KR20100032832A - Liquid crystal aligning agent and liquid crystal display device - Google Patents

Abstract

PURPOSE: A liquid crystal alignment agent is provided to form a liquid crystal alignment film with uniform and good vertical alignment without nonuniformity in printing, when applied to a substrate. CONSTITUTION: A liquid crystal alignment agent comprises (A) at least one polymer selected from the group consisting of polyamic acid and polyimide and (B) a compound containing an epoxy group and a group represented by chemical formula 2o. In chemical formula 2o, R^I is C4-40 alkyl group or C4-40 fluoroalkyl group, or C17-51 hydrocarbon group with a steroid skeleton; Z^I is a single bond, *-O-, *-COO- or *-OCO-; R^II is a cyclohexylene group or a phenylene group; n is 1 or 2, wherein two R^IIs are the same or different when n1 is 2; n2 is 0 or 1; Z^II is *-O-, *-COO- or *-OCO-; n3 is an integer of 0-2; and n4 is 0 or 1.

Description

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

The present invention relates to a liquid crystal aligning agent and a liquid crystal display element.

As a liquid crystal display element, the liquid crystal aligning film containing polyamic acid, a 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, The two sheets are opposed, and positive dielectric anisotropy exists in the clearance gap. TN type with a so-called TN type (Twisted Nematic) liquid crystal cell, in which a layer of a nematic liquid crystal having a layer is formed to form a sandwich cell, and the long axis of the liquid crystal molecules is continuously twisted by 90 ° from one substrate to the other. Liquid crystal display elements are known. In addition, STN (Super Twisted Nematic) type liquid crystal display devices have been developed that have a higher contrast and less visual dependence than TN type liquid crystal display devices. This STN type liquid crystal display element uses a blend of a nematic liquid crystal and a chiral agent, which is an optically active substance, as a liquid crystal, and the birefringence generated when the long axis of the liquid crystal molecules is continuously twisted over 180 ° between the substrates. To use the effect.

In recent years, the development of new liquid crystal display elements has also been actively carried out, and as one of them, as described in Patent Literature 1, two electrodes for driving a liquid crystal are arranged in a comb-tooth pattern on one substrate, and on the substrate surface. A transverse electric field type liquid crystal display element which generates a parallel electric field and controls liquid crystal molecules is proposed. This device is commonly referred to as an in-plane switching type (IPS type) and is known for its excellent viewing angle characteristics.

On the other hand, as a liquid crystal display element having a function different from the above, a vertical alignment called a multi domain vertical alignment (MVA) method or a patterned vertical alignment (PVA) method in which liquid crystal molecules having negative dielectric anisotropy are vertically aligned with a substrate. A type liquid crystal display element is proposed. These vertically-aligned liquid crystal display elements of the MVA method and the PVA method are not only excellent in viewing angle and contrast, but also excellent in terms of the manufacturing process, such as rubbing treatment may not be performed in the formation of the liquid crystal alignment film.

The ability to orient the liquid crystal molecules perpendicularly to the substrate (vertical orientation) is known to be expressed by using a polymer having a bulky substituent in the side chain as a material of the liquid crystal alignment film, and therefore a bulky substituent at the time of synthesis of the polymer. It is proposed to use the monomer (pretilt angle expressing monomer) which has. For example, Patent Document 2 proposes a method of using a polymer obtained by using 1-octadecyloxy-2,4-diaminobenzene as a pretilt angle expressing monomer. Similarly, Patent Documents 3 and 4 describe cholesteryl-3,5-diaminobenzoate, stearyl litocholate (3,5-diaminobenzoate), and cholestanyl-3 as pretilt-angle expressing monomers. , 5-diaminobenzoate and the like, Patent Document 5 describes cholesteryloxy-2,4-diaminobenzene and the like, respectively. By using the polymer synthesize | combined using these pretilt angle expressing monomers in large quantities as a liquid crystal aligning film, it becomes possible to obtain the liquid crystal aligning agent which shows stable vertical alignment property.

In addition, in view of the recent increase in panel size and the improvement of product yield, high liquid crystal alignment agents require high voltage retention and high printability. However, when a polymer synthesized using a large amount of the above-described pretilt angle expressing monomers is used as a liquid crystal aligning agent, in particular, it is known that printability is significantly deteriorated, and good vertical alignment and good printability are traded off each other. trade-off relationship.

Therefore, there is a demand for a liquid crystal aligning agent having both high voltage retention, good vertical alignment and good printability.

[Patent Document 1] Japanese Unexamined Patent Publication No. 7-261181

[Patent Document 2] Japanese Unexamined Patent Publication No. 6-136122

[Patent Document 3] Japanese Patent No. 2893671

[Patent Document 4] Japanese Patent Application Laid-Open No. 2004-331937

[Patent Document 5] Japanese Patent Application Laid-Open No. 2004-262921

An object of the present invention is to provide a liquid crystal aligning agent in which high voltage retention, good vertical alignment and good printability are compatible.

Moreover, the objective of this invention is providing the liquid crystal display element which shows the favorable vertical orientation and high voltage retention.

Still other objects and advantages of the present invention are apparent from the following description.

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

(A) at least one polymer selected from the group consisting of polyamic acid and polyimide, and

(B) a compound having an epoxy group and a group represented by the following formula (2o)

It is achieved by the liquid crystal aligning agent containing these.

(, R ^I of the formula 2o is from 4 to 40 carbons, or an alkyl group or a fluoroalkyl group having a carbon number of 4 to 40, or a hydrocarbon group having a carbon number of 17 to 51 having a steroid skeleton, and;

Z ^I is a single bond, * -O-, * -COO- or * -OCO-, provided that the bond with "*" is on the R ^I side,

R ^II is a cyclohexylene group or a phenylene group,

n1 is 1 or 2,

However, when n1 is 2, two R ^II may be the same or different from each other,

n2 is 0 or 1;

Z ^II is * -O-, * -COO- or * -OCO-, provided that the bond with "*" is on the R ^I side,

n3 is an integer of 0 to 2,

n4 is 0 or 1)

The above objects and advantages of the present invention are second,

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

When the vertical alignment type liquid crystal aligning agent of this invention prints and apply | coats on a board | substrate, printing nonuniformity hardly arises and can form the liquid crystal aligning film which has uniform and favorable vertical alignment property.

The liquid crystal display element of this invention shows favorable vertical alignment property and favorable voltage retention characteristic, and is excellent in display performance. The liquid crystal display element of the present invention can be effectively used in various devices, and can be used in display devices such as a table calculator, a wrist watch, a table clock, a counting plate, a word processor, a personal computer, and a liquid crystal television.

The liquid crystal aligning agent of this invention is (A) 1 or more types of polymers chosen from the group which consists of a polyamic acid and a polyimide, and

(B) A compound having an epoxy group and a group represented by the above formula (2o) (hereinafter also referred to as "(B) compound") is contained.

<(A) polyamic acid, polyimide>

Polyamic acid can be obtained by making tetracarboxylic dianhydride and diamine react, and polyimide can be obtained by dehydrating and closing this polyamic acid.

Tetracarboxylic dianhydride

As tetracarboxylic dianhydride used for the synthesis | combination of a polyamic acid, butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl-1, for example. , 2,3,4-cyclobutanetetracarboxylic dianhydride, 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-cyclopentane Tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5- Tricarboxycyclopentylacetic 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-hexahydro-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, bicyclo [2.2.2] -oct-7- En-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-cyclo Sen-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3 .1.0 ^2,6 ] aliphatic tetracarboxylic dianhydrides and alicyclic tetracarboxylic dianhydrides such as undecane-3,5,8,10-tetraone, compounds represented by the following formulas TI and T-II, respectively; ;

[Formula T-I]

[Formula T-II]

(Wherein R ¹ and R ³ are each a divalent organic group having an aromatic ring, R ² and R ⁴ are each a hydrogen atom or an alkyl group, and a plurality of R ² and R ⁴ may be the same or different, respectively). )

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 dianhydrides, such as a bis (anhydro trimellitate) and the compound represented by following General formula T-1-T-4, etc. are mentioned. These are used individually by 1 type or in combination of 2 or more types.

[Formula T-1]

[Formula T-2]

[Formula T-3]

[Formula T-4]

As a compound represented by the said General formula T-I, For example, the compound etc. represented by each of following General formula T-5-T-7; As a compound represented by the said general formula T-II, the compound etc. which are represented by the following general formula T-8 are mentioned, for example.

[Formula T-5]

[Formula T-6]

[Formula T-7]

[Formula T-8]

Among these, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetra Hydro-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-hexa Hydro-5,8-dimethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -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 '-(tetra Hydrofuran-2 ', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 3 , 5,6- trika Diplopia-2-carboxymethyl norbornane 2: 3,5: 6-dianhydride, 4,9- dioxa-tricyclo [5.3.1.0 ^2,6] undecane -3,5,8,10- tetrahydro-on , Pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenylsulfontetracarboxylic dianhydride, 2,2 ' , 3,3'-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, a compound represented by each of the formulas T-5 to T-7 and the formula T- It is preferable to use 1 or more types (it is called "a specific tetracarboxylic dianhydride" hereafter) chosen from the group which consists of a compound represented by 8 from a viewpoint which can express favorable liquid-crystal orientation.

As specific tetracarboxylic dianhydride, especially 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 2,3,5- tricarboxycyclopentyl 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-oxa Bicyclo [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-carboxymethylnorbornane-2: 3,5: 6-anhydride , 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, pyromellitic dianhydride and the compound represented by the formula (T-5) At least one selected is preferable.

As a usage ratio of such specific tetracarboxylic dianhydride, it is preferable that it is 10 mol% or more with respect to all tetracarboxylic dianhydride, More preferably, it is 20 mol% or more, It is further more preferable that it is 40 mol% or more.

As tetracarboxylic dianhydride used for the synthesis | combination of the polyamic acid in this invention, it is most preferable to use only specific tetracarboxylic dianhydride as mentioned above.

[Diamine]

As diamine used for the synthesis | combination of a polyamic acid, p-phenylenediamine, m-phenylenediamine, 4,4'- diamino diphenylmethane, 4,4'- diamino diphenyl ethane, 4,4, for example. '-Diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 4,4 '-Diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 3,3'-ditrifluoromethyl-4,4'-diaminobiphenyl, 5-amino-1- (4 '-Aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 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-ratio S (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 4,4'- Bis (4-aminophenoxy) biphenyl, 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-aminophenyl) 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-phenyleneisopropylidene) bisaniline, 4,4'- (m-phenyleneisopropylidene) bisaniline, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-diamino- 2,2'-bis (trifluoromethyl) biphenyl, 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] -octa Luo lobby phenyl, 3,5-diamino benzoic acid, 1,4-bis (4-amino-phenyl) -piperazine, to the aromatic diamine compound and the like represented by the following formulas D-1 to D-5, respectively;

[Formula D-1]

[Formula D-2]

[Formula D-3]

[Formula D-4]

[Formula D-5]

(Y in Formula D-4 is an integer of 2-12, z in Formula D-5 is an integer of 1-5)

1,1-methacrylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 1,4-diaminocyclohexane, Isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindanylenedimethylenediamine, tricyclo [6.2.1.0 ^2,7 ] -undecylenedimethyldiamine, 4,4'-methylenebis Aliphatic diamines and alicyclic diamines such as (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-phenylphenanthtridine, 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'-bis (4-aminophenyl) -benzidine, N, N'-bis (4-aminophenyl) -N, N'- Diamine which has two primary amino groups and nitrogen atoms other than the said primary amino group in the molecule | numerators, such as dimethyl-benzidine, the compound represented by following formula (DI), and the compound represented by following formula (D-II);

[Formula D-I]

(In formula DI, R ⁵ is a monovalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, X ¹ is a divalent organic group, R ⁶ is an alkyl group having 1 to 4 carbon atoms, a1 is an integer of 0 to 3)

[Formula D-II]

(Formula D-II, R ⁷ is a divalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, each of X ² is a divalent organic group) And a plurality of X ^{2 's} may be the same or different, and each R ⁸ is an alkyl group having 1 to 4 carbon atoms, and a2 is an integer of 0 to 4, respectively.

Mono substituted phenylenediamines such as compounds represented by the following general formula (D-III);

[Formula D-III]

(In Formula D-III, R ⁹ is -O-, -COO- *, -OCO- *, -NHCO- *, -CONH- *, provided that the bond with "*" above is bonded to R ^10. Or -CO-, R ¹⁰ is a monovalent organic group having 6 to 30 carbon atoms or an alkyl group having a skeleton or group selected from a steroid skeleton, a trifluoromethylphenyl group, a trifluoromethoxyphenyl group and a fluorophenyl group, and R is ¹¹ is an alkyl group having 1 to 4 carbon atoms, a3 is an integer of 0 to 3)

Diamino organosiloxane, such as a compound represented by following formula (D-IV), etc. are mentioned. These diamines can be used individually or in combination of 2 or more types.

[Formula D-IV]

(In formula (D-IV), R <^12> is a C1-C12 hydrocarbon group, respectively, two or more R <^12> may be same or different, respectively, p is an integer of 1-3, q is 1-20 Integer)

The benzene ring of the aromatic diamine may be substituted with one or two or more alkyl groups having 1 to 4 carbon atoms (preferably a methyl group). It is preferable that R <^6> , R <^8> and R <^11> in the said Formula (DI), D-II and D-III are respectively methyl groups, It is preferable that a1, a2 and a3 are each 0 or 1, and it is more preferable that it is 0. .

As a monovalent organic group which has the steroid structure of R <^10> in the said General formula (D-III), it is preferable that it is C1-C51, and it is more preferable that it is C3-C30. As a specific example of R <^10> which has such a steroid skeleton, it is a cholestan-3-yl group, a cholesta-5-en-3-yl group, a cholesta-24-en-3-yl group, cholesta-5,24, for example. -Diene-3-yl group, lanostane-3-yl group, etc. are mentioned.

As a specific example of the compound represented by the said General formula (D-I), For example, the compound etc. which are represented by following General formula (D-6);

[Formula D-6]

As a specific example of a compound represented by the said General formula (D-II), For example, the compound etc. which are represented by following General formula (D-7);

[Formula D-7]

As a specific example of the compound represented by the said General formula (D-III), For example, dodecaneoxy-2,4-diaminobenzene, pentadecaneoxy-2,4-diaminobenzene, hexadecaneoxy-2,4-diamino Benzene, octadecaneoxy-2,5-diaminobenzene, dodecaneoxy-2,5-diaminobenzene, pentadecaneoxy-2,5-diaminobenzene, hexadecaneoxy-2,5-diaminobenzene, And octadecaneoxy-2,5-diaminobenzene and the compounds represented by the following general formulas D-8 to D-16.

[Formula D-8]

[Formula D-9]

[Formula D-10]

[Formula D-11]

[Formula D-12]

[Formula D-13]

[Formula D-14]

[Formula D-15]

[Formula D-16]

As a diamine used when synthesize | combining the polyamic acid in the liquid crystal aligning agent of this invention, p-phenylenediamine, 4,4'- diamino diphenylmethane, 4,4'- diamino diphenyl sulfone is mentioned above. Feed, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 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-phenylenediiso Propylidene) bisaniline, 4,4 '-(m-phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) Biphenyl, 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane, 3,5-diaminobenzo , 1,4-bis- (4-aminophenyl) -piperazine, the compounds represented by the above formulas D-1 to D-5, 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-diaminocarbazole, N, N'-bis (4-aminophenyl) -benzidine, N, N'-bis (4-aminophenyl) -N, N'-dimethylbenzidine, At least one selected from the group consisting of a compound represented by the formula (D-6), a compound represented by the formula (D-7), and 1,3-bis (3-aminopropyl) -tetramethyldisiloxane (hereinafter, "specific Diamine (1) "and at least one selected from the group consisting of compounds represented by the above formula (D-III) (hereinafter referred to as" specific diamine (2) ").

As the specific diamine (1), more preferably p-phenylenediamine, 4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-di Trifluoromethyl-4,4'-diaminobiphenyl, 2,7-diaminofluorene, 4,4'-diaminodiphenylether, 2,2-bis [4- (4-aminophenoxy) Phenyl] propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane, a compound represented by the above formulas D-1 to D-3, 2 , 6-diaminopyridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N, N'-bis (4-aminophenyl) -benzidine, N, N'-bis (4-aminophenyl) -N, N'-dimethylbenzidine, 3,5-diaminobenzoic acid, 1,4-bis- (4-aminophenyl) -piperazine and 1,3-bis (3-aminopropyl) Tetramethyldisiloxane Is at least one member selected from the group consisting.

As specific diamine (2), More preferably, in the compound represented by the said Formula (D-III), the said Formula (D-8), the said Formula (D-10), the said Formula (D-11), the said Formula (D-14), and the said Formula (D-15) It is 1 or more types chosen from the group which consists of compounds represented, respectively.

It is preferable that the diamine used when synthesize | combining the polyamic acid in the liquid crystal aligning agent of this invention contains 10 mol% or more of specific diamine (1) mentioned above with respect to all diamine, and it contains 20 mol% or more. More preferably, it is especially preferable to contain 40 mol% or more. Moreover, it is preferable that the diamine used when synthesize | combining the polyamic acid in the liquid crystal aligning agent of this invention contains 1-60 mol% of specific diamine (2) as mentioned above with respect to all diamine, and is 5-50 mol It is more preferable to contain%, and it is especially preferable to contain 8-40 mol%.

[Synthesis of Polyamic Acid]

The polyamic acid in the liquid crystal aligning agent of this invention can be obtained by making tetracarboxylic dianhydride and diamine as mentioned above react.

As for the usage ratio of the tetracarboxylic dianhydride and diamine used for the synthesis reaction of a polyamic acid, the ratio in which the acid anhydride group of tetracarboxylic dianhydride is 0.5-2 equivalent with respect to 1 equivalent of amino group contained in diamine, More preferably, it is the ratio used as 0.7 to 1.2 equivalent.

The synthesis reaction of the polyamic acid is preferably carried out in an organic solvent under a temperature condition of preferably -20 to 150 ° C, more preferably 0 to 100 ° C. The reaction time is preferably 0.2 to 120 hours, more preferably 0.5 to 72 hours. There is no restriction | limiting in particular as long as it can melt | dissolve the polyamic acid synthesize | combined as an organic solvent which can be used here, For example, N-methyl- 2-pyrrolidone, N, N- dimethylacetamide, N, N- dimethylform Aprotic polar solvents such as amide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea and hexamethylphosphotriamide; and phenol solvents such as m-cresol, xylenol, phenol, and halogenated phenol. In addition, as for the usage-amount of organic solvent (a: However, when using together an organic solvent and the poor solvent mentioned later, these total amounts are mentioned), the total amount (b) of tetracarboxylic dianhydride and diamine is the whole quantity of a reaction solution. It is preferable that it is an amount which will be 0.1-30 weight% with respect to (a + b).

In the organic solvent, alcohol, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like, which are generally known as poor solvents of polyamic acid, can be used in combination without causing precipitation of polyamic acid. Specific examples of such poor solvents include methanol, ethanol, isopropanol, cyclohexanol, 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 malonic acid, 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 Tere, 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, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether and the like.

When the organic solvent and the poor solvent as described above are used in synthesizing the polyamic acid, the use ratio of the poor solvent is preferably 25% by weight or less, more preferably 10% by weight, based on the total of the organic solvent and the poor solvent. It is% or less.

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

This reaction solution may be used as it is for the production of a liquid crystal aligning agent, may be used for the production of a liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution, or after the purified polyamic acid is purified to prepare a liquid crystal aligning agent. Can also be used for

When the polyamic acid is dehydrated and closed to give a polyimide, the reaction solution may be used as it is for the dehydration ring-closure reaction, or the polyamic acid contained in the reaction solution may be isolated and then used for the dehydration ring-closure reaction, or the isolated polyamic acid. After purification, it can be used for dehydration ring closure reaction.

Isolation of a polyamic acid can be performed by pouring the said reaction solution in a large quantity of poor solvents, obtaining a precipitate, and drying this precipitate under reduced pressure, or distilling off the organic solvent in a reaction solution by evaporation under reduced pressure. Moreover, polyamic acid can be refine | purified by the method which melt | dissolves this polyamic acid again in an organic solvent, and then precipitates with a poor solvent, or performs the process of distilling off under reduced pressure with an evaporator once or several times.

Synthesis of 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 making tetracarboxylic dianhydride and diamine react.

As tetracarboxylic dianhydride used when synthesize | combining the polyimide in the liquid crystal aligning agent of this invention, the same thing as the above-mentioned compound is mentioned as tetracarboxylic dianhydride used when synthesize | combining a polyamic acid.

As diamine used when synthesize | combining the polyimide in the liquid crystal aligning agent of this invention, the same thing as the above-mentioned compound is mentioned as the diamine used when synthesize | combining a polyamic acid. It is preferable that this diamine contains the said specific diamine (1). As diamine used when synthesize | combining the polyimide in the liquid crystal aligning agent of this invention, More preferably, p-phenylenediamine, 4,4'- diamino diphenylmethane, 3, 5- diamino benzoic acid, 1, 4-bis- (4-aminophenyl) -piperazine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 1,3-bis (aminomethyl) cyclohexane and 1,3-bis (3 -Aminopropyl) -tetramethyldisiloxane, at least one selected from the group consisting of (hereinafter referred to as "specific diamine (1 ')") and a compound represented by the above formula (D-III) (hereinafter referred to as "specific diamine ( 2 ') ").

It is preferable that the diamine used when synthesize | combining the polyimide in the liquid crystal aligning agent of this invention contains 10 mol% or more of specific diamine (1 ') mentioned above with respect to all diamine, and contains 20 mol% or more It is more preferable, and it is especially preferable to contain 40 mol% or more. Moreover, it is preferable that the diamine used at the time of synthesize | combining the polyimide in the liquid crystal aligning agent of this invention contains 1-60 mol% of specific diamine (2 ') with respect to all the diamine, and it is 5-50. It is more preferable to contain mol%, and it is especially preferable to contain 8-40 mol%.

The polyimide may be a full imide compound in which all of the amic acid structures possessed by the polyamic acid as a raw material are dehydrated and closed. It may be a cargo. It is preferable that the imidation ratio of the polyimide in the liquid crystal aligning agent of this invention is 20% or more, It is more preferable that it is 35 to 99%, It is especially preferable that it is 45 to 95%. 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 amic acid structure 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 imidation ratio can be known by ¹ H-NMR of a polyimide.

The dehydration ring closure of the polyamic acid for synthesizing the polyimide may be performed by (i) heating the polyamic acid, or (ii) dissolving the polyamic acid in an organic solvent, and adding a dehydrating agent and a dehydration ring closure catalyst to the solution. It can carry out by the method of heating as needed.

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 polyimide obtained may fall. The reaction time is preferably 0.5 to 168 hours, more preferably 0.5 to 72 hours.

As a dehydrating agent, acid anhydrides, such as an acetic anhydride, a propionic anhydride, and a trifluoroacetic anhydride, can be used as a dehydrating agent in the method of adding a dehydrating agent and a dehydration ring-closure catalyst in the solution of said polyamic acid of said (ii). It is preferable that the usage-amount of a dehydrating agent shall be 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 this. 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. Moreover, 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. 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 0.5 to 168 hours, more preferably 0.5 to 72 hours.

The polyimide obtained by the said method (i) may be used for manufacture of a liquid crystal aligning agent as it is, or may be used for manufacture of a liquid crystal aligning agent after refine | purifying the obtained polyimide. On the other hand, in the said method (ii), the reaction solution containing a polyimide is obtained. This reaction solution may be used as it is for the production of a liquid crystal aligning agent, or may be used for the production of a liquid crystal aligning agent after removing the dehydrating agent and the dehydration ring-closure catalyst from the reaction solution, or after the polyimide is isolated to be used for the preparation of the liquid crystal aligning agent. You may use it for the manufacture of a liquid crystal aligning agent after refine | purifying an isolated polyimide. 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 mentioned above as a method of isolation and purification of a polyamic acid.

[Terminal Modified Polymer]

The polyamic acid or the polyimide which the liquid crystal aligning agent of the present invention may contain may be a terminal-modified polymer having a controlled molecular weight. By using the polymer of the terminal modification type, the coating characteristic of a liquid crystal aligning agent, etc. can be further improved, without impairing the effect of this invention. Such a terminal-modified polymer can be performed by adding a molecular weight modifier to the polymerization reaction system when synthesizing the polyamic acid. As a molecular weight modifier, an acid-anhydride, a monoamine compound, a monoisocyanate compound, etc. are mentioned, for example.

As said 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. 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 10 parts by weight or less, and more preferably 6 parts by weight or less based on 100 parts by weight of the total of tetracarboxylic dianhydride and diamine used when synthesizing the polyamic acid.

[Solution viscosity]

The polyamic acid or polyimide obtained as described above preferably has a solution viscosity of 20 to 800 mPa · s, more preferably 30 to 500 mPa · s when the solution has a concentration of 10% by weight. Do.

The solution viscosity (mPa · s) of the polymer is a polymer solution having a concentration of 10% by weight using a good solvent of the polymer (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.). It is a value measured at 25 ° C. using an E-type rotational viscometer.

<(B) Compound>

The compound (B) in the liquid crystal aligning agent of the present invention is a compound having an epoxy group and a group represented by the above formula (2o). Such a compound (B),

(b1) 1 mole part of a compound having 2 to 8 epoxy groups (hereinafter referred to as "compound (b1)");

(b2) 1 to (n-1) molar parts of a compound represented by the following formula (hereinafter, referred to as "compound (b2)"), wherein n is the number of epoxy groups of the compound (b1);

It is preferable that it is a compound obtained by making it react.

(In Formula 2, R ^I , R ^II , Z ^I , Z ^II , n1, n2, n3 and n4 have the same meanings as in Formula 2o, respectively.)

[Compound (b1)]

As a compound (b1) in this invention, what has a structure represented by the following general formula (b1-1) or b1-2 is preferable.

[Formula b1-1]

[Formula b1-2]

As a compound (b1) which has a structure represented by the said general formula (b1-1), it is preferable that it has two structures represented by the said general formula (b1-1), As an example thereof, for example, ethylene glycol diglycidyl ether , Propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, benzene-1, 4-diol diglycidyl ether, 2-methylbenzene-1,4-diol diglycidyl ether, 2-ethylbenzene-1,4-diol diglycidyl ether, 2-n-hexylbenzene-1, 4-diol diglycidyl ether, 2-n-dodecylbenzene-1,4-diol diglycidyl ether, 2-trifluoromethylbenzene-1,4-diol diglycidyl ether, 2,5 -Diethylbenzene-1,4-diol diglycidyl ether, etc. are mentioned.

As a compound (b1) which has a structure represented by the said Formula (b1-2), it is preferable to have one or two structures represented by the said Formula (b1-2), for example, N, N, N ', N'- Tetraglycidyl-5-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, N, N, N ', N'-tetraglycidyl-6-amino-1- ( 4'-aminophenyl) -1,3,3-trimethylindane, N, N, N ', N'-tetraglycidyl-2,7-diaminofluorene, N, N, N', N'- Tetraglycidyl-1,4,4 '-(p-phenyleneisopropylidene) bisaniline, N, N, N', N'-tetraglycidyltetramethylenediamine, N, N, N ', N '-Tetraglycidylhexamethylenediamine, N, N, N', N'-tetraglycidyl-3,6-diaminocarbazole, represented by the formulas b1-2-1 to b1-2-4, respectively The compound etc. which are mentioned are mentioned. In the formulas b1-2-1 to b1-2-4, two B or B and-(CH ₂ ) _a -NG ₂ bonded to a benzene ring or a cyclohexane ring are each 1, It is preferably in the 4-position.

[Formula b1-2-1]

[Formula b1-2-2]

[Formula b1-2-3]

[Formula b1-2-4]

(In the above formula, B is a single bond, a methylene group, an alkylene group having 2 to 12 carbon atoms, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -CO-, -O- (CH ₂ ) _g -O-, -S-, -SO _2- , -C (CH ₃ ) _2- , -C (C ₂ H ₅ ) ₂ -or -C (CF ₃ ) _2- , wherein g Is an integer of 1 to 12, and when a plurality of B's are present, a plurality of B's may be the same or different, and each R is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and a fluoroalkyl group having 1 to 4 carbon atoms, a is each independently 0 or 1, b is each independently an integer of 0 to 3, c is each independently an integer of 0 to 4, d is an integer of 0 to 5, e is each independently 0 to An integer of 10, f is an integer of 0 to 11, and each G is a glycidyl group)

As a specific example of the compound represented by the said general formula b1-2-1, For example, N, N- diglycidylaminobenzene, N, N- diglycidyl-2-n-hexylaminobenzene, N, N- Diglycidyl-2,2'-dimethyl-4-aminobiphenyl, N, N- diglycidylaminomethylbenzene and the like;

As a specific example of a compound represented by the said general formula (b1-2-2), For example, N, N- diglycidyl aminocyclohexane, N, N- diglycidyl aminomethyl cyclohexane, etc .;

As a specific example of the compound represented by the said general formula b1-2-3, For example, N, N, N ', N'- tetraglycidyl p-phenylenediamine, N, N, N', N'-tetra Glycidyl-m-phenylenediamine, N, N, N ', N'-tetraglycidyl-2-methyl-1,4-phenylenediamine, N, N, N', N'-tetraglycid Dyl-2-n-propyl-1,4-phenylenediamine, N, N, N ', N'-tetraglycidyl-2-n-hexyl-1,4-phenylenediamine, N, N, N ', N'-tetraglycidyl-2-trifluoromethyl-1,4-phenylenediamine, N, N, N', N'-tetraglycidyl-2,5-dimethyl-1,4- Phenylenediamine, N, N, N ', N'-tetraglycidyl-2,2'-dimethyl-4,4'-diaminobiphenyl, N, N, N', N'-tetraglycidyl -2,2'-diethyl-4,4'-diaminobiphenyl, N, N, N ', N'-tetraglycidyl-2,2'-ditrifluoromethyl-4,4'- Diaminobiphenyl, N, N, N ', N'-tetraglycidyl-3,3'-dimethyl-4,4'-diaminobiphenyl, N, N, N', N'-tetraglyci Dill-3,3'-diethyl-4,4'-diaminobiphenyl, 2,2-bis [4- (N, N-diglycidyl-4-aminophenoxy ) Phenyl] propane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N, N', N'-tetraglycidyl-4,4 ' -Diaminodiphenylethane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylether, N, N, N', N'-tetraglycidyl-4, 4'-diaminodiphenylsulfide, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylsulfone, N, N, N', N'-tetraglycidyl -4,4'-diaminobenzanilide, N, N, N ', N'-tetraglycidyl-4,4'-diamino benzophenone, 2,2-bis [4- (N, N-di Glycidyl-4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (N, N-diglycidyl-4-aminophenyl) hexafluoropropane, 2,2-bis [4- (N, N-diglycidyl-4-aminophenoxy) phenyl] sulfone, 1,4-bis (N, N-diglycidyl-4-aminophenoxy) benzene, 4,4'-bis ( N, N-diglycidyl-4-aminophenoxy) biphenyl, 1,3-bis (N, N-diglycidyl-4-aminophenoxy) benzene, 1,3-bis (N, N -Diglycidyl-3-aminophenoxy) benzene, N, N, N ', N'-tetraglycisy -M- xylene diamine and the like;

As a specific example of the compound represented by the said general formula b1-2-4, For example, N, N, N ', N'- tetraglycidyl-1, 4- diamino cyclohexane, N, N, N', N '-Tetraglycidyl-1,3-bis (aminomethyl) cyclohexane, N, N, N', N'-tetraglycidyl-1,4-bis (aminomethyl) cyclohexane, N, N, N ', N'- tetraglycidyl-4,4'- methylenebis (cyclohexylamine), etc. are mentioned, respectively.

Among these, as the compound (b1), a compound having one or two structures represented by the above formula (b1-2) is preferable in that both the reactivity of the epoxy group and the vertical alignment of the liquid crystal aligning film formed are compatible, and are particularly preferable. N, N-diglycidylaminobenzene, N, N- diglycidylaminomethylcyclohexane, N, N-diglycidylaminomethylbenzene, N, N, N ', N'-tetraglycidyl -p-phenylenediamine, N, N, N ', N'-tetraglycidyl-2,2'-dimethyl-4,4'-diaminobiphenyl, N, N, N', N'-tetra Glycidyl-2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 2,2-bis [4- (N, N-diglycidyl-4-aminophenoxy) phenyl ] Propane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N, N', N'-tetraglycidyl-4,4'-dia Minodiphenylether, N, N, N ', N'-tetraglycidyl-4,4'-diaminobenzophenone, 2,2-bis [4- (N, N-diglycidyl-4- Aminophenoxy) phenyl] hexafluoroprop Plate, N, N, N ', N'-tetraglycidylhexamethylenediamine, N, N, N', N'-tetraglycidyl-1,3-bis (aminomethyl) benzene, N, N, N ', N'- tetraglycidyl-m-xylenediamine and N, N, N', N'- tetraglycidyl-1, 3-bis (aminomethyl) cyclohexane are mentioned.

[Compound (b2)]

Regarding the compound (b2), the alkyl group having 4 to 40 carbon atoms for R ^I in the general formula (2) is preferably an alkyl group having 6 to 40 carbon atoms, specifically, for example, a hexyl group, octyl group, decyl group, dodecyl group, Hexadecyl group, a stearyl group, etc .;

As the fluoroalkyl group having 4 to 40 carbon atoms, a fluoroalkyl group having 4 to 20 carbon atoms is preferable, and specific examples thereof include, for example, trifluoromethylpropyl group, trifluoromethylbutyl group, trifluoromethylhexyl group, and trifluoro Chloromethyldecyl group, pentafluoroethylpropyl group, pentafluoroethylbutyl group, pentafluoroethyloctyl group, etc .;

Examples 17 to 51 hydrocarbon group having a steroid skeleton, for example to the like group represented by the formula R R ^{I I} -1 to -3, respectively.

[Formula R ^I -1]

[Formula R ^I -2]

[Formula R ^I -3]

("*" In the formula R ^I -1 to R ^I -3 represents a bond)

It is preferable that the cyclohexylene group and the phenylene group of R <^II> in the said General formula (2) are a 1, 4- cyclohexylene group and a 1, 4- phenylene group, respectively. As the divalent group represented _by- (R ^II ) _n1 -in the formula (2), when n1 is 1, for example, 1,4-phenylene group, 1,2-cyclohexylene group, etc .;

When n1 is 2, a 4,4'-biphenylene group, a 4,4'-bicyclohexylene group, the group represented by each of following formula is mentioned, respectively as a preferable thing, for example.

(In the above formula, the bond of which "*" is attached is the R ^I side.)

N3 in the general formula (2) is preferably 2.

Preferred compounds (b2) in the present invention include stearic acid, hexyloxybenzoic acid, octyloxybenzoic acid, decyloxybenzoic acid, dodecyloxybenzoic acid, octadecyloxybenzoic acid, trifluoromethylbenzoic acid, trifluoromethoxybenzoic acid, Trifluoromethylpropyloxybenzoic acid, trifluoromethylbutyloxybenzoic acid, hexafluoropropyloxybenzoic acid, compounds represented by the following general formulas b2-1 and b2-2, and the like.

[Formula b2-1]

[Formula b2-2]

Preferred compound (B) in the liquid crystal aligning agent of the present invention includes 1 mol parts of the compound (b1) as described above, and 1 to (n-1) mol parts of the compound (b2), provided that n is an epoxy group of the compound (b1). It is a compound obtained by making it react preferably) in a suitable organic solvent. A more preferable use ratio of compound (b2) to 1 mole part of compound (b1) is 1 to (n / 2) mole parts when n is even, and 1 to {(n + 1) / when n is odd. 2} mole. For example, when the compound (b1) is a compound having two structures represented by the formula (b1-2) (the number of epoxy groups in this case is 4), the compound (b2) is based on 1 mole part of the compound (b1) 1 to 3 mole parts, preferably 1 to 2 mole parts are used.

As an organic solvent which can be used for the said reaction, the organic solvent illustrated as what is used for the synthesis | combination of said polyamic acid is mentioned. Aprotic organic solvents are preferred, specifically N-methyl-2-pyrrolidone, acetonitrile, dimethyl sulfoxide, N, N-dimethylacetamide, N, N-dimethylformamide, N, N -Dimethyl imidazolidinone, dimethyl sulfoxide, (gamma) -butyrolactone, tetramethyl urea, hexamethyl phosphotriamide, etc. are mentioned. As a usage ratio of an organic solvent, it is preferable to set it as the ratio which the ratio of the total weight of a compound (b1) and a compound (b2) in a reaction solution becomes 1 weight% or more, and to set it as the ratio which becomes 5 to 50 weight%. More preferred.

It is preferable to set it as 20-250 degreeC, and, as for the temperature at the time of the said reaction, it is more preferable to set it as 50-180 degreeC. The reaction time is preferably 0.1 to 72 hours, more preferably 0.5 to 48 hours.

In this way, the solution containing a preferable (B) compound is obtained. This solution can also be used for manufacture of the liquid crystal aligning agent of this invention as it is, or it can also be used for manufacture of the liquid crystal aligning agent of this invention after isolating and refine | purifying a compound (B) from a reaction solution. In order to isolate and purify the compound (B) from the reaction solution, it can be carried out by a method such as liquid-liquid extraction, column chromatography, distillation, or the like.

In the preferred compound (B) of the present invention, a part of the epoxy group possessed by the compound (b1) reacts with the compound (b2) to form a group R ^I derived from the epoxy group derived from the compound (b1) and the compound (b2). Bottled. Therefore, when the liquid crystal aligning agent of this invention contains such a (B) compound, the liquid crystal aligning film excellent in the vertical alignment property can be formed, without impairing the printability of a liquid crystal aligning agent.

As a more preferable example of a compound (B), the compound etc. which are respectively represented by following formula B-1-B-4 are mentioned, Especially, Among these, following formula B-1-1-B-1-3, Preference is given to compounds represented by B-2-1 and B-3-1 to B-3-4, respectively. Here, the group represented by the following formula (3-1) and the group represented by the following formula (3-2) may be mixed in the compound (B) of one molecule, and the compound (B) having the group represented by the following formula (3-1) and the following You may mix and use the compound (B) which has group represented by General formula (3-2).

[Formula B-1]

[Formula B-2]

[Formula B-3]

[Formula B-4]

(In the above formula, B is a single bond, a methylene group, an alkylene group having 2 to 12 carbon atoms, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -CO-, -O- (CH ₂ ) _g -O-, -S-, -SO _2- , -C (CH ₃ ) _2- , -C (C ₂ H ₅ ) ₂ -or -C (CF ₃ ) _2- , wherein g Is an integer of 1 to 12, when a plurality of B's are present, a plurality of B's may be the same or different, and each R is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms. a is each independently 0 or 1, b is each independently an integer of 0 to 3, c is each independently an integer of 0 to 4, d is an integer of 0 to 5, e is each independently 0 An integer of 10 to 10, f is an integer of 0 to 11, X ^I is a glycidyl group, X ^II is a group represented by the following Chemical Formula 3-1 or 3-2, and X ^III and X ^IV are each independently Glycidyl group or represented by the following formula 3-1 or 3-2 Im)

[Formula 3-1]

[Formula 3-2]

(In Formulas 3-1 and 3-2, R ^I , R ^II , Z ^I , Z ^II , n1, n2, n3 and n4 have the same meanings as in Formula 2, respectively.)

[Formula B-1-1]

[Formula B-1-2]

[Formula B-1-3]

[Formula B-2-1]

[Formula B-3-1]

[Formula B-3-2]

[Formula B-3-3]

[Formula B-3-4]

(Wherein X ^I to X ^IV , R, c and d each have the same meaning as in Formulas B-1 to B-4 above)

The use ratio of the compound (B) in the liquid crystal aligning agent of this invention is 100 weight of 1 or more types of polymers (henceforth "(A) polymer") chosen from the group which consists of (A) polyamic acid and a polyimide. Preferably it is 0.1-40 weight part with respect to a part, More preferably, it is 0.1-30 weight part, It is further more preferable that it is 0.2-25 weight part.

<Other additives>

Although the liquid crystal aligning film of this invention contains the above-mentioned (A) polymer and (B) compound as an essential component, it may contain other components as needed. As such other components, for example, a compound having one or more epoxy groups in the molecule (C) (except for the compound (B), hereinafter simply referred to as an "epoxy compound"), (D) functional A silane compound etc. are mentioned.

[(C) Epoxy Compound]

The said (C) epoxy compound can be used from a viewpoint of improving the adhesiveness to the board | substrate surface of the liquid crystal aligning film formed further. As the (C) epoxy compound which can be used here, the same thing as the said compound (b1) is mentioned. Among these, ethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 1,3,5,6- tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N', N'- Tetraglycidyl-4,4'-diaminodiphenylmethane, N, N- diglycidyl-benzylamine, N, N- diglycidyl-aminomethylcyclohexane and the like are preferred.

The compounding ratio of these (C) epoxy compounds becomes like this. Preferably it is 30 weight part or less, More preferably, it is 0.1-25 weight part with respect to 100 weight part of (A) polymers. In addition, it is preferable that the sum total of the use ratio of these (C) epoxy compounds, and the use ratio of (B) compound does not exceed 40 weight part with respect to 100 weight part of (A) polymers.

[(D) Functional Silane Compound]

The said (D) functional silane compound can be used from a viewpoint of further improving the printability of the liquid crystal aligning agent of this invention. As such (D) functional silane compound, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N -(2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureido propyltrimethoxysilane, 3-ureidopropyl Triethoxysilane, 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-trimethoxy Silyl-3,6-diazanyl acetate, 9-triethoxysilyl-3,6-diazanyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-ben -3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimeth Oxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, etc. are mentioned.

The use ratio of these (D) functional silane compounds becomes like this. Preferably it is 2 weight part or less with respect to 100 weight part of (A) polymers, More preferably, it is 1 weight part or less.

<Liquid crystal aligning agent>

As for the liquid crystal aligning agent of this invention, the above-mentioned (A) polymer, (B) compound, and the other additive arbitrarily mix | blended as needed are preferably melt-dissolved in an organic solvent, and are comprised.

As an organic solvent which can be used for the liquid crystal aligning agent of this invention, the solvent illustrated as what is used for the synthesis reaction of polyamic acid is mentioned. Moreover, the poor solvent illustrated as what can be used together at the time of the synthesis reaction of a polyamic acid can also be selected suitably, and can be used together. Preferred examples of such organic solvents include, for example, N-methyl-2-pyrrolidone, γ-butyrolactone, γ-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, And the like can be mentioned isoamyl propionate, isoamyl isobutyrate, di-isopentyl ether. These may be used alone, or may be used by mixing two or more kinds. A particularly preferable solvent composition is a composition obtained by combining the above solvents, the (A) polymer, the (B) compound and other additives optionally blended in the liquid crystal aligning agent are not precipitated, and the surface tension of the liquid crystal aligning agent is 25 to 40 mN. It is a composition in the range of / m.

The solid content concentration (the ratio of the total weight of the components except the organic solvent in the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) of the liquid crystal aligning agent of the present invention is appropriately selected in consideration of viscosity, volatility, and the like, but preferably 1 To 10% by weight. That is, although the coating film which becomes a liquid crystal aligning film is formed by apply | coating this to the surface of a board | substrate and removing an organic solvent, when the solid content concentration is less than 1 weight%, the film thickness of this coating film becomes too small and a favorable liquid crystal When the alignment film may be difficult to obtain, while the solid content concentration exceeds 10% by weight, the film thickness of the coating film may be too large to obtain a good liquid crystal alignment film, and the like may be difficult to obtain. A characteristic may 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% 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 manufacturing the liquid crystal aligning agent of this invention becomes like this. Preferably it is 0 degreeC-100 degreeC, More preferably, it is 20 degreeC-60 degreeC.

The liquid crystal aligning agent of this invention can be preferably used especially in order to form the liquid crystal aligning film used for a vertical alignment liquid crystal display element.

<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. As a preferable operation mode in the liquid crystal display element of this invention, a vertical alignment type is mentioned. Hereinafter, the method of manufacturing a vertical alignment liquid crystal display element using the liquid crystal aligning agent of this invention is demonstrated.

The liquid crystal display element of this invention can be manufactured by the process of the following (1)-(3), for example.

(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. A pair of two substrates on which a patterned transparent conductive film is provided is used as a pair, and the liquid crystal aligning agent of the present invention is preferably applied onto each of the transparent conductive film forming surfaces by a roll coater method, a spinner method, a printing method, and an inkjet method. Then, a coating film is formed by heating each application surface. Since the liquid crystal aligning agent of this invention is excellent in printability, it is preferable to use the printing method as a coating method.

Here, as a board | substrate, For example, glass, such as float glass and a soda glass; Transparent substrates containing plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and alicyclic polyolefin can be used.

Examples of the transparent conductive film provided on one side of the substrate include an NESA film containing tin oxide (SnO ₂ ) (registered trademark of PPG Co., Ltd.) and an ITO film containing indium tin oxide (In ₂ O ₃ -SnO ₂ ). Etc. can be used. In order to obtain a patterned transparent conductive film, for example, a transparent conductive film can be formed without a pattern, followed by a method of forming a pattern by photo-etching, a method of using a mask having a desired pattern when forming a transparent conductive film, or the like. . 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 pretreatment for applying a functional silane compound, a functional titanium compound, or the like to the surface on which the coating film should be formed on the substrate surface in advance. May be performed.

After application of the liquid crystal aligning agent, preliminary heating (pre-baking) is preferably performed for the purpose of preventing the liquid dripping of the applied liquid crystal aligning agent. Preliminary baking temperature becomes like this. Preferably it is 30-200 degreeC, More preferably, it is 40-150 degreeC, Especially preferably, it is 40-100 degreeC. The preliminary baking time is preferably 0.1 to 10 minutes, more preferably 0.5 to 5 minutes. Thereafter, a firing (post-baking) step is performed for the purpose of completely removing the solvent. This post-baking temperature becomes like this. Preferably it is 80-300 degreeC, More preferably, it is 120-250 degreeC. The post-baking time is preferably 1 to 300 minutes, more preferably 2 to 120 minutes. When the liquid crystal aligning agent of this invention forms the coating film used as an orientation film by removing an organic solvent after application | coating, but when the polymer contained in the liquid crystal aligning agent of this invention is a polyimide which uses a polyamic acid or an imide ring structure, and an amic acid structure together, The dehydration ring-closing reaction can be advanced by further heating after coating film formation, and it can also be set as the imidized coating film.

The film thickness of the coating film formed here becomes like this. Preferably it is 0.001-1 micrometer, More preferably, it is 0.005-0.5 micrometer.

(2) Although the coating film formed as mentioned above can be used as it is as a liquid crystal aligning film for vertically-aligned liquid crystal display elements, a rubbing process can also be performed to this coating film surface arbitrarily.

A rubbing process can be performed by rubbing a coating film surface in the fixed direction with the roll which wound the cloth which consists of fibers, such as nylon, a rayon, a cotton, for example.

(3) The liquid crystal cell is manufactured by preparing two board | substrates with a liquid crystal aligning film as above-mentioned, and arrange | positioning a liquid crystal between these two board | substrates. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example.

The first method is a conventionally known method. First, two substrates are disposed to face each other so that each liquid crystal alignment film faces each other, the two substrate peripheries are bonded together using a sealant, and the cell surface partitioned by the substrate surface and the sealant. After injecting and filling a liquid crystal in the inside, a liquid crystal cell can be manufactured by sealing an injection hole.

The second method is a method called an ODF (One Drop Fill) method. An ultraviolet-ray curable sealing material is apply | coated to the predetermined place on one board | substrate among two board | substrates with which the liquid crystal aligning film was formed, for example, after dropping a liquid crystal on the liquid crystal aligning film surface, the other board | substrate is bonded so that a liquid crystal aligning film may oppose. Then, a liquid crystal cell can be manufactured by irradiating ultraviolet light to the whole surface of a board | substrate, and hardening a sealing agent.

Also in the case of any of the above methods, the liquid crystal cell is then heated to a temperature at which the used liquid crystal takes an isotropic phase, and then it is preferable to gradually cool the liquid crystal to remove the flow orientation during liquid crystal filling.

Moreover, 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.

Examples of the liquid crystal include nematic liquid crystals and smectic liquid crystals. Especially, a nematic liquid crystal is preferable, For example, a Schiff base liquid crystal, a subfamily clock liquid crystal, a biphenyl liquid crystal, a phenyl cyclohexane type liquid crystal, an ester type liquid crystal, a terphenyl type liquid crystal, a biphenyl cyclohexane type liquid crystal , Pyrimidine-based liquid crystals, dioxane-based liquid crystals, bicyclooctane-based liquid crystals, cuban-based liquid crystals and the like can be used. Furthermore, for these liquid crystals, for example, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonaate, cholesteryl carbonate; Chiral agent sold as brand names "C-15" and "CB-15" (manufactured by Merck); Ferroelectric liquid crystals, such as p-disiloxybenzylidene-p-amino-2-methylbutyl cinnamate, can also be added and used.

As a polarizing plate bonded to the outer surface of a liquid crystal cell, the polarizing plate which sandwiched the polarizing film called "H film | membrane" which absorbed iodine while extending | stretching polyvinyl alcohol, and between the cellulose acetate protective film, or the polarizing plate which consists of H film itself is mentioned.

<Examples>

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

[Solution viscosity]

The solution viscosity (mPa · s) of the polymer was measured at 25 ° C. using an E-type rotational viscometer with respect to a solution having a polymer concentration of 10% by weight using the solvent indicated in each synthesis example.

[Imidization rate]

The polyimide was sufficiently dried under reduced pressure at room temperature, dissolved in deuterated dimethyl sulfoxide, and obtained by the following equation (1) from ¹ H-NMR measured at room temperature using tetramethylsilane as a reference substance.

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

(In Formula 1, A ¹ is the peak area derived from the proton of the NH group appearing near 10 ppm of chemical shift, A ² is the peak area derived from other protons, and α is the precursor (polyamic acid) of the polyimide. Ratio of the number of other protons to one proton of the NH group of

Synthesis of Compound (B)

Synthesis Example B1 (N- (2-hydroxy-3-n-octyloxybenzoyloxy) propyl-N, N ', N'-triglycidyl-m-xylenediamine and N- (3-hydroxy-2- synthesis of a mixture of n-octyloxybenzoyloxy) propyl-N, N ', N'-triglycidyl-m-xylenediamine)

Mix 18.0 g (0.05 mol) of N, N, N ', N'-tetraglycidyl-m-xylenediamine and 12.5 g (0.05 mol) of 4-n-octyloxybenzoic acid in a 200 mL three neck flask under nitrogen atmosphere. Then, 122.2 g of N-methyl-2-pyrrolidone was added and stirred. N- (2-hydroxy-3-n-octyloxybenzoyloxy) propyl-N, N ', N'-triglycidyl-m-xylene was reacted with stirring under nitrogen at 100 DEG C for 4 hours. About 150 g of a solution containing 20% by weight of a mixture of diamine and N- (3-hydroxy-2-n-octyloxybenzoyloxy) propyl-N, N ', N'-triglycidyl-m-xylenediamine Got.

Synthesis Example B2 (N- (2-hydroxy-3-n-dodecyloxybenzoyloxy) propyl-N, N ', N'-triglycidyl-m-xylenediamine and N- (3-hydroxy-2 -n-dodecyloxybenzoyloxy) propyl-N, N ', N'-triglycidyl-m-xylenediamine mixture)

In a 200 mL three-necked flask under nitrogen atmosphere, 18.0 g (0.05 mol) of N, N, N ', N'-tetraglycidyl-m-xylenediamine and 15.3 g (0.05 mol) of 4-n-dodecyloxybenzoic acid were added. Mix and 133.2 g of N-methyl-2-pyrrolidone were added and stirred. By reacting this under stirring at 100 ° C. for 4 hours under nitrogen, N- (2-hydroxy-3-n-dodecyloxybenzoyloxy) propyl-N, N ', N'-triglycidyl-m- About 165 A solution containing 20% by weight of a mixture of xylenediamine and N- (3-hydroxy-2-n-dodecyloxybenzoyloxy) propyl-N, N ', N'-triglycidyl-m-xylenediamine g was obtained.

Synthesis Example B3 (N- (2-hydroxy-3-n-dodecyloxybenzoyloxy) propyl-N, N ', N'-triglycidyl-4,4'-diaminodiphenylmethane and N- ( Synthesis of a mixture of 3-hydroxy-2-n-dodecyloxybenzoyloxy) propyl-N, N ', N'-triglycidyl-4,4'-diaminodiphenylmethane)

21.1 g (0.05 mol) of N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane and 15.3 of 4-n-dodecyloxybenzoic acid in a 200 mL three-necked flask under nitrogen atmosphere g (0.05 mol) was mixed and 145.6 g of N-methyl-2-pyrrolidone was added and stirred. By reacting this under stirring at 100 ° C. for 6 hours under nitrogen, N- (2-hydroxy-3-n-dodecyloxybenzoyloxy) propyl-N, N ', N'-triglycidyl-4, 4'-diaminodiphenylmethane and N- (3-hydroxy-2-n-dodecyloxybenzoyloxy) propyl-N, N ', N'-triglycidyl-4,4'-diaminodiphenyl About 180 g of a solution containing 20% by weight of a mixture of methane was obtained.

Synthesis Example B4 (N- (2-hydroxy-3-trifluoromethylpropyloxybenzoyloxy) propyl-N, N ', N'-triglycidyl-m-xylenediamine and N- (3-hydroxy- Synthesis of a mixture of 2-trifluoromethylpropyloxybenzoyloxy) propyl-N, N ', N'-triglycidyl-m-xylenediamine)

18.0 g (0.05 mol) of N, N, N ', N'-tetraglycidyl-m-xylenediamine and 9.5 g (0.05 mol) of 4-trifluoromethylpropyloxybenzoic acid in a 200 mL three neck flask under nitrogen atmosphere Were mixed, and 110.1 g of N-methyl-2-pyrrolidone was added and stirred. N- (2-hydroxy-3-trifluoromethylpropyloxybenzoyloxy) propyl-N, N ', N'-triglycidyl-m by reacting this under stirring at 100 DEG C for 4.5 hours under nitrogen. A solution containing 20% by weight of a mixture of xylenediamine and N- (3-hydroxy-2-trifluoromethylpropyloxybenzoyloxy) propyl-N, N ', N'-triglycidyl-m-xylenediamine About 136 g was obtained.

Synthesis Example B5 (Synthesis of Mixture of Compound (B-3-2-1-1) and Compound (B-3-2-1-2))

According to Scheme 1 below, a mixture of compound (B-3-2-1-1) and compound (B-3-2-1-2) was synthesized.

In a 200 mL three-necked flask under nitrogen atmosphere, 18.0 g (0.05 mol) of N, N, N ', N'-tetraglycidyl-m-xylenediamine and 24.4 g (0.05 mol) of compound (b2-1) were mixed and And 110.1 g of N-methyl-2-pyrrolidone were added and stirred. A solution containing 20% by weight of a mixture of compound (B-3-2-1-1) and compound (B-3-2-1-2) by reacting this under stirring at 100 ° C. for 4.5 hours under nitrogen. About 192 g were obtained.

Synthesis Example B6 (Synthesis of Mixture of Compound (B-3-2-2-1) and Compound (B-3-2-2-2))

According to Scheme 2 below, a mixture of compound (B-3-2-2-1) and compound (B-3-2-2-2) was synthesized.

In a 200 mL three-necked flask under nitrogen atmosphere, 18.0 g (0.05 mol) of N, N, N ', N'-tetraglycidyl-m-xylenediamine and 17.6 g (0.05 mol) of compound (b2-2) were mixed and And 110.1 g of N-methyl-2-pyrrolidone were added and stirred. A solution containing 20% by weight of a mixture of compound (B-3-2-2-1) and compound (B-3-2-2-2) by reacting this under stirring at 100 DEG C for 4.5 hours under nitrogen. About 187 g were obtained.

Synthesis of Polymer (A)

Synthesis of Polyimide

Synthesis Example PI01 to PI13

Diamine and tetracarboxylic dianhydride in the amounts shown in Table 1 were added to N-methyl-2-pyrrolidone in this order to make a solution having a monomer concentration of 20% by weight, and reacted at 60 ° C for 4 hours to carry out a polya Each solution containing a mymic acid was obtained. Each solution was aliquoted and the solution viscosity measured as a solution of 10 weight% of polyamic acid concentration by adding N-methyl- 2-pyrrolidone is shown in Table 1.

Subsequently, pyridine and acetic anhydride were added to each of the polyamic acid solutions so that the molar number of the pears shown in Table 1 was added to 1 mole of the amic acid unit of the polyamic acid, and then heated to 110 ° C. to perform a dehydration ring closure reaction for 4 hours. It was 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 for the dehydration ring closure reaction in this operation were removed to the outside of the system) to thereby give a polyimide (PI-1). A solution containing 16 wt% to (PI-13) each was obtained.

The solution viscosity measured as the imidation ratio of each polyimide contained in these polyimide solutions, and the N-methyl- 2-pyrrolidone solution of 10 weight% of polyimide concentration is shown in Table 1, respectively.

[Synthesis of Polyamic Acid]

Synthesis Example PA01 to PA03

A solution containing polyamic acid (PA-1) to (PA-3), respectively, by reacting in the same manner as in Synthesis Examples PI01 to PI13 except that diamine and tetracarboxylic dianhydride were used in the amounts shown in Table 1, respectively. Got. Each solution was aliquoted and the solution viscosity measured as a solution of 10 weight% of polyamic acid concentration by adding N-methyl- 2-pyrrolidone is shown in Table 1.

In Table 1, the abbreviation of diamine and tetracarboxylic anhydride is the following meanings, respectively.

<Diamine>

d-1: p-phenylenediamine

d-2: 4,4'-diaminodiphenylmethane

d-3: 2,2'-dimethyl-4,4'-diaminobiphenyl

d-4: 1,3-bis (aminomethyl) cyclohexane

d-5: 1,3-bis (3-aminopropyl) tetramethyldisiloxane

d-6: diamine represented by Chemical Formula D-10

d-7: diamine represented by Chemical Formula D-8

Tetracarboxylic dianhydride

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

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

Example 1

<Production of Liquid Crystal Alignment Agent>

(A) A solution containing the polyimide (PI-1) obtained in Synthesis Example PI01 as the polymer was converted to polyimide (PI-1) to take an amount equivalent to 100 parts by weight, and gamma -butyrolactone was added thereto. , N-methyl-2-pyrrolidone and butyl cellosolve were added, and (B) the compound N- (2-hydroxy-3-n-octyloxybenzoyloxy) propyl-N obtained in Synthesis Example B1 above , N ', N'-triglycidyl-m-xylenediamine and N- (3-hydroxy-2-n-octyloxybenzoyloxy) propyl-N, N', N'-triglycidyl-m-xylene A solution containing a mixture of diamines in an amount equivalent to 5 parts by weight in terms of the compound (B) included therein, and (C) N, N, N ', N'-tetraglycidyl-4 as the epoxy compound. 10 parts by weight of, 4'-diaminodiphenylmethane was added, and the solvent composition was γ-butyrolactone: N-methyl-2-pyrrolidone: butyl cellosolve = 40: 30: 30 (weight ratio), solid content concentration A solution having a weight of 6.5% by weight. When this solution was visually observed, it was a cloudy and transparent solution. The liquid crystal aligning agent was produced by filtering this solution using the filter of 0.2 micrometer of pore diameters, and was used for the following printability evaluation.

In addition, a solution having a solvent composition of γ-butyrolactone: N-methyl-2-pyrrolidone: butyl cellosolve = 40: 30: 30 (weight ratio) and a solid content concentration of 4.0% by weight was prepared as described above. The liquid crystal aligning agent was obtained by filtering using the filter of 0.2 micrometer of pore diameters, and this was used for the evaluation of the following vertical alignment property and voltage retention.

<Evaluation of Printability>

About the liquid crystal aligning agent of 6.5 weight% of solid content concentration manufactured above, the transparent substrate of the glass substrate with a transparent electrode containing an ITO film using a liquid crystal aligning film printer (Nipbon Shashin Insatsu Co., Ltd. product name "Angstromer"). After apply | coating to the electrode surface and heating (pre-baking) for 1 minute on 80 degreeC hotplate, the solvent was removed, and it heated for 10 minutes (postbaking) on the 200 degreeC hotplate, and formed the coating film of average film thickness of 750 Pa. This coating film was visually observed and the degree of printing nonuniformity was investigated. Here, the printability "very good" is the case where no unevenness and surface irregularities on the coating film surface are confirmed at all, and the printability is "good" when the coating unevenness or the surface unevenness is slightly recognized on the coating film surface. Stripe irregularities or surface irregularities or cases where both were clearly identified were evaluated as printability "poor", and the printability of the liquid crystal aligning agent was "very good".

 <Evaluation of Vertical Orientation Evaluation>

[Manufacture of Liquid Crystal Display Element for Vertical Orientation Evaluation]

The liquid crystal aligning agent of 4.0 weight% of solid content concentration prepared above was apply | coated using the spinner on the transparent conductive film containing the ITO film | membrane provided in one side of the glass substrate of thickness 1mm, and then heated for 1 minute on 80 degreeC hotplate. After preliminary baking to remove the solvent, a coating film having a film thickness of 0.08 탆 was formed by heating (postbaking) in a clean oven at 200 ° C for 60 minutes. About this coating film, the rubbing process was performed on the conditions of the roll rotation speed of 400 rpm, the stage moving speed of 3 cm / sec, and the hair pressing indentation length 0.4 mm by the rubbing machine which has the roll which wound up the rayon spring. The board | substrate with this coating film after rubbing was ultrasonically cleaned in pure water for 1 minute, heated and dried for 10 minutes in a clean oven at 100 degreeC, and the board | substrate with a coating film which the rubbing process was completed was manufactured. This series of operations was repeated, and a pair (two sheets) of board | substrates with the coating film of which rubbing process was completed were manufactured.

After applying an aluminum oxide sphere-containing epoxy resin adhesive having a diameter of 3.5 μm to each of the outer edges of each of the coating film forming surfaces of the pair of substrates, the two substrates were faced to face each other so that the rubbing directions of the coating films were antiparallel to each other. And the adhesive was cured. Subsequently, after filling a negative liquid crystal (MLC-6608 by Merck Co., Ltd.) between a liquid crystal injection hole and a board | substrate, sealing a liquid crystal injection hole with an acryl-type photocuring adhesive, and bonding a polarizing plate to both surfaces of the outer side of a board | substrate, for vertical orientation evaluation A liquid crystal display device was manufactured.

[Evaluation of Vertical Orientation]

It was 89.5 degrees when the pretilt angle was measured by the crystal rotation angle method with respect to this liquid crystal display element. It is also known that pretilt angle expressability is attenuated by rubbing treatment. Therefore, it can be said that the liquid crystal aligning film which showed the pretilt angle of 89.0 degrees or more despite having performed the rubbing process is very excellent in the vertical alignment property.

<Evaluation of Voltage Retention Rate>

[Manufacture of Liquid Crystal Display Element for Voltage Retention Rate Evaluation]

In the above, except that the rubbing treatment and the subsequent ultrapure water cleaning and drying operation are not performed, the same as in [Production of the liquid crystal display element for vertical orientation evaluation] in the above <Evaluation of the vertical orientation evaluation>, the liquid crystal display element for voltage retention evaluation Was prepared.

[Evaluation of Voltage Retention Rate]

For the liquid crystal display device manufactured above, after applying a voltage of 5 V at 60 ° C. with an application time of 60 microseconds and a span of 167 microseconds, a voltage retention of 167 milliseconds after the release of the application was measured. The voltage retention of the said liquid crystal display element was 99.3%.

Examples 2 to 45 and Comparative Examples 1 to 11

Except having made the kind and the usage-amount of (A) polymer, (B) compound, and (C) epoxy compound, respectively, as Table 2, the solid content concentration of 6.5 weight% and 4.0 weight% was the same as the said Example 1. The liquid crystal aligning agent of the seed concentration was produced, respectively, and evaluated.

The evaluation results are shown in Table 2.

In addition, abbreviated-name of (B) compound and (C) epoxy compound in Table 2 are respectively the following meanings.

<(B) Compound>

B-1: N- (2-hydroxy-3-n-octyloxybenzoyloxy) propyl-N, N ', N'-triglycidyl-m-xylenediamine synthesized in Synthesis Example B1 and N- ( Mixture of 3-hydroxy-2-n-octyloxybenzoyloxy) propyl-N, N ', N'-triglycidyl-m-xylenediamine

B-2: N- (2-hydroxy-3-n-dodecyloxybenzoyloxy) propyl-N, N ', N'-triglycidyl-m-xylenediamine and N- synthesized in Synthesis Example B2 Mixture of (3-hydroxy-2-n-dodecyloxybenzoyloxy) propyl-N, N ', N'-triglycidyl-m-xylenediamine

B-3: N- (2-hydroxy-3-n-dodecyloxybenzoyloxy) propyl-N, N ', N'-triglycidyl-4,4'-diamino synthesized in Synthesis Example B3 A mixture of diphenylmethane and N- (3-hydroxy-2-n-dodecyloxybenzoyloxy) propyl-N, N ', N'-triglycidyl-4,4'-diaminodiphenylmethane

B-4: N- (2-hydroxy-3-trifluoromethylpropyloxybenzoyloxy) propyl-N, N ', N'-triglycidyl-m-xylenediamine and N synthesized in Synthesis Example B4 A mixture of-(3-hydroxy-2-trifluoromethylpropyloxybenzoyloxy) propyl-N, N ', N'-triglycidyl-m-xylenediamine

B-5: Mixture of the compound (B-3-2-1-1) and the compound (B-3-2-1-2) synthesized in Synthesis Example B5

B-6: Mixture of the compound (B-3-2-2-1) and the compound (B-3-2-2-2) synthesized in Synthesis Example B6

<(C) Epoxy Compound>

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

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

The said (A) polymer is used for manufacture of a liquid crystal aligning agent as the polymer solution obtained by the said synthesis example, respectively, and the usage-amount (weight part) in Table 2 is the value converted into the polymer contained in the used solution. In Examples 26-41 and Comparative Examples 6-10, 2 types of polymers were used as (A) polymer, respectively.

The said (A) polymer and the (B) compound are used for manufacture of a liquid crystal aligning agent as the solution synthesize | combined by the said synthesis example, respectively, and the usage-amount (weight part) of Table 2 is contained in the solution used by all. Or (B) a value in terms of the amount of the compound.

Claims (7)

(A) at least one polymer selected from the group consisting of polyamic acid and polyimide, and (B) a compound having an epoxy group and a group represented by the following formula (2o) It contains, The liquid crystal aligning agent characterized by the above-mentioned. <Formula 2o>

(, R ^I of the formula 2o is from 4 to 40 carbons, or an alkyl group or a fluoroalkyl group having a carbon number of 4 to 40, or a hydrocarbon group having a carbon number of 17 to 51 having a steroid skeleton, and; Z ^I is a single bond, * -O-, * -COO- or * -OCO-, provided that the bond to which "*" is attached is the R ^I side, R ^II is a cyclohexylene group or a phenylene group, n1 is 1 or 2, However, when n1 is 2, two R ^II may be the same or different from each other, n2 is 0 or 1; Z ^II is * -O-, * -COO- or * -OCO-, provided that the bond with "*" is on the R ^I side, n3 is an integer of 0 to 2, n4 is 0 or 1) The compound of claim 1, wherein the compound (B) (b1) 1 mole part of a compound having 2 to 8 epoxy groups; (b2) mole parts of compounds 1 to (n-1) represented by the following formula (2), wherein n is the number of epoxy groups in the compound (b1) The liquid crystal aligning agent which is a compound obtained by making it react. <Formula 2>

(In Formula 2, R ^I , R ^II , Z ^I , Z ^II , n1, n2, n3 and n4 have the same meanings as in Formula 2o, respectively.) The liquid crystal aligning agent according to claim 2, wherein the compound (B) is at least one compound selected from compounds represented by the following general formulas B-1 to B-4. [Formula B-1]

[Formula B-2]

[Formula B-3]

[Formula B-4]

(In the above formula, B is a single bond, a methylene group, an alkylene group having 2 to 12 carbon atoms, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -CO-, -O- (CH ₂ ) _g -O-, -S-, -SO _2- , -C (CH ₃ ) _2- , -C (C ₂ H ₅ ) ₂ -or -C (CF ₃ ) _2- , wherein g Is an integer of 1 to 12, when a plurality of B's are present, a plurality of B's may be the same or different, and each R is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms. a is each independently 0 or 1, b is each independently an integer of 0 to 3, c is each independently an integer of 0 to 4, d is an integer of 0 to 5, e is each independently 0 An integer of 10 to 10, f is an integer of 0 to 11, X ^I is a glycidyl group, X ^II is a group represented by the following Chemical Formula 3-1 or 3-2, and X ^III and X ^IV are each independently Glycidyl group or represented by the following formula 3-1 or 3-2 Im) [Formula 3-1]

[Formula 3-2]

(In Formulas 3-1 and 3-2, R ^I , R ^II , Z ^I , Z ^II , n1, n2, n3 and n4 have the same meanings as in Formula 2, respectively.) The liquid crystal aligning agent of any one of Claims 1-3 which further contains epoxy compounds other than the (B) compound. The liquid crystal aligning agent of any one of Claims 1-4 whose usage ratio of the compound (B) is 0.01-40 weight part with respect to 100 weight part of (A) polymers. The liquid crystal aligning film formed from the liquid crystal aligning agent in any one of Claims 1-5 is provided. The liquid crystal display element characterized by the above-mentioned. (b1) 1 mole part of a compound having 2 to 8 epoxy groups; (b2) molar parts of compounds 1 to (n-1) represented by the formula (2), wherein n is the number of epoxy groups in the compound (b1) Compound obtained by reacting.