TWI495710B - Liquid crystal compound having hexahydro-cyclopenta(1,3)dioxinyl-based structure and liquid crystal composition - Google Patents

Description

Liquid crystal compound and liquid having a dioxa saturated anthracene ring structure Crystal composition

The present invention relates to a liquid crystal compound and a liquid crystal composition comprising the liquid crystal compound, and particularly to a liquid crystal compound having a dioxa saturated anthracene ring structure and a liquid crystal composition comprising the liquid crystal compound.

Liquid crystal materials are mainly used in the dielectric of liquid crystal displays because the applied voltage can change the optical properties of such materials. Electro-optical elements of liquid crystals are well known to those skilled in the art and can encompass a variety of effects. Examples of such devices are liquid crystal cells with dynamic scattering, DAP (Aligned Phase Deformation) liquid crystal cells, guest/host type liquid crystal cells, TN boxes with twisted nematic structure, STN (Super Twisted Nematic) liquid crystal cells, SBE ( Super birefringence effect) Liquid crystal cell and OMI (light film interference) liquid crystal cell. The most common displays are based on the Schadt-Helfrich effect and have a twisted nematic structure. In addition, there are liquid crystal cells for electric field operation parallel to the substrate and the liquid crystal surface, such as an IPS (In-Plane Switching) liquid crystal cell. In particular, TN, STN and IPS liquid crystal cells, especially TN and IPS liquid crystal cells are currently commercially useful applications.

The liquid crystal material must have good chemical and thermal stability and good stability against electric fields and electromagnetic radiation. In addition, the liquid crystal material should have a low viscosity and have a fast reaction time, a low threshold voltage, and a high contrast ratio in the liquid crystal cell. They should also have a liquid crystal phase suitable for the above liquid crystal cell, such as nematic or cholesteric liquid crystal, at the normal operating temperature, i.e., at the widest possible range above and below room temperature (25 ± 3 ° C). phase. However, liquid crystals are usually used by mixing a plurality of components into a mixture, and these components are easily miscible with each other. In addition, other properties of the liquid crystal such as resistivity, dielectric anisotropy, and optical anisotropy must satisfy various requirements depending on the type of liquid crystal cell and the field of application.

The use of liquid crystal compositions on MLC displays, notebook computers, or automotive meters, in addition to problems related to contrast and reaction time, has difficulty in achieving high resistivity, as the resistivity decreases, the contrast of the display It will get worse and may cause problems with afterimages. For TV and video applications, displays with short reaction times are required, in particular, if a liquid crystal composition having a low viscosity value is used, such a short reaction time can be achieved, but the dilution additive generally lowers the clarification point and thus Reduce the working range of the liquid crystal composition. In a TN liquid crystal cell, a liquid crystal composition having the following advantages is required: (1) a wide nematic phase range (especially a lower limit temperature); (2) switchability at an extremely low temperature; (3) high Anti-ultraviolet radiation; (4) low threshold voltage.

However, the liquid crystal composition obtained in the prior art cannot achieve these advantages while maintaining other parameters, so it is still extremely necessary to have no table. These shortcomings are exhibited or exhibited to a lesser extent, but at the same time have extremely high resistivity, high dielectric anisotropy, large operating temperature range, short reaction time (even at low temperatures) and low threshold voltage. Liquid crystal composition.

Accordingly, it is an object of the present invention to provide a liquid crystal compound having a dioxa saturated anthracene ring structure. The liquid crystal compound having the dioxa saturated anthracene ring structure of the invention has good chemical and physical stability, and compared with the liquid crystal compound having a cyclohexyl structure, the liquid crystal compound having the dioxa saturated anthracene ring structure of the invention has Large dielectric anisotropy.

Thus, the present invention has a liquid crystal compound having a dioxa saturated anthracene ring structure, as shown by the general formula (I):

Wherein R ₁ represents -H, -F, unsubstituted C ₁ to C ₁₀ linear or branched alkyl, halogen-substituted C ₁ to C ₁₀ linear or branched alkyl, or a C ₁ to C ₁₀ alkoxy group, wherein one or more of the R ₁ -CH ₂ - may be -O-, -S-, -SiH ₂ -, -CH=CH-, -C≡ C-, -CF=CF-, -CH=CF-, -COO- or -OCO-substitution, provided that the heteroatoms are not directly connected to each other, and the O, S and Si atoms are not directly related to the dioxa-saturated anthracene ring Connected; R ₂ represents -H, -F, -Cl, -CN, -NCS, -SCN, -OCN, -NCO, a unsubstituted C ₁ to C ₂₀ linear or branched alkyl group, a halogen-substituted C ₁ to C ₂₀ linear or branched alkyl group, or a C ₁ to C ₂₀ alkoxy group, wherein One or more of -CH ₂ - in R ₂ may be -O-, -S-, -SiH ₂ -, -CH=CH-, -C≡C-, -CF=CF-, -CH= CF-, , -COO- or -OCO-substitution, provided that the heteroatoms are not directly connected to each other; the ring A ₁ represents , or The rings A ₂ , A ₃ and A ₄ are the same or different and each independently represents a cyclic structure, and the cyclic structure represents , , Wherein the cyclic structure of the rings A ₁ , A ₂ , A ₃ and A ₄ may also be selected from at least one of the following a), b), c) and d): a) the cyclic structure One or more of H may be -D, -F, -Cl, -CN, -CF ₃ , -OCF ₃ , -CH ₂ F, -OCH ₂ F, -CF ₂ H, -OCF ₂ H, - OCH ₃ or -CH ₃ substituted; b) one or more -CH ₂ - in the cyclic structure is substituted by -O-, -SiH ₂ -, -S-, or -CO-, provided that the hetero atom is Not directly connected to each other; c) in the cyclic structure, one or more -CH- in the aromatic ring structure may be substituted by N; d) one or more of the cyclic structures Can be Substituting; Z ₁ represents -CF ₂ O-, -CH ₂ O-, -CH ₂ CH ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -C ₂ F ₄ -, -(CH ₂ ) ₄ -, -C ₄ F ₈ -, -OCF ₂ CF ₂ O-, -CF ₂ CF ₂ CF ₂ O-, -CH ₂ CH ₂ CF ₂ O-, -OCF ₂ CF ₂ CF ₂ -, - CH ₂ CF ₂ OCH ₂ -, -CF=CFCF ₂ O-, -CH=CHCH ₂ CH ₂ -, -C ₂ H ₄ OCH ₂ -, -CH ₂ CH=CHCH ₂ -, -OCH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ O- or a single bond; the Z ₂ , Z ₃ and Z ₄ are the same or different and each independently represents a single bond, -COO-, -CF ₂ O-, -CH ₂ O-, -CH ₂ CH ₂ -, -CF ₂ CH ₂ -, -CF=CF-, -CH=CH-, -CH=CF-, -C ₂ F ₄ -, -(CH ₂ ) ₄ - , -C ₄ F ₈ -, -OCF ₂ CF ₂ O-, -CF ₂ CF ₂ CF ₂ O-, -CH ₂ CH ₂ CF ₂ O-, -CH ₂ CF ₂ OCH ₂ -, -CH=CHCF ₂ O-, -CF ₂ OCH=CH-, -CF ₂ OCF=CH-, -CF ₂ OCH=CF-, -CF=CFCF ₂ O-, -CF ₂ OCF=CF-, -CH=CHCH ₂ CH ₂ -, -C ₂ H ₄ OCH ₂ -, -CH ₂ CH=CHCH ₂ -, -OCH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ O-, -CF=CF-CF=CF-, - C≡C-CF=CF-, -C≡C-CF=CF-C≡C-, -CF=CF-C≡C-CF=CF-, -C≡C-CF ₂ O- or -C≡ C-, wherein any one of Z ₂ , Z ₃ and Z ₄ -CH ₂ - It may be substituted by -SiH ₂ -; m, n and p are the same or different and each independently represents 0, 1 or 2. When m is 2, two Z ₂ and two A ₂ are the same or different; when n is 2, two Z ₃ and two A ₃ are the same or different; when p is 2, two Z ₄ and The two A ₄ are each the same or different.

Another object of the present invention is to provide a liquid crystal composition. The liquid crystal composition has high dielectric anisotropy, low driving voltage, good low-temperature mutual solubility, high clearing point, and fast reaction time, and can be applied to liquid crystal elements containing liquid crystal compounds, such as TN, Display mode liquid crystal elements such as STN, TFT, VA, ECB, OCB, LCP, PDLC, BiNem, LC LENS, FFS, or IPS.

The liquid crystal composition of the present invention comprises at least one of the above liquid crystal compounds having a dioxa saturated anthracene ring structure.

Efficacy of the invention: the invention has a dioxa saturated anthracene ring The liquid crystal compound has a good chemical and physical stability, and the liquid crystal compound having a dioxa saturated anthracene ring structure of the present invention has a large dielectric anisotropy as compared with a liquid crystal compound having a cyclohexyl structure. And the liquid crystal composition including the liquid crystal compound having a dioxa saturated anthracene ring structure has a large dielectric anisotropy and a low driving voltage, and can be used for a liquid crystal element containing a liquid crystal medium such as TN, STN, TFT. Liquid crystal elements of display mode such as VA, ECB, OCB, LCP, PDLC, BiNem, LC LENS, FFS or IPS.

Hereinafter, the present invention will be described in detail: preferably, R ₁ represents -H, -F, unsubstituted C ₁ to C ₅ straight or branched alkyl group, halogen substituted C ₁ to a straight-chain or branched C ₅ alkyl or C ₁ to C ₅ alkoxy group, wherein, in R ₁ one or more -CH ₂ - may be -O -, - S -, - SiH ₂ -, -CH=CH-, -C≡C-, -CF=CF-, -CH=CF-, -COO- or -OCO-substitution, provided that the heteroatoms are not directly connected to each other, and -O- The -S- and Si atoms are not directly bonded to the dioxa-saturated anthracene ring; the R ₂ represents -H, -F, -Cl, -CN, -NCS, a unsubstituted C ₁ to C ₁₀ straight or branched alkyl group, a halogen-substituted C ₁ to C ₁₀ linear or branched alkyl group, or a C ₁ to C ₁₀ alkoxy group, wherein One or more of -CH ₂ - in R ₂ may be -O-, -CH=CH-, -C≡C-, -CF=CF-, -CH=CF-, Or -COO-substitution, provided that the heteroatoms are not directly connected to each other.

Preferably, said ring A ₁ represents , or The rings A ₂ , A ₃ and A ₄ are the same or different and are each independently represented , ,

Preferably, said Z ₁ represents -CF ₂ O-, -CH ₂ O-, -CH ₂ CH ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -C ₂ F ₄ -, - (CH ₂ ) ₄ -, -CH ₂ CH ₂ CF ₂ O-, -CH=CHCH ₂ CH ₂ -, -C ₂ H ₄ OCH ₂ -, -CH ₂ CH=CHCH ₂ -, -CF=CFCF ₂ O -, -CH ₂ CH ₂ CH ₂ O- or a single bond; said Z ₂ , Z ₃ and Z ₄ being the same or different and each independently representing -COO-, -CF ₂ O-, -CH ₂ O- , -CH ₂ CH ₂ -, -CF=CF-, -CH=CH-, -C ₂ F ₄ -, -(CH ₂ ) ₄ -, -C ₄ F ₈ -, -OCF ₂ CF ₂ O-, -CH ₂ CH ₂ CF ₂ O-, -CF=CFCF ₂ O-, -C ₂ H ₄ OCH ₂ -, -OCH ₂ CH ₂ CH ₂ -, -C≡C- or a single bond.

Preferably, the 4 m+n+p.

More preferably, the ring A ₁ represents , The rings A ₂ , A ₃ and A ₄ are the same or different and are each independently represented , , ,

More preferably, said Z ₁ represents -CF ₂ O-, -CH ₂ O-, -CH ₂ CH ₂ -, -CH ₂ CF ₂ -, -C ₂ F ₄ -, -(CH ₂ ) ₄ -, -CF=CFCF ₂ O-, -CH ₂ CH ₂ CF ₂ O-, -C ₂ H ₄ OCH ₂ -, -CH ₂ CH ₂ CH ₂ O- or a single bond; the Z ₂ , Z ₃ and Z ₄ The same or different, and each independently represents -COO-, -CF ₂ O-, -CH ₂ O-, -CH ₂ CH ₂ -, -CF=CF-, -CH=CH-, -C ₂ F ₄ -, -(CH ₂ ) ₄ -, -C ₄ F ₈ -, -OCF ₂ CF ₂ O-, -CF=CFCF ₂ O-, -C≡C- or a single bond.

Preferably, the liquid crystal compound having a dioxa saturated anthracene ring structure represents: Wherein, L ₁ to L ₄ are the same or different, and each independently represents -H, -F or -CH ₃ ; L ₅ to L ₁₆ are the same or different, and each independently represents -H, -F, -OCF ₂ H, -CH ₃ , -OCH ₃ , -OCF ₃ or -CF ₃ .

The preparation method of the liquid crystal compound having the dioxa saturated anthracene ring structure of the invention comprises the following steps:

1) providing an ethanol solution comprising a compound of the formula (III-3) and adding three Ethylamine, under nitrogen atmosphere, the temperature is controlled below 15 ° C and the addition of thallium chloride, after completion, the reaction at a constant temperature of 35 ° C for 6 hours, and then at room temperature (25 ± 3 ° C) reaction about The compound of the formula (III-2) can be obtained in 8 to 15 hours.

2) adding sodium wire to toluene and heating to reflux under a nitrogen atmosphere, followed by adding a mixed solution including toluene, ethanol and a compound of the formula (III-2), followed by heating to reflux After reacting for 6 hours, a compound of the formula (III-1) can be obtained.

3) adding lithium tetrahydrogen aluminum to anhydrous tetrahydrofuran, and controlling the temperature to 0 ° C to -5 ° C under a nitrogen atmosphere, and dropping a tetrahydrofuran solution containing the compound of the general formula (III-1), and then naturally heating up to The compound of the formula (III) can be obtained by stirring at room temperature (25 ± 3 ° C) for 12 hours.

4) The compound of the formula (III) and the compound of the formula (V) are dissolved in dichloromethane, p-toluenesulfonic acid is added, and the mixture is heated to reflux under a nitrogen atmosphere for 5 hours to obtain a formula ( I) Compound.

The compound of the formula (III-3) is commercially available or synthesized according to the following synthesis method: The compound of the formula (III-6) is commercially available or synthesized by a conventional synthesis method. The compound of the formula (III-5) is synthesized according to the synthesis method of Journal of Chemical Crystallography , 2007, 37(4), 233-241. The compound of the formula (III-4) is synthesized according to the synthesis method of Journal of Organic Chemistry , 1981, 46(5); 3082-3087. The compound of the formula (III-3) is synthesized according to the synthesis method of Synlett , 1998, 10, 1049-1050.

The compound of the formula (V) is commercially available or synthesized by a conventional synthesis method, and the conventional synthesis method is, for example but not limited to, a reduction reaction, an oxidation reaction, an esterification reaction, a Wittig reaction, and a carbon-carbon cross-coupling reaction ( Suzuki coupling, Negishi coupling, Heck coupling, Sonogashira coupling and transition metal catalyzed Grignard reagent cross-coupling reaction, etc.), Grignard reaction, or low temperature reaction (such as reaction between -30 ° C and -100 ° C, utilization A low temperature digital thermometer measures the low temperature reaction temperature) and the like.

The invention will now be described in connection with specific embodiments. It is to be understood that the following examples are illustrative of the invention and are not intended to limit the invention. Other combinations and various modifications within the inventive concept can be made without departing from the spirit or scope of the invention.

For ease of expression, in the following examples, the group structure of the liquid crystal compound is represented by the codes listed in Table 1.

Take the following liquid crystal compound as an example: The liquid crystal compound was: 3PUQUF.

Example 1

The synthetic method for preparing the compound HCLC-07 is as follows:

Synthesis of HCLC-07-3

A 500 ml three-necked flask containing a thermometer and a constant pressure funnel was charged with 25 g of HCLC-07-4, 41 g of triethylamine and ethanol. Under a nitrogen atmosphere, the temperature was controlled below 15 ° C and 47.9 g of cerium chloride was added dropwise. After completion, the reaction was carried out at a constant temperature of 35 ° C for 6 hours, and then at room temperature (25 ± 3 ° C). 8 to 15 hours. Then, the mixture was concentrated under reduced pressure, and then dissolved in petroleum ether (PE), washed once with a 5 wt% aqueous solution of sodium hydrogencarbonate, and the organic layer was collected and washed once with water to obtain an organic layer and an aqueous layer, and then the aqueous layer was extracted with PE. Collect all organic layers and dry them. Next, chromatography was carried out using a silica gel column, and the chromatography liquid was collected and concentrated to obtain 32.1 g of a colorless transparent liquid, that is, HCLC-07-3. Purity: 96.3%; yield 93.7%.

Synthesis of HCLC-07-2

150 ml of toluene and 3.6 g of sodium silk were placed in a dry 500 ml three-necked flask, and the mixture was heated to reflux under a nitrogen atmosphere, and then a mixed solution was added and completed in 1 hour, wherein the mixed solution included 20 ml. Toluene, 0.3 ml of ethanol and 32.1 g of HCLC-07-3 were then heated to reflux and allowed to react for 6 hours. After the reaction is completed, it is cooled and washed twice with water, and all the organic layers are collected and dried. 14.2 g of crude product were obtained. Next, chromatography was carried out using a petroleum ether column, and the chromatography liquid was collected and concentrated to obtain 21.5 g of an oily substance, that is, HCLC-07-2. Purity: 95.4% (triisomer); yield 85.4%.

Synthesis of HCLC-07-1

400 ml of anhydrous tetrahydrofuran (THF) was placed in a dry 1 L three-necked flask, followed by a small amount of lithium tetrahydrogenate and stirred. After no bubble generation, the remaining 13.8 g of lithium tetrahydrogenate was added, stirring was continued and nitrogen was used. air. The temperature was controlled at 0 ° C to -5 ° C and a mixture containing 50 ml of THF and 21.5 g of HCLC-07-2 was added. After about 1 hour, the temperature was naturally raised to room temperature (25 ± 3 ° C), and stirring was continued at this temperature for 12 hours. Thereafter, sodium sulfate decahydrate was slowly added to react with an excess of lithium aluminum hydride, and after the solid turned yellow-white, the addition of sodium sulfate decahydrate was stopped. Then, the filtration treatment was carried out, and the obtained cake was washed three times with 150 ml of ethyl acetate, and then, the ethyl acetate washing liquid was combined, and the mixture was washed twice with brine (collecting each brine layer and extracting once with ethyl acetate), collecting all The organic layer was dried and dried to give a dried material. The dried product is mixed with 50 g of 60-100 Å yttrium gel and placed in a column packed with 150 g of 200-300 Å yttrium for chromatography, first eluted with PE:EA=8:1, and the color-developing impurities are obtained. After removal, the mixture was extracted with ethyl acetate:ethanol = 1:1, and the filtrate was collected and concentrated to give 13.8 g of pale yellow oil as HCLC-07-1. Purity: 94.8%; Yield: 72.9%.

Synthesis of HCLC-07

3.7 g of HCLC-07-1 and 4.9 g of trans-4-(3,4,5-trifluorophenyl)cyclohexylcarbaldehyde were placed in a 250 ml three-necked flask under stirring Add p-toluenesulfonic acid. Subsequently, the temperature was raised to reflux under a nitrogen atmosphere and reacted for 5 hours, after which the heating was stopped and the temperature was lowered to room temperature (25 ± 3 ° C). The mixture was washed once with an aqueous solution of sodium hydrogencarbonate, and the organic layer was collected and washed twice with brine, and all organic layers were collected and subjected to water removal with anhydrous sodium sulfate, followed by filtration, and the filtrate was concentrated and concentrated under reduced pressure to give 6.5 g of brown. Oily. The brown oil was subjected to chromatography, and ethyl acetate: petroleum ether = 1:40 was used as a solvent, and the chromatographic solution was collected and concentrated to obtain 3 g of a colorless transparent liquid, followed by 5 ml of ethanol. The recrystallization treatment was carried out 3 times to obtain 0.92 g of a white solid, that is, HCLC-07. Purity: 99.8%; yield 13.5%.

Trans-4-(3,4,5-trifluorophenyl)cyclohexylformaldehyde can be prepared by a conventional method, for example, the method disclosed in Journal of the American Chemical Society , 2001, 123(23). 5414-5417.

¹ H NMR (300MHz, CDCl ₃ ) δ 6.88-6.81 (m, 2H), 4.79 (d, J = 4.1 Hz, 1H), 3.80 (dd, J = 24.8, 15.2 Hz, 1H), 3.72-3.45 (m) , 2H), 2.60-2.46 (m, 1H), 2.08-1.64 (m, 8H), 1.62-1.17 (m, 5H), 1.14-0.96 (m, 2H), 0.94-0.79 (m, 3H).

Example 2

The synthetic method for preparing the compound HCLC-07F is as follows:

[4,4-Difluoro-(3,4,5-trifluorophenoxy)methyl]-3,5-difluorobenzeneboronic acid can be synthesized by a conventional method, for example, European Journal of Organic Chemistry , 2008, V20 The content disclosed by p3479-3487.

Synthesis of HCLC-07F-1

4.0 g of p-bromobenzaldehyde, 6.7 g of 4-difluoro-(3,4,5-trifluorophenoxy)methyl]-3,5-difluorophenylboronic acid, 4.0 g of anhydrous sodium carbonate, 20 mL of deionized water, 50 mL of toluene, and 20 mL of absolute ethanol were placed in a 250 mL dry clean single-necked flask, followed by displacement with argon, and 0.3 g of tetrakis(triphenylphosphine)palladium (Pd[P] was added. (Ph) ₃ ] ₄ ). After heating to reflux under argon atmosphere and reacting for 6 hours, after the reaction, cooling is carried out, and then the organic phase is taken out and subjected to chromatography using a silica gel column, and petroleum ether: ethyl acetate = 6:1 is used for the extraction. The solution was collected, and the solvent was collected and the solvent was removed using a rotary concentrator to obtain 7.6 g of a pale yellow solid, which was then crystallized twice with 15 mL of petroleum ether and 15 mL of absolute ethanol to give 6.5 g of a white solid. HCLC-07F-1. Purity: 99.5%; yield 82%.

Synthesis of HCLC-07F

Place 3.1 g of HCLC-07-1, 6.5 g of HCLC-07F-1, 0.3 g of p-toluenesulfonic acid monohydrate and 100 ml of dichloromethane In a 250 mL three-necked flask, followed by heating to reflux reaction for 6 hours using a water bath, and monitoring HCLC-07F-1 using GC, after the HCLC-07F-1 was completely reacted, it was naturally cooled to room temperature (25 ± 3 ° C). Then, the reaction mixture was poured into a 20 mL portion of a saturated aqueous solution of sodium hydrogencarbonate, and transferred to a separating funnel to carry out liquid separation. The organic layer and the aqueous layer were collected, and the aqueous layer was extracted twice with 50 mL of dichloromethane. All organic layers were then collected and washed twice with saturated aqueous sodium bicarbonate. Next, all the organic layers were collected and then subjected to water removal treatment using 30 g of anhydrous sodium sulfate. Thereafter, filtration was carried out and the filtrate was taken, and the solvent was removed using a rotary concentrator to obtain 8.8 g of a pale yellow solid. Thereafter, column chromatography was carried out, using petroleum ether: ethyl acetate = 8:1 as a solvent, and the solvent was collected and the solvent was removed using a rotary concentrator to obtain 6.9 g of a pale yellow solid. Crystallization treatment of 30 mL of absolute ethanol and 10 ml of toluene gave a white solid of 1.35 g, which was HCLC-07F. Purity: 99.8%, yield 16.4%.

_{^{1 H NMR (300MHz, CDCl 3}} ) δ 7.92-7.46 (m, 4H), 7.36-7.29 (m, 2H), 6.92-6.84 (m, 2H), 5.98 (s, 1H), 4.01-3.65 (m, 2H), 3.54 (dd, J = 24.8, 15.2 Hz, 1H), 2.15 - 1.94 (m, 1H), 1.93-1.63 (m, 2 H), 1.63-1.37 (m, 2H), 1.28 (dt, J = 24.7, 17.9 Hz, 1H), 0.86 (d, J = 12.4 Hz, 3H).

The abbreviations of the test items in the following examples are as follows: Cp (°C): clear point (nematic-isotropic phase transition temperature); η (mPa.s): flow viscosity (20 ° C); Δn: optical orientation Hetero (589 nm, 20 ° C); △ ε: dielectric anisotropy (1 kHz, 25 ° C); Vth (V): threshold voltage (1 kHz, 25 ° C).

Example 3

The liquid crystal composition was formulated in accordance with the liquid crystal compounds and weight percentages listed in Table 2, and the characteristics were measured. The test data are shown in Table 2 below.

Comparative example 3

The liquid crystal composition of Comparative Example 3 was prepared in accordance with the liquid crystal compound and weight percentages listed in Table 3, and the characteristic measurement was performed. The test data are shown in Table 3 below.

Example 4

Liquid crystal compositions were prepared according to the liquid crystal compounds listed in Table 4 and weight percentages, and the characteristics were measured. The test data are shown in Table 4 below:

Comparative example 4

The liquid crystal composition of Comparative Example 4 was prepared in accordance with the liquid crystal compounds and weight percentages listed in Table 5, and the characteristics were measured. The test data are shown in Table 5 below.

Referring to Comparative Examples 3 and 4, the liquid crystal compositions of Examples 3 and 4 of the present invention include a liquid crystal compound having a dioxa saturated anthracene ring structure such that it has a large dielectric anisotropy and a low driving voltage.

In summary, the liquid crystal compound having a dioxa saturated anthracene ring structure of the present invention has good chemical and physical stability, and the present invention has a dioxa saturated anthracene ring as compared with a liquid crystal compound having a cyclohexyl structure. The liquid crystal compound of the structure has a large dielectric anisotropy, and the liquid crystal composition containing the liquid crystal compound having a dioxa saturated anthracene ring structure has a large dielectric anisotropy and a low driving voltage, and can be used for The liquid crystal element of the liquid crystal compound, such as a liquid crystal element of a display mode such as TN, STN, TFT, VA, ECB, OCB, LCP, PDLC, BiNem, LC LENS, FFS, or IPS, can indeed achieve the object of the present invention.

The above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, that is, the simple equivalent changes and modifications made by the scope of the patent application and the patent specification of the present invention, All remain within the scope of the invention patent.

Claims (9)

A liquid crystal compound having a dioxa saturated anthracene ring structure, represented by the general formula (I): Wherein R ₁ represents -H, -F, unsubstituted C ₁ to C ₁₀ linear or branched alkyl, halogen-substituted C ₁ to C ₁₀ linear or branched alkyl, or a C ₁ to C ₁₀ alkoxy group, wherein one or more of the R ₁ -CH ₂ - may be -O-, -S-, -SiH ₂ -, -CH=CH-, -C≡ C-, -CF=CF-, -CH=CF-, -COO- or -OCO-substitution, provided that the heteroatoms are not directly connected to each other, and the O, S and Si atoms are not directly related to the dioxa-saturated anthracene ring Connected; R ₂ represents -H, -F, -Cl, -CN, -NCS, -SCN, -OCN, -NCO, , an unsubstituted C ₁ to C ₂₀ linear or branched alkyl group, a halogen-substituted C ₁ to C ₂₀ linear or branched alkyl group, or a C ₁ to C ₂₀ alkoxy group, Wherein one or more of -CH ₂ - in R ₂ may be -O-, -S-, -SiH ₂ -, -CH=CH-, -C≡C-, -CF=CF-, - CH=CF-, , -COO- or -OCO-substitution, provided that the heteroatoms are not directly connected to each other; the ring A ₁ represents , or Rings A ₂ , A ₃ and A ₄ are the same or different and each independently represents a cyclic structure, and the cyclic structure represents , or Wherein the cyclic structure of the rings A ₁ , A ₂ , A ₃ and A ₄ may also be selected from at least one of the following a), b), c) and d): a) the cyclic structure One or more of -H may be -D, -F, -Cl, -CN, -CF ₃ , -OCF ₃ , -CH ₂ F, -OCH ₂ F, -CF ₂ H, -OCF ₂ H, -OCH ₃ or -CH ₃ substituted; b) one or more -CH ₂ - in the cyclic structure may be substituted by -O-, -SiH ₂ -, -S- or -CO-, provided that the The atoms are not directly connected to each other; c) in the cyclic structure, one or more -CH- in the aromatic ring structure may be substituted by N; d) one or more of the cyclic structures Can be Substituting; Z ₁ represents -CF ₂ O-, -CH ₂ O-, -CH ₂ CH ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -C ₂ F ₄ -, -(CH ₂ ) ₄ -, -C ₄ F ₈ -, -OCF ₂ CF ₂ O-, -CF ₂ CF ₂ CF ₂ O-, -CH ₂ CH ₂ CF ₂ O-, -OCF ₂ CF ₂ CF ₂ -, - CH ₂ CF ₂ OCH ₂ -, -CF=CFCF ₂ O-, -CH=CHCH ₂ CH ₂ -, -C ₂ H ₄ OCH ₂ -, -CH ₂ CH=CHCH ₂ -, -OCH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ O- or a single bond; the Z ₂ , Z ₃ and Z ₄ are the same or different and each independently represents a single bond, -COO-, -CF ₂ O-, -CH ₂ O-, -CH ₂ CH ₂ -, -CF ₂ CH ₂ -, -CF=CF-, -CH=CH-, -CH=CF-, -C ₂ F ₄ -, -(CH ₂ ) ₄ - , -C ₄ F ₈ -, -OCF ₂ CF ₂ O-, -CF ₂ CF ₂ CF ₂ O-, -CH ₂ CH ₂ CF ₂ O-, -CH ₂ CF ₂ OCH ₂ -, -CH=CHCF ₂ O-, -CF ₂ OCH=CH-, -CF ₂ OCF=CH-, -CF ₂ OCH=CF-, -CF=CFCF ₂ O-, -CF ₂ OCF=CF-, -CH=CHCH ₂ CH ₂ -, -C ₂ H ₄ OCH ₂ -, -CH ₂ CH=CHCH ₂ -, -OCH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ O-, -CF=CF-CF=CF-, - C≡C-CF=CF-, -C≡C-CF=CF-C≡C-, -CF=CF-C≡C-CF=CF-, -C≡C-CF ₂ O- or -C≡ C-, wherein any one of Z ₂ , Z ₃ and Z ₄ -CH ₂ - may be substituted by SiH ₂ ; m, n and p are the same or different and each independently represents 0, 1 or 2. When m is 2, two Z ₂ and two A ₂ are the same or different; when n is 2, two Z ₃ and two A ₃ are the same or different; when p is 2, two Z ₄ and The two A ₄ are each the same or different. The liquid crystal compound of claim 1, wherein the R ₁ represents -H, -F, an unsubstituted C ₁ to C ₅ linear or branched alkyl group, and a halogen-substituted C ₁ to C ₅ straight a chain or branched alkyl group, or a C ₁ to C ₅ alkoxy group, wherein one or more of the R ₁ -CH ₂ - may be -O-, -S-, -SiH ₂ -, - CH=CH-, -C≡C-, -CF=CF-, -CH=CF-, -COO- or -OCO-substitution, provided that the heteroatoms are not directly connected to each other, and -O-, -S- And the -Si- atom is not directly connected to the dioxa saturated anthracene ring; the R ₂ represents -H, -F, -Cl, -CN, -NCS, An unsubstituted C ₁ to C ₁₀ linear or branched alkyl group, a halogen-substituted C ₁ to C ₁₀ linear or branched alkyl group, or a C ₁ to C ₁₀ alkoxy group, Wherein one or more of -CH ₂ - in R ₂ may be -O-, -CH=CH-, -C≡C-, -CF=CF-, -CH=CF-, Or -COO-substitution, provided that the heteroatoms are not directly connected to each other. The liquid crystal compound of claim 1, wherein the ring A ₁ represents The rings A ₂ , A ₃ and A ₄ are the same or different and are each independently represented , , , The liquid crystal compound of claim 1, wherein the Z ₁ represents -CF ₂ O-, -CH ₂ O-, -CH ₂ CH ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -C ₂ F ₄ -, -(CH ₂ ) ₄ -, -CH ₂ CH ₂ CF ₂ O-, -CH=CHCH ₂ CH ₂ -, -C ₂ H ₄ OCH ₂ -, -CH ₂ CH=CHCH ₂ -, -CF=CFCF ₂ O-, -CH ₂ CH ₂ CH ₂ O- or a single bond; Z ₂ , Z ₃ and Z ₄ are the same or different and each independently represents -COO-, -CF ₂ O-, - CH ₂ O-, -CH ₂ CH ₂ -, -CF=CF-, -CH=CH-, -C ₂ F ₄ -, -(CH ₂ ) ₄ -, -C ₄ F ₈ -, -OCF ₂ CF ₂ O-, -CH ₂ CH ₂ CF ₂ O-, -CF=CFCF ₂ O-, -C ₂ H ₄ OCH ₂ -, -OCH ₂ CH ₂ CH ₂ -, -C≡C- or a single bond. The liquid crystal compound of claim 1, wherein 4 m+n+p. The liquid crystal compound of claim 3, wherein the ring A ₁ represents The rings A ₂ , A ₃ and A ₄ are the same or different and are each independently represented , , , The liquid crystal compound of claim 4, wherein the Z ₁ represents -CF ₂ O-, -CH ₂ O-, -CH ₂ CH ₂ -, -CH ₂ CF ₂ -, -C ₂ F ₄ -, -( CH ₂ ) ₄ -, -CF=CFCF ₂ O-, -CH ₂ CH ₂ CF ₂ O-, -C ₂ H ₄ OCH ₂ -, -CH ₂ CH ₂ CH ₂ O- or a single bond; the Z ₂ And Z ₃ and Z ₄ are the same or different and each independently represents -COO-, -CF ₂ O-, -CH ₂ O-, -CH ₂ CH ₂ -, -CF=CF-, -CH=CH- , -C ₂ F ₄ -, -(CH ₂ ) ₄ -, -C ₄ F ₈ -, -OCF ₂ CF ₂ O-, -CF=CFCF ₂ O-, -C≡C- or a single bond. The liquid crystal compound according to any one of claims 1 to 7, wherein the liquid crystal compound having a dioxa saturated anthracene ring structure represents: or Wherein, L ₁ to L ₄ are the same or different, and each independently represents -H, -F or -CH ₃ ; L ₅ to L ₁₆ are the same or different, and each independently represents -H, -F, -OCF ₂ H, -CH ₃ , -OCH ₃ , -OCF ₃ or -CF ₃ . A liquid crystal composition comprising at least one liquid crystal compound according to any one of claims 1 to 8.