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CN116162469A - Liquid crystal composition and liquid crystal display device thereof - Google Patents

Liquid crystal composition and liquid crystal display device thereof Download PDF

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Publication number
CN116162469A
CN116162469A CN202111406977.XA CN202111406977A CN116162469A CN 116162469 A CN116162469 A CN 116162469A CN 202111406977 A CN202111406977 A CN 202111406977A CN 116162469 A CN116162469 A CN 116162469A
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liquid crystal
formula
crystal composition
compound
carbon atoms
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CN116162469B (en
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潘帝可
丁文全
王盼盼
戴慧娟
贺笛
徐爽
赵飞
姚利芳
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Jiangsu Hecheng Display Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • C09K19/44—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing compounds with benzene rings directly linked
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods

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Abstract

The invention provides a liquid crystal composition and a liquid crystal display device thereof, wherein the liquid crystal composition comprises at least one compound of a formula I and at least one compound of a formula II; through mutual cooperation among components, the liquid crystal composition has higher clear point, better optical anisotropy, proper dielectric anisotropy, lower rotational viscosity, larger elastic constant K value, higher transmittance and contrast, shorter response time, faster response speed, longer low-temperature storage time and better low-temperature storage stability, so that a liquid crystal display device comprising the liquid crystal composition has proper threshold voltage, wider use temperature range, better contrast, faster response speed, higher transmittance and better low-temperature storage stability, can effectively improve the display performance of the liquid crystal display device, and is particularly suitable for display modes such as IPS, TN, VA, NFFS with quick response.

Description

Liquid crystal composition and liquid crystal display device thereof
Technical Field
The invention belongs to the technical field of liquid crystal materials, and particularly relates to a liquid crystal composition and a liquid crystal display device thereof.
Background
Liquid crystal displays (Liquid Crystal Display, LCD) have been rapidly developed due to their small size, light weight, low power consumption and excellent display quality, and have been widely used in particular in portable electronic information products. As the size of liquid crystal screens for portable computers, office applications, video applications has increased, liquid crystal displays can be used for large screen display and eventually replace Cathode Ray Tube (CRT) displays.
Compared with the traditional display device and display material, the liquid crystal display material has obvious advantages: low driving voltage, small power consumption, high reliability, large display information quantity, color display, no flicker, no harm to human body, automatic production process, low cost, capability of manufacturing liquid crystal displays of various specifications and types, portability and the like. Because of these advantages, the liquid crystal display technology has profound effects on the display and development of microelectronic technology and photoelectric information technology. The liquid crystal material has been widely used in various display occasions by virtue of its good optical properties and photoelectric effect.
In the beginning of the last 70 th century, experimental studies have been made on the fundamental electro-optic characteristics of the uniformly aligned and twisted nematic liquid crystal IPS mode, which is characterized by a pair of electrodes fabricated on the same substrate and no electrode on the other substrate, and the alignment of liquid crystal molecules is controlled by a transverse electric field applied between the pair of electrodes, and thus this mode is also called a transverse field mode. In the IPS mode, nematic liquid crystal molecules are uniformly aligned in parallel between two substrates, and two polarizers are placed orthogonally. In the IPS mode, when no electric field is applied, incident light is blocked by two orthogonal polarizers and is in a dark state, and when an electric field is applied, liquid crystal molecules are rotated to cause retardation, so that light leaks from the two orthogonal polarizers. The panel adopting the IPS mode has the advantages of large visible angle and accurate color reproduction, but has the disadvantages of serious light leakage and slower response speed.
With the wide application of TFT-type LCDs, the performance requirements are continuously increasing, and high display image quality is required to have a faster response speed, lower power consumption and higher low-temperature reliability, and in addition, higher contrast and transmittance are required, especially for IPS-type liquid crystal display modes. This also means that liquid crystal materials are required to have higher contrast and transmittance, higher elastic constant, higher dielectric constant and low temperature reliability, and improvements in these properties are required for liquid crystal materials.
According to the transmittance calculation formula of the IPS mode: t +|Deltaε|/ε ⊥ (T represents transmittance, ". Alpha." represents an "inverse proportion" relationship,. Epsilon.) ⊥ Representing the dielectric constant perpendicular to the molecular axis), attempts may be made to reduce Δεof the liquid crystal medium in order to increase the transmittance of the liquid crystal, but the adjustment range of the driving voltage of the same product is generally limited. In addition, the liquid crystal molecules are inclined to the Z-axis direction under the action of the vertical component of the fringe electric field, so that the optical anisotropy of the liquid crystal molecules is changed, and the formula is adopted
Figure BDA0003373113790000011
(wherein χ is the angle between the optical axis of the liquid crystal layer and the optical axis of the polarizer, Δn is the optical anisotropy, d is the cell pitch, λ is the wavelength), it is known that effective Δn×d affects T, and increasing Δn×d is also considered to increase the transmittance of positive liquid crystals, but the retardation design of each product is fixed.
On the other hand, based on the conventional IPS-LCD light leakage performance test, the person skilled in the art finds that the main cause of the light leakage problem of the liquid crystal display device is: light scattering (LC scattering), rubbing uniformity (rubbing uniformity), color filter light leakage (CF/TFT scattering), and polarization ability (polarization ability), wherein the light scattering accounts for 63% of the influencing factors of the light leakage performance.
According to the following relation:
Figure BDA0003373113790000012
wherein d represents the pitch of the liquid crystal cells, n e Represents the extraordinary refractive index, n o Indicating the ordinary refractive index.
To improve the light scattering of the liquid crystal material, it is necessary to increase the average elastic constant K ave (K ave ＝(K 11 +K 22 +K 33 ) 3) to improve light scattering, at an increase of K ave In the case of (2), light leakage of the liquid crystal material can be reduced.
Further, the relation between Contrast (CR) and brightness (L) is as follows:
CR＝L 255 /L 0 ×100％；
wherein L is 255 Is of on-state brightness, L 0 Is the off-state brightness. It can be seen that significantly affecting CR is L 0 Is a variation of (c). In the off state, L 0 Independent of the dielectric properties of the liquid crystal molecules, and related to LC patterning of the liquid crystal material itself; LC rating smaller, L 0 The smaller the CR, the more significantly the CR will increase.
In view of the above, a common way to improve contrast and transmittance may be considered as follows: (1) The dielectric anisotropy delta epsilon of the liquid crystal composition is kept unchanged by increasing epsilon ⊥ The transmittance can be effectively improved; (2) Increasing the average elastic constant K of the liquid crystal composition ave The value of (2) is better in order degree of liquid crystal molecules and less in light leakage, so that the transmittance is improved.
From the preparation point of the liquid crystal material, various properties of the liquid crystal material are influenced by mutual constraint, and other properties may be changed due to the improvement of certain performance indexes. Therefore, the preparation of the liquid crystal material with proper performances in all aspects has great difficulty, and the development of the liquid crystal material with higher elastic constant, higher contrast and faster response speed is the focus of research in the field.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a liquid crystal composition and a liquid crystal display device thereof, wherein the liquid crystal composition has higher clearing point, better optical anisotropy, proper dielectric anisotropy, larger elastic constant, lower rotational viscosity, higher transmittance, higher contrast ratio, higher response speed and better low-temperature storage stability.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a liquid crystal composition comprising:
At least one compound of formula I:
Figure BDA0003373113790000021
and
At least one compound of formula II:
Figure BDA0003373113790000022
wherein R is 0 Represents a linear or branched alkyl radical having 1 to 12 (e.g.1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12) carbon atoms,
Figure BDA0003373113790000023
At least two-CH groups, one or not adjacent, of said straight or branched alkyl groups having 1 to 12 carbon atoms 2 -may each be independently replaced by-ch=ch-, -c≡c-, -O-, -CO-O-, or-O-CO-; one or at least two of the foregoing groups, -H, may each independently be substituted with-F or-Cl;
R X represents a haloalkyl group having 1 to 5 (e.g., 1, 2, 3, 4, or 5) carbon atoms, a haloalkoxy group having 1 to 4 (e.g., 1, 2, 3, or 4) carbon atoms, or a straight-chain or branched alkyl group having 1 to 12 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12) carbon atoms; at least two-CH groups which are not adjacent to one another in the straight-chain or branched alkyl group having 1 to 12 carbon atoms 2 Can be respectivelyIndependently replaced by-ch=ch-, -c≡c-, -O-, -CO-O-or-O-CO-;
ring(s)
Figure BDA0003373113790000024
And (C) a ring->
Figure BDA0003373113790000025
Each independently represents->
Figure BDA0003373113790000026
Or one or at least two single bonds in the ring are replaced by double bonds >
Figure BDA0003373113790000027
And at most one ring->
Figure BDA0003373113790000028
Or (R) ring->
Figure BDA0003373113790000029
Representation of
Figure BDA00033731137900000210
R 1 And R is 2 Each independently represents a linear or branched alkyl group containing 1 to 12 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12) carbon atoms, or a linear or branched alkenyl group containing 2 to 12 (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12) carbon atoms;
n 1 and n 2 Each independently represents 0 or 1.
In the invention, the compound of the formula I containing cyclohexene structure and the compound of the formula II containing biphenyl structure are compounded, so that the liquid crystal composition has higher clear point, better optical anisotropy, proper dielectric anisotropy, larger elastic constant K value and lower rotational viscosity gamma 1 Higher penetration and higher contrast, shorter response time and faster response speedThe display mode is suitable for display modes such as IPS, TN, VA, NFFS with quick response due to long low-temperature storage time and wider application range.
In the present invention, "can be replaced by … …" independently means that it may or may not be replaced, that is, replaced or not replaced, and all fall within the scope of the present invention; "may each be independently substituted by … …" is the same; also, the positions of "substitution" and "substitution" are arbitrary.
In the invention, short straight lines at one side or two sides of the group represent access bonds and do not represent methyl; for example
Figure BDA0003373113790000031
Figure BDA0003373113790000032
Short straight line on left->
Figure BDA0003373113790000033
Short straight lines on both sides.
In the present invention, the halogen includes fluorine, chlorine, bromine, iodine, or the like; the following description is referred to in the same sense.
In the present invention, the halo means that at least one hydrogen in the group is substituted with halogen (fluorine, chlorine, bromine or iodine).
In a preferred embodiment, the ring
Figure BDA0003373113790000034
And (C) a ring->
Figure BDA0003373113790000035
Each independently represents
Figure BDA0003373113790000036
And at most one ring->
Figure BDA0003373113790000037
Or (R) ring->
Figure BDA0003373113790000038
Representation of
Figure BDA0003373113790000039
In a preferred embodiment, the compound of formula I is selected from the group consisting of:
Figure BDA00033731137900000310
Figure BDA0003373113790000041
Figure BDA0003373113790000042
and
Figure BDA0003373113790000043
Wherein R is X ' means a straight or branched alkyl group containing 1 to 12 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12) carbon atoms.
In a preferred embodiment, the compound of formula I comprises at least one compound selected from the group consisting of compounds of formula I-1 and compounds of formula I-9 in order to obtain a suitable absolute value of the dielectric anisotropy, a better optical anisotropy, a higher clearing point, a larger K value, a smaller rotational viscosity, a shorter response time, a higher transmittance, a better contrast ratio and a longer low temperature storage time.
In a preferred embodiment, the liquid crystal composition of the invention comprises at least two (e.g. two, three, four, etc.) compounds of formula I in order to obtain a suitable absolute value of the dielectric anisotropy, a good optical anisotropy, a high clearing point, a high K value, a low rotational viscosity, a short response time, a high transmittance, a good contrast ratio and a long low temperature storage time.
In a preferred embodiment, R is 0 Represents a linear alkyl group having 1 to 8 (e.g., 1, 2, 3, 4, 5, 6, 7, or 8) carbon atoms or a linear alkenyl group having 2 to 8 (e.g., 2, 3, 4, 5, 6, 7, or 8) carbon atoms.
In a preferred embodiment, the compound of formula II is selected from the group consisting of:
Figure BDA0003373113790000044
Figure BDA0003373113790000051
Figure BDA0003373113790000052
and
Figure BDA0003373113790000053
Wherein R is 1 ' and R 2 ' each independently represents a linear alkenyl group containing 2 to 6 (e.g., 2, 3, 4, 5, or 6) carbon atoms; and
R 1 and R is 2 Each independently represents a straight chain alkyl group containing 1 to 6 (e.g., 1, 2, 3, 4, 5, or 6) carbon atoms.
In a preferred embodiment, the liquid crystal composition according to the invention comprises at least two compounds of the formula II in order to obtain a suitable absolute value of the dielectric anisotropy, a good optical anisotropy, a high clearing point, a high K value, a low rotational viscosity, a short response time, a high transmittance, a good contrast ratio and a long low temperature storage time.
In a preferred embodiment, the liquid crystal composition according to the invention comprises at least one compound of the formula II-5 in order to obtain a suitable absolute value of the dielectric anisotropy, a good optical anisotropy, a high clearing point, a high K value, a low rotational viscosity, a short response time, a high transmittance, a good contrast ratio and a long low temperature storage time.
In a preferred embodiment, the liquid crystal composition of the present invention comprises at least one compound selected from the group consisting of the compounds of formula II-2, the compounds of formula II-3 in order to obtain a suitable absolute value of dielectric anisotropy, a good optical anisotropy, a high clearing point, a large K value, a small rotational viscosity, a short response time, a high transmittance, a good contrast ratio and a long low temperature storage time.
In the present invention, the structure of the alkenyl group illustratively includes, but is not limited to, a group represented by any one of the formulas (V1) to (V9), and particularly preferably is formula (V1), formula (V2), formula (V8) or formula (V9).
Figure BDA0003373113790000054
Figure BDA0003373113790000055
Wherein represents the attachment site of the group. />
In a preferred embodiment, the content of the compound of formula I is adjusted so that the liquid crystal composition comprising it has a suitable absolute value of dielectric anisotropy, a better optical anisotropy, a higher clearing point, a larger K value, a smaller rotational viscosity, a shorter response time, a higher penetration rate, a better contrast ratio and a longer low-temperature storage time.
In a preferred embodiment, the mass percentage of the compound of formula I in the liquid crystal composition is 1% -40%, for example, may be 2%, 3%, 5%, 7%, 9%, 10%, 11%, 13%, 15%, 17%, 19%, 20%, 22%, 25%, 28%, 30%, 31%, 33%, 35%, 37%, 39%, or 40%, and specific point values between the above point values, and the present invention is not exhaustive list of specific point values included in the range, more preferably 3% -25%, for reasons of space and for reasons of brevity.
In a preferred embodiment, the content of the compound of formula II is adjusted so that the liquid crystal composition comprising it has a suitable absolute value of dielectric anisotropy, a better optical anisotropy, a higher clearing point, a larger K value, a smaller rotational viscosity, a shorter response time, a higher penetration rate, a better contrast ratio and a longer low-temperature storage time.
In a preferred embodiment, the mass percentage of the compound of formula II in the liquid crystal composition is 1% -30%, for example, may be 2%, 3%, 4%, 5%, 6%, 8%, 10%, 12%, 14%, 15%, 16%, 18%, 20%, 22%, 25%, 26%, 28% or 30%, and the specific point values between the above point values, are limited in space and for the sake of brevity, the present invention is not exhaustive of the specific point values included in the range, and more preferably 1% -20%.
In a preferred embodiment, the liquid crystal composition further comprises at least one compound of formula N:
Figure BDA0003373113790000061
wherein R is N1 And R is N2 Each independently represents a linear or branched alkyl group having 1 to 12 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12) carbon atoms,
Figure BDA0003373113790000062
Figure BDA0003373113790000063
At least two-CH groups, one or not adjacent, of said straight or branched alkyl groups having 1 to 12 carbon atoms 2 -may each be independently replaced by-ch=ch-, -c≡c-, -O-, -CO-O-, or-O-CO-;
ring(s)
Figure BDA0003373113790000064
And (C) a ring->
Figure BDA0003373113790000065
Each independently represents->
Figure BDA0003373113790000066
The said
Figure BDA0003373113790000067
One or at least two-CH 2 -can be replaced by-O-, single bonds in one or at least two rings can be replaced by double bonds; said->
Figure BDA0003373113790000068
In which-ch=may be replaced by-n=and one or at least two-H of the foregoing groups may be replaced by-F, -Cl or-CN;
Z N1 and Z N2 Each independently represents a single bond, -CO-O-, -O-CO-, -CH 2 O-、-OCH 2 -、-CH＝CH-、-C≡C-、-CH 2 CH 2 -、-CF 2 CF 2 -、-(CH 2 ) 4 -、-CF 2 O-or-OCF 2 -；
L N1 And L N2 Each independently represents-H, halogen, unsubstituted or halogenated linear alkyl groups containing 1 to 3 (e.g., 1, 2, or 3) carbon atoms;
n N1 represents 0, 1, 2 or 3, n N2 Represents 0 or 1, and 0.ltoreq.n N1 +n N2 Less than or equal to 3; when n is N1 When 2 or 3 is represented, the ring
Figure BDA0003373113790000069
Identical or different, Z N1 The same or different.
In a preferred embodiment, the compound of formula N is selected from the group consisting of:
Figure BDA00033731137900000610
Figure BDA0003373113790000071
Figure BDA0003373113790000081
Figure BDA0003373113790000082
and
Figure BDA0003373113790000083
In a preferred embodiment, the compound of formula N is selected from any one or a combination of at least two of the compounds of formula N-1, formula N-2, formula N-3, formula N-4, formula N-6, formula N-7, formula N-9, formula N-12, formula N-14, formula N-15, formula N-17, formula N-22, formula N-23, formula N-30, formula N-32, and formula N-33.
In a preferred embodiment, the liquid crystal composition of the present invention further preferably comprises a combination of at least two of any one of (e.g., 2, 3, 4, 5 or 6, etc.) compounds of formula N-2, formula N-3, formula N-4, formula N-6, formula N-7, formula N-12, formula N-14, formula N-15, formula N-30, formula N-33, etc., in order to obtain an appropriate absolute value of dielectric anisotropy, a better optical anisotropy, a higher clearing point, a larger K value, a smaller rotational viscosity, a shorter response time, a higher transmittance, a better contrast ratio, and a longer low-temperature storage time.
In a preferred embodiment, the liquid crystal composition of the present invention comprises at least one compound selected from the group consisting of a compound of formula N-2, a compound of formula N-3, a compound of formula N-30 and a compound of formula N-33 in order to obtain a suitable absolute value of dielectric anisotropy, a better optical anisotropy, a higher clearing point, a larger K value, a smaller rotational viscosity, a shorter response time, a higher transmittance, a better contrast ratio and a longer low temperature storage time.
In a preferred embodiment, the liquid crystal composition of the present invention comprises at least one compound selected from the group consisting of compounds of formula N-4 and N-7 in order to obtain a suitable absolute value of dielectric anisotropy, a better optical anisotropy, a higher clearing point, a larger K value, a smaller rotational viscosity, a shorter response time, a higher transmittance, a better contrast ratio and a longer low temperature storage time.
In a preferred embodiment, the liquid crystal composition of the present invention comprises at least one compound selected from the group consisting of a compound of formula N-12, a compound of formula N-14 and a compound of formula N-15 in order to obtain a suitable absolute value of dielectric anisotropy, a better optical anisotropy, a higher clearing point, a larger K value, a smaller rotational viscosity, a shorter response time, a higher transmittance, a better contrast ratio and a longer low temperature storage time.
In a preferred embodiment, R is N1 Represents a linear alkyl group having 1 to 6 (e.g., 1, 2, 3, 4, 5 or 6) carbon atoms, a linear alkoxy group having 1 to 6 (e.g., 1, 2, 3, 4, 5 or 6) carbon atoms or a linear alkenyl group having 2 to 6 (e.g., 2, 3, 4, 5 or 6) carbon atoms.
In a preferred embodiment, R N2 Represents a linear alkoxy radical having 1 to 6 (for example 1, 2, 3, 4, 5 or 6) carbon atoms.
In a preferred embodiment, the content of the compound of formula N is adjusted so that the liquid crystal composition of the invention has a suitable absolute value of dielectric anisotropy, a good optical anisotropy, a high clearing point, a high K value, a low rotational viscosity, a short response time, a high penetration rate, a good contrast ratio and a long low-temperature storage time.
In a preferred embodiment, the mass percentage of the compound of formula N in the liquid crystal composition is 1% -60%, for example, 3%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48%, 50%, 52%, 55% or 58%, and the specific values between the above values, are limited in space and for brevity, the invention is not exhaustive.
In a preferred embodiment, the liquid crystal composition is a liquid crystal composition of negative dielectric anisotropy, wherein Δε < 0 (20 ℃,1 KHz), and Δε can be-2.1 to-3.4.
In a preferred embodiment, the liquid crystal composition further comprises at least one compound of formula M:
Figure BDA0003373113790000091
wherein R is M1 And R is M2 Each independently represents a linear or branched alkyl group having 1 to 12 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12) carbon atoms,
Figure BDA0003373113790000092
Figure BDA0003373113790000093
At least two-CH groups, one or not adjacent, of said straight or branched alkyl groups having 1 to 12 carbon atoms 2 -may each be independently replaced by-ch=ch-, -c≡c-, -O-, -CO-O-, or-O-CO-;
ring(s)
Figure BDA0003373113790000101
Ring->
Figure BDA0003373113790000102
And (C) a ring->
Figure BDA0003373113790000103
Each independently represents->
Figure BDA0003373113790000104
Figure BDA0003373113790000105
Said->
Figure BDA0003373113790000106
At least two-CH of one or not adjacent 2 -can be replaced by-O-; the said
Figure BDA0003373113790000107
In which-ch=can be replaced by-n=and at most one-H can be substituted by halogen; and the compound of formula M does not contain +.>
Figure BDA0003373113790000108
Is of a structure of (2);
Z M1 and Z M2 Each independently represents a single bond, -CO-O-, -O-CO-, -CH 2 O-、-OCH 2 -、-C≡C-、-CH＝CH-、-CH 2 CH 2 -or- (CH) 2 ) 4 -；
n M Represents 0, 1 or 2;
when n is M When 2 is represented, the ring
Figure BDA0003373113790000109
Identical or different, Z M2 The same or different.
In a preferred embodiment, the compound of formula M is selected from the group consisting of:
Figure BDA00033731137900001010
Figure BDA0003373113790000111
Figure BDA0003373113790000112
and
Figure BDA0003373113790000113
In a preferred embodiment, the compound of formula M is selected from any one or a combination of at least two of a compound of formula M-1, a compound of formula M-2, a compound of formula M-9, a compound of formula M-10, a compound of formula M-11, a compound of formula M-12, a compound of formula M-13, a compound of formula M-14, a compound of formula M-16, a compound of formula M-19, a compound of formula M-20, a compound of formula M-21, and a compound of formula M-22.
In a preferred embodiment, the liquid crystal composition comprises a compound of formula M-1, a compound of formula M-9, a compound of formula M-11, a compound of formula M-12 in order to obtain a suitable absolute value of dielectric anisotropy, a good optical anisotropy, a high clearing point, a high K value, a small rotational viscosity, a short response time, a high transmittance, a good contrast ratio and a long low temperature storage time.
In a preferred embodiment, the liquid crystal composition comprises at least one compound selected from the group consisting of the compounds of formula M-1 and the compounds of formula M-9, more preferably at least one alkenyl group-containing compound selected from the group consisting of the compounds of formula M-1 and the compounds of formula M-9, in order to obtain a better optical anisotropy, a higher clearing point, a larger K value, a smaller rotational viscosity, a shorter response time, a higher transmittance, a better contrast ratio and a longer low temperature storage time.
In a preferred embodiment, R is M1 And R is M2 Each independently represents a compound having 1 to 8 (e.g., 1A linear alkyl group having from 1 to 8 (e.g., 1, 2, 3, 4, 5, 6, 7 or 8) carbon atoms, a linear alkoxy group having from 2 to 8 (e.g., 2, 3, 4, 5, 6, 7 or 8) carbon atoms, or a linear alkenyl group having from 2 to 8 (e.g., 2, 3, 4, 5, 6, 7 or 8) carbon atoms, and more preferably a linear alkyl group having from 1 to 6 carbon atoms or a linear alkenyl group having from 2 to 6 carbon atoms.
In a preferred embodiment, R is M1 And R is M2 One of which represents a linear alkenyl group having 2 to 6 carbon atoms and the other represents a linear alkyl group having 1 to 6 carbon atoms.
In a preferred embodiment, the content of the compound of formula M is adjusted so that the liquid crystal composition has a suitable absolute value of dielectric anisotropy, a good optical anisotropy, a high clearing point, a high K value, a low rotational viscosity, a short response time, a high penetration rate, a good contrast ratio and a long low-temperature storage time.
In a preferred embodiment, the mass percentage of the compound of formula M in the liquid crystal composition is 0.1% -70%, for example, 0.5%, 1%, 3%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48%, 50%, 52%, 55%, 58%, 60%, 62%, 65% or 68%, and the specific point values between the above point values, are limited in length and for brevity, and the invention is not exhaustive of the specific point values included in the range.
In a preferred embodiment, the liquid crystal composition further comprises at least one compound of formula B:
Figure BDA0003373113790000121
wherein R is B1 And R is B2 Each independently represents-H, halogen, a straight or branched chain containing 1 to 12 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12) carbon atomsAn alkyl group; at least two-CH groups, one or not adjacent, of said straight or branched alkyl groups having 1 to 12 carbon atoms 2 -may each be independently replaced by-ch=ch-, -c≡c-, -S-, -O-, -CO-O-, or-O-CO-; one or at least two of the foregoing groups, -H, may each independently be substituted with-F or-Cl;
ring(s)
Figure BDA0003373113790000122
And (C) a ring->
Figure BDA0003373113790000123
Each independently represents->
Figure BDA0003373113790000124
Figure BDA0003373113790000125
Said->
Figure BDA0003373113790000126
At least two-CH of one or not adjacent 2 -can be replaced by-O-, single bonds in one or at least two rings can be replaced by double bonds; said->
Figure BDA0003373113790000127
-ch=in one or at least two rings may be replaced by-n=in one or more rings; one or at least two of the foregoing groups-H may be replaced by-F, -Cl, -CN, -CH 3 or-OCH 3 Substitution;
Z B1 and Z B2 Each independently represents a single bond, -O-, -S-, -CO-O-, -O-CO-, -CH 2 O-、-OCH 2 -、-CH＝CH-、-C≡C-、-CH 2 CH 2 -、-CF 2 CF 2 -、-(CH 2 ) 4 -、-CF 2 O-or-OCF 2 -；
Y B1 And Y B2 Each independently represents-H, halogen, unsubstituted or halogenated straight chain alkyl groups containing 1 to 3 (e.g., 1, 2, or 3) carbon atoms Straight-chain alkoxy groups of atoms;
X B represents-O-, -S-, -CO-, -CF 2 -, -NH-or-NF-;
n B1 and n B2 Each independently represents 0, 1 or 2; when n is B1 When 2 is represented, the ring
Figure BDA0003373113790000131
Identical or different, Z B1 Identical or different, when n B2 When 2 is indicated, the ring->
Figure BDA0003373113790000132
Identical or different, Z B2 The same or different.
In a preferred embodiment, the compound of formula B is selected from the group consisting of:
Figure BDA0003373113790000133
Figure BDA0003373113790000134
and +.>
Figure BDA0003373113790000135
Wherein Y is B3 And Y B4 Each independently represents-H, -F, -Cl, -CN, -CH 3 or-OCH 3 。
In a preferred embodiment, the liquid crystal composition comprises at least one compound of formula B-1 in order to obtain a suitable absolute value of dielectric anisotropy, a good optical anisotropy, a high clearing point, a high K value, a low rotational viscosity, a short response time, a high transmittance, a good contrast ratio and a long low temperature storage time.
In a preferred embodiment, the mass percentage of the compound of formula B in the liquid crystal composition is 0.1% -30%, for example, may be 0.3%, 0.5%, 0.8%, 1%, 3%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25% or 28%, and the specific values between the above values are limited in space and for brevity, the invention is not exhaustive of the specific values included in the range.
In a preferred embodiment, R is B1 And R is B2 Each independently represents a linear alkyl group containing 1 to 6 (e.g., 1, 2, 3, 4, 5, or 6) carbon atoms, a linear alkoxy group containing 1 to 6 (e.g., 1, 2, 3, 4, 5, or 6) carbon atoms, a linear alkenyl group containing 2 to 6 (e.g., 1, 2, 3, 4, 5, or 6) carbon atoms, an unsubstituted or halogenated linear alkenyloxy group containing 2 to 6 (e.g., 1, 2, 3, 4, 5, or 6) carbon atoms.
In a preferred embodiment, the liquid crystal composition further comprises at least one compound selected from the group consisting of a compound of formula A-1 and a compound of formula A-2:
Figure BDA0003373113790000141
wherein R is A1 And R is A2 Each independently represents a linear or branched alkyl group having 1 to 12 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12) carbon atoms,
Figure BDA0003373113790000142
Figure BDA0003373113790000143
At least two-CH groups, one or not adjacent, of said straight or branched alkyl groups having 1 to 12 carbon atoms 2 -may each be independently replaced by-ch=ch-, -c≡c-, -O-, -CO-O-, or-O-CO-; one or at least two of the foregoing groups, -H, may each independently be substituted with-F or-Cl;
Ring(s)
Figure BDA0003373113790000144
And (C) a ring->
Figure BDA0003373113790000145
Each independently represents
Figure BDA0003373113790000146
Figure BDA0003373113790000147
Said->
Figure BDA0003373113790000148
At least two-CH of one or not adjacent 2 -can be replaced by-O-, single bonds in one or at least two rings can be replaced by double bonds; said->
Figure BDA0003373113790000149
Figure BDA00033731137900001410
-ch=in one or at least two rings may be replaced by-n=in one or more rings; one or at least two of the foregoing groups-H may be substituted with-F or-Cl.
Ring(s)
Figure BDA0003373113790000151
And (C) a ring->
Figure BDA0003373113790000152
Each independently represents
Figure BDA0003373113790000153
Figure BDA0003373113790000154
Said->
Figure BDA0003373113790000155
At least two-CH of one or not adjacent 2 -can be replaced by-O-, single bonds in one or at least two rings can be replaced by double bonds; said->
Figure BDA0003373113790000156
At least two-CH of one or not adjacent 2 -can be replaced by-O-; the said
Figure BDA0003373113790000157
-ch=in one or at least two rings may be replaced by-n=in one or more rings; one or at least two of the foregoing groups-H may be substituted with-F or-Cl;
Z A11 、Z A21 and Z A22 Each independently represents a single bond, -CH 2 CH 2 -、-CF 2 CF 2 -、-CO-O-、-O-CO-、-O-CO-O-、-C≡C-、-CH＝CH-、-CF＝CF-、-CH 2 O-or-OCH 2 -；
L A11 、L A12 、L A13 、L A21 And L A22 Each independently represents-H, halogen, unsubstituted or halogenated linear alkyl groups containing 1 to 3 (e.g., 1, 2, or 3) carbon atoms;
X A1 and X A2 Each independently represents halogen, haloalkyl containing 1 to 5 (e.g., 1, 2, 3, 4, or 5) carbon atoms, haloalkoxy containing 1 to 5 (e.g., 1, 2, 3, 4, or 5) carbon atoms, haloalkenyl containing 2 to 5 (e.g., 2, 3, 4, or 5) carbon atoms, or haloalkenoxy containing 2 to 5 (e.g., 2, 3, 4, or 5) carbon atoms;
n A11 And n A2 Each independently represents 0, 1, 2 or 3; when n is A11 When 2 or 3 is represented, the ring
Figure BDA0003373113790000158
Identical or different, Z A11 The same or different; when n is A2 When 2 or 3 is indicated, the ring->
Figure BDA0003373113790000159
Identical or different, Z A21 The same or different;
n A12 represents 1 or 2; when n is A12 When 2 is represented, the ring
Figure BDA00033731137900001510
The same or different.
In a preferred embodiment, the mass percentage of the compound selected from the group consisting of the compound of formula a-1 and the compound of formula a-2 in the liquid crystal composition is 0.1% to 60%, for example, may be 0.3%, 0.5%, 0.8%, 1%, 3%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48%, 50%, 52%, 55% or 58%, etc.
In a preferred embodiment, the compound of formula A-1 is selected from the group consisting of:
Figure BDA00033731137900001511
Figure BDA0003373113790000161
Figure BDA0003373113790000171
Figure BDA0003373113790000172
and
Figure BDA0003373113790000173
Wherein R is A1 Represents a linear or branched alkyl group containing 1 to 8 (e.g., 1, 2, 3, 4, 5, 6, 7, or 8) carbon atoms; at least two-CH groups, one or not adjacent, of said straight or branched alkyl groups having 1 to 8 carbon atoms 2 -may each be independently replaced by-ch=ch-, -c≡c-, -O-, -CO-O-, or-O-CO-; one of the foregoing groups Each or at least two-H may be independently substituted with-F or-Cl;
R v and R is w Each independently represents-CH 2 -or-O-;
L A11 、L A12 、L A11 '、L A12 '、L A14 、L A15 and L A16 Each independently represents-H or-F;
L A13 and L A13 ' each independently represents-H or-CH 3 ；
X A1 representing-F, -CF 3 or-OCF 3 ；
v and w each independently represent 0 or 1.
In a preferred embodiment, the compound of formula A-1 comprises at least one compound selected from the group consisting of compounds of formula A-1-7, compounds of formula A-1-14, compounds of formula A-1-15, in order to obtain a suitable absolute value of dielectric anisotropy, better optical anisotropy, higher clearing point, larger K value, smaller rotational viscosity, shorter response time, higher transmittance, better contrast ratio and longer low temperature storage time.
In a preferred embodiment, the mass percentage of the compound of formula a-1 in the liquid crystal composition is 0.1% -50%, for example, may be 0.3%, 0.5%, 0.8%, 1%, 3%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45% or 48%, etc.
In a preferred embodiment, the compound of formula A-2 is selected from the group consisting of:
Figure BDA0003373113790000181
Figure BDA0003373113790000191
Figure BDA0003373113790000192
and
Figure BDA0003373113790000193
Wherein R is A2 Represents a linear or branched alkyl group containing 1 to 8 (e.g., 1, 2, 3, 4, 5, 6, 7, or 8) carbon atoms; at least two-CH groups, one or not adjacent, of said straight or branched alkyl groups having 1 to 8 carbon atoms 2 -may each be independently replaced by-ch=ch-, -c≡c-, -O-, -CO-O-, or-O-CO-; one or at least two of the foregoing groups, -H, may each independently be substituted with-F or-Cl;
L A21 、L A22 、L A23 、L A24 and L A25 Each independently represents-H or-F;
X A2 representing-F, -CF 3 、-OCF 3 Or- (CH) 2 ) 2 -CH＝CF 2 。
In a preferred embodiment, the compound of formula A-2 comprises at least one compound selected from the group consisting of a compound of formula A-2-6, a compound of formula A-2-12, a compound of formula A-2-13, and a compound of formula A-2-18 in order to obtain a suitable absolute value of dielectric anisotropy, better optical anisotropy, higher clearing point, larger K value, smaller rotational viscosity, shorter response time, higher transmittance, better contrast ratio, and longer low temperature storage time.
In a preferred embodiment, the mass percentage of the compound of formula a-2 in the liquid crystal composition is 0.1% -50%, for example, may be 0.3%, 0.5%, 0.8%, 1%, 3%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45% or 48%, etc.
In addition to the above-mentioned compounds, the liquid crystal composition of the present invention may contain a usual nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, polymerizable monomer, additive, or the like.
In a preferred embodiment, the liquid crystal composition further comprises at least one additive.
In a preferred embodiment, the additive comprises any one or a combination of at least two of a dopant, an antioxidant, an ultraviolet light absorber, an infrared light absorber, or a light stabilizer.
Possible dopants preferably added to the liquid crystal composition of the present invention are shown below:
Figure BDA0003373113790000201
Figure BDA0003373113790000211
Figure BDA0003373113790000212
and +.>
Figure BDA0003373113790000213
In some embodiments of the invention, the dopant comprises 0% to 5% by weight of the liquid crystal composition; preferably, the dopant comprises 0.01% to 1% by weight of the liquid crystal composition.
The additives such as antioxidants, light stabilizers, and ultraviolet absorbers used in the liquid crystal composition of the present invention are preferably the following:
Figure BDA0003373113790000214
Figure BDA0003373113790000221
Figure BDA0003373113790000231
wherein n represents a positive integer of 1 to 12.
Preferably, the antioxidant is selected from the compounds shown below:
Figure BDA0003373113790000232
in some embodiments of the invention, the additive comprises 0% to 5% by weight of the total weight of the liquid crystal composition; preferably, the additive comprises 0.01% to 1% by weight of the total weight of the liquid crystal composition.
In a second aspect, the present invention provides a liquid crystal display device comprising a liquid crystal composition according to the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
in the liquid crystal composition provided by the invention, the liquid crystal composition has higher clear point, better optical anisotropy, proper dielectric anisotropy and lower rotational viscosity gamma through mutual coordination of components 1 The liquid crystal display device has the advantages of high elasticity constant K value, high transmittance and contrast, short response time, high response speed, long low-temperature storage time and high low-temperature storage stability, can effectively improve the display performance of the liquid crystal display device, and is particularly suitable for display modes such as IPS, TN, VA, NFFS with quick response.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
For convenience of expression, in the following examples and comparative examples, the group structures of the respective components in the liquid crystal composition are represented by codes listed in table 1:
TABLE 1
Figure BDA0003373113790000241
Figure BDA0003373113790000251
Take as an example a compound of the formula:
Figure BDA0003373113790000252
the structure is represented by the codes listed in table 1, and can be expressed as: 1VCPWOn; wherein 1 represents a methyl group at the left end, V represents a vinyl group, C represents a 1, 4-cyclohexylene group, P represents a 1, 4-phenylene group, W represents a 2, 3-difluoro-1, 4-phenylene group, O represents an oxygen substituent, and n represents the number of carbon atoms of the alkyl group at the right end, for example, n is "2", that is, it means that the alkyl group is ethyl.
The shorthand numbers of test items in the following examples and comparative examples are as follows:
cp clearing point (nematic phase-isotropic phase transition temperature, DEG C)
Delta n optical anisotropy (589 nm,20 ℃ C.)
Dielectric anisotropy of delta epsilon (1 kHz,20 ℃ C.)
LTS (-40 ℃) low temperature storage time (-40 ℃, h)
K 11 Spring constant of splay (20 ℃ C.)
K 33 Flexural spring constant (20 ℃ C.)
γ 1 Rotational viscosity (mPa.s, 20 ℃ C.)
Tau response time (ms)
Tr penetration rate (%)
CR contrast ratio (light state transmittance/dark state transmittance)
Wherein, cp: measured by an MP70 melting point instrument;
an: using Abbe refractometer under sodium light (589 nm) source, and testing at 20deg.C;
Δε：Δε＝ε ∥ -ε ⊥ Wherein ε is ∥ For dielectric constant parallel to the molecular axis ε ⊥ For dielectric constants perpendicular to the molecular axis, test conditions when Δε < 0: 20 ℃, 1kHz, VA type test box, box thickness 6 μm, test conditions when delta epsilon > 0: 20 ℃ and 1kHz, TN type test box and box thickness of 7 μm;
γ 1 : the liquid crystal display is obtained by testing by using an LCM-2 liquid crystal physical property evaluation system; test conditions: the temperature is 20 ℃, the voltage is 160-260V, and the thickness of the test box is 20 mu m;
K 11 and K 33 : the capacitance-voltage characteristic (C-V curve) of the liquid crystal material was tested and calculated using an LCR meter and an antiparallel friction box when Δε > 0, test conditions: parallel rubbing cells, cell thickness 7 μm, v=0.1-20V, capacitance-voltage characteristic curves (C-V curves) of liquid crystal materials were tested and calculated using LCR instrument and VA test cell when Δε < 0, test conditions: VA-type test cell, cell thickness 6 μm, v=0.1-20V;
LTS (-40 ℃): placing a nematic liquid crystal medium in a glass bottle, preserving at a constant temperature of-40 ℃, and recording the time when crystal precipitation is observed; for example ". Gtoreq.192" means that no crystals are precipitated yet after storage for 192h at-40 ℃;
tr: using a DMS 505 photoelectric comprehensive tester to test a V-T curve of the dimming device, taking the maximum value of transmittance on the V-T curve as the transmittance of liquid crystal, wherein a test box is of an IPS type, and the thickness of the box is 3.5 mu m;
τ: test using DMS 505 tester at 20 ℃ under the following conditions: 20 ℃, V90 driving, IPS type test box with box thickness of 3.5 μm;
CR: testing the transmittance of the liquid crystal cell, namely Tr, at 255 gray-scale voltage and 0 gray-scale voltage respectively using a DMS 505 tester 255 And Tr 0 From Tr 255 /Tr 0 The test conditions were: IPS type test kit with a thickness of 3.5 μm at 20 ℃.
The compounds used in the examples below may be synthesized by known methods or obtained commercially. These synthetic techniques are conventional and the resulting liquid crystal compositions are tested to meet electronic standards.
Liquid crystal compositions were prepared in accordance with the proportions of the respective liquid crystal compositions in the following examples. The liquid crystal composition is prepared by mixing the components according to a prescribed proportion by a conventional method in the art, such as heating, ultrasonic wave, suspension and the like.
The 5PGP (NA) used in the following examples represents an ultraviolet absorber, and has a structural formula shown below:
Figure BDA0003373113790000261
comparative example 1
Each compound and its mass percentage as listed in table 2 were formulated into a liquid crystal composition to which ultraviolet absorber 5PGP (NA) was added in an amount of 0.3 wt% to prepare a liquid crystal composition of comparative example 1, and filled between two substrates of a liquid crystal display for performance test.
TABLE 2 formulation of liquid Crystal composition and results of Performance parameter test
Figure BDA0003373113790000262
Example 1
Liquid crystal compositions were prepared according to the respective compounds listed in table 3 and their mass percentages, and an ultraviolet absorber 5PGP (NA) was added to the liquid crystal composition at a weight percentage of 0.3% to prepare a liquid crystal composition of example 1, and filled between two substrates of a liquid crystal display for performance test.
TABLE 3 formulation of liquid Crystal compositions and results of Performance parameter tests
Figure BDA0003373113790000263
Figure BDA0003373113790000271
In comparison with comparative example 1, the liquid crystal composition of example 1 of the present invention contains the compound of formula I and the compound of formula II and is compounded with other components to give a liquid crystal composition having an appropriate absolute value of dielectric anisotropy, a larger optical anisotropy, a lower rotational viscosity, a larger elastic constant K (K 11 And K 33 ) Higher penetration, better contrast, shorter response time, smaller rotational viscosity, and longer low temperature storage time.
Example 2
Liquid crystal compositions were prepared according to the respective compounds listed in table 4 and their mass percentages, and an ultraviolet absorber 5PGP (NA) was added to the liquid crystal composition at a weight percentage of 0.3% to prepare a liquid crystal composition of example 2, and filled between two substrates of a liquid crystal display for performance test.
TABLE 4 formulation of liquid Crystal compositions and results of Performance parameter tests
Figure BDA0003373113790000272
Example 3
Liquid crystal compositions were prepared according to the respective compounds listed in table 5 and their mass percentages, and an ultraviolet absorber 5PGP (NA) was added to the liquid crystal composition at a weight percentage of 0.3% to prepare a liquid crystal composition of example 3, and filled between two substrates of a liquid crystal display for performance test.
TABLE 5 formulation of liquid Crystal composition and results of Performance parameter testing
Figure BDA0003373113790000273
Example 4
Liquid crystal compositions were prepared according to the respective compounds listed in table 6 and their mass percentages, and an ultraviolet absorber 5PGP (NA) was added to the liquid crystal composition at a weight percentage of 0.3% to prepare a liquid crystal composition of example 4, and filled between two substrates of a liquid crystal display for performance test.
TABLE 6 formulation of liquid Crystal composition and results of Performance parameter testing
Figure BDA0003373113790000281
Example 5
Liquid crystal compositions were prepared according to the respective compounds listed in table 7 and their mass percentages, and an ultraviolet absorber 5PGP (NA) was added to the liquid crystal composition at a weight percentage of 0.3% to prepare a liquid crystal composition of example 5, and filled between two substrates of a liquid crystal display for performance test.
TABLE 7 formulation of liquid Crystal composition and results of Performance parameter test
Figure BDA0003373113790000282
Example 6
Liquid crystal compositions were prepared according to the respective compounds listed in table 8 and their mass percentages, and an ultraviolet absorber 5PGP (NA) was added to the liquid crystal composition at a weight percentage of 0.3% to prepare a liquid crystal composition of example 6, and filled between two substrates of a liquid crystal display for performance test.
TABLE 8 formulation of liquid Crystal compositions and results of Performance parameter testing
Figure BDA0003373113790000283
Figure BDA0003373113790000291
Example 7
Liquid crystal compositions were prepared according to the respective compounds listed in table 9 and their mass percentages, and an ultraviolet absorber 5PGP (NA) was added to the liquid crystal composition at a weight percentage of 0.3% to prepare a liquid crystal composition of example 7, and filled between two substrates of a liquid crystal display for performance test.
TABLE 9 formulation of liquid Crystal composition and results of Performance parameter testing
Figure BDA0003373113790000292
Example 8
Liquid crystal compositions were prepared according to the respective compounds listed in table 10 and their mass percentages, and an ultraviolet absorber 5PGP (NA) was added to the liquid crystal composition at a weight percentage of 0.3% to prepare a liquid crystal composition of example 8, and filled between two substrates of a liquid crystal display for performance test.
Table 10 formulation of liquid Crystal composition and results of Performance parameter test
Figure BDA0003373113790000293
Figure BDA0003373113790000301
Example 9
Liquid crystal compositions were prepared according to the respective compounds listed in table 11 and their mass percentages, and an ultraviolet absorber 5PGP (NA) was added to the liquid crystal composition at a weight percentage of 0.3% to prepare a liquid crystal composition of example 9, and filled between two substrates of a liquid crystal display for performance test.
TABLE 11 formulation of liquid Crystal compositions and results of Performance parameter tests
Figure BDA0003373113790000302
Example 10
Liquid crystal compositions were prepared according to the respective compounds listed in table 12 and their mass percentages, and an ultraviolet absorber 5PGP (NA) was added to the liquid crystal composition at a weight percentage of 0.3% to prepare a liquid crystal composition of example 10, and filled between two substrates of a liquid crystal display for performance test.
Table 12 formulation of liquid crystal composition and results of performance parameter test
Figure BDA0003373113790000303
Figure BDA0003373113790000311
In summary, the invention compounds the compound of formula I containing cyclohexene structure with the compound of formula II containing biphenyl structure, so that the liquid crystal composition has higher clear point, better optical anisotropy, proper dielectric anisotropy, lower rotational viscosity, larger elastic constant K value (K 11 ≥15.4，K 33 More than or equal to 17), shorter response time (tau < 25.7 ms), smaller rotational viscosity, quicker response speed, higher transmittance (Tr is more than or equal to 14.50 percent and can reach 15.30 percent), higher contrast (CR is 858-1232), and capability of being stably stored for more than 192 hours at the low temperature of minus 40 ℃. The liquid crystal display device containing the liquid crystal composition has proper threshold voltage, wider use temperature range, better contrast ratio, quicker response speed, higher transmittance and better low-temperature storage stability, and is suitable for a display mode with quick response.
The applicant states that the present invention is described by way of the above examples as a liquid crystal composition and a liquid crystal display device thereof, but the present invention is not limited to the above examples, i.e., it is not meant that the present invention must be practiced in dependence upon the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims (10)

1. A liquid crystal composition, characterized in that the liquid crystal composition comprises:
At least one compound of formula I:
Figure FDA0003373113780000011
and
At least one compound of formula II:
Figure FDA0003373113780000012
wherein R is 0 Represents a linear or branched alkyl radical having 1 to 12 carbon atoms,
Figure FDA0003373113780000013
Figure FDA0003373113780000014
At least two-CH groups, one or not adjacent, of said straight or branched alkyl groups having 1 to 12 carbon atoms 2 -may each be independently replaced by-ch=ch-, -c≡c-, -O-, -CO-O-, or-O-CO-; one or at least two of the foregoing groups, -H, may each independently be substituted with-F or-Cl;
R X represents a haloalkyl group having 1 to 5 carbon atoms, a haloalkoxy group having 1 to 4 carbon atoms, a straight-chain or branched alkyl group having 1 to 12 carbon atoms; at least two-CH groups, one or not adjacent, of said straight or branched alkyl groups having 1 to 12 carbon atoms 2 -may each be independently replaced by-ch=ch-, -c≡c-, -O-, -CO-O-, or-O-CO-;
ring(s)
Figure FDA0003373113780000015
And (C) a ring->
Figure FDA0003373113780000016
Each independently represents->
Figure FDA0003373113780000017
Or one or at least two single bonds in the ring are replaced by double bonds>
Figure FDA0003373113780000018
And at most one ring->
Figure FDA0003373113780000019
Or (R) ring->
Figure FDA00033731137800000110
Representation->
Figure FDA00033731137800000111
R 1 And R is 2 Each independently represents a linear or branched alkyl group having 1 to 12 carbon atoms, or a linear or branched alkenyl group having 2 to 12 carbon atoms;
n 1 and n 2 Each independently represents 0 or 1.
2. The liquid crystal composition according to claim 1, wherein the compound of formula I is selected from the group consisting of:
Figure FDA0003373113780000021
Figure FDA0003373113780000022
and
Figure FDA0003373113780000023
Wherein R is X ' means a straight or branched alkyl group containing 1 to 12 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12) carbon atoms.
3. The liquid crystal composition according to claim 1 or 2, wherein the compound of formula II is selected from the group consisting of:
Figure FDA0003373113780000031
Figure FDA0003373113780000032
and
Figure FDA0003373113780000033
Wherein R is 1 ' and R 2 ' each independently represents a linear alkenyl group having 2 to 6 carbon atoms;
R 1 and R is 2 Each independently represents a straight chain alkyl group containing 1 to 6 carbon atoms.
4. A liquid crystal composition according to any one of claims 1 to 3, characterized in that the mass percentage of the compound of formula I in the liquid crystal composition is 1% to 40%, preferably 3% to 25%;
preferably, the mass percentage of the compound of formula II in the liquid crystal composition is 1% -30%, further preferably 1% -20%.
5. The liquid crystal composition according to any one of claims 1 to 4, further comprising at least one compound of formula N:
Figure FDA0003373113780000034
wherein R is N1 And R is N2 Each independently represents a linear or branched alkyl group having 1 to 12 carbon atoms,
Figure FDA0003373113780000035
At least two-CH groups, one or not adjacent, of said straight or branched alkyl groups having 1 to 12 carbon atoms 2 -may each be independently replaced by-ch=ch-, -c≡c-, -O-, -CO-O-, or-O-CO-;
ring(s)
Figure FDA0003373113780000041
And (C) a ring->
Figure FDA0003373113780000042
Each independently represents->
Figure FDA0003373113780000043
The said
Figure FDA0003373113780000044
One or at least two-CH 2 -can be replaced by-O-, single bonds in one or at least two rings can be replaced by double bonds; said->
Figure FDA0003373113780000045
In which-ch=may be replaced by-n=and one or at least two-H of the foregoing groups may be replaced by-F, -Cl or-CN;
Z N1 and Z N2 Each independently represents a single bond, -CO-O-, -O-CO-, -CH 2 O-、-OCH 2 -、-CH＝CH-、-C≡C-、-CH 2 CH 2 -、-CF 2 CF 2 -、-(CH 2 ) 4 -、-CF 2 O-or-OCF 2 -；
L N1 And L N2 Each independently represents-H, halogen, unsubstituted or halogenated linear alkyl groups containing 1 to 3 carbon atoms;
n N1 represents 0, 1, 2 or 3, n N2 Represents 0 or 1, and 0.ltoreq.n N1 +n N2 Less than or equal to 3; when n is N1 When 2 or 3 is represented, the ring
Figure FDA0003373113780000046
Identical or different, Z N1 The same or different.
6. The liquid crystal composition according to claim 5, wherein the compound of formula N is selected from the group consisting of:
Figure FDA0003373113780000047
Figure FDA0003373113780000051
Figure FDA0003373113780000061
Figure FDA0003373113780000062
and
Figure FDA0003373113780000063
Preferably, the mass percentage of the compound of formula N in the liquid crystal composition is 1% -60%.
7. The liquid crystal composition according to any one of claims 1 to 6, further comprising at least one compound of formula M:
Figure FDA0003373113780000071
wherein R is M1 And R is M2 Each independently represents a linear or branched alkyl group having 1 to 12 carbon atoms,
Figure FDA0003373113780000072
At least two-CH groups, one or not adjacent, of said straight or branched alkyl groups having 1 to 12 carbon atoms 2 -may each be independently replaced by-ch=ch-, -c≡c-, -O-, -CO-O-, or-O-CO-;
ring(s)
Figure FDA0003373113780000073
Ring->
Figure FDA0003373113780000074
And (C) a ring->
Figure FDA0003373113780000075
Each independently represents->
Figure FDA0003373113780000076
Figure FDA0003373113780000077
Said->
Figure FDA0003373113780000078
At least two-CH of one or not adjacent 2 -can be replaced by-O-; the said
Figure FDA0003373113780000079
In one or at least two rings-ch=may be replaced by-n=Instead, at most one-H may be substituted by halogen; and the compound of formula M does not contain +.>
Figure FDA00033731137800000710
Is of a structure of (2);
Z M1 and Z M2 Each independently represents a single bond, -CO-O-, -O-CO-, -CH 2 O-、-OCH 2 -、-C≡C-、-CH＝CH-、-CH 2 CH 2 -or- (CH) 2 ) 4 -；
n M Represents 0, 1 or 2;
when n is M When 2 is represented, the ring
Figure FDA00033731137800000711
Identical or different, Z M2 The same or different;
preferably, the compound of formula M is selected from the group consisting of:
Figure FDA00033731137800000712
Figure FDA0003373113780000081
Figure FDA0003373113780000091
Figure FDA0003373113780000092
and
Figure FDA0003373113780000093
Preferably, the mass percentage of the compound of formula M in the liquid crystal composition is 0.1% -70%.
8. The liquid crystal composition according to any one of claims 1 to 7, further comprising at least one compound of formula B:
Figure FDA0003373113780000094
wherein R is B1 And R is B2 Each independently represents-H, halogen, a straight or branched alkyl group containing 1 to 12 carbon atoms; at least two-CH groups, one or not adjacent, of said straight or branched alkyl groups having 1 to 12 carbon atoms 2 -may each be independently replaced by-ch=ch-, -c≡c-, -S-, -O-, -CO-O-, or-O-CO-; one or at least two of the foregoing groups, -H, may each independently be substituted with-F or-Cl;
ring(s)
Figure FDA0003373113780000095
And (C) a ring->
Figure FDA0003373113780000096
Each independently represents->
Figure FDA0003373113780000097
Figure FDA0003373113780000098
Said->
Figure FDA0003373113780000099
At least two-CH of one or not adjacent 2 -can be replaced by-O-, single bonds in one or at least two rings can be replaced by double bonds; said->
Figure FDA00033731137800000910
Figure FDA00033731137800000911
-ch=in one or at least two rings may be replaced by-n=in one or more rings; one or at least two of the foregoing groups-H may be replaced by-F, -Cl, -CN, -CH 3 or-OCH 3 Substitution;
Z B1 and Z B2 Each independently represents a single bond, -O-, -S-, -CO-O-, -O-CO-, -CH 2 O-、-OCH 2 -、-CH＝CH-、-C≡C-、-CH 2 CH 2 -、-CF 2 CF 2 -、-(CH 2 ) 4 -、-CF 2 O-or-OCF 2 -；
Y B1 And Y B2 Each independently represents-H, halogen, unsubstituted or halogenated linear alkyl groups having 1 to 3 carbon atoms, unsubstituted or halogenated linear alkoxy groups having 1 to 3 carbon atoms;
X B represents-O-, -S-, -CO-, -CF 2 -, -NH-or-NF-;
n B1 and n B2 Each independently represents 0, 1 or 2; when n is B1 When 2 is represented, the ring
Figure FDA0003373113780000101
Identical or different, Z B1 Identical or different, when n B2 When 2 is indicated, the ring->
Figure FDA0003373113780000102
Identical or different, Z B2 The same or different;
preferably, the compound of formula B is selected from the group consisting of:
Figure FDA0003373113780000103
Figure FDA0003373113780000111
and
Figure FDA0003373113780000112
Wherein Y is B3 And Y B4 Each independently represents-H, -F, -Cl, -CN, -CH 3 or-OCH 3 ；
Preferably, the mass percentage of the compound of formula B in the liquid crystal composition is 0.1% -30%.
9. The liquid crystal composition according to any one of claims 1-8, wherein the liquid crystal composition further comprises at least one additive.
10. A liquid crystal display device comprising the liquid crystal composition according to any one of claims 1 to 9.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107384439A (en) * 2017-07-27 2017-11-24 默克专利股份有限公司 Liquid crystal media and the liquid crystal display for including it
CN109943347A (en) * 2017-12-20 2019-06-28 石家庄诚志永华显示材料有限公司 Liquid-crystal composition and liquid crystal display element
CN110951493A (en) * 2018-09-27 2020-04-03 默克专利股份有限公司 liquid crystal medium
CN113072962A (en) * 2019-12-17 2021-07-06 默克专利股份有限公司 Liquid-crystalline medium
CN113088294A (en) * 2019-12-19 2021-07-09 默克专利股份有限公司 Liquid-crystalline medium, liquid-crystal display comprising same and compound
CN115003779A (en) * 2020-01-23 2022-09-02 默克专利股份有限公司 Liquid-crystalline medium

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107384439A (en) * 2017-07-27 2017-11-24 默克专利股份有限公司 Liquid crystal media and the liquid crystal display for including it
CN109943347A (en) * 2017-12-20 2019-06-28 石家庄诚志永华显示材料有限公司 Liquid-crystal composition and liquid crystal display element
CN110951493A (en) * 2018-09-27 2020-04-03 默克专利股份有限公司 liquid crystal medium
CN113072962A (en) * 2019-12-17 2021-07-06 默克专利股份有限公司 Liquid-crystalline medium
CN113088294A (en) * 2019-12-19 2021-07-09 默克专利股份有限公司 Liquid-crystalline medium, liquid-crystal display comprising same and compound
CN115003779A (en) * 2020-01-23 2022-09-02 默克专利股份有限公司 Liquid-crystalline medium

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