CN115247071A - Liquid crystal composition and liquid crystal display device comprising same - Google Patents

Liquid crystal composition and liquid crystal display device comprising same Download PDF

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CN115247071A
CN115247071A CN202110460176.5A CN202110460176A CN115247071A CN 115247071 A CN115247071 A CN 115247071A CN 202110460176 A CN202110460176 A CN 202110460176A CN 115247071 A CN115247071 A CN 115247071A
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liquid crystal
ring
independently
carbon atoms
crystal composition
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CN115247071B (en
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姚利芳
贺笛
丁文全
徐爽
吴婷
潘帝可
赵飞
赵李亮
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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
    • 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
    • C09K19/46—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing esters
    • 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 comprising the same. The liquid crystal composition has a large vertical dielectric-to-dielectric ratio, a high average elastic constant, a high penetration rate and a long low-temperature storage time on the basis of maintaining proper optical anisotropy, proper dielectric anisotropy and proper clearing points, so that a liquid crystal display device containing the liquid crystal composition has high contrast, high penetration rate and high low-temperature storage stability, is a liquid crystal material with high overall performance, is suitable for multiple display modes such as IPS (in-plane switching) and NFFS (NFFS), and has a wide application prospect.

Description

Liquid crystal composition and liquid crystal display device comprising same
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 comprising the same.
Background
The liquid crystal material is a mixture of organic rod-shaped small molecular compounds which have liquid fluidity and crystal anisotropy at a certain temperature. Liquid crystal display devices operate by utilizing optical anisotropy and dielectric anisotropy of liquid crystal materials themselves, and are currently widely used. The liquid crystal display device is classified into: PC (phase change), TN (twisted nematic), STN (super twisted nematic), DS (dynamic scattering), FLC (ferroelectric liquid crystal), GH (guest-host), ECB (electrically controlled birefringence), OCB (optically compensated bend), IPS (in-plane switching), VA (vertical alignment), FFS (fringe field switching), FPA (field-induced photo-alignment), and the like.
In the early 70 s of the last century, experimental studies have been conducted on the basic electro-optical characteristics of IPS (in-plane switching) mode of uniformly aligned and twisted nematic liquid crystals, which is characterized in that a pair of electrodes are formed on the same substrate, and the other substrate has no electrode, and the arrangement of liquid crystal molecules is controlled by a lateral electric field applied between the pair of electrodes, so that this mode can also be called a lateral field mode. In the IPS mode, nematic liquid crystal molecules are uniformly arranged in parallel between two substrates, and two polarizing plates are orthogonally arranged. In the IPS mode, when an electric field is not applied, incident light is blocked by two orthogonal polarizing plates to be in a dark state, and when an electric field is applied, liquid crystal molecules rotate to cause retardation, so that light leaks from the two orthogonal polarizing plates. The panel adopting IPS mode has the advantages of large visual angle and accurate color restoration, but has the disadvantages of serious light leakage and slow response speed
With the wide application of TFT-type LCDs, the performance requirements of TFT-type LCDs are continuously increasing, and high display image quality requires 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 means that liquid crystal materials are required to have higher contrast and transmittance, higher elastic constant, higher dielectric constant and low temperature reliability, and improvement of these properties is required.
Transmittance equation T ^ Δ |/ε according to IPS mode ⊥ (T represents transmittance, ". Alpha." represents "inverse proportion" relationship, ε ⊥ Showing a dielectric constant in a direction perpendicular to a molecular axis), it is known that, in order to increase the transmittance of liquid crystal, it is possible to attempt to reduce Δ ∈ of a liquid crystal medium, but generally, the adjustment range of a driving voltage of the same product is limited. In addition, the liquid crystal molecules will tilt in the Z-axis direction under the action of the vertical component of the fringe field, resulting in the change of the optical anisotropy thereof, according to the formula
Figure BDA0003042114870000011
(where χ is an included angle between an optical axis of the liquid crystal layer and an optical axis of the polarizer, Δ n is optical anisotropy, d is cell gap, and λ is wavelength), it can be considered that T is affected by effective Δ n × d, and if the transmittance of the positive liquid crystal is to be improved, Δ n × d can be increased, but the retardation design of each product is fixed.
On the other hand, based on the conventional IPS-LCD light leakage performance test, those skilled in the art find that the main causes of the light leakage problem of the liquid crystal display device include: light scattering (LC scattering), rubbing uniformity (rubbing uniformity), color filter light leakage (CF/TFT scattering), and polarization ability (polarization ability), wherein light scattering accounts for 63% of the contributing factors to light leakage performance.
According to the following relationship:
Figure BDA0003042114870000012
wherein d represents the cell gap, n e Which represents the refractive index of the extraordinary light,n o indicating the ordinary refractive index.
In order to improve the light scattering of the liquid crystal material, it is necessary to increase the average elastic constant K ave (wherein, K is ave ＝(K 11 +K 22 +K 33 ) Div 3) to improve light scattering, at elevated K ave In this case, light leakage of the liquid crystal material can be reduced.
Further, the Contrast (CR) and the luminance (L) are related as follows:
CR＝L 255 /L 0 ×100％；
wherein L is 255 Is at on-state brightness, L 0 Is off state brightness. It can be seen that what significantly affects CR should be L 0 A change in (c). In the off state, L 0 Independent of the dielectric properties of the liquid crystal molecules and of the LC Scattering of the liquid crystal material itself; the smaller the LC Scattering, L 0 The smaller the ratio, the more the CR is significantly improved.
In view of the above, the conventional method for improving the contrast and transmittance can be considered from the following two aspects: (1) By keeping the dielectric anisotropy Delta epsilon of the liquid crystal composition constant, by increasing epsilon ⊥ The transmittance can be effectively improved; (2) Improving the average elastic constant K of the liquid crystal composition ave The value of (b) makes the degree of order of liquid crystal molecules better and the light leakage less, thereby improving the transmittance.
Patent application CN110499162a discloses dibenzo-based compounds represented by the following formula:
Figure BDA0003042114870000021
the dibenzo compound has the advantages of large elastic constant, large dielectric coefficient, very stable structure and the like due to the characteristic structure of benzofuran or benzothiophene, and can provide very excellent performance in TFT liquid crystals with fast response, high transmittance and the like. However, dibenzo compounds have a disadvantage that their use amount is limited, and excessive use of dibenzo compounds leads to a decrease in compatibility and a decrease in performance such as storage at low temperatures.
Therefore, the development of a liquid crystal composition with better intersolubility, low-temperature storage performance and higher comprehensive performance to improve the overall performance of a liquid crystal material is a research focus in the field.
Disclosure of Invention
In view of the defects of the prior art, an object of the present invention is to provide a liquid crystal composition and a liquid crystal display device comprising the same, wherein the liquid crystal composition has a larger average elastic constant, a higher vertical dielectric-to-dielectric ratio, a better transmittance and a longer low-temperature storage time on the basis of maintaining a proper optical anisotropy, a proper dielectric anisotropy and a proper clearing point.
In order 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 BDA0003042114870000022
and
at least one compound of formula II:
Figure BDA0003042114870000023
wherein R is 1 Represents a straight or branched alkyl group having 1 to 12 carbon atoms,
Figure BDA0003042114870000026
Figure BDA0003042114870000024
X R Represents a single bond, -O-or-S-; at least two-CH which are not adjacent to one or more of the straight chain or branched chain alkyl groups containing 1 to 12 carbon atoms 2 -may be independently replaced by-CH = CH-, -O-or-S-, respectively; the described
Figure BDA0003042114870000025
One or not adjacent to each otherAt least two rings having-CH 2 -may be independently replaced by-CH = CH-, -O-or-S-, respectively; one or at least two-H of the foregoing groups may each be independently substituted with halo.
Wherein, when X R When the group represents a single bond, the group is,
Figure BDA0003042114870000031
respectively represent
Figure BDA0003042114870000032
R 2 Represents a straight or branched alkyl group having 1 to 12 carbon atoms,
Figure BDA0003042114870000033
Figure BDA0003042114870000034
One of the foregoing groups or at least two-CH groups which are not adjacent 2 -each may be independently replaced by-CH = CH-, -O-or-S-, one or at least two-H each may be independently substituted by halogen; r 2 Is connected to O at the right end of formula I through a C atom.
m 1 And m 2 Each independently represents an integer of 0 to 6, and may be, for example, 0, 1, 2, 3, 4, 5 or 6.
Wherein m is 1 =0 for X R Directly linked to the ring structure by a single bond.
R 3 represents-H, halogen, straight or branched alkyl having 1 to 12 carbon atoms,
Figure BDA0003042114870000035
The straight chain or branched chain alkyl containing 1 to 12 carbon atoms,
Figure BDA0003042114870000036
Or at least two-CHs which are not adjacent to each other 2 -can be independently replaced by-CH = CH-, -C ≡ C-, -O-, -S-, -CO-O-, or-O-CO-; one or at least two-H of the foregoing groups may each be independently substituted with halogen.
R 4 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 haloalkenyloxy containing 2 to 5 (e.g. 2, 3, 4 or 5) carbon atoms.
Ring (C)
Figure BDA0003042114870000037
Ring (C)
Figure BDA0003042114870000038
Ring (C)
Figure BDA0003042114870000039
And ring
Figure BDA00030421148700000310
Each independently represent
Figure BDA00030421148700000311
The above-mentioned
Figure BDA00030421148700000312
Or at least two-CHs which are not adjacent to each other 2 -may be replaced by-O-, one or at least two of the ring single bonds may be replaced by double bonds; the above-mentioned
Figure BDA00030421148700000313
May be replaced by-N = and one or at least two-H may be substituted by halogen, -CN or methyl.
Ring (C)
Figure BDA00030421148700000314
To represent
Figure BDA00030421148700000315
Z 1 、Z 2 、Z 3 And Z 4 Each is independent of othersRepresents a single bond, -CH in a standing position 2 CH 2 -、-CF 2 CF 2 -、-CO-O-、-O-CO-、-CH 2 O-、-OCH 2 -、-CH＝CH-、-CF＝CF-、-CF 2 O-or-OCF 2 -。
Y 1 And Y 2 Each independently represents-H, -F or-Cl.
X represents-O-, -S-or-CO-.
n represents an integer of 1 to 12, and may be, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.
n 1 、n 2 And n 3 Each independently represents 0, 1 or 2; when n is 1 When representing 2, a ring
Figure BDA0003042114870000041
Same or different, Z 1 The same or different; when n is 2 When representing 2, a ring
Figure BDA0003042114870000042
Same or different, Z 2 The same or different; when n is 3 When representing 2, a ring
Figure BDA0003042114870000043
Same or different, Z 3 The same or different.
n 4 Represents 0, 1, 2 or 3; when n is 4 When represents 2 or 3, a ring
Figure BDA0003042114870000044
Same or different, Z 4 The same or different.
In the present invention, "may be independently replaced by … …" means that they may or may not be replaced, i.e., they may or may not be replaced, and they are within the protection scope of the present invention; "independently each occurrence is replaced by … …"; also, the positions of "substitution" and "substitution" are arbitrary.
In the invention, short straight lines at one side or two sides of a group represent access bonds and do not represent methyl; for example
Figure BDA0003042114870000045
A short straight line on the left side of the body,
Figure BDA0003042114870000046
short straight lines on both sides of O-.
In the present invention, the halogen includes fluorine, chlorine, bromine, iodine, or the like; the same meanings are given below in relation to the same descriptions.
In the present invention, the 1 to 12 carbon atoms may be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms.
In the liquid crystal composition provided by the invention, the compound of the formula I with a specific structure is introduced and is cooperated with the compound of the formula II, so that the liquid crystal composition has higher low-temperature stability, good low-temperature storage performance, higher elastic constant and larger vertical dielectric-dielectric ratio (epsilon) on the basis of maintaining proper optical anisotropy, proper dielectric anisotropy, proper clearing point and other performances ⊥ A/[ Delta ] epsilon value) and higher transmittance, the overall performance of the liquid crystal material is obviously improved, and the liquid crystal material is suitable for various display modes such as IPS (in-plane switching) and NFFS (NFFS).
In a preferred embodiment, R is 1 Represents a straight-chain alkyl group having 1 to 6 (e.g., 1, 2, 3, 4, 5 or 6) carbon atoms straight-chain alkoxy having 1 to 6 (e.g. 1, 2, 3, 4, 5 or 6) carbon atoms,
Figure BDA0003042114870000047
Figure BDA0003042114870000048
Wherein m is 1 Represents an integer of 0 to 4, and may be, for example, 0, 1, 2, 3 or 4.
In a preferred embodiment, R is 1 Represents a linear alkoxy group having 1 to 6 (e.g., 1, 2, 3, 4, 5 or 6) carbon atoms,
Figure BDA0003042114870000049
In a preferred embodiment, R is 2 Represents a straight or branched alkyl group containing 1 to 6 (e.g. 1, 2, 3, 4, 5 or 6) carbon atoms; one or at least two-H of the linear or branched alkyl groups containing 1 to 6 carbon atoms may each be independently substituted with halogen.
In a preferred embodiment, R is 2 Represents an unsubstituted or halogenated straight chain alkyl group containing 1 to 6 (e.g., 1, 2, 3, 4, 5, or 6) carbon atoms, illustratively including but not limited to: methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, perfluoromethyl, perfluoroethyl or-CH 2 -CF 3 And the like.
In a preferred embodiment, n represents an integer of 1 to 6, and may be, for example, 1, 2, 3, 4, 5 or 6.
In a preferred embodiment, Y is 1 And Y 2 Both represent-F.
In a preferred embodiment, X represents-O-or-S-.
In a preferred embodiment, n is 1 And n 2 Both represent 0.
In a preferred embodiment, the compound of formula I is selected from the group consisting of:
Figure BDA0003042114870000051
Figure BDA0003042114870000052
and
Figure BDA0003042114870000053
wherein X represents-O-or-S-.
In a preferred embodiment, R 1 Means containing 1-6 (e.g. 1)Straight chain alkyl of 2, 3, 4, 5 or 6 carbon atoms, straight chain alkoxy containing 1 to 6 (e.g. 1, 2, 3, 4, 5 or 6) carbon atoms,
Figure BDA0003042114870000054
In a preferred embodiment, the content of the compound of formula I is preferably adjusted such that the liquid crystal composition comprising the same has a large vertical dielectric to dielectric ratio, a high average elastic constant, a high transmittance and a long low-temperature storage time.
In a preferred embodiment, the content of the compound of formula I in the liquid crystal composition is 0.1-30% by mass, such as 0.3%, 0.5%, 0.8%, 1%, 3%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25% or 28%, and the specific values therebetween are not exhaustive, and for brevity and clarity, the invention is not intended to be limited to the specific values included in the scope.
In a preferred embodiment, R is 3 Represents a straight 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 which are not adjacent to one or more of the straight chain or branched chain alkyl groups containing 1 to 8 carbon atoms 2 -may be independently replaced by-CH = CH-or-O-, respectively.
In a preferred embodiment, R is 3 Denotes a straight chain alkyl group having 1 to 6 (e.g. 1, 2, 3, 4, 5 or 6) carbon atoms, a straight chain alkoxy group having 1 to 6 (e.g. 1, 2, 3, 4, 5 or 6) carbon atoms or a straight chain alkenyl group having 2 to 6 (e.g. 2, 3, 4, 5 or 6) carbon atoms.
In a preferred embodiment, R is 4 represents-F, -CF 3 or-OCF 3 。
In a preferred embodiment, the ring
Figure BDA0003042114870000061
And ring
Figure BDA0003042114870000062
Each independently represent
Figure BDA0003042114870000063
The above-mentioned
Figure BDA0003042114870000064
Or at least two-CHs which are not adjacent to each other 2 -may be replaced by-O-, and one or at least two of the ring single bonds may be replaced by a double bond; the above-mentioned
Figure BDA0003042114870000065
One or at least two of-H may be substituted by-F or methyl.
In a preferred embodiment, Z is 3 And Z 4 Each independently represents a single bond, -CH 2 CH 2 -、-CH 2 O-、-OCH 2 -、-CF 2 O-or-OCF 2 -。
In a preferred embodiment, the compound of formula II is selected from the group consisting of:
Figure BDA0003042114870000066
Figure BDA0003042114870000071
Figure BDA0003042114870000072
and
Figure BDA0003042114870000081
wherein R is v And R w Each independently represents-CH 2 -or-O-.
L D11 、L D12 、L D13 、L D14 、L D21 、L D22 、L D21 '、L D22 '、L D24 、L D25 And L D26 Each independently represents-H or-F.
L D23 And L D23 ' independently of each other represents-H or-CH 3 。
v and w each independently represent 0 or 1.
In a preferred embodiment, the compound of formula II is selected from any one of the compounds of formula II-1, the compounds of formula II-4, the compounds of formula II-5, the compounds of formula II-13 or the compounds of formula II-14 or a combination of at least two thereof.
In a preferred embodiment, the liquid crystal composition preferably comprises at least one compound of formula II-13 in order to obtain a large vertical dielectric to dielectric ratio, a high average elastic constant, a high transmittance and a long low temperature storage time.
In a preferred embodiment, the content of the compound of formula II is preferably adjusted such that the liquid crystal composition comprising the same has a large ratio of vertical dielectric to dielectric, a high average elastic constant, a high transmittance, and a long low-temperature storage time.
In a preferred embodiment, the content of the compound of formula II in the liquid crystal composition is 0.1-30% by mass, for example, 0.3%, 0.5%, 0.8%, 1%, 3%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25% or 28%, and the specific values therebetween are not exhaustive, and for brevity and conciseness, the invention does not provide an exhaustive list of specific values included in the range.
In a preferred embodiment, the liquid crystal composition further comprises at least one compound of formula M:
Figure BDA0003042114870000082
wherein R is M1 And R M2 Each independently represents a compound containing 1 to 12 (e.g., 1, 2, 3, b),4, 5, 6, 7, 8, 9, 10, 11 or 12) carbon atoms, straight or branched alkyl, C,
Figure BDA0003042114870000083
Figure BDA0003042114870000084
At least two-CH which are not adjacent to one or more of the straight chain or branched chain alkyl groups containing 1 to 12 carbon atoms 2 -may be independently replaced by-CH = CH-, -C.ident.C-, -O-, -CO-O-or-O-CO-, respectively.
Ring (C)
Figure BDA0003042114870000085
Ring (C)
Figure BDA0003042114870000086
And ring
Figure BDA0003042114870000087
Each independently represent
Figure BDA0003042114870000088
Figure BDA0003042114870000089
The above-mentioned
Figure BDA00030421148700000810
Or at least two-CHs which are not adjacent to each other 2 -may be replaced by-O-, one or at least two of the ring single bonds may be replaced by double bonds; the above-mentioned
Figure BDA00030421148700000811
May be replaced by-N = and at most one-H may be substituted by halogen.
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 representing 2, a ring
Figure BDA0003042114870000091
Same 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 BDA0003042114870000092
Figure BDA0003042114870000101
Figure BDA0003042114870000111
in a preferred embodiment, R is M1 And R M2 Each independently represents a straight chain alkyl group containing 1 to 8 (e.g., 1, 2, 3, 4, 5, 6, 7 or 8) carbon atoms, a straight chain alkoxy group containing 1 to 8 (e.g., 1, 2, 3, 4, 5, 6, 7 or 8) carbon atoms, or a straight chain alkenyl group containing 2 to 8 (e.g., 2, 3, 4, 5, 6, 7 or 8) carbon atoms.
In a preferred embodiment, the compound of formula M is selected from any one of the compounds of formula M-1, the compounds of formula M-2, the compounds of formula M-6, the compounds of formula M-12, the compounds of formula M-13, the compounds of formula M-16, the compounds of formula M-19, the compounds of formula M-21, the compounds of formula M-26, the compounds of formula M-28 or the compounds of formula M-30, or a combination of at least two thereof.
In a preferred embodiment, the liquid crystal composition comprises at least one alkenyl-terminated compound of formula M-1 and/or compound of formula M-12 in order to obtain a higher vertical dielectric to dielectric ratio, a higher average elastic constant, a higher transmittance and a longer storage time at low temperature.
In a preferred embodiment, the liquid crystal composition comprises at least one R for obtaining a larger vertical dielectric to dielectric ratio, a higher average elastic constant, a higher transmittance and a longer low-temperature storage time M1 A compound of formula M-19 which is alkenyl.
In a preferred embodiment, the liquid crystal composition comprises any one or a combination of at least two selected from the group consisting of a compound of formula M-26, a compound of formula M-28, and a compound of formula M-30, in order to obtain a larger vertical dielectric to dielectric ratio, a higher average elastic constant, a higher transmittance, and a longer low-temperature storage time.
In a preferred embodiment, the content of the compound of formula M is adjusted such that the liquid crystal composition comprising the same has a large vertical dielectric to dielectric ratio, a high average elastic constant, a high transmittance and a long low-temperature storage time.
In a preferred embodiment, the content of the compound of formula M in the liquid crystal composition is 0.1-80% by mass, for example, 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%, 58%, 60%, 62%, 65%, 68%, 70%, 72%, 75% or 78%, and the specific values therebetween are not limited to space and are not exhaustive, and for the sake of brevity, the invention does not include the specific values included in the range.
In a preferred embodiment, the liquid crystal composition further comprises at least one compound of formula B:
Figure BDA0003042114870000112
wherein R is B1 And R B2 Each independently represents a straight chain containing 1 to 12 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12) carbon atomsA chain or branched alkyl group,
Figure BDA0003042114870000113
Figure BDA0003042114870000114
m B Represents an integer of 0 to 6, and may be, for example, 0, 1, 2, 3, 4, 5 or 6; one of the foregoing groups or at least two-CH not adjacent 2 -may be independently replaced by-CH = CH-, -C ≡ C-, -S-, -CO-O-, or-O-CO-, respectively, and one or at least two-H may be independently substituted by-F or-Cl, respectively; r B1 And R B2 Are all connected to O in formula B through a C atom.
Ring(s)
Figure BDA0003042114870000121
And ring
Figure BDA0003042114870000122
Each independently represent
Figure BDA0003042114870000123
Figure BDA0003042114870000124
The above-mentioned
Figure BDA0003042114870000125
Or at least two-CHs which are not adjacent to each other 2 -may be replaced by-O-, one or at least two of the ring single bonds may be replaced by double bonds; the above-mentioned
Figure BDA0003042114870000126
Can be replaced by-N = and one or at least two-H can be replaced by-F, -Cl, -CN, -CH 3 or-OCH 3 And (4) substitution.
Z B1 And Z B2 Each independently represents a single bond, -O-, or-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, unsubstituted or halogenated straight chain alkoxy groups containing 1 to 3 (e.g. 1, 2 or 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 representing 2, a ring
Figure BDA0003042114870000127
Same or different, Z B1 Same or different when n B2 When representing 2, a ring
Figure BDA0003042114870000128
Same 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 BDA0003042114870000129
Figure BDA0003042114870000131
and
Figure BDA0003042114870000132
wherein Y is B3 And Y B4 Each independently represents-H, -F, -Cl, -CN, -CH 3 or-OCH 3 。
In a preferred embodiment, R B1 And R B2 Each independently represents a straight-chain alkyl group having 1 to 6 (e.g., 1, 2, 3, 4, 5 or 6) carbon atoms,
Figure BDA0003042114870000133
m B Represents an integer of 0 to 4, and may be, for example, 0, 1, 2, 3 or 4; preferably, m B Represents 0.
In a preferred embodiment, Z B1 And Z B2 Each independently represents a single bond, -O-, or-S-, -CO-O-, -O-CO-, -CH 2 O-、-OCH 2 -、-CH＝CH-、-C≡C-、-CH 2 CH 2 -、-CF 2 CF 2 -、-CF 2 O-or-OCF 2 -; preferably, Z B1 And Z B2 All represent single bonds.
In a preferred embodiment, X B represents-O-or-S-.
In a preferred embodiment, the liquid crystal composition comprises at least one compound of formula B-1 in order to obtain a large vertical dielectric to dielectric ratio, a high average elastic constant, a high transmittance and a long low-temperature storage time.
In a preferred embodiment, the content of the compound of formula B is adjusted such that the liquid crystal composition comprising it has a large vertical dielectric to dielectric ratio, a high average elastic constant, a high transmittance and a long low-temperature storage time.
In a preferred embodiment, the content of the compound of formula B in the liquid crystal composition is 0.1-30% by mass, such as 0.3%, 0.5%, 0.8%, 1%, 3%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25% or 28%, and the specific values therebetween are not exhaustive, and for brevity and conciseness, the invention is not limited to the specific values included in the range.
In a preferred embodiment, the liquid crystal composition further comprises at least one compound of formula A-1 and/or formula A-2;
Figure BDA0003042114870000134
wherein, the first and the second end of the pipe are connected with each other,R A1 and R A2 Each independently represents a straight 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 BDA0003042114870000135
Figure BDA0003042114870000136
At least two-CH which are not adjacent to one or more of the straight chain or branched chain alkyl groups containing 1 to 12 carbon atoms 2 -may be independently replaced by-CH = CH-, -C ≡ C-, -O-, -CO-O-, or-O-CO-, respectively; one or at least two of the foregoing groups-H may each be independently substituted with-F or-Cl.
Ring (C)
Figure BDA0003042114870000141
Ring(s)
Figure BDA0003042114870000142
Ring (C)
Figure BDA0003042114870000143
And ring
Figure BDA0003042114870000144
Each independently represent
Figure BDA0003042114870000145
The described
Figure BDA0003042114870000146
Or at least two-CHs which are not adjacent to each other 2 -may be replaced by-O-; the above-mentioned
Figure BDA0003042114870000147
May be replaced by a double bond; the above-mentioned
Figure BDA0003042114870000148
In one or at least two rings of-CH = may be replaced by-N = and one or at least two-H may be substituted by-F, -Cl or-CN.
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-、-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, unsubstituted or halogenated straight chain alkyl containing 1 to 3 (e.g. 1, 2 or 3) carbon atoms, halogen.
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, haloalkenyloxy 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 represents 2 or 3, a ring
Figure BDA0003042114870000149
Same or different, Z A11 The same or different; when n is A2 When represents 2 or 3, a ring
Figure BDA00030421148700001410
Same or different, Z A21 The same or different.
n A12 Represents 1 or 2; when n is A12 When represents 2, a ring
Figure BDA00030421148700001411
The same or different.
In a preferred embodiment, the compound of formula a-1 is selected from the group consisting of:
Figure BDA00030421148700001412
Figure BDA0003042114870000151
Figure BDA0003042114870000152
and
Figure BDA0003042114870000153
wherein R is A1 Represents a straight 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 which are not adjacent to one or more of the straight chain or branched chain alkyl groups containing 1 to 8 carbon atoms 2 -may be independently replaced by-CH = CH-, -C ≡ C-, -O-, -CO-O-, or-O-CO-, respectively; one or at least two of the foregoing groups-H may each be independently substituted with-F or-Cl.
L A11 、L A12 、L A14 、L A15 And L A16 Each independently represents-H or-F.
L A13 represents-H or-CH 3 。
X A1 represents-F, -CF 3 or-OCF 3 。
In a preferred embodiment, the content of the compound of formula a-1 in the liquid crystal composition is 0.1 to 50% by mass, for example, 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% by mass.
In a preferred embodiment, the compound of formula a-2 is selected from the group consisting of:
Figure BDA0003042114870000161
Figure BDA0003042114870000171
Figure BDA0003042114870000172
and
Figure BDA0003042114870000173
wherein R is A2 Represents a straight 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 which are not adjacent to one or more of the straight chain or branched chain alkyl containing 1 to 8 carbon atoms 2 -may be independently replaced by-CH = CH-, -C ≡ C-, -O-, -CO-O-, or-O-CO-, respectively; one or at least two of the foregoing groups-H may each be independently substituted with-F or-Cl.
L A21 、L A22 、L A23 、L A24 And L A25 Each independently represents-H or-F.
X A2 represents-F, -CF 3 、-OCF 3 or-CH 2 CH 2 CH＝CF 2 。
In a preferred embodiment, the liquid crystal composition comprises at least one compound of formula A-2-5 in order to obtain a large vertical dielectric to dielectric ratio, a high average elastic constant, a high transmittance and a long low temperature storage time.
In a preferred embodiment, the content of the compound of formula a-2 in the liquid crystal composition is 0.1 to 50% by mass, and may be, for example, 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%, or the like.
In a preferred embodiment, the content of the compound of formula a-2-5 in the liquid crystal composition is 0.1-15% by mass, for example, 0.3%, 0.5%, 0.8%, 1%, 3%, 5%, 8%, 10%, 12% or the like.
In addition to the above compounds, the liquid crystal composition of the present invention may contain conventional nematic liquid crystals, smectic liquid crystals, cholesteric liquid crystals, polymerizable monomers, additives, and the like; the additives include dopants, antioxidants, ultraviolet absorbers, infrared absorbers, or light stabilizers, etc.
Possible dopants which are preferably added to the liquid crystal composition of the invention are shown below:
Figure BDA0003042114870000174
Figure BDA0003042114870000181
Figure BDA0003042114870000182
and
Figure BDA0003042114870000183
in some embodiments of the invention, the dopant comprises 0% to 5% by weight of the liquid crystal composition; preferably, the dopant accounts for 0.01-1% of the liquid crystal composition by weight.
Further, additives such as an antioxidant and a light stabilizer used in the liquid crystal composition of the present invention are preferably as follows:
Figure BDA0003042114870000191
Figure BDA0003042114870000201
Figure BDA0003042114870000211
wherein n represents a positive integer of 1 to 12.
Preferably, the light stabilizer is selected from the group consisting of the light stabilizers shown below:
Figure BDA0003042114870000212
in some embodiments of the invention, the light stabilizer comprises from 0% to 5% by weight of the total liquid crystal composition; preferably, the light stabilizer accounts for 0.01 to 1 percent of the total weight of the liquid crystal composition; more preferably, the light stabilizer is 0.01 to 0.1 percent of the total weight of the liquid crystal composition.
In a second aspect, the present invention provides a liquid crystal display device comprising the liquid crystal composition according to the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
the liquid crystal composition provided by the invention has a larger vertical dielectric-dielectric ratio, a higher average elastic constant, a higher penetration rate, a better contrast ratio and a longer low-temperature storage time on the basis of maintaining proper optical anisotropy, proper dielectric anisotropy and a proper clearing point through the mutual cooperation of the compound of the formula I and the compound of the formula II, is a liquid crystal material with better overall performance, is suitable for various display modes such as IPS (in-plane switching) and NFFS (NFFS), and has a wide application prospect.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
For convenience of expression, in each of the following examples and comparative examples, the group structures of the components in the liquid crystal composition are represented by the codes shown in Table 1:
TABLE 1
Figure BDA0003042114870000213
Figure BDA0003042114870000221
Compounds of the following formula are exemplified:
Figure BDA0003042114870000222
the structural formula is represented by the code listed in table 1, and can be expressed as: nD2PUQUF; wherein D represents 1,3-dioxane-2,5 base, 2 represents ethylene, P represents 1,4-phenylene, U represents 2,6-difluoro-1,4-phenylene, and Q represents
Figure BDA0003042114870000231
F represents a fluorine substituent and n represents the number of carbon atoms of the left alkyl group, for example n is "2", i.e. the alkyl group is ethyl.
The abbreviations for the test items in the following examples and comparative examples are as follows:
cp clearing Point (nematic phase-isotropic phase transition temperature, ° C)
Δ n optical anisotropy (589nm, 25 ℃ C.)
Delta epsilon dielectric anisotropy (1kHz, 25 ℃ C.)
ε ⊥ Dielectric constant perpendicular to molecular axis (1kHz, 25 ℃ C.)
ε ⊥ The ratio of/. DELTA.. Epsilon.vertical dielectric to dielectric (1kHz, 25 ℃ C.)
K 11 Splay spring constant (25 ℃ C.)
K 22 Distortion elastic constant (25 ℃ C.)
K 33 Flexural modulus of elasticity constant (25 ℃ C.)
K ave Average elastic constant (25 ℃ C.)
Tr (%) penetration (%)
LTS (-30 ℃) low-temperature storage time (-30 ℃, h)
Wherein the content of the first and second substances,
cp: measured by an MP70 melting point instrument;
Δ n: testing with Abbe refractometer under sodium lamp (589 nm) at 25 deg.C;
Δε：Δε＝ε ∥ -ε ⊥ wherein, epsilon ∥ Is a dielectric constant parallel to the molecular axis,. Epsilon ⊥ For the dielectric constant perpendicular to the molecular axis, test conditions: the temperature is 25 ℃, the frequency is 1kHz, the test box is TN type, and the box thickness is 7 μm;
K 11 、K 22 and K 33 : using an LCR instrument and an antiparallel rubbing box, testing the C-V curve of the liquid crystal and calculating to obtain the C-V curve; and (3) testing conditions are as follows: a 7 μm antiparallel friction cell, V = 0.1-20V;
K ave ＝
Figure DA00030421148735133983
(K 11 +K 22 +K 33 )；
tr: using a DMS 505 photoelectric comprehensive tester to test a V-T curve of the dimming device, taking the maximum value of the transmittance on the V-T curve as the transmittance of liquid crystal, wherein the test box is of a positive IPS type and has the thickness of 3.5 mu m;
LTS (-30 ℃): the liquid crystals were poured into glass bottles and stored in an incubator at-30 ℃ for the time recorded when crystal precipitation was observed.
The compounds used in the following examples can be synthesized by known methods or obtained commercially. These synthesis techniques are conventional and the resulting liquid crystal compositions are tested for compliance with electronic compound standards.
Illustratively, the compounds of formula I are prepared by the following synthetic routes:
Figure BDA0003042114870000232
Figure BDA0003042114870000241
wherein R is 1 、R 2 Ring of
Figure BDA0003042114870000242
Ring (C)
Figure BDA0003042114870000243
Z 1 、Z 2 、Y 1 、Y 2 、n 1 、n 2 And n has the same defined range as in formula I;
x represents-O-or-S-;
U 1 and U 2 Each independently represents halogen, and more preferably chlorine, bromine or iodine.
The following compounds of formula I are exemplified, and the specific synthetic methods are as follows:
synthesis example 1
2OB (S) O4O1 (formula I-4), the molecular structure is as follows:
Figure BDA0003042114870000244
50g of compound A1-1 (4 '-ethoxy-2', 3,3 '-trifluoro- [1,1' -biphenyl ] -2-ol), 50.7g of dimethylaminothioformyl chloride and 37.6g of triethylamine are fully dissolved by 200mL of isododecane, reflux reaction is carried out for 18h at the temperature of 165 ℃ under the protection of nitrogen, the temperature is controlled to be 25 ℃, suction filtration is carried out, recrystallization is carried out by ethanol, suction filtration is carried out, and a filter cake is dried to obtain 35g of brown solid of compound B1-1 (3-ethoxy-4,6-difluorodibenzo [ B, d ] thiophene), wherein the yield is 71%.
Figure BDA0003042114870000245
Under the protection of nitrogen, 600mL of tetrahydrofuran is added into a 2L three-necked flask, and 200g of the compound B1-1 obtained in the step (1) is added under stirring. And cooling to-80 ℃, dropwise adding 454mL of n-butyllithium under stirring at a controlled temperature, and after dropwise adding, keeping the temperature and reacting for 2 hours. Controlling the temperature to be minus 80 to minus 70 ℃, dripping 214g of triisopropyl borate, and controlling the temperature to react for 2 hours after finishing dripping. Adding 10% diluted hydrochloric acid to quench the reaction, distilling the reaction product, and pulping the reaction product at room temperature by using petroleum ether to obtain off-white solid C1-1 ((7-ethoxy-4,6-difluorodibenzo [ b, d ] thiophen-3-yl) boric acid) of which the total amount is 186.5g and the yield is 80%.
Figure BDA0003042114870000246
And (3) adding 600mL of tetrahydrofuran into a 2L three-necked bottle, adding 150g of the compound C1-1 obtained in the step (2), dropwise adding 170g of hydrogen peroxide while stirring, controlling the temperature to be below 50 ℃, and reacting at room temperature for 4 hours. Adding sodium bisulfite to quench until no oxidation occurs, distilling, and pulping with petroleum ether at room temperature to obtain brown solid D1-1 (7-ethoxy-4,6-difluorodibenzo [ b, D ] thiophene-3-ol) 102g in total, with a yield of 74.7%.
Figure BDA0003042114870000251
Adding 200mL of N, N-Dimethylformamide (DMF) into a 250mL three-necked bottle, adding 1-30g of the compound D obtained in the step (3), 17g of 1-chloro-4-methoxybutane, 29.8g of potassium carbonate and 1.8g of potassium iodide while stirring, heating to 70 ℃, reacting for 5 hours, adding 500mL of water into a reaction system, pulping, adding 300mL of ethanol, pulping at room temperature, drying at 50 ℃, passing through a silica gel column, concentrating, and recrystallizing petroleum ether to obtain 35g of a target product white solid with the yield of 89.7%.
Structural characterization of the target product by Mass Spectrometry (MS): 45 (54%), 55 (11%), 87 (100%), 223 (10%), 252 (21%), 280 (4%), 366 (6%).
Synthesis example 2
2OB (O) O4O1 (formula I-4), the molecular structure is as follows:
Figure BDA0003042114870000252
the preparation method differs from the synthesis example 1 only in that the step (1) is different:
Figure BDA0003042114870000253
under the protection of nitrogen, DMF is added into a 500mL three-necked bottle, and 240g K is added under stirring 2 CO 3 And 240g of Compound A1-1 (4 '-ethoxy-2', 3,3 '-trifluoro- [1,1' -biphenyl]-2-alcohol), heating to 130 ℃, and carrying out reflux reaction for 6h. Adding 400mL of water and 400mL of Ethyl Acetate (EA) into the reaction solution for extraction, and extracting the water layer twice by using 800mL of EA; the organic layers were combined, stirred and dried over anhydrous sodium sulfate for 30min, and then concentrated under reduced pressure at 30 ℃ to constant weight to give 195g of B1-2 (3-ethoxy-4,6-difluorodibenzo [ B, d ] as a white solid]Furan), yield 88%.
The reaction of compound B1-2 according to steps (2) to (4) in synthesis example 1 gave 33g of the objective product as a white solid in a yield of 83%.
The target product was structurally characterized by Mass Spectrometry (MS): 45 (55%), 55 (10%), 87 (100%), 207 (10%), 236 (20%), 264 (3%), 350 (7%).
Liquid crystal compositions were prepared according to the following compounding ratios of the liquid crystal compositions in the examples. The liquid crystal composition is prepared by a conventional method in the art, such as mixing in a prescribed ratio by heating, ultrasonic wave, suspension, etc.
Example 1
A liquid crystal composition having the components and performance parameters shown in table 2:
TABLE 2
Figure BDA0003042114870000254
Figure BDA0003042114870000261
Comparative example 1
A liquid crystal composition having the components and performance parameters shown in table 3:
TABLE 3
Figure BDA0003042114870000262
As can be seen from the comparison of example 1 with comparative example 1, the liquid crystal composition of the present invention has a larger vertical dielectric to dielectric ratio and a larger K value while maintaining a suitable optical anisotropy, a suitable clearing point and a suitable dielectric anisotropy ave Values, higher penetration and longer low temperature storage time.
Example 2
A liquid crystal composition having the components and performance parameters shown in table 4:
TABLE 4
Figure BDA0003042114870000263
Figure BDA0003042114870000271
Example 3
A liquid crystal composition having the components and performance parameters shown in table 5:
TABLE 5
Figure BDA0003042114870000272
Example 4
A liquid crystal composition having the components and performance parameters shown in table 6:
TABLE 6
Figure BDA0003042114870000273
Figure BDA0003042114870000281
Example 5
A liquid crystal composition having the components and performance parameters shown in table 7:
TABLE 7
Figure BDA0003042114870000282
Example 6
A liquid crystal composition having the components and performance parameters shown in table 8:
TABLE 8
Figure BDA0003042114870000283
Figure BDA0003042114870000291
Example 7
A liquid crystal composition having the components and performance parameters shown in table 9:
TABLE 9
Figure BDA0003042114870000292
Example 8
A liquid crystal composition having the components and performance parameters shown in table 10:
TABLE 10
Figure BDA0003042114870000293
As can be seen from the above examples, the liquid crystal composition of the present invention maintains proper optical anisotropy by the mutual synergy between the compound of formula I and the compound of formula IIHas a larger vertical dielectric to dielectric ratio epsilon based on a proper clearing point and proper dielectric anisotropy ⊥ The value of the/delta epsilon reaches 1.15-1.56, and the average elastic constant (K) is higher ave Not less than 12.2), higher penetration rate, tr not less than 15.4%, longer low-temperature storage time, and can be stably stored for more than 240h at the low temperature of minus 30 ℃, so that the liquid crystal display device containing the liquid crystal display device has better contrast, better penetration rate and better low-temperature storage stability, and the overall performance of the liquid crystal device is improved.
The applicant states that the present invention is illustrated by the above examples to a liquid crystal composition of the present invention and a liquid crystal display device comprising the same, but the present invention is not limited to the above examples, i.e. it is not meant that the present invention must be implemented by the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. A liquid crystal composition, comprising:
at least one compound of formula I:
Figure FDA0003042114860000011
and
at least one compound of formula II:
Figure FDA0003042114860000012
wherein R is 1 Represents a linear or branched alkyl group having 1 to 12 carbon atoms,
Figure FDA0003042114860000013
Figure FDA0003042114860000014
X R Represents a single bond, -O-or-S-; at least two-CH which are not adjacent to one or more of the straight chain or branched chain alkyl groups containing 1 to 12 carbon atoms 2 -may be independently replaced by-CH = CH-, -O-, or-S-, respectively; the above-mentioned
Figure FDA0003042114860000015
Figure FDA0003042114860000016
Or non-adjacent at least two rings of-CH 2 -may be independently replaced by-CH = CH-, -O-or-S-, respectively; one or at least two-H of the foregoing groups may each be independently substituted with halogen;
R 2 represents a straight or branched alkyl group having 1 to 12 carbon atoms,
Figure FDA0003042114860000017
Figure FDA0003042114860000018
One of the foregoing groups or at least two-CH groups which are not adjacent 2 -each may be independently replaced by-CH = CH-, -O-or-S-, one or at least two-H each may be independently substituted by halogen;
m 1 and m 2 Each independently represents an integer of 0 to 6;
R 3 represents-H, halogen, straight or branched alkyl having 1 to 12 carbon atoms,
Figure FDA0003042114860000019
Figure FDA00030421148600000110
The straight chain or branched chain alkyl containing 1 to 12 carbon atoms,
Figure FDA00030421148600000111
Or non-adjacent toAt least two-CH 2 -may be independently replaced by-CH = CH-, -C ≡ C-, -O-, -S-, -CO-O-, or-O-CO-, respectively; one or at least two-H of the foregoing groups may each be independently substituted with halo;
R 4 represents halogen, haloalkyl containing 1 to 5 carbon atoms, haloalkoxy containing 1 to 5 carbon atoms, haloalkenyl containing 2 to 5 carbon atoms or haloalkenyloxy containing 2 to 5 carbon atoms;
ring (C)
Figure FDA0003042114860000021
Ring (C)
Figure FDA0003042114860000022
Ring (C)
Figure FDA0003042114860000023
And ring
Figure FDA0003042114860000024
Each independently represent
Figure FDA0003042114860000025
The above-mentioned
Figure FDA0003042114860000026
Or at least two-CHs which are not adjacent to each other 2 -may be replaced by-O-, one or at least two of the ring single bonds may be replaced by double bonds; the above-mentioned
Figure FDA0003042114860000027
May be replaced by-N = and one or at least two-H may be substituted by halogen, -CN or methyl;
ring(s)
Figure FDA0003042114860000028
Represent
Figure FDA0003042114860000029
Z 1 、Z 2 、Z 3 And Z 4 Each independently represents a single bond, -CH 2 CH 2 -、-CF 2 CF 2 -、-CO-O-、-O-CO-、-CH 2 O-、-OCH 2 -、-CH＝CH-、-CF＝CF-、-CF 2 O-or-OCF 2 -；
Y 1 And Y 2 Each independently represents-H, -F or-Cl;
x represents-O-, -S-or-CO-;
n represents an integer of 1 to 12;
n 1 、n 2 and n 3 Each independently represents 0, 1 or 2; when n is 1 When represents 2, a ring
Figure FDA00030421148600000210
Same or different, Z 1 The same or different; when n is 2 When representing 2, a ring
Figure FDA00030421148600000211
Same or different, Z 2 The same or different; when n is 3 When representing 2, a ring
Figure FDA00030421148600000212
Same or different, Z 3 The same or different;
n 4 represents 0, 1, 2 or 3; when n is 4 When represents 2 or 3, a ring
Figure FDA0003042114860000031
Same or different, Z 4 The same or different.
2. The liquid crystal composition according to claim 1, wherein n represents an integer of 1 to 6;
preferably, said Y is 1 And Y 2 Both represent-F;
preferably, said X represents-O-or-S-;
preferably, said n is 1 And n 2 Both represent 0.
3. Liquid crystal composition according to claim 1 or 2, characterized in that the compound of formula I is selected from the group consisting of:
Figure FDA0003042114860000032
Figure FDA0003042114860000033
and
Figure FDA0003042114860000034
wherein X represents-O-or-S-.
4. The liquid crystal composition according to any one of claims 1 to 3, wherein the compound of formula II is selected from the group consisting of:
Figure FDA0003042114860000041
Figure FDA0003042114860000051
Figure FDA0003042114860000052
and
Figure FDA0003042114860000053
wherein R is v And R w Each independently represents-CH 2 -or-O-;
L D11 、L D12 、L D13 、L D14 、L D21 、L D22 、L D21 '、L D22 '、L D24 、L D25 and L D26 Each independently represents-H or-F;
L D23 and L D23 ' independently of each other represents-H or-CH 3 ；
v and w each independently represent 0 or 1.
5. Liquid crystal composition according to any one of claims 1 to 4, characterized in that it further comprises at least one compound of formula M:
Figure FDA0003042114860000061
wherein R is M1 And R M2 Each independently represents a straight or branched alkyl group having 1 to 12 carbon atoms,
Figure FDA0003042114860000062
At least two-CH which are not adjacent to one or more of the straight chain or branched chain alkyl groups containing 1 to 12 carbon atoms 2 -may be independently replaced by-CH = CH-, -C ≡ C-, -O-, -CO-O-, or-O-CO-, respectively;
ring (C)
Figure FDA0003042114860000063
Ring (C)
Figure FDA0003042114860000064
And ring
Figure FDA0003042114860000065
Each independently represent
Figure FDA0003042114860000066
Figure FDA0003042114860000067
The above-mentioned
Figure FDA0003042114860000068
Or at least two-CHs that are not adjacent to each other 2 -may be replaced by-O-, one or at least two of the ring single bonds may be replaced by double bonds; the above-mentioned
Figure FDA0003042114860000069
May be replaced by-N = and at most one-H may be substituted by halogen;
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 representing 2, a ring
Figure FDA00030421148600000610
Same or different, Z M2 The same or different.
6. Liquid crystal composition according to any one of claims 1 to 5, characterized in that it further comprises at least one compound of formula B:
Figure FDA00030421148600000611
wherein R is B1 And R B2 Each independently represents a straight or branched alkyl group having 1 to 12 carbon atoms,
Figure FDA0003042114860000071
m B Represents an integer of 0 to 6; one or at least one of the foregoing groups not adjacenttwo-CH 2 -may be independently replaced by-CH = CH-, -C ≡ C-, -S-, -CO-O-, or-O-CO-, respectively, and one or at least two-H may be independently substituted by-F or-Cl, respectively;
ring (C)
Figure FDA0003042114860000072
And ring
Figure FDA0003042114860000073
Each independently represent
Figure FDA0003042114860000074
Figure FDA0003042114860000075
The above-mentioned
Figure FDA0003042114860000076
Or at least two-CHs which are not adjacent to each other 2 -may be replaced by-O-, one or at least two of the ring single bonds may be replaced by double bonds; the above-mentioned
Figure FDA0003042114860000077
Figure FDA0003042114860000078
Can be replaced by-N = and one or at least two-H can be replaced by-F, -Cl, -CN, -CH 3 or-OCH 3 Substitution;
Z B1 and Z B2 Each independently represents a single bond, -O-, or-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 containing 1 to 3 carbon atoms, unsubstituted or halogenated straight-chain alkyl containingStraight-chain alkoxy of 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 representing 2, a ring
Figure FDA0003042114860000079
Same or different, Z B1 Same or different when n B2 When representing 2, a ring
Figure FDA00030421148600000710
Same or different, Z B2 The same or different.
7. The liquid crystal composition according to any one of claims 1 to 6, wherein the mass percentage of the compound of formula I in the liquid crystal composition is 0.1 to 30%; the mass percentage content of the compound of the formula II in the liquid crystal composition is 0.1-30%; the mass percentage content of the compound of the formula M in the liquid crystal composition is 0.1-80%; the mass percentage content of the compound of the formula B in the liquid crystal composition is 0.1-30%.
8. The liquid crystal composition according to any one of claims 1 to 7, further comprising at least one compound of formula a-1 and/or formula a-2;
Figure FDA0003042114860000081
wherein R is A1 And R A2 Each independently represents a linear or branched alkyl group having 1 to 12 carbon atoms,
Figure FDA0003042114860000082
At least two-CH which are not adjacent to one or more of the straight chain or branched chain alkyl groups containing 1 to 12 carbon atoms 2 -may each independently be-CH = CH-,-C.ident.C-, -O-, -CO-O-or-O-CO-substitution; one or at least two of the foregoing groups-H may each be independently substituted with-F or-Cl;
ring (C)
Figure FDA0003042114860000083
Ring (C)
Figure FDA0003042114860000084
Ring (C)
Figure FDA0003042114860000085
And ring
Figure FDA0003042114860000086
Each independently represent
Figure FDA0003042114860000087
The described
Figure FDA0003042114860000088
Or at least two-CHs that are not adjacent to each other 2 -may be replaced by-O-; the above-mentioned
Figure FDA0003042114860000089
One or at least two of the ring single bonds may be replaced by a double bond; the above-mentioned
Figure FDA00030421148600000810
May be replaced by-N = and one or at least two-H may be substituted by-F, -Cl or-CN;
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-、-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,Unsubstituted or halogenated straight-chain alkyl groups containing 1 to 3 carbon atoms, halogen;
X A1 and X A2 Each independently represents halogen, haloalkyl containing 1 to 5 carbon atoms, haloalkoxy containing 1 to 5 carbon atoms, haloalkenyl containing 2 to 5 carbon atoms or haloalkenyloxy containing 2 to 5 carbon atoms;
n A11 and n A2 Each independently represents 0, 1, 2 or 3; when n is A11 When represents 2 or 3, a ring
Figure FDA0003042114860000091
Same or different, Z A11 The same or different; when n is A2 When represents 2 or 3, a ring
Figure FDA0003042114860000092
Same or different, Z A21 The same or different;
n A12 represents 1 or 2; when n is A12 When representing 2, a ring
Figure FDA0003042114860000093
The same or different.
9. Liquid crystal composition according to any of claims 1 to 8, characterized in that it comprises at least one additive.
10. A liquid crystal display device, characterized in that it comprises the liquid crystal composition according to any one of claims 1 to 9.
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Citations (4)

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Publication number Priority date Publication date Assignee Title
JP2000297051A (en) * 1999-04-15 2000-10-24 Chisso Corp 2,7-disubstituted fluorene derivative and liquid crystal composition comprising the same
CN104371744A (en) * 2013-08-02 2015-02-25 默克专利股份有限公司 Liquid crystal medium
TW201925435A (en) * 2017-11-30 2019-07-01 日商捷恩智股份有限公司 Compounds having dibenzothiophene ring, liquid crystal composition, and liquid crystal display element
CN110300746A (en) * 2017-02-27 2019-10-01 捷恩智株式会社 Compound, liquid-crystal composition and liquid crystal display element with dibenzofurans ring

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000297051A (en) * 1999-04-15 2000-10-24 Chisso Corp 2,7-disubstituted fluorene derivative and liquid crystal composition comprising the same
CN104371744A (en) * 2013-08-02 2015-02-25 默克专利股份有限公司 Liquid crystal medium
CN110300746A (en) * 2017-02-27 2019-10-01 捷恩智株式会社 Compound, liquid-crystal composition and liquid crystal display element with dibenzofurans ring
TW201925435A (en) * 2017-11-30 2019-07-01 日商捷恩智股份有限公司 Compounds having dibenzothiophene ring, liquid crystal composition, and liquid crystal display element
JP2021028299A (en) * 2017-11-30 2021-02-25 Jnc株式会社 Compound having dibenzothiophene ring, liquid crystal composition and liquid crystal display element

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