an alicyclic tetracarboxylic dianhydride, it is 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl- 1,2,3,4- cyclobutane tetracarboxylic acid, for example. Dianhydrides, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1 , 2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4, 5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic dianhydride, cis-3,7-dibutylcycloocta-1,5-diene-1, 2,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,5,6-tricarbonyl-2-carboxynorbornane-2: 3,5: 6-dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic 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-5-methyl -5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexa Hydro-5-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4, 5,9b-hexahydro-7-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3 , 3a, 4,5,9b-hexahydro-7-ethyl-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, 1,3,3a, 4,5,9b-hexahydro-8-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2 -c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) Naphtho [1,2-c] -furan-1,3-dione, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene- 1,2-dicarboxylic dianhydride, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 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-carboxynorbornane-2: 3,5: 6- dianhydride, 4,9-dioxatri Cyclo "5.3.1.0 ^2,6 " undecane-3,5,8,10-tetraone, a compound represented by the following formulas (II) and (III),

(In formula, R <^1> and R <^3> represents the divalent organic group which has an aromatic ring, R <^2> and R <^4> represents a hydrogen atom or an alkyl group, and ^two or more R <^2> and R <^4> may be same or different, respectively.)

In addition, aliphatic tetracarboxylic dianhydrides, such as butane tetracarboxylic dianhydride;

Pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenylsulfontetracarboxylic dianhydride, 1,4,5 , 8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylethertetracarboxylic dianhydride, 3,3 ', 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3', 4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic Acid dianhydrides, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydrides, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydrides, 4 , 4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3', 4,4 '-Biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphineoxide dianhydride , p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (tri Phenylphthalic acid) -4,4'-diphenylmethane dianhydride, ethylene glycol-bis (anhydrotrimelitate), propylene glycol-bis (anhydrotrimelitate), 1,4-butanediol-bis (anhydrotri Mellitate), 1,6-hexanediol-bis (anhydrotrimellitate), 1,8-octanediol-bis (anhydrotrimelitate), 2,2-bis (4-hydroxyphenyl) propane- Aromatic tetracarboxylic dianhydride, such as a bis (anhydro trimellitate) and the compound represented by following General formula (1)-(4), is mentioned. These are used individually by 1 type or in combination of 2 or more types.

1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride in the tetracarboxylic dianhydride, 1 , 2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5- Tricarboxycyclopentylacetic acid dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, cis-3,7-dibutyl Cycloocta-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 3,5,6-tricarbonyl-2-carboxynorbornane-2: 3,5: 6- dianhydride Water, 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, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5- (tetrahydro-2,5-dioxo-3- Ranyl) -naphtho [1,2-c] furan-1,3-dione, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 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 anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2: 3,5: 6-imide-free Water, 4,9-dioxatricyclo "5.3.1.0 ^2,6 " undecane-3,5,8,10-tetraone, among the compounds represented by the formula (II), the following formulas (5) to (7) Alicyclic tetracarboxylic dianhydride, such as a compound represented by), and alicyclic tetracarboxylic dianhydride, such as a compound represented by following General formula (8), among the compounds represented by the said General formula (III) has favorable liquid-crystal orientation It is preferable at the point which can express. As particularly preferred, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5- Tricarboxycyclopentylacetic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c ] Furan-1,3-dione, cis-3,7-dibutylcycloocta-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 3,5,6-tricarbonyl 2-carboxynorbornane-2: 3,5: 6-anhydride, 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-carboxynorbornane-2: 3,5: 6-anhydride, 4,9-dioxatricyclo "5.3.1.0 ^2,6 " undecane-3,5, 8,10- Trad-one and to be a compound represented by the formula (5).

As a preferable thing in other tetracarboxylic dianhydrides other than an alicyclic tetracarboxylic dianhydride, a butane tetracarboxylic dianhydride, a pyromellitic dianhydride, 3,3 ', 4,4'- Benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylsulfontetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 1, 4,5,8-naphthalene tetracarboxylic dianhydride etc. are mentioned.

It is preferable that alicyclic tetracarboxylic dianhydride is 50 mol% or more with respect to all tetracarboxylic dianhydride among these tetracarboxylic dianhydrides.

<Diamine>

As a diamine used for the synthesis | combination of the said polyamic acid other than a specific polyamic acid polymer, p-phenylenediamine, m-phenylenediamine, 4,4'- diamino diphenylmethane, 4,4'-diamino Diphenylethane, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl -4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 4,4'-diaminodiphenylether, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4 ' -Diaminobiphenyl, 5-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethyl Indan, 3,4'-diaminodiphenylether, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 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 [4- (4-ami Nophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2,7-diaminofluorene, 9,9-dimethyl-2,7-diaminofluorene, 9,9-bis (4-amino Phenyl) fluorene, 4,4'-methylene-bis (2-chloroaniline), 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro- 4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 1,4,4 '-(p-phenyleneisopropyl Liden) bisaniline, 4,4 '-(m-phenyleneisopropylidene) bisaniline, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoro Propane, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluoro Aromatic diamines such as lobbyphenyl;

1,1-methacrylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine , 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindenylenedimethylenediamine, tricyclo [6.2.1.0 ^2,7 ] -undecylene Aliphatic and alicyclic diamines such as dimethyldiamine, 4,4'-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane, and 1,4-bis (aminomethyl) cyclohexane;

2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrazine, 5, 6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis (3-aminopropyl) piperazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino- 6-phenyl-1,3,5-triazine, 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazine, 4,6-dia Mino-2-vinyl-s-triazine, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5- Diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridine lactate, 3,8-diamino-6-phenylphenanthridine, 1,4-diaminopiperazine, 3,6-diaminoacridine, bis (4-aminophenyl) phenylamine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6- Aminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N'-di (4-aminophenyl) -benzidine, N, N'-di (4-aminophenyl) -N, N'- Diamines having two primary amino groups and a nitrogen atom other than the primary amino group in the molecule, such as dimethyl-benzidine; Diamino organosiloxane etc. which are represented by following General formula (IV) are mentioned. These diamines can be used individually or in combination of 2 or more types.

(IV)

(IV)

(In formula, R <^5> represents a C1-C12 hydrocarbon group, two or more R <^5> may be same or different, p is an integer of 1-3 and q is an integer of 1-20.)

Among them, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 2,2'-dimethyl-4,4'-diaminobiphenyl, 1, 5-diaminonaphthalene, 2,7-diaminofluorene, 9,9-dimethyl-2,7-diaminofluorene, 4,4'-diaminodiphenylether, 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 -Cyclohexanediamine, 4,4'-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane, 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-diamino Carbazole, N-methyl-3,6- Amino carbazole, N- ethyl-3,6-diamino-carbazole, N- phenyl-3,6-diamino-carbazole, N, N'- di (4-amino-phenyl) benzidine, etc. are preferred.

When giving the pretilt angle expression property to the liquid crystal aligning agent of this invention, some or all of Q <^1> and Q <^2> in the said General formula (1a) and (1b) are the following general formula (Q-1) and the following general formula (Q-2) It is preferable that it is 1 or more types of group represented by. That is, diamine (hereinafter also referred to as "specific diamine") having a group represented by the following general formula (Q-1) or the following general formula (Q-2) is used. These are used individually by 1 type or in combination of 2 or more types.

(Q-1)

(Q-1)

Wherein X is a single bond, -O-, -CO-, -COO-, -OCO-, -NHCO-, -CONH-, -S- or an arylene group, and R ⁶ is an alkyl group having 10 to 20 carbon atoms , A monovalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms or a monovalent organic group having a fluorine atom having 6 to 20 carbon atoms)

(Q-2)

(Q-2)

Wherein X is a single bond, -O-, -CO-, -COO-, -OCO-, -NHCO-, -CONH-, -S- or an arylene group, and R ⁷ is an alicyclic ring having 4 to 40 carbon atoms Divalent organic group having a formula skeleton)

In the above general formula (Q-1), examples of the alkyl group having 10 to 20 carbon atoms represented by R ⁶ include n-decyl group, n-dodecyl group, n-pentadecyl group, n-hexadecyl group and n- An octadecyl group, n-eicosyl group, etc. are mentioned. Moreover, as an organic group which has a C4-C40 alicyclic skeleton represented by R <^6> in the said General formula (Q-1) and R <^7> in the said General formula (Q-2), it is cyclobutane and cyclopentane, for example. Group which has alicyclic skeleton derived from cycloalkane, such as cyclohexane and cyclodecane; Groups having a steroid skeleton such as cholesterol and cholestanol; The group which has alicyclic skeleton which has bridges, such as norbornene and adamantane, etc. are mentioned. Among these, a group having a steroid skeleton is particularly preferred. The organic group having an alicyclic skeleton may be a group substituted with a halogen atom, preferably a fluorine atom or a fluoroalkyl group, preferably a trifluoromethyl group.

Moreover, as group which has a C6-C20 fluorine atom represented by R <^6> in the said General formula (Q-1), it is C6 or more, such as n-hexyl group, n-octyl group, n-decyl group, for example. Linear alkyl groups; Alicyclic hydrocarbon groups having 6 or more carbon atoms such as a cyclohexyl group and a cyclooctyl group; The group which substituted one part or all part of hydrogen atoms in organic groups, such as a C6 or more aromatic hydrocarbon group, such as a phenyl group and a biphenyl group, by replacing them with fluoroalkyl groups, such as a fluorine atom or a trifluoromethyl group, is mentioned.

In addition, X in Formula (Q-1) and Formula (Q-2) is a single bond, -O-, -CO-, -COO-, -OCO-, -NHCO-, -CONH-, -S Or an arylene group, As an arylene group, a phenylene group, a tolylene group, a biphenylene group, a naphthylene group, etc. are mentioned, for example. Among these, the group represented by -O-, -CO0- or -OCO- is particularly preferred. Specific examples of the diamine having a group represented by the general formula (Q-1) include dodecaneoxy-2,4-diaminobenzene, pentadecaneoxy-2,4-diaminobenzene and hexadecaneoxy-2,4-dia Minobenzene, an octadecaneoxy-2, 4- diamino benzene, and the compound represented by following General formula (9)-(13) are mentioned as a preferable thing.

Moreover, as a specific example of the diamine which has group represented by the said General formula (Q-2), the diamine represented by following General formula (14)-(16) is mentioned as a preferable thing.

Particularly preferred among these compounds include compounds represented by the above formulas (9), (11), (13) and (14).

Although the use ratio with respect to the total diamine amount of a specific diamine changes also with the magnitude | size of the pretilt angle to express, 0-5 mol% for TN type and STN type liquid crystal display elements, and in the case of a vertically-aligned type liquid crystal display element 5-100 mol% is preferable in this.

Synthesis of Polyamic Acid

The use ratio of the tetracarboxylic dianhydride and the diamine provided in the synthesis reaction of the polyamic acid (including the specific polyamic acid polymer) is such that the acid anhydride group of the tetracarboxylic dianhydride is 0.2 to 2 equivalents to 1 equivalent of the amino group of the diamine. A ratio is preferable, More preferably, it is a ratio which becomes 0.3-1.2 equivalent.

Synthesis reaction of polyamic acid is performed in organic solvent, Preferably it is -20 degreeC-150 degreeC, More preferably, it is performed on the temperature conditions of 0-100 degreeC.

The organic solvent is not particularly limited as long as it can dissolve the polyamic acid synthesized. For example, 1-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, Amide solvents such as 3-butoxy-N, N-dimethylpropanamide, 3-methoxy-N, N-dimethylpropanamide, 3-hexyloxy-N, N-dimethylpropanamide, dimethyl sulfoxide, γ Aprotic polar solvents such as butyrolactone, tetramethylurea and hexamethylphosphortriamide; Phenol solvents, such as m-cresol, xylenol, a phenol, and a halogenated phenol, can be illustrated. In addition, it is preferable that the usage-amount ((alpha)) of an organic solvent is an amount which normally becomes 0.1-30 weight% with respect to the total amount ((alpha) + (beta)) of the total reaction solution of tetracarboxylic dianhydride and a diamine compound.

In the organic solvent, alcohol, ketone, ester, ether, halogenated hydrocarbon, hydrocarbon, and the like, which are poor solvents of polyamic acid, can be used in combination without causing precipitation of the resulting polyamic acid. As a specific example of such a poor solvent, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol, propylene glycol, 1,4-butanediol, Triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxy propionate, ethyl ethoxy Propionate, diethyl oxalate, diethyl malonate, 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 monome Ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, Chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, isoamylpropionate, isoamylisobutyrate, diisopentyl ether and the like.

As described above, a reaction solution obtained by dissolving the polyamic acid is obtained. The reaction solution is poured into a large amount of poor solvent to obtain a precipitate, and the precipitate is dried under reduced pressure, or the reaction solution is distilled off under reduced pressure in an evaporator to obtain a polyamic acid. In addition, the polyamic acid can be purified by dissolving the polyamic acid again in an organic solvent and then precipitating with a poor solvent once or several times.

<Dehydration ring closure reaction>

The polyimide which comprises the liquid crystal aligning agent of this invention can be synthesize | combined by dehydrating and ring-closing part or all of the said polyamic acid. The polyimide used for this invention has 40 mol% or more of ratio of the repeating unit which has an imide ring in all the repeating units (henceforth "imidization ratio"), Preferably it is 50 mol% or more. By using the polymer whose imidation ratio is 40 mol% or more, the liquid crystal aligning agent which can form a liquid crystal aligning film with a short residual image removal time is obtained. The imidation ratio can be calculated | required by the following method.

Imidization  Polymer Imidization rate  How to measure

After drying the imidized polymer under reduced pressure at room temperature, it is dissolved in deuterated dimethyl sulfoxide, ¹ H-NMR is measured at room temperature using tetramethylsilane as a reference substance, and can be obtained by the formula represented by the following formula (ii). .

<Equation ii>

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

A ¹ : peak area derived from NH proton (10 ppm)

A ² : peak area derived from other protons

α: ratio of the number of other protons to one proton of the NH group in the precursor (polyamic acid) of the polymer

The dehydration ring closure of the polyamic acid may be achieved by (i) heating the polyamic acid, or (ii) dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to the solution, and heating it as necessary. Is done.

Preferably the reaction temperature in the method of heating the polyamic acid of said (i) 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 and when reaction temperature exceeds 200 degreeC, the molecular weight of the imidation polymer obtained may fall.

On the other hand, in the method of adding a dehydrating agent and a dehydration 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 usage-amount 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 repeating units of a 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 that the usage-amount of a dehydration ring-closure catalyst shall be 0.01-10 mol with respect to 1 mol of dehydrating agents used. The imidation ratio can be made higher, so that the usage-amount of the said dehydrating agent and dehydration ring closure agent is large. On the other hand, as an organic solvent used for dehydration ring-closure reaction, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid is mentioned. And the reaction temperature of dehydration ring-closure reaction becomes like this. Preferably it is 0-180 degreeC, More preferably, it is 10-150 degreeC. Moreover, the specific polymer obtained can be refine | purified by performing the same operation as the purification method of polyamic acid with respect to the reaction solution obtained in this way.

<Terminal modified polymer>

The polyamic acid and the polyimide used in the present invention may be of a terminal modified form of which the molecular weight is controlled. By using this terminal modified polymer, the effect of this invention is not impaired, and the application | coating characteristic of a liquid crystal aligning agent, etc. can be improved. Such a terminally modified polymer can be synthesized by adding an acid anhydride, a monoamine compound, a monoisocyanate compound or the like to the reaction system when synthesizing the polyamic acid. Here, as an acid anhydride, 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. Can be. As the monoamine compound, for example, 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. Moreover, as a monoisocyanate compound, phenyl isocyanate, naphthyl isocyanate, etc. are mentioned, for example.

Solution viscosity

It is preferable that the polymer used for the aligning agent of this invention has a viscosity of 20-800 mPa * s, and, as for 10% solution, it is more preferable to have a viscosity of 30-500 mPa * s.

The solution viscosity (mPa · s) of the polymer was measured at 25 ° C. using an E-type rotational viscometer with respect to a solution diluted to a predetermined solid content concentration using a predetermined solvent.

[Liquid crystal aligning agent]

The liquid crystal aligning agent of this invention consists of a specific compound or a specific polyamic-acid polymer, Preferably the said polymer and the other component which are added optionally are melt | dissolved in the organic solvent normally.

The liquid crystal aligning agent of this invention can contain an epoxy compound and a functional silane containing compound in the point which improves the adhesiveness to the surface of a board | substrate within the range which does not impair the desired physical property. Examples of such epoxy compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether. , Neopentyl 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'-diaminodiphenylmethane, 3- (N-allyl-N-glycidyl) aminopropyltrimethoxysilane , 3- (N, N-diglycidyl) aminopropyltrimethoxysilane, N, N- diglycidyl-benzylamine, N, N- diglycidyl-aminomethylcyclohexane, etc. are mentioned. . As the epoxy group-containing compound, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl Ether, neopentyl 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-diglycidyl Aminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl-benzylamine, N, N-digly Cydyl-aminomethylcyclohexane etc. are mentioned as a preferable thing. The compounding ratio of these epoxy group containing compounds becomes like this. Preferably it is 40 weight part or less, More preferably, it is 0.1-30 weight part with respect to 100 weight part of polymers.

As such a functional silane containing 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-ureidopropyltri Ethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N- Trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecan, 10-triethoxysilyl-1,4,7-triazadecan, 9-trimethoxysilyl -3,6-diazanyl acetate, 9-triethoxysilyl-3,6-diazanyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N- Jyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltri Methoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, etc. are mentioned. The blending ratio of the functional silane-containing compound is preferably 4 parts by weight or less based on 100 parts by weight of the polymer.

As an organic solvent which comprises the liquid crystal aligning agent of this invention, 1-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, 3-butoxide -N, N-dimethylpropanamide, 3-methoxy-N, N-dimethylpropanamide, 3-hexyloxy-N, N-dimethylpropanamide, isoamylpropionate, isoamylisobutyrate, diisopentyl Ether and the like. Of these, 3-butoxy-N, N-dimethylpropanamide, 3-methoxy-N, N-dimethylpropanamide, and 3-hexyloxy-N, N-dimethylpropanamide exhibit good printability. Particularly preferred.

Although solid content concentration in the liquid crystal aligning agent of this invention is selected in consideration of viscosity, volatility, etc., Preferably it exists in the range of 1 to 10 weight%. That is, although the liquid crystal aligning agent of this invention is apply | coated to the surface of a board | substrate, and the coating film used as a liquid crystal aligning film is formed, when solid content concentration is less than 1 weight%, the film thickness of this coating film becomes too small and a favorable liquid crystal aligning film is not obtained, solid content concentration When the content exceeds 10% by weight, the film thickness of the coating film becomes too large to obtain a good liquid crystal aligning film, and the viscosity of the liquid crystal aligning agent increases, resulting in poor coating properties.

On the other hand, the range of especially preferable solid content concentration changes with methods 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% is especially preferable. In the case of the printing method, the solid content concentration is in the range of 3 to 9% by weight, and the solution viscosity is particularly preferably 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 manufacturing the liquid crystal aligning agent of this invention becomes like this. Preferably it is 0 degreeC-200 degreeC, More preferably, it is 20 degreeC-60 degreeC.

<Liquid crystal display element>

The liquid crystal display element obtained using the liquid crystal aligning agent of this invention can be manufactured by the following method, for example.

(1) The liquid crystal aligning agent of this invention is apply | coated to one surface of the board | substrate with which the patterned transparent conductive film is provided by the offset printing method, the spin coating method, or the inkjet printing method, and then a coating film is formed by heating a coating surface. Here, as a board | substrate, For example, glass, such as float glass and a soda glass; A transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and alicyclic polyolefin can be used. Examples of the transparent conductive film provided on one surface of the substrate include an NESA film (registered trademark of PPG Co., Ltd.) containing tin oxide (SnO ₂ ), an ITO film containing indium tin oxide (In ₂ O ₃ -SnO ₂ ), and the like. Can be used. The photoetching method and the method using a preliminary mask are used for patterning these transparent conductive films. In application | coating of a liquid crystal aligning agent, in order to make adhesiveness of a board | substrate surface, a transparent conductive film, and a coating film more favorable, you may apply | coat a functional silane containing compound, a functional titanium containing compound, etc. previously on the said surface of a board | substrate. . After application of the liquid crystal aligning agent, preliminary heating (prebaking) is preferably performed for the purpose of preventing the drop 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. After that, a calcination (post-baking) step is performed for the purpose of completely removing the solvent and thermally imidating the polyamic acid. This baking (post-baking) temperature becomes like this. Preferably it is 80-300 degreeC, More preferably, it is 120-250 degreeC. Although the liquid crystal aligning agent of this invention containing a polyamic acid forms the coating film used as an oriented film by removing an organic solvent after application | coating, it can also be made into a more imidized coating film by advancing dehydration ring closure by further heating. The film thickness of the coating film formed becomes like this. Preferably it is 0.001-1 micrometer, More preferably, it is 0.005-0.5 micrometer.

(2) The rubbing treatment which rubs the formed coating film surface in the fixed direction with the roll which rolled up the cloth which consists of fibers, such as nylon, rayon, and cotton, for example, is performed. Thereby, the orientation ability of a liquid crystal molecule is provided to a coating film, and it becomes a liquid crystal aligning film. In addition, ultraviolet rays as disclosed in, for example, Japanese Patent Laid-Open No. 6-222366 or Japanese Patent Laid-Open No. 6-281937 are applied to a liquid crystal alignment film formed by the liquid crystal aligning agent of the present invention. By partially irradiating, a resist film is partially formed on the surface of the liquid crystal aligning film subjected to the treatment such as changing the pretilt angle or the rubbing treatment as disclosed in Japanese Patent Laid-Open No. Hei 5-107544. After the rubbing treatment is performed in a direction different from the rubbing treatment, the resist film is removed and the treatment such as changing the liquid crystal alignment ability of the liquid crystal alignment film can be performed to improve the field of view characteristics of the liquid crystal display element.

(3) Two board | substrates with a liquid crystal aligning film were manufactured as mentioned above, and two board | substrates were opposingly arranged through a clearance gap (cell spacing) so that the rubbing direction in each liquid crystal aligning film might be orthogonal or antiparallel, The periphery of the substrate is bonded using a sealant, the liquid crystal is injected and filled into the cell gap partitioned by the substrate surface and the sealant, and the injection hole is sealed to form a liquid crystal cell. The polarizing plate is bonded to the outer surface of the liquid crystal cell, that is, the other surface side of each substrate constituting the liquid crystal cell so that its polarization direction is coincident with or perpendicular to the rubbing direction of the liquid crystal alignment film formed on one surface of the substrate. The device is obtained.

Here, as the sealant, for example, an epoxy resin containing aluminum oxide spheres as a curing agent and a spacer can be used.

Examples of the liquid crystals include nematic liquid crystals and smectic liquid crystals. Among them, nematic liquid crystals are preferred, and for example, Schiff base liquid crystals, subfamily clock liquid crystals, biphenyl liquid crystals, phenylcyclohexane liquid crystals, ester liquid crystals, A terphenyl type liquid crystal, a biphenyl cyclohexane type liquid crystal, a pyrimidine type liquid crystal, a dioxane type liquid crystal, a bicyclooctane type liquid crystal, a cuban type liquid crystal, etc. can be used. In addition, these liquid crystals are sold, for example, as cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonate and cholesteryl carbonate, and trade names "C-15" and "CB-15" (manufactured by Merck). A chiral agent etc. can also be added and used. Ferroelectric liquid crystals such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate can also be used.

Moreover, as a polarizing plate joined to the outer surface of a liquid crystal cell, the polarizing plate which sandwiched the polarizing film called H film | membrane which absorbed iodine, and extended | stretched polyvinyl alcohol between the cellulose acetate protective films, or the polarizing plate which consists of H film itself is mentioned.

<Example>

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not restrict | limited to these Examples.

[Printability Evaluation]

A glass substrate of 127 mm (D) x 127 mm (W) x 1.1 mm (H) having an ITO film formed on an entire surface of one side was prepared, and a printing machine (Nippon Shashin Insatsu Co., Ltd. product) for liquid crystal alignment film application was prepared on this glass substrate. After filtration of the liquid crystal aligning agent obtained in the said experiment using the angstromer S-40L) with the microfilter of 0.2 micrometer of pore diameters, it applied to the transparent electrode surface. It dried with the hotplate adhesive predryer set to 80 degreeC, baked at 200 degreeC for 60 minutes, and formed the liquid crystal aligning film on the glass substrate with an ITO film. The nonuniformity of the obtained alignment film was visually evaluated based on the following criteria.

(Circle): No nonuniformity is observed at all.

(Triangle | delta): A nonuniformity is observed slightly.

X: A nonuniformity is observed clearly.

[Voltage retention rate]

A voltage of 5 V was applied to the liquid crystal display element at 60 ° C. with an application time of 60 microseconds and a span of 167 milliseconds, and then the voltage retention after 167 milliseconds from the release of the application was measured. The measurement apparatus used VHR-1 by Toyo Technica.

[Bake Test]

A cell having an ITO electrode as shown in FIG. 1 was prepared. DC voltage 6.0V was applied to electrode A and DC voltage 0.5V to electrode B at room temperature for 24 hours. After the stress was released, a DC voltage of 0.1 to 5.0 V was applied to the electrodes A and B in a 0.1 V pitch. The baking characteristics were judged by the luminance difference between the electrodes A and B at the respective voltages. When the luminance difference was large, it was determined that the baking characteristic was bad.

(Circle): Luminance difference is hardly known.

(Triangle | delta): A luminance difference exists slightly.

Synthesis of Specific Compound 1

The nickel catalyst used for this reaction is easily inactivated by reaction with oxygen and water vapor in the atmosphere. Therefore, the solvent and reagent used for the reaction were previously used by removing impurities by distillation and recrystallization treatment. The polymerization reaction was carried out in a nitrogen atmosphere.

The polymerization reaction can be found in the literature [T. Kanbara, J. Polym. Sci. Part-A, Polym. Chem., 38, 4194 (2000). Into a four-necked flask with nitrogen gas inside, 15 ml of 4,4'-dichlorobiphenyl (1 mmol) and benzidine (1 mmol) and toluene were added and stirred for several minutes, followed by 288 mg of sodium-tert-butoxide ( 3 mmol), bis (1,5-cyclooctadiene) nickel (0) (Ni (cod) ₂ ) 28 mg (0.1 mmol), and 1,1'-bis (diphenylphosphino) ferrocene (DPPF) 166 mg (0.3 mmol) was added at room temperature. The reaction solution was heated to 60 deg. C while stirring in a nitrogen atmosphere to initiate the reaction. After reacting at 60 DEG C for 24 hours, a very small amount of benzidine (0.05 mmol) was added, and the end of the polymer was sealed with benzidine to terminate the polymerization. After cooling to room temperature, the reaction solution was poured into 200 ml of a mixture of aqueous ammonia and methanol, the obtained precipitate was separated by filtration, and the recovered precipitate was further washed with methanol and ether to obtain specific compound A-1.

Synthesis of Specific Compound 2

Particular compound A-2 includes a plurality of structures as described above.

Three-necked flask was mixed with THF solution of specific Compound A-1 and excess sodium amide. After the solution was heated to reflux for 2 hours, the reaction solution was cooled, and an excess amount of epibromohydrin was added dropwise. It heated to 80 degreeC, and then stirred for 6 hours. The reaction solution was filtered, and the filtrate was separated and washed in the order of chloroform / 10% aqueous hydrochloric acid solution and saturated brine. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off. Specific residue A-2 was obtained by performing methanol reprecipitation on the residue.

Polyimide Synthesis Example 1

112 g (0.50 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetra as tetracarboxylic dianhydride 157 g (0.50 mol) of hydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione, 96 g (0.89 mol) of p-phenylenediamine as a diamine compound ), 25 g (0.10 mol) of 3,3 '-(tetramethyldisiloxane-1,3-diyl) bis (propylamine), and 13 g (0.020) of 3,6-bis (4-aminobenzoyloxy) cholestane Mole) and 8.1 g (0.030 mole) of n-octadecylamine as a monoamine were dissolved in 960 g of N-methyl-2-pyrrolidone, and it was made to react at 60 degreeC for 6 hours. A little aliquot of the obtained polyamic-acid solution was added, NMP was added, and the viscosity was measured in the solution of 10% of solid content concentration, and it was 60 mPa * S. Subsequently, 2700 g of N-methyl-2-pyrrolidone was added to the obtained polyamic-acid solution, 396 g of pyridine and 409 g of acetic anhydride were added, and dehydration ring-closing was carried out at 110 degreeC for 4 hours. After the imidation reaction, the solvent in the system was solvent-substituted with fresh γ-butyrolactone (pyridines and acetic anhydride used in the imidation reaction were removed from the system by this operation), and the solid content concentration was 15 wt% and the solid content concentration was 10%. About 2000 g of the solution of the imidation polymer (it is called "polyimide (ga-1)") of 70 mPa * S of the viscosity of (si- (butyrolactone solution), and the imidation ratio about 95% was obtained.

Polyimide Synthesis Example 2

224 g (1.0 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride, 108 g (1.0 mol) of p-phenylenediamine as a diamine compound, and cholestaryl-3,5 7.8 g (0.015 mol) of -diaminobenzoate was dissolved in 3039 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours to obtain a polyamic acid solution having a solution viscosity of about 260 mPa · S. Subsequently, 2700 g of N-methyl-2-pyrrolidone was added to the obtained polyamic-acid solution, 396 g of pyridine and 306 g of acetic anhydride were added, and dehydration ring-closing was carried out at 110 degreeC for 4 hours. After the imidation reaction, the solvent in the system was solvent-substituted with fresh γ-butyrolactone (pyridine and acetic anhydride used in the imidation reaction were removed out of the system by this operation), and the solid content concentration was about 9.0 wt% and the solid content concentration was 10. About 3000 g of the solution of the imidation polymer (it is called "imidization polymer (ga-2)") of% viscosity ((gamma-butyrolactone solution) of 250 mPa * S and imidation ratio of about 51% was obtained.

Polyamic Acid Synthesis Example 1

1,2,3,4-cyclobutanetetracarboxylic dianhydride 196 g (1.0 mol) as tetracarboxylic dianhydride, 2,2'-dimethyl-4,4'- diamino biphenyl 212 as a diamine compound g (1.0 mol) was dissolved in 370 g of N-methyl-2-pyrrolidone and 3300 g of γ-butyrolactone, and reacted at 40 ° C. for 3 hours. Polyamic acid having a viscosity of 160 mPa · S (referred to as “polya” About 3700 g of a solution of "mic acid (na-1)" was obtained.

Polyamic Acid Synthesis Example 2

1,2,3,4-cyclobutanetetracarboxylic dianhydride 95 g (0.50 mol) as tetracarboxylic dianhydride, 109 g (0.50 mol) pyromellitic dianhydride, 2,7-dia as diamine compound 196 g (1.0 mol) of minofluorene was dissolved in 230 g of N-methyl-2-pyrrolidone and 2060 g of γ-butyrolactone, and reacted at 40 ° C. for 3 hours, followed by 1350 g of γ-butyrolactone. Was added to obtain a solution of about 3600 g of a polyamic acid solution (referred to as "polyamic acid (B-2)") with a solution viscosity of 125 mPa · S at a solid content concentration of 10%.

Example 1

Γ-butyrolactone so that the polyimide (ga-1) obtained in polyimide synthesis example 1 and the polyamic acid (b-1) obtained in polyamic acid synthesis example 1 are polyimide: polyamic acid = 20: 80 (weight ratio) It dissolved in the / N-methyl-2-pyrrolidone / butyl cellosolve mixed solvent (weight ratio 71/17/12). 2 parts by weight of N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane are added to 100 parts by weight of the polymer, and specific compound A-1 is added to this solution. 10 parts by weight was added to 100 parts by weight of the polymer to prepare a solution having a solid concentration of 3.5% by weight and a solution of 6.0% by weight. After fully stirring each solution, it filtered using the filter of 1 micrometer of pore diameters, and manufactured the liquid crystal aligning agent of this invention.

The solution of 3.5 weight% of solid content concentration among the said liquid crystal aligning agents was apply | coated using the spinner on the transparent conductive film which consists of an ITO film provided in the one surface of the glass substrate of thickness 1mm (rotation speed: 2,500 rpm, application time: 1 minute) and dried at 200 ° C. for 1 hour to form a film having a dry film thickness of 0.08 μm. The rubbing process was performed by the rubbing machine which has the roll which wound the cloth made from rayon on this film at roll rotation speed 400rpm, stage movement speed 3cm / sec, and hairpin indentation length 0.4mm. The liquid crystal aligning film coated substrate was ultrasonically cleaned in ultrapure water for 1 minute and dried in a clean oven at 100 ° C for 10 minutes. Next, after apply | coating the aluminum oxide sphere containing epoxy resin adhesive of 5.5 micrometers in diameter to each outer edge which has a liquid crystal aligning film of the said liquid crystal aligning film coating board | substrate of a pair of transparent electrode / transparent electrode board | substrate, a liquid crystal aligning film surface mutually Overlaid so as to face opposite, and the adhesive was cured. Subsequently, after filling a nematic liquid crystal (MLC-6221 made by Merck Co., Ltd.) between a liquid crystal injection hole and a board | substrate, the liquid crystal injection hole is sealed with an acryl-type photocuring adhesive agent, a polarizing plate is bonded to both surfaces of the outer side of a board | substrate, and a TN liquid crystal display element Was prepared. Voltage retention evaluation and baking evaluation of the obtained liquid crystal display element were performed in accordance with the method as described above.

Moreover, printability evaluation was performed in accordance with the method described above using the solution of 6.0 weight% of solid content concentration.

Examples 2-4

Polyimide, polyamic acid, and the specific compound were carried out in the same procedure as in Example 1 except for using those shown in Table 1 below.

Example 5

The polyimide (ga-2) obtained in the polyimide synthesis example 2 was dissolved in N-methyl-2-pyrrolidone / butyl cellosolve mixed solvent (weight ratio 50/50), and N, N, N ', N' 2 parts by weight of tetraglycidyl-4,4'-diaminodiphenylmethane was added to 100 parts by weight of the polymer, and 10 parts by weight of the specific compound A-1 was added to 100 parts by weight of the polymer to obtain a solid content of 3.5% by weight. Solution and 6.0 wt% solution were prepared. After fully stirring each solution, it filtered using the filter of 1 micrometer of pore diameters, and manufactured the liquid crystal aligning agent of this invention. The manufacturing method of a liquid crystal display element, the evaluation method of a liquid crystal display element, and the aligning agent printability evaluation method were performed by the method similar to Example 1.

Example 6

It carried out by the same procedure as Example 5 except having used the thing shown in Table 1 as a specific compound.

Comparative Examples 1 and 2

The polyimide and the polyamic acid were used in the same procedure as in Example 1 except that the compounds shown in Table 1 were used and no specific compound was added.

Comparative Example 3

The same procedure as in Example 5 was carried out except that no specific compound was added.

Comparative Examples 4 to 5

The polyimide and the polyamic acid were used in the same procedure as in Example 1, except that the compounds shown in Table 1 were used, and a compound having the following structure (Compound X) was used instead of the specific compound. Compound X was synthesized according to the method described in Japanese Patent Laid-Open No. 2000-44683.

Comparative Example 6

The same procedure as in Example 5 was carried out except that Compound X was added instead of the specific compound.

Comparative Examples 7 to 8

The polyimide and the polyamic acid were used in the same procedure as in Example 1 except that the compounds shown in Table 1 were used, and a compound (Compound Y) having the following structure was used instead of the specific compound. Compound Y was synthesized according to the method described in WO2002 / 100949. The molecular weight was Mn = 15,000 and Mw = 30,000.

Comparative Example 9

The same procedure as in Example 5 was carried out except that Compound Y was added instead of the specific compound.

1 is a cell with an ITO electrode prepared for the evaluation of the baking test.

Claims (7)

The compound represented by following formula (1) is contained, The liquid crystal aligning agent characterized by the above-mentioned. <Formula 1>

(Wherein, R ₁ to R ₈ are each independently a hydrogen atom, an alkyl group or an alkoxy group, R ₉ to R ₁₂ are each independently a hydrogen atom, an aromatic group or an aliphatic group, A is a hydrogen atom or an aliphatic group, n is an integer from 1 to 100) The compound of claim 1, wherein in Formula 1, R ₁ to R ₈ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and R ₉ to R ₁₂ are all hydrogen atoms, and A Is a hydrogen atom, n is an integer of 1-100, the liquid crystal aligning agent. A compound according to claim 1, wherein R ₁ to R ₈ in Formula 1 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, R ₉ and R ₁₁ are aromatic groups, and R ₁₀ and R ₁₂ is a hydrogen atom or an aliphatic group, A is a hydrogen atom or an aliphatic group, and n is an integer of 1 to 100. The compound of claim 1, wherein R ₁ to R ₈ in Formula 1 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, R ₉ and R ₁₁ are aromatic groups, R ₁₀ and R <_12> is an aliphatic group containing a hydrogen atom or an epoxy group, A is an aliphatic group containing a hydrogen atom or an epoxy group, and n is an integer of 1-100. The polyamic-acid polymer obtained by reaction of the compound of Claim 2 and tetracarboxylic dianhydride is contained, The liquid crystal aligning agent characterized by the above-mentioned. At least one selected from the group consisting of a polyamic acid containing a repeating unit represented by the following general formula (1a) and a polyimide containing a repeating unit represented by the following general formula (1b). Liquid crystal aligning agent which further contains a polymer. <Formula 1a>

(Wherein P ¹ is a tetravalent organic group and Q ¹ is a divalent organic group) <Formula 1b>

(Wherein P ² is a tetravalent organic group and Q ² is a divalent organic group) The liquid crystal aligning film obtained using the liquid crystal aligning agent in any one of Claims 1-6 is provided, The liquid crystal display element characterized by the above-mentioned.

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