JP2003267982A - Phenylenediamine having siloxane part, liquid-crystal orientation material containing polymer using the phenylenediamine and liquid-crystal display element containing the liquid-crystal orientation material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a liquid-crystal orientation material having excellent heat resistance and orientation stability, providing an arbitrary pretilt angle, having high voltage retention ratio and slight sticking. <P>SOLUTION: The phenylenediamine is represented by formula (1) in which R<SP>1</SP>is represented by formula (2) (X is -CH<SB>2</SB>- or -CH<SB>2</SB>CH<SB>2</SB>-; A<SP>1</SP>is 1,4-phenylene or 1,4-cyclohexylene; A<SP>2</SP>, A<SP>3</SP>and A<SP>4</SP>are each independently single bond, 1,4- phenylene or 1,4-cyclohexylene; B<SP>1</SP>, B<SP>2</SP>and B<SP>3</SP>are each independently a single bond or -CH<SB>2</SB>CH<SB>2</SB>-; B<SP>4</SP>is a 1-10C alkyl group; R<SP>2</SP>is a hydrogen or a 1-15C hydrocarbon group; R<SP>3</SP>, R<SP>4</SP>, R<SP>5</SP>, R<SP>6</SP>and R<SP>7</SP>are each a 1-10C alkyl group; p is an integer of ≥1). The polyimide, polyamide or polyamide-imide is obtained by using the diamine and has ≥2,000 weight-average molecular weight. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel phenylenediamine compound having a siloxane moiety, a polyimide, a polyamide, a polyamideimide synthesized from the phenylenediamine compound as a raw material, and a liquid crystal alignment material produced by using these as a raw material. Further, the present invention is a liquid crystal cell containing the liquid crystal alignment material,
The present invention relates to a liquid crystal display device.

[0002]

2. Description of the Related Art Liquid crystal display elements are
It is necessary that the liquid crystal be aligned with an appropriate pretilt angle. For example, T which is currently the mainstream of liquid crystal displays
In the N-TFT type display element, the liquid crystal is required to have a pretilt angle of several degrees to 10 degrees with respect to the plane of the substrate. In the VA (vertically aligned) mode, it is necessary to vertically align liquid crystal molecules when no voltage is applied. The material design of the liquid crystal alignment material is important for controlling the pretilt angle. In recent years, polyimide, which is excellent in heat resistance and orientation stability, is mainly used as an orientation material. It is known that such a polyimide increases the pretilt angle of liquid crystal by introducing a large substituent into the diamine as a raw material. A phenylenediamine having a siloxane moiety and a liquid crystal aligning material using the same, which have been developed for such purposes, are described in, for example, JP-A-4-294327 and JP-A-9-230354. However, in order to satisfy other physical properties required for the alignment material, such as having a high voltage holding ratio and little seizure, further development of a new phenylenediamine and an alignment material using the same is required. It was

[0003]

An object of the present invention is to provide a novel phenylenediamine derivative having a siloxane moiety and a polyimide, a polyamide, and a polyamideimide using the same, as a liquid crystal aligning material satisfying the above required characteristics. Is.

[0004]

Means for Solving the Problems As a result of intensive research and development by the present inventors, as a result of an alignment material using phenylenediamine having a siloxane moiety as a raw material, alignment stability of liquid crystal and other It has been found that a display element having a significantly improved voltage holding ratio and image sticking can be obtained without impairing the characteristics of 1. Means for achieving the above object are as follows.

[1] A phenylenediamine represented by the following formula (1). (R ¹ is represented by the following formula (2), and R ² is hydrogen or a monovalent hydrocarbon group having 1 to 15 carbon atoms.) (X is —CH ₂ — or —CH ₂ CH ₂ —; A ¹ is 1,4-cyclohexylene, 1,4-phenylene or 1,4-phenylene substituted with 1 to 4 fluorines. A ² , A ³ and A ⁴ are each independently a single bond,
1,4-cyclohexylene, 1,4-phenylene or 1,4-phenylene substituted with 1 to 4 fluorines; B ¹ , B ² and B ³ are each independently a single bond or-
CH ₂ CH ₂ -,; B ⁴ is alkylene of 1 to 10 carbon ^{atoms; R 3, R 4, R} 5, R 6, and R ⁷ are each independently a carbon number of 1 to 10 Alkyl; p
Is an integer of 1 or more. )

[2] A ¹ is 1,4-phenylene or trans-1,4-cyclohexylene; A ² , A ³ and A ⁴ are each independently a single bond, 1,4-cyclohexylene or 1 , 4-phenylene; B ¹ , B ² and B ³ are single bonds, R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are methyl, and p is 1, [1. ] The phenylenediamine of item.

[3] A polyimide having a weight average molecular weight of 2000 or more, containing the repeating unit represented by the following formula (3), which uses the phenylenediamine described in the above item [1]. (A ⁵ is a tetravalent organic group, and A ⁵ and R ¹ may be different for each repeating unit.)

[4] The polyimide described in the above item [3], wherein A ⁵ is a tetravalent organic group represented by the following formula (4) or (5).

[5] The polyimide described in the item [3] or [4], which uses the phenylenediamine described in the item [2].

[6] A polyamide having a weight average molecular weight of 2000 or more, containing the repeating unit represented by the following formula (6), which uses the phenylenediamine described in the above item [1]. (A ⁶ is a divalent organic group, R ² is hydrogen or a monovalent hydrocarbon group having 1 to 15 carbon atoms, and A ⁶ , R ¹ and R
² may be different for each repeating unit. )

[7] The polyamide described in [6] above, which uses the phenylenediamine described in [2] above.

[8] A polyamideimide having a weight average molecular weight of 2000 or more, which contains the phenylenediamine according to the above item [1] and contains a repeating unit of the following formula (3). (A ⁵ is a tetravalent organic group, and A ⁵ and R ¹ may be different for each repeating unit.)

[9] A polyamideimide containing the repeating unit of the following formula (6), which uses the phenylenediamine described in the above item [1] and has a weight average molecular weight of 2000 or more. (A ⁶ is a divalent organic group, R ² is hydrogen or a monovalent hydrocarbon group having 1 to 15 carbon atoms, and A ⁶ , R ¹ and R
² may be different for each repeating unit. )

[10] The polyamide-imide according to the item [8] or [9], which uses the phenylenediamine according to the item [2].

[11] An alignment material for liquid crystal, which comprises the polyimide described in any one of the above [3] to [5].

[12] A liquid crystal alignment material containing the polyamide according to the above [6] or [7].

[13] An alignment material for liquid crystals, which comprises the polyamide-imide according to any one of the above items [8] to [10].

[14] A liquid crystal cell containing the alignment material for liquid crystal according to any one of [11] to [13].

[15] A liquid crystal display device including the liquid crystal alignment material according to any one of the above [11] to [13].

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The first aspect of the present invention is phenylenediamine represented by the following formula (1). Hereinafter, this phenylenediamine may be abbreviated as the compound (1). In the formula, R ¹ is represented by the formula (2), and R ² is hydrogen or a monovalent hydrocarbon group having 1 to 15 carbon atoms. In the formula, X is —CH ₂ — or —CH ₂ CH ₂ —. A ¹
Is 1,4-cyclohexylene, 1,4-phenylene or 1,4-phenylene substituted with 1 to 4 fluorines, preferably 1,4-cyclohexylene or 1,4-phenylene. B ⁴ is alkylene having 1 to 10 carbon atoms. R < ³ >, R < ⁴ >, R < ⁵ >, R < ⁶ >, and R < ⁷ > are each independently alkyl having 1 to 10 carbon atoms, and may be linear or branched. Specific examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, isobutyl, t-butyl and the like. In order to exhibit good properties as the liquid crystal aligning material of the present invention, methyl, ethyl, propyl, butyl,
Short chain alkyls such as isopropyl, isobutyl, and t-butyl are preferred. Considering the ease of synthesis, methyl is more preferable. p is an integer of 1 or more. In order to exhibit good characteristics as the liquid crystal aligning material of the present invention, 1 to 10 is required.
0 is preferred. Considering easiness of synthesis, 1 is more preferable.

The positions of the two amino groups of the compound (1) are not particularly limited, but in order to exhibit good characteristics as the liquid crystal aligning material of the present invention, the 2,4-position, based on the position of R ¹ ,
The 2,5-position and the 3,5-position are preferable, and the 3,5-position is particularly preferable.

The compound (1) is effective for the above-mentioned object of the present invention, and among them, particularly preferable compounds are A ¹ , A ² , A ³ and A exemplified in Tables 1 to 4 below. ⁴ , B
Compound No. 1 having a combination of ¹ , B ² , B ³ , and B ⁴ . 1
~ No. 104 can be mentioned. B in the table is 1,
4-phenylene and Ch represent 1,4-cyclohexylene, but in the case of 1,4-cyclohexylene, trans is preferable to cis as the conformation.

[0023]

[0024]

[0025]

[0026]

No. 1-9, No. 20-22, No.
Polyimide, polyamide or polyamide-imide using the compound (1) of 66 to 72 is particularly suitable as a liquid crystal aligning material for a normal TN liquid crystal display element that requires a pretilt angle of about 5 to 10 degrees. No. 10-19, N
o. 23-65, No. Polyimide, polyamide or polyamide-imide using the compound (1) of 73 to 104 is particularly suitable as a liquid crystal alignment material for vertical alignment.

The polyamide using the compound (1) in which R ² is a monovalent hydrocarbon group has a high voltage holding ratio and has a significantly improved electric property such as less seizure, especially when used as a liquid crystal aligning material. It will be what you did. In this case, R ²
Is preferably an alkyl group having 1 to 15 carbon atoms or an oxygen-containing alkyl group. The alkyl group or oxygen-containing alkyl group may be linear or branched, and specific examples include methyl, ethyl, propyl, butyl, pentyl, hexyl,
Heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, isopropyl, isobutyl, sec-butyl, t-butyl, isopentyl, neopentyl, t-pentyl, 1-
Methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, isohexyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl,
4-ethylpentyl, 2,4-dimethylhexyl, 2,
3,5-triethylheptylmethoxy, ethoxy, propyloxy, butyloxy, pentyloxy, hexyloxy, methoxymethyl, methoxyethyl, methoxypropyl, methoxybutyl, methoxypentyl, methoxyhexyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, ethoxybutyl , Ethoxypentyl, ethoxyhexyl, hexyloxymethyl, hexyloxyethyl, hexyloxypropyl, hexyloxybutyl, hexyloxypentyl, hexyloxyhexyl and the like.

R ² may be an organic group having an unsaturated bond or an alicyclic structure, an organic group having an aromatic ring, a halogen-, nitrogen-, silicon- or phosphorus-containing organic group, etc., provided that there is no problem with the liquid crystal orientation. Absent. Further, these organic groups may have a substituent in the structure.

The compound (1) is copolymerized with a tetracarboxylic acid dianhydride in a solvent to form a polyamic acid, and then, depending on the conditions, becomes a polyimide. At this time, the compound (1) may be used alone, or two or more kinds of the compound (1) may be combined. Further, the compound (1) may be used in combination with another diamine. In order to further improve the properties, a polyamide obtained by reacting the compound (1) with another dicarboxylic acid may be added here. Although the compound (1) may be used alone as a component of this polyamide, two or more kinds of the compound (1) may be used, or the compound (1) and other known diamine may be used in combination. . Instead of this polyamide, polyamide imide obtained by reacting the compound (1) with a mixture of other tetracarboxylic acid and dicarboxylic acid may be used. Further, a third component such as an aminosilicon compound may be added to these in order to improve the adhesion of the orientation material to the glass substrate and adjust the hardness.

The polyamide or polyamide-imide as the above additive is added in an amount of 0.01 to 30% by weight, preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, based on the polyamic acid or polyimide. % Addition is more preferred.

The ratio of amide groups of polyamideimide r = (number of amide groups / (number of amide groups + number of imide groups)) × 100 can be arbitrarily selected within the range of 0.1 to 99%. Here, when r is 50% or more, it is preferable for use as the above-mentioned additive. When r is 20% or less, the polyamide-imide alone can be used as the alignment material.

The polyamide of the present invention can be used alone as a liquid crystal aligning material, but may be used by adding it to other polyamic acid, polyimide, polyamide or the like. Further, an aminosilicon compound or the like may be added in order to improve the adhesion to the glass substrate and adjust the hardness.

The tetracarboxylic dianhydride which is a component of the repeating unit of the formula (3) is, for example, pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2 , 2 ', 3,3'-biphenyltetracarboxylic dianhydride,
2,3,3 ', 4'-biphenyltetracarboxylic dianhydride, 2,
2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,3,
3 ', 4'-biphenyltetracarboxylic dianhydride, 3,3', 4,
4'-benzophenone tetracarboxylic dianhydride, bis (3,
4-dicarboxyphenyl) ether dianhydride, bis (3,4-
Dicarboxyphenyl) sulfone dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, bis (dicarboxyphenyl) methane dianhydride Substance, cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride,
Cyclohexane tetracarboxylic dianhydride, dicyclohexane tetracarboxylic dianhydride, dicyclopentane tetracarboxylic dianhydride, bis (dicarboxycyclohexyl) ether dianhydride, bis (dicarboxycyclohexyl) sulfone dianhydride, bis (Dicarboxycyclohexyl) methane dianhydride, 1,2-dicarboxy-4-succinic-1,2,3,4-tetrahydronaphthalene dianhydride, 2,3,5
-Tricarboxycyclopentaneacetic acid dianhydride, 5,6-dicarboxy-1-methyl-3-succinic-1-cyclohexene dianhydride, 2,3,5,6-tetracarboxybicyclo [2.2
・ 1] Cyclopentane dianhydride, and 2,2'-bis (3,4-
Dicarboxyphenyl) -1,1,1,3,3,3, -hexafluoropropane dianhydride may be mentioned. Some of these compounds include isomers, but a mixture of these isomers may also be used. In addition, these compounds
You may use together more than one kind. The tetracarboxylic dianhydride used in the present invention may be other than the above compounds.

The dicarboxylic acid which is a component of the repeating unit of the formula (6) is, for example, terephthalic acid, isophthalic acid,
1,3-phenylene diacetic acid, 1,4-phenylene diacetic acid, 1,4-phenylene diacrylic acid, 4,4 ′-(hexafluoroisopropyridin) bisbenzoic acid, 4,
Acyclic dicarboxylic acids such as 4′-oxybisbenzoic acid, 5-alkoxyisophthalic acid, tetrafluoroterephthalic acid, tetrafluoroisophthalic acid, diphenic acid, 4,4′-biphenyldicarboxylic acid, naphthalenedicarboxylic acid derivative, glutaric acid, etc., Maleic acid, fumaric acid, muconic acid, tetrafluorooxalic acid, hexafluoroglutaric acid, perfluoroadipic acid, cyclohexyl oxalic acid, 1,1-cyclohexyl adipic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid Acid, 1,4-cyclohexanedicarboxylic acid, 1,
Mention may be made of 3-adamantanedicarboxylic acid, 1,3-adamantanediacetic acid, cis-5-norbornene-endo-dicarboxylic acid and 1,3-cyclobutanedicarboxylic acid. These carboxylic acids may be used as carboxylic acid chloride. Further, the carboxylic acid used in the present invention may be other than the above compounds.

Examples of the diamine other than the compound (1) used in the polyimide, polyamide or polyamideimide of the present invention include trimethylenediamine, tetramethylenediamine, hexamethylenediamine, 1,12-dodecanediamine, 1,4- Diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, p- and m-phenylenediamine, 1,4-diamino-2-butylbenzene, 1,4 -Diamino-2-dodecyloxybenzene, bis (4-aminophenyl) ether, 4,4'-diaminodiphenylmethane, 4,4'-
Diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-2,2'-dimethyldiphenylmethane, 4,4'-diamino-
3,3 ', 5,5'-Tetramethyldiphenylmethane, 1,2-bis (4
-Aminophenyl) ethane, 1,2-bis (4-amino-2-methylphenyl) ethane, bis (4-aminophenyl) sulfone, bis (4-aminophenyl) sulfide, bis (4-
(3-Aminophenoxy) phenyl) sulfone, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, bis (4- (4-aminophenoxy) phenyl) sulfone, benzidine, 2,2'-diamino Benzophenone, 2,2'-diaminobenzophenone, 2,2-bis (4-aminophenyl) propane, 1,5-diaminonaphthalene, 4,4'-diamino-3-octyldiphenylmethane, 2,2-bis (4- Aminophenyl)-
1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-
(4-Aminophenoxy) phenyl) -1,1,1,3,3,3-hexafluoropropane, 4,4'-bis (4-aminophenoxy) biphenyl, 1,1-bis (4- (4- Aminophenoxy)
Phenyl) cyclohexane, 1,1-bis (4- (4-aminophenoxy) phenyl) -4-propylcyclohexane, 1,1
-Bis (4- (4-aminobenzyl) phenyl) -cyclohexane, 1,3-bis (4- (4-aminobenzyl) phenyl) propane, 1,4-bis (4-aminophenoxy) benzene, and bis- Mention may be made of p-aminophenylaniline. The diamine used in the present invention may be other than the above compounds.

The solvent used to dissolve the polyimide, polyamide or polyamideimide of the present invention is N-methyl-2-
Pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), ethylene glycol monobutyl ether (B
C), ethylene glycol monoethyl ether, g-butyrolactone and the like.

The polyamic acid of the present invention in these solvents at a concentration of 0.1 to 30% by weight, preferably 1 to 10% by weight,
At least one of polyimide, polyamide, and polyamide-imide, and other components are dissolved. This solution is brushed, dipped, spinner, spray,
It is applied on the substrate by a printing method or the like. Then 50-150
After evaporating the solvent at C, preferably 80-120 C,
A film is formed by heating at 150 to 400 ° C., preferably 180 to 280 ° C. The adhesion between the film and the substrate can be improved by treating the surface of the substrate with a silane coupling agent before coating and forming a film on it. Then, the film surface is rubbed in one direction with a cloth or the like to obtain a liquid crystal alignment material.

The use of the liquid crystal aligning material of the present invention can improve the characteristics of all known liquid crystal display elements.
Particularly, the liquid crystal aligning material of the present invention is very effective in improving the image sticking of the liquid crystal display element for TFT which requires a particularly high voltage holding ratio. As examples of the liquid crystal composition used in such a liquid crystal display device for TFT, Japanese Patent No. 3086228 and Japanese Patent No. 263 are disclosed.
5435, Japanese Patent Publication No. 5-501735, Japanese Patent Publication No. 9-255960, and the like. Therefore, the liquid crystal aligning material of the present invention is particularly preferably used in combination with the liquid crystal composition described therein.

The compound (1) of the present invention can be easily synthesized by the following method. The compound represented by formula (1-b) can be synthesized by reacting the acid chloride represented by formula (1-a) with a copper reagent derived from dichlorobromobenzene. The dichlorobromobenzene used here is easily available as a commercial product or by synthesizing according to a known method. The acid chloride represented by (1-a) can be easily synthesized by the method described in JP-A-56-158751. The carbonyl group of (1-c) is referred to as Synthesis, 633 (197).
Silane reduction (1-d) according to the method described in 4)
Then, it can be induced to (1-f) by reacting with a compound represented by (1-e) according to a known method using chloroplatinic acid as a catalyst. Where (1-e)
Is easily available as a commercial product or by synthesizing according to a known method. This (1-f) is
w. Chem. Int. Ed. , Vol. 38,
According to the method described in 2413 (1999), the compound is reacted with a benzylamine derivative to give (1-g), and this is subjected to a hydrogenolysis reaction according to a conventional method to easily obtain (1).

[0041]

In the formula, A ¹ , A ² , A ³ , B ¹ , B ² , B ³ ,
^{B 4, R 2, R 3} , R 4, R 5, R 6, R 7, and p represents the same meaning as above, Y is a single bond or CH ₂ - represents, R ¹⁰ has the following structure formula (7)-(9) (R ¹¹ represents a terminal alkenyl group having 2 to 10 carbon atoms.)
Represents either

The compound (1) is the following copper reagent (1-h)
And acid chloride (1-i) can be used to produce the compound in the same manner as above. (Wherein A ¹ , A ² , A ³ , B ¹ , B ² , B ³ , R ¹⁰ , and Y
Represents the same meaning as described above, and Z represents a chlorine atom or a nitro group. )

The copper reagent (1-h) used here can be derived from a halide synthesized by the method described in WO 97/37959 or the like. As the acid chloride, a commercially available product may be used, or the acid chloride may be synthesized and used according to a known method.

The phenylenediamine compound of the present invention can be used in various polyimide coating agents, polyimide resin molded products, films, fibers and the like, in addition to the polyimide resin for liquid crystal alignment material. Further, raw materials for polyamide resin, polyamide-imide resin, polyurea resin,
Alternatively, it can be used as a curing agent for epoxy resin.

[0046]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the examples. In the examples, NMR was measured in deuterated chloroform.
GPC was used to measure the molecular weight, polystyrene was used as a standard solution, and DMF was used as the eluent.

Evaluation Method of Liquid Crystal Display Element The evaluation method of the liquid crystal display element used in the examples will be described. 1. The pretilt angle crystal rotation method was used. 2. Burn-in (residual charge) The residual charge was measured by the method described in Miyake et al., IEICE Technical Report, EID 91-111, p19. This residual charge was used as an index of image sticking. That is, the more residual charge is, the easier the image sticking is. The voltage applied to the liquid crystal cell during measurement was 5
It is an AC voltage in which an alternating current of 0 mV and 1 kHz and a triangular wave having a frequency of 0.0036 Hz are superimposed. 3. The voltage holding ratio was measured by the method described in "Mizushima et al., Proc. The AC pulse voltage used for measurement is
The gate width was 69 μs, the frequency was 60 Hz, and the wave height was ± 4.5 V.

Example 1 3,5-Diamino-4 '-(4- (1,1,1,3,3
-Pentamethyldisiloxanyl) butyl) diphenylmethane (in the general formulas (1) and (2), X is -CH ₂
And A ¹ is a 1,4-phenylene group, A ² , A ³ and A ⁴ are single bonds, B ¹ , B ² and B ³ are single bonds, and B ⁴ is a butylene group. Yes R ³ , R ⁴ , R ⁵ , R ⁶ ,
And R ⁷ each represent a methyl group, p is 1, and the compound in which the position of the amino group is at the 3,5 position relative to the substituent) is 5.5 g (0.23 mol) of magnesium and 300 ml of tetrahydrofuran (THF). 4 (3-butenyl) bromobenzene synthesized according to the method described in JP-A-9-286742 in an amount of 47.0 g (0.
A solution of 223 mol) in THF (100 ml) was added dropwise to give a Grignard reagent. Copper iodide 42.0 g (0.22 m
ol) and 500 ml of THF in a mixture at -30 ° C.
The Grignard reagent was added below and the temperature was raised to 0 ° C. To this reaction mixture was added 3,5-dinitrobenzoic acid 35.
A solution of 0 g (0.152 mol) in 100 ml of THF-
The mixture was added at 30 ° C or lower, and then stirred at room temperature for 1 hour. The reaction mixture was poured into ice water (500 ml), and toluene (20 ml) was added.
0 ml) was added and the organic layer was separated. The organic layer is purified water (3
(00 ml) and then dried over anhydrous magnesium sulfate. After evaporating the solvent, the residue is purified by column chromatography (silica gel / toluene),
4 '-(3-butenyl) -3,5-dinitrobenzophenone was obtained. Yield 24.1 g, yield 49%.

24.0 g (73.5 mmo) of this compound
To 150 ml of a solution of 1) of trifluoroacetic acid, 47 ml (0.29 mol) of triethylsilane was added at room temperature, and the mixture was stirred at room temperature for 3 days. After distilling off the solvent under reduced pressure,
Toluene was added to the residue, and the mixture was washed with an aqueous sodium hydrogen carbonate solution. The organic layer was dried over anhydrous magnesium sulfate. After evaporating the solvent, the residue was purified by column chromatography (silica gel / heptane: toluene = 1: 1) to obtain 4 ′-(3-butenyl) -3,5-dinitrodiphenylmethane. Yield 11.5g, Yield 50
%.

9.0 g (29 mmol) of this compound and 1,1,1,3,3-pentamethyldisiloxane 8.
To a solution of 5 g (57 mmol) in 30 ml of toluene, 80
At 10 ° C, a solution of chloroplatinic acid in isopropyl alcohol (10
Wt%, 0.15 ml) was added. After stirring at 80 ° C. for 2 days, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel / heptane: toluene = 1: 1) to give 3,5-dinitro-4 ′-(4- (1 ，
1,1,3,3-Pentamethyldisiloxanyl) butyl) diphenylmethane was obtained. Yield 10.8g, Yield 8
1%.

10.8 g of this compound was dissolved in 200 ml of a toluene-ethanol mixed solvent to prepare 5% Pd / C1.0.
g was added and a hydrogenation reaction was carried out. After the reaction, the catalyst was filtered and the solvent was evaporated. The residue was subjected to column chromatography (silica gel / toluene: methanol = 10:
1) and purified by recrystallization (heptane) 3,5
-Diamino-4 '-(4- (1,1,1,3,3-pentamethyldisiloxanyl) butyl) diphenylmethane was obtained. Yield 4.4 g, 47% yield. ¹ H NMR; d 7.0-7.2 (m, 4H), 5.96 (d, 2H, J = 1.90Hz),
5.88 (t, 1H, J = 1.95Hz), 3.74 (s, 2H), 3.51 (brs,
4H), 2.56 (t, 2H, J = 7.70Hz), 1.5-1.7, 1.3-1.4, 0.5-
0.6 (m, 6H), 0.05, 0.03 (s, 15H). Melting point; 72.9-74.4 ℃

Example 2 3,5-diamino-4 '-(4- (4- (2- (1,
1,1,3,3-Pentamethyldisiloxanyl) ethyl) cyclohexyl) cyclohexyl) diphenylmethane (in the general formulas (1) and (2), X is —CH ₂ —
And A ¹ is a 1,4-phenylene group, A ² and A ³ are trans-1,4-cyclohexylene groups, A ⁴ is a single bond, and B ¹ , B ² and B ³ are single bonds. There, B ⁴ is an ethylene group ^{R 3, R 4, R 5} , R 6, and R ⁷ represents a methyl group, p is 1, the position of the amino group is the 3,5-position relative to the substituent In the following: 4- (4- (4) synthesized according to WO 97/37959
-Ethynylcyclohexyl) cyclohexyl) bromobenzene was used as the starting material and was synthesized according to the above method. ¹ H NMR; d 7.0-7.2 (m, 4H), 5.97 (d, 2H, J = 2.00Hz),
5.89 (t, 1H, J = 1.95Hz), 3.75 (s, 2H), 3.60 (brs,
4H), 0.8-2.6 (m, 24H), 0.05, 0.03 (s, 15H).

Example 3 3,5-diamino-1- (2- (4- (2- (1,1,
1,3,3-Pentamethyldisiloxanyl) ethyl) cyclohexyl) ethyl) benzene (in the general formulas (1) and (2), X is —CH ₂ CH ₂ — and A ¹ is 1,
4-cyclohexylene group, A ² , A ³ and A ⁴ are single bonds, B ¹ , B ² and B ³ are single bonds, B ⁴ is an ethylene group and R ³ , R ⁴ and R ⁵ , R ⁶ and R ⁷ represent a methyl group, p is 1 and the amino group is in the 3,5 position relative to the substituent) Synthesis of 4-ethynylcyclohexyl synthesized according to WO 97/37959 It was synthesized according to the above method using bromomethane as a starting material. ¹ H NMR; d 5.97 (d, 2H, J = 1.95Hz), 5.88 (t, 1H, J =
1.95Hz), 3.55 (brs, 4H), 0.8-2.6 (m, 18H), 0.05, 0.
03 (s, 15H).

Example 4 (Synthesis of Polyamic Acid) In a 50 ml three-necked flask, the composition of Example 1 was performed.
1.0 g (2.5 mmol) of 5-diamino-4 ′-(4- (1,1,1,3,3-pentamethyldisiloxanyl) butyl) diphenylmethane was added and dissolved in 10 g of NMP. Here, pyromellitic anhydride (PMDA) 0.
54 g (2.5 mmol) was added and stirred for 1 hour. Then, this solution was diluted with 21 g of NMP to obtain a transparent solution containing about 5% by weight of polyamic acid. The weight average molecular weight of this solution was 58,000, and the viscosity at 25 ° C. was 1640 mPa · s. Hereinafter, this solution is referred to as varnish A.

Example 5 (Synthesis of Polyamide) A 100 ml three-necked flask was synthesized in Example 1 with 3,
1.0 g (2.5 mmol) of 5-diamino-4 ′-(4- (1,1,1,3,3-pentamethyldisiloxanyl) butyl) diphenylmethane and 4,4′-diaminodiphenylmethane (hereinafter DDM 740mg
(3.7 mmol), terephthalic acid (TPA) 1.0 g
(6.0 mmol), lithium chloride 1.3 g (31 mm
ol) was added and dissolved in NMP (20 ml). Triphenyl phosphite (4.0 g, 13 mmol) was added dropwise thereto, and the mixture was reacted at 100 ° C. for 4 hours in a nitrogen stream. After cooling, the reaction product was added to 300 ml of methanol to reprecipitate the polymer. This crude product was treated twice with 150 ml of pure water,
It was washed by boiling once with 150 ml of methanol for about 30 minutes each. 2.5g polyamide dried in vacuum at 120 ℃ for 7 hours
Got The weight average molecular weight at this time was 190,000.

2.5 g of the above polyamide in a three neck flask
Was added and dissolved in NMP (50 ml). 60 here
290 mg (7.2 mmol) of sodium hydride was added, and the mixture was stirred at room temperature for 3 hours. Methyl iodide (1.3 g, 9.2 mmol) was added to this solution, and the mixture was further reacted at room temperature for 2 hours. The reaction product was reprecipitated in 700 ml of pure water, filtered, and then boiled and washed twice with 350 ml of pure water for 30 minutes each time, and then pure water / IPA (1/1 w / w) mixed solvent 10
It was washed once with 0 ml. It was vacuum dried at 120 ° C. for 8 hours to obtain 2.4 g of polymethylamide. This polymer is called polyamide A. The weight average molecular weight at this time is 102,
000, and the substitution rate of the amido hydrogen for the methyl group is N
It was 100% from the measurement of MR.

Example 6 (Synthesis of Polyamide-imide) In a 50 ml three-necked flask, the compound prepared in Example 1 was used.
1.0 g (2.5 mmol) of 5-diamino-4 ′-(4- (1,1,1,3,3-pentamethyldisiloxanyl) butyl) diphenylmethane was added and dissolved in 20 g of NMP. Here, pyromellitic anhydride (PMDA) 27
0 mg (1.2 mmol) was added, and the mixture was stirred in a nitrogen stream for 1 hour. Then terephthalic acid chloride (TPACl)
250 mg (1.2 mmol) and 1 ml of pyridine
Was added and the mixture was further stirred for 2 hours. After completion of the reaction, 20 ml of acetic anhydride was added and the reaction was carried out at 100 ° C. for 1 hour. After cooling, the reaction product was added to 300 ml of methanol to reprecipitate the polymer. This crude product was washed with 150 ml of pure water twice and once with 150 ml of methanol for 30 minutes each by boiling.
Vacuum-dried at 120 ° C for 7 hours and polyamide-imide 1.2
g was obtained. The weight average molecular weight at this time was 110,000.
Met.

1.0 g of the above polyamideimide was placed in a three-necked flask and dissolved in NMP (20 ml). Here, 94 mg of 60% sodium hydride (2.3 mmo
1) was added, and the mixture was stirred at room temperature for 3 hours. To this solution, 430 g (3.0 mmol) of methyl iodide was added and further reacted at room temperature for 2 hours. The reaction product was reprecipitated in 300 ml of pure water, filtered, washed twice with 150 ml of pure water for 30 minutes each, and washed once with 50 ml of pure water / IPA (1/1 w / w) mixed solvent. It was vacuum dried at 120 ° C. for 8 hours to obtain 960 mg of the intended polyamideimide. This polymer is called polyamide imide A. At this time, the weight average molecular weight was 43,000, and the substitution rate of the amido hydrogen for the methyl group was 97% according to the NMR measurement.

Example 4 above except that a part of the diamine was changed.
The polyamic acid, polyamide, and polyamideimide shown in Table 2 were prepared according to the methods of Examples 6 to 6 (Examples 4 to
6 is also listed again). In the table, numerical values in parentheses indicate mol%, and CBTDA represents 1,2,3,4-cyclobutanetetracarboxylic acid anhydride.

Application Example 1 0.18 ml and 18.2 ml of varnish A and varnish C were placed in a three-necked flask, 0.02 ml of a 5 wt% NMP solution of polyamide A was further added, and the mixture was stirred at room temperature for 1 hour. Thereafter, 12 ml of BC was added to obtain a resin composition of about 3% by weight. This composition was dropped on a transparent glass substrate having an ITO electrode on one surface and applied by a spinner method (2500 rpm, 20 seconds). 80 after application
After evaporating the solvent for 5 minutes at ℃, 250 ℃ in the oven
A heat treatment was performed for 30 minutes to obtain a resin film having a film thickness of about 65 nm. The glass substrate on which this resin film was formed was rubbed, and these two were put together so that the rubbing directions were antiparallel, and a liquid crystal cell with a cell thickness of 20 μm was assembled. The following liquid crystal composition 1 was injected into this cell, subjected to isotropic treatment at 110 ° C. for 30 minutes, and cooled to room temperature to obtain a liquid crystal display device. The residual charge of this liquid crystal display device was 0.01 V at 25 ° C., and the voltage holding ratios at 20, 60 and 90 ° C. were 98.6, 98.2 and 96.
It was 2%. The pretilt angle of this display element was measured and found to be 5.4 degrees.

[0061]

Application Example 2 A liquid crystal display device was obtained in the same manner as in Application Example 1 except that the following liquid crystal composition 2 was used instead of the liquid crystal composition 1. The residual charge of this liquid crystal display device is 0.02 V at 25 ° C.,
The voltage holding ratios at 20, 60 and 90 ° C. were 98.4, 98.0 and 95.7%, respectively. The pretilt angle of this display element was measured and found to be 4.7 degrees.

[0063]

Application Example 3 A liquid crystal display device was manufactured in the same manner as in Application Example 1 except that varnish B was used instead of varnish A and polyamide B was used instead of polyamide A, and the residual charge was measured. However, it was 0.02 V at 25 ° C., and the voltage holding ratios at 20, 60 and 90 ° C. were 98.5 and 97.
9 and 96.9%. The pretilt angle is 89
It was degree.

Application Example 4 Except that polyamide C was used instead of polyamide A,
A liquid crystal display device was manufactured by the method according to Application Example 1, and the residual charge was measured and found to be 0.01 V at 25 ° C.
The voltage holding ratios at 20, 60 and 90 ° C. were 98.4, 97.9 and 96.5%, respectively. The pretilt angle was 5.1 degrees.

Application Example 5 A liquid crystal display device was manufactured in the same manner as in Application Example 1, except that polyamideimide A was used instead of polyamide A.
When the residual charge was measured, it was 0.02 V at 25 ° C., and the voltage holding ratios at 20, 60 and 90 ° C. were 98.2, 97.5 and 95.9%, respectively.
The pretilt angle was 5.6 degrees.

Comparative Example According to the method described in JP-A-4-294327,
The compound of formula (10) was synthesized. Varnish D and polyamide D were prepared by the method according to Example 4 or Example 5 except that the compound of Example 1 was replaced with this (10). The weight average molecular weight of the polyamide was 95,000. Using these, a liquid crystal display device was manufactured by the method according to Application Example 1, and the residual charge and the voltage holding ratio thereof were measured. As a result, the residual charge was 0.12 V at 25 ° C.
The voltage holding ratio at 0, 60 and 90 ° C is 9 each
It was 5.4, 94.3 and 91.7%. The pretilt angle was 4.8 degrees.

[0068]

When a polymer obtained by copolymerizing phenylenediamine represented by the formula (1) of the present invention with tetracarboxylic dianhydride and / or dicarboxylic acid is used as a part of the liquid crystal aligning material, It is possible to manufacture a liquid crystal display device having a high retention rate and greatly improved image sticking. Compound (1) can be produced inexpensively by a short synthetic route. Therefore, the present invention makes it possible to provide a high-performance liquid crystal display device at a lower cost. Further, the phenylenediamine derivative represented by the formula (1), the polyimide, the polyamide, and the polyamideimide using the same can be used as a polymer raw material such as a selective permeation membrane or a conductive material such as polyaniline.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H090 HB08Y HD12 HD17 MA04                       MB01                 4H027 BD01 BD04 BD12 BD13 CM04                       CQ04 CR04 CT03 CT04 CT05                 4H049 VN01 VP02 VQ78 VR23 VR41                       VU20                 4J001 DA01 DB01 DB02 DB03 DC14                       DC15 DC16 DD01 DD03 DD20                       EB04 EB07 EB14 EB16 EB23                       EB36 EB37 EB44 EB46 EC45                       EC46 EE82C EE83C FB03                       FB05 FC03 FC05 GA13 JA07                       JA12 JA17 JB01 JC01                 4J043 PA01 PA02 PA04 PC196                       QB26 QB31 RA34 SA06 SA46                       SA47 SA85 SB01 SB02 TA22                       TA47 TA70 TA71 TB01 TB02                       UA022 UA032 UA042 UA121                       UA122 UA132 UA262 UA432                       UA672 UB152 UB302 VA011                       VA022 VA051 VA062 XA16                       XA19 ZA55 ZB23

Claims (15)

[Claims] 1. A phenylenediamine represented by the following formula (1). (R ¹ is represented by the following formula (2), and R ² is hydrogen or a monovalent hydrocarbon group having 1 to 15 carbon atoms.) (X is —CH ₂ — or —CH ₂ CH ₂ —; A ¹ is 1,4-cyclohexylene, 1,4-phenylene or 1,4-phenylene substituted with 1 to 4 fluorines. A ² , A ³ and A ⁴ are each independently a single bond,
1,4-cyclohexylene, 1,4-phenylene or 1,4-phenylene substituted with 1 to 4 fluorines; B ¹ , B ² and B ³ are each independently a single bond or-
CH ₂ CH ₂ -,; B ⁴ is alkylene of 1 to 10 carbon ^{atoms; R 3, R 4, R} 5, R 6, and R ⁷ are each independently a carbon number of 1 to 10 Alkyl; p
Is an integer of 1 or more. ) 2. A ¹ is 1,4-phenylene or trans-1,4-cyclohexylene; A ² , A ³ and A
⁴ are each independently a single bond, 1,4-cyclohexylene or 1,4-phenylene; B ¹ , B ² and B
The phenylenediamine according to claim 1, wherein ³ is a single bond, R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ are methyl and p is 1. 3. A phenylenediamine according to claim 1, which contains a repeating unit represented by the following formula (3):
A polyimide having a weight average molecular weight of 2000 or more. (A ⁵ is a tetravalent organic group, and A ⁵ and R ¹ may be different for each repeating unit.) 4. The polyimide according to claim 3, wherein A ⁵ is a tetravalent organic group represented by the following formula (4) or formula (5). 5. The polyimide according to claim 3 or 4, wherein the phenylenediamine according to claim 2 is used. 6. A phenylenediamine according to claim 1, which comprises a repeating unit represented by the following formula (6):
A polyamide having a weight average molecular weight of 2000 or more. (A ⁶ is a divalent organic group, R ² is hydrogen or a monovalent hydrocarbon group having 1 to 15 carbon atoms, and A ⁶ , R ¹ and R
² may be different for each repeating unit. ) 7. The polyamide according to claim 6, which uses the phenylenediamine according to claim 2. 8. A polyamideimide containing the phenylenediamine according to claim 1 and containing a repeating unit of the following formula (3) and having a weight average molecular weight of 2000 or more. (A ⁵ is a tetravalent organic group, and A ⁵ and R ¹ may be different for each repeating unit.) 9. A polyamideimide containing the phenylenediamine according to claim 1 and containing a repeating unit of the following formula (6) and having a weight average molecular weight of 2000 or more. (A ⁶ is a divalent organic group, R ² is hydrogen or a monovalent hydrocarbon group having 1 to 15 carbon atoms, and A ⁶ , R ¹ and R
² may be different for each repeating unit. ) 10. The polyamide-imide according to claim 8 or 9, which uses the phenylenediamine according to claim 2. 11. A liquid crystal alignment material containing the polyimide according to any one of claims 3 to 5. 12. An alignment material for liquid crystals, which comprises the polyamide according to claim 6 or 7. 13. An alignment material for a liquid crystal, which comprises the polyamideimide according to any one of claims 8 to 10. 14. A liquid crystal cell comprising the alignment material for liquid crystals according to claim 11. 15. A liquid crystal display device comprising the alignment material for liquid crystal according to claim 11.