JP2003015135A - Vertical alignment type liquid crystal aligning agent - Google Patents

Abstract

(57) [Problem] To provide a vertical alignment type liquid crystal alignment agent which is excellent in vertical alignment and has a short afterimage erasing time of a liquid crystal display element and is preferably used for an MVA type liquid crystal display element. SOLUTION: This invention provides a vertical alignment type liquid crystal aligning agent containing a polymer component having specific two kinds of repeating units.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a vertical alignment type liquid crystal aligning agent. More specifically, the vertical alignment property, the printability, the afterimage erasing time of the liquid crystal display element is short, and
-Domainverticalalignmen
The present invention relates to a vertical alignment type liquid crystal aligning agent which is particularly suitable for a liquid crystal display device of the t) type.

[0002]

2. Description of the Related Art At present, as a liquid crystal display element, a liquid crystal alignment film made of polyamic acid, polyimide or the like is formed on the surface of a substrate provided with a transparent conductive film to form a liquid crystal display element substrate, and two of them are opposed to each other. A layer of a nematic liquid crystal having a positive dielectric anisotropy is formed in the gap to form a cell having a sandwich structure, and the long axis of the liquid crystal molecules is continuously moved from one substrate to the other substrate. The so-called TN (Twisted Nemati)
A TN type liquid crystal display device having a c) type liquid crystal cell is known. In addition, the contrast is higher than that of the TN type liquid crystal display element, and the STN (Super
A Twisted Nematic) type liquid crystal display element and a vertical alignment type liquid crystal display element have been developed. This S
The TN type liquid crystal display device uses a nematic type liquid crystal blended with a chiral agent which is an optically active substance as a liquid crystal, and the long axis of the liquid crystal molecule is continuously twisted between the substrates over 180 degrees. It utilizes the resulting birefringence effect. For these, "liquid crystal" Vo
l. 3 No. 2 117 (1999) and JP-A-11-258605, ITO is used.
MVA that controls the orientation of liquid crystal by forming protrusions on top
A vertical alignment type liquid crystal display element called a system has been proposed. The MVA type liquid crystal display element has excellent viewing angles, contrasts, and the like, and is also excellent in terms of manufacturing process, such that rubbing treatment is not required in forming the liquid crystal alignment film.
A liquid crystal alignment film suitable for the MVA system is required to have properties such as excellent vertical alignment and a short afterimage erasing time of a liquid crystal display element.

[0003]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide an excellent vertical alignment property and a short afterimage erasing time of a liquid crystal display device.
It is an object of the present invention to provide a vertical alignment type liquid crystal aligning agent which is suitably used for a VA type liquid crystal display device. Other objects and advantages of the present invention will be apparent from the following description.

[0004]

According to the present invention, the above objects and advantages of the present invention are (A) a repeating unit represented by the following formula (I-1) and (B) a repeating unit represented by the following formula (I- A vertical alignment type liquid crystal aligning agent characterized by containing a polymer component having a repeating unit represented by 2).

[0005]

[Chemical 5]

(In the formula, P ¹ is a tetravalent organic group, and Q ^{1 is}
Is a divalent organic group. )

[0007]

[Chemical 6]

(In the formula, P ² is a tetravalent organic group, and Q ²
Is a divalent group represented by the following formula (Q-1) or the following formula (Q-2). )

[0009]

[Chemical 7]

(In the formula, X is a single bond, --O--, --CO
-, -COO-, -OCO-, -NHCO-, -CON
H-, -S- or an arylene group, R ¹ 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 fluorine having 6 to 20 carbon atoms. It is a monovalent organic group having an atom. )

[0011]

[Chemical 8]

(In the formula, X is a single bond, --O--, --CO
-, -COO-, -OCO-, -NHCO-, -CON
It is an H-, -S- or arylene group, and R ² is a divalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms. )

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The vertical alignment type liquid crystal aligning agent of the present invention is usually constituted by dissolving the polymer component in an organic solvent. The polymer component in the present invention includes (A) the above formula (I-
A polyamic acid having a repeating unit represented by 1) (hereinafter, also referred to as “component (A)”) and (B) the above formula (I).
-2) containing an imidized polymer having a repeating unit represented by the following (hereinafter, also referred to as "component (B)"),
(A) An amic acid prepolymer having a repeating unit represented by the formula (I-1), and (B) an imide prepolymer having a repeating unit represented by the formula (I-2). It is preferable that the block copolymer contains a block copolymer, and the above is particularly preferable. In the above, the polyamic acid of the component (A) is obtained by reacting tetracarboxylic dianhydride and diamine,
The imidized polymer as the component (B) is a tetracarboxylic dianhydride and H2N-Q2-NH2 (wherein Q2 is the formula (I-
It is obtained by subjecting a polyamic acid obtained by reacting a diamine having a structure represented by the same definition as 2) (hereinafter, also referred to as “specific diamine”) to dehydration ring closure.

(A) Polyamic acid <Tetracarboxylic dianhydride> Specific examples of the tetracarboxylic dianhydride used in the synthesis of the polyamic acid of the component (A) include, for example, 1,2,3,4- Cyclobutane tetracarboxylic acid dianhydride, 1,2-dimethyl-1,2,3,
4-Cyclobutanetetracarboxylic acid 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-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-Tricarboxycyclopentyl acetic acid dianhydride 3,5,6-tricarbonyl-2-
Carboxynorbornane-2: 3,5: 6-dianhydride,
2,3,4,5-Tetrahydrofuran tetracarboxylic 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, Three
a, 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, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,
2-dicarboxylic acid dianhydride, bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, 3-oxabicyclo [3,2,1] octane −
2,4-dione-6-spiro-3 ′-(tetrahydrofuran-2 ′, 5′-dione), the following formulas (I) and (I
An alicyclic tetracarboxylic dianhydride such as represented by I);

[0015]

[Chemical 9]

(In the formula, R ³ and R ⁵ represent a divalent organic group having an aromatic ring, R ⁴ and R ⁶ represent a hydrogen atom or an alkyl group, and a plurality of R ⁴ and R ⁶ are present. , Each may be the same or different.)

Aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride; pyromellitic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3' , 4,4'-Biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyl ether tetracarboxylic dianhydride 3,3', 4,
4'-Dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ', 4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4 , 4'-Bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4 '
-Bis (3,4-dicarboxyphenoxy) diphenyl sulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride 3,3 ',
4,4'-perfluoroisopropylidene diphthalic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene- Bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylether dianhydride, bis (triphenylphthalic acid) ) -4,4'-Diphenylmethane dianhydride, ethylene glycol-bis (anhydrotrimellitate), propylene glycol-bis (anhydrotrimellitate), 1,4-butanediol-bis (anhydrotrimellitate) ) 1,6-hexanediol-bis (anhydrotrimellitate), 1,8-octanediol-bis (anhydrotrimeritate) Riteto),
2,2-bis (4-hydroxyphenyl) propane-bis (anhydrotrimellitate), the following formula (1)-
An aromatic tetracarboxylic dianhydride such as an aromatic tetracarboxylic dianhydride having a steroid skeleton represented by (4) can be mentioned. These may be used alone or in combination of two or more.

[0018]

[Chemical 10]

Of these, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,
2,3,4-cyclobutanetetracarboxylic dianhydride,
1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5- Tricarboxycyclopentyl acetic acid dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, cis-3,7
-Dibutylcycloocta-1,5-diene-1,2,5,6
-Tetracarboxylic acid dianhydride, 3,5,6-tricarbonyl-2-carboxynorbornane-2: 3,5: 6-dianhydride, 1,3,3a, 4,5,9b-hexahydro-5-
(Tetrahydro-2,5-dioxo-3-furanyl)-
Naft [1,2-c] furan-1,3-dione, 1,3,3
a, 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-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'-
(Tetrahydrofuran-2 ′, 5′-dione), among compounds represented by the above formula (I), compounds represented by the following formulas (5) to (7) and compounds represented by the above formula (II) Among them, a compound represented by the following formula (8), butanetetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,
4'-benzophenone tetracarboxylic dianhydride, 3,
From the viewpoint that 3 ′, 4,4′-biphenylsulfone tetracarboxylic acid dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, etc. can express good liquid crystal alignment and electrical characteristics. Preferably, these are used alone or in combination of two or more.

[0020]

[Chemical 11]

<Diamine> Examples of the diamine used for synthesizing the polyamic acid as the component (A) include p-phenylenediamine, m-phenylenediamine and 4,4 ′.
-Diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 2,2'-
Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 4,4'-diaminodiphenyl ether, 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-Trimethylindane, 3,4'-diaminodiphenyl ether, 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-aminophenoxy) 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-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-phenylene isopropylidene) bisaniline,
4,4 '-(m-phenyleneisopropylidene) bisaniline, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-diamino-2, Aromatic diamines such as 2'-bis (trifluoromethyl) biphenyl, 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl;

1,1-meta-xylylenediamine, 1,3-
Propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine,
1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine,
Aliphatic and cycloaliphatic diamines such as hexahydro-4,7-methanoindanylene dimethylene diamine, tricyclo [6.2.1.02,7] -undecylenedimethyl diamine, 4,4'-methylene bis (cyclohexyl amine);

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-diamino-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- Two primary amino groups in the molecule such as diamino-6-phenylphenanthridine, 1,4-diaminopiperazine, 3,6-diaminoacridine, bis (4-aminophenyl) phenylamine and the primary amino group A diamine having a nitrogen atom other than the following formula (II
Examples thereof include diaminoorganosiloxane represented by I). These diamines can be used alone or in combination of two or more.

[0024]

[Chemical 12]

(In the formula, R7 represents a hydrocarbon group having 1 to 12 carbon atoms, a plurality of R7s may be the same or different, p is an integer of 1 to 3, and q is 1 to Two
It is an integer of 0. )

Of these, p-phenylenediamine,
4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 2,2'-dimethyl-4,4 '
-Diaminobiphenyl, 1,5-diaminonaphthalene,
2,7-Diaminofluorene, 4,4'-diaminodiphenyl ether, 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-cyclohexane Diamine, 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 and the like are preferable.

(B) Imidized Polymer <Tetracarboxylic acid dianhydride> The tetracarboxylic acid dianhydride used in the synthesis of the imidized polymer of the component (B) is the polyamic acid of the component (A) described above. The same thing as the tetracarboxylic dianhydride used for the synthesis of an acid can be mentioned.

Of these, alicyclic tetracarboxylic acid dianhydrides are preferable, and specifically, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride and 1,3-dimethyl-
1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4 -Cyclopentanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 5- (2,5
-Dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, cis-
3,7-dibutylcycloocta-1,5-diene-1,2,
5,6-Tetracarboxylic acid dianhydride, 3,5,6-tricarbonyl-2-carboxynorbornane-2: 3,5:
6-Dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3- Zion,
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-furanyl) -naphtho [1,2-c] furan-1,3- Zion,
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), the above formula ( Among the compounds represented by I), the compounds represented by the above formulas (5) to (7) and the compounds represented by the above formula (8) among the compounds represented by the above formula (II) are favorable. From the viewpoint of being able to develop liquid crystal alignment and electrical characteristics, as particularly preferable ones,
1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentylacetic acid 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, cis-3,7-dibutylcycloocta-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, Three, five,
6-tricarbonyl-2-carboxynorbornane-
2: 3,5: 6-dianhydride, 3-oxabicyclo [3,3
2,1] octane-2,4-dione-6-spiro-3 ′
Examples thereof include-(tetrahydrofuran-2 ', 5'-dione) and the compound represented by the above formula (1). These may be used alone or in combination of two or more.

From the viewpoint of the electrical characteristics of the obtained liquid crystal alignment film, the alicyclic tetracarboxylic dianhydride is used in an amount of 50 mol% or more based on the total tetracarboxylic dianhydride. Preferably. That is, in the above formula (I-2), the repeating unit in which the tetravalent organic group represented by P2 is a group having an alicyclic structure is
It is preferably 50 mol% or more of all repeating units in the component (B).

Preferred tetracarboxylic acid dianhydrides other than the alicyclic tetracarboxylic acid dianhydride (preferably used in combination with the alicyclic tetracarboxylic acid dianhydride) include the above formulas (1) to ( Aromatic tetracarboxylic dianhydrides having a steroid skeleton represented by 4) can be mentioned.

<Diamine> The specific diamine used in the synthesis of the imidized polymer as the component (B) is represented by the above formula (Q-1).
And a diamine having a group represented by the above formula (Q-2). These may be used alone or in combination of two or more.

In the above formula (Q-1), the alkyl group having 10 to 20 carbon atoms represented by R ¹ is, for example, n
-Decyl group, n-dodecyl group, n-pentadecyl group, n
-Hexadecyl group, n-octadecyl group, n-eicosyl group and the like. Further, as the organic group having an alicyclic skeleton having 4 to 40 carbon atoms, which is represented by R ¹ in the above formula (Q-1) and R ² in the above formula (Q-2),
For example, a group having an alicyclic skeleton derived from cycloalkane such as cyclobutane, cyclopentane, cyclohexane, and cyclodecane; a group having a steroid skeleton such as cholesterol and cholestanol; a group having a bridged alicyclic skeleton such as norbornene and adamantane And so on.
Of these, a group having a steroid skeleton is particularly preferable. The organic group having an alicyclic skeleton is a halogen atom, preferably a fluorine atom or a fluoroalkyl group,
It may preferably be a group substituted with a trifluoromethyl group.

Further, the group having a fluorine atom having 6 to 20 carbon atoms represented by R ¹ in the above formula (Q-1) includes, for example, n-hexyl group, n-octyl group, n-decyl group and the like. A linear alkyl group having 6 or more carbon atoms; an alicyclic hydrocarbon group having 6 or more carbon atoms such as cyclohexyl group and cyclooctyl group; an aromatic hydrocarbon group having 6 or more carbon atoms such as phenyl group and biphenyl group A group obtained by substituting a part or all of the hydrogen atoms in the organic group with a fluorine atom or a fluoroalkyl group such as a trifluoromethyl group.

The above formula (Q-1) and the above formula (Q
X in -2) is a single bond, -O-, -CO-, -C.
OO-, -OCO-, -NHCO-, -CONH-,-
It is an S- or arylene group, and examples of the arylene group include a phenylene group, a tolylene group, a biphenylene group, and a naphthylene group. Of these, particularly preferred are groups represented by -O-, -COO-, and -OCO-.

Specific examples of the diamine having a group represented by the above formula (Q-1) include dodecanoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecanooxy-2,4-diaminobenzene. , Octadecanoxy-2,4-diaminobenzene, and compounds represented by the following formulas (9) to (14) can be mentioned as preferable ones.

[0036]

[Chemical 13]

Specific examples of the diamine having a group represented by the above formula (Q-2) include the following formulas (15) to (1).
The diamine represented by 7) can be mentioned as a preferable example.

[0038]

[Chemical 14]

Of these, particularly preferred are the above formulas (9), (10), (13), (14),
The compound represented by (15) may be mentioned.

The proportion of the specific diamine used in the synthesis of the component (B) is preferably 5 mol% or more, more preferably 10 mol% or more, based on all diamines used in the synthesis of the component (B). When the proportion of the specific diamine used is less than 5 mol%, a sufficient effect may not be obtained on the vertical alignment property. That is, the ratio of the repeating unit represented by the above formula (I-2) in all the repeating units having an imide ring is preferably 5 mol% or more, and particularly preferably 10 mol% or more.

Examples of other diamines which can be used in combination with the specific diamine include the same diamines as those used in the synthesis of the polyamic acid as the component (A). Of these, p-phenylenediamine, 4,
4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 2,2'-dimethyl-4,4'-
Diaminobiphenyl, 1,5-diaminonaphthalene, 2,
7-diaminofluorene, 4,4'-diaminodiphenyl ether, 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), 1,4-bis (4-aminophenoxy) benzene, 4, 4'-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, diamino represented by the above formula (III) Organosiloxane and the like are preferable. These are 1 type alone or 2
Used in combination of two or more species.

[0042]Synthesis of polyamic acid Polyamic acid ((A) component and (B) component precursor)
Tetracarboxylic acid dianhydride and dia
The ratio of min to be used is 1 equivalent of amino group of diamine
And the acid anhydride group of tetracarboxylic dianhydride is 0.2 to
A ratio of 2 equivalents is preferable, and 0.3 is more preferable.
It is a ratio of about 1.2 equivalents. Synthesis of polyamic acid
The reaction is usually carried out in an organic solvent at -20 ° C to 150 ° C.
It is carried out under a temperature condition of 0 ° C, preferably 0 to 100 ° C.

The organic solvent is not particularly limited as long as it can dissolve the polyamic acid to be synthesized. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide. Aprotic polar solvents such as dimethyl sulfoxide, γ-butyrolactone, tetramethylurea and hexamethylphosphortriamide; and phenolic solvents such as m-cresol, xylenol, phenol and halogenated phenol. Further, the amount (α) of the organic solvent used is usually the total amount (β) of the tetracarboxylic dianhydride and the diamine compound, and the total amount (α + β) of the reaction solution.
It is preferable that the amount is 0.1 to 30% by weight with respect to.

The organic solvent includes alcohols, ketones, esters, which are poor solvents for polyamic acid,
Ethers, halogenated hydrocarbons, hydrocarbons and the like can be used in combination so long as the polyamic acid to be produced does not precipitate. Specific examples of such a poor solvent include, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, 4-hydroxy-4.
-Methyl-2-pentanone (diacetone alcohol),
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 methoxypropionate, 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 monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, Examples thereof include 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene and xylene.

As described above, a reaction solution obtained by dissolving the polyamic acid is obtained. Then, the reaction solution is poured into a large amount of a poor solvent to obtain a precipitate, and the precipitate is dried under reduced pressure to obtain a polyamic acid. Further, the polyamic acid can be purified by performing the step of dissolving the polyamic acid again in the organic solvent and then precipitating it in the poor solvent once or several times.

[0046]Synthesis of imidized polymer (component (B)) The component (B) contains a part or all of the polyamic acid.
It can be synthesized by dehydration ring closure. The present invention
The component (B) used in
Ratio of repeating units having a mid ring (hereinafter referred to as “imidization
Ratio) is 40 mol% or more, preferably 70 mol
% Or more. A polymer having an imidization ratio of 40 mol% or more
By using it, a liquid crystal alignment film with a short afterimage erasing time can be obtained.
A liquid crystal aligning agent that can be formed is obtained.

The dehydration ring closure of the polyamic acid is carried out 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-closing catalyst to this solution, if necessary. It is carried out by a method of heating. The reaction temperature in the method of heating the polyamic acid (i) is preferably 50 to 200 ° C, more preferably 60 to 170 ° C. If the reaction temperature is lower than 50 ° C, the dehydration ring closure reaction may not proceed sufficiently, and if the reaction temperature exceeds 200 ° C, the molecular weight of the imidized polymer obtained may decrease. On the other hand, in the method (ii) of adding a dehydrating agent and a dehydration ring-closing catalyst to the solution of polyamic acid, as the dehydrating agent, for example, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride should be used. You can The amount of the dehydrating agent used depends on the desired imidization ratio, but it is preferably 0.01 to 20 mol per 1 mol of the repeating unit of the polyamic acid. Further, as the dehydration ring-closing catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, triethylamine and the like can be used. However, it is not limited to these. The amount of the dehydration ring-closing catalyst used is preferably 0.01 to 10 mol per 1 mol of the dehydrating agent used. The imidization ratio can be increased as the amount of the dehydrating agent and dehydrating ring-closing agent used increases. Examples of the organic solvent used for the dehydration ring-closing reaction include the organic solvents exemplified as those used for the synthesis of polyamic acid. The reaction temperature for the dehydration ring closure reaction is preferably 0.
˜180 ° C., and more preferably 10˜150 ° C. In addition, the imidized polymer obtained can be purified by performing the same operation as in the method for purifying a polyamic acid on the reaction solution thus obtained.

[0048]End-modified polymer The component (A) and the component (B) used in the present invention are
It may be of a terminal-modified type in which the amount of offspring is adjusted. This
By using the end-modified polymer of
Improves application characteristics of liquid crystal aligning agent without damaging the result
can do. Such a terminal-modified polymer is
When synthesizing polyamic acid, acid monoanhydride, monoamid
Compounds, monoisocyanate compounds, etc. are added to the reaction system.
It can be synthesized by adding. Where acid
Examples of the anhydride include maleic anhydride and phthalic anhydride.
Acid, itaconic anhydride, n-decylsuccinic anhydride
, N-dodecyl succinic anhydride, n-tetrade
Sylsuccinic anhydride, n-hexadecylsuccini
Cookic acid anhydride and the like can be mentioned. Also,
Examples of the min compound include aniline and cyclohexyl.
Amine, n-butylamine, n-pentylamine, n-
Hexyl amine, n-heptyl amine, n-octyl amine
Min, n-nonylamine, n-decylamine, n-un
Decylamine, n-dodecylamine, n-tridecylamine
Min, n-tetradecylamine, n-pentadecylami
N, n-hexadecylamine, n-heptadecylamine
N-octadecylamine, n-eicosylamine
Can you name some? Also, monoisocyanate conversion
Examples of the compound include phenyl isocyanate and naphthyl.
Examples thereof include isocyanate.

[0049]Logarithmic viscosity of polymer The polymer used in the present invention has a logarithmic viscosity (η_ln)of
The value is preferably 0.05 to 10 dl / g, more preferably
It is 0.05-5 dl / g. Logarithm in the present invention
Viscosity (η_lnThe value of) is calculated by dissolving N-methyl-2-pyrrolidone.
Used as a medium with a concentration of 0.5 g / 100 ml
The viscosity of a certain solution was measured at 30 ° C.
It is obtained by (i).

[0050]

[0051]Block copolymer As the polymer component used in the present invention, the block shown above is used.
In the case of using a block copolymer, an amino group or
An amic acid prepolymer having an acid anhydride group and a terminal
Imide prepolymer having acid anhydride group or amino group
And were synthesized respectively, and the amino group at the end of each prepolymer was synthesized.
Block copolymerization by combining the acid anhydride group with
Get the body. The synthetic method of the amic acid prepolymer is described above.
The method for synthesizing polyamic acid
The method of synthesizing the repolymer is based on the combination of the above-mentioned imidized polymers.
It is the same as the method. Also, the selection of the functional group at the end
Is a tetracarboxylic dianhydride during the synthesis of polyamic acid
Can be done by adjusting the amount of diamine and
It

[0052]Liquid crystal aligning agent The liquid crystal aligning agent of the present invention is the above polymer component, preferably
The components (A) and (B) are usually dissolved and contained in an organic solvent.
It is configured to have. Polyamic acid as component (A)
The mixing ratio of the imidized polymer which is the component (B) is preferably
In particular, 99.99 / 0.01 to 10/90, particularly preferred
Specifically, it is 99.9 / 0.1-40 / 60. The present invention
The temperature for preparing the liquid crystal aligning agent is preferably 0 ° C to
200 ° C., more preferably 20 ° C. to 60 ° C.
It

Examples of the organic solvent which constitutes the liquid crystal aligning agent of the present invention include 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 Examples thereof include ether acetate and diethylene glycol monoethyl ether acetate.

The solid content concentration in the liquid crystal aligning agent of the present invention is selected in consideration of viscosity, volatility, etc., but is preferably in the range of 1 to 10% by weight. That is, the liquid crystal aligning agent of the present invention is applied to the surface of a substrate to form a coating film which becomes a liquid crystal aligning film, but when the solid content concentration is less than 1% by weight, the film thickness of this coating film is If it is too small to obtain a good liquid crystal alignment film, and if the solid content concentration exceeds 10% by weight, the film thickness of the coating film becomes too large to obtain a good liquid crystal alignment film. In addition, the viscosity of the liquid crystal aligning agent increases, and the coating characteristics deteriorate.

The liquid crystal aligning agent of the present invention may contain a functional silane-containing compound or an epoxy compound from the viewpoint of improving the adhesiveness to the substrate surface within a range that does not impair the desired physical properties. Examples of such a functional silane-containing compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl). -3-
Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane Silane, N-
Ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7
-Triazadecane, 10-triethoxysilyl-1,4,
7-triazadecane, 9-trimethoxysilyl-3,6
-Diazanonyl acetate, 9-triethoxysilyl-
3,6-diazanonyl acetate, N-benzyl-3-
Aminopropyltrimethoxysilane, N-benzyl-3
-Aminopropyltriethoxysilane, N-phenyl-
3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxy Silane etc. can be mentioned.

Examples of such epoxy compounds include 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-
Xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N',-tetraglycidyl-4,4'-diaminodiphenylmethane, 3- (N-allyl-N-glycidyl) ) Aminopropyltrimethoxysilane, 3- (N, N-diglycidyl)
Aminopropyltrimethoxysilane etc. can be mentioned. The compounding ratio of these functional silane-containing compounds and epoxy compounds is usually 100 parts by weight of the polymer,
It is 40 parts by weight or less, preferably 0.1 to 30 parts by weight. In particular, by adding an epoxy compound, the scratch resistance of the obtained liquid crystal alignment film can be further improved. Particularly preferred epoxy compounds are N, N, N ',
N ',-tetraglycidyl-m-xylenediamine, 1,
3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N',-tetraglycidyl-4,
4'-diaminodiphenylmethane, 3- (N-allyl-N-glycidyl) aminopropyltrimethoxysilane,
Nitrogen-containing epoxy compounds such as 3- (N, N-diglycidyl) aminopropyltrimethoxysilane.

The liquid crystal aligning agent of the present invention can be suitably used for a vertical alignment type liquid crystal display device in which at least one substrate forming a liquid crystal cell has a projection shape. Examples of the liquid crystal display element include an MVA type liquid crystal display element. What is MVA mode? "Liquid Crystal Vol. 3 No. 2 1
17 (1999) "and Japanese Patent Laid-Open No. 11-258605, a vertical alignment mode in which a protrusion is used as an alignment control means is shown. The protrusion may be formed on each of the TFT substrate side and the color filter side. It may have a protrusion on the color filter side and a slit on the TFT side.

[0058]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[Imidization Rate Measuring Method] The polymer was dried under reduced pressure at room temperature and then dissolved in deuterated dimethylsulfoxide.
The NMR was measured and determined by the formula shown in the following formula (ii). Imidization rate (%) = (1−A ¹ / A ² × α) × 100 (ii) A ¹ : proton-derived peak area of NH group (10 pp
m) A ² : other proton-derived peak area α: N in the polymer precursor (polyamic acid)
Ratio of number of other protons to one proton of H group

[Manufacturing Method of Liquid Crystal Display Element] As shown in FIG. 1, I having a protrusion formed by using a positive resist.
A glass substrate with TO (A) and a glass substrate (B) having an ITO pattern were each printed with a liquid crystal aligning agent and dried at 80 ° C. for 1 minute and then at 180 ° C. for 1 hour to obtain a dry film thickness of 600 Å. A coating film was formed. Two substrates with the liquid crystal alignment film formed as described above were prepared, and a particle diameter of 3.5 μm was formed on the outer edge of the substrate (B).
The epoxy resin-based adhesive containing aluminum oxide spheres was applied by the screen printing method, and then the two substrates were bonded so as to have the positional relationship shown in FIG. Liquid crystal MLC6608 manufactured by Merck Ltd. is injected and filled into the cell gap defined by the adhesive on the surface and the outer edge of the substrate,
Then, the injection hole was sealed with an epoxy adhesive to produce a vertical alignment type liquid crystal display element.

[Vertical orientation] When the voltage is OFF and AC 1
The liquid crystal display device at 2 V (peak-peak) was observed under crossed Nicols. [Voltage holding ratio] After applying a voltage of 5 V to the liquid crystal display element for a duration of 60 microseconds and a span of 167 milliseconds,
The voltage holding ratio was measured 167 milliseconds after the application was released.
As a measuring device, VHR-1 manufactured by Toyo Technica Co., Ltd. was used.

[Afterimage erasing time of liquid crystal display element] DC3.0V, AC6.0V (peak-peak) in the liquid crystal display element
After applying a rectangular wave of 30 Hz and 3.0 V superposed with each other at an ambient temperature of 70 ° C. for 20 hours, the voltage was turned off and the time until the afterimage was erased was measured by visual observation.

<Synthesis of Polymer> Synthesis Examples 1 to 9 Synthesis compositions 3, 4, and 6 were prepared by adding N-methyl-2-pyrrolidone to the composition shown in Table 1 in the order of diamine and tetracarboxylic dianhydride. , 8 and 9 were reacted at a solid content concentration of 30% at 60 ° C. for 6 hours, and Synthesis Examples 1, 2, 5, 7 and 10 were reacted at a solid content concentration of 20% at room temperature for 6 hours, and the logarithm shown in Table 1 was used. Polyamic acids I to X having a viscosity were obtained.

[0064]

[Table 1] Numbers in parentheses are mol% TCAAH: 2,3,5-tricarboxycyclopentyl acetic acid dianhydride CB: 1,2,3,4-cyclobutanetetracarboxylic acid anhydride PMDA: pyromellitic dianhydride PDA: p- Phenylenediamine DDE: 4,4'-diaminodiphenyl ether DDM: 4,4'-diaminodiphenylmethane MTB: 2,2'-dimethyl-4,4'-diaminobiphenyldiamine: diaminediamine represented by formula (9): formula Diaminediamine represented by (10): Diaminediamine represented by formula (13): Bisaminopropyltetramethyldisiloxane

Synthesis Examples 11 to 18 Each polyamic acid shown in Table 2 was diluted to a solid content concentration of 5% with N-methyl-2-pyrrolidone, and the addition amount per mol of the diamine used for the synthesis of each polyamic acid was adjusted. Table 2
Add pyridine and acetic anhydride as shown in 1
The imidized polymers ~ were synthesized by stirring at 10 ° C for 4 hours. By reprecipitating this polymer solution with diethyl ether, a white powder of an imidized polymer was obtained. The imidization ratio of the obtained polymer is also shown in Table 2.

[0066]

[Table 2]

Examples 1-14, Comparative Examples 1-3 Polyamic acid ((A) component) obtained in Synthesis Examples 1-18, imidized polymer ((B) component) and, if necessary, as an additive. N, N, N ', N'-tetraglycidyl-
4,4′-diaminodiphenylmethane (epoxy compound) was mixed in a composition as shown in Table 3 to obtain a solid content concentration of 6.0.
% To obtain a vertical alignment type liquid crystal aligning agent of the present invention.
A liquid crystal display device was produced using this liquid crystal aligning agent, and various evaluations were performed. The results are shown in Table 4.

[0068]

[Table 3] * The numbers in parentheses are as follows. Component (A) / Component (B): wt% with respect to the entire polymer Solvent: wt% of each solvent type with respect to the entire solvent * Additive amount is parts by weight of the additive with respect to 100 parts by weight of the polymer. * The abbreviations of solvent types are as follows. BL: gamma butyrolactone NMP: N-methyl-2-pyrrolidone BC: butyl cellosolve DAA: 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol)

[0069]

[Table 4]

[0070]

According to the liquid crystal aligning agent of the present invention, it is possible to obtain a liquid crystal aligning film which has a good vertical aligning property, a short afterimage erasing time, and is suitable for a MVA type liquid crystal display device.

[Brief description of drawings]

FIG. 1 shows a schematic view of an MVA type liquid crystal cell used in an example of the present invention.

[Explanation of symbols]

1 Color filter side electrode (ITO) 2 Liquid crystal alignment film 3 Pixel electrode (ITO) 4 Alignment control means (projection) 5 Alignment control means (slit) 6 Liquid crystal molecules

Continued front page    F term (reference) 2H090 HB08Y HB13Y KA04 MA01                 4J043 PA04 QB26 SA06 SA07 SA14                       SA43 SA44 SA46 SA47 SA49                       SA52 SA54 SA55 SA61 SA63                       SA64 SA72 SA78 SB01 SB02                       SB03 TA01 TA03 TA12 TA21                       TA22 TA43 TA67 TA68 TA72                       TB01 TB02 UA012 UA022                       UA032 UA041 UA042 UA061                       UA062 UA081 UA082 UA121                       UA122 UA131 UA132 UA141                       UA142 UA151 UA152 UA231                       UA241 UA251 UA261 UA262                       UA361 UA381 UA391 UA411                       UA421 UA591 UA622 UA63                       UA652 UA76 UA761 UB011                       UB012 UB021 UB022 UB061                       UB062 UB122 UB131 UB132                       UB151 UB152 UB171 UB172                       UB221 UB281 UB282 UB301                       UB302 UB312 UB351 UB382                       UB401 UB402 ZB21

Claims (3)

[Claims] 1. A polymer component having (A) a repeating unit represented by the following formula (I-1) and (B) a repeating unit represented by the following formula (I-2). A characteristic vertical alignment type liquid crystal aligning agent. [Chemical 1] (In the formula, P ¹ is a tetravalent organic group, and Q ¹ is a divalent organic group.) (In the formula, P ² is a tetravalent organic group, and Q ² is the following formula (Q
-1) or a divalent group represented by the following formula (Q-2). ) [Chemical 3] (In the formula, X is a single bond, -O-, -CO-, -COO.
-, -OCO-, -NHCO-, -CONH-, -S-
Or an arylene group, wherein R ¹ has 10 to 20 carbon atoms
1 having an alkyl group of 4 to 40 carbon atoms
It is a monovalent organic group or a monovalent organic group having a fluorine atom having 6 to 20 carbon atoms. ) [Chemical 4] (In the formula, X is a single bond, -O-, -CO-, -COO.
-, -OCO-, -NHCO-, -CONH-, -S-
Alternatively, it is an arylene group, and R ² is a divalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms. ) 2. The polymer component contains 5 mol% or more of the repeating unit represented by the general formula (I-2) in all repeating units having an imide ring.
The vertical alignment type liquid crystal aligning agent described. 3. The vertical alignment type liquid crystal aligning agent according to claim 1, wherein at least one substrate forming the liquid crystal cell is used for a vertical alignment type liquid crystal display device having a protrusion shape.