JP2906683B2 - Liquid crystal alignment film, liquid crystal holding substrate and liquid crystal display device having the same, and material for liquid crystal alignment film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal alignment film, a liquid crystal sandwiching substrate having the same, a liquid crystal display device, and a material for the liquid crystal alignment film.

[0002]

2. Description of the Related Art Conventionally, an STN (super twisted nematic) system has been used for a liquid crystal display element for a large display in order to improve visual characteristics. this is,
The long axis direction of the liquid crystal molecules is twisted by 240 to 270 ° in the cell (240 to 270 ° twist). An alignment film material that can stably obtain a high pretilt angle is indispensable for manufacturing an STN mode liquid crystal display element. Further, with the development of color display elements, there is a demand for an alignment film material that can form a film at a low curing temperature due to the limitation on heat resistance of a color filter. Therefore, in order to obtain an alignment film having such a high pretilt angle, (1) a method using a polyimide in which a fluoroalkyl group is bonded to a chain carbon (Japanese Patent Laid-Open No. 62-1)
No. 74725, U.S. Pat. No. 4,735,492), and (2) a method of adding an amine compound having a long-chain fluoroalkyl group to a polyimide (JP-A-1-18005).
No. 18), (3) Method of adding a metal complex having a long-chain fluoroalkyl group (Proceedings of the 13th Symposium on Liquid Crystal Symposium 1)
October 987) and the like. However, any of these methods has a disadvantage that a stable pretilt angle cannot be obtained.

[0003]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art and provides a liquid crystal alignment film stably exhibiting a high pretilt angle, a liquid crystal holding substrate, a liquid crystal display element and a liquid crystal alignment film having the same. To provide a composition for use.

[0004]

The liquid crystal alignment film of the present invention is represented by

Embedded image [However, in formula 4, a tetravalent residue of R tetracarboxylic dianhydride, Rf is selected from the group consisting is -C _n F _2n-1 (where n 6 to 12
, Which contains one double bond,
It may be branched, and the hydrogen of the benzene ring has 1 carbon atom.
To 5 alkyl groups, an alkoxy group having 1 to 5 carbon atoms,
Element is intended to include fluorinated polyimide comprising structural units represented by may be substituted by chlorine or bromine].

In the chemical formula 4, the substituent which may be bonded to the benzene ring includes a lower group (that is, a group having 1 to 5 carbon atoms).
) , Lower (i.e., C1-5) alkoxy groups, fluorine, chlorine, bromine and the like.

The above-mentioned fluorine-containing polyimide further comprises

Embedded image Wherein R 'is a tetravalent residue of tetracarboxylic dianhydride, and X is

Embedded image (In the chemical formula 6, the hydrogen of the benzene ring may be the same as in the chemical formula 4, and represents a divalent residue of the diamine excluding the group represented by the chemical formula 4. ).

It is preferable that the fluorine-containing polyimide contains the structural unit represented by the chemical formula (4) and the structural unit represented by the chemical formula (5) such that the latter / former has a molar ratio of 0/100 to 95/5, In particular, it is preferable to include it so as to be 0/100 to 90/10. A fluorine-containing polyimide having a small number of structural units represented by Chemical Formula 4 tends to have low moisture resistance.

The liquid crystal alignment film is formed of ITO (Indium Tin Oxi).
The liquid crystal holding substrate having the liquid crystal alignment film can be formed on an appropriate substrate such as a glass substrate on which a transparent electrode such as de) is formed.

An electrode is provided by a known method using the above-mentioned liquid crystal holding substrate, and the liquid crystal has a liquid crystal holding substrate on which the liquid crystal alignment film is provided facing the liquid crystal. It can be a display element.

The liquid crystal alignment film can be manufactured using a liquid crystal alignment film material containing a polyimide resin described below.

The above-mentioned polyimide resin comprises (a) tetracarboxylic dianhydride and (b)

Embedded image (However, Rf in Chemical Formula 7 is the same as in Chemical Formula 4, and the hydrogen of the benzene ring may be appropriately substituted with a substituent such as a lower alkyl group, a lower alkoxy group, fluorine, chlorine, or bromine.) The diamine containing the fluorinated aromatic diamine compound is subjected to a condensation reaction.

The tetracarboxylic dianhydride includes:
Pyromellitic anhydride, 2,2 bis (2,3-dicarboxyphenyl) hexafluoropropane dianhydride, 3,
3 ', 4,4'-diphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7, -naphthalenetetracarboxylic dianhydride, 2,2 ', 3,3'-diphenyltetracarboxylic dianhydride, 2,2-bis (3,4, -dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride Anhydride, 3,4,9,1
O-perylenetetracarboxylic dianhydride, bis (3,4
-Dicarboxyphenyl) ether dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride,
2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-
1,4,5,8, tetracarboxylic dianhydride, 2,3
6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,
9,10-tetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride,
1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride Anhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, benzene-1,2,3,3
4-tetracarboxylic dianhydride, 3,4,3 ', 4'-
Benzophenonetetracarboxylic dianhydride, 2,3
2 ′, 3-benzophenonetetracarboxylic dianhydride,
2,3,3 ', 4'-benzophenonetetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride , Ethylene tetracarboxylic dianhydride,
Decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,
6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, cyclopentane-1,2,2
3,4-tetracarboxylic dianhydride, pyrrolidine-2,
3,4,5-tetracarboxylic dianhydride, 1,2,3
4-butanetetracarboxylic dianhydride, bicyclo-
(2,2,2) -oct (7) -ene-2,3,5,6
-Tetracarboxylic dianhydride, 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride, 3,4,3',
4'-biphenyltetracarboxylic dianhydride, 2,3
2 ', 3'-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) methylphenylsilane dianhydride, bis (3 , 4-Dicarboxyphenyl) diphenylsilane dianhydride, bis (3,4-
Dicarboxyphenyl) dimethylsilane dianhydride, 1,
4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldicycloxane dianhydride , P-phenylbis (trimellitic acid monoester anhydride) ethylene glycol bis (trimellitic anhydride), propanediol bis (trimellitic anhydride), butanediol bis (trimellitic anhydride), pentanediol Bis (trimellitic anhydride), hexanediol bis (trimellitic anhydride), octanediol bis (trimellitic anhydride), decanediol bis (trimellitic anhydride),
2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis [4- (3
4-dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride,
1,4-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride), 1,3
-Bis (2-hydroxyhexafluoroisopropyl)
Benzene bis (trimellitic anhydride), butanediol bis (trimellitic anhydride), pentanediol bis (trimellitic anhydride), hexanediol bis (trimellitic anhydride), octanediol bis (trimellitic acid) Anhydride), decanediol bis (trimellitic anhydride), 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-
Bis [4- (3,4-dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride), 1,3-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride)
And two or more kinds may be mixed and used.

The fluorine-containing aromatic diamine compound represented by the above formula (1) is a novel compound and has a long-chain or bulky perfluoroalkenyl group in the molecule. The fluorinated aromatic diamine compound is preferably used in an amount of 5 to 100 mol%, particularly preferably 10 to 100 mol%, based on the total amount of the diamine compound used. If the amount of the fluorinated aromatic diamine compound is too small, the effect of improving the moisture resistance tends to decrease.

Examples of the fluorinated aromatic diamine compound represented by the formula (7) include 1,3-diamino-5- (perfluorononenyloxy) benzene and 1,3-diamino-4-
Methyl-5- (perfluorononenyloxy) benzene, 1,3-diamino-4-methoxy-5- (perfluorononenyloxy) benzene, 1,3-diamino-
2,4,6-trifluoro-5- (perfluorononenyloxy) benzene, 1,3-diamino-4-chloro-
5- (perfluorononenyloxy) benzene, 1,3
-Diamino-4-bromo-5- (perfluorononenyloxy) benzene, 1,2-diamino-4- (perfluorononenyloxy) benzene, 1,2-diamino-4
-Methyl-5- (perfluorononenyloxy) benzene, 1,2-diamino-4-methoxy-5- (perfluorononenyloxy) benzene, 1,2-diamino-
3,4,6-trifluoro-5- (perfluorononenyloxy) benzene, 1,2-diamino-4-chloro-
5- (perfluorononenyloxy) benzene, 1,2
-Diamino-4-bromo-5- (perfluorononenyloxy) benzene, 1,4-diamino-3- (perfluorononenyloxy) benzene, 1,4-diamino-2
-Methyl-5- (perfluorononenyloxy) benzene, 1,4-diamino-2-methoxy-5- (perfluorononenyloxy) benzene, 1,4-diamino-
2,3,6-trifluoro-5- (perfluorononenyloxy) benzene, 1,4-diamino-2-chloro-
5- (perfluorononenyloxy) benzene, 1,4
-Diamino-2-bromo-5- (perfluorononenyloxy) benzene, 1,3-diamino-5- (perfluorohexenyloxy) benzene, 1,3-diamino-
4-methyl-5- (perfluorohexenyloxy) benzene, 1,3-diamino-4-methoxy-5- (perfluorohexenyloxy) benzene, 1,3-diamino-2,4,6-trifluoro-5 -(Perfluorohexenyloxy) benzene, 1,3-diamino-4-chloro-5- (perfluorohexenyloxy) benzene, 1,3-diamino-4-bromo-5- (perfluorohexenyloxy) benzene, , 2-diamino-4
-(Perfluorohexenyloxy) benzene, 1,2
-Diamino-4-methyl-5- (perfluorohexenyloxy) benzene, 1,2-diamino-4-methoxy-5- (perfluorohexenyloxy) benzene,
1,2-diamino-3,4,6-trifluoro-5-
(Perfluorohexenyloxy) benzene, 1,2-
Diamino-4-chloro-5- (perfluorohexenyloxy) benzene, 1,2-diamino-4-bromo-5
-(Perfluorohexenyloxy) benzene, 1,4
-Diamino-3- (perfluorohexenyloxy) benzene, 1,4-diamino-2-methyl-5- (perfluorohexenyloxy) benzene, 1,4-diamino-2-methoxy-5- (perfluorohexenyloxy) ) Benzene, 1,4-diamino-2,3,6-trifluoro-5- (perfluorohexenyloxy) benzene, 1,4-diamino-2-chloro-5- (perfluorohexenyloxy) benzene, 4-diamino-2
-Bromo-5- (perfluorohexenyloxy) benzene and the like.

The perfluorononenyl group is -C ₉
A F ₁₇ group, the perfluoro hexenyl -C ₆ F
_{There are 11} units, and so on. In the compounds illustrated above, instead of perfluoro root sulfonyl group or a perfluoroalkyl hexenyl group, -C ₁₀ F ₁₉ group, can be exemplified similarly compounds having -C ₁₂ F ₂₃ group and the like.

The fluorine-containing aromatic diamine compound represented by the above formula (7) is

Embedded image (However, in Chemical formula 8, Rf is the same as Chemical formula 4, and R ¹ and R ² each independently represent an alkyl group which may be substituted or an aryl group which may be substituted; May be appropriately substituted with a substituent such as a lower alkyl group, a lower alkoxy group, fluorine, chlorine, or bromine, and the two urethane groups are each ortho-, meta-, or para-position to the ether bond to the aromatic ring. Connected to the position)
By subjecting the fluorine-containing aromatic diurethane compound represented by the formula to a deprotection reaction of a urethane-type protecting group.

As the compound represented by the formula 8, 1,3
-Bis (N- (methyloxycarbonyl) amino) -5
-(Perfluorononenyloxy) benzene, 1,3-
Bis (N- (ethyloxycarbonyl) amino) -5
(Perfluorononenyloxy) benzene, 1,3-bis (N- (propyloxycarbonyl) amino) -5
(Perfluorononenyloxy) benzene, 1,3-bis (N- (i-propyloxycarbonyl) amino)-
5- (perfluorononenyloxy) benzene, 1,3
-Bis (N- (butyloxycarbonyl) amino) -5
-(Perfluorononenyloxy) benzene, 1,3-
Bis (N- (i-butyloxycarbonyl) amino)-
5- (perfluorononenyloxy) benzene, 1,3
-Bis (N- (t-butyloxycarbonyl) amino)
-5- (perfluorononenyloxy) benzene, 1,
3-bis (N- (pentyloxycarbonyl) amino)
-5- (perfluorononenyloxy) benzene, 1,
3-bis (N- (hexyloxycarbonyl) amino)
-5- (perfluorononenyloxy) benzene, 1,
3-bis (N- (heptyloxycarbonyl) amino)
-5- (perfluorononenyloxy) benzene, 1,
3-bis (N- (octyloxycarbonyl) amino)
-5- (perfluorononenyloxy) benzene, 1,
3-bis (N- (benzyloxycarbonyl) amino)
-5- (perfluorononenyloxy) benzene, 1,
3-bis (N- (phenyloxycarbonyl) amino)
-5 (perfluorononenyloxy) benzene, 1,2
-Bis (N-methyloxycarbonyl) amino) -4-
(Perfluorononenyloxy) benzene, 1,2-bis (N- (ethyloxycarbonyl) amino) -4-
(Perfluorononenyloxy) benzene, 1,2-bis (N- (propyloxycarbonyl) amino) -4-
(Perfluorononenyloxy) benzene, 1,2-bis (N- (ipropyloxycarbonyl) amino) -4
-(Perfluorononenyloxy) benzene, 1,2-
Bis (N- (butyloxycarbonyl) amino) -4-
(Perfluorononenyloxy) benzene, 1,2-bis (N- (i-butyloxycarbonyl) amino) -4
-(Perfluorononenyloxy) benzene, 1,2-
Bis (N- (t-butyloxycarbonyl) amino)-
4- (perfluorononenyloxy) benzene, 1,2
-Bis (N- (pentyloxycarbonyl) amino)-
4- (perfluorononenyloxy) benzene, 1,2
-Bis (N- (hexyloxycarbonyl) amino)-
4- (perfluorononenyloxy) benzene, 1,2
-Bis (N- (heptyloxycarbonyl) amino)-
4- (perfluorononenyloxy) benzene, 1,2
-Bis (N- (octyloxycarbonyl) amino)-
4- (perfluorononenyloxy) benzene, 1,2
-Bis (N- (benzyloxycarbonyl) amino)-
4- (perfluorononenyloxy) benzene, 1,2
-Bis (N- (phenyloxycarbonyl) amino)-
4- (perfluorononenyloxy) benzene, 1,4
-Bis (N- (methyloxycarbonyl) amino) -3
-(Perfluorononenyloxy) benzene, 1,4-
Bis (N- (ethyloxycarbonyl) amino) -3-
(Perfluorononenyloxy) benzene, 1,4-bis (N- (propyloxycarbonyl) amino) -3-
(Perfluorononenyloxy) benzene, 1,4-bis (N- (i-propyloxycarbonyl) amino)-
3- (perfluorononenyloxy) benzene, 1,4
-Bis (N- (butyloxycarbonyl) amino) -3
-(Perfluorononenyloxy) benzene, 1,4-
Bis (N- (i-butyloxycarbonyl) amino)-
3- (perfluorononenyloxy) benzene, 1,4
-Bis (N- (t-butyloxycarbonyl) amino)
-3- (perfluorononenyloxy) benzene, 1,
4-bis (N- (pentyloxycarbonyl) amino)
-3- (perfluorononenyloxy) benzene, 1,
4-bis (N- (hexyloxycarbonyl) amino)
-3- (perfluorononenyloxy) benzene, 1,
4-bis (N- (heptyloxycarbonyl) amino)
-3- (perfluorononenyloxy) benzene, 1,
4-bis (N- (octyloxycarbonyl) amino)
-3- (perfluorononenyloxy) benzene, 1,
4-bis (N- (benzyloxycarbonyl) amino)
-3- (perfluorononenyloxy) benzene, 1,
4-bis (N-phenyloxycarbonyl) amino)-
3- (perfluorononenyloxy) benzene, 1,3-
Bis (N- (methyloxycarbonyl) amino) -5
(Perfluorohexenyloxy) benzene, 1,3-
Bis (N- (ethyloxycarbonyl) amino) -5
(Perfluorohexenyloxy) benzene, 1,3-
Bis (N- (propyloxycarbonyl) amino) -5
-(Perfluorohexenyloxy) benzene, 1,3
-Bis (N- (i-propyloxycarbonyl) amino) -5- (perfluorohexenyloxy) benzene, 1,3-bis (N- (butyloxycarbonyl) amino) -5- (perfluorohexenyloxy) benzene , 1,3-bis (N- (i-butyloxycarbonyl) amino) -5- (perfluorohexenyloxy)
Benzene, 1,3-bis (N- (t-butyloxycarbonyl) amino) -5- (perfluorohexenyloxy) benzene, 1,3-bis (N- (pentyloxycarbonyl) amino) -5- (per Fluorohexenyloxy) benzene, 1,3-bis (N- (hexyloxycarbonyl) amino) -5- (perfluorohexenyloxy) benzene, 1,3-bis (N- (heptyloxycarbonyl) amino) -5 (Perfluorohexenyloxy) benzene, 1,3-bis (N- (octyloxycarbonyl) amino) -5- (perfluorohexenyloxy) benzene, 1,3-bis (N- (benzyloxycarbonyl) amino)- 5- (perfluorononenyloxy) benzene, 1,3-bis (N- (phenyloxycarbonyl) Amino) -5- (perfluorohexenyloxy) benzene, 1,2-bis (N- (methyloxycarbonyl) amino) -4- (perfluorohexenyloxy) benzene, 1,2-bis (N- (ethyloxy) Carbonyl) amino) -4- (perfluorohexenyloxy) benzene, 1,2-bis (N-propyloxycarbonyl) amino) -4- (perfluorohexenyloxy) benzene, 1,2-bis (N- (i -Propyloxycarbonyl) amino) -4- (perfluorohexenyloxy) benzene, 1,2-bis (N-
(Butyloxycarbonyl) amino) -4- (perfluorohexenyloxy) benzene, 1,2-bis (N-
(I-butyloxycarbonyl) amino) -4- (perfluorohexenyloxy) benzene, 1,2-bis (N- (t-butyloxycarbonyl) amino) -4-
(Perfluorohexenyloxy) benzene, 1,2-
Bis (N- (pentyloxycarbonyl) amino) -4
-(Perfluorohexenyloxy) benzene, 1,2
-Bis (N- (hexyloxycarbonyl) amino)-
4- (perfluorohexenyloxy) benzene, 1,
2-bis (N- (heptyloxycarbonyl) amino)
-4- (perfluorohexenyloxy) benzene,
1,2-bis (N- (octyloxycarbonyl) amino) -4- (perfluorohexenyloxy) benzene, 1,2-bis (N- (benzyloxycarbonyl)
Amino) -4- (perfluorohexenyloxy) benzene, 1,2-bis (N- (phenyloxycarbonyl) amino) -4- (perfluorohexenyloxy)
Benzene, 1,4-bis (N- (methyloxycarbonyl) amino) -3- (perfluorohexenyloxy)
Benzene, 1,4-bis (N- (ethyloxycarbonyl) amino) -3- (perfluorohexenyloxy)
Benzene, 1,4-bis (N- (propyloxycarbonyl) amino) -3- (perfluorohexenyloxy) benzene, 1,4-bis (N- (i-propyloxycarbonyl) amino) -3- (per Fluorohexenyloxy) benzene, 1,4-bis (N- (butyloxycarbonyl) amino) -3- (perfluorohexenyloxy) benzene, 1,4-bis (N- (i-butyloxycarbonyl) amino)- 3- (perfluorohexenyloxy) benzene, 1,4-bis (N- (t-butyloxycarbonyl) amino) -3- (perfluorohexenyloxy) benzene, 1,4-bis (N- (pentyloxycarbonyl) ) Amino) -3- (Perfluorohexenyloxy) benzene, 1,4-bis (N-
(Hexyloxycarbonyl) amino) -3- (perfluorohexenyloxy) benzene, 1,4-bis (N
-(Heptyloxycarbonyl) amino) -3- (perfluorohexenyloxy) benzene, 1,4-bis (N- (octyloxycarbonyl) amino) -3-
(Perfluorohexenyloxy) benzene, 1,4-
Bis (N- (benzyloxycarbonyl) amino) -3
-(Perfluorononenyloxy) benzene, 1,4-
Bis (N- (phenyloxycarbonyl) amino) -3
-(Perfluorohexenyloxy) benzene and the like. In this way the compounds exemplified in place of perfluoro root sulfonyl group or a perfluoroalkyl hexenyl group, group -C ₁₀ F _19, compounds having a group -C ₁₂ F ₂₃ or the like can be exemplified similarly.

The urethane-type protecting group specifically means —COOR ¹ and —COOR ² in Chemical formula 8.

The deprotection reaction can be carried out, for example, by the following method. A solution of the above fluorinated aromatic diurethane compound in an organic solvent such as ethyl acetate, dimethylformamide, dimethylacetamide, benzene, xylene, acetone, tetrahydrofuran or the like is charged with a hydrogen gas at 0 to 100 ° C. in the presence of a catalyst such as palladium carbon. A method of passing hydrogen gas (particularly preferably around room temperature) (the time of passing hydrogen gas may be determined as appropriate, but usually 1 to 10 hours is sufficient), dissolving the fluorine-containing aromatic diurethane compound in the organic solvent as described above. HF, HBr, HCl, H ₂
A method of adding and reacting a hydrogen acid such as SO ₄ (hydrogen acid is
The reaction is preferably carried out in an equivalent amount or more with respect to the fluorine-containing aromatic diurethane compound. When HF is used, the reaction is preferably carried out at room temperature or lower, particularly at 0 ° C or lower. The reaction is preferably performed at around room temperature. Further, the reaction time is determined as appropriate,
Usually, 0.1 to 1 hour is sufficient when HF is used, and 1 to 10 hours when other hydrogen acid is used.) The above-mentioned fluorinated aromatic diurethane compound is converted into sodium hydrogen carbonate, potassium hydrogen carbonate, water, etc. A method in which the reaction is carried out in the presence of a basic compound such as sodium oxide or potassium hydroxide and water (water is preferably used in an equivalent amount or more with respect to the fluorinated aromatic diurethane compound. Alternatively, water, an alcohol such as methanol or ethanol, or cresol may be used as a solvent).

The thus obtained aromatic diamine compound represented by Chemical Formula 7 can be purified by recrystallization from alcohol or the like.

The fluorinated aromatic diurethane compound represented by the above formula 8 is

Embedded image [However, in Chemical formula 9, Rf is the same as Chemical formula 4, and the hydrogen of the aromatic ring may be appropriately substituted with a substituent such as a lower alkyl group, a lower alkoxy group, fluorine, chlorine, bromine, etc. Carboxyl groups are respectively bonded to the aromatic ring at the ortho, meta or para position with respect to the ether bond].

Embedded image (Wherein, R ³ represents a lower alkyl group or an aryl group).

Embedded image wherein an alcohol represented by R ⁴ OH (where R ⁴ represents an alkyl group which may have a substituent or an aryl group which may have a substituent) The reaction can be carried out in a solvent or without solvent in the presence of a base.

Examples of the dicarboxylic acid compound represented by the above formula include 5- (perfluorononenyloxy) isophthalic acid, 4- (perfluorononenyloxy) phthalic acid, and 2- (perfluorononenyloxy) terephthalic acid. , 4-methyl-5- (perfluorononenyloxy)
Isophthalic acid, 4-methoxy-5- (perfluorononenyloxy) isophthalic acid, 2,4,6-trifluoro-5- (perfluorononenyloxy) isophthalic acid,
4-chloro-5- (perfluorononenyloxy) isophthalic acid, 4-bromo-5- (perfluorononenyloxy) isophthalic acid, 4-methyl-5- (perfluorononenyloxy) phthalic acid, 4- Methoxy-5- (perfluorononenyl) phthalic acid, 3,4,6-trifluoro-5- (perfluorononenyloxy) phthalic acid,
-Chloro-5- (perfluorononenyloxy) phthalic acid, 4-bromo-5- (perfluorononenyloxy)
Phthalic acid, 2-methyl-5- (perfluorononenyloxy) terephthalic acid, 4-methoxy-5- (perfluorononenyloxy) terephthalic acid, 2,3,6-trifluoro-5- (perfluorononene Nyloxy) terephthalic acid, 2-chloro-5- (perfluorononenyloxy) terephthalic acid, 2-bromo-5- (perfluorononenyloxy) terephthalic acid, 5- (perfluorohexenyloxy) isophthalic acid, -(Perfluorohexenyloxy) phthalic acid, 2- (perfluorohexenyloxy) terephthalic acid, 4-methyl-5- (perfluorohexenyloxy) isophthalic acid, 4-methoxy-
5- (perfluorohexenyloxy) isophthalic acid,
2,4,6-trifluoro-5- (perfluorohexenyloxy) isophthalic acid, 4-chloro-5- (perfluorohexenyloxy) isophthalic acid, 4-bromo-
5- (perfluorohexenyloxy) isophthalic acid,
4-methyl-5- (perfluorohexenyloxy) phthalic acid, 4-methoxy-5- (perfluorohexenyloxy) phthalic acid, 3,4,6-trifluoro-5-
(Perfluorohexenyloxy) phthalic acid, 4-chloro-5- (perfluorohexenyloxy) phthalic acid,
4-bromo-5- (perfluorohexenyloxy) phthalic acid, 2-methyl-5- (perfluorohexenyloxy) terephthalic acid, 4-methoxy-5- (perfluorohexenyloxy) terephthalic acid, 2,3,6 -Trifluoro-5- (perfluorohexenyloxy) terephthalic acid, 2-chloro-5- (perfluorohexenyloxy) terephthalic acid, 2-bromo-5- (perfluorohexenyloxy) terephthalic acid and the like. This way the compounds exemplified in place of perfluoro root sulfonyl group or a perfluoroalkyl hexenyl group, -C ₁₀ F ₁₉
Compounds having a group, —C ₁₂ F ₂₃ group, and the like can also be exemplified.

The above-mentioned perfluorononenyloxyisophthalic acid and perfluorohexenyloxyisophthalic acid can be prepared, for example, by trimerizing hexafluoropropene or dimerizing hexafluoropropene according to the method described in JP-A-60-511146.
And hydroxyisophthalic acid in an aprotic polar solvent at room temperature or lower in the presence of a base catalyst.

The perfluorononenyl group includes, for example,

Embedded image And a perfluorohexenyl group includes, for example,

Embedded image There is a group.

In the above method, it is also possible to produce other dicarboxylic acids by using oligomers other than trimers and dimers of hexafluoropropene and oligomers of other fluoroalkenes.

Further, the dicarboxylic acid represented by the above-mentioned chemical formula 9 can be converted to an ester such as diphenyl ester or dibenzyl ester of hydroxy-dicarboxybenzene according to the method described in JP-A-50-112243. After reacting an oligomer of a fluoroalkene such as fluoropropene trimer or tetrafluoroethylene pentamer in the presence of a proton acceptor in an aprotic organic solvent at around room temperature or below in the presence of a base catalyst, The reaction product can be produced by isolating the reaction product, hydrolyzing the reaction product in the presence of a basic compound such as sodium hydroxide, potassium hydroxide or the like, and further appropriately treating the product with an acid such as hydrochloric acid. The reaction product and the final product are appropriately purified by means such as washing and recrystallization.

Examples of the azide compound represented by the above formula include diphenyl phosphoryl azide, diethyl phosphoryl azide, di-p-nitrophenyl phosphoryl azide,
And dimorpholylphosphoryl azide.

Examples of the alcohol represented by Chemical formula 11 include methanol, ethanol, propanol, i-propanol, butanol, i-butanol, t-butanol, pentanol, hexanol, heptanol, octanol, phenol and benzyl alcohol.

In the synthesis reaction for obtaining the fluorine-containing aromatic diurethane compound represented by the above formula 8, Takayuki Shioiri and Shunichi Yamada, Journal of Synthetic Organic Chemistry, Vol. 31, No. 8, No. 666-67.
A new Curtius reaction as shown on page 4 (1973) can be applied. That is, the desired fluorinated aromatic diurethane compound can be obtained by reacting the dicarboxylic acid compound represented by the chemical formula 9, the azide compound represented by the chemical formula 10, and the alcohol represented by the chemical formula 11 in the presence of a base. As the base, it is preferable to use a tertiary amine such as trimethylamine, triethylamine and pyridine. The above reaction is carried out in an organic solvent or using an alcohol represented by Chemical formula 11 as a solvent. As the organic solvent, benzene,
It is preferable to use toluene, tetrahydrofuran, dioxane, diethyl ether, or the like. These solvents may be used as a mixture of two or more as long as they are compatible with each other.

In the above reaction, the dicarboxylic acid compound represented by the chemical formula (9) and the azide compound represented by the chemical formula (10) react in the middle, and the carboxylic acid azide and the carboxylic acid azide undergo a thermal rearrangement reaction to form an isocyanate compound. However, the reaction can proceed with or without isolation of these intermediates. The conditions for the above reaction differ depending on the reagent used and are not particularly limited, but the following conditions are preferred.

First, the dicarboxylic acid compound represented by the chemical formula (9), the azide compound represented by the chemical formula (10), the tertiary amine and the alcohol represented by the chemical formula (11) are reacted at once, and the desired fluorine-containing compound is apparently processed in one step. When an aromatic diurethane compound is obtained, the reaction temperature is preferably from -80 to 250 ° C, particularly preferably from room temperature to 150 ° C. The azide compound, the tertiary amine, and the alcohol are used in an amount of 0.5 to 5.0 molar equivalents, 0.5 to 3.0 molar equivalents, and 0.5 molar equivalents to a large excess with respect to the dicarboxylic acid compound, respectively. Is preferred.

Second, when the carboxylic acid azide is isolated once, first, the dicarboxylic acid compound and the azide compound are reacted in the presence of the tertiary amine, and the resulting carboxylic acid azide is isolated. I do. At this time, the reaction temperature is preferably −80 to 100 ° C., and the azide compound and the tertiary amine are 0.5 to 5.0 mole equivalent and 0.5 to 3.0 mole, respectively, based on the dicarboxylic acid compound. It is preferable to use an equivalent amount. Next, the isolated carboxylic acid azide is reacted in an alcohol in an amount of 0.5 molar equivalent to a large excess thereof to obtain the desired fluorinated aromatic diurethane compound. The reaction temperature at this time is preferably from -80 to 250C.

Third, when isolating the isocyanate compound once, first, the dicarboxylic acid compound represented by the chemical formula 9 and the azide compound represented by the chemical formula 10 are reacted in the presence of a tertiary amine to obtain the isocyanate compound. Is isolated. At this time, it is preferable to use 0.5 to 5.0 molar equivalents of the azide compound and 0.5 to 3.0 molar equivalents of the tertiary amine with respect to the dicarboxylic acid compound, and the reaction temperature is preferably -80 to 250 ° C. . Next, the obtained isocyanate is reacted in an alcohol in an amount of 0.5 molar equivalent to a large excess with respect to the isocyanate to obtain a fluorinated aromatic diurethane compound. At this time, the reaction temperature is preferably from -80 to 250C.

The first to third methods are appropriately selected in consideration of the yield and the like.

The fluorine-containing aromatic diurethane compound thus obtained can be purified by recrystallization from hexane or the like.

Examples of the diamine compound which can be used in combination with the aromatic diamine compound represented by the above formula include 4-aminophenyl-3-aminobenzoic acid, 2,2-bis (4-aminophenyl) propane, and 2,6-diamino Pyridine, bis (4-aminophenyl) diethylsilane, bis- (4
-Aminophenyl) diphenylsilane, bis- (4-aminophenyl) ethylphosphine oxide, bis-
(4-aminophenyl) -N-butylamine, bis-
(4-aminophenyl) -N-methylamine, N- (3
-Aminophenyl) -4-aminobenzamide, 4-aminophenyl-3-aminobenzoic acid, 3,3'-diaminodiphenylmethane, 3,3'-diaminodiphenylether, 3,3'-diaminodiphenylsulfone, 3,
3'-diaminodiphenylpropane, 3,3'-diaminodiphenylsulfide, p-phenylenediamine, m
Phenylenediamine, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenylmethane, 3,
3′-diaminobenzophenone, 4,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl ether, 3,
4′-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,4-bis (β-amino-t-butyl)
Toluene, bis (p-β-amino-t-butyl-phenyl) ether, bis (p-β-methyl-γ-amino-pentyl) benzene, bis-p- (1,1-dimethyl-5)
-Aminopentyl) benzene, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, tetramethylenediamine, propylenediamine, 3-methylheptamethylenediamine, 4,4'-dimethylheptamethylenediamine, 2,11-diaminododecane, 1,
2-bis (3-aminopropoxy) ethane, 2,2-dimethylpropylenediamine, 3-methoxy-hexamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 5-methylnonamethylene Diamine, 2,17-diaminoicosadecane, 1,4-diaminocyclohexane, 1,10
-Diamino-1,10-dimethyldecane, 1,12-diaminooctadecane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (4- (4
-Aminophenoxy) phenyl) hexafluoropropane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'diaminophenylmethane, 3,3'-dimethoxy-4,4 '-Diaminodiphenylmethane, 3,3'diethoxy-4,4'-
Diaminodiphenylmethane, 3,3'-difluoro-
4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 3,3 '
-Dibromo-4,4'-diaminodiphenylmethane,
3,3'-di (trifluoromethyl) -4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4 '
-Diaminodiphenyl ether, 3,3'-diisopropyl-4,4'-diaminodiphenyl ether, 3,
3'-dimethoxy-4,4'-diaminodiphenyl ether, 3,3'-diethoxy-4,4'-diaminodiphenyl ether, 3,3'-difluoro-4,4'-diaminodiphenyl ether, 3,3'-dichloro- 4,
4'-diaminodiphenyl ether, 3,3'-dibromo-4,4'-diaminodiphenyl ether, 3,3 '
-Di (trifluoromethyl) -4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 3,3'-dimethoxy-4,
4'-diaminodiphenylsulfone, 3,3'-diethoxy-4,4'diaminodiphenylsulfone, 3,3 '
-Difluoro-4,4'-diaminodiphenylsulfone, 3,3'-dichloro-4,4'-diaminodiphenylsulfone, 3,3'-dibromo-4,4'-diaminodiphenylsulfone, 3,3'-di (Trifluoromethyl) -4,4′-diaminodiphenylsulfone, 3,
3'-dimethyl-4,4'-diaminodiphenylpropane, 3,3'-dimethoxy-4,4'-diaminodiphenylpropane, 3,3'-diethoxy-4,4'-diaminodiphenylpropane, 3,3 ' -Difluoro-4,
4'-diaminodiphenylpropane, 3,3'-dichloro-4,4'-diaminodiphenylpropane, 3,3 '
-Dibromo-4,4'-diaminodiphenylpropane,
3,3′-di (trifluoromethyl) -4,4′-diaminodiphenylpropane, 3,3′-dimethyl-4,
4'-diaminodiphenyl sulfide, 3,3'-dimethoxy-4,4'-diaminodiphenyl sulfide,
3,3'-diethoxy-4,4'-diaminodiphenylsulfide, 3,3'-difluoro-4,4'-diaminodiphenylsulfide, 3,3'-dichloro-4,
4'-diaminodiphenylsulfide, 3,3'-dibromo-4,4'-diaminodiphenylsulfide, 3,
3'-di (trifluoromethyl) -4,4'-diaminodiphenylsulfide, 3,3'-dimethyl-4,4 '
-Diaminodiphenylhexafluoropropane, 3,
3'-dimethoxy-4,4'-diaminodiphenylhexafluoropropane, 3,3'-diethoxy-4,4 '
-Diaminodiphenylhexafluoropropane, 3,
3'-difluoro-4,4'-diaminodiphenylhexafluoropropane, 3,3'-dichloro-4,4'-
Diaminodiphenylhexafluoropropane, 3,3 '
-Dibromo-4,4'-diaminodiphenylhexafluoropropane, 3,3'-di (trifluoromethyl)-
4,4'-diaminodiphenylhexafluoropropane, 3,3'-dimethyl-4,4'-diaminobenzophenone, 3,3'-dimethoxy-4,4'-diaminobenzophenone, 3,3'-diethoxy-4, 4'-diaminobenzophenone, 3,3'-difluoro-4,4 '
-Diaminobenzophenone, 3,3'-dichloro-4,
4'-diaminobenzophenone, 3,3'-dibromo-
4,4′-diaminobenzophenone, 3,3′-di (trifluoromethyl) -4,4′-diaminobenzophenone, 3,3′-dimethylbenzidine, 3,3 ′, 5
5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetraisopropyl-4,
4'-diaminodiphenylmethane, 3,3 ', 5,5'
-Tetramethoxy-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetraethoxy-4,4'-
Diaminodiphenylmethane, 3,3 ′, 5,5′-tetrafluoro-4,4′-diaminodiphenylmethane,
3,3 ′, 5,5′-tetrachloro-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetrabromo-4,4′-diaminodiphenylmethane, 3,3 ′,
5,5'-tetra (trifluoromethyl) -4,4'-
Diaminodiphenylmethane, 3,3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylether,
3,3 ′, 5,5′-tetraethyl-4,4′-diaminodiphenyl ether, 3,3 ′, 5,5′-tetramethoxy-4,4′-diaminodiphenyl ether, 3,
3 ′, 5,5′-tetraethoxy-4,4′-diaminodiphenyl ether, 3,3 ′, 5,5′-tetrafluoro-4,4′-diaminodiphenyl ether, 3,
3 ′, 5,5′-tetrachloro-4,4′-diaminodiphenyl ether, 3,3 ′, 5,5′-tetrabromo-4,4′-diaminodiphenyl ether, 3,3 ′,
5,5'-tetra (trifluoromethyl) -4,4'-
Diaminodiphenyl ether, 3,3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylsulfone,
3,3 ′, 5,5′-tetramethoxy-4,4′-diaminodiphenylsulfone, 3,3 ′, 5,5′-tetraethoxy-4,4′-diaminodiphenylsulfone,
3,3 ′, 5,5′-tetrafluoro-4,4′-diaminodiphenylsulfone, 3,3 ′, 5,5′-tetrachloro-4,4′-diaminodiphenylsulfone, 3,
3 ′, 5,5′-tetrabromo-4,4′-diaminodiphenylsulfone, 3,3 ′, 5,5′-tetra (trifluoromethyl) -4,4′-diaminodiphenylsulfone, 3,3 ′, 5,5'-tetramethyl-4,4'-
Diaminodiphenylpropane, 3,3 ', 5,5'-tetramethoxy-4,4'-diaminodiphenylpropane, 3,3', 5,5'-tetraethoxy-4,4'-
Diaminodiphenylpropane, 3,3 ′, 5,5′-tetrafluoro-4,4′-diaminodiphenylpropane, 3,3 ′, 5,5′-tetrachloro-4,4′-diaminodiphenylpropane, 3, 3 ′, 5,5′-tetrabromo-4,4′-diaminodiphenylpropane,
3,3 ', 5,5'-tetra (trifluoromethyl)-
4,4′-diaminodiphenylpropane, 3,3 ′,
5,5'-tetramethyl-4,4'-diaminodiphenylsulfide, 3,3 ', 5,5'-tetramethoxy-
4,4′-diaminodiphenyl sulfide, 3,3 ′,
5,5′-tetraethoxy-4,4′-diaminodiphenylsulfide, 3,3 ′, 5,5′-tetrafluoro-4,4′-diaminodiphenylsulfide, 3,
3 ′, 5,5′-tetrachloro-4,4′-diaminodiphenylsulfide, 3,3 ′, 5,5′-tetrabromo-4,4′-diaminodiphenylsulfide, 3,
3 ′, 5,5′-tetra (trifluoromethyl) -4,
4′-diaminodiphenyl sulfide, 3,3 ′, 5
5'-tetramethyl-4,4'-diaminodiphenylhexafluoropropane, 3,3 ', 5,5'-tetramethoxy-4,4'-diaminodiphenylhexafluoropropane, 3,3', 5,5 ' -Tetraethoxy-4,
4'-diaminodiphenylhexafluoropropane,
3,3 ′, 5,5′-tetrafluoro-4,4′-diaminodiphenylhexafluoropropane, 3,3 ′,
5,5′-tetrachloro-4,4′-diaminodiphenylhexafluoropropane, 3,3 ′, 5,5′-tetrabromo-4,4′-diaminodiphenylhexafluoropropane, 3,3 ′, 5,5 '-Tetra (trifluoromethyl) -4,4'-diaminodiphenylhexafluoropropane, 3,3', 5,5'-tetramethyl-
4,4′-diaminobenzophenone, 3,3 ′, 5
5'-tetramethoxy-4,4'-diaminobenzophenone, 3,3 ', 5,5'-tetraethoxy-4,4'
-Diaminobenzophenone, 3,3 ', 5,5'-tetrafluoro-4,4'-diaminobenzophenone, 3,
3 ′, 5,5′-tetrachloro-4,4′-diaminobenzophenone, 3,3 ′, 5,5′-tetrabromo-
4,4′-diaminobenzophenone, 3,3 ′, 5
5′-tetra (trifluoromethyl) -4,4′-diaminobenzophenone, 3,3 ′, 5,5′-tetraisopropyl-4,4′-diaminodiphenylmethane, 3,
3'-diisopropyl-5,5'-dimethyl-4,4 '
-Diaminodiphenylmethane, 3,3'-diisopropyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-diisopropyl-5,5'-dimethyl-4,4'-diaminodiphenylether, 3,
3'-diisopropyl-5,5'-diethyl-4,4 '
-Diaminodiphenyl ether, 3,3'-diisopropyl-5,5'-dimethyl-4,4'-diaminodiphenylpropane, 3,3'-diisopropyl-5,5'-
Diethyl-4,4'-diaminodiphenylpropane,
3,3′-diisopropyl-5,5′-dimethyl-4,
There are 4′-diaminodiphenylsulfone, 3,3′-diisopropyl-5,5′-diethyl-4,4′-diaminodiphenylsulfone and the like, and two or more kinds may be used in combination.

The polyimide resin can be produced by reacting a tetracarboxylic dianhydride component with a diamine component at an appropriate temperature. In this reaction, the degree of imidization can be appropriately adjusted by selecting appropriate conditions. For example, 100 ° C. or higher,
By reacting at 0 ° C. or higher, if necessary, in the presence of a catalyst such as tributylamine, triethylamine, and triphenyl phosphite, a completely or almost completely imidized polyimide can be produced (the catalyst is It is preferably used in an amount of from 0 to 15% by weight, particularly preferably from 0.01 to 15% by weight, based on the total amount of the reaction components). It is possible to produce polyamic acids which are solid and are completely or almost imidized. Further, a polyimide precursor in which imidization has partially progressed can be produced.

Further, the above-mentioned polyamic acid or the precursor of the polyimide partially imidized is further added with 100%.
Acetic acid anhydride, propionic anhydride, acid anhydrides such as benzoic anhydride, and ring closing agents such as carbodiimides such as dicyclohexylcarbodiimide at 120 ° C.
Further, if necessary, a ring-closing catalyst such as pyridine, isoquinoline, trimethylamine, aminopyridine, imidazole or the like is added to chemically ring-close (imidize) (the ring-closing agent and the ring-closing catalyst are each 1 to 1 mol of the acid anhydride. It is preferable to use within the range of 8 moles), and it is possible to produce a polyimide in which imidization is almost or completely completed. These reactions are preferably performed in the presence of an organic solvent.

Examples of the organic solvent which can be used in the above include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, hexamethylphosphoramide, phenol, m-cresol, and chlorinated solvent. There is an organic polar solvent such as benzene, and two or more kinds thereof may be used as a mixture as long as they are mutually compatible. In addition, a general-purpose solvent such as toluene, xylene, cellosolve acetate, and methyl cellosolve can be used together with these organic polar solvents as long as the solubility of the polyimide resin (polyimide or its precursor) is not reduced.

In the polyimide resin thus obtained, a polyimide precursor, particularly a polyamic acid,
It is dissolved in N, N-dimethylacetamide at a concentration of 0.1 g / dl and has a reduced viscosity of 0.1 d when measured at 30 ° C.
It is preferably at least 1 / g. Also, polyimide is
The glass transition temperature can be easily adjusted to 150 to 300 ° C, and the thermal decomposition temperature can be easily adjusted to 350 ° C or more. Furthermore, this polyimide has a water absorption of 1%.
It can be easily adjusted to below, especially below 0.5%.

Among the polyimide resins, the polyamic acid is represented by the following formula:

Embedded image [However, in Chemical formula 14, R and Rf are the same as Chemical formula 4, and the hydrogen of the benzene ring may be appropriately substituted with a substituent such as a lower alkyl group, a lower alkoxy group, fluorine, chlorine, bromine and the like. ] Is included.

This polyamic acid is further represented by

Embedded image (However, in Chemical formula 15, R 'and X are the same as Chemical formula 5.)
May be included.

The structural unit represented by Chemical Formula 14 and the structural unit represented by Chemical Formula 15 have a molar ratio of the latter / former of 0/100.
９５95/5 is preferable, and especially 0
/ 100 to 90/10 is preferable.

The material for the liquid crystal alignment film contains the above-mentioned polyimide resin, but is preferably a material (varnish) obtained by dissolving this polyimide resin in an organic solvent. As the organic solvent, those exemplified above as those which can be used in the production of the polyimide resin can be used. The selection of the organic solvent to be used is determined in consideration of the solubility of the polyimide-based resin. Among the polyimide-based resins, a polyimide precursor such as polyamic acid has good solubility in the organic solvent.

The material for a liquid crystal alignment film is applied on a suitable substrate such as a glass substrate on which a transparent electrode such as ITO (Indium Tin Oxide) is formed in advance, and dried to form a polyimide layer. As a coating method, a dipping method, a printing method, a spraying method, or the like is used. Drying temperature is 60
To 350 ° C., preferably in the range of 100 to 300 ° C., but when a polyimide precursor such as polyamic acid is used as the polyimide resin, the temperature is not lower than the temperature at which ring-closing imidization occurs. 200 ° C. or higher is preferred. The heating time is 1 minute to 6 hours, preferably 1 minute to
3 hours. In order to improve the adhesion between the substrate and the polyimide layer, a coupling agent such as a silane coupling agent or a titanium coupling agent may be used between them.

The polyimide layer thus formed is used as a liquid crystal alignment film by rubbing the surface. Further, a liquid crystal display device can be obtained by a known method using a liquid crystal holding substrate having the liquid crystal alignment film.

The liquid crystal alignment film is particularly suitable for an STN type liquid crystal display device having a twist angle of 240 to 270 °.

[0048]

EXAMPLES The present invention will be described below with reference to examples, but the scope of the present invention is not limited by these examples. The 5- (perfluorononenyloxy) isophthalic acid used below is a compound represented by the following formula (16).

Embedded image

Synthesis Example 15 0.16 g (1.0 mmol) of 1- (perfluorononenyloxy) isophthalic acid, 0.66 g (2.4 mmol) of diphenylphosphoryl azide
l), 0.24 g (2.4 mmol) of triethylamine
Was reacted in 10 mL of t-butanol at a reflux temperature for 20 hours. After completion of the reaction, t-butanol was distilled off, ether was added thereto, and the mixture was washed with diluted hydrochloric acid and an aqueous solution of sodium hydrogen carbonate. The ether was distilled off, and the residue was recrystallized from hexane to obtain 1,3-bis-N- (t-butyloxycarbonyl) amino) -5-perfluorononenyloxybenzene, which was the target substance, at a yield of 86%. .

The physical properties and elemental analysis of this compound are shown below. (1) Melting point 69-71 ° C (2) ¹ H-NMR spectrum (solvent acetone-d ₆ , T
8.72 ppm (2H, NH, s);
61 ppm (1H, Aromatic, t), 7.09 ppm
(2H, Aromatic, s), 1.49 ppm (9H, t-
Bu, t) [() indicate the integrated intensity ratio of hydrogen, the group as the basis of absorption, and the type of peak in order, s is a singlet,
t shows a triple line. The same applies to the following. (3) ¹⁹ F-NMR spectrum (solvent acetone-d ₆ ,
Benzotrifluoride standard); 11.32 ppm (3
F, CF ₃ , d), -3.54 ppm (6F, CF ₃ ,
s), - 4.82ppm (6F, CF 3, d) -99.
70 ppm (1F, CF, quart.), -101.49
ppm (1F, CF, quint.) [Figures in parentheses indicate the integrated intensity ratio of fluorine, the group and peak as the basis of absorption, s is a singlet, d is a doublet, quart. Is a quadruple line, quint. Indicates a quintet. The same applies to the following. (4) IR absorption spectrum; 3336 cm ^-1 (NH,
Urethane), 1710 cm ^-1 (C = O, urethane), 1
548 cm ^-1 (N-H, urethane), 1244 cm
^-1 (CF) (5) Partial analysis value (%): as shown in Table 1.

[Table 1]

From the above, the formation of the desired product was confirmed. Its structural formula is shown below.

Embedded image

Synthesis Example 2 1,3-Bis (N- (t-butyloxycarbonyl) amino) -5- (perfluorononenyloxy)
To 0.200 g (0.265 mmol) of benzene was added 4.0 mL of 4N sodium bicarbonate / methanol, and the mixture was stirred at room temperature for 4 hours. Next, methanol was distilled off and extracted with ether. After the ether solution was washed with water, ether was distilled off, and column separation was carried out with ether / hexane to give 1,3-diamino-5- (perfluorononenyloxy) benzene, which was the target substance, in a yield of 65%. Obtained.

The analysis data of the obtained 1,3-diamino-5- (perfluorononenyloxy) benzene is shown below. (1) Melting point 105.5-106.9 ° C. (2) ¹ H-NMR spectrum (solvent acetone-d ₆ , T
5.87 (1H, Aromatic, t) 5.63
(2H, Aromatic, t) 4.75 (4H, NH2, s) (3) ¹⁹ F-NMR spectrum (solvent acetone-d ₆ ,
Benzotrifluoride standard); 11.03 (3F, C
_{F 3, d) -3.68 (6F} , CF 3, s) -4.98
_{(6F, CF 3, d)} -99.71 (1F, CF, quar
t. ) -101.67 (1F, CF, quint.) (4) IR absorption spectrum; 3452 cm ^-1 , 3380
^{cm -1, 1628cm -1 (N-} H, an amine), 1298
^{cm -1, 1238cm -1, 1190cm -1} (C-F) (5) Elemental analysis (%): as shown in Table 2.

[Table 2]

From the above, it was confirmed that the compound was the target compound. The structural formula of this compound is shown below.

Embedded image

Synthesis Example 3 4 equipped with a thermometer, a stirring device, a drying tube and a nitrogen introduction tube
8 g of dried N, N-dimethylacetamide and 1.1 g (2 mmol) of 1,3-diamino-5- (perfluorononenyloxy) benzene of Chemical Formula 18 were placed in a one-necked flask and stirred. After the diamine was dissolved, 0.89 g (2 mmol) of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride was added little by little while cooling in an ice bath. After completion of the addition, the mixture was reacted for 5 hours while cooling in an ice bath to obtain a polyamic acid solution.

Synthesis Example 4 A thermometer, a stirring device, a drying tube, and a nitrogen introducing tube 4
Dried N-methyl-2-pyrrolidone 8 in a one-necked flask
g, and then the 1,3-diamino-5-
1.1 g of (perfluorononenyloxy) benzene (2
Mmol) and stirred. After the diamine was dissolved, 0.64 g (2 mmol) of 3,4,3 ', 4'-benzophenonetetracarboxylic dianhydride was added little by little. After completion of the addition, the mixture was reacted at room temperature for 5 hours to obtain a polyamic acid solution.

Synthesis Example 5 4 equipped with a thermometer, a stirring device, a drying tube and a nitrogen introduction tube
8 g of N, N-dimethylacetamide was placed in a single-necked flask, and then 0.55 g (1 mmol) of 1,3-diamino-5- (perfluorononenyloxy) benzene of the formula (18) and 4,4′-diaminophenyl 0.2 g of ether
(1 mmol) and stirred until a homogeneous solution was obtained. Next, at room temperature, 0.58 g (2 mmol) of 3,4,3 ', 4'-biphenyltetracarboxylic dianhydride was added little by little. After completion of the addition, the reaction was carried out at room temperature for 5 hours to obtain a polyamic acid.

Synthesis Example 6 4 equipped with a thermometer, a stirring device, a drying tube and a nitrogen introduction tube
8 g of N, N-dimethylformamide was placed in a one-necked flask, and then 0.06 g (0.1 mmol) of 1,3-diamino-5- (perfluorononenyloxy) benzene of Chemical Formula 18 and 4,4′- Diaminodiphenylmethane
38 g (1.9 mmol) was added and stirred until a homogeneous solution was obtained. Next, while cooling in an ice bath, 0.82 g (2 mmol) of ethylene glycol bis (trimellitic anhydride) was added little by little. After completion of the addition, the mixture was reacted for 3 hours while cooling in an ice bath, and then for 2 hours at room temperature to obtain a polyamic acid.

Synthesis Example 7 4 equipped with a thermometer, stirring device, drying tube and nitrogen introduction tube
8 g of N, N-dimethylacetamide in a one-necked flask,
0.4 g (2 mmol) of 4,4'-diaminodiphenyl ether was added and stirred until a homogeneous solution was obtained. After the diamine was dissolved, 0.89 g (2 mmol) of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride was added little by little while cooling in an ice bath. After completion of the addition, the reaction was carried out for 5 hours while cooling in an ice bath.
A polyamic acid was obtained.

Synthesis Example 8 0.89 g of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride in Synthesis Example 7
Polyamide acid was obtained according to Synthesis Example 7, except that 0.64 g (2 mmol) of benzophenonetetracarboxylic dianhydride was used instead of (2 mmol).

Table 3 shows the measurement results of the reduced viscosities of the polyamic acids obtained in Synthesis Examples 3 to 8. A solution of these polyamic acids was applied on a glass substrate by spin coating, and heated at 150 ° C., 200 ° C., 250 ° C., and 300 ° C. for 30 minutes each to obtain a polyimide film. Using the polyimide film obtained,
The results of measuring the glass transition temperature, the thermal decomposition temperature, the water absorption and the dielectric constant of the polyimide are shown in Table 3 below.

The conditions for measuring the above characteristics are as follows. (1) Reduced viscosity of polyamic acid A solution of polyamic acid was poured into water or methanol, and the precipitated polyamic acid was separated into three and dried. This polyamic acid was dissolved in N, N-dimethylacetamide at a concentration of 0.1 g / dl and measured at 30 ° C. (2) Glass transition temperature of polyimide Using DSC-7 type manufactured by PerkinElmer, and heating rate 10 ° C
The measurement was performed at a sample amount of about 10 mg / min. (3) Thermal decomposition temperature of polyimide Measured at a heating rate of 10 ° C./min using a differential thermal balance (TG-7000, manufactured by Vacuum Riko Co., Ltd.). (4) Water Absorption of Polyimide The polyimide film was immersed in water at room temperature for 24 hours, and determined from the weight change before and after that. (5) Dielectric constant of polyimide Measured using a dielectric constant measuring device under the conditions of a frequency of 10 kHz and room temperature.

[0063]

[Table 3]

The infrared absorption spectra of the polyamic acids obtained in Synthesis Examples 3 to 6 and the polyimides obtained therefrom were measured. The results are shown in the drawing as follows. (1) Polyimide from polyamic acid obtained in Synthesis Example 3: FIG. (2) Polyamic acid obtained in Synthesis Example 3: FIG. (3) Polyimide from polyamic acid obtained in Synthesis Example 4: FIG. (4) Polyamic acid obtained in Synthesis Example 4: FIG. (5) Polyimide from polyamic acid obtained in Synthesis Example 5: FIG. (6) Polyamic acid obtained in Synthesis Example 5: FIG. (7) Polyimide from polyamic acid obtained in Synthesis Example 6: FIG. (8) Polyamic acid obtained in Synthesis Example 6: FIG.

The polyamic acid obtained in Synthesis Examples 3 to 6 and the polyimide obtained from this polyamic acid contain the following structural units. In the following, Rf ′
Represents a group represented by the above formula (12). (1) Structural unit of polyimide from polyamic acid obtained in Synthesis Example 3:

Embedded image (2) Structural unit from polyamic acid obtained in Synthesis Example 3:

Embedded image (3) Structural unit of polyimide from polyamic acid obtained in Synthesis Example 4:

Embedded image (4) Structural unit of polyamic acid obtained in Synthesis Example 4:

Embedded image (5) Structural units of polyimide from polyamic acid obtained in Synthesis Example 5:
50 mol%.

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Embedded image (6) Structural units of the polyamic acid obtained in Synthesis Example 5: 50 mol% of the following chemical formula 25 and 50 mol% of the following chemical formula 26.

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Embedded image (7) Structural units of polyimide from the polyamic acid obtained in Synthesis Example 6: 5 mol% of the following formula 27 and 95 mol% of the following chemical formula 28.

Embedded image

Embedded image (8) Structural units of the polyamic acid obtained in Synthesis Example 6: 5 mol% of the following chemical formula 29 and 95 mol% of the following chemical formula 30.

Embedded image

Embedded image

Examples 1 to 4 and Comparative Example 2 The polyamic acid obtained in Synthesis Examples 3 to 8 was diluted to about 5% with the solvent used during the synthesis to prepare a composition for a liquid crystal alignment film. This solution was spin-coated on two glass substrates with ITO transparent electrodes and dried by heating at 250 ° C. for 1 hour to form a polyimide layer having a thickness of 500 °. Next, the surface of the polyimide layer is rubbed to obtain a liquid crystal holding substrate. The two substrates are combined with the polyimide layers facing each other so that the rubbing directions are antiparallel. (Hitachi Kasei Kogyo Co., Ltd.), and heat-cured at 120 ° C. for 2 hours to assemble a test liquid crystal display cell. Liquid crystal ZLI-1132 (trade name, manufactured by Merck) was sealed in the test liquid crystal display cell at room temperature to form a liquid crystal cell. The liquid crystal of T _NI (71
After heating for 1 hour at 120 ° C., which is the above temperature, the cell was measured for its Bretilt angle using laser light. Table 4 shows the polyamic acid used (synthesis example of producing this).
The results measured together with are shown.

[Table 4]

Next, using the polyamic acid solution (composition for liquid crystal alignment film) obtained in Synthesis Examples 3 to 6, an ITO transparent electrode was formed so as to have 640 × 200 dots in the same manner as described above. A polyimide layer is formed on the substrate which has been rubbed, and the surface of the
The cell was assembled so as to be twisted, and a liquid crystal adjusted by adding a chiral agent S-811 (manufactured by Merck) to the liquid crystal at room temperature was sealed, and heated at 120 ° C. for 1 hour to form a liquid crystal display device. Each of the obtained liquid crystal display devices has a 6
The display was able to be driven by 40 × 200 dots, and high display quality was obtained without occurrence of poor orientation such as domains.

[0068]

According to the liquid crystal alignment film of the first aspect,
A high pretilt angle can be obtained stably, and the liquid crystal holding substrate according to claim 2 can also exhibit an excellent pretilt angle.
The liquid crystal display element according to the third aspect also exhibits an excellent pretilt angle, and the liquid crystal alignment film according to the first aspect can be obtained from the liquid crystal alignment film material according to the fourth and fifth aspects.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of a polyimide from a polyamic acid obtained in Synthesis Example 3.

FIG. 2 is an infrared absorption spectrum of a polyamic acid obtained in Synthesis Example 3.

FIG. 3 is an infrared absorption spectrum of a polyimide from the polyamic acid obtained in Synthesis Example 4.

FIG. 4 is an infrared absorption spectrum of a polyamic acid obtained in Synthesis Example 4.

FIG. 5 is an infrared absorption spectrum of a polyimide from the polyamic acid obtained in Synthesis Example 5.

FIG. 6 is an infrared absorption spectrum of a polyamic acid obtained in Synthesis Example 5.

FIG. 7 is an infrared absorption spectrum of a polyimide from the polyamic acid obtained in Synthesis Example 6.

FIG. 8 is an infrared absorption spectrum of the polyamic acid obtained in Synthesis Example 6.

Continuing on the front page (72) Inventor Toshihiko Kato 48, Wadai, Tsukuba, Ibaraki Prefecture Inside the Tsukuba Development Laboratory, Hitachi Chemical Co., Ltd. (72) Inventor Yasuo Miyadera 48, Wadai, Tsukuba, Ibaraki Prefecture Tsukuba Development Co., Ltd. Inside the laboratory (72) Inventor Ninobu Sato 4-3-1-1, Higashicho, Hitachi City, Ibaraki Prefecture Inside the Yamazaki Plant, Hitachi Chemical Co., Ltd. (72) Inventor Shunichiro Uchimura 4-13-1, Higashimachi, Hitachi City, Ibaraki Prefecture Hitachi Chemical Yamazaki Factory Co., Ltd. (58) Field surveyed (Int.Cl. ⁶ , DB name) G02F 1/1337

Claims (5)

(57) [Claims] [Claim 1] [However, in Formula 1, tetravalent residue of R tetracarboxylic dianhydride, Rf is selected from the group consisting is -C _n F _2n-1 (where n 6 to 12
Which contains one double bond,
May be branched, hydrogen of the benzene ring is 1 carbon atoms
5 alkyl groups, C1-5 alkoxy groups,
Or a fluorine-containing polyimide comprising a structural unit represented by the following formula: 2. A liquid crystal holding substrate having the liquid crystal alignment film according to claim 1. 3. A liquid crystal display device comprising a liquid crystal sandwiching substrate provided with an electrode, wherein the liquid crystal alignment film according to claim 1 is provided on said electrode so as to face the liquid crystal. (4) [However, in Formula 2, tetravalent residue of R tetracarboxylic dianhydride, Rf is selected from the group consisting is -C _n F _2n-1 (where n 6 to 12
Which contains one double bond,
May be branched, hydrogen of the benzene ring is 1 carbon atoms
5 alkyl groups, C1-5 alkoxy groups,
Or a fluorine-containing polyamic acid comprising a structural unit represented by the formula: 5. A tetracarboxylic dianhydride and a compound represented by the formula [However, in reduction 3, Rf is, -C _n F _2n-1 indicates the (where n is an integer of 6-12), which includes one double bond, May be branched, hydrogen benzene ring, charcoal
Alkyl group having 1 to 5 carbon atoms, alkoxy having 1 to 5 carbon atoms
Group, may be substituted with fluorine, chlorine or bromine.
Each amino group is bonded to the benzene ring at an ortho-position, a meta-position, or a para-position with respect to an ether bond.] A polyimide system obtained by reacting a diamine compound containing a fluorine-containing aromatic diamine compound represented by the formula: A liquid crystal alignment film material containing a resin.