JPS62127828A - Composition for oriented film for liquid crystal - Google Patents

Abstract

PURPOSE:To obtain a liquid crystal display device having excellent quality and visual sensation characteristic without decreasing yield by using a component having fluorine atoms for at least one of a carboxylic acid anhydride, diamine and diaminomonamide and incorporating the polyamide acid obtd. by bringing the carboxylic acid anhydride, diamine and diaminomoamide into reaction into the titled compsn. CONSTITUTION:The component having the fluorine atoms is used for at least one of the carboxylic acid anhydride, diamine and diaminomonoamide and the polyamide acid obtd. by bringing the carboxylic acid anhydride, diamine and diaminomonoamide into reaction is incorporated into the above-mentiond compsn. For example, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]hexafluoropropane is used as the carboxylic acid anhydride contg. fluorine and, for example, 2, 2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane is used for the diamine contg. fluorine.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to a composition for a liquid crystal alignment film.

(Prior art) Super twisted birefringence effect (5upper twisted birefringence effect)
irefringence effect) (T,
J, 5cbfferand J, Nehring
, Appl, phys, Leff, 4th day (1
0), 1021 (1984)) has extremely superior contrast and visual characteristics compared to conventional TN liquid crystal display devices.

Since the alignment control film used for this purpose needs to have a high pretilt angle, an inorganic obliquely vapor deposited film such as silicon oxide or the like has been mainly used.

(Problems to be Solved by the Invention) However, the inorganic obliquely deposited film has selectivity to liquid crystals, and it is difficult to achieve good alignment of all liquid crystal compositions.

In addition, high temperature heating during assembly of the two films causes uneven orientation, lowering the yield and resulting in poor productivity, and the contrast and visual characteristics required for an alignment control film cannot be satisfied.

The present invention provides a composition for a liquid crystal alignment film that eliminates this drawback.

(Means for Solving the Problems) The present invention is obtained by reacting a carboxylic acid anhydride, a diamine, and a diamino monoamide, using at least one of the carboxylic acid anhydride, a diamine, and a diamino monoamide as a component having a fluorine atom. The present invention relates to a composition for a liquid crystal alignment film containing a polyamic acid.

The polyamic acid used in the present invention is synthesized by a stirring reaction of a carboxylic anhydride, a diamine, and a diamino monoamide. These reactions are carried out under anhydrous conditions, preferably at 50%
℃ or below.

Regarding the reaction ratio of the carboxylic anhydride, diamine, and diaminomonoamide, it is preferable that the number of moles of the carboxylic anhydride and the number of moles of the diamine and diaminomonoamide be equimolar. Diaminomonoamide is preferably used in an amount of 0.1 to 50 molti based on the total amount of diamine and diaminomonoamide. This reaction is carried out in the presence of a solvent such as dimethylacetamide, dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, or the like.

In the present invention, a carboxylic anhydride, a diamine, and a diaminomonoamide are reacted by using at least one of the carboxylic anhydride and the diamine as a component having a fluorine atom.

Examples of carboxylic acid anhydrides containing fluorine atoms include '
2.2-bis[:4-(3,4-dicarboxyphenoxy)phenyl]hexafluoropropane.

2.2-bis(3,4-dicarboxyphenyl)hexafluoropropane, bis(3,4-dicarboxyphenyl)hexafluoro. P. bread, 4.4'-bis[4-(
3,4-dicarboxyphenoxy)phenyl]hexafluoropropane, (trifluoromethyl)pyromellitic acid, bis(trifluoromethyl)pyromellitic acid, 5.5'
-bis(trifluoromethylsin-a, ,S,'4.
4'-tetracarboxybiphenyl, 2.2:5.5'
-tetrakis(trifluoromethyl) -3,3:4.
4'-tetracarboxybiphenyl, 5,5'-bis(
trifluoromethyl)-a, a; 4. a'-Tetracarboxydiphenyl ether, 5.5'-bis(trifluoromethyl)-3,3:4.4'-tetracarboxybenzophenone, bis[(trifluoromethyl)dicarboxyphenoxy]benzene, bis[(trifluoromethyl) Methylindicarboxyphenoxy]biphenyl, bis[(trifluoromethyl)dicarboxyphenoxy](trifluoromethyl)benzene, bis[(trifluoromethyl)dicarboxyphenoxy]bis(trifluoromethyl)biphenyl, bis[(trifluoromethyl)dicarboxyphenoxy](trifluoromethyl)benzene, fluoromethyl) dicarboxyphenoxyc diphenyl ether, bis(dicarboxyphenoxy)(trifluoromethyl)benzene, bis(dicarboxyphenoxy)bis(trifluoromethyl)benzene, bis(dicarboxyphenoxy)tetrakis(trifluoromethyl)benzene, Bis(dicarboxyphenoxy)bis(trifluoromethyl)biphenyl, bis(dicarboxyphenoxy)tetrakis(trifluoromethyl)biphenyl, 2.2-bis[4
-(2,3-dicarboxybenzoyloxy)phenyl]hexafluoropropane, 2,2-bis[4-(
3,4-dicarboxybenzoyloxyJ-3-bromophenyl]hexafluoropropane, 2,2-his(4(3,4-)hlupoxopenzoyloxy/) -a
, s-dibromophenyl]hexafluoropropane,
2.2-bisC4-<3.4-dicarboxybenzoyloxyl-3,5-dimethylphenyl]hexafluoropropane, 2.2-bis(4-(3,4-dicarboxybenzoyloxy)phenyl)octa Fluorobutane, 2,2-bis[4-(2-trifluoromethyl-3
,4-dicarboxybenzoyloxy)phenyl]hexafluorofuropane, 1,3-bis[:4-(3,4-
dicarboxybenzoyloxy)phenyl]hexafluoropropane, 1,5-bisC4-(3,4-dicarboxypenzoyloxy)phenyl]tecafluorobentane, 1.6-bis(4-(3,4-dicarboxybenzoyloxy)phenyl) Carboxybenzoyloxy)phenyl]dodecafluorohexane, 1.
7-bis(4-(3,4-dicarboxybenzoyloxy)phenylcotetradecafluorohebutane, 1.5-
Bis(4-(3,4-dicarboxybenzoyloxy)
-3,5-dibromophenyl]decafluoropentane,
1.5-bis(4-(3,4-dicarboxybenzoyloxy)-3,5-bistrifluoromethylphenyl)
Tecafluoropentane, 1.5-bis(4-(2-trifluoromethyl-3,5-dicarboxybenzoyloxy)phenyl)tecafluorobentane, 2.2-bis[4-(3,4-dicarboxyphenoxy) ) phenyl]hexafluoropropane, 2-bis(4-(2,3
-dicarboxyphenoxy)phenyl]hexafluoropropane, bis2-bis[4-(3,4-dicarboxyphenoxy)-3-bromophenyl]hexafluoropropane, 2,2-bis[4-(3, 4-dicarboxyphenoxy)-3,5-dibromophenyl]hexafluoropropane, 2,2-bis[:4-(3,4-dicarboxyphenoxy)-3,5-dimethylphenyl]hexafluoropropane .

λ2-bis(4-(3,4-dicarboxyphenoxy)
phenyl]octafluorobutane, 2,2-bis(4-
(3,4-dicarboxy-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 1.3-
Bis[4-(3,4-dicarboxyphenoxy)phenyl]hexafluoropropane, 1,5-bis(4-(3
,4-dicarboxyphenoquine)phenyl]decafluoropentane, 1,6-bis(4-(3,4-dicarboxyphenoxy)phenyl]dodecafluorohexane, 1
．． 7-bis[:4-(3,4-dicarboxyphenoxy)phenylcotetradecafluoropentane, 1,5-bis[4-(3,4-dicarboxyphenoxy)-3,5
-dibromophenyl]decafluoropentane, 1°5-
bis(4-(3,4-dicarboxyphenoxy)-3,
5-bistrifluoromethylphenyl]tecafluorobentane, 1,5-bis(4-(3,4-dicarboxy-
2-Trifluoromethylphenoxy)phenyl]decafluoropentane and the like are used.

Also, as a diamine containing a fluorine atom.

For example, '2,2-bis(4-(4-aminophenoxy))
phenyl]hexafluoropropane, 2,2-bis[4
-(3-aminophenoxy)phenyl]hexafluoropropane, λ2-bis[4-(2-aminophenoxy)
phenyl]hexafluoropropane, 2,2-bis(:
4-(2-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4.
4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4.4'-bis(4-amino-3
-trifluoromethylphenoxy)piphenyl, 4.4
'-Bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfone, 4.4'-bis(3-amino-5-trifluoromethylphenoquine)diphenylsulfone, 2.2-bis[:4-( 4-amino-2-
Trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-bis((4-aminophenoxy)phenyl)hexafluoropropane, etc. are used.As the diaminomonoamide having a fluorine atom, for example, 4.4'- Bis[(4-aminophenoxy)phenyl]hexafluoropopan-3-carbonamide and the like are used.

As the diamino monoamide, for example, 1,4-diaminobenzene-2-carbonamide, 4,4'-diaminodiphenyl ether-3-carbonamide, etc. are used.

Examples of carboxylic anhydrides include pyromellitic anhydride, 2,3,6.7-naphthalenetetracarboxylic anhydride, 3,3:4,4'-diphenyltetracarbo:
yW & anhydride, 1,2,5.6-naphthalenetetracarboxylic anhydride, λ2:a, 3'-diphenyltetracarboxylic anhydride, thiophene-2,3,4,5-tetracarboxylic anhydride, 2 .2-bis(3,4-biscarboxyphenyl)propane anhydride, 3,4-dicarboxyphenylsulfone hydrate, perylene-3,4,9,
10-tetracarboxylic anhydride, bis(3,4-dicarboxyphenyl)ether anhydride, 3.3:4.4
'-Hensephenonetetracarboxylic anhydride and the like are used.

In addition, examples of diamines include m-fuconylene diamine, p-phenylene diamine, m-xylene diamine,
p-xylene diamine, 4.4'-diaminodiphenyl ether, 4.4'-diaminodiphenylmethane, 3.
3'-dimethyl-4,4'-diaminodiphenylmethane, a,3:s,s'-tetramethyl-4゜4'-diaminodiphenylmethane, 2.2'-bis(4-aminophenyl)propane, 4.4 '-methylene dianiline, benzidine, 4,4'-diaminodiphenylsulfite,
4.4'-diaminodiphenylsulfone, 1.5-diaminonaphthalene, 3.3'-dimethylbenzidine, 3
．． 3'-dimethoxybenzidine and the like are used.

fluorine-containing carboxylic acid anhydride, carboxylic acid anhydride,
Two or more types of the diamine having fluorine, the diaminomonoamide having diamine fluorine, and the diaminomonoamide each may be used in combination.

In addition, for the purpose of improving adhesion to glass substrates, metals, etc., the two reaction components are combined with the general formula (in the formula, R is a divalent hydrocarbon group * R1e 几2. R3 and R4 are monovalent hydrocarbon groups, n is an integer of 1 or more.

) Diaminosiloxanes shown in can also be used together.

There is nothing wrong with that.

The above polyamic acid can be coated on the liquid crystal holding substrate and electrodes using dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methyl-
As a 0.01 to 40% by weight solution of 2-pyrrolidone, etc.
This can be done by dip method, spinner method, spray method, printing method,
This is done by coating the substrate and electrodes using a brush coating method or the like.

After coating: 100°C to 400°C, preferably 250°C to 35°C
A heat treatment is performed at 0° C. to dehydrate and ring-close the polyamic acid to obtain a polyimide isoindoroquinasili/dione polymer coating. This polymer film is subjected to a rubbing treatment to form a liquid crystal alignment film. The tilt angle between the liquid crystal alignment film and the liquid crystal was 2 to 3 degrees with conventional polymeric polyimide coatings, but when the composition of the present invention was used as the liquid crystal alignment film, the tilt angle was up to about 2O4. The composition for a liquid crystal alignment film containing a polyamic acid, which is made possible by the present invention, is particularly suitable for an SBE type liquid crystal display device.

(Example) This will be explained using an example.

In the example, the measurement of the tilt angle is as described in the Journal of
Applied Physics (Jpn, J.

Appl, Phys,) Volume 19, Page 2013 (198
It was carried out by the method described in 0).

Example 1 2,2-bis[4-
(4-aminophenoxy)phenyl]hexafluoropropane 0.9 mol, 4.4'-diaminodiphenyl ether-3-carbonamide 01 mol and 2.2-bis(
:4-(3,4-dicarboxyphenoxy)phenyl]
5 weight 4N-methyl-5% of polyamic acid, which is a precursor of polyimidoisoindoquinazolinedione polymer, obtained by condensing 1.0 mol of hexafluoropropane dianhydride at 25°C for 5 hours and then at 80°C for 5 hours. Using a spinner, a 2-pyrrolidone solution was applied to a glass substrate (3cm x 3cm, thickness 21nllll) on which an indium oxide electrode was formed.
) was applied. After coating, the coating was heated at 250° C. for 1 hour for dehydration and ring closure to form a polyimidoinoindroquinazolinedione polymer film having a thickness of 600 to 800 Å.

Next, using a pair of substrates on which the film had been rubbed in a certain direction with gauze, a liquid crystal (ZLI-2293 (manufactured by Merck & Co., Ltd.) and a right-handed chiral agent CB15 (BDH Co., Ltd.)
ZLI-229 was added with 3.07% by weight of L I-2293 and 8811 (manufactured by Merck & Co.)
A liquid crystal display device (thickness: approximately 6.3 μm) was produced by encapsulating a 3.33% by weight mixture of 3. When the tilt angle was measured, it was 4.9°.

When voltage was applied to this device and the rise characteristics and contrast were observed, they were found to be extremely good.

Example 2 2,2-bis(4-
(4-aminophenoxy)phenyl]hexafluoropropane 0.8 mol, 0.2 mol of 4,4'-diaminodiphenyl ether-3-carbonamide) and H λ3: 4
．． Using a 5wt% N-methyl-2-pyrrolidone solution of polyamic acid obtained by condensing 1.0 mol of 4'-biphenyltetracarboxylic dianhydride at 25°C for 6 hours and then at 80°C for 6 hours. A liquid crystal display device exhibiting characteristics similar to those of Example 1 was obtained. When the tilt angle was measured, it was 53°.

(Effects of the Invention) By using the composition for a liquid crystal alignment film according to the present invention as an alignment control film, a liquid crystal display device with excellent contrast and visual characteristics can be obtained without reducing the yield.

Agent: Patent attorney Kunihiko Wakabayashi.

〜、4ノ

Claims (1)

[Claims] 1. For liquid crystal alignment films containing polyamic acid obtained by reacting tricarboxylic anhydrides, diamines, and diaminomonoamides with at least one of carboxylic anhydrides, diamines, and diaminomonoamides as a component having a fluorine atom. Composition.