JP2002003454A - Novel diamino compound, polymer synthesized using the diamino compound, varnish, alignment film and liquid crystal display device using the polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel diamino compound which gives a polymer such as polyimide useful for applications such as a liquid crystal alignment film, a precursor thereof, a polymer such as polyimide obtained using the diamino compound, and It is an object to provide a varnish, a liquid crystal alignment film, and a liquid crystal display device using a polymer. The diamino compound is represented by the following general formula:
It is a compound represented by (1). Embedded image In the formula, each of R ¹ and R ² independently represents hydrogen or a linear or branched alkyl group having 1 to 3 carbon atoms, and Q represents a single bond or a substituted or unsubstituted 1 to 5 carbon chain. And m and l are each independently 0 or an integer of 1 to 4, and n is 0 or 1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel diamino compound, and more particularly to a novel diamino compound in which three or four benzene rings which may be substituted with a lower alkyl group have 1 to 1 carbon atoms.
The present invention relates to a polycyclic aromatic diamine linked by an alkylene group of No. 5, a raw material compound thereof, and a production method thereof. Also,
The present invention relates to a polymer obtained using the diamino compound as a raw material, a varnish using the polymer, an alignment film formed using the varnish, and a liquid crystal display device having the alignment film.

[0002]

2. Description of the Related Art Alignment films used in liquid crystal display devices include:
Various polymeric materials have been used. In these alignment films, liquid crystal alignment and electrical characteristics are particularly important, and a polymer material having characteristics suitable for the alignment film is being studied retroactively from its synthetic raw material. Various polyamide-based and polyimide-based alignment films have been proposed as alignment films from the viewpoints of liquid crystal alignment, electrical characteristics, heat resistance, types of liquid crystal compounds, and chemical resistance to detergents.

In general, polyimide is obtained by dehydration cyclization of a polyamic acid synthesized from a tetracarboxylic acid or a dianhydride thereof, a dicarboxylic acid diacid halide or the like (hereinafter referred to as "tetracarboxylic acids") and a diamino compound as a starting material. The polyamide is obtained by reacting a dicarboxylic acid or a diacid halide (hereinafter referred to as “dicarboxylic acids”) with a diamino compound. In addition, a polyamide imide can be obtained by reacting a mixture of a tetracarboxylic acid and a dicarboxylic acid, or a reaction of a tricarboxylic acid or a tricarboxylic acid monoanhydride (hereinafter, referred to as “tricarboxylic acids”) with a diamino compound.

As described above, diamino compounds are one of the important raw materials constituting polyamides, polyamideimides, and polyimides, and the physical properties of the above-mentioned polymers can be greatly changed depending on the structure.

[0005] Liquid crystal display elements using nematic liquid crystal are mainly used, and are TN type in which the liquid crystal is twisted by 90 °, STN type in which the liquid crystal is twisted by 180 ° or more.
IPS (In-Plane Swit) with improved visual characteristics by using a TFT type with a thin film transistor and a lateral electric field type
(ching) type has been put to practical use, and a display element of a type (VA mode) in which liquid crystal molecules are aligned almost vertically when no voltage is applied has also reached the stage of practical use.

[0006] As the demands for liquid crystal display devices have increased, the liquid crystal materials and alignment films constituting the display devices have also been required to have higher performance in various properties. The alignment film is required to have not only the liquid crystal alignment property but also a small residual charge, a large voltage holding ratio, a small current value, and electrical characteristics capable of imparting these reliability to a liquid crystal display device using the same. I have.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its main object to provide an alignment film having excellent electric characteristics. A polymer for forming such an alignment film, It is an object of the present invention to provide a varnish in which a polymer is dissolved in a solvent, a novel diamino compound and a diamine precursor which are raw materials of the polymer, and a method for producing the same. Further, the present invention provides
It is an object of the present invention to provide a liquid crystal display device having an alignment film formed using the varnish and having excellent electric characteristics such as a small residual charge, a large voltage holding ratio, and a small current value.

[0008]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have found that three or four benzene rings which may be substituted with a lower alkyl group have 1 to 5 carbon atoms. A polymer film formed from a polymer obtained by reacting a diamino compound component including a polycyclic diamino compound linked by an alkylene group with a tetracarboxylic acid, a dicarboxylic acid, a tricarboxylic acid or a mixture thereof, The inventors have found that an alignment film has both excellent liquid crystal alignment properties and electrical properties, and have completed the present invention.

That is, the present invention provides the following general formula (1)

Embedded image (Wherein, each of R ¹ and R ² represents a straight-chain or branched alkyl group having 1 to 3 carbon atoms which may be the same or different, and Q represents a single bond or a substituted group having 1 to 5 carbon atoms. Wherein m and l are each independently 0 or an integer of 1 to 4, and n is 0 or 1.

The present invention provides a compound represented by the formula (1)
A diamino compound in which H ₂ is bonded to the 4-position and the 4′-position of the phenyl group, wherein, in the general formula (1), m = 0 and l = 0
Wherein in the general formula (1), m =
1, a diamino compound wherein l = 1 and R ¹ and R ² are methyl groups, wherein in the above general formula (1), m = 0 and l = 1
A diamino compound wherein R ² is a methyl group; a diamino compound wherein m = 1, l = 0 and R ¹ is a methyl group in the general formula (1);
the diamino compound where n = 0, the diamino compound where n = 1 in the general formula (1), and the diamino compound where n = 1 and Q is a single bond in the general formula (1) Is included.

Another aspect of the present invention provides a compound represented by the following general formula (2):

Embedded image (Wherein, R ³ represents a hydrogen atom or an oxygen atom, m,
l, R ¹ , R ² , Q and n are as described above), which is a diamine precursor represented by the general formula (1).

Another aspect of the present invention is to provide a compound represented by the following general formula (2) in the presence of a reduction catalyst:

Embedded image (Wherein each symbol is as defined above), which reduces a triple bond and a nitro group of a starting compound represented by the following general formula:
(1)

Embedded image (Wherein each symbol is as described above).

Another aspect of the present invention is to provide a method for producing copper,
In the presence of a catalyst system in which a metal-based catalyst comprising a compound containing at least one element of tin, boron and magnesium and a palladium-based catalyst are added as essential components, and where necessary triphenylphosphine is added, the following general formula (3) )

Embedded image (Wherein, m, R ¹ , Q and n are as described above)
And an ethynylphenyl compound represented by the following general formula (4)

Embedded image (Wherein, l, R ² and R ³ are as described above, and X ¹ represents a bromine or iodine atom) A compound represented by the general formula (2) reacting with a halogenated benzene compound represented by the following formula: It is a manufacturing method of. Alternatively, in the presence of the above-mentioned catalyst, the following general formula (5)

Embedded image Wherein m, R ¹ , Q, n and X ¹ are as described above, and a compound represented by the following general formula (6)

Embedded image This is a method for producing a compound represented by the general formula (2) by reacting with an ethynylbenzene derivative represented by the following formula:

Another aspect of the present invention provides a compound represented by the following general formula (7):
(8), (9) and (10)

Embedded image [In the above formula, R ⁴ is an amine residue of the diamino compound represented by the general formula (1).

Embedded image (Where R ¹ , R ² , Q, m, l and n are as described above), a divalent group represented by R ^5, a tetravalent organic group, and R ⁶ Represents a divalent organic group, R ⁹ represents a trivalent organic group, R ⁷ represents hydrogen or a monovalent organic group, and R ⁸ represents hydrogen. Having a logarithmic viscosity number of 0.1 to 5 measured at 30 ° C. in N-methyl-pyrrolidone.
dl / g.

[0015] The invention of the above polymer is characterized in that the polymer has a general formula
Polyamide acid or polyamic acid ester containing a structural unit represented by (7), the polymer is a polyimide containing a structural unit represented by a general formula (8), and the polymer is represented by a general formula (9) A polyamide containing a structural unit, the polymer is a partially imidized polyamic acid or a partially imidized polyamic acid ester containing both the structural units represented by the general formulas (7) and (8), or the polymer is a compound represented by the general formula (10) And a polyamide imide containing a structural unit represented by formula (1): The polymer has the following general formula (12), (13), (14) and (15)

Embedded image (Wherein, R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ have the meanings described above, and R ¹⁰ is derived from a diamino compound other than the diamino compound represented by the general formula (1). A polymer containing a structural unit selected from the group consisting of divalent groups).

Another aspect of the present invention is to provide at least one of the above polymers.
A varnish comprising a seed and an organic solvent capable of dissolving the polymer. The varnish invention includes a varnish in which the organic solvent contains an aprotic polar solvent and a glycol-based solvent.

Still another aspect of the present invention is a liquid crystal display device having an alignment film formed using the varnish.

The invention of the above liquid crystal display element is represented by the following general formula (2)
3a), (23b) or (23c)

Embedded image (In the above formula, ring A represents trans-1,4-cyclohexylene, ring B is trans-1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene Or a fluorine-substituted 1,4-phenylene, ring C represents trans-1,4-cyclohexylene, 1,4-phenylene or a fluorine-substituted 1,4-phenylene, and Z _a
Single bond independently each _{(-), - CH 2 CH} 2 -, -
_{CH 2 CH 2 CH 2 CH 2} -, - COO -, - CF 2 O-,
—OCF ₂ — or —CH ＝ CH—, wherein _Ra is an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group, or any non-adjacent methylene group in the alkyl group or the fluorine-substituted alkyl group. -O- or -CH = C
Represents a substituted group in H-, X _a is F, Cl, -CF _{3,
-CF 2 H, -CFH 2, -OCF} 3, -OCF 2 H, -O
It represents CF ₂ CF ₂ H or -OCF ₂ CFHCF _3, L _a
And L _b each independently represent hydrogen or a fluorine atom), and the above-mentioned liquid crystal display device using a liquid crystal composition containing at least one liquid crystal compound represented by the formula:

The invention of the liquid crystal display device is represented by the following general formula (2)
4) or (25)

Embedded image (In the formula, R _a, the L _a and L _b represents the meanings as defined above, ring D is trans-1,4-cyclohexylene, 1,4-phenylene, 1,3-dioxane-2,5
-Diyl or pyrimidine-2,5-diyl, ring E represents trans-1,4-cyclohexylene, pyrimidine-2,5-diyl, 1,4-phenylene or fluorine-substituted 1,4-phenylene, F represents trans-1,4-cyclohexylene or 1,4-phenylene, rings D, E and F may be the same or different, and Z _b represents a single bond (−), —CH ₂ CH ₂ — or Represents -COO-, and _Xb represents -CN or -C≡C-CN;
q and r are each independently 0 or 1), and the above-mentioned liquid crystal display device using a liquid crystal composition containing at least one compound represented by the formula:

The invention of the liquid crystal display element is represented by the following general formula (2)
6a), (26b) or (26c)

Embedded image(In the above formula, ring A, R_a, Rings F and Z_bIs defined above
Z means _bAre the same or different
May be R_bIs an alkyl group having 1 to 10 carbon atoms,
A hydrogen-substituted alkyl group, or the aforementioned alkyl group or
Any non-adjacent methylene in a nitrogen-substituted alkyl group
Represents a group in which the group is substituted with -O- or -CH = CH-,
They are R_aAnd may be the same or different, and L_c
And L_dEach independently represents a hydrogen or fluorine atom
Represents, L_cAnd L_dAt least one of which has a fluorine atom
A liquid containing at least one liquid crystal compound represented by
The liquid crystal display device using the crystal composition is included.

According to the invention of the liquid crystal display element, any one of the above liquid crystal compositions or a liquid crystal composition containing at least two of the above liquid crystal compositions can be added to the following general formula (27a), (27b) or (27c)

Embedded image (In the above formula, ring A, R _a , ring E and R _b have the same meaning as defined above, each of ring A and ring E may be the same or different, and each of Z _c is independently A single bond, —CH ₂ CH ₂ —, —C≡C—, —CH ＝ CH— or —COO—), and a liquid crystal composition further containing at least one liquid crystal compound. The present invention also includes a liquid crystal display device and the above liquid crystal display device using any one of the above liquid crystal compositions and a liquid crystal composition containing at least one optically active compound.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION Diamino Compound The diamino compound of the present invention has the following general formula (1)

Embedded image It is represented by

The diamino compound of the present invention has the general formula (1) in which n is 0, is composed of three benzene rings linked by an ethylene (dimethylene) group, and the benzene rings at both ends are each substituted with an amino group. And n is 1, and two pairs of two benzene rings linked by an ethylene group further comprise four benzene rings linked by a linking group Q, and the benzene rings at both ends are each an amino group. Includes substituted compounds of general formula (1). There is no particular limitation on the substitution position by the amino group on the benzene ring at both ends, but it is preferable that the 4-position of the phenyl group is substituted.

In the general formula (1), the linking group Q is a single bond or an optionally substituted alkylene group having 1 to 5 carbon atoms, for example, methylene, ethylene (dimethylene), trimethylene (1,3-propylene), Tetramethylene (1,4
-Butene), linear alkylene groups such as pentamethylene (1,5-pentene); methylmethylene, ethylmethylene (1,
1-propane), dimethylmethylene (2,2-propane),
Substituted methylene groups such as propylmethylene (1,1-butane) and methylethylmethylene (2,2-butane); methylethylene (1,2-propylene), ethylethylene
(1,2-butene), 1,2-dimethylethylene (2,3-butene), 1,1-dimethylethylene, propylethylene
(1,2-pentene), 1-methyl-2-ethylethylene
Substituted ethylene groups such as (2,3-pentene), methylethylethylene (isopentene) and trimethylethylene;
Methyltrimethylene (1,3-butene), 2-methyltrimethylene, ethyltrimethylene (1,3-pentene), 2
-Alkylene groups such as -ethyltrimethylene, substituted 1,1-dimethyltrimethylene and substituted trimethylene groups such as 1,2-dimethyltrimethylene; 1-methyltetramethylene and substituted tetramethylene groups such as 2-methyltrimethylene; And the substituent may be further substituted with fluorine. Preferably it is a single bond or a linear alkylene group, more preferably a single bond or an ethylene group.

In the general formula (1), each of R ¹ and R ² may be the same or different and each may be a linear or branched alkyl group having 1 to 3 carbon atoms, specifically, a methyl group or an ethyl group. , A propyl group or an isopropyl group, m
And l are each independently 0 or an integer of 1 to 4, and the substitution position of each benzene ring with an alkyl group is not particularly limited.

In the general formula (1), 1,3-bis (4-aminophenethyl) benzene, 1,4-bis (3-aminophenethyl) benzene, 1,4 -Bis (2-aminophenethyl) benzene,
1,4-bis (4-aminophenethyl) -2-methylbenzene, 1,4-bis (4-aminophenethyl) -2,5-dimethylbenzene, 1,4-bis (4-amino-2-methylphenethyl) ) Benzene, 1,4-bis (4-amino-3-
Methylphenethyl) benzene, 1,4-bis (4-amino-2,3-dimethylphenethyl) benzene, [4- (4-amino-2-methylphenethyl) phenethyl] -4'-amino-3'-methylbenzene And a compound in which at least one selected from a methyl group, an ethyl group, a propyl group, and an isopropyl group is further introduced on each benzene ring.

In the general formula (1), as a 4-ring diamino compound wherein n = 1 and Q is a single bond, bis [4- (4-
Aminophenethyl) phenyl], bis [4- (3-aminophenethyl) phenyl], bis [4- (2-methylaminophenethyl) phenyl], bis [4- (4-aminophenethyl)
-2-methylphenyl], bis [4- (4-amino-2-
[Methylphenethyl) phenyl], [4- (4-aminophenethyl) phenyl] -4 '-(4-amino-2-methylphenethyl) benzene, and the like, and further methyl, ethyl, and propyl groups on each benzene ring And at least one compound selected from isopropyl groups.

In the general formula (1), n = 1 and the linking group Q
Is a methylene group having 1 carbon atom or a substituted methylene group;
Bis [4- (4-aminophenethyl) phenyl] methane, bis [4- (4-aminophenethyl) -3-methylphenyl] methane, bis [4- (4-amino-2-methyl) Phenethyl) phenyl] methane, 1,1
-Bis [4- (4-aminophenethyl) phenyl] ethane,
1,1-bis [4- (4-aminophenethyl) phenyl] propane, 2,2-bis [4- (4-aminophenethyl) phenyl] propane, 1,1-bis [4- (4-aminophenethyl) Phenyl] butane, 2,2-bis [4- (4-aminophenethyl) phenyl] butane, 1,1-bis [4- (4-aminophenethyl) phenyl] pentane, 2,2-bis [4-
Examples thereof include (4-aminophenethyl) phenyl] pentane and the like, and compounds in which an alkyl group having 1 to 3 carbon atoms is further introduced on each benzene ring.

For example, as a compound having a methyl group introduced on each benzene ring, [4- (4-aminophenethyl) -2-methylphenyl] methyl-4 '-(4-aminophenethyl) -3'-methyl Benzene, [4- (4-aminophenethyl) -2-methylphenyl] methyl-4'-
(4-aminophenethyl) benzene, [4- (4-aminophenethyl) -2-methylphenyl] methyl-4 '-(4-
Aminophenethyl) -3′-methylbenzene, [4- (4
-Aminophenethyl) -2,3-dimethylphenyl] methyl-4 '-(4-aminophenethyl) benzene, [4- (4
-Aminophenethyl) -2,6-dimethylphenyl] methyl-4 '-(4-aminophenethyl) benzene, [4-
(4-aminophenethyl) -2,5-dimethylphenyl] methyl-4 '-(4-aminophenethyl) benzene, [4-
(4-amino-3-methylphenethyl) -2,3-dimethylphenyl] methyl-4 '-(4-amino-3-methylphenethyl) -2'-methylbenzene, [4- (4-amino-2- Methylphenethyl) -2,3-dimethylphenyl] methyl-4 '-(4-amino-2-methylphenethyl) -3'-methylbenzene, [4- (4-aminophenethyl) -2,5-dimethylphenyl] Methyl-4 '-(4
-Aminophenethyl) -2'-methylbenzene, [4-
(4-aminophenethyl) -2,3-dimethylphenyl]
Methyl-4 '-(4-amino-3-methylphenethyl)
-3'-methylbenzene, [4- (4-aminophenethyl) -2,3-dimethylphenyl] methyl-4 '-(4-
Aminophenethyl) -2 ', 3'-dimethylbenzene,
[4- (4-aminophenethyl) -2,6-dimethylphenyl] methyl-4 '-(4-aminophenethyl) -2',
3'-dimethylbenzene, [4- (4-aminophenethyl) -2,6-dimethylphenyl] methyl-4 '-(4-
Aminophenethyl) -2 ', 5'-dimethylbenzene,
[4- (4-aminophenethyl) -2,5-dimethylphenyl] methyl-4 '-(4-aminophenethyl) -2',
3'-dimethylbenzene, [4- (4-aminophenethyl) -2,5-dimethylphenyl] methyl-4 '-(4-
(Aminophenethyl) -2 ', 5'-dimethylbenzene.

In the general formula (1), as a compound wherein n = 1 and the linking group Q is ethylene (dimethylene) having 2 carbon atoms or a substituted ethylene group, 1,2-bis [4- (4-
Aminophenethyl) phenyl] ethane, 1,2-bis [4-
(4-aminophenethyl) phenyl] methylethane, 1,2
-Bis [4- (4-aminophenethyl) phenyl] ethylethane, 1,2-bis [4- (4-aminophenethyl) phenyl] -1,1-dimethylethane, 1,2-bis [4- (4-
Aminophenethyl) phenyl] -1,2-dimethylethane, 1,2-bis [4- (4-aminophenethyl) phenyl] propylethane, 1,2-bis [4- (4-aminophenethyl) phenyl] methylethyl Examples include ethane and the like, and compounds in which an alkyl group having 1 to 3 carbon atoms is further introduced on each benzene ring.

Further, the linking group Q is replaced by the above-mentioned single bond, methylene group and ethylene group, trimethylene having 3 carbon atoms,
1-methyltrimethylene, 2-methyltrimethylene, 1
-Ethyltrimethylene, 2-ethyltrimethylene; tetramethylene having 4 carbon atoms, 1-methyltetramethylene, 2
-Methyltetramethylene; and compounds having 5 carbon atoms as pentamethylene.

Among these, the following compounds can be exemplified as useful diamino compounds. 1,4-bis (4
-Aminophenethyl) benzene, 1,4-bis (4-amino-2-methylphenethyl) benzene, 1,4-bis (4
-Aminophenethyl) -2-methylbenzene, 1,4-bis (4-aminophenethyl) -2,5-dimethylbenzene, bis [4- (4-aminophenethyl) phenyl], bis
[4- (4-amino-2-methylphenethyl) phenyl], bis [4- (4-aminophenethyl) phenyl] methane, bis [4- (4-amino-2-methylphenethyl) phenyl] methane, bis [ 4- (4-amino-3-methylphenethyl) phenyl] methane, bis [4- (4-amino-
2,3-dimethylphenethyl) phenyl] methane, bis [4
-(4-amino-2,5-dimethylphenethyl) phenyl]
Methane, bis [4- (4-aminophenethyl) -2-methylphenyl] methane, bis [4- (4-aminophenethyl)
-3-methylphenyl] methane, bis [4- (4-aminophenethyl) -2,3-dimethylphenyl] methane, 1,2
-Bis [4- (4-aminophenethyl) phenyl] ethane,
1,2-bis [4- (4-amino-2-methylphenethyl)
Phenyl] ethane, 1,2-bis [4- (4-amino-3-
Methylphenethyl) phenyl] ethane, 1,2-bis [4-
(4-Amino-2,3-dimethylphenethyl) phenyl] ethane, 1,2-bis [4- (4-amino-2,5-dimethylphenethyl) phenyl] ethane, 1,2-bis [4- (4 −
Aminophenethyl) -2-methylphenyl] ethane, 1,
2-bis [4- (4-aminophenethyl) -3-methylphenyl] ethane, 1,2-bis [4- (4-aminophenethyl) -2,3-dimethylphenyl] ethane, 2,2-bis
[4- (4-aminophenethyl) phenyl] propane, 2,
2-bis [4- (4-amino-2-methylphenethyl) phenyl] propane, 2,2-bis [4- (4-amino-3-
Methylphenethyl) phenyl] propane, 2,2-bis [4
-(4-amino-2,3-dimethylphenethyl) phenyl]
Propane, 2,2-bis [4- (4-amino-2,5-dimethylphenethyl) phenyl] propane, 2,2-bis [4-
(4-aminophenethyl) -2-methylphenyl] propane, 2,2-bis [4- (4-aminophenethyl) -3-methylphenyl] propane, 2,2-bis [4- (4-aminophenethyl) -2,3-dimethylphenyl] propane,
3-bis [4- (4-aminophenethyl) phenyl] propane, 1,3-bis [4- (4-amino-2-methylphenethyl) phenyl] propane, 1,3-bis [4- (4-amino -3-methylphenethyl) phenyl] propane, 1,3
-Bis [4- (4-amino-2,3-dimethylphenethyl)
Phenyl] propane, 1,3-bis [4- (4-amino-
2,5-dimethylphenethyl) phenyl] propane, 1,3
-Bis [4- (4-aminophenethyl) -2-methylphenyl] propane, 1,3-bis [4- (4-aminophenethyl) -3-methylphenyl] propane, 1,3-bis [4-
(4-aminophenethyl) -2,3-dimethylphenyl] propane, 1,4-bis [4- (4-aminophenethyl) phenyl] butane, 1,4-bis [4- (4-amino-2-methyl) Phenethyl) phenyl] butane, 1,4-bis [4- (4
-Amino-3-methylphenethyl) phenyl] butane;
1,4-bis [4- (4-amino-2,3-dimethylphenethyl) phenyl] butane, 1,4-bis [4- (4-amino-2,5-dimethylphenethyl) phenyl] butane, 4
-Bis [4- (4-aminophenethyl) -2-methylphenyl] butane, 1,4-bis [4- (4-aminophenethyl) -3-methylphenyl] butane, 1,4-bis [4-
(4-aminophenethyl) -2,3-dimethylphenyl] butane, 1,5-bis [4- (4-aminophenethyl) phenyl] pentane, 1,5-bis [4- (4-amino-2-methyl) Phenethyl) phenyl] pentane, 1,5-bis [4-
(4-Amino-3-methylphenethyl) phenyl] pentane, 1,5-bis [4- (4-amino-2,3-dimethylphenethyl) phenyl] pentane, 1,5-bis [4- (4-
Amino-2,5-dimethylphenethyl) phenyl] pentane, 1,5-bis [4- (4-aminophenethyl) -2-methylphenyl] pentane, 1,5-bis [4- (4-aminophenethyl)- 3-methylphenyl] pentane, 1,5-
Bis [4- (4-aminophenethyl) -2,3-dimethylphenyl] pentane.

The following compounds are particularly useful as raw materials for the synthesis of polymers. 1,4-bis (4-aminophenethyl) benzene, bis [4- (4-aminophenethyl) phenyl], bis [4- (4-aminophenethyl) phenyl] methane, 1,2-bis [4- (4 -Aminophenethyl) phenyl] ethane, 2,2-bis [4- (4-aminophenethyl)
Phenyl] propane, 1,3-bis [4- (4-aminophenethyl) phenyl] propane, 1,4-bis [4- (4-aminophenethyl) phenyl] butane, 1,5-bis [4-
(4-aminophenethyl) phenyl] pentane, 1,4-bis (4-amino-2-methylphenethyl) benzene, bis
[4- (4-Amino-2-methylphenethyl) phenyl], bis [4- (4-amino-2-methylphenethyl) phenyl] methane, 1,2-bis [4- (4-amino-2-methyl) Phenethyl) phenyl] ethane, 2,2-bis [4-
(4-Amino-2-methylphenethyl) phenyl] propane, 1,3-bis [4- (4-amino-2-methylphenethyl) phenyl] propane, 1,4-bis [4- (4-amino-2 -Methylphenethyl) phenyl] butane, 1,5-
Bis [4- (4-amino-2-methylphenethyl) phenyl] pentane.

Diamine Precursor The diamine precursor of the present invention has the following general formula (2)

Embedded image (Wherein R ³ represents hydrogen or oxygen, m, l, R ¹ , R
² , Q and n are as described above), and hydrogen reduction in the presence of a reduction catalyst produces the diamino compound represented by the general formula (1). .

The precursor compound is represented by the general formula (2) wherein n is 0
A diamino compound and a dinitro compound having three benzene rings connected by a triple bond (ethynylene group), and the benzene rings at both ends are respectively substituted with an amino group or a nitro group, and n is 1. A diamino compound and a dinitro compound in which two pairs of two benzene rings linked by a bond further comprise four benzene rings linked by a linking group Q, and the benzene rings at both ends are respectively substituted with an amino group or a nitro group. Is included. There is no particular limitation on the substitution position by an amino group or a nitro group on the benzene ring at both ends, but it is preferable that the 4-position of the phenyl group is substituted.

Production of diamino compound By reducing the compound represented by the above general formula (2) with hydrogen, when the compound is a diamino compound, a triple bond is formed.
In the case of a dinitro compound, the triple bond and the nitro group are reduced to produce the desired diamino compound represented by the general formula (1).

Hydrogen reduction of the diamine precursor represented by the general formula (2) is carried out in the presence of a reduction catalyst such as platinum / carbon, platinum oxide, Raney nickel, Pd / carbon or the like, in the presence of an aromatic solvent such as toluene or xylene. In an alcohol solvent such as methanol, ethanol, etc., an ether solvent such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, an ester solvent such as ethyl acetate, an organic solvent such as tetrahydrofuran, acetic acid, etc. , Sulfuric acid, phosphoric acid, acetic acid,
Addition of an inorganic or organic acid such as oxalic acid or trifluoroacetic acid can be carried out at normal pressure or under pressure at a temperature of 0 to 150 ° C.

Production of Diamine Precursor The diamino or dinitro compound of the diamine precursor is prepared from a metal catalyst comprising a compound containing at least one of copper, tin, boron and magnesium in an organic solvent; In the presence of a catalyst system containing a catalyst as an essential component and optionally adding triphenylphosphine, the following general formula (3)

Embedded image (Wherein, m, R ¹ , Q and n are as described above)
And an ethynylphenyl compound represented by the following general formula (4)

Embedded image (Wherein l, R ² and R ³ are as described above, and X ¹ represents bromine or iodine) or reacted with a halogenated benzene compound represented by the following general formula (5)

Embedded image Wherein m, R ¹ , Q, n and X ¹ represent the same meaning as defined above, and a compound represented by the following general formula:
(6)

Embedded image (Wherein l, R ² and R ³ are as described above), and can be synthesized by reacting with an ethynylbenzene derivative represented by the following formula:

Each of the starting compounds represented by the general formulas (3), (4), (5) and (6) is a known compound, and can be easily synthesized by a known method. Can also be easily obtained.

In the above reaction, a metal catalyst, palladium
System catalyst and triphenylphosphine (Ph_Three3 consisting of P)
Different catalysts are used. Metal catalyst and palladium catalyst
The medium is an essential component, and triphenylphosphine is necessary
More. That is, palladium-based catalyst
Kis (triphenylphosphine) palladium ((Ph_ThreeP)_FourP
When using d), do not add triphenylphosphine.
You may not. However, using other palladium compounds
Need to add triphenylphosphine.
You. As a palladium catalyst, tetrakis (triphenyl)
Ruphosphine) palladium ((Ph_ThreeP)_FourPd), Screw (Trif
Phenylphosphine) dichloropalladium ((Ph_ThreeP)_TwoPdC
l _Two), Palladium carbon (Pd / C), palladium acetate
(Pd (OAc)_Two) Can be used. Reactivity, cheap
(Ph_ThreeP)_TwoPdCl_TwoIs preferably used
Is done.

As the metal-based catalyst, a metal catalyst such as copper, tin, boron and magnesium, an inorganic metal catalyst such as copper iodide, and an organic metal catalyst such as copper acetate can be used. In particular, copper iodide is preferably used in terms of reactivity, safety and economy.

As the reaction solvent, amine solvents such as triethylamine, diethylamine, diisopropylamine and the like are used, and triethylamine is particularly preferably used. In order to increase the solubility of the starting compound and the reaction product, an ether solvent such as tetrohydrofuran or ethylene glycol dimethyl ether which is inactive with respect to the starting compound and the reaction product may be added to the amine solvent.

In the above reaction solvent, the compound represented by the general formula (3) and the compound represented by the general formula (4), or the compound represented by the general formula (5) and the compound represented by the general formula (5) 6) The compound represented by the formula (6) is mixed by stirring.
After adding various kinds of catalysts and reacting at a temperature of room temperature to 150 ° C., after the reaction is completed, the reaction mixture is poured into ice, washed with water, extracted, distilled, the solvent is separated, and the compound is purified by the general formula. A diamine precursor comprising a diamino compound or a dinitro compound in which a benzene ring represented by (2) is connected by a triple bond is obtained.

The amount of each catalyst added at the time of the reaction is 0.001 to 0.001 of the palladium catalyst with respect to the compound represented by the general formula (3) or the compound represented by the general formula (6) as a substrate. 1 equivalent, preferably 0.001 to 0.01 equivalent, metal catalyst 0.001 to 0.1 equivalent, preferably 0.001 to 0.01
Eq, and Ph ₃ P0.001~0.5 equivalents, preferably 0.001 to 0.05 equivalents.

Polymer The diamino compound represented by the general formula (1) is used as a diamine component to be introduced into polyamides, polyamic acids, polyamic esters, polyimides, polyamideimides, and random and block copolymers thereof. And imparts to these polymers both properties derived from the presence of the benzene ring and properties derived from linear alkyl.

The polymer of the present invention has the above-mentioned general formula in a molecular chain.
Polymers containing at least one selected from structural units represented by the following general formulas (7), (8), (9) and (10) derived from the diamino compound represented by (1) Having a logarithmic viscosity of 0.1 to 0.1 in N-methyl-2-pyrrolidone, measured at 30 ° C.
The polymer is 5 dl / g. Here, the logarithmic viscosity number is ηinh represented by the following equation. ηinh = ln (η / η ₀ ) / C (where η and η ₀ use an Ubbelohde viscometer,
It is a value measured at a temperature of 30 ± 0.01 ° C. η is the solution,
η ₀ is the measured value of the solvent, and C is the solution concentration of 0.5 g / d
l. However, in the case of a polyimide insoluble in N-methyl-2-pyrrolidone, the measurement was carried out using a polyamic acid or a polyamic acid ester as its precursor.
When the logarithmic viscosity number is less than 0.1 dl / g, the coating properties are poor, and when it exceeds 5 dl / g, the solubility in a solvent is poor, and neither is preferred. “Polymer A” is a homopolymer composed of only one compound belonging to any of the following structural units represented by the general formula, a copolymer composed of two or more compounds, and two types of the following structural units. It means a random or block copolymer containing the above, or a random or block copolymer containing one or more of the following structural units and a structural unit not belonging to any of the following structural units. On the other hand, the following general formula (7) containing a diamine residue of the diamino compound represented by the general formula (1) in the molecular chain,
A polymer that does not contain any of the structural units represented by (8), (9) and (10) is generically referred to as "Polymer B".

[0047]

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The above general formulas (7), (8), (9) and (10)
In the formula, R ⁴ represents a divalent group represented by the following general formula (11), which is a diamine residue of the diamino compound represented by the general formula (1).

Embedded image (In the formula, each symbol is as described above.)

[0049] In the general formula (7) and (8), R ⁵ is a tetravalent organic residue group derived from tetracarboxylic acids, they may be the same or different. Many aliphatic, alicyclic, and aromatic compounds are known as tetracarboxylic acids, and there is no particular limitation as long as they are tetravalent organic residues.

For example, aliphatic tetracarboxylic dianhydrides include ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, pentane tetracarboxylic dianhydride, hexane tetracarboxylic dianhydride, heptane tetracarboxylic dianhydride. Acid dianhydride;

As the alicyclic tetracarboxylic dianhydride,
Cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, bicyclo (2,2,2) -oct (7) -ene-2,3,5,6-tetracarboxylic dianhydride, cyclohexane- 1,2,5,6-tetracarboxylic dianhydride, 3,4,3 ', 4'-dicyclohexyltetracarboxylic dianhydride, 3,3'-bicyclohexyl-
1,1 ', 2,2'-tetracarboxylic dianhydride, 2,3,
5-tricarboxycyclopentylacetic acid dianhydride, 5-
(2,5-dioxotetrahydrofuryl) -3-methyl-
3-cyclohexene-1,2-dicarboxylic dianhydride,
1,3,3a, 4,5,9b-Hexahydro-5-tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,
2, -c] -Furan-1,3-dione, 3,5,6-tricarboxynorbonane-2-acetic acid dianhydride, 2,3,4,5
- tetrahydrofuran tetracarboxylic acid dianhydride, tetracyclo [6,2,1 ^3.6, 0 ^2.7] Dodekano -4,5,9,10-
Tetracarboxylic acid dianhydride, 3,4-dicarboxy-
1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, furantetracarboxylic dianhydride, thiophenetetracarboxylic dianhydride, which are substituted with lower alkyl groups such as methyl group and ethyl group And the like.

As the aromatic tetracarboxylic dianhydride,
Pyromellitic dianhydride, 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, naphthalene dianhydride such as 2 3,3,4,4'-biphenylsulfonetetracarboxylic dianhydride, 3,3,4,4'-biphenylether tetracarboxylic dianhydride, such as 3,3,6,7-naphthalene dianhydride 3,3 ', 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride,
4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride,
4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoropyridene diphthalic dianhydride, 3,3', 4,4'-biphenyl Tetracarboxylic dianhydride, bis (phthalic acid) phenylsulfin oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-
Bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalan) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalan) -4,4'-diphenylmethane dianhydride, pyrazinetetracarboxylic Acid dianhydride, pyridinetetracarboxylic dianhydride and the like. Examples of the tetracarboxylic acids further include tetracarboxylic acids and dicarboxylic diacid halides corresponding to the above acid dianhydrides.

The general formula (7) is formed by reacting the diamino compound represented by the general formula (1) with the tetracarboxylic acid and a polyamic acid produced by reacting the polyamic acid with an alcohol. It represents a structural unit of a polyamic acid ester, and the general formula (8) represents a structural unit of a polyimide formed by dehydrating and ring-closing a polyamic acid having the structural unit represented by the general formula (7).

R ⁷ in the general formula (7) is hydrogen or a monovalent organic residue of an alcohol. The alcohol may be any one which can react with a carboxyl group of a polyamic acid to form an ester. There is no particular limitation.

Known methods for producing polyamic acid from a diamino compound and a tetracarboxylic acid, producing a polyamic acid ester from a polyamic acid and an alcohol, and producing a polyamic acid ester from a diamino compound and a tetracarboxylic acid ester are known. Can be adopted. Usually, a polyamic acid is obtained by reacting a diamino compound with a tetracarboxylic acid at a temperature of 0 to 100 ° C. in an aprotic polar organic solvent such as N-methyl-2-pyrrolidone.

Further, the polyamide acid containing the structural unit represented by the general formula (8) is formed by heating or dehydrating and closing the polyamic acid containing the structural unit represented by the general formula (7) by using a catalyst. I do. By setting the imidation ratio of the polyamic acid to less than 100%, a partially imidized polyamic acid is obtained, and a diamino compound and / or an acid anhydride group present at the end of the polyimide chain are further added to the reactive amino group and / or acid anhydride group. A partially imidized polyamic acid having both an imide group and an amic acid group in one molecule can be obtained by reacting a tetracarboxylic acid or the like. These partially imidized polyamic acids are also included in the present invention.

When a polyimide containing the structural unit represented by the general formula (8) is used for a varnish such as a liquid crystal aligning agent, the polyimide is required to be soluble in an organic solvent.
Organic solvent-soluble polyimides suitable for this purpose include those wherein R ⁵ in the general formula (8) is, for example, butanetetracarboxylic dianhydride, tricarboxycyclopentylacetic dianhydride, or 5- (2,5-dioxo). Tetrahydrofuryl) -3-
Methylcyclohexene, 3,5,6-tricarboxynorbonane-2-acetic acid dianhydride, tetracyclo [6,2,
1 ^3.6 0 ^2.7] Dodekano -4,5,9,10- tetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4
Aliphatic or aliphatic such as tetrahydronaphthalene-1-succinic dianhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, diphenylsulfonetetracarboxylic dianhydride, siloxane group-containing tetracarboxylic dianhydride; It is preferably a residue of an alicyclic tetracarboxylic dianhydride or an aromatic tetracarboxylic dianhydride.

R ⁶ in the general formula (9) is a divalent organic group which is a residue of a dicarboxylic acid. As dicarboxylic acids, many of aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, and heterocyclic dicarboxylic acids are known, and if they are divalent organic groups that are carboxylic acid residues, particularly, No restrictions.

For example, as the aliphatic dicarboxylic acid, malonic acid, oxalic acid, dimethylmalonic acid, succinic acid, fumaric acid,
Glutaric acid, adipic acid, muconic acid, 2-methyl adipic acid, trimethyl adipic acid, pimelic acid, 2,2-dimethyl glutaric acid, 3,3-diethyl succinic acid, azelaic acid, sebacic acid, suberic acid and the like. .

As alicyclic dicarboxylic acids, 1,1-cyclopropanedicarboxylic acid, 1,2-cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, 1,2-
Cyclobutanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 3,4-diphenyl-1,2-cyclobutanedicarboxylic acid, 2,4-diphenyl-1,3-cyclobutanedicarboxylic acid, 3,4-bis (2-hydroxyphenyl )
-1,2-cyclobutanedicarboxylic acid, 2,4-bis (2
-Hydroxyphenyl) -1,3-cyclobutanedicarboxylic acid, 1-cyclobutene-1,2-dicarboxylic acid, 1-
Cyclobutene-3,4-dicarboxylic acid, 1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid Acid, 1,3-cyclohexanedicarboxylic acid, 1,
4-cyclohexanedicarboxylic acid, 1,4- (2-norbornene) dicarboxylic acid, norbornene-2,3-dicarboxylic acid, bicyclo [2.2.2] octane-1,4-dicarboxylic acid, bicyclo [2.2. 2] octane-2,3-dicarboxylic acid, 2,5-dioxo-1,4-bicyclo [2.2.2] octanedicarboxylic acid, 1,3-adamantanedicarboxylic acid, 4,8-dioxo-1,3 -Adamantane dicarboxylic acid, 2,6-spiro [3.3] heptane dicarboxylic acid, 1,
3-adamantane acetic acid, camphoric acid and the like.

As aromatic dicarboxylic acids, o-phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, 5-aminoisophthalic acid, 5-hydroxyisophthalic acid, 2,5- Dimethyl terephthalic acid, tetramethyl terephthalic acid, 1,4
-Naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-anthracenedicarboxylic acid, 1,4-anthraquinonedicarboxylic acid, 2,5-biphenyl Dicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 1,5-biphenylenedicarboxylic acid, 4,4 "-terphenyldicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylethanedicarboxylic acid, 4,4'-diphenylpropanedicarboxylic acid,
4'-diphenylhexafluoropropane dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid,
4'-bibenzyldicarboxylic acid, 4,4'-stilbenecarboxylic acid, 4,4'-trandicarboxylic acid, 4,4'-
Carbonyl dibenzoic acid, 4,4'-sulfonyl dibenzoic acid, 4,4'-dithiodibenzoic acid, p-phenylene diacetate, 3,3'-p-phenylenedipropionic acid, 4-carboxycinnamic acid, p Phenylenediacrylic acid, 3,
3 '-[4,4'-(methylenedi-p-phenylene)] dipropionic acid, 4,4 '-[4,4'-(oxydi-p-phenylene)] dipropionic acid, 4,4 '-[ 4,4 '-(oxydi-p-phenylene)] dibutyric acid, (isopropylidenedi-
(p-phenylenedi) oxodibutyric acid, bis (p-carboxyphenyl) dimethylsilane, 1,5- (9-oxofluorene) dicarboxylic acid, 3,4-furandicarboxylic acid,
5-thiazoledicarboxylic acid, 2-phenyl-4,5-
Thiazole dicarboxylic acid, 1,2,5-thiadiazole-
3,4-dicarboxylic acid, 1,2,5-oxadiazole-
3,4-dicarboxylic acid, 2,3-pyridinedicarboxylic acid,
2,4-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, 3,6
-Pyridinedicarboxylic acid and the like. The dicarboxylic acids further include the above-mentioned dicarboxylic acid anhydrides and carboxylic acid monoacid halides.

The polyamide having the structural unit represented by the general formula (9) is obtained by converting the diamino compound represented by the general formula (1) and a dicarboxylic anhydride to a triphenoxyphosphine.
Condensing agents such as (PhO) ₃ P, dichlorophenoxyphosphine (PhO) PCl ₂ , dichlorophenylphosphine oxide PhPOCl ₂ and pyridine and dimethyl sulfoxide, N
-In the presence of a solvent such as methylpyrrolidone, N, N-dimethylformamide or N, N-dimethylacetamide
It can be produced by reacting in the range of 20 to 300 ° C. If the reactivity is low, dicarboxylic acid dihalide may be used instead of dicarboxylic anhydride.

In the general formula (10), R ⁸ has the same meaning as described above, and R ⁹ represents a trivalent organic group derived from tricarboxylic acids, which may be the same or different. As tricarboxylic monoanhydrides, aliphatic tricarboxylic monoanhydrides, alicyclic tricarboxylic monoanhydrides, aromatic tricarboxylic monoanhydrides, and many heterocyclic tricarboxylic monoanhydrides are known, from which There is no particular limitation as long as it is a trivalent organic group derived.

In the present invention, the above general formulas (7), (8),
A copolymer containing only the structural units represented by (9) and (10) or one or more of them and the structural units represented by the following general formulas (12), (13), (14) and (15) The union is included in "Polymer A".

The polymer of the present invention also includes a mixture of polymer A and polymer B. The polymer of the present invention has the general formula
At least 1 mol% of at least one structural unit represented by (7), (8), (9) and (10), preferably 20% or more.
Only the polymer A containing at least 50 mol%, more preferably at least 50 mol%, or a mixture of the polymer A and the polymer B is included. Further, when the polymer of the present invention is used as a liquid crystal alignment film, polyimide is preferred. However, not only completely imidized polyimide but also partially imidized polyamic acid or partially imidized polyamic acid ester in which the structure of the precursor is partially left is preferable. Therefore, as the polymer used in the varnish for preparing the liquid crystal alignment film, polyimide or a precursor thereof is preferable.If the polyimide is soluble in a solvent, a polyimide solution is used.If insoluble, the precursor is a polyamic acid or polyamic acid ester. Is preferably used. When the polymer used for the liquid crystal alignment film is expressed in more detail using the structural unit, the structural unit (8)
Or only a part of the structural unit (7),
A polymer having a structure replaced with one or more structural units selected from the group consisting of (12) and (13). However, a polymer composed of other structural units is not excluded as the liquid crystal alignment film, and an optimum structure is selected depending on the application.

[0066]

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The above general formulas (12), (13), (14) and (15)
In the formula, R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ have the above-mentioned meanings, and R ⁵ , R ⁶ , R ⁵ , R ⁶ ,
It may be the same as or different from R ⁷ , R ⁸ and R ⁹ . R
¹⁰ represents a divalent organic group which is a diamine residue of the diamino compound represented by the general formula (1).

As diamino compounds other than the diamino compound represented by the general formula (1), many diamines such as aliphatic diamine, alicyclic diamine, aromatic diamine, silyloxy group-containing diamine, and fluorine-substituted diamine are known. R ¹⁰ is not particularly limited as long as it is a divalent group which is a residue of these diamines.

Examples of the aliphatic diamino compound include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine and the like, and alkylenediamines having an oxygen atom in the alkylene group.

As the alicyclic diamino compound, for example, 1,4-diaminodicyclohexane, 1,3-bis
(Aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 4,4'-diaminodicyclohexylmethane, bis (2-methyl-4-aminocyclohexyl) methane, isophoronediamine, 2,5-bis (aminomethyl ) -Bicycloheptane, 2,6-bisaminomethyl-bicycloheptane, 2,3-diaminobicyclo [2,
2,1] heptane, 2,5-diaminobicyclo [2,2,1]
Heptane, 2,6-diaminobicyclo [2,2,1] heptane, 2,7-diaminobicyclo [2,2,1] heptane, 2,2
3-diamino-7-azabicyclo [2,2,1] heptane,
2,5-diamino-7-azabicyclo [2,2,1] heptane, 2,6-diamino-7-azabicyclo [2,2,1] heptane, 2,3-diamino-7-thiabicyclo [2,2,
1] heptane, 2,5-diamino-7-thiabicyclo [2,
2,1] heptane, 2,6-diamino-7-thiabicyclo
[2,2,1] heptane, 2,3-diaminobicyclo [2,2,
2] octane, 2,5-diaminobicyclo [2,2,2] octane, 2,6-diaminobicyclo [2,2,2] octane,
2,5-diaminobicyclo [2,2,2] octane-7-ene, 2,5-diamino-7-azabicyclo [2,2,2] octane, 2,5-diamino-7-oxabicyclo [2,5- Two,
2] octane, 2,5-diamino-7-thiabicyclo [2,
2,2] octane, 2,6-diaminobicyclo [3,2,1]
Octane, 2,6-diaminoazabicyclo [3,2,1] octane, 2,6-diaminooxabicyclo [3,2,1] octane, 2,6-diaminothiabicyclo [3,2,1] octane, 2,6-diaminobicyclo [3,2,2] nonane,
6-diaminobicyclo [3,2,2] nonan-8-ene,
2,6-diamino-8-azabicyclo [3,2,2] nonane, 2,6-diamino-8-oxabicyclo [3,2,2]
Nonane, 2,6-diamino-8-thiabicyclo [3,2,
2] nonane and the like.

As the aromatic diamino compound, for example, 2,2-bis (4-aminophenyl) propane, 2,6
-Diaminopyridine, bis- (4-aminophenyl) diethylsilane, bis- (4-aminophenyl) diphenylsilane, bis- (4-aminophenyl) ethylphosphine oxide, bis- (4-aminophenyl) -N-butylamine N, N-bis- (4-aminophenyl) -N-methylamine, N- (3-aminophenyl) -4-aminobenzamide, 3,3'-diaminodiphenylmethane, 3,
3'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfone, 2,2-bis (3-aminophenyl) propane, 1,3-bis (3-aminophenyl) propane, 3,3'-diamino Diphenyl sulfide, 2,3,
5,6-tetramethyl-p-phenylenediamine, 2,5
-Dimethyl-p-phenylenediamine, p-phenylenediamine, m-phenylenediamine, p-xylenediamine, m-xylenediamine, p-xylylenediamine, m-xylylenediamine, 2,4-diaminotoluene, 2,6 -Diaminotoluene, 1,2-bis (3-diaminophenyl) ethane, 1,1-bis (3-diaminophenyl) ethane, 4,4'-diaminodiphenylhexafluoropropane, 2,2-bis (4-amino Phenyl) hexafluoropropane, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl sulfide, 4,4 '
-Diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, bis [4- (4-aminophenoxy) phenyl]
Methane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-amino Phenoxy) phenyl] propane, 2,2-bis [4- (4-
Aminophenoxy) phenyl] propane, 2,2-bis [4
-(4-aminophenoxy) phenyl] butane, 4,4'-
Bis (4-aminophenoxy) diphenyl ketone, bis
[4- (4-aminophenoxy) phenyl] sulfone, bis
[4- (4-aminophenoxy) phenyl] sulfide,
1,3-bis [4- (4-aminophenoxy) phenyl] benzene, 1,4-bis [4- (4-aminophenoxy) phenyl] benzene, 4,4'-bis [4- (4-aminophenoxy) ) Phenyl] biphenyl, 1,2-bis [4- (4-aminophenoxy) phenyl] cyclohexane, 1,3-bis [4- (4-aminophenoxy) phenyl] cyclohexane, 1,4-bis [4- ( 4-aminophenoxy) phenyl] cyclohexane, bis [4- (4-aminophenoxy)
Phenyl] hexafluoropropane, 2,2-bis [4-
(2-Aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (3-carbamoyl-4-aminophenoxy) [Phenyl] hexafluoropropane, 2,2-bis- (3-sulfamoyl-
4-aminophenyl) hexafluoropropane, 2,2-
Bis- (3-carboxy-4-aminophenyl) hexafluoropropane, 2,2-bis [4- (3-sulfamoyl-4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (3 -Carboxy-4-aminophenoxy) phenyl] hexafluoropropane,
3-bis [2,2- [4- (4-aminophenoxy) phenyl] hexafluoroisopropyl] benzene, 2,4-bis (β-amino-t-butyl) toluene, bis (p-β-
Methyl-γ-aminopentyl) benzene, bis p- (1,
1-dimethyl-5-aminopentyl) benzene, bis (p
-Β-amino-t-butylphenyl) ether, bis (4
-Aminobenzoyloxy) methane, bis (4-aminobenzoyloxy) ethane, bis (4-aminobenzoloxy)
Propane, bis (4-aminobenzoyloxy) cyclohexane and the like, and the benzene ring of these aromatic diamino compounds is a lower alkyl group such as a methyl group, an ethyl group,
Examples thereof include diamino compounds further substituted with halogen atoms such as F and Cl.

In particular, an alignment film for a liquid crystal display device formed by using a polymer synthesized from a diamino compound having a side chain group having 3 or more, preferably 6 or more carbon atoms has a large pretilt angle for liquid crystal molecules. give.

The pretilt angle tends to increase as the length of the side group of the diamino compound used in the synthesis of the polymer increases, and to increase as the amount of the diamino compound having the longer side group increases. Therefore, it can be adjusted by the length of the side chain group of the diamino compound or the amount of the diamino compound having a long side chain group.

Various diamino compounds having a long side chain group are known, and a representative one thereof is represented by the following general formula:
(16), (17), (18), (19), (20), (21) and (22) are shown.

[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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The above general formulas (16), (17), (18) and (19)
In the formula, R ⁴¹ , R ⁴² and R ⁴³ in the formula represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, Y represents a single bond or a methylene bond, and ring A represents a benzene ring or Represents a cyclohexane ring, Z represents a single bond, a methylene bond, an ethylene bond or an ether bond,
r is a compound of 0 to 3, s is an integer of 0 to 5, and t is an integer of 0 to 3. Further, any ring in the general formula (16) may be substituted with a lower alkyl group, and in the steroid skeleton of the general formulas (17) and (18), any ring may be reduced, expanded, or cleaved. Or a three-membered ring, and the unsaturated bond at any position may be increased or decreased, and may be further substituted with any monovalent organic group.

In the diamino compound represented by the general formula (20), R ⁴⁴ and R ⁴⁵ in the formula represent an alkyl group having 1 to 12 carbon atoms, and X represents a single bond, a methylene bond, an ethylene bond or an ether bond. Wherein u is an integer of 0 to 3, and any benzene ring is a compound which may be substituted with a lower alkyl group.

[0084] diamino compound represented by the general formula (21), R ⁴⁸ in the formula represents hydrogen, fluorine, a hydrocarbon group, a fluorinated hydrocarbon group, an alkoxy group, a cyano group or a hydroxy group, R ⁴⁶ And R ⁴⁷ are 1 to 3 aromatic rings and / or
Or an alicyclic ring, they may be attached at a linking group shown in X ^3, X ³ and X ⁴ each independently represent a single bond, -O -, - COO -, - OCO -, - NH-,
-CONH- or _{- (CH 2) n - (} n is an integer of from 1 to 5)
And R ⁴⁶ and / or R ⁴⁷ are compounds which may form a steroid skeleton together with X ³ and X ⁴ .

In the diamino compound represented by the general formula (22), A ^{1 in} the formula represents a hydrogen atom, an alkyl, alkoxy or alkoxyalkyl group having 1 to 12 carbon atoms.
² is a single bond or one carbon atom in which oxygen may be present in the chain.
Is a compound in which m is an integer of 0 to 3 and n is an integer of 1 to 5.

The groups having a steroid skeleton represented by the general formulas (17), (18) and (21) include cholesteryl, androsteryl,
β-cholesteryl, epiandosteryl, erygosteryl, estolyl, 11α-hydroxymethylsteryl,
11α-progesteryl, lanosteryl, melatranil, methyltestosterol, lenothisteryl, pregnenonyl, β-sitosteryl, stigmasteryl, testosteryl, cholesterol acetate and the like.

As the diamino compound, a silyloxy group-containing diamine such as 1,3-bis (3-aminopropyl) -1,1,3,3-tetraphenyldisiloxane,
1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane, 1,3-bis (4-aminobutyl) -1,1,3,3-tetramethyldisiloxane, etc. A polymer having a structural unit into which is introduced is preferably used as a copolymer component at the time of producing the polymer, since the alignment film formed from the polymer containing the polymer improves the adhesion to a substrate.

Further, various monoamine compounds and / or monocarboxylic anhydrides are used for treating the reactive terminal of the polyamic acid represented by the general formulas (7) and (11). As these monoamine compounds, similar to the above diamino compounds, silyloxy group-containing amines, for example,
Para-aminophenyltrimethoxysilane, para-aminophenyltriethoxysilane, metaaminophenyltrimethoxysilane, metaaminophenyltriethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane and the like are preferably used.

In the present invention, photosensitivity can be imparted to a polymer by using a compound having a photosensitive group introduced into any of tetracarboxylic acids, dicarboxylic acids or diamino compounds in the synthesis of the polymer.

Varnish The varnish of the present invention contains the above polymers and an organic solvent capable of dissolving them. As the organic solvent, a solvent usually used for a polyamic acid, a polyamic acid ester, a polyamide, a polyamideimide, a soluble polyimide or the like is used. For example, N-methyl-2-pyrrolidone, dimethylimidazolidinone, N-methylcaprolactam, N-methylpropionamide, N, N-dimethylacetamide, dimethylsulfoxide, N, N-dimethylformamide, N, N-diethylformamide, An aprotic polar organic solvent which is a parent solvent for the polymer such as diethylacetamide and γ-butyrolactone is exemplified. These organic solvents can be used in combination of two or more, for example, γ-butyrolactone and N-methyl-
By using 2-pyrrolidone or a mixed solvent of γ-butyrolactone and dimethylimidazolidinone, the coating property of the varnish can be improved. Also, a combination of γ-butyrolactone and an aprotic polar organic solvent other than the above can be suitably used.

In addition to the above-mentioned solvent, other solvent systems having a low surface tension for the purpose of improving coating properties, such as alkyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monobutyl ether, etc. Ethylene glycol monoalkyl ethers, such as diethylene glycol monoalkyl ether such as diethylene glycol monoethyl ether, ethylene glycol monoalkyl or phenyl acetate, triethylene glycol monoalkyl ether, propylene glycol monoalkyl ether such as propylene glycol monobutyl ether, and diethyl malonate such as Organic solvents, such as dialkyl malonates, which are poorer solvents for the polymer than the parent solvent can be used. These organic solvents can be used in appropriate combination of two or more kinds according to the use environment of the varnish.

The varnish varies depending on the purpose of use.
Usually, it contains about 0.1 to 40% by weight of a polymer component. Particularly when used as a liquid crystal alignment agent, if the polymer concentration is low, the viscosity is too low, and if the polymer concentration is high, the viscosity is too high, and it is difficult to form a suitable alignment film having a film thickness using it. Become.

The varnish may contain an imidizing agent or an imidizing catalyst for a polyamic acid, a photopolymerization initiator, a surfactant, an antistatic agent, a coloring agent, a silane-based, titanium-based, epoxy-based coupling agent, an inorganic Alternatively, additives such as organic fillers and fine particle powders can be contained according to the purpose of use.

The varnish of the present invention includes a liquid crystal aligning agent, various protective films, an insulating film, a material for forming a color filter, TA
It can be widely used as material B and other various coating materials.

Alignment Film The alignment film of the present invention comprises a polymer film which is formed on a substrate using a liquid crystal alignment agent which is one embodiment of the varnish, and is subjected to an alignment treatment.

The method for applying the liquid crystal aligning agent onto the substrate is not particularly limited as long as it is a commonly used method, and examples thereof include a spinner method, a printing method, a dipping method, and a dropping method.

The liquid crystal aligning agent film formed on the substrate is dried and the amide acid structural unit represented by the general formula (7), which is usually contained in the coating film, is subjected to dehydration and ring closure to obtain the general formula (8). For the reaction for producing the imide structural unit represented, a method similar to the general method of dehydration and ring closure of polyamic acid is employed.

For example, a method in which a substrate on which a liquid crystal aligning agent coating film is formed is heated in an oven, a hot plate, or an infrared furnace to evaporate the solvent at a relatively low temperature, and then heated at a temperature of 150 to 300 ° C. Is preferably adopted. In this case, it is effective to add a catalyst for promoting the imidization of the polyamic acid to the liquid crystal aligning agent in advance.

As an orientation treatment of the imidized polymer film,
A method of rubbing the surface of the film in a certain direction using a general rubbing device can be adopted. As a substrate on which an alignment film is formed, usually, a transparent electrode such as ITO
A substrate with a TFT is used.

Liquid Crystal Display Device The liquid crystal display device of the present invention is a device having an ordinary structure in which the substrate on which the alignment film is formed is brought into contact with a liquid crystal composition layer with the alignment film surface inside. This liquid crystal display device has excellent liquid crystal alignment, a controlled pretilt angle, an extremely high voltage holding ratio, and a small residual charge by having the alignment film.

The liquid crystal composition used for the liquid crystal display device is as follows:
It is a multi-component mixture of various liquid crystal compounds, and the combination of these liquid crystal compounds is not particularly limited, and can be appropriately selected depending on the type of the display element.

One embodiment of the liquid crystal composition used in the liquid crystal display device of the present invention is represented by the following general formula (23a), (23b) or (23c)
Is a mixture of liquid crystal compounds containing a compound selected according to the purpose from the group consisting of the liquid crystal compounds represented by

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In the above formula, ring A represents trans-1,4-cyclohexylene, and ring B represents trans-1,4-cyclohexylene, 1,3-dioxane-2,5-diyl,
Represents 4-phenylene or fluorine-substituted 1,4-phenylene, and ring C is trans-1,4-cyclohexylene,
Represents 4-phenylene or fluorine-substituted 1,4-phenylene, a single bond are each independently of _{Z a (-), - CH} 2
_{CH 2 -, - CH 2 CH} 2 CH 2 CH 2 -, - COO -, -
CF ₂ O—, —OCF ₂ — or —CH ＝ CH—,
_Ra is an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group, or an arbitrary non-adjacent methylene group in the alkyl group or the fluorine-substituted alkyl group substituted with -O- or -CH = CH-. represents a group, X _a is F, C
_{l, -CF 3, -CF 2 H} , -CFH 2, -OCF 3, -O
_{CF 2 H, -OCF 2 CF 2} H or -OCF ₂ CFHCF
Represents _3, and one or more atoms constituting the compound may be substituted with an isotope.

The compounds belonging to the above liquid crystal compound group have a positive dielectric anisotropy value and are excellent in thermal stability and chemical stability, and therefore have a particularly high voltage holding ratio and / or a large specific resistance value. Is a compound useful for the preparation of a liquid crystal composition for a TFT which requires the following.

The liquid crystal composition for a TFT generally comprises a compound selected from the above liquid crystal compound group in an amount of 0.1 to 99.9% by weight, preferably 10 to 97% by weight, more preferably 10 to 97% by weight, based on the total amount of the liquid crystal composition. Preferably, the content is 40 to 95% by weight. These compounds can also be used in a liquid crystal composition for an STN or TN liquid crystal display element. In this case, the content of these compounds is preferably 50% by weight or less. further,
The liquid crystal composition may contain a known compound for adjusting various properties such as a threshold voltage, a liquid crystal phase temperature range, a refractive index anisotropy, a dielectric anisotropy, and a viscosity.

Another embodiment of the liquid crystal composition is represented by the following general formula (24)
Alternatively, it is a mixture of liquid crystal compounds containing a compound selected according to the purpose from the group consisting of the liquid crystal compounds represented by (25).

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[0107] In the above formula, the R _a, L _a and L _b have the same meaning as defined above, ring D is trans-1,4-cyclohexylene, 1,4-phenylene, 1,3-dioxane -
Represents 2,5-diyl or pyrimidine-2,5-diyl, and ring E represents trans-1,4-cyclohexylene, pyrimidine-2,5-diyl, 1,4-phenylene or fluorine-substituted 1,4-phenylene And ring F is trans-1,
Represents 4-cyclohexylene or 1,4-phenylene, wherein rings D, E and F may be the same or different,
Z _b represents a single bond _{(-), - CH 2 CH} 2 - or -COO-
And X _b represents —CN or —C≡C—CN, and q and r are each independently 0 or 1.

The compounds belonging to the above liquid crystal compound group generally have a large positive dielectric anisotropy value, and are particularly used for the purpose of reducing the threshold voltage of the liquid crystal composition. It is also used for adjusting the refractive index anisotropy value, increasing the clearing point, and expanding the nematic range. Further, these compounds are particularly useful for STN or TN liquid crystal compositions because they can improve the steepness of the voltage-transmittance characteristics of the liquid crystal composition.

The liquid crystal composition for STN or TN usually contains 0.1 to 99.9% by weight of a compound selected from the group consisting of the liquid crystal compounds represented by the general formula (24) or (25). , Preferably 10-97% by weight, more preferably 4% by weight.
It contains 0 to 95% by weight.

Another embodiment of the liquid crystal composition is represented by the following general formula (26)
It is a mixture of liquid crystal compounds containing a compound selected according to the purpose from the group consisting of the liquid crystal compounds represented by a), (26b) or (26c).

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In each of the above formulas, ring A, R _a , ring F and Z _b have the meanings as defined above, each of Z _b may be the same or different, and R _b has 1 to 1 carbon atoms. 10 alkyl group, a fluorine-substituted alkyl group or the alkyl group or a group obtained by substituting non-adjacent any methylene group -O- or -CH = CH- in the fluorine-substituted alkyl group, they are R _a And L _c and L _d each independently represent a hydrogen atom or a fluorine atom, and at least one of L _c and L _d represents a fluorine atom.

The compounds belonging to the above liquid crystal compound group usually show a negative dielectric anisotropy value. The bicyclic compound represented by the general formula (26a) is mainly used for adjusting a threshold voltage, a viscosity, and a refractive index anisotropy value. General formula (2
The tricyclic compound represented by 6b) is used for the purpose of expanding the nematic phase range, for example, increasing the clearing point, and adjusting the refractive index anisotropy value. Further, 3 represented by the general formula (26c)
The ring compound is used for expanding the nematic phase range, lowering the threshold voltage, and increasing the refractive index anisotropy value.

When the amount of the above compound in the liquid crystal composition increases, the threshold voltage of the composition decreases and the viscosity increases. Therefore, a small amount is used as long as the threshold voltage satisfies the required value. It is desirable to do. However, the absolute value of the dielectric anisotropy value of these compounds is 5 or less,
When the amount is less than the weight%, voltage driving may be difficult. The amount of the compound used in the liquid crystal composition for TFT is 40% by weight or more, preferably 50 to 95% by weight.
In addition, these compounds can be used for the purpose of controlling the elastic constant and the voltage-transmittance curve of a liquid crystal composition having a positive dielectric anisotropy value. % Or less is preferable.

Each of the liquid crystal compositions further comprises, as a second component, at least one compound selected from the group consisting of liquid crystal compounds represented by the following general formulas (27a), (27b) and (27c). It is preferable to include

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In the above formula, ring A, R _a , ring E and R _b have the meanings as defined above, each of ring A and ring E may be the same or different, and each of Z _c is independently a single _{bond, -CH 2 CH 2 -, -} C≡C -, - C
H represents CH- or -COO-.

The compounds belonging to the above liquid crystal compounds are generally neutral compounds having a small absolute value of the dielectric anisotropy value. The compound represented by the general formula (27a) is used mainly for adjusting the viscosity and the refractive index anisotropy of each of the liquid crystal compositions. The compound represented by the general formula (27b) or (27c) is used for the purpose of expanding a nematic range and adjusting a refractive index anisotropy value, for example, by increasing a clearing point of each of the liquid crystal compositions.

When the amount of these compounds used in each of the liquid crystal compositions is increased, the threshold voltage increases and the viscosity decreases. Therefore, as long as the threshold voltage of the liquid crystal composition satisfies the required value, it is preferable to increase the amount of use thereof. The general formula (23a), (23b) or (23c)
In a liquid crystal composition for a TFT containing a liquid crystal compound represented by the following formula as a main component, these compounds can be contained in an amount of 40% by weight or less, preferably 35% by weight or less. In a liquid crystal composition for STN or TN containing a liquid crystal compound represented by the general formula (24) or (25) as a main component, these compounds are contained in an amount of 70% by weight or less, preferably 60% by weight or less.
It can be contained in the following amounts.

In each of the above liquid crystal compositions, OCB (Optically Compensated Birefrin) was used as a component other than the liquid crystal compound.
gence) An optically active compound that aims to induce a helical structure of the liquid crystal composition, adjust the twist angle, and prevent reverse twist, except in special cases such as liquid crystal compositions for mode. Is usually added.

For this purpose, any of known optically active compounds can be used. Preferred examples of the optically active compound include compounds represented by the following formula.

[0120]

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These optically active compounds are usually added to each of the liquid crystal compositions to adjust the twist pitch. The twist pitch is 40 for TFT and TN.
To 200 μm, for STN, 6 to 20 μm, for bistable TN (Bistable TN) mode, 1.5 to 200 μm.
It is adjusted by adding an optically active substance in the range of 4 μm.

Each of the above liquid crystal compositions is prepared by a commonly used method such as a method of dissolving each component at a high temperature.

The liquid crystal display device of the present invention is optimized by adding an appropriate additive to the liquid crystal composition according to the intended use. These additives are described in various documents and are well known to those skilled in the art. Usually, a chiral doped material (chirald) that induces the helical structure of the liquid crystal, adjusts the required twist angle, and prevents reverse twist
opant) is added to the liquid crystal composition.

The liquid crystal display device of the present invention is characterized in that, in addition to the TNT, TN, bistable TN and STN liquid crystal display devices using the above liquid crystal composition, merocyanine, styryl, azo, azomethine, etc. Guest-host (GH) mode liquid crystal display device containing dichroic dyes such as azoxy, quinophthalone, anthraquinone and tetrazine, and NC with microcapsulated nematic liquid crystal
AP, polymer dispersed liquid crystal display (PDLCD) typified by polymer network liquid crystal display (PNLCD) in which three-dimensional network polymer is formed in liquid crystal, birefringence control (ECB) mode and dynamic scattering (DS) Mode liquid crystal display device.

[0125]

The present invention will be described in more detail with reference to Examples and Comparative Examples. Example 1 Synthesis of diamino compound 1-1 1,4-bis (4-aminophenethyl) benzene a) 1,4-bis (2- (4-nitrophenyl) ethynyl)
Benzene 1,2-Diethynylbenzene 2 was placed in a 2-liter three-necked flask equipped with a stirrer, thermometer, and nitrogen purge device.
9.0 g and 103.0 g of 4-bromonitrobenzene were added, dissolved in 300 ml of triethylamine and 300 ml of ethylene glycol dimethyl ether, and copper iodide 0.12 was added.
g, 0.90 g of Ph ₃ P and 0.42 g of (Ph ₃ P) ₂ .PdCl _{2, the} temperature was raised, and the mixture was stirred for 3 hours under the condition of heated reflux. After confirming the completion of the reaction by gas chromatography, the crystals precipitated in the reaction solution were separated by filtration, and the crystals were washed with water, ethanol and toluene in that order, dried in a desiccator under reduced pressure, and expressed by the general formula (2). Thus, 84.6 g of 1,4-bis (2- (4-nitrophenyl) ethynyl) benzene contained in the dinitro compound obtained was obtained. NMR of the obtained compound
The spectrum is shown in FIG.

B) 1,4-bis (4-aminophenethyl)
Benzene A Pd / C catalyst (5% product, water 55.9%) was placed in a 1 liter autoclave equipped with a stirrer and a nitrogen purge device.
4.38 g, 87.5 g of 1,4-bis (2- (4-nitrophenyl) ethynyl) benzene and 650 ml of tetrahydrofuran were added thereto, and contacted with hydrogen gas while stirring at 50 ° C. and 8 kg / cm ² under pressure. I let it. After stopping absorption of hydrogen,
The catalyst was filtered off and the solution was concentrated. After dissolving the crystals in chloroform and performing column chromatography on activated alumina and silica gel, the solution is concentrated again, and the concentrate is recrystallized with a toluene solvent to give a compound represented by the general formula (1). 60.1 g of 1,4-bis (4-aminophenethyl) benzene contained in a tricyclic diamino compound
I got Melting point: 187.5-188.4 ° C. Analysis of this compound by mass spectrum revealed a molecular weight of 316.
showed that. The GC chart and GC mass spectrum of the obtained compound are shown in FIGS. 5 and 6, respectively.

1-2 1,4-bis (4-amino-2-methylphenethyl) benzene a) 1,4-bis (4-amino-2-methylphenylethynyl) benzene Stirrer, thermometer and nitrogen purging apparatus 1,4-diethynylbenzene 5.
0 g and 16.0 g of 4-bromo-3-methylaniline, 0.10 g of copper iodide dissolved in 50 ml of triethylamine and 50 ml of ethylene glycol dimethyl ether, Ph ₃
0.30 g of P and 0.20 g of (Ph ₃ P) ₂ .PdCl ₂ were added to start heating, and the mixture was stirred for 3 hours under the condition of heated reflux.
After confirming the completion of the reaction by gas chromatography, the crystals precipitated in the reaction solution were separated by filtration, and the crystals were washed with water, ethanol and toluene in that order, dried in a desiccator under reduced pressure, and expressed by the general formula (2). Thus, 12.0 g of 1,4-bis (4-amino-2-methylphenylethynyl) benzene contained in the diamino compound was obtained.

B) 1,4-bis (4-amino-2-methylphenethyl) benzene A 1-liter autoclave equipped with a stirrer and a nitrogen purge device was charged with a Pd / C catalyst (5% product, water 55.9%).
0.6 g, 12.0 g of 1,4-bis (4-amino-2-methylphenylethynyl) benzene and 100 ml of tetrahydrofuran were added thereto, and the mixture was added at 50 ° C. and 8 kg / cm ² under pressure.
It was brought into contact with hydrogen gas while stirring. After stopping absorption of hydrogen, the catalyst was filtered off and the solution was concentrated. After dissolving the crystals in chloroform and performing column chromatography on activated alumina and silica gel, the solution was re-concentrated,
By recrystallizing the concentrate with toluene solvent,
8.0 g of 1,4-bis (4-amino-2-methylphenethyl) benzene included in the tricyclic diamino compound represented by the general formula (1) was obtained. Analysis by mass spectrum of this compound showed a molecular weight of 344.

1-3 1,4-bis (4-aminophenethyl) benzene a) 1,4-bis (2- (4-nitrophenyl) ethynyl)
Benzene 3.20 g of 4-nitroethynylbenzene and 3.20 g of 1,4-diiodobenzene were placed in a 1-liter three-necked flask equipped with a stirrer, a thermometer and a nitrogen purge device, and 25 ml of triethylamine and ethylene glycol dimethyl ether were added. 0.05 g of copper iodide dissolved in 25 ml, Ph ₃
0.15 g of P and 0.10 g of (Ph ₃ P) ₂ .PdCl ₂ were added to start heating, and the mixture was stirred for 3 hours under the condition of heated reflux.
After confirming the completion of the reaction by gas chromatography, the crystals precipitated in the reaction solution were separated by filtration, and the crystals were washed with water, ethanol and toluene in that order, dried in a desiccator under reduced pressure, and expressed by the general formula (2). 3.0 g of 1,4-bis (2- (4-nitrophenyl) ethynyl) benzene contained in the resulting dinitro compound was obtained.

B) 1,4-bis (4-aminophenethyl)
Benzene A Pd / C catalyst (5% product, water 55.9%) was placed in a 1 liter autoclave equipped with a stirrer and a nitrogen purge device.
0.3 g, 1,4-bis (2- (4-nitrophenyl)
(Ethynyl) benzene 3.0 g and tetrahydrofuran 2
Then, the mixture was contacted with hydrogen gas while stirring at 50 ° C. under a pressure of 8 kg / cm ² . After stopping absorption of hydrogen, the catalyst was filtered off and the solution was concentrated. After dissolving the crystals in chloroform and performing column chromatography on activated alumina and silica gel, the solution is concentrated again, and the concentrate is recrystallized with a toluene solvent to obtain a compound of the general formula
1, included in the tricyclic diamino compound represented by (1),
2.1 g of 4-bis (4-aminophenethyl) benzene were obtained. Melting point: 187.5-188.4 ° C. Analysis by mass spectrum of this compound showed a molecular weight of 316.

1-4 1,2-bis (4- (4-aminophenyl)
Phenethyl) phenyl) ethane a) 1,2-bis (4- (4-nitrophenyl) ethynylf
Enyl) ethane 1 l with stirrer, thermometer and nitrogen purge
4-nitroethynylbenzene in a 3-neck flask
7.1 g and 1,2-bis (4-iodophenyl) ethane 7.
0 g, triethylamine 50 ml, ethylene glycol
Copper iodide 0.1 dissolved in 50 ml of dimethyl ether
0g, Ph_Three0.30 g of P and (Ph_ThreeP)_Two・ PdCl _Two0.20g
To start heating, and stirred for 3 hours under heated reflux conditions.
Stirred. Check the end of the reaction by gas chromatography.
After that, the crystals precipitated in the reaction solution were filtered off, and the crystals were washed with water and ethanol.
Wash sequentially with ethanol and toluene and reduce in a desiccator.
And dried in a dinitro compound represented by the general formula (2).
1,2-bis (4- (4-nitrophenyl) ethini contained
6.0 g of (phenyl) ethane were obtained.

B) 1,2-Bis (4- (4-aminophenethyl) phenyl) ethane A 1-liter autoclave equipped with a stirrer and a nitrogen purge device was charged with a Pd / C catalyst (5% product, water 55.9). %
0.6g, 1,2-bis (4- (4-nitrophenyl)
6.0 g of ethynylphenyl) ethane and 200 ml of tetrahydrofuran were added, and the mixture was contacted with hydrogen gas at 50 ° C. under a pressure of 8 kg / cm ² with stirring. After stopping absorption of hydrogen,
The catalyst was filtered off and the solution was concentrated. After dissolving the crystals in chloroform and performing column chromatography on activated alumina and silica gel, the solution is concentrated again, and the concentrate is recrystallized with a toluene solvent to obtain a compound represented by the general formula (1). 4.1 g of 1,2-bis (4- (4-aminophenethyl) phenyl) ethane contained in the ring diamino compound was obtained. Analysis by mass spectrum of this compound showed a molecular weight of 412.

Example 2 Synthesis of Polymer In the following examples, the following abbreviations are used. Tetracarboxylic dianhydride Pyromellitic dianhydride PMDA Cyclobutanetetracarboxylic dianhydride CBDA Butanetetracarboxylic dianhydride BTDA Diamino compound 1,4-bis (4-aminophenethyl) benzene DPEB 1,1-bis [ 4- (4-aminophenoxy) phenyl] -4- (n-pentylcyclohexyl) cyclohexane PP5HH 4,4'-diaminodiphenylmethane DPM 4,4'-diaminodiphenylether DPER 1,4-bis (4-aminophenoxy) benzene DPB Solvent N-methyl-2-pyrrolidone NMP butyl cellosolve BC

Preparation of Polyamic Acid and Varnish 2.9599 g of DPEB as a diamino compound and dehydrated NMP of a solvent were placed in a 200 ml four-necked flask equipped with a thermometer, a stirrer, a raw material charging port and a nitrogen gas inlet.
50.00 g was added and dissolved under stirring in a stream of dry nitrogen.
While maintaining the temperature of the reaction system at 5 to 70 ° C., 2.0401 g of PMDA was added as tetracarboxylic dianhydride and 2
The reaction was performed for 0 hours. Then, 45.00 g of BC was added to make the polymer concentration 5% by weight, and the solution viscosity was 30 to 35 mPa.
-The point at which s was reached was taken as the reaction end point. Polyamic acid-containing varnish having a structural unit represented by the general formula (7) (E2-
1) was obtained and stored at -20 ° C.

Varnishes (E2-2), (E2-3) and (E2-4) Varnishes (E2-1) except that the starting materials tetracarboxylic dianhydride and diamino compound were changed as shown in Table 1.
A varnish containing 5% by weight of a polyamic acid having a logarithmic viscosity number of 1.1 dl / g was prepared in the same manner as described above. The polymer contained in the varnish (E2-2) is a polyamic acid homopolymer having a structural unit represented by the general formula (7),
The polymer contained in the varnish (E2-3) contains a polyamic acid random copolymer including a plurality of structural units represented by the general formula (7). In varnish (E2-4), a polymer comprising a structural unit represented by the general formula (7),
It is conceivable to include a polymer comprising the structural unit represented by 2) and a polymer having both structural units. These varnishes were stored at -20C.

[0136]

[Table 1]

The varnishes for comparison (C2-1) and (C2-
2) Varnish (E2-1) except that the starting materials tetracarboxylic dianhydride and diamino compound were changed as shown in Table 1.
In the same manner as described above, a comparative varnish containing 5% by weight of a polyamic acid having a logarithmic viscosity number of 1.1 dl / g was prepared.
These varnishes are varnishes containing a polyamic acid copolymer comprising a structural unit represented by the general formula (12), and stored at -20 ° C.

Example 3 Liquid Crystal Alignment Film and Liquid Crystal Display Element 3-1 Preparation of Liquid Crystal Alignment Film Varnishes (E2-1) to (E2-4) prepared in Example 2
Each of the varnishes for comparison (C2-1) and (C2-2) was diluted with BC to prepare a coating solution having a polymer concentration of 3%. Each of the coating solutions prepared on a glass substrate with an ITO transparent electrode was applied by a spinner method,
After preheating on a hot plate for about 5 minutes,
Heat treatment was performed in an oven at 30 ° C. for 30 minutes to dehydrate and imidize the polyamic acid to form a polyimide thin film having a structural unit represented by the general formula (8) and / or (13). Next, the surface of the polyimide thin film was rubbed with a rubbing device and subjected to an alignment treatment to obtain a liquid crystal alignment film.

3-2 Liquid Crystal Display Element a) Cell for Pretilt Angle Measurement A spacer for 20 μm was sprayed on the alignment film surface of the substrate on which the liquid crystal alignment film was formed, leaving a liquid crystal injection hole with the alignment film surface inside. The periphery was sealed with an epoxy curing agent to form an anti-parallel cell with a gap of 20 μm. A liquid crystal composition having an NI point of 81.3 ° C. and a refractive index anisotropy of 0.092 was injected into the cell, and the liquid crystal injection hole was sealed with a photocuring agent. Next, heat treatment was performed at 110 ° C. for 30 minutes to obtain a pretilt angle measurement cell.

Each component and weight% of the used liquid crystal composition
Is shown below.

Embedded image

B) Cell for Evaluation of Electric Characteristics A spacer having a thickness of 7 μm was sprayed on the surface of the alignment film of the substrate on which the liquid crystal alignment film was formed. To form an anti-parallel cell with a gap of 7 μm. The same liquid crystal composition as described above was injected into this cell, the liquid crystal injection hole was sealed with a photocuring agent, and the liquid crystal injection hole was cured by UV irradiation, and the liquid crystal was sealed. Next, a heat treatment was performed at 110 ° C. for 30 minutes to obtain a cell for evaluating electrical characteristics.

C) Evaluation of characteristics of liquid crystal alignment film and liquid crystal display element The following characteristics were evaluated using each cell prepared above.
It was shown to. Pretilt Angle The pretilt angle was measured by a crystal rotation method using a pretilt angle measuring cell.

Liquid Crystal Alignment The pretilt angle measuring cell was observed under a microscope at right angles to Nicol, and disorder in the alignment of liquid crystal molecules was observed. When the stage on which the cell was mounted was rotated by 45 ° from the position of the dark field to the position of the bright field to uniformly transition from dark to bright, it was defined as “good”.

Residual Charge An AC of 50 mV and 1 kHz is applied to the above-prepared cell for measuring electric characteristics, and a DC triangular wave having a frequency of 0.0036 Hz is superimposed thereon, and the DC voltage is changed from 0 V → + 10 V → 0 V → −1.
By sweeping from 0 V to 0 V, a hysteresis curve shown in FIG. 1 was obtained. From FIG. 1, α ₁ , α ₂ , α ₃ and α ₄ were measured, and the width of hysteresis was calculated by the following equation to evaluate the residual charge (V). Residual charge (V) = (| α ₁ −α ₂ | + | α ₄ −α ₃ |) / 2

Voltage holding ratio Using the apparatus shown in FIG. 2, a cell for measuring electrical characteristics, a gate width of 69 μs, a frequency of 60 Hz and a wave height of ± 4.5 V shown in FIG. 3 were used.
Was applied to the source, and the changing drain (Vd) was read from an oscilloscope to obtain a Vd curve. In the Vd curve shown in FIG. 3, the percentage of the area of the shaded area with respect to the area of the rectangle indicated by the dotted line was calculated as the voltage holding ratio.

[0146]

[Table 2]

Evaluation Results In the examples, E3-1 is an aromatic tetracarboxylic dianhydride, E3-2 is an alicyclic tetracarboxylic dianhydride, and E3-3 is an alicyclic tetracarboxylic dianhydride. E3-4 is a polyimide liquid crystal alignment film in which a diamino compound having a side chain group is further used in combination with an aliphatic tetracarboxylic dianhydride. On the other hand, C3-1 and C3-2 in Comparative Examples are polyimide alignment films using a diamino compound containing an ether diamino compound as a main component.

As shown in Table 2, the alignment properties of liquid crystal molecules, which are the most basic characteristics as alignment films, were all good. E3-1 to E3-3 of the examples have the same small pretilt angles as those of the comparative examples C3-1 and C-2.
As shown in FIG. 4, it can be seen that the pretilt angle can be increased, that is, the pretilt angle can be controlled by using the diamino compound having a side chain group in combination. Further, all of the electrical characteristics, the residual charge and the voltage holding ratio are much better than the comparative example using a diamino compound containing an ether diamino compound as a main component. The film was formed in a uniform thickness without any repelling during coating in both the examples and the comparative examples.

[0149]

The diamino compound of the present invention is a polyamic acid, a polyamic ester, a polyamide, a polyimide,
It is extremely useful as a raw material compound of a polymer in which a diamine such as polyamideimide is used. Polyamic acid synthesized using the diamino compound of the present invention, polyamic acid ester, polyamide, polyimide, polyamide imide,
And polymers such as copolymers thereof are useful as main components of production raw materials such as films, sheets, molded products, fibers, and varnishes for forming liquid crystal alignment films, protective films, insulating films, color filters, and various coatings. It is. In addition, the liquid crystal alignment film of the present invention exhibits excellent liquid crystal alignment properties,
A liquid crystal display device using the same is provided with excellent electrical properties such as excellent residual charge, voltage holding ratio, and reliability.

[Brief description of the drawings]

FIG. 1 is a CV hysteresis curve of a liquid crystal display element.

FIG. 2 is a circuit diagram of an apparatus used for measuring a voltage holding ratio.

FIG. 3 shows a source rectangular wave Vs and a drain rectangular wave Vd at the time of voltage holding ratio measurement.

FIG. 4 is an NMR spectrum of the diamine precursor compound obtained in Example 1-1a.

FIG. 5 shows G of the diamino compound obtained in Example 1-1b.
C chart.

FIG. 6 shows G of the diamino compound obtained in Example 1-1b.
C mass spectrum.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07C 209/36 C07C 209/36 217/90 217/90 C08G 73/10 C08G 73/10 C09K 19/12 C09K 19/12 19/14 19/14 19/20 19/20 19/30 19/30 19/34 19/34 G02F 1/13 500 G02F 1/13 500 1/1337 520 1/1337 520 F term (reference) 2H090 HB08 HB09 4H006 AA01 AA02 AA03 AB64 AC11 AC24 AC51 AC52 BA05 BA06 BA11 BA25 BA31 BA53 BB10 4H027 BA01 BD04 BD13 BD24 BE04 CP04 CQ04 CR04 CS04 CT04 4H039 CA39 CA40 CA41 CA71 CA72 CB10 CB30 TA03 TB03 TB03 PA03 TB03 TB03 PA03 UA012 UA022 UA032 UA082 UA122 UA132 UA141 UA151 UA252 UB011 UB122 XA19 ZB11 ZB23

Claims (28)

[Claims] 1. The following general formula (1): (Wherein, each of R ¹ and R ² represents a linear or branched alkyl group having 1 to 3 carbon atoms which may be the same or different, and Q represents a single bond or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms. And m and l are each independently 0 or an integer of 1 to 4, and n is 0 or 1. 2. The diamino compound according to claim 1, wherein in formula (1), —NH ₂ is bonded to the 4- and 4-positions of the phenyl group. 3. The diamino compound according to claim 1, wherein m = 0 and 1 = 0 in the general formula (1). 4. The compound according to claim 1, wherein m = 1 and l = 1 in the general formula (1), and R ¹ and R ² are methyl groups.
The diamino compound according to the above. 5. The diamino compound according to claim 1, wherein in formula (1), m = 0 and l = 1, and R ² is a methyl group. 6. The diamino compound according to claim 1, wherein m = 1 and l = 0 in the general formula (1), and R ¹ is a methyl group. 7. The diamino compound according to claim 1, wherein in formula (1), n = 0. 8. The diamino compound according to claim 1, wherein in formula (1), n = 1. 9. In the general formula (1), n = 1 and Q
Is a single bond, The diamino compound in any one of Claims 1-6. 10. The following general formula (2): (Wherein, each of R ¹ and R ² represents a linear or branched alkyl group having 1 to 3 carbon atoms which may be the same or different, R ³ represents a hydrogen atom or an oxygen atom,
Q represents a single bond or an optionally substituted alkylene bond having 1 to 5 carbon atoms, m and l are each independently an integer of 0 or 1 to 4, and n is 0 or 1)
A compound represented by the formula: 11. In the presence of a reduction catalyst, a compound represented by the following general formula (2): Consisting of reducing a compound represented by the following general formula
(1) (In each formula, each of R ¹ and R ² represents a linear or branched alkyl group having 1 to 3 carbon atoms which may be the same or different, R ³ represents a hydrogen atom or an oxygen atom, Represents a single bond or an optionally substituted alkylene bond having 1 to 5 carbon atoms, m and l are each independently an integer of 0 or 1 to 4, and n is 0 or 1. A method for producing a diamino compound. 12. A metal-based catalyst and a palladium-based catalyst comprising a compound containing at least one element of copper, tin, boron and magnesium in an organic solvent, and triphenylphosphine is added as necessary. In the presence of a catalyst system, the following general formula (3) And an ethynylphenyl compound represented by the following general formula (4): Reacting with a halogenated benzene compound represented by the following general formula (2): (In each formula, each of R ¹ and R ² represents a linear or branched alkyl group having 1 to 3 carbon atoms which may be the same or different, R ³ represents a hydrogen atom or an oxygen atom, Represents a single bond or an optionally substituted alkylene bond having 1 to 5 carbon atoms, X ¹ represents bromine or iodine, m and l are each independently an integer of 0 or 1 to 4, and n is 0 or 1). 13. In an organic solvent, a metal-based catalyst and a palladium-based catalyst comprising a compound containing at least one element of copper, tin, boron and magnesium are added as essential components, and triphenylphosphine is added as required. In the presence of a catalyst system, the following general formula (5) And a compound represented by the following general formula (6): Reacting with an ethynylbenzene derivative represented by the following general formula (2): (In each formula, each of R ¹ and R ² represents a linear or branched alkyl group having 1 to 3 carbon atoms which may be the same or different, R ³ represents a hydrogen atom or an oxygen atom, Represents a single bond or an optionally substituted alkylene bond having 1 to 5 carbon atoms, X ¹ represents a bromine or iodine atom, and m and l each independently represent 0 or 1 to
And n is 0 or 1). 14. The following general formulas (7), (8), (9) and (10): [In the above formula, R ⁴ is an amine residue of the diamino compound represented by the general formula (1) according to claim 1, wherein R ⁴ is an amine residue of the following general formula (11): (Here, each of R ¹ and R ² represents a linear or branched alkyl group having 1 to 3 carbon atoms which may be the same or different, R ³ represents a hydrogen atom or an oxygen atom, and Q represents Represents a single bond or an optionally substituted alkylene bond having 1 to 5 carbon atoms, m and l are each independently an integer of 0 or 1 to 4, and n is 0 or 1. R ⁵ represents a tetravalent organic group, R ⁶ represents a divalent organic group, R ⁹ represents a trivalent organic group, and R ⁷ represents a hydrogen atom or a monovalent organic group. And R ⁸ represents hydrogen.] Wherein the logarithmic viscosity number measured at 30 ° C. in N-methyl-2-pyrrolidone is 0.1. ~
A polymer that is 5 dl / g. 15. The polymer according to claim 14, which is a polyamic acid or a polyamic acid ester containing a structural unit represented by the general formula (7). 16. The polymer according to claim 14, which is a polyimide containing a structural unit represented by the general formula (8). 17. The polymer according to claim 14, which is a polyamide containing a structural unit represented by the general formula (9). 18. The polymer according to claim 14, which is a partially imidized polyamic acid or a partially imidized polyamic acid ester containing the structural units represented by formulas (7) and (8). 19. The polymer according to claim 14, which is a polyamideimide containing a structural unit represented by the general formula (10). 20. A varnish comprising at least one of the polymers according to claim 14 and an organic solvent. 21. The varnish according to claim 20, wherein the organic solvent contains an aprotic polar solvent and a glycol-based solvent. 22. An alignment film formed using the varnish according to claim 20. 23. A liquid crystal display device comprising the alignment film according to claim 22. 24. The following general formula (23a), (23b) or (23c): [In the above formula, ring A represents trans-1,4-cyclohexylene, ring B is trans-1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene Or a fluorine-substituted 1,4-phenylene, ring C represents trans-1,4-cyclohexylene, 1,4-phenylene or a fluorine-substituted 1,4-phenylene, and Z _a
Single bond independently each _{(-), - CH 2 CH} 2 -, -
_{CH 2 CH 2 CH 2 CH 2} -, - COO -, - CF 2 O-,
—OCF ₂ — or —CH ＝ CH—, wherein _Ra is an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group, or any non-adjacent methylene group in the alkyl group or the fluorine-substituted alkyl group. -O- or -CH = C
Represents a substituted group in H-, X _a is F, Cl, -CF _{3,
-CF 2 H, -CFH 2, -OCF} 3, -OCF 2 H, -O
It represents CF ₂ CF ₂ H or -OCF ₂ CFHCF _3, L _a
And _Lb each independently represent a hydrogen atom or a fluorine atom.] A liquid crystal display device according to claim 23, comprising a liquid crystal composition containing at least one liquid crystal compound represented by the formula: 25. The following general formula (24) or (25): [In the above formula, R _a, L _a and L _b are as defined in claim 26, ring D trans-1,4-cyclohexylene, 1,4-phenylene, 1,3-dioxane -2,
Represents 5-diyl or pyrimidine-2,5-diyl,
Ring E represents trans-1,4-cyclohexylene, pyrimidine-2,5-diyl, 1,4-phenylene or fluorine-substituted 1,4-phenylene, and ring F represents trans-1,4-phenylene
Represents cyclohexylene or 1,4-phenylene, and ring D, ring E and ring F may be the same or different;
_b is a single bond _{(-), - CH 2 CH} 2 - or -COO- the stands, and X _b represents -CN or -C≡C-CN, q and r are each independently is 0 or 1 ]
24. The liquid crystal display device according to claim 23, wherein a liquid crystal composition containing at least one compound represented by the following formula is used. 26. The following general formula (26a), (26b) or (26c): (In the above formula, ring A is as defined in claim 24, the ring F, R _a and Z _b are as defined in claim 25, each of Z _b may be the same or different, R _b represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group, or any non-adjacent methylene group in the alkyl group or the fluorine-substituted alkyl group, represented by —O—
Or a group substituted with -CH = CH-,
It may be the same or different and _a, and L _c and L _d
Each independently represents a hydrogen atom or a fluorine atom,
The liquid crystal display device according to claim 23 using a liquid crystal composition comprising at least one liquid crystal compound in which at least one of _c and L _d is expressed by a fluorine atom). 27. The liquid crystal composition according to claim 24 or a liquid crystal composition obtained by mixing two or more thereof, further comprising the following general formula (27a), (27b) or (27c): 16] (Wherein, rings A and R _b are as defined in claim 26, rings E and R _a are as defined in claim 25, and each of ring A and ring E is the same or different. At best, independently a single bond, each of Z _c, -CH ₂
CH ₂ —, —C≡C—, —CH ＝ CH— or —COO
The liquid crystal display device according to claim 23, wherein a liquid crystal composition containing at least one liquid crystal compound represented by-is used. 28. The liquid crystal display device according to claim 23, wherein a liquid crystal composition further comprising at least one optically active compound is used in the liquid crystal composition according to claim 24.