TW202016268A - Liquid crystal composition and display device thereof wherein the liquid crystal display device has a higher transmittance, a higher contrast and a faster response speed, and is suitable for liquid crystal display elements driven by AM-TFTs - Google Patents

Abstract

The present invention discloses a liquid crystal composition. The liquid crystal composition comprises: one or more compounds of general formula I; one or more compounds of general formula M; and one or more compound of general formula A-1. The present invention also discloses a liquid crystal display device including the liquid crystal composition. While maintaining clearing points, optical anisotropy, dielectric anisotropy and low-temperature storage stability in a normal level, the liquid crystal composition of the present invention further has a larger vertical dielectric constant [epsilon]⊥, a larger ratio of vertical dielectric constant to dielectric constant ([epsilon]⊥ / [DELTA][epsilon]), a larger average elastic constant Kave, a smaller rotational viscosity [gamma]1, a greater VHR (initial), VHR (UV) and VHR (high temperature) (that is, better reliability), and a higher transmittance, so that the liquid crystal display device including the liquid crystal composition of the present invention has a higher transmittance, a higher contrast, and a faster response speed, which is particularly suitable for liquid crystal display elements driven by active matrix thin film transistors.

Description

Liquid crystal composition and its display device

The invention relates to the field of liquid crystal materials, in particular to liquid crystal compositions and display devices.

The liquid crystal display element can be used in various household electrical appliances such as clocks and electronic calculators, measuring devices, automobile panels, word processors, computers, printers, and televisions. According to the type of display mode, it is divided into PC (phase change, phase change), TN (twist nematic, twisted nematic), STN (super twisted nematic, super twisted nematic), ECB (electrically controlled birefringence, electronically controlled birefringence), Types such as OCB (optically compensated bend), IPS (in-plane switching), VA (vertical alignment), etc. According to the driving method of the device, it can be divided into PM (passive matrix) type and AM (active matrix) type. PM is divided into static (static) and multiplex (multiplex) and other types. AM is divided into TFT (thin film transistor, thin film transistor), MIM (metal insulator metal, metal-insulating layer-metal) and other types. The types of TFTs are amorphous silicon and polycrystal silicon. The latter is divided into high-temperature type and low-temperature type according to the manufacturing process. Liquid crystal display elements are classified into a reflective type using natural light, a transmissive type using backlight, and a semi-transmissive type using two light sources of natural light and backlight according to the type of light source.

In the low information volume, the passive mode is generally used for driving, but with the increase of the information volume, the display size and the number of display channels increase, and the phenomenon of crosstalk and contrast reduction becomes serious, so the active matrix (AM) mode is generally used for driving At present, thin-film transistors (TFTs) are mostly used for driving. In the AM-TFT element, the TFT switching device is addressed in a two-dimensional grid, recharges the picture element electrode within a limited time of on, and then turns off again until it is addressed in the next cycle. Therefore, between two addressing cycles, the voltage on the pixel point is not expected to change, otherwise the transmittance of the pixel point will change, resulting in unstable display. The discharge rate of the pixel point depends on the electrode capacity and the resistivity of the dielectric material between the electrodes. Therefore, the liquid crystal material is required to have a high resistivity, and the liquid crystal material is required to have a suitable optical anisotropy Δn (Δn value is generally around 0.08-0.13), and a lower threshold voltage to achieve lower driving voltage and lower power The purpose of consumption; it is also required to have a lower viscosity to meet the needs of rapid response. Such liquid crystal compositions have been reported in many literatures, such as WO9202597, WO9116398, WO9302153, WO9116399, CN1157005A, and so on.

In the early 1970s, researchers have conducted experimental studies on the basic electro-optical characteristics of uniformly aligned and twisted aligned nematic liquid crystal IPS modes, which are characterized by a pair of electrodes fabricated on the same substrate, while the other There is no electrode on the substrate, and the arrangement of liquid crystal molecules is controlled by the transverse electric field applied between the electrodes. Therefore, this mode can also be called a transverse field mode. In the IPS mode, nematic liquid crystal molecules are evenly arranged in parallel between the two substrates, and the two polarizers are placed orthogonally. In the IPS mode, when no electric field is applied, the incident light is blocked by two orthogonal polarizers and becomes dark. When the electric field is applied, the liquid crystal molecules rotate to cause a delay, so light leaks from the two orthogonal polarizers.

Because IPS mode devices are simple to manufacture and have a wide viewing angle, they become the most attractive way to improve viewing angle characteristics and achieve large-area display.

The IPS mode display device can use positive or negative liquid crystal, because the transmittance saturation voltage (that is, the driving voltage at the maximum transmittance) decreases with the increase of the absolute value of Δε, so the transmission of positive liquid crystal The rate saturation voltage is lower than that of negative liquid crystals, and the response speed is faster, but negative liquid crystals have better transmittance than positive liquid crystals. This is mainly due to the different rotation of positive and negative liquid crystals under the electric field. According to the transmittance formula transmittance ∝△ε/ε _{⊥ of the} IPS mode, positive transmittance IPS liquid crystals can be doped with negative liquid crystals, so that the transmittance of the liquid crystal display can be greatly improved while maintaining a low driving voltage. Although there has been a method in the prior art to increase the transmittance by adding a negative liquid crystal monomer to a positive liquid crystal composition, the doping of the negative liquid crystal monomer will cause the dielectric value of the liquid crystal composition to decrease, while This makes the reliability of the LCD display worse and the response speed slower.

， 其中，d表示液晶盒的間距，n_e 表示非尋常光折射率，並且n_o 表示尋常光折射率。由該關係式可知，LC Scattering與K_ave 成反比例，在提高K_ave 的情況下，可以降低液晶材料的漏光。In addition, research shows that the most important factor affecting the contrast of liquid crystal display elements is light leakage of liquid crystal materials, and the main factor affecting light leakage is light scattering (LC Scattering), and the relationship between LC Scattering and the average elastic constant K _ave is as follows: LC Scattering ∝

, Where d represents the pitch of the liquid crystal cell, n _e represents the extraordinary refractive index, and n _o represents the ordinary refractive index. From this relationship, it can be seen that LC Scattering is inversely proportional to K _ave , and when K _ave is increased, light leakage of the liquid crystal material can be reduced.

In addition, the relationship between contrast (CR) and brightness (L) is as follows: CR=L ₂₅₅ /L ₀ ×100%, where L ₂₅₅ is the on-state brightness and L ₀ is the off-state brightness. It can be seen that it is the change in L ₀ that should significantly affect CR. In the off state, L ₀ has nothing to do with the dielectric of the liquid crystal molecules, and it is related to the LC Scattering of the liquid crystal material itself. The smaller the LC Scattering, the smaller the L ₀ and CR will be significantly improved.

A liquid crystal display element containing a liquid crystal composition having a large absolute value of dielectric anisotropy can lower the base voltage value, lower the driving voltage, and can further reduce power consumption.

A liquid crystal display element containing a liquid crystal composition with a lower threshold voltage can effectively reduce the power consumption of display, especially in consumables, such as mobile phones, tablet computers and other portable electronic products have a longer battery life. However, for liquid crystal compositions with a lower threshold voltage (generally containing large dielectric groups), the order of liquid crystal molecules is low, and the K _ave value, which reflects the order of liquid crystal molecules, is also reduced, which affects the liquid crystal. Light leakage and contrast of materials are usually difficult to balance.

The low viscosity liquid crystal composition can increase the response speed of the liquid crystal display element. When the response speed of the liquid crystal display element is fast, it can be suitable for animation display. In addition, when the liquid crystal composition is injected into the liquid crystal cell of the liquid crystal display element, the injection time can be shortened, and the workability can be improved.

The prior art discloses a liquid crystal composition with lower power consumption and faster response speed, such as patent document CN102858918A, but the liquid crystal composition in the prior art has environmental problems (such as the use of chlorine-containing compounds) and a short service life (such as Poor stability to UV or heat), low contrast (such as whitening of the display screen in daylight), and the inability to take into account the requirements for proper optical anisotropy, proper dielectric anisotropy, and high in LCD TVs, tablet computers, etc. The performance balance of voltage retention, good UV stability and high temperature stability cannot meet all the indicators at the same time.

From the perspective of the preparation of liquid crystal materials, the properties of liquid crystal materials are mutually constrained and influenced, and the improvement of a certain performance index may cause other properties to change. Therefore, the preparation of liquid crystal materials with suitable properties in all aspects often requires creative work.

The liquid crystal material is an important part of the liquid crystal display. At present, the global liquid crystal display has a great market demand. It is mostly used in electronic and electrical products, but its life cycle is short. The short life cycle naturally has problems such as waste pollution. In today's environment where environmental protection issues are increasingly valued by all walks of life, if you can control it from the source, that is, choose environmentally friendly green materials in the modulation process of liquid crystal materials, you can greatly Reduce the environmental cost of disposal of waste LCDs. Therefore, the preparation of liquid crystal materials that are suitable in all aspects and economical, green and environmentally friendly often requires creative work.

Object of the invention: In view of the defects of the prior art, the object of the present invention is to provide a large verticality while maintaining the clear point, optical anisotropy, dielectric anisotropy and low-temperature storage stability at normal levels Dielectric constant ε _⊥ , larger ratio of vertical dielectric to dielectric ε _⊥ /Δε, larger average elastic constant K _ave , smaller rotational viscosity γ1, greater VHR (initial) and VHR (UV) And VHR (high temperature) (that is, better reliability), and higher transmittance, can make the liquid crystal display device containing it have higher transmittance, higher contrast, and faster response speed, and especially It is suitable for liquid crystal compositions in liquid crystal display devices driven by active matrix thin film transistors (AM-TFTs). An object of the present invention is also to provide a display device including the liquid crystal composition.

Ⅰ； 一種或多種通式M的化合物

M；以及 一種或多種通式A-1的化合物

A-1， 其中， R₁ 和R_A1 各自獨立地表示含有1-12個碳原子的直鏈或支鏈的烷基、

、

或

，所述含有1-12個碳原子的直鏈或支鏈的烷基中的1個或不相鄰的2個以上的-CH₂ -可分別獨立地被-CH＝CH-、-C≡C-、-O-、-CO-、-CO-O-或-O-CO-替代，並且所述含有1-12個碳原子的直鏈或支鏈的烷基、

、

或

中的一個或更多個-H可分別獨立地被-F或-Cl取代； R_M1 和R_M2 各自獨立地表示-H、含有1-12個碳原子的直鏈或支鏈的烷基、

、

或

，所述含有1-12個碳原子的直鏈或支鏈的烷基中的1個或不相鄰的2個以上的-CH₂ -可分別獨立地被-CH＝CH-、-C≡C-、-O-、-CO-、-CO-O-或-O-CO-替代； Z₁ 、Z₂ 和Z₃ 各自獨立地表示單鍵、-CH₂ CH₂ -、-CF₂ CF₂ -、-CO-O-、-O-CO-、-O-CO-O-、-CH＝CH-、-CF＝CF-、-CH₂ O-或-OCH₂ -； Z_A11 表示單鍵、-CH₂ CH₂ -、-CF₂ CF₂ -、-CO-O-、-O-CO-、-O-CO-O-、-CH＝CH-、-CF＝CF-、-CH₂ O-或-OCH₂ -； Z_M1 和Z_M2 各自獨立地表示單鍵、-CO-O-、-O-CO-、-CH₂ O-、-OCH₂ -、-CH＝CH-、-C≡C-、-CH₂ CH₂ -或-(CH₂ )₄ -； L₁ 、L₂ 、L₃ 、L₄ 、L_A11 、L_A12 和L_A13 各自獨立地表示-H、含有1-3個碳原子的烷基或鹵素； X和X_A1 各自獨立地表示鹵素、含有1-5個碳原子的鹵代烷基或鹵代烷氧基、含有2-5個碳原子的鹵代烯基或鹵代烯氧基； 環

和環

各自獨立地表示

或

，其中，

中一個或更多個-CH₂ -可被-O-替代，一個或更多個環中單鍵可被雙鍵替代，

中的一個或更多個-H可被-CN、-F或-Cl取代，一個或更多個環中-CH=可被-N=替代； 環

、環

和環

各自獨立地表示

或

，其中，

中的一個或更多個-CH₂ -可被-O-替代，

中的至多一個-H可被鹵素取代； 環

和環

各自獨立地表示

、

、

或

，其中，

、

和

中一個或更多個-CH₂ -可被-O-替代，一個或更多個環中單鍵可被雙鍵替代，

和

中的一個或更多個-H可被-CN、-F或-Cl取代，一個或更多個環中-CH=可被-N=替代； n1和n2各自獨立地表示0、1或2，且0≤n1+n2≤3，且當n1=2時，環

可以相同或不同，Z₁ 可以相同或不同，當n2=2時，環

可以相同或不同，Z₂ 可以相同或不同； n_M1 和n_A11 各自獨立地表示0、1、2或3，且當n_M1 =2或3時，環

可以相同或不同，Z_M2 可以相同或不同，當n_A11 =2或3時，環

可以相同或不同，Z_A11 可以相同或不同；並且 n_A12 表示1或2，且當n_A12 =2時，環

可以相同或不同。 Technical Solution of the Invention: In order to achieve the above object of the invention, the invention provides a liquid crystal composition, the liquid crystal composition comprising: one or more compounds of the general formula I

Ⅰ; one or more compounds of general formula M

M; and one or more compounds of general formula A-1

A-1, wherein R ₁ and R _A1 each independently represent a linear or branched alkyl group containing 1-12 carbon atoms,

,

or

, The linear or branched alkyl group containing 1-12 carbon atoms, one or two or more non-adjacent -CH ₂ -can be independently -CH=CH-, -C≡ C-, -O-, -CO-, -CO-O- or -O-CO-, and the linear or branched alkyl group containing 1-12 carbon atoms,

,

or

One or more of -H in each may be independently substituted by -F or -Cl; R _M1 and R _M2 each independently represent -H, a linear or branched alkyl group containing 1-12 carbon atoms,

,

or

, The linear or branched alkyl group containing 1-12 carbon atoms, one or two or more non-adjacent -CH ₂ -can be independently -CH=CH-, -C≡ C-, -O-, -CO-, -CO-O- or -O-CO- substitution; Z ₁ , Z ₂ and Z ₃ each independently represent a single bond, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -CO-O-, -O-CO-, -O-CO-O-, -CH=CH-, -CF=CF-, -CH ₂ O- or -OCH ₂ -; Z _A11 represents single Bond, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -CO-O-, -O-CO-, -O-CO-O-, -CH=CH-, -CF=CF-, -CH ₂ O- or -OCH ₂ -; Z _M1 and Z _M2 each independently represent a single bond, -CO-O-, -O-CO-, -CH ₂ O-, -OCH ₂ -, -CH=CH-, -C≡C-, -CH ₂ CH ₂ -or -(CH ₂ ) ₄ -; L ₁ , L ₂ , L ₃ , L ₄ , L _A11 , L _A12 and L _A13 each independently represent -H and contain 1 -Alkyl or halogen with 3 carbon atoms; X and X _A1 each independently represent halogen, haloalkyl or haloalkoxy containing 1-5 carbon atoms, haloalkenyl or halo containing 2-5 carbon atoms Alkenoxy; ring

And ring

Express independently

or

,among them,

One or more -CH ₂ -may be replaced by -O-, one or more single bonds in the ring may be replaced by double bonds,

One or more of -H may be substituted by -CN, -F or -Cl, and one or more rings -CH= may be replaced by -N=; ring

,ring

And ring

Express independently

or

,among them,

One or more of -CH ₂ -can be replaced by -O-,

At most one of -H may be substituted by halogen; ring

And ring

Express independently

,

,

or

,among them,

,

with

One or more -CH ₂ -may be replaced by -O-, one or more single bonds in the ring may be replaced by double bonds,

with

One or more of -H may be replaced by -CN, -F or -Cl, and one or more rings -CH= may be replaced by -N=; n1 and n2 each independently represent 0, 1 or 2 , And 0≤n1+n2≤3, and when n1=2, the ring

May be the same or different, Z ₁ may be the same or different, when n2=2, the ring

May be the same or different, Z ₂ may be the same or different; n _M1 and n _A11 each independently represent 0, 1, 2 or 3, and when n _M1 = 2 or 3, the ring

Can be the same or different, Z _M2 can be the same or different, when n _A11 = 2 or 3, the ring

May be the same or different, Z _A11 may be the same or different; and n _A12 represents 1 or 2, and when n _A12 = 2, the ring

Can be the same or different.

In some embodiments of the present invention, the content of the compound of formula I is necessary according to the solubility at low temperature, transition temperature, electrical reliability, transmittance, contrast, birefringence, process adaptability, drip marks, burn-in screen , Dielectric anisotropy and other required performance and suitable adjustment.

With respect to the weight percentage of the compound of the general formula I in the liquid crystal composition of the present invention, it is preferable that the weight percentage of the compound of the general formula I in the liquid crystal composition of the present invention is a lower limit relative to the total weight of the liquid crystal composition of the present invention The values are 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 20%, 30% or 40%; relative to the total weight of the liquid crystal composition of the present invention, the upper limit of the weight percentage of the compound of formula I in the liquid crystal composition of the present invention is preferably 60%, 55%, 50% , 45%, 40%, 35%, 30%, 28%, 27%, 26%, 25.5%, 25%, 24.5%, 24%, 22%, 20%, 18%, 16% or 15%.

In some embodiments of the present invention, the compound of formula I comprises 0.1% to 60% by weight of the liquid crystal composition.

In some embodiments of the present invention, in the compound of general formula I, when n1=0 and n2=1, at least one of Z ₂ and Z ₃ is not a single bond; when n1=1 and n2=0, At least one of Z ₁ and Z ₃ is not a single bond.

In some embodiments of the present invention, in the compound of general formula I, R ₁ is preferably a linear or branched alkyl or alkoxy group containing 1-8 carbon atoms, a group containing 2-8 carbon atoms Straight-chain or branched alkenyl or alkenyloxy; more preferably straight-chain or branched alkyl or alkoxy containing 1-5 carbon atoms, straight-chain or branched chain containing 2-5 carbon atoms Of alkenyl or alkenyloxy.

和環

各自獨立地表示

、

、

、

、

、

、

、

、

、

、

、

、

、

、

、

、

或

。In some embodiments of the invention, the ring

And ring

Express independently

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

or

.

In some embodiments of the invention, L ₁ , L ₂ , L ₃ and L ₄ each independently represent —H, —CH ₃ , —F or —Cl.

Ⅰ-1；

Ⅰ-2；

Ⅰ-3；

Ⅰ-4；

Ⅰ-5；

Ⅰ-6；

Ⅰ-7；

Ⅰ-8；以及

Ⅰ-9， 其中， L₁ 、L₂ 和L₅ 各自獨立地表示-H或-F；並且 R_x 和R_y 各自獨立地表示-CH₂ -或-O-。In some embodiments of the invention, the compound of general formula I is selected from the group consisting of:

Ⅰ-1;

Ⅰ-2;

Ⅰ-3;

Ⅰ-4;

Ⅰ-5;

Ⅰ-6;

Ⅰ-7;

Ⅰ-8; and

Ⅰ-9, wherein L ₁ , L ₂ and L ₅ each independently represent -H or -F; and R _x and R _y each independently represent -CH ₂ -or -O-.

In some embodiments of the invention, preferably, in the compounds of general formula I-1 to general formula I-8, L ₅ represents -H.

In some embodiments of the invention, the compound of general formula I is preferably selected from the group consisting of general formula I-1, general formula I-2, general formula I-3, general formula I-4, general formula I-5, general formula Ⅰ-6, a group consisting of compounds of formula I-7 and formula I-8.

In some embodiments of the present invention, the liquid crystal composition of the present invention preferably contains at least two compounds of general formula I, wherein at least one compound of general formula I is selected from general formula I-1, general formula I-2, general formula Ⅰ-3, general formula I-4, general formula I-5, general formula I-6, general formula I-7 and general formula I-8.

In some embodiments of the present invention, the liquid crystal composition of the present invention preferably contains at least three compounds of general formula I, wherein at least one compound of general formula I is selected from general formula I-1, general formula I-2, general formula I -3, the general formula I-4, the general formula I-5, the general formula I-6, the general formula I-7 and the general formula I-8 compound; further preferably contains at least two selected from the general formula I- 1. Compounds of the general formula I-2, general formula I-3, general formula I-4, general formula I-5, general formula I-6, general formula I-7 and general formula I-8 .

In some embodiments of the present invention, in the compound of the general formula M, R _M1 and R _M2 are each independently preferably a linear alkyl group containing 1 to 10 carbon atoms, a linear group containing 1 to 9 carbon atoms A chain alkoxy group, or a linear alkenyl group containing 2 to 10 carbon atoms; more preferably a linear alkyl group containing 1 to 8 carbon atoms, a linear chain containing 1 to 7 carbon atoms Alkoxy, or a straight-chain alkenyl group containing 2 to 8 carbon atoms; still more preferably a straight-chain alkyl group containing 1 to 5 carbon atoms, a straight-chain alkoxy group containing 1 to 4 carbon atoms Group, or a straight-chain alkenyl group containing 2 to 5 carbon atoms.

In some embodiments of the invention, R _M1 and R _M2 are each independently preferably a straight-chain alkenyl group containing 2 to 8 carbon atoms; further each independently preferably are a straight-chain alkenyl group containing 2 to 5 carbon atoms Alkenyl.

In some embodiments of the present invention, preferably, one of R _M1 and R _M2 is a straight-chain alkenyl group containing 2 to 5 carbon atoms, and the other is a straight-chain alkenyl group containing 1 to 5 carbon atoms. Chain alkyl.

In some embodiments of the present invention, preferably, both R _M1 and R _M2 are linear alkyl groups containing 1 to 8 carbon atoms, or linear alkoxy groups containing 1 to 7 carbon atoms Further preferably, both R _M1 and R _M2 are linear alkyl groups containing 1 to 5 carbon atoms, or linear alkoxy groups containing 1 to 4 carbon atoms.

In some embodiments of the present invention, preferably, one of R _M1 and R _M2 is a straight-chain alkyl group containing 1 to 5 carbon atoms, and the other is a straight-chain alkyl group containing 1 to 5 carbon atoms. A chain alkyl group, or a linear alkoxy group containing 1 to 4 carbon atoms; more preferably, both R _M1 and R _M2 are linear alkyl groups containing 1 to 5 carbon atoms.

， 其中，*表示所鍵結的環結構中的碳原子。The alkenyl group in the present invention is preferably selected from groups represented by any one of formula (V1) to formula (V9), particularly preferably formula (V1), formula (V2), formula (V8) or formula ( V9). The groups represented by formula (V1) to formula (V9) are as follows:

, Where * represents the carbon atom in the bonded ring structure.

， 其中，*表示所鍵結的環結構中的碳原子。The alkenyloxy group in the present invention is preferably selected from the group represented by any one of formula (OV1) to formula (OV9), particularly preferably formula (OV1), formula (OV2), formula (OV8) or formula (OV9). The groups represented by formula (OV1) to formula (OV9) are as follows:

, Where * represents the carbon atom in the bonded ring structure.

M1；

M2；

M3；

M4；

M5；

M6；

M7；

M8；

M9；

M10

M11；

M12；

M13；

M14；

M15；

M16；

M17；

M18；

M19；

M20；

M21；

M22；

M23；以及

M24。In some embodiments of the invention, the compound of general formula M is selected from the group consisting of:

M1;

M2;

M3;

M4;

M5;

M6;

M7;

M8;

M9;

M10

M11;

M12;

M13;

M14;

M15;

M16;

M17;

M18;

M19;

M20;

M21;

M22;

M23; and

M24.

In some embodiments of the invention, the content of the compound of general formula M must depend on the solubility at low temperatures, transition temperature, electrical reliability, birefringence, process adaptability, dripping traces, burn-in screen, dielectric anisotropy Adjust the performance as required.

Regarding the weight percentage of the compound of the general formula M in the liquid crystal composition of the present invention, the weight percentage of the compound of the general formula M in the liquid crystal composition of the present invention is preferably lower than the total weight of the liquid crystal composition of the present invention. The limits are 0.1%, 1%, 10%, 20%, 30%, 40% or 50%; relative to the total weight of the liquid crystal composition of the present invention, the compound of the general formula M accounts for The preferred upper limit of the weight percentage is 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 35% or 25%.

In some embodiments of the present invention, the compound of formula M accounts for 0.1%-90% of the liquid crystal composition by weight.

Regarding the content of the compound of the general formula M, when the viscosity of the liquid crystal composition of the present invention needs to be kept low and the response time is short, it is preferable that the lower limit value is higher and the upper limit value is higher; When the liquid crystal composition of the invention has a high clearing point and good temperature stability, it is preferable that the lower limit value is higher and the upper limit value is higher; in order to keep the driving voltage low and the dielectric anisotropy When the absolute value of becomes larger, it is preferable to lower the lower limit value and lower the upper limit value.

In some embodiments of the present invention, when importance is attached to reliability, both R _M1 and R _M2 are preferably alkyl; when emphasis is placed on reducing the volatility of the compound, it is preferred that both R _M1 and R _M2 are alkoxy When it is important to lower the viscosity, it is preferred that at least one of R _M1 and R _M2 is an alkenyl group.

In some embodiments of the invention, the compound of general formula M is particularly preferably free of general formula M1, general formula M2, general formula M3, general formula M4, general formula M7, general formula M8, general formula M9, general formula M10, general formula Formula M11, Formula M13, Formula M15, Formula M16, Formula M17, Formula M18, Formula M19, Formula M20, Formula M21, Formula M22, Formula M23 and Formula M24 group.

In some embodiments of the invention, the compound of general formula M is preferably selected from the group consisting of general formula M1, general formula M2, general formula M4, general formula M9, general formula M11, general formula M13, general formula M20, general formula M21, Group consisting of compounds of general formula M22 and general formula M23.

In some embodiments of the present invention, in the compound of the general formula M1, R _M1 represents a linear or branched alkyl or alkoxy group containing 1 to 7 carbon atoms; further preferably containing 1 to 5 carbon atoms Linear or branched alkyl or alkoxy.

With respect to the weight percentage of the compound of the general formula M1 in the liquid crystal composition of the present invention, the weight percentage of the compound of the general formula M1 in the liquid crystal composition of the present invention is preferably relative to the total weight of the liquid crystal composition of the present invention The lower limit is 1%, 3%, 5%, 7%, 10%, 13%, 15%, 17%, 20%, 23%, 25% or 30%; relative to the total of the liquid crystal composition of the present invention By weight, the preferred upper limit of the weight percentage of the compound of the general formula M1 in the liquid crystal composition of the present invention is 60%, 55%, 50%, 45%, 40%, 37%, 35%, 33%, 30% , 27%, 25%, 23%, 20%, 17%, 15%, 13% or 10%.

In order to improve the response time of the liquid crystal composition of the present invention in particular, it is preferable that the compound of the general formula M1 where R _M1 is ethyl, n-propyl, butyl or pentyl, and R _M2 is methyl or methoxy, is generally Compounds of formula M1 where R _M1 is ethyl, n-propyl, butyl or pentyl, and R _M2 is ethyl or ethoxy, or compounds of general formula M1 where R _M1 is n-propyl, butyl Or pentyl, and R _M2 is n-propyl or propoxy.

With respect to the total weight of the liquid crystal composition of the present invention, the preferred lower limit of the weight percentage of the compound of the general formula M1 in which R _M1 is n-propyl and R _M2 is ethyl in the liquid crystal composition of the present invention is 1%, 2%, 3%, 5%, 7%, 10%, 13%, 15%, 18% or 20%; relative to the total weight of the liquid crystal composition of the present invention, R _M1 in the compound of formula _M1 The upper limit of the weight percentage of the compound of n-propyl group and R _M2 being ethyl group in the liquid crystal composition of the present invention is preferably 20%, 17%, 15%, 13%, 10%, 8%, 7% Or 6%.

With respect to the weight percentage of the compound of the general formula M2 in the liquid crystal composition of the present invention, the weight percentage of the compound of the general formula M2 in the liquid crystal composition of the present invention is preferably lower than the total weight of the liquid crystal composition of the present invention The limit value is 1%, 2%, 3%, 5%, 7% or 10%; relative to the total weight of the liquid crystal composition of the present invention, the weight percentage of the compound of the general formula M2 in the liquid crystal composition of the present invention is preferably The upper limit is 20%, 15%, 13%, 10%, 8%, 7%, 6%, 5% or 3%.

With respect to the weight percentage of the compound of the general formula M4 in the liquid crystal composition of the present invention, the weight percentage of the compound of the general formula M4 in the liquid crystal composition of the present invention is preferably lower than the total weight of the liquid crystal composition of the present invention The limit value is 1%, 2%, 3%, 5%, 7% or 10%; relative to the total weight of the liquid crystal composition of the present invention, the weight percentage of the compound of the general formula M4 in the liquid crystal composition of the present invention is preferably The upper limit is 20%, 15%, 13%, 10%, 8%, 7%, 6%, 5% or 3%.

Regarding the weight percentage of the compound of the general formula M9 in the liquid crystal composition of the present invention, the lower limit of the weight percentage of the compound of the general formula M9 in the liquid crystal composition of the present invention is preferably relative to the total weight of the liquid crystal composition of the present invention Values are 1%, 2%, 3%, 5%, 7%, 10%, 14%, 16%, 20%, 23%, 26%, 30%, 35% or 40%; relative to the liquid crystal of the present invention The total weight of the composition, the upper limit of the weight percentage of the compound of the general formula M9 in the liquid crystal composition of the present invention is preferably 50%, 40%, 35%, 30%, 20%, 15%, 10% or 5 %.

或

。In some embodiments of the present invention, depending on the properties required for solubility at low temperatures, transition temperature, electrical reliability, birefringence, etc., it is preferred that in compounds containing the general formula M9, R _M1 contains 2-4 carbon atoms The compound of the linear or branched alkenyl group, and R _M2 is CH ₃ -, the linear or branched alkenyl group containing 2-4 carbon atoms is more preferably

or

.

或

、且R_M2 為CH₃ -的化合物的占本發明的液晶組合物的重量百分比優選的下限值為1%，3%，5%，7%，9%，11%，12%，13%，18%或21%，並且優選上限值為45%，40%，35%，30%，25%，23%，20%，18%，15%，13%，10%或8%。在同時含有所述兩種化合物時，相對于本發明的液晶組合物總重量，所述兩種化合物的占本發明的液晶組合物的重量百分比優選的下限值為3%，5%，7%，9%，11%，13%，15%，19%，24%或30%，並且優選上限值為45%，40%，35%，30%，25%，23%，20%，18%，15%、13%、11%或9%。With respect to the total weight of the liquid crystal composition of the present invention, R _M1 in the compound of the general formula M9 is

or

The preferred lower limit of the weight percentage of the compound of R _{M2 which} is CH ₃ -in the liquid crystal composition of the present invention is 1%, 3%, 5%, 7%, 9%, 11%, 12%, 13% , 18% or 21%, and preferably the upper limit is 45%, 40%, 35%, 30%, 25%, 23%, 20%, 18%, 15%, 13%, 10% or 8%. When the two compounds are contained at the same time, with respect to the total weight of the liquid crystal composition of the present invention, the preferred lower limit of the weight percentage of the two compounds in the liquid crystal composition of the present invention is 3%, 5%, 7 %, 9%, 11%, 13%, 15%, 19%, 24% or 30%, and preferably the upper limit is 45%, 40%, 35%, 30%, 25%, 23%, 20%, 18%, 15%, 13%, 11% or 9%.

With respect to the weight percentage of the compound of the general formula M10 in the liquid crystal composition of the present invention, the weight percentage of the compound of the general formula M10 in the liquid crystal composition of the present invention is preferably lower than the total weight of the liquid crystal composition of the present invention The limits are 1%, 2%, 3%, 4%, 5%, 7%, 10%, 14%, 16% or 20%; relative to the total weight of the liquid crystal composition of the present invention, the compound of formula M10 The preferred upper limit of the weight percentage of the liquid crystal composition of the present invention is 45%, 40%, 35%, 30%, 20%, 15%, 10% or 5%.

或

。In some embodiments of the present invention, depending on the properties required for solubility at low temperature, transition temperature, electrical reliability, birefringence, etc., it is preferred that in compounds containing the general formula M10, R _M1 contains 2-4 carbon atoms The compound of the linear or branched alkenyl group, and R _M2 is CH ₃ -, the linear or branched alkenyl group containing 2-4 carbon atoms is more preferably

or

.

或

、且R_M2 為CH₃ -的化合物的占本發明的液晶組合物的重量百分比優選的下限值為1%，3%，4%，5%，7%，9%，11%，12%，13%，18%或20%，並且優選上限值為40%，35%，30%，25%，23%，20%，18%，15%，13%，10%或8%。在同時含有所述兩種化合物時，相對于本發明的液晶組合物的總重量，所述兩種化合物的占本發明所述液晶組合物的重量百分比優選的下限值為3%，5%，7%，9%，11%，13%，15%，19%，24%或30%，優選上限值為45%，40%，35%，30%，25%，23%，20%，18%，15%或13%。With respect to the total weight of the liquid crystal composition of the present invention, R _M1 in the compound of the general formula M10 is

or

The preferred lower limit of the weight percentage of the compound of R _{M2 which} is CH ₃ -in the liquid crystal composition of the present invention is 1%, 3%, 4%, 5%, 7%, 9%, 11%, 12% , 13%, 18% or 20%, and preferably the upper limit value is 40%, 35%, 30%, 25%, 23%, 20%, 18%, 15%, 13%, 10% or 8%. When the two compounds are contained at the same time, with respect to the total weight of the liquid crystal composition of the present invention, the preferred lower limit of the weight percentage of the two compounds in the liquid crystal composition of the present invention is 3%, 5% , 7%, 9%, 11%, 13%, 15%, 19%, 24% or 30%, the preferred upper limit is 45%, 40%, 35%, 30%, 25%, 23%, 20% , 18%, 15% or 13%.

Regarding the weight percentage of the compound of the general formula M11 in the liquid crystal composition of the present invention, it is preferably: the lower limit of the weight percentage of the compound of the general formula M11 in the liquid crystal composition of the present invention relative to the total weight of the liquid crystal composition of the present invention Values are 1%, 2%, 3%, 5%, 7%, 10%, 14%, 16%, 20%, 23%, 26%, 30%, 35% or 40%; relative to the liquid crystal of the present invention The total weight of the composition, the upper limit of the weight percentage of the compound of the general formula M11 in the liquid crystal composition of the present invention is preferably 50%, 40%, 35%, 30%, 20%, 15%, 10% or 5 %.

或

、且R_M2 為正丙基的化合物，或優選R_M1 為正丙基、正丁基或正戊基、且R_M2 為CH₃ O-的化合物；特別優選R_M1 為正丙基、且R_M2 為C₂ H₅ -的化合物。In some embodiments of the invention, the compound of general formula M11 is preferably a compound where R _M1 is n-propyl or n-pentyl, and R _M2 is C ₂ H ₅ -, or preferably R _M1 is

or

And R _M2 is n-propyl, or preferably R _M1 is n-propyl, n-butyl or n-pentyl, and R _M2 is CH ₃ O-; particularly preferably R _M1 is n-propyl and R _M2 is a C ₂ H ₅ -compound.

Regarding the weight percentage of the compound of the general formula M13 in the liquid crystal composition of the present invention, it is preferably: the lower limit of the weight percentage of the compound of the general formula M13 in the liquid crystal composition of the present invention relative to the total weight of the liquid crystal composition of the present invention Values are 1%, 2%, 3%, 5%, 7%, 10%, 14%, 16%, 20%, 23%, 26%, 30%, 35% or 40%; relative to the liquid crystal of the present invention The total weight of the composition, the upper limit of the weight percentage of the compound of the general formula M13 in the liquid crystal composition of the present invention is preferably 50%, 40%, 35%, 30%, 20%, 15%, 10% or 5 %.

或

、而另一者為CH₃ -或C₂ H₅ -的化合物。In some embodiments of the present invention, the compounds of the general formula M13 preferably R _M1 and R _M2 each independently represent a compound of a linear or branched alkyl group containing 2-5 carbon atoms, or preferably R _M1 and R _M2 One of

or

And the other is a CH ₃ -or C ₂ H ₅ -compound.

With respect to the weight percentage of the compound of the general formula M15 in the liquid crystal composition of the present invention, it is preferably: the lower limit of the weight percentage of the compound of the general formula M15 in the liquid crystal composition of the present invention relative to the total weight of the liquid crystal composition of the present invention Values are 1%, 2%, 3%, 5%, 7%, 10%, 12%, 14%, 16%, 18%, 20%, 23%, 26%, 30%, 35% or 40%; With respect to the total weight of the liquid crystal composition of the present invention, the upper limit of the weight percentage of the compound of the general formula M15 in the liquid crystal composition of the present invention is preferably 50%, 40%, 35%, 30%, 25%, 22 %, 20%, 18%, 15%, 12%, 10%, 8% or 5%.

With respect to the weight percentage of the compound of the general formula M16 in the liquid crystal composition of the present invention, it is preferably: the lower limit of the weight percentage of the compound of the general formula M16 in the liquid crystal composition of the present invention relative to the total weight of the liquid crystal composition of the present invention Values are 1%, 2%, 3%, 5%, 7%, 10%, 12%, 14%, 16%, 18%, 20%, 23%, 26%, 30%, 35% or 40%; With respect to the total weight of the liquid crystal composition of the present invention, the upper limit of the weight percentage of the compound of the general formula M16 in the liquid crystal composition of the present invention is preferably 50%, 40%, 35%, 30%, 25%, 22 %, 20%, 18%, 15%, 12%, 10%, 8% or 5%.

With respect to the weight percentage of the compounds of the general formula M20 to M24 in the liquid crystal composition of the present invention, it is preferable that the compounds of the general formula M20 to M24 account for the percentage of the liquid crystal composition of the present invention relative to the total weight of the liquid crystal composition of the present invention The preferred lower limit of the total weight percentage is 1%, 2%, 3%, 5%, 7%, 10%, 14%, 16% or 20%; relative to the total weight of the liquid crystal composition of the present invention, the general formula The preferred upper limit value of the compounds of M20 to M24 as a percentage of the total weight of the liquid crystal composition of the present invention is 30%, 25%, 23%, 20%, 18%, 15%, 12%, 10% or 5% .

A-1-1；

A-1-2；

A-1-3；

A-1-4；

A-1-5；

A-1-6；

A-1-7；

A-1-8；

A-1-9；

A-1-10；

A-1-11；

A-1-12；

A-1-13；

A-1-14；

A-1-15；

A-1-16；

A-1-17；以及

A-1-18， 其中， R_A1 表示含有1-8個碳原子的直鏈或支鏈的烷基、

、

或

，所述含有1-8個碳原子的直鏈或支鏈的烷基中的1個或不相鄰的2個以上的-CH₂ -可分別獨立地被-CH＝CH-、-C≡C-、-O-、-CO-、-CO-O-或-O-CO-替代，並且存在於這些基團中的一個或更多個-H可分別獨立地被-F或-Cl取代； R_v 和R_w 各自獨立地表示-CH₂ -或-O-； L_A11 、L_A12 、L_A11 ^’ 、L_A12 ^’ 、L_A14 、L_A15 和L_A16 各自獨立地表示-H或-F； L_A13 和L_A13 ^’ 各自獨立地表示-H或-CH₃ ； X_A11 表示-F、-CF₃ 或-OCF₃ ；並且 v和w各自獨立地表示0或1。In some embodiments of the invention, the compound of general formula A-1 is selected from the group consisting of:

A-1-1;

A-1-2;

A-1-3;

A-1-4;

A-1-5;

A-1-6;

A-1-7;

A-1-8;

A-1-9;

A-1-10;

A-1-11;

A-1-12;

A-1-13;

A-1-14;

A-1-15;

A-1-16;

A-1-17; and

A-1-18, where R _A1 represents a linear or branched alkyl group containing 1-8 carbon atoms,

,

or

, One or two or more non-adjacent -CH ₂ -in the linear or branched alkyl group containing 1-8 carbon atoms can be independently -CH=CH-, -C≡ C-, -O-, -CO-, -CO-O- or -O-CO- are substituted, and one or more -H present in these groups may be independently substituted by -F or -Cl, respectively ; R _v and R _w each independently represent -CH ₂ -or -O-; L _A11 , L _A12 , L _A11 ^' , L _A12 ^' , L _A14 , L _A15 and L _A16 each independently represent -H or -F ; L _A13 and L _A13 ^' each independently represent -H or -CH ₃ ; X _A11 represents -F, -CF ₃ or -OCF ₃ ; and v and w each independently represent 0 or 1.

Regarding the weight percentage of the compound of the general formula A-1 in the liquid crystal composition of the present invention, it is preferably: the weight percentage of the compound of the general formula A-1 in the liquid crystal composition of the present invention relative to the total weight of the liquid crystal composition of the present invention The preferred lower limit is 0.1%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 12%, 14%, 15%, 17% , 18% or 20%; relative to the total weight of the liquid crystal composition of the present invention, the preferred upper limit of the weight percentage of the compound of formula A-1 in the liquid crystal composition of the present invention is 80%, 60%, 55 %, 50%, 45%, 40%, 35%, 30% or 25%.

In some embodiments of the present invention, the compound of the general formula A-1 accounts for 0.1%-80% by weight of the liquid crystal composition.

Regarding the preferable content of the compound of the general formula A-1, when the viscosity of the liquid crystal composition of the present invention is kept low and the response speed is fast, it is preferable to make the lower limit value slightly lower and the upper limit value slightly Further, in the case where the clearing point of the liquid crystal composition of the present invention is kept high and the temperature stability is good, it is preferable to make the lower limit value slightly lower and the upper limit value slightly lower; When the driving voltage is kept low and the absolute value of dielectric anisotropy is to be increased, it is preferable to make the lower limit value slightly higher and the upper limit value slightly higher.

In some embodiments of the invention, the compound of general formula A-1 is preferably selected from the group consisting of general formula A-1-7, general formula A-1-13, general formula A-1-14 and general formula A-1- Group of 15 compounds.

A-2， 其中， R_A2 表示含有1-12個碳原子的直鏈或支鏈的烷基、

、

或

，所述含有1-12個碳原子的直鏈或支鏈的烷基中的1個或不相鄰的2個以上的-CH₂ -可分別獨立地被-CH＝CH-、-C≡C-、-O-、-CO-、-CO-O-或-O-CO-替代，並且所述含有1-12個碳原子的直鏈或支鏈的烷基、

、

或

中的一個或更多個-H可分別獨立地被-F或-Cl取代； Z_A21 和Z_A22 各自獨立地表示單鍵、-CH₂ CH₂ -、-CF₂ CF₂ -、-CO-O-、-O-CO-、-O-CO-O-、-CH＝CH-、-CF＝CF-、-CH₂ O-或-OCH₂ -； L_A21 和L_A22 各自獨立地表示-H、含有1-3個碳原子的烷基或鹵素； X_A2 表示鹵素、含有1-5個碳原子的鹵代烷基或鹵代烷氧基、含有2-5個碳原子的鹵代烯基或鹵代烯氧基； 環

和環

各自獨立地表示

、

、

或

，其中，

、

和

中至多一個-CH₂ -可被-O-替代，一個或更多個環中單鍵可被雙鍵替代，

和

中的一個或更多個-H可被-CN、-F或-Cl取代，一個或更多個環中-CH=可被-N=替代；並且 n_A2 表示0、1、2或3，且當n_A2 =1且Z_A21 和Z_A22 均表示單鍵時，環

和環

還可以各自獨立地表示

；當n_A2 =2或3時，環

可以相同或不同，Z_A21 可以相同或不同。In some embodiments of the invention, the liquid crystal composition further comprises one or more compounds of general formula A-2:

A-2, where R _A2 represents a linear or branched alkyl group containing 1-12 carbon atoms,

,

or

, The linear or branched alkyl group containing 1-12 carbon atoms, one or two or more non-adjacent -CH ₂ -can be independently -CH=CH-, -C≡ C-, -O-, -CO-, -CO-O- or -O-CO-, and the linear or branched alkyl group containing 1-12 carbon atoms,

,

or

One or more of -H may be independently substituted by -F or -Cl; Z _A21 and Z _A22 each independently represent a single bond, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -CO- O-, -O-CO-, -O-CO-O-, -CH=CH-, -CF=CF-, -CH ₂ O- or -OCH ₂ -; L _A21 and L _A22 each independently represent- H, alkyl or halogen containing 1-3 carbon atoms; X _A2 represents halogen, haloalkyl or haloalkoxy containing 1-5 carbon atoms, haloalkenyl or halo containing 2-5 carbon atoms Alkenyloxy; ring

And ring

Express independently

,

,

or

,among them,

,

with

At most one -CH ₂ -can be replaced by -O-, one or more single bonds in the ring can be replaced by double bonds

with

One or more of -H may be replaced by -CN, -F or -Cl, one or more rings -CH= may be replaced by -N=; and n _A2 represents 0, 1, 2 or 3, And when n _A2 =1 and Z _A21 and Z _A22 both represent single bonds, the ring

And ring

Can also be expressed independently

; When n _A2 = 2 or 3, the ring

They can be the same or different, and Z _A21 can be the same or different.

A-2-1；

A-2-2；

A-2-3；

A-2-4；

A-2-5；

A-2-6；

A-2-7；

A-2-8；

A-2-9；

A-2-10；

A-2-11；

A-2-12；

A-2-13；

A-2-14；以及

A-2-15， 其中， R_A2 表示含有1-8個碳原子的直鏈或支鏈的烷基，所述含有1-8個碳原子的直鏈或支鏈的烷基中的1個或不相鄰的2個以上的-CH₂ -可分別獨立地被-CH＝CH-、-C≡C-、-O-、-CO-、-CO-O-或-O-CO-替代，並且存在於這些基團中的一個或更多個-H可分別獨立地被-F或-Cl取代； L_A21 、L_A22 、L_A23 、L_A24 和L_A25 各自獨立地表示-H或-F；並且 X_A2 表示-F、-CF₃ 、-OCF₃ 或-CH₂ CH₂ CH=CF₂ 。In some embodiments of the invention, the compound of general formula A-2 is selected from the group consisting of:

A-2-1;

A-2-2;

A-2-3;

A-2-4;

A-2-5;

A-2-6;

A-2-7;

A-2-8;

A-2-9;

A-2-10;

A-2-11;

A-2-12;

A-2-13;

A-2-14; and

A-2-15, wherein R _A2 represents a linear or branched alkyl group containing 1-8 carbon atoms, one of the linear or branched alkyl groups containing 1-8 carbon atoms Or two or more non-adjacent -CH ₂ -can be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O-, or -O-CO- , And one or more -H present in these groups may be independently substituted by -F or -Cl; L _A21 , L _A22 , L _A23 , L _A24 and L _A25 each independently represent -H or- F; and X _A2 represents -F, -CF ₃ , -OCF ₃ or -CH ₂ CH ₂ CH=CF ₂ .

Regarding the weight percentage of the compound of the general formula A-2 in the liquid crystal composition of the present invention, it is preferably: the weight percentage of the compound of the general formula A-2 in the liquid crystal composition of the present invention relative to the total weight of the liquid crystal composition of the present invention The preferred lower limit is 0.1%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 12%, 14%, 15%, 17% , 18% or 20%; relative to the total weight of the liquid crystal composition of the present invention, the upper limit of the weight percentage of the compound of formula A-2 in the liquid crystal composition of the present invention is preferably 80%, 75%, 70 %, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30% or 25%.

In some embodiments of the present invention, the compound of the general formula A-2 accounts for 0.1%-80% by weight of the liquid crystal composition.

Regarding the preferable content of the compound of the general formula A-2, when the viscosity of the liquid crystal composition of the present invention is kept low and the response speed is fast, it is preferable to make the lower limit value slightly lower and the upper limit value slightly Further, in the case where the clearing point of the liquid crystal composition of the present invention is kept high and the temperature stability is good, it is preferable to make the lower limit value slightly lower and the upper limit value slightly lower; When the driving voltage is kept low and the absolute value of dielectric anisotropy is to be increased, it is preferable to make the lower limit value slightly higher and the upper limit value slightly higher.

In some embodiments of the invention, the compound of general formula A-2 is preferably selected from the group consisting of general formula A-2-4, general formula A-2-8, general formula A-2-11 and general formula A-2- Group of 12 compounds.

In addition to the above-mentioned compounds, the liquid crystal composition of the present invention may contain general nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, antioxidant, ultraviolet absorber, infrared absorber, polymerizable monomer, light stabilizer, etc. .

；

；

；

；

；

；

；

；

；

；

；

；以及

。The following shows possible dopants preferably added to the liquid crystal composition according to the present invention.

;

;

;

;

;

;

;

;

;

;

;

;as well as

.

In some embodiments of the present invention, preferably, the weight percentage of the dopant in the liquid crystal composition is 0-5%; more preferably, the weight percentage of the dopant in the liquid crystal composition is 0-1%.

其中，n表示1-12的正整數。In addition, additives such as antioxidants and light stabilizers used in the liquid crystal composition of the present invention are preferably the following:

Among them, n represents a positive integer of 1-12.

Preferably, the light stabilizer is selected from the following light stabilizers:

In some embodiments of the present invention, preferably, the light stabilizer accounts for 0-5% of the total weight of the liquid crystal composition; more preferably, the light stabilizer accounts for 0-1% of the total weight of the liquid crystal composition; Particularly preferably, the light stabilizer accounts for 0.01-0.1% of the total weight of the liquid crystal composition.

In some embodiments of the present invention, the clearing point Cp of the liquid crystal composition ranges from 80 to 120°C; the absolute value of the dielectric anisotropy Δε ranges from 3 to 12; and the optical anisotropy Δn ranges from 0.08 to 0.12; the ratio of vertical dielectric to dielectric ε _⊥ /Δε is not less than 0.46; the average elastic constant K _{ave is} not less than 13.3; at -30 ℃, the low temperature storage time is more than 500 h.

Another aspect of the present invention also provides a liquid crystal display comprising the liquid crystal composition provided by the present invention.

Beneficial effect: The liquid crystal composition of the present invention also has a large vertical dielectric constant ε _⊥ while maintaining a clear point, optical anisotropy, dielectric anisotropy, and low-temperature storage stability at normal levels. Large vertical dielectric to dielectric ratio ε _⊥ /Δε, larger average elastic constant K _ave , smaller rotational viscosity γ1, larger VHR (initial) and VHR (UV) and VHR (high temperature) (ie Better reliability), and higher transmittance, so that the liquid crystal display device including the liquid crystal composition of the present invention has higher transmittance, higher contrast, and faster response speed, which is particularly suitable for active Liquid crystal display elements driven by matrix thin-film transistors (AM-TFT).

The present invention will be described below in conjunction with specific embodiments. It should be noted that the following embodiments are examples of the present invention, which are only used to illustrate the present invention, but not to limit the present invention. Other combinations and various improvements within the concept of the present invention can be made without departing from the gist or scope of the present invention.

In the present invention, unless otherwise specified, the ratios are weight ratios, and all temperatures are degrees Celsius.

For ease of expression, in the following examples, the group structure of the liquid crystal composition is represented by the codes listed in Table 1: Table 1 Group structure codes of liquid crystal compounds

該結構式如用表1所列代碼表示，則可表達為：nCCGF，代碼中的n表示左端烷基的C原子數，例如n為“3”，即表示該烷基為-C₃ H₇ ；代碼中的C代表環己烷基，G代表2-氟-1,4-亞苯基，F代表氟。Take the following structural formula as an example:

If the structural formula is represented by the code listed in Table 1, it can be expressed as: nCCGF, n in the code represents the number of C atoms of the left alkyl group, for example, n is "3", which means that the alkyl group is -C ₃ H ₇ ; C in the code represents cyclohexane, G represents 2-fluoro-1,4-phenylene, and F represents fluorine.

The abbreviated codes of the test items in the following examples are as follows: Cp clearing point (nematic-isotropic phase transition temperature, °C) Δn optical anisotropy (589 nm, 25 °C) ε _⊥ dielectric perpendicular to the molecular axis Constant Δε Dielectric anisotropy (1 KHz, 25°C) ε _⊥ /Δε Ratio of vertical dielectric to dielectric γ1 Rotational viscosity (mPa·s, 25°C, unless otherwise stated) LTS Low temperature storage stability (°C, Store 500 h without devitrification temperature) K ₁₁ Spreading elastic constant K ₂₂ Torsional elastic constant K ₃₃ Flexural elastic constant K _ave Average elastic constant VHR (Initial) Initial voltage retention rate (%) VHR (UV) After UV light irradiation Voltage retention rate (%) VHR (high temperature) Voltage retention rate (%) after 150 h at 150 ℃ for 1 h

Among them, the optical anisotropy was measured with an Abbe refractometer under a sodium light (589 nm) light source at 25°C.

Δε=ε _‖ -ε _⊥ , where ε _‖ is the dielectric constant parallel to the molecular axis, ε _⊥ is the dielectric constant perpendicular to the molecular axis, test conditions: 25℃, 1KHz, test box is TN90 type, box thickness 7 μm.

γ1 was tested using the TOYO6254 liquid crystal physical property evaluation system; the test temperature was 25°C, the test voltage was 90 V, and the test cell thickness was 20 μm.

（K₁₁ +K₂₂ +K₃₃ ）。K ₁₁ , K ₂₂ and K ₃₃ are calculated by using the LCR instrument and anti-parallel friction box to test the CV curve of the liquid crystal. Test conditions: 7 μm anti-parallel friction box, V=0.1~20 V; K _ave =

(K ₁₁ +K ₂₂ +K ₃₃ ).

VHR (initial) was tested using the TOY06254 liquid crystal physical property evaluation system; the test temperature was 60°C, the test voltage was 5 V, the test frequency was 6 Hz, and the test cell thickness was 9 μm.

VHR (UV) is tested using the TOY06254 liquid crystal physical property evaluation system; the test is performed after irradiating the liquid crystal material with UV light with a wavelength of 365 nm and an energy of 6000 mJ/cm ² at a test temperature of 60°C and a test voltage of 5 V. The frequency is 6 Hz and the test cell thickness is 9 μm.

VHR (high temperature) was tested using the TOY06254 liquid crystal physical property evaluation system; the liquid crystal was tested at 150°C for 1 h at a high temperature, the test temperature was 60°C, the test voltage was 5 V, the test frequency was 6 Hz, and the test cell thickness was 9 μm.

Each component used in the following examples can be synthesized by a well-known method or obtained through a commercial route. These synthesis techniques are conventional, and the resulting liquid crystal compounds have been tested to meet the standards for electronic compounds.

The liquid crystal composition was prepared according to the ratio of each liquid crystal composition specified in the following examples. The preparation of the liquid crystal composition is carried out according to a conventional method in the art, such as heating, ultrasonic waves, suspension, etc. in a prescribed ratio.

The liquid crystal compositions given in the following examples were prepared and studied. The composition of each liquid crystal composition and the test results of its performance parameters are shown below.

Comparative example 1

The liquid crystal composition of Comparative Example 1 was prepared according to the compounds and weight percentages listed in Table 2, which was filled between the two substrates of the liquid crystal display for performance testing. The test data is shown in the following table: 3 Table 2 Liquid crystal composition formula And its test performance

Examples 1

The liquid crystal composition of Example 1 is prepared according to the compounds and weight percentages listed in Table 3, which is filled between the two substrates of the liquid crystal display for performance testing. The test data is shown in the following table: Table 3 Liquid crystal composition formulation and Its test performance

From the comparison between Comparative Example 1 and Example 1, it can be seen that the liquid crystal composition of the present invention has a high clearing point and a large vertical dielectric under the premise of having substantially equivalent dielectric anisotropy and optical anisotropy The ratio of electricity to dielectric ε _⊥ /Δε, larger average elastic constant K _ave , smaller rotational viscosity γ1, larger VHR (initial) and VHR (UV) and VHR (high temperature) (that is, better reliability Properties), and better low-temperature stability, which indicates that the liquid crystal composition of the present invention is more suitable for liquid crystal display devices that require high contrast, high transmittance, fast response, and a wide nematic phase temperature range.

Comparative example 2

The liquid crystal composition of Comparative Example 2 was prepared according to the compounds and weight percentages listed in Table 4, which was filled between the two substrates of the liquid crystal display for performance testing. The test data is shown in the following table: Table 4 Liquid crystal composition formulation and Its test performance

Examples 2

The liquid crystal composition of Example 2 is prepared according to the compounds and weight percentages listed in Table 5, which is filled between two substrates of the liquid crystal display for performance testing. The test data is shown in the following table: Table 5 Liquid crystal composition formulation and Its test performance

From the comparison between Comparative Example 2 and Example 2, it can be seen that the liquid crystal composition of the present invention has a large vertical dielectric and dielectric under the premise of having substantially equivalent clearing point, optical anisotropy and dielectric anisotropy Electrical ratio ε _⊥ /Δε, larger average elastic constant K _ave , smaller rotational viscosity γ1, larger VHR (initial) and VHR (UV) and VHR (high temperature) (that is, better reliability), As well as better low-temperature stability, this indicates that the liquid crystal composition of the present invention is more suitable for liquid crystal display devices that require high contrast, high transmittance, fast response, and a wide nematic phase temperature range.

Examples 3

The liquid crystal composition of Example 3 was prepared according to the compounds and weight percentages listed in Table 6, which was filled between the two substrates of the liquid crystal display for performance testing. The test data is shown in the following table: Table 6 Liquid crystal composition formulation and Its test performance

Examples 4

The liquid crystal composition of Example 4 was prepared according to the compounds and weight percentages listed in Table 7, which was filled between the two substrates of the liquid crystal display for performance testing. The test data is shown in the following table: Table 7 Liquid crystal composition formulation and Its test performance

Examples 5

The liquid crystal composition of Example 5 was prepared according to the compounds and weight percentages listed in Table 8, which was filled between the two substrates of the liquid crystal display for performance testing. The test data is shown in the following table: Table 8 Liquid crystal composition formulation and Its test performance

Examples 6

The liquid crystal composition of Example 6 was prepared according to the compounds and weight percentages listed in Table 9, which was filled between the two substrates of the liquid crystal display for performance testing. The test data is shown in the following table: Table 9 Liquid crystal composition formulation and Its test performance

As can be seen from the above examples, the liquid crystal composition of the present invention has a large vertical dielectric constant ε while maintaining the clearing point, optical anisotropy, dielectric anisotropy, and low-temperature storage stability at normal levels _⊥ , larger vertical dielectric to dielectric ratio ε _⊥ /Δε, larger average elastic constant _Kave , smaller rotational viscosity γ1, larger VHR (initial) and VHR (UV) and VHR (high temperature ) (That is, better reliability), and higher transmittance, so that the liquid crystal display device including the liquid crystal composition of the present invention has higher transmittance, higher contrast, and faster response speed, which is particularly It is suitable for liquid crystal display devices driven by active matrix thin film transistors (AM-TFT).

The above embodiments are only for explaining the technical concept and features of the present invention. The purpose is to allow those familiar with the technology to understand and implement the content of the present invention, and cannot limit the scope of protection of the present invention. The equivalent changes or modifications made should be covered in the protection scope of the present invention.

Claims (13)

A liquid crystal composition comprising: one or more compounds of general formula I

Ⅰ; one or more compounds of general formula M

M; and one or more compounds of general formula A-1

A-1, wherein R ₁ and R _A1 each independently represent a linear or branched alkyl group containing 1-12 carbon atoms,

,

or

, The linear or branched alkyl group containing 1-12 carbon atoms, one or two or more non-adjacent -CH ₂ -can be independently -CH=CH-, -C≡ C-, -O-, -CO-, -CO-O- or -O-CO-, and the linear or branched alkyl group containing 1-12 carbon atoms,

,

or

One or more of -H in each may be independently substituted by -F or -Cl; R _M1 and R _M2 each independently represent -H, a linear or branched alkyl group containing 1-12 carbon atoms,

,

or

, The linear or branched alkyl group containing 1-12 carbon atoms, one or two or more non-adjacent -CH ₂ -can be independently -CH=CH-, -C≡ C-, -O-, -CO-, -CO-O- or -O-CO- substitution; Z ₁ , Z ₂ and Z ₃ each independently represent a single bond, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -CO-O-, -O-CO-, -O-CO-O-, -CH=CH-, -CF=CF-, -CH ₂ O- or -OCH ₂ -; Z _A11 represents single Bond, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -CO-O-, -O-CO-, -O-CO-O-, -CH=CH-, -CF=CF-, -CH ₂ O- or -OCH ₂ -; Z _M1 and Z _M2 each independently represent a single bond, -CO-O-, -O-CO-, -CH ₂ O-, -OCH ₂ -, -CH=CH-, -C≡C-, -CH ₂ CH ₂ -or -(CH ₂ ) ₄ -; L ₁ , L ₂ , L ₃ , L ₄ , L _A11 , L _A12 and L _A13 each independently represent -H and contain 1 -Alkyl or halogen with 3 carbon atoms; X and X _A1 each independently represent halogen, haloalkyl or haloalkoxy containing 1-5 carbon atoms, haloalkenyl or halo containing 2-5 carbon atoms Alkenoxy; ring

And ring

Express independently

or

,among them,

One or more -CH ₂ -may be replaced by -O-, one or more single bonds in the ring may be replaced by double bonds,

One or more of -H may be substituted by -CN, -F or -Cl, and one or more rings -CH= may be replaced by -N=; ring

,ring

And ring

Express independently

or

,among them,

One or more of -CH ₂ -can be replaced by -O-,

At most one of -H may be substituted by halogen; ring

And ring

Express independently

,

,

or

,among them,

,

with

One or more -CH ₂ -may be replaced by -O-, one or more single bonds in the ring may be replaced by double bonds,

with

One or more of -H may be replaced by -CN, -F or -Cl, and one or more rings -CH= may be replaced by -N=; n1 and n2 each independently represent 0, 1 or 2 , And 0≤n1+n2≤3, and when n1=2, the ring

May be the same or different, Z ₁ may be the same or different, when n2=2, the ring

May be the same or different, Z ₂ may be the same or different; n _M1 and n _A11 each independently represent 0, 1, 2 or 3, and when n _M1 = 2 or 3, the ring

Can be the same or different, Z _M2 can be the same or different, when n _A11 = 2 or 3, the ring

May be the same or different, Z _A11 may be the same or different; and n _A12 represents 1 or 2, and when n _A12 = 2, the ring

Can be the same or different. The liquid crystal composition as described in item 1 of the patent application scope, wherein when n1=0 and n2=1, at least one of Z ₂ and Z ₃ is not a single bond; when n1=1 and n2=0, Z At least one of ₁ and Z ₃ is not a single bond. The liquid crystal composition as described in item 1 or 2 of the patent application, wherein the compound of general formula I is selected from the group consisting of:

Ⅰ-1;

Ⅰ-2;

Ⅰ-3;

Ⅰ-4;

Ⅰ-5;

Ⅰ-6;

Ⅰ-7;

Ⅰ-8; and

Ⅰ-9, wherein L ₁ , L ₂ and L ₅ each independently represent -H or -F; and R _x and R _y each independently represent -CH ₂ -or -O-. The liquid crystal composition as described in item 3 of the patent application range, wherein in the compounds of the general formula I-1 to the general formula I-8, L ₅ represents -H. The liquid crystal composition as described in item 1 of the patent application range, wherein the compound of formula I accounts for 0.1% to 60% by weight of the liquid crystal composition. The liquid crystal composition according to item 1 of the patent application scope, wherein the compound of the general formula M is selected from the group consisting of:

M1;

M2;

M3;

M4;

M5;

M6;

M7;

M8;

M9;

M10

M11;

M12;

M13;

M14;

M15;

M16;

M17;

M18;

M19;

M20;

M21;

M22;

M23; and

M24. The liquid crystal composition as described in item 1 or 6 of the patent application range, wherein the compound of the general formula M accounts for 0.1%-90% by weight of the liquid crystal composition. The liquid crystal composition as described in item 1 of the patent application range, wherein the compound of the general formula A-1 is selected from the group consisting of the following compounds:

A-1-1;

A-1-2;

A-1-3;

A-1-4;

A-1-5;

A-1-6;

A-1-7;

A-1-8;

A-1-9;

A-1-10;

A-1-11;

A-1-12;

A-1-13;

A-1-14;

A-1-15;

A-1-16;

A-1-17; and

A-1-18, where R _A1 represents a linear or branched alkyl group containing 1-8 carbon atoms,

,

or

, One or two or more non-adjacent -CH ₂ -in the linear or branched alkyl group containing 1-8 carbon atoms can be independently -CH=CH-, -C≡ C-, -O-, -CO-, -CO-O- or -O-CO- are substituted, and one or more -H present in these groups may be independently substituted by -F or -Cl, respectively ; R _v and R _w each independently represent -CH ₂ -or -O-; L _A11 , L _A12 , L _A11 ^' , L _A12 ^' , L _A14 , L _A15 and L _A16 each independently represent -H or -F ; L _A13 and L _A13 ^' each independently represent -H or -CH ₃ ; X _A1 represents -F, -CF ₃ or -OCF ₃ ; and v and w each independently represent 0 or 1. The liquid crystal composition as described in item 1 or 8 of the patent application range, wherein the compound of the general formula A-1 accounts for 0.1%-80% by weight of the liquid crystal composition. The liquid crystal composition as described in item 1 of the patent application scope, wherein the liquid crystal composition further comprises one or more compounds of the general formula A-2

A-2, where R _A2 represents a linear or branched alkyl group containing 1-12 carbon atoms,

,

or

, The linear or branched alkyl group containing 1-12 carbon atoms, one or two or more non-adjacent -CH ₂ -can be independently -CH=CH-, -C≡ C-, -O-, -CO-, -CO-O- or -O-CO-, and the chain alkyl group containing 1-12 carbon atoms,

,

or

One or more of -H may be independently substituted by -F or -Cl; Z _A21 and Z _A22 each independently represent a single bond, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -CO- O-, -O-CO-, -O-CO-O-, -CH=CH-, -CF=CF-, -CH ₂ O- or -OCH ₂ -; L _A21 and L _A22 each independently represent- H, alkyl or halogen containing 1-3 carbon atoms; X _A2 represents halogen, haloalkyl or haloalkoxy containing 1-5 carbon atoms, haloalkenyl or halo containing 2-5 carbon atoms Alkenyloxy; ring

And ring

Express independently

,

,

or

,among them,

,

with

At most one -CH ₂ -can be replaced by -O-, one or more single bonds in the ring can be replaced by double bonds

with

One or more of -H may be replaced by -CN, -F or -Cl, one or more rings -CH= may be replaced by -N=; and n _A2 represents 0, 1, 2 or 3, And when n _A2 =1 and Z _A21 and Z _A22 both represent single bonds, the ring

And ring

Can also be expressed independently

; When n _A2 = 2 or 3, the ring

They can be the same or different, and Z _A21 can be the same or different. The liquid crystal composition according to item 10 of the patent application scope, wherein the compound of the general formula A-2 is selected from the group consisting of:

A-2-1;

A-2-2;

A-2-3;

A-2-4;

A-2-5;

A-2-6;

A-2-7;

A-2-8;

A-2-9;

A-2-10;

A-2-11;

A-2-12;

A-2-13;

A-2-14; and

A-2-15, wherein R _A2 represents a linear or branched alkyl group containing 1-8 carbon atoms, one of the linear or branched alkyl groups containing 1-8 carbon atoms Or two or more non-adjacent -CH ₂ -can be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O-, or -O-CO- , And one or more -H present in these groups may be independently substituted by -F or -Cl; L _A21 , L _A22 , L _A23 , L _A24 and L _A25 each independently represent -H or- F; and X _A2 represents -F, -CF ₃ , -OCF ₃ or -CH ₂ CH ₂ CH=CF ₂ . The liquid crystal composition as described in item 1 or 11 of the patent application range, wherein the compound of the general formula A-2 accounts for 0.1%-80% by weight of the liquid crystal composition. A display device comprising the liquid crystal composition according to any one of items 1-12 of the patent application.