JPH06234706A - New compound, its production, liquid crystal composition and liquid crystal element - Google Patents

Abstract

PURPOSE:To obtain a new compound, suitably usable as a component of a chirally tilted smectic liquid crystal phase and capable of imparting high spontaneous polarization or high-speed responsiveness, etc., by blending the compound with other low-molecular or polymeric liquid crystal compounds. CONSTITUTION:This new compound is expressed by formula I (m is 1-20; n is 1-20), e.g. 4-(2-fluorooctyloxy)phenyl 4-perfluorooctylbenzoate expressed by formula II. The compound expressed by formula I is obtained by binding a 4-(2-fluoroalkyloxy)phenol expressed by formula III to a 4-(perfluoroalkyl)benzoic acid expressed by formula IV through ester bond. Furthermore, this liquid crystal composition is obtained by blending this new compound therein. This liquid crystal element is suitably used as an optical printer head, a liquid crystal display element, an optical Fourier transformation element, a light valve, etc., employing this liquid crystal composition as a liquid crystal material.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel compound suitably used as a material for a liquid crystal composition, a method for producing the same, a liquid crystal composition containing the novel compound, and an optical printer using the liquid crystal composition as a liquid crystal material. The present invention relates to a liquid crystal element suitably used for a head, a liquid crystal display element, an optical Fourier transform element, a light valve and the like.

[0002]

2. Description of the Related Art A compound in which a perfluoroalkyl group is introduced into a molecule having a fluorine-substituted asymmetric skeleton is already known, and is said to be suitable as a component of a chiral tilted smectic liquid crystal phase (special feature: Front flat 2-5
No. 03803).

However, the chiral smectic liquid crystal composition containing this compound cannot be said to have sufficient characteristics in terms of spontaneous polarization value and high-speed response.

[0004]

The present invention can be suitably used as a component of a chiral tilted smectic liquid crystal phase, and by blending it with other low molecular weight or high molecular weight liquid crystal compounds, the liquid crystal compositions thereof are shown. It is an object of the present invention to provide a novel compound capable of improving the liquid crystal properties of the liquid crystal phase and imparting high spontaneous polarization and high-speed response.

Another object of the present invention is to provide a novel production method for producing the above novel compound.

Another object of the present invention is to provide a liquid crystal composition containing the above novel compound, which has improved liquid crystal properties.

Another object of the present invention is to provide a liquid crystal device using the above liquid crystal composition.

[0008]

That is, the present invention provides a novel compound represented by the following general formula.

[0009]

[Chemical 4] (In the formula, m represents an integer of 1 to 20 and n represents an integer of 1 to 20.) The novel compound of the present invention comprises at least one of them as a low-molecular or high-molecular liquid crystal compound or a liquid crystal composition thereof. By blending them, liquid crystal characteristics such as spontaneous polarization value and high-speed response can be improved. For example, when added to a smectic C liquid crystal (S _C liquid crystal) compound or composition or a chiral smectic C liquid crystal (S _C ^* liquid crystal) compound or composition, the S _C ^* liquid crystal composition having a high response speed due to the low viscosity of the novel compound Can be obtained.

The novel compound of the present invention comprises, for example, esterifying 4- (2-fluoroalkyloxy) phenol represented by the following general formula with 4- (perfluoroalkyl) benzoic acid represented by the following general formula. Can be manufactured by.

[0011]

[Chemical 5] (In the formula, m represents an integer of 1 to 20 and n represents an integer of 1 to 20.) 4- (2-fluorooctyloxy) phenyl 4-perfluorooctylbenzoate was synthesized by the method of synthesizing the novel compound of the present invention. Take for example.

[0012]

[Chemical 6] In the presence of copper iodide, optically active epichlorohydrin and n-
The optically active 2-fluorooctanol (i) is obtained by reacting pentylmagnesium bromide, treating with a base, and then reacting with a hydrogen fluoride-pyridine complex.

[0013]

[Chemical 7] When the optically active 2-fluorooctanol (i) is reacted with p-toluenesulfonic acid chloride, the above optically active 2-
Fluorooctyl-p-toluenesulfonate (ii)
Is obtained.

[0014]

[Chemical 8] 4-Benzyloxyphenol and sodium hydride are reacted in a dimethylformamide solvent, and optically active 2-fluorooctyl-p-toluenesulfonate (i
When i) is added and the mixture is heated and reacted, the above-mentioned 4- (2-fluorooctyloxy) phenol (iii) is obtained.

[0015]

[Chemical 9] When perfluorooctyl iodide and copper are reacted in dimethyl sulfoxide, 4-iodobenzoic acid is added thereto and the mixture is heated and reacted, the above-mentioned 4-perfluorooctylbenzoic acid (iv) is obtained.

[0016]

[Chemical 10] When 4-perfluorooctylbenzoic acid (iv) and thionyl chloride are reacted by heating, 4- (2-fluorooctyloxy) phenol (iii) is added in a triethylenediamine-tetrahydrofuran / benzene solution, and the reaction is carried out by heating as described above. Perfluorooctylbenzoic acid 4- (2-
Fluorooctyloxy) phenyl (v) is obtained.

The liquid crystal composition of the present invention comprises a smectic liquid crystal compound and at least one novel compound of the present invention. The smectic liquid crystal compound is not particularly limited, and the liquid crystal compound may be a low molecular weight compound or a high molecular weight liquid crystal compound. In particular, S _C liquid crystal compound, S _C ^*
By mixing the liquid crystal compound with the novel compound of the present invention, a liquid crystal composition having a high response speed can be obtained.

In the liquid crystal composition of the present invention, various smectic liquid crystal compounds used as liquid crystal materials can be used as the smectic liquid crystal compound.
Preferably, the compounds represented by the following formulas are used alone or in combination.

[0019]

[Chemical 11] (In the formula, R ¹ represents an alkyl group having 8 to 10 carbon atoms, R ² represents an alkyl group having 6 to 11 carbon atoms, and X represents O or OCO.)
Specific examples of such a smectic liquid crystal compound include:
Examples include pyrimidine compounds as shown below.

[0020]

[Chemical 12] The content ratio of the novel compound in the liquid crystal composition is not uniquely determined depending on the types of the smectic liquid crystal compound and the novel compound, but is appropriately determined, but the ratio of the novel compound to the smectic liquid crystal compound is 0.01 to 20% by weight. Preferably. In particular, the above pyrimidine compound and compound (v)
In the case of the combination with, it is preferable to add 2 to 6% by weight of the compound (v).

The liquid crystal composition of the present invention is excellent in responsiveness and has a response speed required for colorizing a liquid crystal display device.

A liquid crystal device using the liquid crystal composition of the present invention as a liquid crystal material has excellent characteristics based on the unique characteristics of the liquid crystal composition.

The structure of the liquid crystal element of the present invention is not limited as long as the above liquid crystal composition of the present invention is used as a liquid crystal material, but normally, a liquid crystal containing the liquid crystal composition of the present invention is used. It has a structure in which a material is sandwiched between two opposing substrates with electrodes. Further, if necessary, an alignment layer such as a rubbing layer may be provided between the electrode layer of the substrate with electrodes and the liquid crystal material layer.

[0024]

The present invention will be described in more detail below with reference to examples of the present invention and comparative examples thereof, but the present invention is not limited to these examples.

Example 1 Synthesis of 4- (2-fluorooctyloxy) phenol

[0026]

[Chemical 13] 0.88 g (4.40 g) of monobenzyl hydroquinone in a 30 ml round-bottomed flask equipped with a pick-up cooling tube.
Millimol) and 3 ml of dry dimethylformamide,
Further, 0.18 g of 60% sodium hydride was added and stirred well. Here, optically active 2-fluorooctyl p-
1.20 g (4.00 mmol) of toluene sulfonate
And dry dimethylformamide (3 ml), and
Heated for 6 hours. After completion of the reaction, 10 ml of water was added and the mixture was extracted with diethyl ether and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (hexane: ethyl acetate = 3: 1) to obtain a benzyl compound. Further, this was dissolved in 5 ml of a mixed solvent of diethyl ether and methanol, and 5% palladium-carbon.
14 g was added and atmospheric pressure catalytic hydrogenation was performed. The reaction mixture was filtered through fold-fold, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (hexane: ethyl acetate = 3: 1) to give 4- (2-fluorooctyloxy) phenol (0.70 g, yield). Obtained at 73.5%.

Specific rotation [α] ²⁵ _D = + 1.44 °,
[Α] ²⁵ _Hg = + 3.97 ° (c1.46, CHCl ₃ )

Synthesis of 4- (perfluorooctyl) benzoic acid

[0029]

[Chemical 14] 5.46 g (10.0 mmol) of perfluorooctyl iodide, 3.10 g (48.8 mmol) of finely ground copper plate and 15 ml of dry dimethyl sulfoxide were mixed and heated at 110 ° C. for 1 hour.

2.48 g of 4-iodobenzoic acid (10.0
What was dissolved in dry dimethylsulfoxide was added, and the mixture was reacted at 110 ° C. for 6 hours. The reaction solution was pleated and filtered, 2M sulfuric acid and water were added, and the mixture was extracted with ether. After drying over magnesium sulfate overnight, the solvent was distilled off under reduced pressure, and the residue was recrystallized from ethyl acetate to obtain 3.19 g (5.89 mmol) of the desired product in a yield of 58.9%.

4-Perfluorooctylbenzoic acid 4-
Synthesis of (2-fluorooctyloxy) phenyl

[0032]

[Chemical 15] 0.38 g of 4-perfluorooctylbenzoic acid in a 30 ml round-bottomed flask equipped with a pickle condenser and a pickpocket.
(0.70 mmol) and thionyl chloride (3 ml) were added to 1
Heated at 00 ° C. for 1.5 hours. After completion of the reaction, thionyl chloride was removed by azeotropic distillation with benzene. 2 ml of dry tetrahydrofuran and 0.15 g (0.6 g of optically active 4- (2-fluorooctyloxy) phenol)
3 mmol) and 0.08 g (0.72 mmol) of triethylenediamine dried with potassium hydroxide in dry benzene were added. The mixture was stirred at room temperature for 30 minutes and heated at 70 ° C. for 5 hours. After the reaction, 1M hydrochloric acid 2ml, water 10ml
Was added, extracted with diethyl ether, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by thin layer chromatography (developing solvent hexane: ethyl acetate = 8: 1). Further recrystallized from hexane / 95% ethanol to give 4-perfluorooctylbenzoic acid 4- (2-
Yield 0.15 g of fluorooctyloxy) phenyl
(0.20 mmol), yield 31.3%.

Specific rotation [α] ²⁸ _D = + 0.64 °,
[Α] ²⁶ _Hg = + 1.17 ° (c0.94, CHCl ₃ ) The obtained compound was identified by ¹ H-NMR, ¹³ C-NMR,
It was confirmed by IR and MS (EI) spectrum analysis that the desired compound was obtained.

Results of ¹ H-NMR spectrum analysis

[0035]

[Chemical 16] δ (ppm), peak multiplicity, coupling constant 0.88 t J _ab = 6.73 Hz 3H ^a 1.22 to 1.93 m 8H ^b , H ^c , H ^d 4.00 to 4.18 m H _{^{f, H g 4.76~4.95 m J ef}} = 49Hz H e 6.98 d J hi = 9.0Hz 2H h 7.14 d J ih = 9.0Hz 2Hi 7.77 d J kj = 8. 3 Hz 2H ^k 8.33 d J _jk = 8.3 Hz 2H ^j

_{Results of} 19 _{F-NMR spectrum analysis}

[0037]

[Chemical 17]

Results of IR spectrum analysis 1120-1330 cm ^-1 : CF 1737 cm ^-1 : C = O

The phase transition behavior of the compound synthesized above is as follows, and it did not show a liquid crystal phase by itself. This compound has a high melting point because it has a structure in which the optically active site is not branched by a fluorine atom and has an ether bond with the core site.

[0040] A host liquid crystal composition was prepared by blending the following compounds as the smectic host liquid crystal compound in the following proportions.

[0041]

[Chemical 18] The phase transition behavior and tilt angle θ of this host liquid crystal composition are shown below.

[0042] The tilt angle θ is 20 ° (30 ° C.) at maximum. [S _C : Smectic C phase, S _A : Smectic A phase, N: Nematic phase] A composition obtained by adding the compound (v) synthesized by the above method to the above host liquid crystal composition in a ratio shown in Table 1. And
A liquid crystal element having a cell thickness of 1.3 μm was produced using this liquid crystal composition, and the optical response time (μsec) was measured while changing the temperature. The optical response time is 10% to 90% of the transmitted light intensity.
The time (τ _10-90 ) that changes to%. Measurement is 670
nm semiconductor laser was used as a light source, detection was performed with a photomultiplier, and observation was performed with a digital oscilloscope.
The applied voltage was ± 10 V and a 20 Hz rectangular wave. Table 1 shows the measurement results of the optical response time. FIG. 1 shows a graph in which τ _10-90 in Table 1 is plotted against temperature (Tc-T).

[0043]

[Table 1]

[0044]

INDUSTRIAL APPLICABILITY According to the present invention, a novel compound having a high spontaneous polarization and a high-speed response can be obtained by blending it with another liquid crystal compound. Moreover, the novel manufacturing method of this novel compound was able to be provided. In addition, the liquid crystal composition and liquid crystal device of the present invention have excellent properties based on the unique properties of the novel compound of the present invention.

[Brief description of drawings]

FIG. 1 is a graph showing the relationship between the temperature and the optical response time of the liquid crystal compound of the present invention.

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[Procedure amendment]

[Submission date] July 22, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Brief description of the drawing

[Correction method] Change

[Correction content]

[Brief description of drawings]

FIG. 1 is a graph showing the relationship between temperature and optical response time of a liquid crystal compound of the present invention.

Claims (5)

[Claims] 1. A novel compound represented by the following general formula. [Chemical 1] (In the formula, m represents an integer of 1 to 20, and n represents an integer of 1 to 20.) 2. A novel compound represented by the following formula. [Chemical 2] 3. A 4- (2-fluoroalkyloxy) phenol represented by the following general formula and a 4- (perfluoroalkyl) benzoic acid represented by the following general formula are ester-bonded to each other. 1. A method for producing the novel compound described in 1. [Chemical 3] (In the formula, m represents an integer of 1 to 20, and n represents an integer of 1 to 20.) 4. A liquid crystal composition comprising a smectic liquid crystal compound and the compound according to claim 1 or 2. 5. A liquid crystal device using the liquid crystal composition according to claim 4 as a liquid crystal material.