TW202227598A - Negative dielectric anisotropy liquid crystal composition and liquid crystal display device - Google Patents

Abstract

The invention relates to a negative dielectric anisotropy liquid crystal composition and a liquid crystal display device. The negative dielectric anisotropy liquid crystal composition comprises at least one compound as shown in a formula I; at least one compound as shown in formula II; and at least one compound as shown in formula III. The negative dielectric anisotropy liquid crystal composition can obtain reduced viscosity on the basis of maintaining a proper optical anisotropy value and dielectric anisotropy, so that the response time can be shortened, and quick response can be realized.

Description

Negative dielectric anisotropic liquid crystal composition and liquid crystal display device

The present invention relates to the technical field of liquid crystal materials. More specifically, it relates to a liquid crystal composition and a liquid crystal display device.

At present, the application range of liquid crystal compounds is expanding more and more widely, and it can be applied to various types of displays, electro-optical devices, sensors, and the like. There are many kinds of liquid crystal compounds used in the above-mentioned display field, among which nematic liquid crystal is the most widely used. Nematic liquid crystals have been used in passive TN, STN matrix displays and systems with TFT active matrix.

For the application field of thin film transistor technology (TFT-LCD), although the market has been very large and the technology has gradually matured in recent years, people's requirements for display technology are also constantly improving, especially in the realization of fast response, reducing the driving voltage to reduce power consumption, etc. As one of the important optoelectronic materials of liquid crystal display, liquid crystal material plays an important role in improving the performance of liquid crystal display.

With the continuous development of TFT-LCD, wide viewing angle mode has become the goal pursued in the industry. At present, the mainstream wide viewing angle technology mainly adopts VA vertical orientation, IPS in-plane switch and FFS fringe field switch and other display types. The liquid crystal medium is required to have higher light transmittance and smaller color shift. In particular, in the IPS in-plane switch and FFS fringe field switch types, an in-plane electric field will be generated between the electrodes when a voltage is applied, so that the light penetration in this area is limited, which will increase energy consumption and affect the display effect. Liquid crystal compositions are widely used because of their excellent performance in color shift and the effect of vertical electric fields.

However, the viscosity of the general-purpose negative liquid crystal compositions currently on the market is generally high, which is not conducive to the improvement of the response speed. Therefore, it is an urgent problem to be solved in the art to develop a liquid crystal composition that can maintain a suitable optical anisotropy value and dielectric anisotropy and obtain a reduced viscosity to have a faster response speed.

One aspect of the present invention provides a negative dielectric anisotropy liquid crystal composition, which can obtain a reduced viscosity on the basis of maintaining a suitable optical anisotropy value and dielectric anisotropy, thereby reducing the response time, which is beneficial to Achieve quick response.

In addition, the negative dielectric anisotropic liquid crystal composition of the present invention has a higher voltage holding ratio (VHR) after being irradiated with UV light, so that defects such as afterimages in the final display can be overcome/reduced.

Another aspect of the present invention provides a liquid crystal display device, which has a fast response time by including the negative dielectric anisotropic liquid crystal composition of the present invention. Further, since the liquid crystal display device of the present invention adopts a negative dielectric anisotropic liquid crystal composition with high transmittance, defects such as afterimages are reduced, and thus display advantages of reduced power consumption and improved stability can be obtained.

The present invention includes the following technical solutions.

In one aspect, the present invention provides a negative dielectric anisotropic liquid crystal composition, comprising:

at least one compound represented by formula I;

at least one compound of formula II; and,

I

Ⅱ

III At least one compound of formula III:

I

II

III

in,

R ₁ represents H or an alkyl group with 1 to 8 carbon atoms or an alkenyl group with 2 to 8 carbon atoms, wherein below 4 Hs are optionally substituted by F;

R ₂ represents H or an alkyl group with 1 to 8 carbon atoms or an alkenyl group with 2 to 8 carbon atoms, wherein one or two non-adjacent -CH ₂ - are optionally substituted by O, and 4 or less H is optionally substituted with F;

m is selected from 1 or 2, and n is selected from 3 or 4;

R ₃ , R ₄ , R ₅ , and R ₆ each independently represent an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or Alkenyloxy with 3 to 5 carbon atoms; and, H on any carbon atom in R ₃ , R ₄ , R ₅ and R ₆ is independently optionally substituted by F;

Z ₁ represents a single bond or -CH ₂ O-;

p, q, r each independently represent 0, 1 or 2;

、

、

、

、

、

各自獨立地表示選自下述的基團組成的組：

、

、

、

、

、

、

、

。

,

,

,

,

,

Each independently represents a group selected from the group consisting of:

,

,

,

,

,

,

,

.

In another aspect, the present invention provides a liquid crystal display device comprising the negative dielectric anisotropy liquid crystal composition of the present invention; the liquid crystal display device is an active matrix display device or a passive matrix display device.

Invention effect

The beneficial effect of the present invention is that, compared with the prior art, the liquid crystal composition has a reduced viscosity on the basis of maintaining an appropriate optical anisotropy value and dielectric anisotropy, thereby reducing the response time and facilitating the realization of Quick response. In addition, the liquid crystal composition of the present invention has a high VHR after being irradiated with UV light, so that defects such as afterimages in the final display can be overcome/reduced.

[Liquid Crystal Composition]

The negative dielectric anisotropic liquid crystal composition of the present invention comprises:

at least one compound represented by formula I;

at least one compound of formula II; and,

I

Ⅱ

III At least one compound of formula III.

I

II

III

Wherein, R ₁ represents H or an alkyl group with 1 to 8 carbon atoms or an alkenyl group with 2 to 8 carbon atoms, wherein 4 or less Hs are optionally substituted by F, such as optionally 0, 1, 2 One, three or four Hs are replaced by F.

R ₂ represents H or an alkyl group with 1 to 8 carbon atoms or an alkenyl group with 2 to 8 carbon atoms, wherein one or two non-adjacent -CH ₂ - are optionally substituted by O, and 4 or less H is optionally substituted with F. For example, optionally 0, 1, 2, 3 or 4 Hs are replaced by F.

The aforementioned "alkyl group having 1 to 8 carbon atoms" may be a straight-chain alkyl group, a branched-chain alkyl group, or a cyclic alkyl group, and examples thereof include methyl, ethyl, n-propyl, and isopropyl. , cyclopropyl, n-butyl, isobutyl, tert-butyl, cyclobutyl, n-pentyl, isopentyl, cyclopentyl, hexyl, heptyl, octyl, etc.

The aforementioned "alkenyl group having 2 to 8 carbon atoms" may be a straight-chain alkenyl group, a branched-chain alkenyl group, or an alkenyl group with a cyclic alkyl chain, and is not particularly limited. For example, vinyl, propenyl, butenyl, 2-methylpropenyl, 1-pentenyl, 2-pentenyl, 2-methyl-1-butenyl, 3-methyl-1 -butenyl, 2-methyl-2-butenyl, pentenyl, hexenyl, heptenyl, etc.

m is selected from 1 or 2, and n is selected from 3 or 4.

R ₃ , R ₄ , R ₅ , and R ₆ each independently represent an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or An alkenyloxy group having 3 to 5 carbon atoms; and H on any carbon atom in R ₃ , R ₄ , R ₅ , and R ₆ is independently optionally substituted by F.

Examples of the aforementioned "alkyl group having 1 to 5 carbon atoms" include methyl, ethyl, propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl Butyl, n-pentyl, isopentyl, tert-amyl, etc.

Examples of the aforementioned "alkoxy group having 1 to 5 carbon atoms" include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-butoxy, pentyloxy, tert-amyloxy, etc.

Examples of the aforementioned "alkenyl having 2 to 5 carbon atoms" include vinyl, propenyl, butenyl, 2-methpropenyl, 1-pentenyl, 2-pentenyl, 2- -Methyl-1-butenyl, 3-methyl-1-butenyl, 2-methyl-2-butenyl, etc.

As the above-mentioned "alkenyloxy group having 3 to 5 carbon atoms", for example, vinyloxy group, propenyloxy group, butenyloxy group, 2-methacryloxy group, 1-pentenyloxy group, 2- -Pentenyloxy, 2-methyl-1-butenyloxy, 3-methyl-1-butenyloxy, 2-methyl-2-butenyloxy, etc.

Z ₁ represents a single bond or -CH ₂ O-;

p, q, r each independently represent 0, 1 or 2;

、

、

、

、

、

各自獨立地表示選自下述的基團組成的組：

、

、

、

、

、

、

、

。

,

,

,

,

,

Each independently represents a group selected from the group consisting of:

,

,

,

,

,

,

,

.

I-1

I-2

I-3

I-4

I-5

I-6

I-7

I-8

I-9

I-10

I-11

I-12

I-13

I-14

I-15

I-16

I-17

I-18

I-19 Preferably, the compound represented by the aforementioned formula I is selected from the group consisting of the compounds represented by the following formulae I1 to I19.

I-1

I-2

I-3

I-4

I-5

I-6

I-7

I-8

I-9

I-10

I-11

I-12

I-13

I-14

I-15

I-16

I-17

I-18

I-19

R ₁ represents H or an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, wherein 4 or less of H are optionally substituted by F. R ₁ is preferably H or an alkenyl group having 2 to 8 carbon atoms, more preferably H or an alkenyl group having 2 to 4 carbon atoms, and still more preferably hydrogen, vinyl or propenyl.

R ₂ represents H or an alkyl group with 1 to 8 carbon atoms or an alkenyl group with 2 to 8 carbon atoms, wherein one or two non-adjacent -CH ₂ - are optionally substituted by O, and 4 or less H is optionally substituted with F. R ₂ is preferably a group in which one -CH ₂ - is substituted by O in an alkyl group having 1 to 8 carbon atoms, for example, methoxy, ethoxy, propoxy, butoxy, pentyloxy , hexyloxy, heptyloxy, octyloxy, etc. Preferably it is methoxy or ethoxy.

Ⅱ-1

Ⅱ-2

Ⅱ-3

Ⅱ-4

Ⅱ-5

Ⅱ-6

Ⅱ-7

Ⅱ-8

Ⅱ-9

Ⅱ-10 In the negative dielectric anisotropic liquid crystal composition of the present invention, preferably, the compound represented by the aforementioned formula II is selected from the group consisting of the compounds represented by the following formulas II-1 to II-10.

II-1

II-2

II-3

II-4

II-5

II-6

II-7

II-8

II-9

II-10

或者氫。R ₃、R ₄優選為碳原子數為1~5的直鏈烷基或者碳原子數為2～5的烯基。 R ₃ and R ₄ have the same definitions as above, and each independently represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or An alkenyloxy group having 3 to 5 carbon atoms; and H on any carbon atom in R ₃ and R ₄ is independently optionally substituted by F. (F) represents fluorine

or hydrogen. R ₃ and R ₄ are preferably straight-chain alkyl groups having 1 to 5 carbon atoms or alkenyl groups having 2 to 5 carbon atoms.

Ⅲ-1

Ⅲ-2

Ⅲ-3

Ⅲ-4

Ⅲ-5

Ⅲ-6

Ⅲ-7

Ⅲ-8

Ⅲ-9

Ⅲ-10

Ⅲ-11

Ⅲ-12

Ⅲ-13

Ⅲ-14

Ⅲ-15

Ⅲ-16

Ⅲ-17 In the negative dielectric anisotropic liquid crystal composition of the present invention, preferably, the compound represented by the aforementioned formula III is selected from the group consisting of compounds represented by the following formulae III-1 to III-17.

Ⅲ-1

Ⅲ-2

Ⅲ-3

Ⅲ-4

Ⅲ-5

Ⅲ-6

Ⅲ-7

Ⅲ-8

Ⅲ-9

Ⅲ-10

Ⅲ-11

Ⅲ-12

Ⅲ-13

Ⅲ-14

Ⅲ-15

Ⅲ-16

Ⅲ-17

R ₅ and R ₆ each independently represent an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkyl group having 3 to 5 carbon atoms. The alkenyloxy group of 5; and, H on any carbon atom in R ₅ and R ₆ is independently optionally substituted by F. R ₅ and R ₆ are each independently preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group or an ethoxy group. In the negative dielectric anisotropic liquid crystal composition of the present invention, relative to the total amount of the liquid crystal composition, the weight percentage of the liquid crystal compound represented by the aforementioned formula I is 1 to 50%. , viscosity, VHR, rotational viscosity/elastic constant, etc., is preferably 1 to 40%, more preferably 10 to 40%.

In the negative dielectric anisotropic liquid crystal composition of the present invention, with respect to the total amount of the liquid crystal composition, the weight percentage of the liquid crystal compound represented by the aforementioned formula II is 1-60%. , viscosity, VHR, rotational viscosity/elastic constant, etc., is preferably 10 to 50%, more preferably 20 to 50%.

In the negative dielectric anisotropic liquid crystal composition of the present invention, relative to the total amount of the liquid crystal composition, the weight percentage of the liquid crystal compound represented by the aforementioned formula III is 1 to 50%. , viscosity, VHR, rotational viscosity/elastic constant, etc., is preferably 10 to 50%, more preferably 20 to 50%.

Ⅳ In another embodiment of the negative dielectric anisotropic liquid crystal composition of the present invention, from the viewpoint of further reducing the viscosity and improving the response speed, preferably, it further comprises one or more compounds represented by the following formula IV:

Ⅳ

In formula IV, R ₇ and R ₈ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a carbon atom number 2~7 alkenyloxy, cyclopentyl, cyclobutyl, cyclopropyl, -CF ₃ , -CN, -F, or -OCF ₃ , and optionally 4 or less hydrogen atoms in R ₇ are fluorine Substitution, optionally 4 or less hydrogen atoms in R ₈ are substituted with fluorine.

、

、

、

、

、

、

、

、

、

、

、或者、

，其中任意H原子任選被-F或者-CH ₃取代； The rings B each independently represent

,

,

,

,

,

,

,

,

,

,

,or,

, wherein any H atom is optionally substituted by -F or -CH ₃ ;

或者

； The rings C each independently represent

or

;

Z ₂ represents an alkyl group with 1 to 6 carbon atoms, an alkoxy group with 1 to 6 carbon atoms or a single bond;

s and t each independently represent 1, 2 or 3.

Examples of the aforementioned alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl.

Examples of the aforementioned "alkenyl group having 2 to 7 carbon atoms" include vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, and 3-butenyl. , 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5 -hexenyl, 1-heptenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl, 5-heptenyl, 6-heptenyl, etc.

As the aforementioned "alkoxy group having 1 to 8 carbon atoms", for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, and an octyloxy group can be mentioned. Base et al.

As the above-mentioned "alkenyloxy group having 2 to 7 carbon atoms", for example, vinyloxy group, allyloxy group, 3-butenyloxy group, 3-pentenyloxy group, 4- Pentenyloxy, 3-hexenyloxy, 4-hexenyloxy, 5-hexenyloxy, 3-heptenyloxy, 4-heptenyloxy, 5-heptene oxy, 6-heptenyloxy, etc.

Four or less hydrogen atoms in R ₇ are optionally substituted with fluorine. For example, optionally 0, 1, 2, 3 or 4 hydrogen atoms in _R7 are replaced with fluorine atoms.

Four or less hydrogen atoms in R ₈ are optionally substituted with fluorine. For example, optionally 0, 1, 2, 3 or 4 hydrogen atoms in _R7 are replaced with fluorine atoms.

When the liquid crystal composition of the present invention contains the compound represented by the aforementioned formula IV, the weight percentage content of the aforementioned compound represented by the formula IV in the liquid crystal composition can be, for example, 1 to 20%, so as to obtain suitable Δn, Δε, In view of viscosity, VHR, rotational viscosity/elastic constant, etc., 10 to 20% is preferable.

Ⅳ-

1

Ⅳ-

2

Ⅳ-

3

Ⅳ-

4

Ⅳ-

5

Ⅳ-

6

Ⅳ-

7

Ⅳ-

8

Ⅳ-

9

Ⅳ-

10

Ⅳ-

11

Ⅳ-

12

Ⅳ-

13

Ⅳ-

14

Ⅳ-

15

Ⅳ-

16

Ⅳ-

17

Ⅳ-

18

Ⅳ-

19

Ⅳ-

20

Ⅳ-

21

Ⅳ-

22

Ⅳ-

23

Ⅳ-

24

Ⅳ-

25

Ⅳ-

26

Ⅳ-

27

Ⅳ-

28

Ⅳ-

29

Ⅳ-

30

Ⅳ-

31

Ⅳ-

32

Ⅳ-

33

Ⅳ-

34

Ⅳ-

35

Ⅳ-

36。 The compound represented by the aforementioned formula IV is preferably selected from the group consisting of compounds represented by the following formulae IV-1 to IV-36.

Ⅳ-

1

Ⅳ-

2

Ⅳ-

3

Ⅳ-

4

Ⅳ-

5

Ⅳ-

6

Ⅳ-

7

Ⅳ-

8

Ⅳ-

9

Ⅳ-

10

Ⅳ-

11

Ⅳ-

12

Ⅳ-

13

Ⅳ-

14

Ⅳ-

15

Ⅳ-

16

Ⅳ-

17

Ⅳ-

18

Ⅳ-

19

Ⅳ-

20

Ⅳ-

twenty one

Ⅳ-

twenty two

Ⅳ-

twenty three

Ⅳ-

twenty four

Ⅳ-

25

Ⅳ-

26

Ⅳ-

27

Ⅳ-

28

Ⅳ-

29

Ⅳ-

30

Ⅳ-

31

Ⅳ-

32

Ⅳ-

33

Ⅳ-

34

Ⅳ-

35

Ⅳ-

36.

V-1

V-2

V-3

V-4

V-5。 In another embodiment of the liquid crystal composition of the present invention, from the viewpoint of further improving the VHR to reduce defects such as image sticking, preferably, it further comprises one or more compounds represented by the following formulae V-1 to V-5 :

V-1

V-2

V-3

V-4

V-5.

The compounds represented by the aforementioned formulas V-1 to V-5 are polymerizable components. By including the compounds represented by the aforementioned formulas V-1 to V-5 in the negative dielectric anisotropy liquid crystal composition of the present invention, the system formed by the components in the liquid crystal composition and the polymerizable compound can be irradiated by UV light. A high VHR can be obtained after the photo is taken, so that the display advantages of reduced power consumption and improved stability can be obtained, and defects such as afterimages in the final display can be overcome.

In the liquid crystal composition of the present invention, with respect to the sum of the compounds represented by formula I, formula II, formula III, formula IV, etc., which are liquid crystal media (excluding polymerizable components), the aforementioned polymerizable components of formula V- The weight percentage of the compounds represented by 1 to V-5 is, for example, 0.01 to 2%, preferably 0.1 to 1%, and more preferably 0.2 to 0.8%.

In the liquid crystal composition of the present invention, in addition to the liquid crystal compounds listed above, those skilled in the art can also add other liquid crystal compounds without destroying the desired properties of the liquid crystal composition.

Optionally, various functional dopants can be added to the liquid crystal composition of the present invention, and these dopants include, for example, antioxidants, ultraviolet absorbers, and chiral agents.

[Liquid crystal display device]

A second aspect of the present invention provides a liquid crystal display device, which is not particularly limited as long as it contains the liquid crystal composition described in any one of the above. The liquid crystal display device of the present invention may be an active matrix display device or a passive matrix display device. Those skilled in the art can select a suitable liquid crystal display element and structure of the liquid crystal display according to the required performance.

Example

In order to illustrate the present invention more clearly, the present invention will be further described below with reference to the preferred embodiments. Those skilled in the art should understand that the content specifically described below is illustrative rather than restrictive, and should not limit the protection scope of the present invention.

In the present invention, the preparation methods are conventional methods unless otherwise specified. The raw materials used can be obtained from public commercial sources unless otherwise specified. The percentages refer to mass percentages. Liquid crystal monomer.

[Liquid Crystal Composition]

Liquid crystal compositions of different compositions were prepared in Examples 1 to 7 and Comparative Examples 1 to 3, wherein the monomer structure, amount (weight percentage) of the specific compounds used in each example, and properties of the resulting liquid crystal medium The parameter test results are shown in Tables 1 to 11 below.

The temperature unit involved in each embodiment is °C, and the specific meanings and test conditions of other symbols are as follows:

Gamma1 (mPa.s) represents the rotational viscosity coefficient of the liquid crystal compound. The measurement method is as follows: equipment INSTEC: ALCT-IR1, test box thickness 18 microns vertical box, temperature 25 ℃, abbreviated as "G1";

K ₁₁ is the torsional elastic constant, K ₃₃ is the splay elastic constant, and the test conditions are: 25°C, INSTEC:ALCT-IR1, 18-micron vertical box;

Δε represents dielectric anisotropy, 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℃, INSTEC: ALCT-IR1, 18 micron vertical box;

Δn represents optical anisotropy, Δn= _{ne -no} , where no is the refractive index of ordinary light, _ne is the refractive index of extraordinary light _, test conditions: 589 nm, 25±0.2°C.

VHR represents the voltage holding rate (%) after ultraviolet light irradiation, and the test conditions are 20±2° C., the voltage is ±5V, the pulse width is 10ms, and the voltage holding time is 16.7ms. The test equipment is TOYO Model 6254 liquid crystal performance comprehensive tester. In the ultraviolet photopolymerization of the polymerizable compound for VHR test, ultraviolet light with a wavelength of 313 nm and an irradiation light intensity of 0.5 Mw/cm ² was used for light irradiation, and the irradiation time was 2 minutes.

In the present invention, the preparation method of the liquid crystal composition is as follows: each liquid crystal monomer is weighed according to a certain proportion and put into a stainless steel beaker, the stainless steel beaker containing each liquid crystal monomer is placed on a magnetic stirring apparatus to heat and melt, and the After most of the liquid crystal monomer in the stainless steel beaker is melted, a magnetic rotor is added to the stainless steel beaker, the mixture is stirred evenly, and the liquid crystal composition is obtained after cooling to room temperature.

The obtained liquid crystal composition was filled between two substrates of a liquid crystal display for performance testing.

C

P

G

U

GI

Y

A

D

(C1)

(C2)

(C3)

(C4)

B

B(S) 表（二）：端基與鏈接基團的對應代碼 端基與鏈接基團 對應代碼 C _nH _2n+1- n C _nH _2n+1O- nO -OCF ₃ OT -CF ₃ T -CF ₂O- Q -CH ₂O- M -F F -CN N -CH ₂CH ₂- E -CH=CH- V -C≡C- T -COO- Z -CH=CH-C _nH _2n+1 Vn

C(5)

C(4)

C(3)1 舉例：

AVCCY-V-O2

CPP-1V-2 RM-1

RM-2

RM-3

RM-4

RM-5

RM-6

The structures of the liquid crystal monomers used in the application examples of the present invention are represented by the following codes, and the code representation methods of the liquid crystal ring structures, end groups and connecting groups are shown in Tables (1) and (2) below. Table (1): Corresponding codes of ring structure ring structure Corresponding code

C

P

G

U

GI

Y

A

D

(C1)

(C2)

(C3)

(C4)

B

B(S) Table (2): Corresponding codes of end groups and linking groups End and Linking Groups Corresponding code C _n H _2n+1 - n C _n H _2n+1 O- nO -OCF ₃ OT -CF ₃ T -CF ₂ O- Q -CH ₂ O- M -F F -CN N -CH ₂ CH ₂ - E -CH=CH- V -C≡C- T -COO- Z -CH=CH-C _n H _2n+1 Vn

C(5)

C(4)

C(3)1 Example:

AVCCY-V-O2

CPP-1V-2 RM-1

RM-2

RM-3

RM-4

RM-5

RM-6

Using the liquid crystal compounds represented by the aforementioned formulas I to III and other components, the liquid crystal compositions of Examples 1 to 8 exhibiting negative dielectric anisotropy were obtained. The composition and content are shown in Tables 1 to 8 below. Table 1 The composition ratio of the liquid crystal composition of Example 1 and its performance parameters Compound formula Liquid crystal structure Weight percentage (%) Performance parameters II CC-2-3 15.0 Δn 0.1136 Δε -2.61 K ₁₁ (pN) 14.7 K ₃₃ (pN) 20.5 Gamma 1(mPa . s) 89.3 K ₃₃ /K ₁₁ 1.39 VHR(16.7ms) 99.92% II CC-5-V 5.0 II CC-3-V 20.0 Ⅲ CCY-3-O2 15.0 I CVCCY-1V-O2 5.0 I CVCPY-V-O2 5.0 Ⅲ CPY-3-O2 10.0 Ⅲ CY-3-O2 5.0 II PP-2-3 10.0 Ⅲ PYP-3-O2 10.0 Table 2 Composition ratio and performance parameters of the liquid crystal medium of Example 2 Compound formula Liquid crystal structure Weight percentage (%) Performance parameters II CC-2-3 5.0 Δn 0.1418 Δε -3.83 K ₁₁ (pN) 18.1 K ₃₃ (pN) 22.0 Gamma 1(mPa . s) 89.1 K ₃₃ /K ₁₁ 1.22 VHR(16.7ms) 99.91% II CC-3-5 5.0 II CC-3-V 15.0 Ⅲ CCMY-3-O2 15.0 I CVAPY-1V-O2 10.0 I CVPPY-V-O2 10.0 Ⅲ CPY-3-O2 15.0 Ⅲ CY-3-O2 10.0 II CPP-1-2V1 5.0 Ⅲ PYP-2-3 10.0 Table 3 Composition ratio and performance parameters of the liquid crystal medium of Example 3 Compound formula Liquid crystal structure Weight percentage (%) Performance parameters II CC-2-3 15.0 Δn 0.1176 Δε -3.30 K ₁₁ (pN) 17.5 K ₃₃ (pN) 22.3 Gamma 1(mPa . s) 99.3 K ₃₃ /K ₁₁ 1.27 VHR(16.7ms) 99.85% II CC-3-V 20.0 Ⅲ CCMY-3-O2 10.0 Ⅲ CCY-3-O2 10.0 I CVPYP-V-O2 10.0 Ⅲ CPY-3-O2 5.0 I CVCPY-1V-O2 10.0 I PVCCY-V-O2 10.0 Ⅲ PY-3-O2 5.0 II CPP-1-2V 5.0 Table 4 Composition ratio of the liquid crystal medium of Example 4 and its performance parameters Compound formula Liquid crystal structure Weight percentage (%) Performance parameters II CC-3-V 10.0 Δn 0.1546 Δε -4.73 K ₁₁ (pN) 23.8 K ₃₃ (pN) 27.9 Gamma 1(mPa . s) 101.5 K ₃₃ /K ₁₁ 1.17 VHR(16.7ms) 99.93% Ⅲ CCMY-3-O2 10.0 II CCP-V-1 10.0 Ⅲ CCY-3-O2 10.0 I CVCPY-V-O2 15.0 I PVCPY-1V-O2 15.0 I CVPYP-V-O2 10.0 Ⅲ CPY-3-O2 10.0 Ⅲ PY-3-O2 10.0 Table 5 Composition ratio and performance parameters of the liquid crystal medium of Example 5 Compound formula Liquid crystal structure Weight percentage (%) Performance parameters I CVCPY-V-O2 10.0 Δn 0.1509 Δε -2.46 K ₁₁ (pN) 18.4 K ₃₃ (pN) 22.4 Gamma 1(mPa . s) 79.9 K ₃₃ /K ₁₁ 1.22 VHR(16.7ms) 99.95% II CC-3-V 30.0 II CPP-V-1 10.0 Ⅲ CCY-3-O2 10.0 I CVPYP-V-O2 10.0 I PVCPY-V-O2 10.0 Ⅲ PYP-2-3 10.0 Ⅳ CVEB-1V-O2 10.0 Table 6 Composition ratio and performance parameters of the liquid crystal medium of Example 6 Compound formula Liquid crystal structure Weight percentage (%) Performance parameters II CC-3-V 25.0 Δn 0.1494 Δε -2.71 K ₁₁ (pN) 16.2 K ₃₃ (pN) 19.5 Gamma 1(mPa . s)78.6 K ₃₃ /K ₁₁ 1.20 VHR(16.7ms) 99.95% II CC-2-3 5.0 I PVPYP-V-O2 10.0 II CPP-3-2V1 10.0 I CVCPY-1V-O2 5.0 I CVPYP-V-O2 5.0 Ⅲ CCY-3-O2 5.0 Ⅲ CPY-3-O2 5.0 Ⅲ PY-3-O2 5.0 Ⅲ PYP-2-3 5.0 Ⅳ CVMB-V-O2 10 Ⅳ CVMB(S)-V-O2 10 Table 7 Composition ratio and performance parameters of the liquid crystal medium of Example 7 Compound formula Liquid crystal structure Weight percentage (%) Performance parameters II CC-3-V 30.0 Δn 0.1282 Δε -3.42 K ₁₁ (pN) 14.0 K ₃₃ (pN) 16.0 Gamma 1(mPa . s) 79.5 K ₃₃ /K ₁₁ 1.14 VHR(16.7ms) 99.97% II CC-2-3 5.0 Ⅲ CCY-3-O2 5.0 Ⅲ CCMY-3-O2 5.0 I CVPYP-V-O2 10.0 I CVCPY-V-O2 10.0 Ⅲ CPY-3-O2 10.0 Ⅲ PY-3-O2 15.0 Ⅳ CVEB-V-O3 5.0 Ⅳ PVEB-V-O3 5.0 V RM-1 0.8 Table 8 Composition ratio and performance parameters of the liquid crystal medium of Example 8 Compound formula Liquid crystal structure Weight percentage (%) Performance parameters II CC-3-V 30.0 Δn 0.1291 Δε -3.49 K ₁₁ (pN) 12.6 K ₃₃ (pN) 15.2 Gamma 1(mPa . s) 78.5 K ₃₃ /K ₁₁ 1.21 VHR(16.7ms) 99.96% II CPP-1-2V1 5.0 Ⅲ CCY-3-O2 5.0 Ⅲ CMY-3-O2 5.0 I CVPYP-1V-O2 5.0 I CVCPY-1V-O2 10.0 Ⅲ CPY-3-O2 15.0 Ⅲ PY-3-O2 15.0 Ⅳ CVEB-V-O3 5.0 Ⅳ PVEB-V-O3 5.0 V RM-2 0.2

The formula of Comparative Example 1 is shown in the following Table 9, and its components do not contain the compound combination of the present invention, and a comparative experiment is done with Example 1. Table 9 Composition ratio and performance parameters of the liquid crystal medium of Comparative Example 1 Compound formula Liquid crystal structure Weight percentage (%) Performance parameters II CC-2-3 15.0 Δn 0.1127 Δε -2.73 K ₁₁ (pN) 15.3 K ₃₃ (pN) 19.8 Gamma 1(mPa . s) 101.8 K ₃₃ /K ₁₁ 1.29 VHR(16.7ms) 99.70% II CC-5-V 5.0 II CC-3-V 20.0 Ⅲ CCY-3-O2 20.0 Ⅲ CPY-3-O2 15.0 Ⅲ CY-3-O2 5.0 II PP-2-3 10.0 Ⅲ PYP-3-O2 10.0

In the aforementioned comparative example 1, the compound of general formula I in Example 1 is replaced by a general-type negative liquid crystal compound. It can be found from the comparison between the example and the comparative example that the compound of formula I, formula II, and formula III is not used together. Compared with the comparative examples shown, the examples containing the negative dielectric anisotropic liquid crystal composition of the present invention used in combination of formula I, formula II and formula III can maintain a suitable optical anisotropy value, dielectric anisotropy On the basis of performance, it is combined with reduced viscosity, which can reduce response time and improve response speed. Further, compared with the comparative example, the examples containing the negative dielectric anisotropic liquid crystal composition of the present invention used in combination of formula I, formula II and formula III also obtained an improved VHR value, so that a reduction in power consumption and a The display advantage of improved stability is beneficial to avoid/reduce the occurrence of display afterimages.

Although the present invention does not exhaust all the claimed liquid crystal mixtures, those skilled in the art can foresee that, on the basis of the disclosed above-mentioned embodiments, other similar liquid crystal materials can be obtained by a similar method only by combining their own professional attempts. No creative work is required. Due to limited space, only representative embodiments are listed here.

The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims (11)

A negative dielectric anisotropic liquid crystal composition, comprising: at least one compound represented by formula I; at least one compound represented by formula II; and, at least one compound represented by formula III:

I

II

III wherein, R ₁ represents H or an alkyl group with 1 to 8 carbon atoms or an alkenyl group with 2 to 8 carbon atoms, wherein 4 or less H is optionally substituted by F; R ₂ represents H or a carbon number of 1~8 alkyl groups or 2~8 carbon atoms alkenyl groups, wherein one or two non-adjacent -CH ₂ - are optionally substituted by O, and Hs below 4 are optionally substituted by F; m is selected From 1 or 2, n is selected from 3 or 4; R ₃ , R ₄ , R ₅ , R ₆ each independently represent an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, An alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 3 to 5 carbon atoms; and, H on any carbon atom in R ₃ , R ₄ , R ₅ , and R ₆ is independently optionally F is substituted; Z ₁ represents a single bond or -CH ₂ O-; p, q, r each independently represent 0, 1 or 2;

,

,

,

,

,

Each independently represents a group selected from the group consisting of:

,

,

,

,

,

,

,

. The negative dielectric anisotropic liquid crystal composition according to claim 1, wherein the compound represented by the formula I is selected from the group consisting of the compounds represented by the following formulas I1 to I19:

I-1

I-2

I-3

I-4

I-5

I-6

I-7

I-8

I-9

I-10

I-11

I-12

I-13

I-14

I-15

I-16

I-17

I-18

I-19 R ₁ represents H or an alkyl group with 1 to 8 carbon atoms or an alkenyl group with 2 to 8 carbon atoms, and optionally 4 or less H is substituted by F; R ₂ represents H or a carbon number of An alkyl group of 1 to 8 or an alkenyl group of 2 to 8 carbon atoms, wherein one or two non-adjacent CH ₂ are optionally substituted by O, and optionally 4 or less H are substituted by F. The negative dielectric anisotropic liquid crystal composition according to claim 1 or 2, wherein the compound represented by the formula II is selected from the group consisting of compounds represented by the following formulas II-1 to II-10:

II-1

II-2

II-3

II-4

II-5

II-6

II-7

II-8

II-9

II-10 R ₃ and R ₄ each independently represent an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a carbon atom number is an alkenyloxy group of 3 to 5; hydrogen on any carbon atom in R ₃ and R ₄ is independently optionally substituted by fluorine; (F) represents

F or H. The negative dielectric anisotropic liquid crystal composition according to any one of claims 1 to 3, wherein the compound represented by the formula III is selected from the following compounds represented by the formulas III-1 to III-17. group of:

Ⅲ-1

Ⅲ-2

Ⅲ-3

Ⅲ-4

Ⅲ-5

Ⅲ-6

Ⅲ-7

Ⅲ-8

Ⅲ-9

Ⅲ-10

Ⅲ-11

Ⅲ-12

Ⅲ-13

Ⅲ-14

Ⅲ-15

Ⅲ-16

III-17 R ₅ and R ₆ each independently represent an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a carbon atom number is an alkenyloxy group of 3 to 5, and H on any carbon atom in R ₅ and R ₆ is independently optionally substituted by F. The negative dielectric anisotropic liquid crystal composition according to any one of claims 1 to 4, further comprising one or more compounds represented by the following formula IV:

IV In the formula IV, R ₇ and R ₈ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, Alkenyloxy, cyclopentyl, cyclobutyl, cyclopropyl, -CF ₃ , -CN, -F, or -OCF ₃ having 2 to 7 carbon atoms, and optionally 4 or less hydrogens in R ₇ Atoms are substituted with fluorine, and optionally 4 or less hydrogen atoms in R ₈ are substituted with fluorine; each of the rings B independently represents

,

,

,

,

,

,

,

,

,

,

,or,

, wherein any H atom is optionally substituted by -F or -CH ₃ ; Ring C independently represents

or

; Z ₂ represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a single bond; s and t each independently represent 1, 2 or 3. The negative dielectric anisotropic liquid crystal composition according to claim 5, wherein the compound represented by the formula IV is selected from the group consisting of compounds represented by the following formula IV-1 to formula IV-36:

Ⅳ-

1

Ⅳ-

2

Ⅳ-

3

Ⅳ-

4

Ⅳ-

5

Ⅳ-

6

Ⅳ-

7

Ⅳ-

8

Ⅳ-

9

Ⅳ-

10

Ⅳ-

11

Ⅳ-

12

Ⅳ-

13

Ⅳ-

14

Ⅳ-

15

Ⅳ-

16

Ⅳ-

17

Ⅳ-

18

Ⅳ-

19

Ⅳ-

20

Ⅳ-

twenty one

Ⅳ-

twenty two

Ⅳ-

twenty three

Ⅳ-

twenty four

Ⅳ-

25

Ⅳ-

26

Ⅳ-

27

Ⅳ-

28

Ⅳ-

29

Ⅳ-

30

Ⅳ-

31

Ⅳ-

32

Ⅳ-

33

Ⅳ-

34

Ⅳ-

35

Ⅳ-

36. The negative dielectric anisotropic liquid crystal composition according to any one of claims 1 to 6, further comprising one or more compounds represented by the following formulae V-1 to V-5:

V-1

V-2

V-3

V-4

V-5. The negative dielectric anisotropic liquid crystal composition according to any one of claims 1 to 4, wherein the weight percentage of the compound represented by the formula I is 1-50%, and the compound represented by the formula II The weight percentage of the compound represented by the formula III is 1-60%, and the weight percentage of the compound represented by the formula III is 1-50%. The negative dielectric anisotropic liquid crystal composition according to claim 5 or 6, wherein the weight percentage of the compound represented by the formula I is 1-50%, and the weight of the compound represented by the formula II is 1-50%. The percentage content is 1-60%, the weight percentage of the compound represented by the formula III is 1-50%, and the weight percentage of the compound represented by the formula IV is 1-20%. The negative dielectric anisotropic liquid crystal composition according to claim 7, wherein the weight percentage of the compound represented by the formula I is 1-50%, and the weight percentage of the compound represented by the formula II The content is 1 to 60%, the weight percentage of the compound shown in the formula III is 1 to 50%, the weight percentage of the compound shown in the formula IV is 1 to 20%, and the weight percentage of the compound shown in the formula V is 1 to 20%. The weight percentage of the compounds shown is 0.01 to 1%. A liquid crystal display device, comprising the negative dielectric anisotropic liquid crystal composition according to any one of claims 1 to 10; the liquid crystal display device is an active matrix display device or a passive matrix display device.