TW496892B - Racemic compound and anti-ferroelectric liquid crystal composition containing the compound - Google Patents

Abstract

A racemic compound of the formula (1) and an anti-ferroelectric liquid crystal composition consisting essentially of said racemic compound and one anti-ferroelectric liquid crystal compound of the formula (2) or a mixture of two or more compounds selected from anti-ferroelectric liquid crystal compounds of the formula (2), said composition of the present invention, exhibiting a small spontaneous polarization and a fast response so that a display device having a high display quality can be achieved.

Description

496892 A7 B7 V. Description of the invention (Reverse. The screen is set to reflect the new thin display and physical display. The combined crystal quantification liquid consumes low content, and the organic substance group is combined with this operation. The spin is used to eliminate electricity. And Low Ying K. It ’s new, because an unidentified crystal of the product set has a liquid crystal display, an electro-hydraulic liquid iron, and an external device. The self-installation display and the type information are used for various purposes. In application, so far, so far, the power can be installed to display the display crystal. The display device is installed on the display with the display display, its crystals are more liquid, and various types of large-scale display should be effective and effective. At the same high level, the installation of the Fan Li display machine shows the positive T electric power, CR and the following knowledge, the situation is more familiar with the equipment, the quality of the moment, the liquid crystal fluid and the sexual equipment installed The crystal is liquid, and the liquid crystal array is installed as a display-type crystal by the moment. The liquid method can be used to move the precursor and its photodrive. A 0-moment order is used to make the K element. The structure of the simple crystalline liquid is driven by the I array and the frequency is dependent on the reason. Install it as a high K device, wait for the drive, and measure it as large as M. It is difficult and appropriate. For a low installation ratio, it shows that the liquid crystal sound of the question is much higher than that of the breakout. M ， Placement ο Installed so the slow-smoothness liquid-speed type should be loud enough to obtain, K difficult, difficult questions and driving techniques (please read the precautions on the back _ • items, then fill in. Pack- -Write this page) Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs for the installation of crystal liquid 39 drive feHF S Moment of frame frame frequency side view separately required element diagram, but the crystal film is thin, And Gao Chengran is right.,, Good body M is not crystallized ~ law electricity. Moving film resource driving thin investment array large rectangular single order need to be compared, far production method to build line driving array, the main birth moment is a harmony spell. Live} skills, physical performance M, array K momentary nature. Live fast, the degree of speed and speed should respond to the sound string, and the question-to-question ratio is the method of pairing, the trend is to drive a small array but set a single crystal The paper size of the paper is applicable to the Chinese National Standard (CNS) Α4 specification (210 × 297 mm) 496 892 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (2) A liquid crystal display device with high image quality and high effect ratio display video frame can be obtained. Therefore, TF T in the active matrix drive method Law is gaining mainstream status. At present, large liquid crystal devices with a size of 10 to 20 inches are being opened, and the problem of viewing angle dependence inherent in devices using anisotropic liquid crystals is extremely serious. In order to solve the problem of viewing angle dependence, various technical studies have been carried out, and the results can be displayed at a viewing angle of about 140 ° without causing a degree of inversion. However, the contrast is still greatly affected by the viewing angle, and the flat contrast characteristics of the wide viewing angle achieved by CR can not be obtained at present. Under the above circumstances, a liquid crystal display device using a ferroelectric liquid crystal is attracting attention as a liquid crystal display device with a fast response. The surface-stabilized liquid crystal display device (SSFLC) disclosed by C 1 a r k and La g e m 1 1 has attracted attention because of its fast response speed and wide viewing angle, which has never been seen before. Its switching characteristics have been studied in detail, and Xu ferroelectric liquid crystal compounds have been synthesized to obtain optimal physical properties. On the other hand, in order to complete the practical device, there are many technical obstacles to be overcome, such as difficulty in alignment control, alignment damage caused by mechanical vibration, etc. It is difficult to achieve the memory effect and control layer structure, and these problems have been overcome. Can be made into finished products. However, the ferroelectric liquid crystal display device still has a problem, that is, it cannot display color, because it cannot handle grayscale in principle, and it is difficult to display a video frame, because high-speed response cannot be achieved yet. < In addition, the development of another high-speed response liquid crystal display device is also in progress, and has a different switching mechanism from SSFLC. This kind of liquid crystal display device Li Yi 41 (Please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 specification (21〇 × 297 mm) 496892 Employees of the Central Standards Bureau of the Ministry of Economic Affairs Cooperative cooperative printing A7 B7 V. Description of the invention (5) Switching between tristable states using a liquid crystal with an antiferroelectric phase (hereinafter referred to as "antiferroelectric liquid crystal") Japanese Journal of Applied Physics, Vol. 7 L 7 2 9 pages, 1 9 8 8). The antiferroelectric liquid crystal has the following three stable states. That is, the above three stable states are the two uniform states (U r, II 1) seen in the two ferroelectric crystal states, and the third state. C handa η et al reported that the above three states are antiferroelectric phases (Japanese Journal of Applied Physics, Volume 2 8 L 1 2 6 1 pages, 1 9 8 9, and Japanese Journal of Applied Physics, Volume 2 8 L 1 2 6 5 Page, 1 9 8 9). The above-mentioned switching in the tristable state is the first feature of the antiferroelectric liquid crystal. The second feature of antiferroelectric liquid crystals is the presence of bright iron thresholds for the applied voltage. In addition, it has a memory effect when an appropriate voltage is set, which is the third feature of the antiferroelectric liquid crystal. Furthermore, the fourth feature of the antiferroelectric liquid crystal is that its layer structure can be easily switched when an electric field is applied (Japanese Journal of Applied Physics, Vol. 28, L119, 1989, and Vol. 9, L 1 1 1 p. 1, 9 9 0 :). Due to this feature, the manufactured liquid crystal display device is almost flawless and has a semi-recoverable ability for alignment. By using the top-up characteristic, a liquid crystal device having a fast response speed and excellent contrast can be achieved. In addition, it has been proven that antiferroelectric liquid crystal devices can achieve grayscale display, which is almost impossible for ferroelectric liquid crystal devices. Therefore, it is possible to move towards full-color display and further increase the importance of antiferroelectric liquid crystals (International Conference on Ferroelectric Liquid Crystals No. 4, p. 77, 193). In this case, efforts are being made to achieve An antiferroelectric liquid crystal display device, but the development of a practical device is currently encountering the following problems. -5 one (please read the notes on the back before filling in the tribute)

This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) 496892 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (4) When using antiferroelectric liquid crystal as a display device, it is generally An antiferroelectric liquid crystal is sandwiched between two glass substrates coated with an insulating layer and an alignment layer. The insulating layer is necessary to prevent a short circuit between substrates, and requires a certain thickness that cannot completely prevent a short circuit. On the other hand, an alignment layer is required to align the liquid crystal molecules in one direction, and a certain thickness M is required to reduce the alignment defects that occur when the liquid crystal molecules are aligned to a minimum. When a voltage is applied to the liquid crystal device thus formed, if the thickness of the culvert layer and the alignment layer is small, or if the insulating layer or the alignment layer does not exist at all, the applied voltage will sharply change from the antiferroelectric state to the iron. Phase shift of electrical states. However, if the insulating layer and the alignment have a certain thickness required for practical use, a phase shift from the antiferroelectric state to the ferroelectric state occurs at a moderate voltage. In the antiferroelectric liquid crystal drive, after the writing voltage that produces a memory effect is applied, a holding voltage lower than the writing voltage is continuously applied for a predetermined period of time. If the voltage is applied to the upper part, a moderate shift from the antiferroelectric state to the cypress occurs. In the ferroelectric state, that is, the liquid crystal display device has a low threshold, the holding voltage that can be used is limited to a very narrow range. In extreme cases, the holding voltage cannot be set and the memory effect cannot be guaranteed. This means that the antiferroelectric liquid crystal display device is no longer available as it is, which is a serious problem. In addition, the lower the steepness of the threshold value in the device, the narrower the range in which the holding voltage can be selected, and the lower the driving edge. Therefore, a practical device needs a threshold of high steepness, and a liquid crystal material that can give such a threshold of steepness. In fact, when antiferroelectric liquid crystal is used in a liquid crystal device, it is desirable to provide a material having a high steepness threshold. 6--------- 4 ^ -I (Please read the precautions on the back before filling this page), 1T This paper size is applicable to China National Standard (CNS) A4 specification (210 × 297 mm) Ministry of Economic Affairs Printed by the Employees Cooperative of the Central Bureau of Standards 496892 A7 B7 V. Description of the Invention (5) Experiment 2 The steepness of the threshold value of the known liquid crystal device is closely related to the thickness of both the insulating layer and the alignment layer. It has been studied to determine what factors can explain the epiphysis relationship. In the next study, both the insulating layer and the alignment layer are collectively referred to as the "alignment layer." For easy understanding of this study, reference is made to Figures 1 to 3 as follows. Figure 1 shows the equivalent circuit of an antiferroelectric liquid crystal device. Figure 2 shows the simulation result of the steepness of the threshold value when no alignment layer is present. Figure 3 shows the threshold value of the threshold value when no alignment layer is present. Simulation results of steepness. The equivalent circuit shown in Figure 1 includes a current source that generates a polarized reverse current according to the applied voltage; the alignment layer is an electrostatic capacitor C connected in series with the antiferroelectric liquid crystal; M and the drive circuit are ideal voltage sources. In Figure 1, the driving voltage applied to the device by the facility is V e X. The polarized reverse current is used to charge. The voltage generated between the upper and lower surfaces of the alignment layer is V c. The effective voltage actually applied to the liquid crystal is V eff, the natural polarization of the liquid crystal is P, the electrode area of the liquid crystal device is S, the thickness of the alignment layer is d ′, and the dielectric constant of the alignment history is ε ′. Then V c ⑴ is calculated as follows: ⑴: V c = PS / C = PS d '/ (S ε') = P (d '/ ε') According to the above equation, V eff κ is expressed by: : Veff = Vex-Vc = Vex-P (< Γ / ε '). It can be known from the formula that the voltage applied to the liquid crystal is the voltage applied to the liquid crystal, minus the polarization P of the liquid crystal, and Thickness df, and alignment 7-This paper size applies to Chinese National Standard (CNS) A4 specification (210X 297 mm) -------- install-(Please read the precautions on the back before filling this page ), 11 496892 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Invention Description (6) The product of the inverse of the permittivity of the (1) layer. The thickness of the liquid crystal layer when the liquid crystal cell is filled is set to d. The electric field V eff actually applied to the liquid crystal is expressed by the following formula (3): (3): Eeff = Veff / d. On the other hand, the apparent electric field strength E ex Μ The following formula ⑷ means: e: E e X = V e X / d = (V eff + V c) / d = Veff / d + P (d, / e,) / d: Eeff + a P where cx = df / (e fd) ----- ⑸ If no alignment layer exists, the second term of formula ⑷ is 0, because Eex = Eeff. Although the antiferroelectric liquid crystal indicates the hysteresis of its optical response to the applied voltage, four threshold values can be considered for the hysteresis. Each threshold value is E e f f (= E e X), in which case these threshold values are not prone to electric fields. Fig. 2 shows the situation. If there is an alignment layer, the formula (6) is modified to obtain the following formula (6): (6): Eeff = Eex ~ a P means that the effective electric field applied to the liquid crystal is a · P lower than the applied electric field Eex. As a result, As shown in Figure 3, due to a · P, the hysteresis is suppressed to a large extent. The above research shows that most of the hysteresis strain is caused by the interaction between the natural polarization and the alignment layer. Therefore, if a liquid crystal device is required to reduce hysteresis strain, the above interaction can be effectively reduced to minimize it. The measures specifically taken for the purpose of lifting include the use of an alignment layer with a high dielectric constant, a means for reducing the thickness of the alignment layer, or a method for reducing the natural polarization of the liquid crystal, as can be seen from the above equation (6). Among the above measures, one 8 one (please read the precautions on the back before filling out this page)-installed ·, 11 This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) 496892 A7 B7 V. Invention Note (7) It is difficult to obtain an alignment layer material with a high dielectric constant. Therefore, the measures that can be taken are measures to reduce the thickness of the alignment calendar or to reduce the natural polarization of the liquid crystal material. Generally speaking, an antiferroelectric liquid crystal compound has a relatively large natural polarization, while a liquid crystal material with excellent physical properties has a natural polarization of 200 a C / cm 2 or more. Therefore, unless the thickness of the alignment layer is greatly reduced, the strain of the hysteresis is quite large. However, when the thickness of the alignment layer is reduced, defects in the alignment state of the liquid crystal molecules occur to such an extent that no contrast can be obtained. Therefore, the measures for reducing the thickness of the alignment layer and correcting the hysteresis strain are greatly limited. On the other hand, in order to reduce the natural polarization of the liquid crystal material, it is inevitable to take measures to mix an appropriate compound without the natural polarization with the liquid crystal material, that is, to dilute the liquid crystal material to reduce its concentration. However, since the response speed of the liquid crystal is determined by the product of the applied voltage and the natural polarization, another new problem occurs, that is, the natural polarization is simply caused by mixing the appropriate compounds (please read the precautions on the back before filling (This page) ► Binding and printing. Printed by the Consumer Cooperatives of the Central Standards Bureau of Dibei Department. Physicochemical open crystal want to synthesize spin test solution structure group. In order to eliminate the need for electricity, the iron structure reverses the structure of the crystal structure and the crystal structure of the crystal structure. From the speed of learning, such as Zhuang Nianguo, chemistry should be stagnant, and it has become a lingering stagnation. The new low magnetic supply lowers the pressure point, lowers the power supply, and the full power is not lowered. It will have to be limited by people, and the clarity will increase. When the low-frequency base is selected, the lighting condition is set by pressing, and the self-loading is in the form of bright liquid. At this time, the low-power generation is low and the liquid is lower than before. The iron drop is: Standards are applicable to Chinese National Standard (CNS) Α4 specifications (210X 297 mm) 496892 A7 B7 V. Description of invention (8

X CH, (1) where m is an integer from 8 to 10, η is an integer from 3 to 8, and X is a hydrogen atom or a fluorine atom. In addition, according to the present invention, an antiferroelectric liquid crystal composition is provided, which basically comprises one or more racemic compounds of the following general formula:

X C „H2 r〇 \ Q ^ coo

ch3 • COO-CHCnH2n + (l) (Please read the notes on the back before filling out this page) One pack · (where n is an integer from 9 to 10, ri is an integer from 3 to 8, and X is a hydrogen or fluorine atom) , K and antiferroelectric liquid crystal compounds of the general formula ⑵

A

R wherein R is a C6—Ci2 straight-chain alkyl group, Z is a hydrogen atom or a fluorine atom, A is -CH 3 or -CF 3, r is 0 or 1, and C * is an asymmetric carbon atom, but A is- For CH3, r is 0, p is an integer from 4 to 10, and when A is-CF3 and Γ is 0, p is an integer from 6 to 8, and when A is -CF3 and r is 1, s is 5 to 8. The integer and p are integers of 2 or 4. More specific examples of the present invention will be described below. In the general formula of the racemic compound of the present invention, / π is an integer from δ to 10, κ 9 is preferred, η is an integer from 3 to 8, κ 6 is preferred, X is a hydrogen atom or a fluorine atom, and κ A fluorine atom is preferred. 10- This paper size is applicable to China National Standard (CNS) Α4 specification (210X 297 mm)

COO-C ^ HtiCHJsOl ^ H ^ (2) Printed by the Consumers' Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs 496892 A7 B7 V. Description of the invention (9) The racemic compound of the above general formula ⑴ can be prepared, for example, by the following method (1 )

COOH < 1 >

(2) CH3COO

-COOH + S02C1-> CH3COO- CH3 I (3) < 2 > + HO_CHCnH2n "-> CH3COO (4) < 3 >

F

COC1 < 2 > (Please read the notes on the back before filling this page)

F

CH3 I COOCHCnH, n + 1 < 3 >

CH3 I COOCHCnH2n + 1 < 4 > Printing Order CmH2m + 1 (5) < 1 > + S02C1 COC1 < 5 > (6) < 5 > + < 4 > 4 The production method of the racemic compound of the above general formula is briefly described as follows: < '⑴ represents that the alkyl bromide and 4-hydroxybenzoic acid are reacted to be esterified. ⑵ indicates that 4-ethoxyl-2-fluorobenzoic acid is converted to chloride. 1 1 1 This paper is in accordance with the Chinese National Standard (CNS) A4 specification (210X 297 mm). 496892 Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Printing A7 B7 V. Description of the invention (10) ③ It means that the chlorine is reacted with 2-alkyl alcohol to be esterified. ⑷ means deacetylation. (5) represents the conversion of p-alkoxybenzoic acid to cyanide. (6) Represents M + Cl plus M esterification (to form the final product). The antiferroelectric liquid crystal composition basically includes a racemic compound of the general formula ⑴, and an antiferroelectric liquid crystal compound of the general formula ⑵. In the general formula VII, R is a C 6 C 12 straight alkyl group, K C 8′10 is preferred, Z is a hydrogen atom or a fluorine atom, A is -CH 3 or -CF 3, and r is 0 or 1. Furthermore, the definitions of p and s depend on the type of A and the value of r >. That is, when A is -CH3 and r is 0, p is an integer from 4 to 10. If A is -CF3 and r is 0, then p is an integer from 6 to 8. If A is -CF 3 and r is 1, then s is an integer from 5 to 8, and p is an integer from 2 or 4. In the compound of the general formula ②, K A is -CF 3 and r is 1, or A is -C Η 3, r is 0, and p is an integer of 4 to 6. The antiferroelectric liquid crystal compound of the general formula ⑵ can be easily prepared by, for example, the K-down method. A =-CF 3, ρ = 2, r = 1 and s = 5 in the general formula ， are made by the following methods: (a) AcO-Ph (Z) -CCX) H + S0C12 -► AcO- Ph (Z) -COC1 (b) (a) + HOC * H (CF3) (CH2) 5〇C2H5 -► AcO-Ph (Zb COOC * H (CF3) (CH2) 5OC2H5 (c) (b) + Ph-CH2NH2 -► HO-Ph (Z) -COOC * H (CF3) (CH2) 5OC2H5 (d) RO-Ph-Ph-COOH + S0C12 -► RO-Ph-Ph-COCl (e) (b) + (d) 4 an antiferroelectric liquid crystal compound, in the above formula, AC 0-is an acetamidine voltage, -P h (Z)-is a 1,4- phenylene group, in which fluorine may be substituted, and Ph-is a phenyl group ， -Ph- is 1,4-secondary benzene- 12-(Please read the notes on the back before filling this page) > Packing-The size of the paper is applicable to Chinese National Standard (CNS) A4 (210X 297 mm) ) 496892 A7 B7 V. Description of the invention (11) Voltage, C # is an asymmetric carbon atom. The above method is briefly described below. (A) represents (a) the obtained chlorinated product reacts with an alcohol to form an ester. (B) (B) represents the deethylation of the obtained ester. (C) represents the chlorination of 4'-alkoxybiphenyl-4-carboxylic acid. (Θ) represents (c) the obtained phenol and (d) the obtained chlorination. The products react with each other to form liquid crystals. The antiferroelectric liquid crystal composition of the present invention basically comprises a racemic compound of the general formula ⑴, and an antiferroelectric liquid crystal compound of the general formula 。. Specifically, the total amount of the compounds of the formula At least 70 mol 5¾ and K is preferably at least 80 mol%. The mixing ratio (ω: ⑵) of the compound of the general formula 逑 to the compound of the general formula ⑵, in terms of molar ratio, κ 1: 9 9 to 40:60 is preferred, and K5: 95 to 35:65 is more preferred. Furthermore, a compound of the general formula (I) or a mixture of at least two compounds can be used. At least two compounds of formula (I) are used. The mixture can be used to obtain a liquid crystal display device with excellent alignment characteristics and threshold sharpness, and displays a high contrast. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) In the antiferroelectric liquid crystal composition of the invention, the upper limit of the temperature range of the antiferroelectric phase is at least 40 1C, and the lower limit is 0 ° C or below. Outside the temperature range of the temperature range M in which the antiferroelectric liquid phase exists, at least a dish-like shape The A phase of liquid crystal molecules exists. The antiferroelectric liquid crystal composition of the present invention Preferably (for an antiferroelectric liquid crystal display device in which a composition is interposed between a pair of electrode substrates. The present invention can provide novel racemic compounds, M and containing racemic racemization.-13-This paper size is applicable to Chinese National Standard (CNS) Λ4 specification (210X 297 mm) 496892 Printed by A7, Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs B7 V. Description of the invention (12) Novel antiferroelectric liquid crystal composition. In addition, the novel antiferroelectric liquid crystal composition of the present invention can provide an antiferroelectric liquid crystal display device with excellent threshold value steepness, an antiferroelectric phase with a wide temperature range, high display response, and high K display quality. Examples The present invention will be described in more detail with reference to comparative examples, but the present invention is not limited thereto. Fen_Example 1 Zhihao 3-Ga-4- (1-Carbofluorenyl) Carboxyl-Cyclosylbenzoate (Formula; W: m = 9. Η = β. X = F (Ε ΐ)) ⑴ Production of p-nonoxybenzoic acid Take 12.7 g (0.0917 mol) of p-hydroxybenzoic acid, 28.5 g of n-nonyl bromide and 10.2 g of potassium hydroxide, added to 15 0 0 A mixture of ml of ethanol and 200 ml of water was allowed to react at reflux for 10 hours. An additional 500 ml of water was added and the mixture was stirred for 3 hours. After completion of the reaction, concentrated hydrochloric acid was added to acidify the reaction mixture. Then, the solvent was distilled off, and the remaining product was cooled to room temperature, and then filtered to obtain a colorless solid. The solid was sufficiently washed with water, and recrystallized from chloroform to obtain a target product (yield: 75%). (2) Preparation of 4-Z-HYDROXY-2 -fluoro-1- (1-methyl-1, South-H2, 1-Carbon, 1-Benzene) benzene in 10.8 g (0.06 mole) of 4-Ethyloxy-2-fluoride Benzoic acid was added with sulfurous acid to make the mixture reflux for 7 hours. Distill the excess of sulfurous chlorine, and add 10 ml of pyridine and 5.3 g (0.2 mol) of 2-octanol. The resulting mixture was stirred at room temperature throughout the day, diluted with 200 ml of diethyl ether, and the organic layer was sequentially washed with dilute hydrochloric acid, 1 N sodium hydroxide aqueous solution and water, a 14- (Please read the precautions on the back before filling this page ) > refill

， 1T This paper size is applicable to Chinese National Standard (CNS) A4 specification (2) 〇 × 297 mm 496892 Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Distillation Kl B7 V. Description of the invention (15) Dry on magnesium sulfate. The solvent was distilled off, and the obtained crude target product M was purified by silica gel column chromatography using hexane / ethyl acetate as a solvent to obtain the target product (yield 90%. (3) Seiho 2- Fluoride-4-锊 -1-(1 -methylheptyl chloride, a carpenter) Take out 9.7 g (0 * 0 3 6 1 mole) of the compound obtained in the above cage, and dissolve it in 250 ml of ethanol. 7.7 g (0.0772 mol) of benzylamine was added dropwise. The mixture was stirred at room temperature all day and diluted with 300 ml of ether. The diluted mixture was washed with dilute hydrochloric acid and water in order and dried over magnesium sulfate. The solvent was distilled off. The target product was separated and purified by silica gel column chromatography (yield: 98¾). 诰 诰 3-fluoro_ 4 _ (1-methylsulphonylcarbanyl fluorenyl) ~ 4-iF Thousands of chloride cage __ 1 ml of the compound obtained from the above, add 15 ml of thionyl chloride, and heat the mixture to reflux for 5 hours. Distill off the excess thionyl chloride, then add 2 ml of pyridine and the above. The obtained compound was 2.12 millimolar, and the mixture was reacted at room temperature for 10 hours. After the reaction was completed, the reaction mixture was diluted with 300 ml of ether, and the diluted mixture was used sequentially Acid release, 1 N sodium carbonate aqueous solution, washed with water, and the organic phase was dried over magnesium sulfate. The solvent was distilled off, and the target product was separated by silica gel column chromatography (yield: 81%). ≪ Table 1 shows the NMR data of the compound obtained in Example 1. The formula of the compound is shown in formula (E 1). ™ 1 5-(Please read the precautions on the back before filling out this page) The paper size applies to the Chinese National Standard (CNS ) Λ4 specification (2) 0 × 297 mm) 496892

A B V. Description of the invention (14 Table 1 Chemical transfer 1H 2H 3 Η 4 Η 5 Η 6 Η 7Η Example (E 1) 4. 1 7. 0 8.1 7 · 1 7 · 1 8. 0 5.2

(E1) (Please read the precautions on the back before filling in this page) Comparative Example 1 Take the antiferroelectric liquid crystal compound (2A and 2B) shown in the following formula and mix it at a mixing ratio of 7 0/3 0 to obtain an antiferroelectric liquid crystal.组合 物。 Composition. Table 2 shows the phase order of the obtained composition. The liquid crystal composition measures the natural polarization of 60 υ, M, and the response time of the transition from the antiferroelectric state to the ferroelectric state. The results are shown in Table 2. 2Α: C9H190-Ph-Ph-C00-Ph (3F) -C00-C * H (CF3) (CH2) 5CX: 2H5 Printed by the Consumer Consumption Cooperative of the Central Standards Bureau of Didi Ministry (Formula (2): R = C9H19 / Z = F, A = CF3, r = 1, s = 5 and p = 2) 2B: C8H170-Ph-Ph-C00-Ph (3F) -COO-C * H (CH3) C5Hn (Formula (2): R = C8H17, Z = F, A = CH3, r = 0 p = 5) Measure or evaluate the optical response hysteresis of the above composition. The response time and natural polarization are as follows. 16-This paper size is in accordance with Chinese National Standard (CNS) A4 (210X 297 mm) 496892 A7 B7 V. Description of the invention (15) I have 0 electrodes and friction polyimide film (: 30 mm) The liquid crystal cell (the thickness of the cell is 2 u π) is filled with an isotropic liquid crystal composition. The cell is then gradually cooled at a rate of κ1. Ο υ / min, K is aligned with the liquid crystal, and the cell is interposed in a cross polarization The orientation of the layer of the liquid crystal is parallel to the analyzer or polarizer. The response time for the transition from the antiferroelectric state to the ferroelectric state is defined as the 2 5 V case at an application frequency of 10 Hz at 60 ° C Below, if 1 〇 Ο I represents the maximum transmission, 0% represents the minimum transmission, the amount of time required to change the transmission from 10% to 90%. Natural polarization is to apply a 2 5 V triangular wave at 60 ° C, and The polarization reaction is determined by measuring the conversion current. Rich_Example 2 The antiferroelectric liquid crystal composition containing the antiferroelectric liquid crystal compounds (2 A and 2 B) used in Comparative Example 1 and the racemic compound (E 1 obtained in Example 1) were taken. ), According to the mixing ratio of 2 A / 2 B / E 1 5 6/2 4/2 0 (molar ratio) plus M to obtain an antiferroelectric liquid crystal composition The phase order, natural polarization, and response time of the composition obtained were measured or evaluated in the same manner as in Comparative Example 1. The results are shown in Table 2. Although the natural polarization was reduced, it still showed a higher response ability. (Please first (Please read the notes on the back and fill in this page) Yin Fan-17, a staff consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs-This paper size applies to China National Standards (CNS) Α4 specifications (210 × 297 mm) 496892; Η ... 5 A 7 j… B7 “. ,, ", • 一-～… ---------------- V. Description of the invention (l6) Table 2 Phase order natural polarization (nC / ciH 2 ) Response time (usecond) Example 2 Cr (< -20) SCA * (76) SA (92) I 116 38 Comparative example 1 Cr (< -10) SCA * (95) SC " (97) SA ( 105) I 176 53 (Please read the notes on the back before filling this page) In the comparison order, the values in parentheses indicate the transition temperature (dead), Cr is the crystalline phase, SCA * is the antiferroelectric phase, and SC * is iron Electrical phase, SA is a smectic A liquid crystal phase and I is an isotropic phase. Printed by the staff of the Central Standards Bureau of the Ministry of Labor and Co-operative Society This paper is printed in accordance with China National Standards (CNS) Λ4 specifications 210X 297 mm) 496892 ΰόΛ'ι '. In η J ... L Henry -TiV] ·' - - · γ

Vex Vc Veff P ip S cT £ r Eeff d Ci V. Description of the invention (丨 ^) 1 Description of the component symbols: The driving voltage applied to the device is charged by the polarization inversion current between the upper and lower surfaces of the alignment layer The generated voltage is actually applied to the effective voltage of the liquid crystal. Polarization of the liquid crystal and the voltage transfer current of the liquid crystal device. The thickness of the alignment layer. The dielectric constant of the alignment layer. The electric field of the liquid crystal layer. The thickness of the liquid crystal layer. No alignment layer. (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs a 18 This paper size applies to China National Standard (CNS) A4 (210X297 mm)

Claims (1)

496892, applied for a patent case ".---........., No. 8 7 1 04966" Anti-ferroelectric liquid crystal composition that racemates this compound "patent case (please read the precautions on the back first) (Fill in this page again) (Amended on December 24, 88) Six patent applications: 1. A racemic compound shown in the general formula 用以 to form antiferroelectric liquid crystals: X _ / ch3 C00 ″ HCnH2n + 1 (1 ) Where m is an integer from 8 to 10, n is an integer from 3 to 6, and X is a fluorine atom. 2. The racemic compound according to item 1 of the patent application, wherein m in the general formula ⑴ is 9. 3. The racemic compound according to item 1 of the patent application, wherein η in the general formula ⑴ is 6. 4. An antiferroelectric liquid crystal composition, which mainly contains one or more of the general formula ⑴ racemic compounds: Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs COO-/ (JVc00-CHCnH2n + 1 (1) (where η is an integer from 8 to 10, η is an integer from 3 to 6, and X is a fluorine atom), and an antiferroelectric liquid crystal compound of the general formula ②: This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 496892 A8 B8 C8 Patent application scope R COO-C # H [(CH2) sO] rCpH2p + 1 (2) A Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (where 1 ?. is a C6-C12 linear alkyl group, and Z is a hydrogen atom or a fluorine atom , A is -CH3 or -CF3, ι · is 0 or 1, and C * is an asymmetric carbon atom, but when A is -CH3, r is 0, p is an integer from 4 to 10, and A is -CF3 and r Is 0, ρ is an integer from 6 to 8, and if A is -CF3 and r is 1, s is an integer from 5 to 8, and p is an integer from 2 or 4, where the composition contains the general formula ⑴ The racemic compound and the antiferroelectric liquid crystal compound of the general formula ⑵ have a molar ratio (0): ⑵) of 1:99 to 40:60. 5. The composition as claimed in item 4 of the patent application, wherein m in the general formula ⑴ is 9. 6 · The composition according to item 4 of the patent application, wherein η in the general formula 为 is 6. 7 · The composition as claimed in item 4 of the patent application, wherein A in the general formula 为 is -CF3 and r is 1. 8) The composition of item 4 in the scope of patent application, wherein A in the general formula ⑵ is -CH3, r is 0, and P is an integer of 4 to 6. 9 · If the composition of item 4 of the patent application range, wherein the upper limit of the temperature range of the antiferroelectric phase of the composition is at least 40 ° C, the lower limit is 0 ° c or less, and the temperature in the temperature range where the antiferroelectric phase exists is higher. Outside the scope, to the size of this paper, the Chinese National Standard (CNS) A4 specification (210 X 297 mm) is applied (Please read the precautions on the back before filling this page}, ^ .τ- Interpretation · 496892 A8 B8 C8 D8 The scope of patent application rarely includes the phase A of dish-shaped liquid crystal molecules. 10. — An antiferroelectric liquid crystal display device, including the antiferroelectric liquid crystal composition as described in item 4 of the patent application, interposed on a pair of electrode substrates (Please read the notes on the back before filling out this page) Printed on the paper by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, the paper size is applicable to China National Standard (CNS) A4 (210X297 mm)