JP3435752B2 - Diamino compound and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a diamino compound suitable for a liquid crystal alignment film and a method for producing the same.

[0002]

2. Description of the Related Art A liquid crystal display element used in a clock or a calculator has a twisted nematic structure in which an arrangement direction of nematic liquid crystal molecules is twisted by 90 degrees between a pair of upper and lower electrode substrates. Hereinafter, abbreviated as TN) mode is mainly adopted. In addition, a super twisted nematic (hereinafter abbreviated as STN) mode having a large twist angle of 180 to 300 degrees has been developed, and a liquid crystal display device having a good display quality even on a large screen can be obtained. Further, in recent years, since matrix display and color display have come to be performed, a large number of pixel electrodes and an MIM (metal-insulation phase-metal) adopting an active type twisted nematic mode capable of performing ON-OFF of these pixel electrodes. ) Elements and TF
The development of T (Field Effect Thin Film Transistor) elements has become popular.

A problem common to all of these modes is that when the same screen is displayed for a long time and then moved to another screen, the previous image remains as an afterimage. In particular, in order to obtain a high quality liquid crystal display device, it is a very important problem to improve the afterimage phenomenon. The cause of the afterimage phenomenon is due to the DC component applied to the liquid crystal display element.
It is considered that the electric double layer is generated by the ionic component of impurities contained in the liquid crystal on the surface of the alignment film, the electric charges are biased between the upper and lower substrates, and the potential difference is caused by keeping the bias stable. . In particular, in the TFT element, the DC component cannot be removed due to the characteristics of the element.
The afterimage phenomenon is more noticeable and more serious than TN and STN. In addition, in the TFT mode, a high voltage holding ratio is required to prevent flickering of the screen.

As an alignment film used in such a liquid crystal display device, an organic film such as polyimide or polyamide is mainly used, and in JP-A-51-65960,

[0005]

[Chemical 5]

A liquid crystal display device having a liquid crystal alignment film using a polyimide resin having a repeating unit represented by the following is disclosed. However, an afterimage phenomenon is likely to occur in an element using a polyimide alignment film obtained by using such a polyether compound.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above problems, and is suitable for obtaining a polyimide raw material from which a liquid crystal alignment film having an excellent voltage holding ratio without an afterimage phenomenon can be obtained. Another object of the present invention is to provide a diamino compound and a method for producing the same.

[0008]

As a result of intensive research and development, the inventors of the present invention have found that the afterimage phenomenon has a correlation with the polarity of the surface of the alignment film, and as a polyimide raw material for the alignment film, the polarity is reduced. It was found that the afterimage phenomenon can be suppressed by using a diamino compound having a certain specific structure capable of producing the present invention, and completed the present invention. The diamino compound does not have a polar atom such as —O— and —SO ₂ —,
By increasing the molecular weight of amine, the proportion of imide groups is relatively reduced and the proportion of polar components is minimized.

The details of the present invention will be described below. 1) General formula

[0010]

[Chemical 6]

A diamino compound represented by: 2) General formula

[0012]

[Chemical 7]

The diphenylcyclohexane derivative represented by

[0014]

[Chemical 8]

After condensation of the para-nitrobenzoyl chloride derivative represented by the formula (1), a carbonyl group and a nitro group are reduced, and a general formula

[0016]

[Chemical 9]

A method for producing a diamino compound represented by:

The diamino compound of the present invention is represented by the above formula (1), and specific examples thereof include 1,1-bis [4- (4-aminobenzyl) phenyl] cyclohexane and 1,1. -Bis [4- (4-aminobenzyl) phenyl] -4-methylcyclohexane, 1,1-bis [4
-(4-Aminobenzyl) phenyl] -4-ethylcyclohexane, 1,1-bis [4- (4-aminobenzyl) phenyl] -4-propylcyclohexane, 1,1
-Bis [4- (4-aminobenzyl) phenyl] -4-
Butylcyclohexane, 1,1-bis [4- (4-aminobenzyl) phenyl] -4-pentylcyclohexane, 1,1-bis [4- (4-aminobenzyl) phenyl] -4-hexylcyclohexane, 1,1 -Bis [4
-(4-aminobenzyl) phenyl] -4-heptylcyclohexane, 1,1-bis [4- (4-aminobenzyl) phenyl] -4-octylcyclohexane,

1,1-bis [4- (4-amino-3-methylbenzyl) phenyl] -4-methylcyclohexane, 1,1-bis [4- (4-amino-3-methylbenzyl) phenyl]- 4-ethylcyclohexane, 1,1
-Bis [4- (4-amino-3-methylbenzyl) phenyl] -4-propylcyclohexane, 1,1-bis [4- (4-amino-3-methylbenzyl) phenyl]
-4-Butylcyclohexane, 1,1-bis [4- (4
-Amino-3-methylbenzyl) phenyl] -4-pentylcyclohexane, 1,1-bis [4- (4-amino-3-methylbenzyl) phenyl] -4-hexylcyclohexane, 1,1-bis [4- (4-amino-3-methylbenzyl) phenyl] -4-heptylcyclohexane, 1,1-bis [4- (4-amino-3-methylbenzyl) phenyl] -4-octylcyclohexane,

1,1-bis [4- (4-aminobenzyl) -3-methylphenyl] -4-methylcyclohexane, 1,1-bis [4- (4-aminobenzyl) -3-
Methylphenyl] -4-ethylcyclohexane, 1,1
-Bis [4- (4-aminobenzyl) -3-methylphenyl] -4-propylcyclohexane, 1,1-bis [4- (4-aminobenzyl) -3-methylphenyl]
-4-Butylcyclohexane, 1,1-bis [4- (4
-Aminobenzyl) -3-methylphenyl] -4-pentylcyclohexane, 1,1-bis [4- (4-aminobenzyl) -3-methylphenyl] -4-hexylcyclohexane, 1,1-bis [4- (4-Aminobenzyl) -3-methylphenyl] -4-heptylcyclohexane, 1,1-bis [4- (4-aminobenzyl) -3
-Methylphenyl] -4-octylcyclohexane,

1,1-bis [4- (4-aminobenzyl) -2-methylphenyl] -4-methylcyclohexane, 1,1-bis [4- (4-aminobenzyl) -2-
Methylphenyl] -4-ethylcyclohexane, 1,1
-Bis [4- (4-aminobenzyl) -2-methylphenyl] -4-propylcyclohexane, 1,1-bis [4- (4-aminobenzyl) -2-methylphenyl]
-4-Butylcyclohexane, 1,1-bis [4- (4
-Aminobenzyl) -2-methylphenyl] -4-pentylcyclohexane, 1,1-bis [4- (4-aminobenzyl) -2-methylphenyl] -4-hexylcyclohexane, 1,1-bis [4- (4-Aminobenzyl) -2-methylphenyl] -4-heptylcyclohexane, 1,1-bis [4- (4-aminobenzyl) -2
-Methylphenyl] -4-octylcyclohexane,

1,1-bis [4- (4-amino-3-methylbenzyl) phenyl] cyclohexane, 1,1-bis [4- (4-amino-3-ethylbenzyl) phenyl] cyclohexane, 1,1 -Bis [4- (4-amino-3-propylbenzyl) phenyl] cyclohexane,
1,1-bis [4- (4-amino-3-fluorobenzyl) phenyl] cyclohexane,

1,1-bis [4- (4-aminobenzyl) -3-methylphenyl] cyclohexane, 1,1-
Bis [4- (4-aminobenzyl) -3-ethylphenyl] cyclohexane, 1,1-bis [4- (4-aminobenzyl) -3-propylphenyl] cyclohexane,
1,1-bis [4- (4-aminobenzyl) -3-fluorophenyl] cyclohexane,

1,1-bis [4- (4-amino-3-ethylbenzyl) phenyl] -4-methylcyclohexane, 1,1-bis [4- (4-amino-3-propylbenzyl) phenyl]- 4-methylcyclohexane, 1,
1-bis [4- (4-amino-3-fluorobenzyl)
Phenyl] -4-methylcyclohexane,

1,1-bis [4- (4-aminobenzyl) -3-ethylphenyl] -4-methylcyclohexane, 1,1-bis [4- (4-aminobenzyl) -3-
Propylphenyl] -4-methylcyclohexane, 1,
1-bis [4- (4-aminobenzyl) -3-fluorophenyl] -4-methylcyclohexane,

1,1-bis [4- (4-amino-3-ethylbenzyl) phenyl] -4-ethylcyclohexane, 1,1-bis [4- (4-amino-3-propylbenzyl) phenyl]- 4-ethylcyclohexane, 1,
1-bis [4- (4-amino-3-fluorobenzyl)
Phenyl] -4-ethylcyclohexane,

1,1-bis [4- (4-aminobenzyl) -3-ethylphenyl] -4-ethylcyclohexane, 1,1-bis [4- (4-aminobenzyl) -3-
Propylphenyl] -4-ethylcyclohexane, 1,
1-bis [4- (4-aminobenzyl) -3-fluorophenyl] -4-ethylcyclohexane,

1,1-bis [4- (4-amino-3-ethylbenzyl) phenyl] -4-propylcyclohexane, 1,1-bis [4- (4-amino-3-propylbenzyl) phenyl]- 4-propylcyclohexane,
1,1-bis [4- (4-amino-3-fluorobenzyl) phenyl] -4-propylcyclohexane,

1,1-bis [4- (4-aminobenzyl) -3-ethylphenyl] -4-propylcyclohexane, 1,1-bis [4- (4-aminobenzyl) -3
-Propylphenyl] -4-propylcyclohexane,
1,1-bis [4- (4-aminobenzyl) -3-fluorophenyl] -4-propylcyclohexane, and the like.

For the production of the diamino compound of the present invention,
This will be specifically described. The diphenylcyclohexane or its derivative used in the present invention is represented by the above formula (2), and specific examples include 1,1-diphenylcyclohexane, 1,1-diphenyl-4-methylcyclohexane, 1,1. -Diphenyl-4-ethylcyclohexane, 1,1-diphenyl-4-propylcyclohexane, 1,1-diphenyl-4-butylcyclohexane,
1,1-diphenyl-4-pentylcyclohexane,
1,1-diphenyl-4-hexylcyclohexane,
1,1-diphenyl-4-heptylcyclohexane,
1,1-diphenyl-4-octylcyclohexane,

1,1-bis (2-methylphenyl) cyclohexane, 1,1-bis (2-methylphenyl) -4
-Methylcyclohexane, 1,1-bis (2-methylphenyl) -4-ethylcyclohexane, 1,1-bis (2-methylphenyl) -4-propylcyclohexane, 1,1-bis (2-methylphenyl)- 4-butylcyclohexane, 1,1-bis (2-methylphenyl)
-4-pentylcyclohexane, 1,1-bis (2-methylphenyl) -4-hexylcyclohexane, 1,1
-Bis (2-methylphenyl) -4-heptylcyclohexane, 1,1-bis (2-methylphenyl) -4-octylcyclohexane,

1,1-bis (3-methylphenyl) cyclohexane, 1,1-bis (3-methylphenyl) -4
-Methylcyclohexane, 1,1-bis (3-methylphenyl) -4-ethylcyclohexane, 1,1-bis (3-methylphenyl) -4-propylcyclohexane, 1,1-bis (3-methylphenyl)- 4-butylcyclohexane, 1,1-bis (3-methylphenyl)
-4-pentylcyclohexane, 1,1-bis (3-methylphenyl) -4-hexylcyclohexane, 1,1
-Bis (3-methylphenyl) -4-heptylcyclohexane, 1,1-bis (3-methylphenyl) -4-octylcyclohexane,

1,1-bis (2-ethylphenyl) cyclohexane, 1,1-bis (2-ethylphenyl) -4
-Methylcyclohexane, 1,1-bis (2-ethylphenyl) -4-ethylcyclohexane, 1,1-bis (2-ethylphenyl) -4-propylcyclohexane, 1,1-bis (2-ethylphenyl)- 4-butylcyclohexane, 1,1-bis (2-ethylphenyl)
-4-pentylcyclohexane, 1,1-bis (2-ethylphenyl) -4-hexylcyclohexane, 1,1
-Bis (2-ethylphenyl) -4-heptylcyclohexane, 1,1-bis (2-ethylphenyl) -4-octylcyclohexane,

1,1-bis (3-ethylphenyl) cyclohexane, 1,1-bis (3-ethylphenyl) -4
-Methylcyclohexane, 1,1-bis (3-ethylphenyl) -4-ethylcyclohexane, 1,1-bis (3-ethylphenyl) -4-propylcyclohexane, 1,1-bis (3-ethylphenyl)- 4-butylcyclohexane, 1,1-bis (3-ethylphenyl)
-4-pentylcyclohexane, 1,1-bis (3-ethylphenyl) -4-hexylcyclohexane, 1,1
-Bis (3-ethylphenyl) -4-heptylcyclohexane, 1,1-bis (3-ethylphenyl) -4-octylcyclohexane,

1,1-bis (2-propylphenyl) cyclohexane, 1,1-bis (2-propylphenyl)
-4-methylcyclohexane, 1,1-bis (2-propylphenyl) -4-ethylcyclohexane, 1,1-
Bis (2-propylphenyl) -4-propylcyclohexane, 1,1-bis (2-propylphenyl) -4-
Butylcyclohexane, 1,1-bis (2-propylphenyl) -4-pentylcyclohexane, 1,1-bis (2-propylphenyl) -4-hexylcyclohexane, 1,1-bis (2-propylphenyl) -4 -Heptylcyclohexane, 1,1-bis (2-propylphenyl) -4-octylcyclohexane,

1,1-bis (3-propylphenyl) cyclohexane, 1,1-bis (3-propylphenyl)
-4-methylcyclohexane, 1,1-bis (3-propylphenyl) -4-ethylcyclohexane, 1,1-
Bis (3-propylphenyl) -4-propylcyclohexane, 1,1-bis (3-propylphenyl) -4-
Butylcyclohexane, 1,1-bis (3-propylphenyl) -4-pentylcyclohexane, 1,1-bis (3-propylphenyl) -4-hexylcyclohexane, 1,1-bis (3-propylphenyl) -4 -Heptylcyclohexane, 1,1-bis (3-propylphenyl) -4-octylcyclohexane,

1,1-bis (2-fluorophenyl) cyclohexane, 1,1-bis (2-fluorophenyl)
-4-Methylcyclohexane, 1,1-bis (2-fluorophenyl) -4-ethylcyclohexane, 1,1-
Bis (2-fluorophenyl) -4-propylcyclohexane, 1,1-bis (2-fluorophenyl) -4-
Butylcyclohexane, 1,1-bis (2-fluorophenyl) -4-pentylcyclohexane, 1,1-bis (2-fluorophenyl) -4-hexylcyclohexane, 1,1-bis (2-fluorophenyl) -4 -Heptylcyclohexane, 1,1-bis (2-fluorophenyl) -4-octylcyclohexane,

1,1-bis (3-fluorophenyl) cyclohexane, 1,1-bis (3-fluorophenyl)
-4-methylcyclohexane, 1,1-bis (3-fluorophenyl) -4-ethylcyclohexane, 1,1-
Bis (3-fluorophenyl) -4-propylcyclohexane, 1,1-bis (3-fluorophenyl) -4-
Butylcyclohexane, 1,1-bis (3-fluorophenyl) -4-pentylcyclohexane, 1,1-bis (3-fluorophenyl) -4-hexylcyclohexane, 1,1-bis (3-fluorophenyl) -4 -Heptylcyclohexane, 1,1-bis (3-fluorophenyl) -4-octylcyclohexane, and the like.

If necessary, two or more kinds of these compounds may be used in combination. These diphenylcyclohexanes or their derivatives can be used to reduce the carbonyl group of diphenylcyclohexanone derivatives, dehydrate alcohols produced by the Grignard reaction between diphenylcyclohexanone derivatives and alkylmagnesium halides, and further reduce the resulting double bonds by catalytic hydrogen reduction. It can be easily obtained by reducing by the method described above, or by dehydrating the alcohol compound produced by the reaction of the diphenylcyclohexanone derivative and alkyllithium, and further reducing the resulting double bond by a method such as catalytic hydrogen reduction.

The para-nitrobenzoyl chloride or its derivative used in the present invention is represented by the above formula (3), and specific examples thereof include 4-nitrobenzoyl chloride, 2-methyl-4-nitrobenzoyl chloride, 2-ethyl-4-nitrobenzoyl chloride,
2-propytyl-4-nitrobenzoyl chloride, 2
-Fluoro-4-nitrobenzoyl chloride, 3-methyl-4-nitrobenzoyl chloride, 3-ethyl-
4-nitrobenzoyl chloride, 3-propytyl-4
-Nitrobenzoyl chloride, 3-fluoro-4-nitrobenzoyl chloride, and the like. Also,
If necessary, these two or more compounds may be used in combination.

A catalyst is usually used in the reaction of diphenylcyclohexane or its derivative with para-nitrobenzoyl chloride or its derivative. The catalyst includes AlCl ₃ , SbCl ₅ , FeCl ₃ , TeCl ₂ , S
Examples thereof include nCl ₄ , TiCl ₄ , BiCl ₃ , ZnCl _{2 and the} like, but AlCl ₃ is preferable from the viewpoint of reactivity. Also,
In the reaction, a solvent is used if necessary. The solvent includes carbon disulfide, dichloromethane, chloroform, dichloroethane, nitrobenzene and the like, and nitrobenzene is preferable.

In the reaction, the catalyst and para-nitrobenzoyl chloride or its derivative are mixed with stirring in the absence of solvent or in a solvent, and diphenylcyclohexane or its derivative (dissolved in a solvent as necessary) at 0 ° C to 150 ° C. ) Is added dropwise and reacted. When the reaction rate decreases, the reaction temperature may be raised, but it must be carried out within the range not exceeding 150 ° C. After the completion of the reaction, in order to deactivate the catalyst, the reaction mixture is poured into ice, and the solvent and the like are removed by washing with water, distillation, steam distillation, etc.
A 1-bis [4- (4-aminobenzyl) phenyl] cyclohexane derivative is obtained.

The reduction of the carbonyl group can be carried out by reacting a trialkylsilane, specifically triethylsilane, in the presence of a catalyst such as trifluoromethanesulfonic acid or titanium tetrachloride. The reaction temperature at that time is preferably between 0 ° C and 100 ° C. A solvent may be used in the reaction, and halogenated hydrocarbons such as dichloromethane, chloroform and dichloroethane are preferred. To reduce the nitro group, in a solvent such as toluene, xylene, methanol, ethanol, tetrahydrofuran,
Using a catalyst such as platinum / carbon, platinum oxide, Raney nickel, palladium / carbon (hereinafter abbreviated as Pd-C),
It is carried out by hydrogen reduction at 10 to 80 ° C. under normal pressure or pressure. The substituents R, X in the formulas (2) and (3),
By appropriately selecting Y and Z, the desired diamino compound can be produced.

[0044]

EXAMPLES The compounds of the present invention will be illustrated below in more detail with reference to Examples, and products obtained by using the compounds, that is, liquid crystal alignment films of polyimide resin will be shown as application examples. It is not limited to these examples.

In the application examples and application comparative examples shown below, the degree of the afterimage phenomenon was measured by the CV curve method. The C-V curve method uses a liquid crystal cell of 25 mV and 1 kHz.
Is applied, and a direct current triangular wave (hereinafter, referred to as DC voltage) having a frequency of 0.0036 Hz is further overlapped, and D
It is a method of recording the capacitance C which changes by sweeping the C voltage in the range of -10V to 10V. When the DC voltage is swept to the positive side (0 → 10V), the capacity increases. Next, the capacitance is reduced by sweeping to the negative side (10 → 0V). When the voltage is swept from 0 to the negative side (0 → -10V), the capacity increases again, and when the voltage is swept to the positive side (-10 → 0V), the capacity decreases again. The waveform after repeating this for several cycles is as shown in FIG. When the bias of the charges is generated on the surface of the liquid crystal alignment film and the bias is stabilized, the voltage draws a hysteresis curve on both the positive side and the negative side. For the residual charge, draw two tangents on the C-V curve on both the positive side and the negative side, and find the intersections (α _{1 to} α ₄ ) of these and the capacitance (C ₀ ) when the DC voltage is 0, respectively. , The positive side is | α ₁ −α ₂ |, the negative side is | α ₃ −α ₄ |, and the average voltage difference between these two points is calculated, that is, (| α ₁ −α ₂ | │ ＋ │α ₃ −
It is determined by finding α ₄ |) / 2. If the film thickness of the liquid crystal cell and the film thickness of the alignment film are the same, this value is
It is a parameter for stabilizing the bias of electric charge. That is, the residual image phenomenon can be alleviated by using an alignment film having a small residual charge.

The voltage holding ratio was measured by a circuit as shown in FIG. The measurement method is as follows: gate pulse width 69 μs, frequency 60
It was performed by reading a drain (V _D ) which was changed by applying a rectangular wave (V _S ) of Hz and a wave height of ± 4.5 V to the source with an oscilloscope. For example, when a positive rectangular wave is applied to the source, the drain (V _D ) shows a positive value until the next negative rectangular wave is applied. if,
When the retention rate is 100%, V _D shown in FIG. 3 takes a rectangular orbit represented by a dotted line, but normally V _D becomes a solid line orbit that gradually approaches 0. Therefore, the area of the measured track (the area surrounded by the track where V = 0 and the track), that is, the shaded area was calculated, and this was repeated four times to obtain the average value. The area when the voltage did not decrease at all was defined as 100%, while the relative value of the measured area was defined as the voltage holding ratio (%). The pretilt angle was measured by using the crystal rotation method.

Example 1 375.70 g of aluminum chloride and 65 of nitrobenzene
0 ml was mixed, and 212.00 g of para-nitrobenzoyl chloride was added under ice cooling and dissolved. Next, a solution of 78.43 g of 1,1-diphenylcyclohexane in 150 ml of nitrobenzene was added dropwise over 30 minutes. Thirty minutes after the completion of dropping, the ice bath was removed, and the temperature was gradually raised to 75 ° C. over 4 hours with a mantle heater. After confirming the completion of the reaction by liquid chromatography, the reaction solution was poured into 2.5 liters of ice and then extracted with 1.0 liter of chloroform. This solution was washed with a 6N-HCl aqueous solution, a sodium hydrogen carbonate aqueous solution, saline and water, and after removing chloroform by a rotary evaporator, nitrobenzene was removed by steam distillation. By recrystallizing from ethyl acetate, 118.64 g of black-purple crystals of 1,1-bis [4- (4-nitrobenzoyl) phenyl] cyclohexane were obtained. Melting point 174.2-
It was 176.1 ° C. 1,1-bis [4- (4-nitrobenzoyl) phenyl] cyclohexane 106.63
g was dissolved in 1300 ml of dichloromethane, and a solution of 120 g of titanium tetrachloride in 200 ml of dichloromethane was added dropwise over 1 hour under ice cooling. Subsequently, a solution of 115.5 g of triethylsilane in 150 ml of dichloromethane was added dropwise over 90 minutes. Thirty minutes after the completion of dropping, the ice bath was removed and the mixture was stirred at room temperature for 4 hours. After confirming the completion of the reaction by liquid chromatography, the reaction solution was neutralized with an aqueous sodium carbonate solution and washed with water. After removing dichloromethane with a rotary evaporator, the residue was dissolved in toluene and treated with an alumina column, and the solvent was distilled off from the eluate. The concentrate was recrystallized with an ethyl acetate solvent to obtain 93.5 g of pale yellow 1,1-bis [4- (4-nitrobenzyl) phenyl] cyclohexane crystals. The melting point was 125.4-126.5 ° C. 1,
1-Bis [4- (4-nitrobenzyl) phenyl] cyclohexane 98.93 g was added to tetrahydrofuran 1100.
Dissolve in milliliter, Pd-C catalyst (5% product, water content 5
5.9 g (containing 5.9%) was added, and the mixture was cooled with water at normal pressure and brought into contact with hydrogen gas while stirring. After the absorption of hydrogen ceased, the catalyst was filtered off and the solution was concentrated. By recrystallizing the concentrate with a toluene solvent, 71.71 g of 1,1-bis [4- (4-aminobenzyl) phenyl] cyclohexane, which is the diamino compound of the present invention, was obtained. The melting point was 154.4 to 155.5 ° C. The proton nuclear magnetic resonance spectrum ( ¹ H-NMR) of this compound is shown in FIG.
The R chart is shown in FIG.

Example 2 4,4-diphenylcyclohexanone 5 under nitrogen blanket
4.0 g of the product was dissolved in 700 ml of dehydrated and purified tetrahydrofuran with stirring and cooled with dry ice-acetone. Next, 200 ml of n-butyllithium (1.6 mol / liter, hexane solution) was added dropwise over 2 hours. Two hours after the completion of dropping, cooling was stopped and the temperature was raised to room temperature over 4 hours. After confirming the completion of the reaction by liquid chromatography, 300 ml of a saturated ammonium chloride aqueous solution was poured into the reaction solution, followed by extraction with 700 ml of toluene. This solution was washed with brine and the toluene was removed by a rotary evaporator. Then, this was dissolved in 450 ml of toluene, and an ion exchange resin (Amberlyst 15E, manufactured by Organo Co.) 2.
8 g was mixed and heated under reflux for 3 hours. After the ion exchange resin was filtered off, the toluene was removed by a rotary evaporator, and the residue was dissolved in toluene / heptane = 1/4 (v / v) and purified by a silica gel column to give 4,4-
Diphenyl-1-butylcyclohexene (including 4,4-diphenyl-1-butylidenecyclohexane) 32.
97 g are obtained. Tetrahydrofuran 20 was added to 32.0 g of 4,4-diphenyl-1-butylcyclohexene (including 4,4-diphenyl-1-butylidenecyclohexane).
It was dissolved in 0 ml of acetic acid and 300 ml of acetic acid, 1.0 g of platinum oxide was added, and the mixture was cooled with water under normal pressure and brought into contact with hydrogen gas while stirring. After the absorption of hydrogen was stopped, the catalyst was filtered off, 2 liters of water was added, and the mixture was extracted with 1 liter of toluene. This solution was washed with water, toluene was removed by a rotary evaporator, and 1,1-diphenyl-4-
30.58 g of butylcyclohexane was obtained. Aluminum chloride (101.22 g) and nitrobenzene (200 ml) were mixed, and para-nitrobenzoyl chloride (57.10 g) was added under ice-cooling and dissolved. Next, a solution of 30.00 g of 1,1-diphenyl-4-butylcyclohexane in 50 ml of nitrobenzene was added dropwise over 30 minutes. Thirty minutes after the completion of dropping, the ice bath was removed, and the temperature was gradually raised to 67 ° C. over 5 hours with a mantle heater. After confirming the completion of the reaction by liquid chromatography, the reaction solution was poured into 1.5 liter of ice, and then chloroform 1.0
Extracted in liters. This solution is a 6N-HCl aqueous solution,
After washing with an aqueous solution of sodium hydrogen carbonate, saline and water, and removing the chloroform with a rotary evaporator,
Nitrobenzene was removed by steam distillation. By dissolving in toluene and purifying with a silica gel column, 1,1
-Bis [4- (4-nitrobenzoyl) phenyl] -4
45.40 g of -butylcyclohexane was obtained. 1,1-
Bis [4- (4-nitrobenzoyl) phenyl] -4-
Butylcyclohexane 45.40 g was added to dichloromethane 6
Dissolve in 60 ml, and under ice cooling, add 16.9 ml of a solution of 36.9 g of trifluorosulfuric acid in 80 ml of dichloromethane.
It dripped over time. Subsequently, triethylsilane 47.
A solution of 38 g of 80 ml of dichloromethane was added dropwise over 90 minutes. Thirty minutes after the completion of dropping, the ice bath was removed and the mixture was stirred at room temperature for 5 hours. After confirming the completion of the reaction by liquid chromatography, the reaction solution was neutralized with an aqueous sodium carbonate solution and washed with water. After removing dichloromethane with a rotary evaporator, the residue was dissolved in toluene and treated with an alumina column, and the solvent was distilled off from the eluate to obtain 1,1-bis [4- (4-nitrobenzyl) phenyl] -4-butyl. 38.0 g of cyclohexane was obtained. 1,1-bis [4
38.0 g of-(4-nitrobenzyl) phenyl] -4-butylcyclohexane was dissolved in 500 ml of tetrahydrofuran, and a Pd-C catalyst (5% product, moisture 55.
4.0 g (containing 9%) was added, and the mixture was cooled with water at normal pressure and brought into contact with hydrogen gas while stirring. After the absorption of hydrogen ceased, the catalyst was filtered off and the solution was concentrated. Concentrate the ethanol 87
%, And 13% methanol 13% to recrystallize the diamino compound of the present invention, 1,1-bis [4
14.22 g of-(4-aminobenzyl) phenyl] -4-butylcyclohexane was obtained. Melting point is 58.5-6
It was 0.1 ° C. The proton nuclear magnetic resonance spectrum ( ¹ H-NMR) of this compound is shown in FIG. 6, and the IR chart is shown in FIG.
Shown in.

Application Example 1 50 g of dehydrated and refined N-methyl-2-pyrrolidone was placed in a 200 ml four-necked flask equipped with a stirrer, a thermometer, a condenser and a nitrogen purging device, and then 1,1-
Bis [4- (4-aminobenzyl) phenyl] cyclohexane (7.43 g) was charged and dissolved with stirring. This is 13 ℃
After cooling, 3.69 g of pyromellitic dianhydride was added at once, and the reaction was stirred while cooling. After 1 hour, 0.11 g of para-aminophenyltrimethoxysilane was added, and the mixture was reacted with stirring at 20 ° C. for 1 hour. After that, the reaction solution is
A clear solution of 10% by weight of polyamic acid was obtained by diluting with 51.1 g of -methyl-2-pyrrolidone (NMP). The viscosity of this solution at 25 ° C. was 1870 centipoise. Add butyl cellosolve and N to this solution.
Add 1: 1 mixed solution with MP to add polyamic acid to 3
After diluting to a weight percentage, it was applied by spin coating (spinner method) on a transparent glass substrate having an ITO electrode on one side.
The rotation conditions were 5000 rpm and 15 seconds. 10 after coating
After drying at 0 degrees for 10 minutes, 2 hours in the oven
The temperature was raised to 00 ° C., and heat treatment was performed at 200 ° C. for 90 minutes to obtain a film thickness of about 600 Å polybenzylimide. The coating surfaces of the two substrates on which the polybenzylimide film was formed were rubbed to form a liquid crystal alignment film, and a liquid crystal cell having a cell thickness of 6 microns was assembled so that the rubbing directions were parallel and opposed to each other. Made T
The liquid crystal FB01 for FT was enclosed. 30 after encapsulation at 120 ° C
The liquid crystal element was obtained by performing isotropic treatment for minutes and gradually cooling to room temperature. For the measurement of the pretilt angle, a liquid crystal cell containing a liquid crystal ZLI-1132 manufactured by Merck & Co. Inc. and having a cell thickness of 20 μm was similarly prepared. The alignment of this liquid crystal element was good, and the pretilt angle of this liquid crystal measured by the crystal rotation method was 7.3 degrees. The residual charge of this cell was 0.06 V at 25 ° C., and the retention rate was 97.4%.

Application Example 2 50 g of dehydrated and purified N-methyl-2-pyrrolidone in a 200 ml four-necked flask equipped with a stirrer, a thermometer, a condenser and a nitrogen purging device, and then 1,1-
Bis [4- (4-aminobenzyl) phenyl] cyclohexane (7.43 g) was charged and dissolved with stirring. This is 13 ℃
After cooling, the mixture was charged with 3.68 g of methylcyclobutanetetracarboxylic dianhydride at once, and the mixture was stirred while cooling. After one hour, 0.33 g of paraaminophenyltrimethoxysilane was added, and the mixture was reacted with stirring at 20 ° C. for 1 hour. Then, the reaction solution was mixed with N-methyl-2-pyrrolidone (N
A transparent solution containing 10% by weight of polyamic acid was obtained by diluting with 53.0 g of MP). The viscosity of this solution at 25 ° C. was 104.5 centipoise. A 7: 3 mixed solution of butyl cellosolve and NMP was added to this solution to dilute the polyamic acid to 3% by weight, and then applied by spin coating (spinner method) on a transparent glass substrate provided with an ITO electrode on one side. . Rotation condition is 3000 rpm, 1
It was 5 seconds. After the coating film is dried at 100 ° C for 10 minutes, the temperature is raised to 200 ° C in an oven for 1 hour, and
A heat treatment was performed at 0 ° C. for 90 minutes to obtain a film thickness of about 600 Å polybenzylimide. The coating surfaces of the two substrates on which the polybenzylimide film was formed were rubbed to form a liquid crystal alignment film, and a liquid crystal cell having a cell thickness of 6 microns was assembled so that the rubbing directions were parallel and opposed to each other. The liquid crystal FB01 for TFT was enclosed. After encapsulation, isotropic treatment was performed at 120 ° C. for 30 minutes, and the liquid crystal element was obtained by gradually cooling to room temperature. For the measurement of the pretilt angle, a liquid crystal cell containing a liquid crystal ZLI-1132 manufactured by Merck & Co. Inc. and having a cell thickness of 20 μm was similarly prepared. The alignment of this liquid crystal element was good, and the pretilt angle of this liquid crystal measured by the crystal rotation method was 3.1 degrees. The residual charge of this cell is 25
The temperature was 0.01 V and the voltage holding ratio was 97.3%.

Application Example 3 50 g of dehydrated and purified N-methyl-2-pyrrolidone in a 200 ml four-necked flask equipped with a stirrer, a thermometer, a condenser and a nitrogen purging device, and then 1,1-
Bis [4- (4-aminobenzyl) phenyl] -4-butylcyclohexane (8.36 g) was charged and dissolved with stirring.
This is cooled to 13 ° C. and pyromellitic dianhydride 3.6 is added.
9 g was added at once, and the mixture was reacted with stirring while cooling.
After one hour, para-aminophenyltrimethoxysilane.
11 g was added and reacted at 20 ° C. for 1 hour with stirring. Then, the reaction solution was mixed with N-methyl-2-pyrrolidone (NMP) 5
Dilution with 9.4 g gave a clear solution of 10% by weight polyamic acid. The viscosity of this solution at 25 ° C. was 1540 centipoise. A 1: 1 mixed solution of butyl cellosolve and NMP was added to this solution to dilute the polyamic acid to 3% by weight, and then applied by spin coating (spinner method) on a transparent glass substrate having an ITO electrode on one side. . The rotation conditions were 5000 rpm and 15 seconds. After the coating film is dried at 100 ° C for 10 minutes, the temperature is raised to 200 ° C in an oven for 1 hour, and the temperature is increased to 9 ° C at 200 ° C.
A heat treatment was performed for 0 minutes to obtain a film thickness of about 600 Å polybenzylimide. The coating surfaces of the two substrates on which the polybenzylimide film was formed were rubbed to form a liquid crystal alignment film, and a liquid crystal cell having a cell thickness of 6 microns was assembled so that the rubbing directions were parallel and opposed to each other. The liquid crystal FB01 for TFT was enclosed. After encapsulation, isotropic treatment was performed at 120 ° C. for 30 minutes, and the liquid crystal element was obtained by gradually cooling to room temperature. For the measurement of the pretilt angle, a liquid crystal cell containing a liquid crystal ZLI-1132 manufactured by Merck & Co. Inc. and having a cell thickness of 20 μm was similarly prepared. The orientation of this liquid crystal element was good, and the pretilt angle of this liquid crystal measured by the crystal rotation method was 5.
It was 0 degrees. The residual charge of this cell is 0.
The voltage was 07 V and the retention rate was 95.6%.

Application Comparative Example 1 2,6-bis [4- (4-aminophenoxy) phenyl] propane 8.06 g and pyromellitic dianhydride 4.
36 g and p-aminophenyltrimethoxysilane 0.1
1 g was polymerized to obtain a polyamic acid solution. A 1: 1 mixed solution of butyl cellosolve and NMP was added to this solution to dilute the polyamic acid to 3% by weight, and then IT was coated on one side.
It was applied by a spin coating method (spinner method) on a transparent glass substrate provided with an O electrode. The rotation conditions were 3000 rpm and 15 seconds. After the coating film is dried at 100 degrees for 10 minutes, the temperature is raised to 200 ° C in an oven for 1 hour, and the temperature is increased to 200 ° C.
At 90 ° C. for 90 minutes to obtain a film thickness of about 600 Å polyether imide. The coating surfaces of the two substrates on which the polyetherimide film was formed were each rubbed to form a liquid crystal alignment film, and a liquid crystal cell with a cell thickness of 6 microns was assembled so that the rubbing directions were parallel and opposed to each other. The liquid crystal FB01 for TFT was enclosed. After encapsulation, perform isotropic treatment at 120 ° C for 30 minutes,
The liquid crystal element was obtained by gradually cooling to room temperature. For the measurement of the pretilt angle, a liquid crystal cell containing a liquid crystal ZLI-1132 manufactured by Merck & Co. Inc. and having a cell thickness of 20 μm was similarly prepared. The alignment of this liquid crystal element was good, and the pretilt angle of this liquid crystal measured by the crystal rotation method was 3.7 degrees. The residual charge of this cell was 0.20 V at 25 ° C., and the voltage holding ratio was 90.0%.

Application Comparative Example 2 Polymerization of 8.02 g of 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 3.92 g of methylcyclobutanetetracarboxylic dianhydride and 0.11 g of paraaminophenyltrimethoxysilane. Then, a polyamic acid solution was obtained. A 7: 3 mixed solution of butyl cellosolve and NMP was added to this solution to dilute the polyamic acid to 3% by weight, and then applied by spin coating (spinner method) on a transparent glass substrate provided with an ITO electrode on one side. . The rotation conditions were 5000 rpm and 15 seconds. 1 at 100 degrees after coating
After drying for 0 minutes, the temperature was raised to 200 ° C. over 1 hour in an oven, and heat treatment was performed at 200 ° C. for 90 minutes to obtain a polyetherimide having a film thickness of about 600 Å. The coated surfaces of the two substrates on which the polyetherimide film was formed were rubbed to form liquid crystal alignment films, and the cell thickness was set to 6 so that the rubbing directions were parallel and opposed to each other.
A micron liquid crystal cell was assembled, and a TFT liquid crystal FB01 manufactured by Chisso Corporation was enclosed. After encapsulation, isotropic treatment was performed at 120 ° C. for 30 minutes, and the liquid crystal element was obtained by gradually cooling to room temperature. For the measurement of the pretilt angle, a liquid crystal cell containing a liquid crystal ZLI-1132 manufactured by Merck & Co. Inc. and having a cell thickness of 20 μm was similarly prepared. The alignment of this liquid crystal element was good, and the pretilt angle of this liquid crystal measured by the crystal rotation method was 1.5 degrees. The residual charge of this cell was 0.15 V at 25 ° C, and the voltage holding ratio was 8
It was 9.0%.

Application Comparative Example 3 3.46 g of 4,4-diaminophenyl ether, 4.36 g of pyromellitic dianhydride and 0.11 g of paraaminophenyltrimethoxysilane were polymerized to obtain a polyamic acid solution. A 1: 1 mixed solution of butyl cellosolve and NMP was added to this solution to dilute the polyamic acid to 3% by weight, and then applied by spin coating (spinner method) on a transparent glass substrate having an ITO electrode on one side. . The rotation conditions were 3000 rpm and 15 seconds. 1 at 100 degrees after coating
After drying for 0 minutes, the temperature was raised to 200 ° C. in an oven for 1 hour, and heat treatment was performed at 200 ° C. for 90 minutes to obtain a film thickness of about 600 Å polyether imide. The coated surfaces of the two substrates on which the polyetherimide film was formed were rubbed to form liquid crystal alignment films, and the cell thickness was set to 6 so that the rubbing directions were parallel and opposed to each other.
A micron liquid crystal cell was assembled, and a TFT liquid crystal FB01 manufactured by Chisso Corporation was enclosed. After encapsulation, isotropic treatment was performed at 120 ° C. for 30 minutes, and the liquid crystal element was obtained by gradually cooling to room temperature. For the measurement of the pretilt angle, a liquid crystal cell containing a liquid crystal ZLI-1132 manufactured by Merck & Co. Inc. and having a cell thickness of 20 μm was similarly prepared. The alignment of this liquid crystal element was good, and the pretilt angle of this liquid crystal measured by the crystal rotation method was 0.5 degrees. The residual charge of this cell was 0.90 V at 25 ° C, and the voltage holding ratio was 7.
It was 8.0%.

[0055]

INDUSTRIAL APPLICABILITY The present invention provides a novel diamino compound and a method for producing them. A polyimide compound using the diamino compound as a raw material has an excellent effect as a liquid crystal alignment film. For example, the polyimide compound becomes a liquid crystal alignment film that is uniform and has a high pretilt angle over the entire substrate having a wide display area required for an STN liquid crystal display element by a normal rubbing treatment. Further, the liquid crystal display element using the liquid crystal alignment film is of high quality with excellent voltage holding ratio without occurrence of afterimage phenomenon. It is considered that this is caused by the phenylcyclohexane ring of the starting diamino compound and the alkyl group bonded to it. The diamino compound of the present invention having such characteristics was designed mainly as a raw material intermediate for a liquid crystal alignment film, but it can also be used for other polyimide, polymer compounds such as polyamide and modification thereof.
It is expected to be used for other purposes such as epoxy cross-linking material and to introduce new properties into polymer compounds.

[0056]

[Brief description of drawings]

FIG. 1 is a diagram showing a CV hysteresis curve.

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

[Figure 3] V _S, the gate pulse width 69μs, frequency 60
It is a rectangular wave of Hz and a wave height of ± 4.5V. V _D is a waveform read by an oscilloscope by applying V _S to the source of the circuit shown in FIG.

FIG. 4 ¹ H-NM of diamino compound obtained in Example 1
It is an R spectrum figure.

5 is an IR chart diagram of the diamino compound obtained in Example 1. FIG.

FIG. 6 ¹ H-NM of diamino compound obtained in Example 2
It is an R spectrum figure.

7 is an IR chart diagram of the diamino compound obtained in Example 2. FIG.

Continuation of front page (51) Int.Cl. ⁷ identification code FI C08G 73/10 C08G 73/10 (56) Reference JP-A-6-157434 (JP, A) JP-A-3-214122 (JP, A) JP-A-3-89319 (JP, A) JP-A-6-138465 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C07C 211/00 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A general formula: A diamino compound represented by. 2. A general formula: The diphenylcyclohexane derivative represented by the general formula: After the condensation of the para-nitrobenzoyl chloride derivative represented by the formula, the carbonyl group and the nitro group are reduced, and the general formula: The manufacturing method of the diamino compound represented by.