CN115216308A - 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
CN115216308A
CN115216308A CN202110406491.XA CN202110406491A CN115216308A CN 115216308 A CN115216308 A CN 115216308A CN 202110406491 A CN202110406491 A CN 202110406491A CN 115216308 A CN115216308 A CN 115216308A
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liquid crystal
independently
carbon atoms
crystal composition
linear
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杨亚非
贺笛
徐爽
丁文全
王盼盼
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Jiangsu Hecheng Display Technology Co Ltd
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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
    • C09K19/46—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

Abstract

The invention provides a liquid crystal composition and a liquid crystal display device thereof. Compared with the prior art, the liquid crystal composition has higher clearing point, larger absolute value of dielectric anisotropy, smaller threshold voltage, smaller roughness of the surface of a polymer layer, smaller pretilt angle, faster angular velocity, lower polymer residue, higher VHR and better stability of the pretilt angle under the condition of maintaining proper optical anisotropy, proper K value and proper rotational viscosity, so that a liquid crystal display device comprising the liquid crystal composition has wider temperature use range and smaller threshold voltage, can effectively accelerate the production process of a PSA type liquid crystal display, accelerates the production efficiency, can effectively improve the problems of image sticking, uneven display and broken bright points existing in the conventional PSA type liquid crystal display, and has higher practical application value.

Description

Liquid crystal composition and liquid crystal display device thereof
Technical Field
The invention relates to the field of liquid crystal, in particular to a liquid crystal composition and a liquid crystal display device comprising the same.
Background
Liquid Crystal Displays (LCDs) have been rapidly developed due to their small size, light weight, low power consumption and excellent Display quality, and are widely used particularly in portable electronic information products. Liquid crystal displays can be classified into types of PC (phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), IPS (in-plane switching), FFS (fringe field switching), VA (vertical alignment), and PSA (polymer stable alignment), etc., according to the type of display mode.
The PSA type liquid crystal display mode is a mode in which a small amount (more typically < 1wt%, such as 0.3 wt%) of one or more polymerizable compounds is added to a liquid crystal composition, and it can be ensured that liquid crystal molecules are polymerized or crosslinked in situ (typically by UV photopolymerization) in a state having an initial orientation with or without applying a voltage between electrodes after the liquid crystal composition is filled into a liquid crystal cell, thereby fixing the orientation of the liquid crystal molecules. With the continuous development of the PSA type liquid crystal display element, it is applied to various conventional liquid crystal display devices such as known PSA-VA, PSA-OCB, PSA-IPS, PSA-FFS and PSA-TN type liquid crystal displays. In a PSA type liquid crystal display, the liquid crystal composition containing the polymerizable compound is located between two substrates, wherein each substrate is provided with an electrode structure, or both electrode structures are placed on only one of the substrates. In addition, either or both of the substrates may contain an alignment layer disposed on the substrate or electrode structure (if present) to induce initial alignment of the liquid crystal composition. As with conventional liquid crystal displays, PSA type liquid crystal displays can operate as either active matrix displays or passive matrix displays. In the case of active matrix displays the individual pixels are addressed by integrated non-linear active elements, such as transistors, whereas in the case of passive matrix displays the individual pixels are typically addressed according to a multiplexing method known in the art.
After filling the liquid crystal composition into the display device, the polymerizable compounds contained in the liquid crystal composition are typically polymerized or crosslinked in situ by UV photopolymerization by exposing the liquid crystal composition to UV radiation, and preferably while applying a voltage to the electrode structure. As a result of UV exposure, the polymerized or crosslinked polymerizable compounds phase separate from the other compounds in the liquid crystal composition and form polymer layers on the substrate surface, where they cause a pre-tilt angle of the liquid crystal molecules with respect to the substrate. For liquid crystal displays of the PSA-VA, PSA-OCB, PSA-FFS and PSA-TN type, the polymerization of the polymerizable compounds is preferably carried out with application of a voltage; for the liquid crystal display of the PSA-IPS type, voltage may be applied or not, preferably not.
Generally, in the production process of PSA type liquid crystal displays, UV photopolymerization is carried out by two steps:
in a first step (hereinafter referred to as the "UV1 step"), the liquid crystal composition is exposed to UV radiation emitted by a radiation source (hereinafter referred to as the "light source") while applying a voltage to the electrode structure to produce a pre-tilt angle. The more preferred polymerizable compound should produce a smaller pretilt angle in the same time or the same pretilt angle in a shorter UV1 irradiation time (i.e., faster angular velocity) to improve production efficiency, shorten tact time (tact time) in mass production, and reduce costs, while the faster the angular velocity of the polymerizable compound, the more favorable the polymerizable compound can be to complete polymerization, thereby reducing polymer residues. In order to increase the angular velocity, it is preferable to use UV1 radiation of a shorter wavelength, and in order to increase the Voltage Holding Ratio (VHR), it is preferable to use UV1 radiation of a longer wavelength, and thus a faster angular velocity and a higher Voltage Holding Ratio are generally difficult to be compatible;
in the second step (hereinafter referred to as the "UV2 step"), the liquid crystal composition is exposed to UV radiation without applying a voltage to the electrode structure to ensure that any residual polymerizable compound that did not polymerize during the UV1 step is thoroughly polymerized. It is desirable that the variation in the pretilt angle after the UV2 step be as small as possible to reduce the possibility of display unevenness of the PSA type liquid crystal display due to UV process unevenness (unevenness of external conditions such as light, heat, stress, etc.). At the same time, the UV radiation intensity in the UV2 step should be reduced to avoid or reduce negative effects (such as reduced reliability or image sticking).
If the polymer particles are too large and the sizes of the polymer particles are not uniform in the UV1 and UV2 processes, the polymer can be distributed unevenly, so that the problem of 'broken bright spots' of the PSA type liquid crystal display is caused. After UV1 and UV2 processing, the remaining unreacted polymerizable compounds may polymerize in an uncontrolled manner after the display is fabricated and the quality of the image display, for example, residual polymerizable compounds may polymerize under the influence of UV light from the environment or backlight illumination, the pretilt angle may change and the transmittance may change after multiple addressing periods in the on display area, while the pretilt angle and the transmittance may remain unchanged in the off display area, thereby creating an "image sticking" effect.
However, in the prior art, it was found that not all liquid crystal compositions could be perfectly matched with the polymerizable compounds, and after UV1 and UV2 treatment, there were problems that the residual polymerizable compounds could not be completely polymerized or the pretilt angle was slow. Meanwhile, the poor intersolubility of the liquid crystal composition and the polymerizable compound can lead to poor rigidity of a polymer network formed after the polymerizable compound is polymerized, so that when the PSA type liquid crystal display element continuously displays the same pattern for a long time, the structure of the polymer network is changed, the pre-tilt angle of liquid crystal molecules is changed, and the situation of poor display is caused.
However, with the development of technology, the LCD display quality requirement in the LCD display industry is more strict, and especially in the TV industry, the TV size generally increases, the LCD generation line also increases, and the difficulty of the manufacturing process of the large-size LCD panel also increases significantly. Therefore, how to ensure the display quality is an urgent problem to be solved. In addition to the continuous optimization of the panel manufacturing process, the continuous development of liquid crystal materials is also one of the solutions, and especially for the PSA type liquid crystal display, the selection of liquid crystal compositions to be used in combination with polymerizable compounds is a research focus.
Currently, problems common in the production of PSA type liquid crystal displays include the residue or removal of polymerizable compounds and the stability of the pretilt angle. In PSA type liquid crystal displays, after polymerizing the polymerizable compounds by applying UV1 radiation and UV2 radiation to produce the pretilt angle, a small amount of unreacted polymerizable compounds may polymerize in an uncontrolled manner after the display is made, affecting the quality of the display, e.g. the residual polymerizable compounds may polymerize under the influence of UV light from the environment or backlight illumination, the pretilt angle may change over a number of addressing cycles in the switched-on display area, the transmittance may change as well, and the pretilt angle and transmittance may remain unchanged in the switched-off display area, resulting in an "image sticking" effect. Therefore, it is desirable that the polymerizable compound is polymerized as completely as possible during the production of the PSA type liquid crystal display, and the residual polymerizable compound can react in a controlled manner, and the faster the polymerization speed, the more advantageous it is to achieve the desire. Furthermore, it is also desirable that the change in the pre-tilt angle is small after a number of addressing periods have elapsed.
Therefore, it is desired to develop a liquid crystal composition that can satisfy the above requirements at the same time or at least one of the above requirements.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a liquid crystal composition which has higher clearing point, larger absolute value of dielectric anisotropy, smaller threshold voltage and smaller roughness of the surface of a polymer layer, forms smaller pre-tilt angle in the same time under the action of UV1, has faster angular velocity, has lower polymer residue after UV2 action for 70min, has higher VHR after UV2 action for 70min and has better stability of the pre-tilt angle under the condition of maintaining proper optical anisotropy, proper K value and proper rotational viscosity.
The present invention further provides a liquid crystal display device comprising the above liquid crystal composition.
The technical scheme is as follows: in order to achieve the above object, the present invention provides a liquid crystal composition comprising a polymerizable compound, the liquid crystal composition comprising:
at least one compound of the general formula I
Figure BDA0003022486870000031
And
at least one compound of the formula II
Figure BDA0003022486870000032
Wherein the content of the first and second substances,
R 1 represents a linear or branched, halogenated or non-halogenated alkyl group containing from 1 to 5 carbon atoms;
R 2 represents-H, halogen, -CN, -Sp 2 -P 2 Or a linear or branched alkyl group having 1 to 12 carbon atoms,
Figure BDA0003022486870000033
Figure BDA0003022486870000034
Or
Figure BDA0003022486870000035
In which a linear or branched alkyl radical having 1 to 12 carbon atoms,
Figure BDA0003022486870000036
Or
Figure BDA0003022486870000037
One or more-CH's not adjacent to each other 2 -may be independently replaced by-CH = CH-, -C ≡ C-, -O-, -CO-O-, or-O-CO-, respectively, and one or more-H may be independently substituted by-F or-Cl, respectively;
R 3 and R 4 Each independently represents a linear or branched alkyl group having 1 to 12 carbon atoms,
Figure BDA0003022486870000041
Or
Figure BDA0003022486870000042
In which one or more than two non-adjacent-CH groups in the linear or branched alkyl group containing 1-12 carbon atoms 2 -can be independently replaced by-CH = CH-, -C ≡ C-, -O-, -CO-O-or-O-CO-, respectively, in such a way that-O-is not directly linked;
l each independently represents halogen, -CN or-Sp 2 -P 2 ；
L 1 、L 2 And L 3 Each independently represents halogen or-CN;
P 1 and P 2 Each independently represents a polymerizable group;
Sp 1 and Sp 2 Each independently represents a spacer group or a single bond;
Z 1 and Z 2 Each independently represents-O-, -S-, -CO-) -CO-O-, -O-CO-) -O-CO-O-, -CH 2 O-、-OCH 2 -、-CH 2 S-、-SCH 2 -、-CF 2 O-、-OCF 2 -、-CF 2 S-、-SCF 2 -、-(CH 2 ) n -、-CF 2 CH 2 -、-CH 2 CF 2 -、-(CF 2 ) n -、-CH＝CH-、-CF＝CF-、-CH＝CF-、-CF＝CH-、-C≡C-、-CH＝CH-CO-O-、-O-CO-CH＝CH-、-CH 2 CH 2 -CO-O-、-O-CO-CH 2 CH 2 -、-CR 1 R 2 -or a single bond, wherein R 1 And R 2 Each independently represents-H or a linear or branched alkyl group containing 1 to 12 carbon atoms, and n represents an integer of 1 to 4;
r 1 、r 2 、r 3 and r 4 Each independently represents 0, 1, 2 or 3, when r 1 、r 2 And r 3 When each independently represents 2 or 3, L may be the same or different, and when r is 4 When represents 2 or 3，L 3 May be the same or different; and is provided with
n 1 And n 2 Each independently represents 0, 1 or 2, and n 1 +n 2 When n is more than or equal to 1 1 When the expression is shown in the figure 2,
Figure BDA0003022486870000043
may be the same or different when n 2 When the expression is shown in the figure 2,
Figure BDA0003022486870000044
may be the same or different.
In some embodiments of the invention, R 1 Represents a linear alkyl group containing 1 to 5 carbon atoms, e.g. -CH 3 、-C 2 H 5 、-C 3 H 7 、-C 4 H 9 or-C 5 H 11 。
In some embodiments of the invention, R is selected to achieve a lower threshold voltage, a lower polymer layer surface roughness, a lower pre-tilt angle, a faster angulation speed, a lower polymer residue, a higher VHR, and better pre-tilt angle stability 1 Preferably represents-CH 3 。
In some embodiments of the invention, L each independently represents-F, -Cl, -CN, or-Sp 2 -P 2 。
In some embodiments of the invention, r 1 And r 2 Each independently represents 0 or 1.
In some embodiments of the invention, Z 1 And Z 2 Each independently represents a single bond.
In some embodiments of the invention, R 2 represents-Sp 2 -P 2 。
In some embodiments of the invention, the compound of formula I is selected from the group consisting of:
Figure BDA0003022486870000051
Figure BDA0003022486870000052
and
Figure BDA0003022486870000053
wherein, the first and the second end of the pipe are connected with each other,
l 'and L' each independently represent-F, -Cl, -CN or-Sp 2 -P 2 。
In some embodiments of the invention, the compound of formula I is selected from the group consisting of a compound of formula I-1, a compound of formula I-2, a compound of formula I-3, a compound of formula I-4, and a compound of formula I-8.
In some embodiments of the present invention, the compound of formula I is selected from the group consisting of a compound of formula I-1, a compound of formula I-2, a compound of formula I-4, and a compound of formula I-8 in order to obtain a lower threshold voltage, a lower surface roughness of the polymer layer, a lower pre-tilt angle, a faster angular velocity, a lower polymer residue, a higher VHR, and a better pre-tilt angle stability.
The polymerizable groups referred to in the present invention are groups suitable for polymerization reactions (e.g., radical or ionic bond polymerization, polyaddition or polycondensation) or groups suitable for addition or condensation on the polymer backbone. For chain polymerization, polymerizable groups comprising-CH = CH-or-C ≡ C-are particularly preferred, and for ring-opening polymerization, for example oxetane or epoxy groups are particularly preferred.
The term "polymerizable groups" each independently means
Figure BDA0003022486870000061
Figure BDA0003022486870000062
Figure BDA0003022486870000063
or-SH; preferably, a "polymerizable groupThe groups "each independently represent
Figure BDA0003022486870000064
Figure BDA0003022486870000065
or-SH; further preferably, each of the "polymerizable groups" independently represents
Figure BDA0003022486870000066
Or
Figure BDA0003022486870000067
As used herein, the term "spacer group" is known to those skilled in the art and is described in the literature (e.g., pure appl. Chem.2001,73 (5), 888 and c.tscierske, g.pelzl, s.diele, angelw.chem.2004, 116, 6340-6368). As used herein, the term "spacer group" means a flexible group that links a mesogenic group and a polymerizable group in a polymerizable compound. Typical spacer groups are for example- (CH) 2 )p 1 -、-(CH 2 CH 2 O)q 1 -CH 2 CH 2 -、-(CH 2 CH 2 S)q 1 -CH 2 CH 2 -、-(CH 2 CH 2 NH)q 1 -CH 2 CH 2 -、-CR 0 R 00 -(CH 2 ) p1 -or- (SiR) 0 R 00 -O)p 1 -, in which p 1 Represents an integer of 1 to 12, e.g. 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, etc., q 1 Represents an integer of 1 to 3, e.g. 2,R 0 And R 00 Each independently represents-H or a linear or branched alkyl group having 1 to 12 carbon atoms,
Figure BDA0003022486870000068
Or
Figure BDA0003022486870000069
A particularly preferred spacer group is- (CH) 2 )p 1 -、-(CH 2 )p 1 -O-、-(CH 2 )p 1 -O-CO-、-(CH 2 )p 1 -CO-O-、-(CH 2 )p 1 -O-CO-O-or-CR 0 R 00 -(CH 2 ) p1 -。
In some embodiments of the invention, sp 1 And Sp 2 All represent single bonds.
In some embodiments of the invention, the weight percentage of the compound of formula I to the liquid crystal composition is 0.001% to 5%, e.g., 0.005%, 0.01%, 0.05%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, etc.; preferably, the compound of the general formula I accounts for 0.01-2% of the liquid crystal composition by weight.
In some embodiments of the invention, L 1 、L 2 And L 3 Each independently represents-F, -Cl or-CN.
In some embodiments of the invention, the compound of formula II is selected from the group consisting of:
Figure BDA0003022486870000071
Figure BDA0003022486870000072
and
Figure BDA0003022486870000073
in some embodiments of the invention, the compound of formula II is selected from the group consisting of a compound of formula II-1, a compound of formula II-2, a compound of formula II-3, and a compound of formula II-6.
In some embodiments of the present invention, the compound of formula II is preferably a compound of formula II-1 in order to obtain a smaller threshold voltage, a smaller surface roughness of the polymer layer, a smaller pre-tilt angle, a faster angular velocity, a lower polymer residue, a higher VHR and a better pre-tilt angle stability.
In some embodiments of the present invention, the liquid crystal composition comprises at least two compounds of formula II in order to obtain a smaller threshold voltage, a smaller surface roughness of the polymer layer, a smaller pre-tilt angle, a faster angular velocity, a lower polymer residue, a higher VHR and a better pre-tilt angle stability; preferably, the liquid crystal composition comprises at least two compounds of formula II-1.
In some embodiments of the invention, R 3 And R 4 Preferably each independently a linear alkyl group containing 1 to 10 carbon atoms, or a linear alkenyl group containing 2 to 10 carbon atoms; r 3 And R 4 Further preferably each independently a linear alkyl group having 1 to 8 carbon atoms, or a linear alkenyl group having 2 to 8 carbon atoms; r 3 And R 4 Still more preferably each independently a linear alkyl group having 1 to 5 carbon atoms or a linear alkenyl group having 2 to 5 carbon atoms.
In some embodiments of the present invention, it is preferable to adjust the content of the compound of formula II to obtain a smaller threshold voltage, a smaller surface roughness of the polymer layer, a smaller pre-tilt angle, a faster angular velocity, a lower polymer residue, a higher VHR, and a better pre-tilt angle stability.
In some embodiments of the invention, the weight percentage of the compound of formula II to the liquid crystal composition is 0.1% to 30%, e.g., 0.1%, 0.5%, 1%, 2%, 4%, 6%, 8%, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, 30%, etc.; preferably, the compound of the general formula II accounts for 1-25% of the liquid crystal composition by weight.
In the present invention, the expression method of drawing a straight line through a ring structure represents that an access bond of a group is at an arbitrary bondable position of the ring structure.
In some embodiments of the invention, the liquid crystal composition of the invention further comprises at least one compound of formula M:
Figure BDA0003022486870000081
wherein, the first and the second end of the pipe are connected with each other,
R M1 and R M2 Each independently represents a linear or branched alkyl group having 1 to 12 carbon atoms,
Figure BDA0003022486870000082
Or
Figure BDA0003022486870000083
Wherein one or two or more non-adjacent-CH groups of a linear or branched alkyl group having 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 BDA0003022486870000084
Ring (C)
Figure BDA0003022486870000085
And ring
Figure BDA0003022486870000086
Each independently represent
Figure BDA0003022486870000087
Or
Figure BDA0003022486870000088
Wherein
Figure BDA0003022486870000089
Of one or more-CH 2 -may be replaced by-O-and one or more single bonds in the ring may be replaced by double bonds, and wherein
Figure BDA00030224868700000810
At most one-H in (a) 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 -; and is provided with
n M Represents 0, 1 or 2, wherein when n M When =2, ring
Figure BDA00030224868700000811
May be the same or different, Z M2 May be the same or different.
The alkenyl group in the present invention is preferably selected from the group represented by any one of the formulae (V1) to (V9), and particularly preferably the formula (V1), the formula (V2), the formula (V8) or the formula (V9). The groups represented by the formulae (V1) to (V9) are shown below:
Figure BDA0003022486870000091
wherein denotes the carbon atom in the ring structure to which it is bonded.
The alkenyloxy group in the present invention is preferably selected from groups represented by any one of formulae (OV 1) to (OV 9), and particularly preferably formula (OV 1), formula (OV 2), formula (OV 8) or formula (OV 9). The groups represented by formulae (OV 1) to (OV 9) are shown below:
Figure BDA0003022486870000092
wherein denotes the carbon atom in the ring structure to which it is bonded.
In some embodiments of the invention, the compound of formula M is selected from the group consisting of:
Figure BDA0003022486870000093
Figure BDA0003022486870000101
Figure BDA0003022486870000111
and
Figure BDA0003022486870000112
in some embodiments of the invention, the compound of formula M is selected from the group consisting of a compound of formula M-1, a compound of formula M-6, a compound of formula M-12, a compound of formula M-13, a compound of formula M-16, a compound of formula M-19, and a compound of formula M-30.
In some embodiments of the present invention, the compound of formula M is preferably selected from the group consisting of a compound of formula M-1, a compound of formula M-12, and a compound of formula M-16 in order to obtain a smaller threshold voltage, a smaller surface roughness of the polymer layer, a smaller pre-tilt angle, a faster angular velocity, a lower polymer residue, a higher VHR, and a better pre-tilt angle stability.
In some embodiments of the present invention, it is preferable to adjust the content of the compound of formula M to obtain a smaller threshold voltage, a smaller surface roughness of the polymer layer, a smaller pre-tilt angle, a faster angular velocity, a lower polymer residue, a higher VHR, and a better pre-tilt angle stability.
In some embodiments of the invention, the weight percentage of the compound of formula M to the liquid crystal composition is 0.1% to 80%, e.g., 0.1%, 1%, 2%, 4%, 6%, 8%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 20%, 22%, 24%, 25%, 26%, 28%, 30%, 32%, 34%, 35%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, 50%, 52%, 54%, 56%, 58%, 60%, 62%, 64%, 66%, 68%, 70%, 72%, 74%, 76%, 78%, 80%; preferably, the compound of the general formula M accounts for 1-60% of the liquid crystal composition by weight.
In some embodiments of the present invention, the content of the compound of formula M must be properly adjusted depending on desired properties such as solubility at low temperature, transition temperature, electrical reliability, birefringence, process adaptability, drop trace, burn-in, dielectric anisotropy, and the like.
The content of the compound of the formula M is preferably higher in the lower limit and higher in the upper limit when the viscosity of the liquid crystal composition of the present invention needs to be kept low and the response time is short; further, when the liquid crystal composition of the present invention needs to have a high clearing point and good temperature stability, the lower limit value of the content is preferably high and the upper limit value of the content is preferably high; in order to keep the driving voltage low and to increase the absolute value of the dielectric anisotropy, it is preferable that the lower limit of the content is low and the upper limit of the content is low.
In some embodiments of the invention, preferably, R M1 And R M2 Each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 9 carbon atoms, or a linear or branched alkenyl group having 2 to 10 carbon atoms; further preferably, R M1 And R M2 Each independently represents a linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched alkoxy group having 1 to 7 carbon atoms, or a linear or branched alkenyl group having 2 to 8 carbon atoms; still further preferably, R M1 And R M2 Each independently represents a linear or branched alkyl group having 1 to 5 carbon atoms, a linear or branched alkoxy group having 1 to 4 carbon atoms, or a linear or branched alkenyl group having 2 to 5 carbon atoms.
In some embodiments of the invention, preferably, R M1 And R M2 Each independently represents a straight-chain alkenyl group having 2 to 8 carbon atoms; further preferably, R M1 And R M2 Each independently represents a straight-chain alkenyl group having 2 to 5 carbon atoms.
In some embodiments of the invention, preferably, R M1 And R M2 One of which is a linear alkenyl group having 2 to 5 carbon atoms and the other is a linear alkyl group having 1 to 5 carbon atoms.
In some embodiments of the invention, preferably, R M1 And R M2 Each independently represents a linear alkyl group having 1 to 8 carbon atoms, or a linear alkoxy group having 1 to 7 carbon atoms; further preferably, R M1 And R M2 Each independently represents a linear alkyl group having 1 to 5 carbon atoms or a linear alkoxy group having 1 to 4 carbon atoms.
In some embodiments of the invention, preferably, R M1 And R M2 Either of which is a linear alkyl group having 1 to 5 carbon atoms and the other is a linear alkyl group having 1 to 5 carbon atoms or a linear alkoxy group having 1 to 4 carbon atoms; further preferably, R M1 And R M2 Each independently is a linear alkyl group containing 1 to 5 carbon atoms.
In some embodiments of the invention, R is preferred when reliability is a concern M1 And R M2 Are all alkyl; in the case where importance is attached to reduction in volatility of the compound, R is preferably M1 And R M2 Are both alkoxy groups; when importance is attached to the reduction in viscosity, R is preferably M1 And R M2 At least one of which is alkenyl.
In some embodiments of the invention, the liquid crystal composition of the invention further comprises at least one compound of formula N:
Figure BDA0003022486870000121
wherein the content of the first and second substances,
R N1 and R N2 Each independently represents a linear or branched alkyl group having 1 to 12 carbon atoms, a linear or branched alkoxy group having 1 to 11 carbon atoms, a linear or branched alkenyl group having 2 to 12 carbon atoms,
Figure BDA0003022486870000122
Or
Figure BDA0003022486870000123
Ring (C)
Figure BDA0003022486870000124
And a ring
Figure BDA0003022486870000125
Each independently represent
Figure BDA0003022486870000126
Or
Figure BDA0003022486870000127
Wherein
Figure BDA0003022486870000128
One or more-CH of 2 -may be replaced by-O-and one or more single bonds in the ring may be replaced by a double bond, wherein
Figure BDA0003022486870000129
May each be independently substituted with-F, -Cl, or-CN, and one or more rings-CH = may be replaced with-N =;
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, an alkyl group containing 1 to 3 carbon atoms or halogen;
n N1 represents 0, 1, 2 or 3,n N2 Represents 0 or 1, and 0. Ltoreq. N N1 +n N2 Is less than or equal to 3, wherein when n is N1 When =2 or 3, a ring
Figure BDA0003022486870000131
May be the same or different, Z N1 May be the same or different; and is
When n is more than or equal to 0 N1 +n N2 Less than or equal to 1, and when the compound of the general formula N is a biphenyl structure, R N1 And R N2 Not being an alkoxy group at the same time.
In some embodiments of the invention, the compound of formula N is selected from the group consisting of:
Figure BDA0003022486870000132
Figure BDA0003022486870000141
Figure BDA0003022486870000151
Figure BDA0003022486870000152
and
Figure BDA0003022486870000153
in some embodiments of the invention, the compound of formula N is selected from the group consisting of a compound of formula N-2, a compound of formula N-3, a compound of formula N-5, a compound of formula N-6, a compound of formula N-10, a compound of formula N-11, a compound of formula N-13, a compound of formula N-15, a compound of formula N-18, a compound of formula N-24, and a compound of formula N-26.
In some embodiments of the present invention, the compound of formula N is preferably selected from the group consisting of compounds of formula N-2 and compounds of formula N-5 in order to obtain a smaller threshold voltage, a smaller surface roughness of the polymer layer, a smaller pre-tilt angle, a faster angular velocity, a lower polymer residue, a higher VHR and a better pre-tilt angle stability.
In some embodiments of the present invention, the compound of formula N is preferably selected from the group consisting of compounds of formula N-3 and compounds of formula N-6 in order to obtain a smaller threshold voltage, a smaller surface roughness of the polymer layer, a smaller pre-tilt angle, a faster angular velocity, a lower polymer residue, a higher VHR and a better pre-tilt angle stability.
In some embodiments of the present invention, the compound of formula N is preferably selected from the group consisting of compounds of formula N-10 and compounds of formula N-11 in order to obtain a smaller threshold voltage, a smaller surface roughness of the polymer layer, a smaller pre-tilt angle, a faster angular velocity, a lower polymer residue, a higher VHR and a better pre-tilt angle stability.
In some embodiments of the present invention, it is preferable to adjust the content of the compound of formula N to achieve a smaller threshold voltage, a smaller surface roughness of the polymer layer, a smaller pre-tilt angle, a faster angular velocity, a lower polymer residue, a higher VHR, and a better pre-tilt angle stability.
In some embodiments of the invention, the weight percentage of the compound of formula N to the liquid crystal composition is 0.1% to 60%, e.g., 0.1%, 1%, 2%, 4%, 6%, 8%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 20%, 22%, 24%, 25%, 26%, 28%, 30%, 32%, 34%, 35%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, 50%, 52%, 54%, 56%, 58%, 60%; preferably, the compound of the general formula N accounts for 1-55% of the liquid crystal composition by weight.
In some embodiments of the present invention, when it is desired to keep the viscosity of the liquid crystal composition of the present invention low and the response time short, it is preferable that the lower limit value and the upper limit value of the content of the compound of formula N are low; further, when it is necessary to keep the clearing point of the liquid crystal composition of the present invention high and the temperature stability is good, the lower limit value and the upper limit value of the content of the compound of the general formula N are preferably low; in addition, when the absolute value of the dielectric anisotropy is increased in order to keep the driving voltage low, it is preferable that the lower limit value and the upper limit value of the content of the compound of the general formula N are increased.
In some embodiments of the inventionPreferably, R N1 And R N2 Each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 9 carbon atoms, or a linear or branched alkenyl group having 2 to 10 carbon atoms; further preferably, R N1 And R N2 Each independently represents a linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched alkoxy group having 1 to 7 carbon atoms, or a linear or branched alkenyl group having 2 to 8 carbon atoms; even further preferably, R N1 And R N2 Each independently represents a linear or branched alkyl group having 1 to 5 carbon atoms, a linear or branched alkoxy group having 1 to 4 carbon atoms, or a linear or branched alkenyl group having 2 to 5 carbon atoms.
In some embodiments of the invention, the liquid crystal composition of the invention further comprises at least one compound of formula A-1 and/or formula A-2:
Figure BDA0003022486870000171
wherein the content of the first and second substances,
R A1 and R A2 Each independently represents a linear or branched alkyl group having 1 to 12 carbon atoms,
Figure BDA0003022486870000172
Or
Figure BDA0003022486870000173
Wherein one or two or more non-adjacent-CH groups of a linear or branched alkyl group having 1 to 12 carbon atoms 2 -straight-chain or branched alkyl which may be independently replaced by-CH = CH-, -C ≡ C-, -O-, -CO-O-or-O-CO-and which contains 1 to 12 carbon atoms,
Figure BDA0003022486870000174
Or
Figure BDA0003022486870000175
One or more ofH may each be independently substituted by-F or-Cl;
ring (C)
Figure BDA0003022486870000176
Ring (C)
Figure BDA0003022486870000177
Ring(s)
Figure BDA0003022486870000178
And ring
Figure BDA0003022486870000179
Each independently represent
Figure BDA00030224868700001710
Or
Figure BDA00030224868700001711
Wherein
Figure BDA00030224868700001712
And
Figure BDA00030224868700001713
one or more-CH of 2 -may each independently be replaced by-O-, and one or more single bonds in the ring may each independently be replaced by a double bond, wherein
Figure BDA00030224868700001714
And
Figure BDA00030224868700001715
may each be independently substituted with-F, -Cl, or-CN, and-CH = in one or more rings may each be independently substituted with-N =;
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, an alkyl group containing 1 to 3 carbon atoms or halogen;
X A1 and X A2 Each independently represents halogen, straight or branched haloalkyl or haloalkoxy having 1 to 5 carbon atoms, or straight or branched haloalkenyl or haloalkenyloxy having 2 to 5 carbon atoms;
n A11 represents 0, 1, 2 or 3, wherein when n is A11 When =2 or 3, ring
Figure BDA00030224868700001716
May be the same or different, Z A11 May be the same or different;
n A12 represents 1 or 2, wherein when n A12 When =2, ring
Figure BDA00030224868700001717
May be the same or different; and is
n A2 Represents 0, 1, 2 or 3, wherein when n A2 When =2 or 3, a ring
Figure BDA00030224868700001718
May be the same or different, Z A21 May be the same or different.
In some embodiments of the invention, the compound of formula a-1 is selected from the group consisting of:
Figure BDA0003022486870000181
Figure BDA0003022486870000191
Figure BDA0003022486870000192
and
Figure BDA0003022486870000193
wherein the content of the first and second substances,
R A1 represents a linear or branched alkyl group having 1 to 8 carbon atoms, wherein one or two or more-CH groups which are not adjacent to each other are present in the linear or branched alkyl group having 1 to 8 carbon atoms 2 -may be independently replaced by-CH = CH-, -C ≡ C-, -O-, -CO-O-, or-O-CO-, respectively, and one or more-hs present in these groups may be independently substituted by-F or-Cl, respectively;
R v and R 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 ' independently of each other represents-H or-CH 3 ；
X A1 represents-F, -CF 3 or-OCF 3 (ii) a And is
v and w each independently represent 0 or 1.
In some embodiments of the invention, the weight percentage of the compound of formula a-1 to the liquid crystal composition is 0.1% to 50%, e.g., 0.1%, 1%, 2%, 4%, 6%, 8%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 20%, 22%, 24%, 25%, 26%, 28%, 30%, 32%, 34%, 35%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, 50%.
With respect to the preferable content of the compound of the general formula A-1, in the case where the viscosity of the liquid crystal composition of the present invention is kept low and the response speed is high, it is preferable that the lower limit value of the content is slightly low and the upper limit value of the content is slightly low; further, when the clearing point of the liquid crystal composition of the present invention is kept high and the temperature stability is good, it is preferable that the lower limit value of the content is slightly low and the upper limit value of the content is slightly low; in order to increase the absolute value of the dielectric anisotropy while keeping the driving voltage low, it is preferable to make the lower limit of the content slightly higher and the upper limit of the content slightly higher.
In some embodiments of the invention, the compound of formula a-2 is selected from the group consisting of:
Figure BDA0003022486870000201
Figure BDA0003022486870000211
Figure BDA0003022486870000212
and
Figure BDA0003022486870000221
wherein the content of the first and second substances,
R A2 represents a linear or branched alkyl group having 1 to 8 carbon atoms, wherein one or two or more-CH groups which are not adjacent to each other are present in the linear or branched alkyl group having 1 to 8 carbon atoms 2 -may be independently replaced by-CH = CH-, -C ≡ C-, -O-, -CO-O-, or-O-CO-, respectively, and one or more-H present in these groups may be independently substituted by-F or-Cl, respectively;
L A21 、L A22 、L A23 、L A24 and L A25 Each independently represents-H or-F; and is
X A2 represents-F, -CF 3 、-OCF 3 or-CH 2 CH 2 CH＝CF 2 。
In some embodiments of the invention, the weight percentage of the compound of formula a-2 to the liquid crystal composition is 0.1% to 50%, e.g., 0.1%, 1%, 2%, 4%, 6%, 8%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 20%, 22%, 24%, 25%, 26%, 28%, 30%, 32%, 34%, 35%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, 50%.
With respect to the preferable content of the compound of the general formula a-2, in the case where the viscosity of the liquid crystal composition of the present invention is kept low and the response speed is high, it is preferable that the lower limit value of the content is slightly low and the upper limit value of the content is slightly low; further, when the clearing point of the liquid crystal composition of the present invention is kept high and the temperature stability is good, it is preferable that the lower limit value of the content is slightly low and the upper limit value of the content is slightly low; in order to increase the absolute value of the dielectric anisotropy while keeping the driving voltage low, it is preferable to make the lower limit of the content slightly higher and the upper limit of the content slightly higher.
In some embodiments of the present invention, the liquid crystal composition of the present invention further comprises at least one compound of formula B:
Figure BDA0003022486870000222
wherein the content of the first and second substances,
R B1 and R B2 Each independently represents-H, halogen, straight or branched chain alkyl containing 1-12 carbon atoms, wherein one or more than two-CH in the straight or branched chain alkyl containing 1-12 carbon atoms 2 May be independently represented by-CH = CH-in a manner not directly connected to-O-, respectively-C.ident.C-, -O-, -S-, -CO-O-, -O-CO-,
Figure BDA0003022486870000223
or
Figure BDA0003022486870000224
And one or more-H of the foregoing groups may each be independently substituted with-F or-Cl;
ring(s)
Figure BDA0003022486870000225
And ring
Figure BDA0003022486870000226
Each independently represent
Figure BDA0003022486870000227
Or
Figure BDA0003022486870000228
Wherein
Figure BDA0003022486870000229
And
Figure BDA00030224868700002210
one or more-CH of 2 -may each independently be replaced by-O-, and one or more single bonds in the ring may each independently be replaced by a double bond, wherein
Figure BDA0003022486870000231
And
Figure BDA0003022486870000232
can be independently substituted by-F, -Cl, -CN, -CH 3 or-OCH 3 Substituted, and-CH = in one or more rings may each independently be replaced by-N =;
X B represents-O-) -S-, -CO-, -CF 2 -, -NH-or-NF-;
Y B1 and Y B2 Each independently represents-H, halogen, a halogenated or non-halogenated alkyl group having 1 to 3 carbon atoms, or a halogenated or non-halogenated alkoxy group having 1 to 3 carbon atoms;
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 -; and is
n B1 And n B2 Each independently represents 0, 1 or 2, wherein when n B1 When =2, ring
Figure BDA0003022486870000233
May be the same or different, Z B1 May be the same or different, wherein when n is B2 When =2, ring
Figure BDA0003022486870000234
May be the same or different, Z B2 May be the same or different.
In some embodiments of the invention, the compound of formula B is selected from the group consisting of:
Figure BDA0003022486870000235
Figure BDA0003022486870000236
and
Figure BDA0003022486870000241
wherein, the first and the second end of the pipe are connected with each other,
Y B3 and Y B4 Each independently represents-H, -F, -Cl, -CN, -CH 3 or-OCH 3 (ii) a And is provided with
Z B1 ' represents-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 -。
In some embodiments of the present invention, the compound of formula B is preferably a compound of formula B-1 in order to obtain a smaller threshold voltage, a smaller surface roughness of the polymer layer, a smaller pre-tilt angle, a faster angular velocity, a lower polymer residue, a higher VHR and a better pre-tilt angle stability.
In some embodiments of the invention, the weight percentage of the compound of formula B to the liquid crystal composition is 0.1% to 30%, e.g., 0.1%, 1%, 2%, 4%, 6%, 8%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 20%, 22%, 24%, 25%, 26%, 28%, or 30%; preferably, the compound of the general formula B accounts for 0.1-20% of the liquid crystal composition by weight.
In some embodiments of the invention, preferably, R B1 And R B2 Each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 9 carbon atoms, or a linear or branched alkenyl group having 2 to 10 carbon atoms; further preferably, R B1 And R B2 Each independently represents a linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched alkoxy group having 1 to 7 carbon atoms, or a linear or branched alkenyl group having 2 to 8 carbon atoms; still further preferably, R B1 And R B2 Each independently represents a linear or branched alkyl group having 1 to 5 carbon atoms, a linear or branched alkoxy group having 1 to 4 carbon atoms, or a linear or branched alkenyl group having 2 to 5 carbon atoms.
In some embodiments of the invention, the liquid crystal composition of the invention further comprises at least one self-aligning agent of general formula SA:
Figure BDA0003022486870000242
wherein the content of the first and second substances,
R S1 represents Sp-P, a linear or branched alkyl group having 1 to 12 carbon atoms,
Figure BDA0003022486870000243
Or
Figure BDA0003022486870000244
In which one or more than two non-adjacent-CH groups in the linear or branched alkyl group containing 1-12 carbon atoms 2 -is independently replaceable by-CH = CH-, -C.ident.C-, -O-, -CO-O-or-O-CO-and contains 1-12 carbon atomsA linear or branched alkyl group of,
Figure BDA0003022486870000245
Or
Figure BDA0003022486870000246
Each of one or more-H may be independently substituted with-F or-Cl;
R S2 represents an anchor group:
Figure BDA0003022486870000251
p represents 1 or 2, and-Sp when p represents 2 d -X 2 May be the same or different;
o represents 0 or 1;
X 1 and X 2 Each independently represents-H, -OH, -SH, -NH 2 、-NHR 11 、-NR 11 2 、NHC(O)-R 11 、-OR 11 -C (O) OH, -CHO or a linear or branched, halogenated or unhalogenated alkyl group containing 1 to 12 carbon atoms;
wherein, X 1 And X 2 At least one of them is selected from-OH, -SH, -NH 2 、-NHR 11 -C (O) OH or-CHO;
Sp a 、Sp c and Sp d Each independently represents a spacer group or a single bond;
Sp b each independently represent
Figure BDA0003022486870000252
Or
Figure BDA0003022486870000253
Ring(s)
Figure BDA0003022486870000254
And ring
Figure BDA0003022486870000255
Each independently represent
Figure BDA0003022486870000256
Or
Figure BDA0003022486870000257
Wherein
Figure BDA0003022486870000258
Of one or more-CH 2 -may be replaced by-O-and one or more single bonds in the ring may be replaced by double bonds;
ls independently represent-F, -Cl, -CN, -NO 2 、-NCO、-NCS、-OCN、-SCN、-C(O)N(R 0 ) 2 、-C(O)R 0 Straight-chain or branched alkyl containing 1 to 12 carbon atoms,
Figure BDA0003022486870000259
Or
Figure BDA00030224868700002510
Wherein one or two or more non-adjacent-CH groups of a linear or branched alkyl group having 1 to 12 carbon atoms 2 -straight-chain or branched alkyl which may be independently replaced by-CH = CH-, -C ≡ C-, -O-, -CO-O-or-O-CO-and which contains 1 to 12 carbon atoms,
Figure BDA00030224868700002511
Or
Figure BDA00030224868700002512
Each of which may be independently substituted by-F;
R 0 and R 11 Each independently represents a linear or branched alkyl group having 1 to 12 carbon atoms;
p represents a polymerizable group;
sp represents a spacer group or a single bond;
n s1 represents 0 or 1;
n s2 represents 0, 1, 2 or 3, when n s2 When the compound is represented by 2 or 3,
Figure BDA00030224868700002513
may be the same or different;
p s1 、p s2 、p s3 and p s4 Each independently represents 0, 1 or 2, wherein 1. Ltoreq. P s1 +p s2 ≤2；
p s5 And p s6 Each independently represents 0 or 1; and is
Z 1 And Z 2 Each independently represents-O-, -S-, -CO-, -CO-O-, -O-CO-O-, -CH 2 O-、-OCH 2 -、-CH 2 S-、-SCH 2 -、-CF 2 O-、-OCF 2 -、-CF 2 S-、-SCF 2 -、-(CH 2 ) n -、-CF 2 CH 2 -、-CH 2 CF 2 -、-(CF 2 ) n -、-CH＝CH-、-CF＝CF-、-CH＝CF-、-CF＝CH-、-C≡C-、-CH＝CH-CO-O-、-O-CO-CH＝CH-、-CH 2 CH 2 -CO-O-、-O-CO-CH 2 CH 2 -、-CR 1 R 2 -or a single bond, wherein R 1 And R 2 Each independently represents-H or a linear or branched alkyl group having 1 to 12 carbon atoms, and n represents an integer of 1 to 4.
In some embodiments of the invention, the self-aligning agent of general formula SA is selected from the group consisting of:
Figure BDA0003022486870000261
Figure BDA0003022486870000271
Figure BDA0003022486870000281
Figure BDA0003022486870000291
and
Figure BDA0003022486870000292
in some embodiments of the invention, R S2 To represent
Figure BDA0003022486870000293
or-Sp a -X 1 。
In some embodiments of the invention, R S2 To represent
Figure BDA0003022486870000294
or-Sp a -X 1 ，
Wherein Sp d ' represents a spacer group or a single bond;
X 2 ' represents-H, -OH, -SH, -NH 2 、-NHR 11 、-NR 11 2 、NHC(O)-R 11 、-OR 11 -C (O) OH, -CHO or a linear or branched, halogenated or unhalogenated alkyl group containing 1 to 12 carbon atoms, wherein R 11 Represents a linear or branched alkyl group having 1 to 12 carbon atoms.
In some embodiments of the invention, R S2 Selected from the group consisting of:
Figure BDA0003022486870000295
Figure BDA0003022486870000301
wherein, the first and the second end of the pipe are connected with each other,
R S2 bonded to by a dotted line
Figure BDA0003022486870000302
On the ring structure.
In some embodiments of the invention, the weight percentage of the compound of formula SA to the liquid crystal composition is 0.001% to 5%, e.g., 0.001%, 0.005%, 0.05%, 0.1%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, 0.6%, 0.65%, 0.7%, 0.75%, 0.8%, 0.85%, 0.9%, 0.95%, 1.0%, 2%, 3%, 4%, or 5%, etc.; preferably, the compound of the general formula SA accounts for 0.1-2% of the liquid crystal composition by weight.
In addition to the above compounds, the liquid crystal composition of the present invention may contain a conventional nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, dopant, antioxidant, ultraviolet absorber, infrared absorber, polymerizable monomer, light stabilizer, and the like.
Possible dopants which are preferably added to the liquid-crystal compositions according to the invention are shown below:
Figure BDA0003022486870000311
Figure BDA0003022486870000321
and
Figure BDA0003022486870000322
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 BDA0003022486870000323
Figure BDA0003022486870000331
Figure BDA0003022486870000341
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 BDA0003022486870000342
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.
The liquid crystal composition containing a polymerizable compound of the present invention can be polymerized even in the absence of a polymerization initiator, but a polymerization initiator may be contained therein in order to promote the polymerization. As the polymerization initiator, benzoin ethers, benzophenones, acetophenones, benzil ketals, acylphosphine oxides and the like can be exemplified.
The liquid crystal composition of the present invention can be imparted with liquid crystal alignment ability by polymerization of a polymerizable compound in the liquid crystal composition, and the amount of transmitted light in a liquid crystal display device is controlled by utilizing birefringence in the liquid crystal composition.
As for the method of polymerizing the polymerizable compound, since it is desired that the polymerization proceeds rapidly, a method of performing the polymerization by irradiating active energy rays such as ultraviolet rays or electron beams is preferable. When ultraviolet light is used, either a polarized light source or an unpolarized light source may be used. In addition, when the polymerization is performed in a state where the liquid crystal composition is sandwiched between two substrates, at least the substrate on the irradiation surface side must have appropriate transparency to the active energy ray. In addition, polymerization may be performed by irradiating only a specific portion with active energy rays while polymerizing the portion using a mask during light irradiation, and then changing the orientation state of the unpolymerized portion by changing the conditions such as an electric field, a magnetic field, or temperature. In particular, when ultraviolet exposure is performed, it is preferable to perform ultraviolet exposure while applying a voltage to the liquid crystal composition.
The temperature at the time of irradiation with active energy rays such as ultraviolet rays or electron beams is preferably within a temperature range in which the liquid crystal state of the liquid crystal composition of the present invention is maintained. It is preferred to carry out the polymerization at a temperature close to room temperature (i.e., 15-35 ℃). As the lamp generating ultraviolet rays, a metal halide lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, or the like can be used. The wavelength of the ultraviolet light to be irradiated is preferably ultraviolet light having a wavelength outside the absorption wavelength range of the liquid crystal composition, and the ultraviolet light is preferably blocked if necessary. The intensity of the ultraviolet ray to be irradiated is preferably 0.1mW/cm 2 -50 mW/cm 2 . When ultraviolet rays are irradiated, the intensity thereof may be changed, and the time for irradiating ultraviolet rays is appropriately selected according to the intensity of the irradiated ultraviolet rays, preferably 10s to 600s.
As used herein, the terms "tilt" and "tilt angle" will be understood as the tilt alignment of liquid crystal molecules with respect to the surface of a liquid crystal cell in a liquid crystal display device (in the present invention, a PSA type liquid crystal display device is preferred). The tilt angle means an average angle (< 90 °) formed between the longitudinal molecular axis of the liquid crystal molecules (liquid crystal director) and the surface of the outer plate of the liquid crystal cell. A low value of the tilt angle (i.e. a large angle deviating from 90 °) corresponds to a large tilt.
The invention also provides a liquid crystal display device, preferably a PSA type liquid crystal display device, more preferably a PS-VA, PS-OCB, PS-IPS, PS-FFS, PS-UB-FFS, PS-positive-VA or PS-TN type liquid crystal display device, comprising the liquid crystal composition.
Has the beneficial effects that: compared with the prior art, the liquid crystal composition has higher clearing point, larger absolute value of dielectric anisotropy, smaller threshold voltage, smaller roughness of the surface of a polymer layer, smaller pretilt angle, faster angular velocity, lower polymer residue, higher VHR and better stability of the pretilt angle under the condition of maintaining proper optical anisotropy, proper K value and proper rotational viscosity, so that a liquid crystal display device comprising the liquid crystal composition has wider temperature use range and smaller threshold voltage, can effectively accelerate the production process of a PSA type liquid crystal display, accelerates the production efficiency, can effectively improve the problems of image sticking, uneven display and broken bright points existing in the conventional PSA type liquid crystal display, and has higher practical application value.
Detailed Description
The invention will be illustrated with reference to specific embodiments. It should be noted that the following examples are illustrative of the present invention, and are not intended to limit the present invention. Other combinations and various modifications within the spirit or scope of the present invention may be made without departing from the spirit or scope of the present invention.
For ease of expression, in each of the following examples, the group structure of each compound is represented by the code listed in Table 1:
group Structure code for Compounds of Table 1
Figure BDA0003022486870000361
Compounds of the following formula are exemplified:
Figure BDA0003022486870000362
the structural formula is represented by the code listed in Table 1, and can be expressed as: nCCGF, wherein n in the code represents the number of C atoms of the left alkyl group, for example, n is 3, namely, the alkyl group is-C 3 H 7 (ii) a C in the code represents 1, 4-cyclohexylene, G represents 2-fluoro-1, 4-phenylene and F represents a fluoro substituent.
The test items in the following examples are abbreviated as follows:
cp clearing Point (nematic phase-transition temperature of isotropic phase,. Degree.C.)
Δ n optical anisotropy (589nm, 25 ℃ C.)
Delta epsilon dielectric anisotropy (1KHz, 25 ℃ C.)
γ 1 Rotational viscosity (mPa. Multidot.s, 25 ℃ C.)
K 11 Elasticity constant of splay
K 33 Flexural elastic constant
Vth threshold voltage (V, characteristic voltage of 10% relative contrast in normally black mode)
Ra roughness (nm)
PTA pretilt angle (°)
Stability of the PTA Pre-Tilt Angle (Pre-Tilt Angle Change after fixed time of applied Voltage, °)
VHR Voltage holding ratio (%)
Wherein, the first and the second end of the pipe are connected with each other,
cp: obtained by a melting point tester.
Δ n: obtained by testing at 25 deg.C with Abbe refractometer under sodium lamp (wavelength 589 nm) as light source.
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: test cells of type 25 ℃, 1KHz and VA (6 μm thick box).
γ 1 : testing by using an LCM-2 type liquid crystal physical property evaluation system; and (3) testing conditions: 25 ℃, 160V-260V and the thickness of the test box is 20 mu m.
K 11 And K 33 : the C-V curve of the liquid crystal material was measured using an LCR meter and a VA type test cell, and calculated, and the test conditions were: 6 μm VA-type test cell, V =0.1-20V.
Vth: the test result is obtained by using a DMS 505 tester, and the test conditions are as follows: the VA liquid crystal box has the thickness of 4 mu m, the test frequency of 60Hz and the test waveform of a square shape.
Ra: after the liquid crystal composition containing the polymerizable compound is polymerized by UV illumination, liquid crystal molecules are washed away, and then the morphology roughness of the polymerized polymer layer is tested by using an Atomic Force Microscope (AFM).
PTA: using a crystal rotation method, a liquid crystal is poured into a VA type test cell (cell thickness 3.5 μm), a voltage (15v, 60hz) is applied, and at the same time, irradiation is performed using ultraviolet light UV1, so that polymerizable compounds are polymerized to form a pre-tilt angle PTA1, and then, irradiation of ultraviolet light UV2 is continued to the liquid crystal composition having formed the pre-tilt angle PTA1, so as to eliminate residual polymerizable compounds in the PTA1 state, where the pre-tilt angle formed by the polymerizable compounds is PTA2. The present invention examines the polymerization speed of the polymerizable compound by comparing the magnitude of the pretilt angle formed when UV1 is irradiated for the same time (the smaller the pretilt angle, the faster the polymerization speed) or the time required to form the same pretilt angle (the shorter the required time, the faster the polymerization speed).
Δ PTA: after a pre-tilt angle of 88 ± 0.2 ° is formed by subjecting a test cell used in the test of the pre-tilt angle PTA to a UV1 step and a UV2 step, a SW wave of 60Hz, an AC voltage of 20V, and a DC voltage of 2V are applied to the test cell, and after a fixed period of time in an environment of 40 ℃ and the presence of a backlight, the pre-tilt angle of the test cell is tested, and Δ PTA (168 h) = PTA (initial) -PTA (168 h), the smaller Δ PTA (168 h) indicates the better stability of the pre-tilt angle.
Polymer residue: after applying UV2 for 70min, the liquid crystals eluted from the liquid crystal test cell were examined by High Performance Liquid Chromatography (HPLC), the content of polymerizable compounds therein being referred to as polymer residue.
VHR: after applying UV2 for 70min, tested using the TOY06254 type liquid crystal physical property evaluation system, test conditions: a VA-type test cell having a cell thickness of 3.5 μm at 60 ℃ at 5V at 6 Hz.
The components used in the following examples can be synthesized by a known method or obtained commercially. These synthesis techniques are conventional and the resulting liquid crystal compounds are tested to meet the standards for electronic compounds.
Liquid crystal compositions were prepared according to the formulation of each liquid crystal composition specified in the following examples. The liquid crystal composition is prepared according to conventional methods in the art, such as mixing in proportion by heating, ultrasonic wave, suspension, etc.
The polymerizable compound used in each of the following examples has the structure shown in table 2 below.
TABLE 2 Structure and code of polymerizable Compounds
Figure BDA0003022486870000381
Liquid crystal compositions of control Host-1, host-1 and Host-2 were prepared according to the respective compounds and their weight percentages listed in Table 3, and filled between two substrates of a liquid crystal display for performance test.
TABLE 3 liquid crystal composition formulation and Performance parameter test results
Figure BDA0003022486870000391
The polymerizable compound RM-01 was added to 100 parts by weight of the liquid crystal composition control Host-1 and Host-1, as the comparative example 1-2, the polymerizable compounds RM-1, RM-2, and RM-3 were added to 100 parts by weight of the liquid crystal composition control Host-1, respectively, as the comparative example 3-5, the polymerizable compounds RM-1, RM-2, and RM-3 were added to 100 parts by weight of the liquid crystal composition Host-1, as the example 1-3, the polymerizable compounds RM-1, RM-2, and RM-3 were added to 100 parts by weight of the liquid crystal composition Host-2, respectively, as the example 4-6, and the specific parts by weight of the polymerizable compounds and the results of the relevant performance tests are shown in the following Table 4:
Figure BDA0003022486870000401
as can be seen from the comparison of comparative examples 1 to 5 and examples 1 to 6, the liquid crystal composition of the present invention has a higher clearing point, a larger absolute value of dielectric anisotropy, a smaller threshold voltage, a smaller surface roughness of the polymer layer, a smaller pre-tilt angle within the same time under the action of UV1, a faster angular velocity, a lower polymer residue after the action of UV2 for 70min, a higher VHR after the action of UV2 for 70min, and a better stability of the pre-tilt angle while maintaining a proper optical anisotropy, a proper K value, and a proper rotational viscosity.
Liquid crystal compositions of control Host-2, host-3 and Host-4 were prepared according to the respective compounds and weight percentages thereof listed in Table 5, and filled between two substrates of a liquid crystal display to perform a performance test.
TABLE 5 liquid crystal composition formulations and performance parameter test results
Figure BDA0003022486870000411
The polymerizable compound RM-01 was added to 100 parts by weight of the liquid crystal composition control Host-2 and Host-3 as comparative examples 6-7, the polymerizable compounds RM-1, RM-2 and RM-3 were added to 100 parts by weight of the liquid crystal composition control Host-2, respectively, as comparative examples 8-10, the polymerizable compounds RM-1, RM-2 and RM-3 were added to 100 parts by weight of the liquid crystal composition Host-3, respectively, as examples 7-9, the polymerizable compounds RM-1, RM-2 and RM-3 were added to 100 parts by weight of the liquid crystal composition Host-4, respectively, as examples 10-12, the polymerizable compounds RM-1, RM-2 and RM-4 were added to 100 parts by weight of the liquid crystal composition Host-4, respectively, as examples 13-14, the specific parts by weight of the polymerizable compounds and the results of the related performance tests are shown in Table 6 below:
Figure BDA0003022486870000431
as is clear from the comparison of comparative examples 6 to 10 and examples 7 to 12, the liquid crystal composition of the present invention has a higher clearing point, a larger absolute value of dielectric anisotropy, a smaller threshold voltage, a smaller surface roughness of the polymer layer, a smaller pre-tilt angle within the same time under the action of UV1, a faster angular velocity, a lower polymer residue after the action of UV2 for 70min, a higher VHR after the action of UV2 for 70min, and a better stability of the pre-tilt angle while maintaining a suitable optical anisotropy, a suitable K value, and a suitable rotational viscosity.
Example 13
0.6 part by weight of a compound of SA-2-1
Figure BDA0003022486870000441
100 parts by weight of Host-1 was added, and 0.6 part by weight of RM-1 was added as a polymerizable compound. The resulting liquid crystal composition was filled into "non-aligned" test cells (cell thickness d 3.5 μm each, with ITO coating on both sides (structured ITO in case of multi-domain switching), no alignment layer and no passivation layer).
The liquid crystal display forms a spontaneous vertical alignment with respect to the substrate surface, and the orientation is stabilized until the clearing point and the resulting VA cell can be switched inversely. Cross polarizers are required to show switching.
By using additives like the compounds of formula SA-2-1, VA, PM-VA, PVA, MVA, HT-VA, VA-IPS and other similar display technologies no longer require alignment layers (e.g. no PI coating) based on a combination of Δ ε < 0 and vertical alignment.
Example 14
0.6 part by weight of a compound of SA-4-1
Figure BDA0003022486870000442
To 100 parts by weight of Host-2, and 0.6 part by weight of RM-2 as a polymerizable compound were added. The resulting liquid crystal composition was filled into "non-aligned" test cells (cell thickness d 3.5 μm each, with ITO coating on both sides (structured ITO in case of multi-domain switching), no alignment layer and no passivation layer).
The liquid crystal display forms a spontaneous vertical alignment with respect to the substrate surface, and the orientation is stable until the clearing point and the resulting VA cell can be switched in reverse. Cross polarizers are required for display switching.
By using additives like the compounds of formula SA-4-1, alignment layers (e.g., without PI coatings) are no longer required for VA, PM-VA, PVA, MVA, HT-VA, VA-IPS and other similar display technologies based on a combination of Δ ε < 0 and vertical alignment.
Example 15
0.5 part by weight of a compound of SA-4-2
Figure BDA0003022486870000451
To 100 parts by weight of Host-3, and 0.5 part by weight of RM-3 as a polymerizable compound were added. The resulting liquid crystal composition was filled into "non-aligned" test cells (cell thickness d 3.5 μm each, with ITO coating on both sides (structured ITO in case of multi-domain switching), no alignment layer and no passivation layer).
The liquid crystal display forms a spontaneous vertical alignment with respect to the substrate surface, and the orientation is stable until the clearing point and the resulting VA cell can be switched in reverse. Cross polarizers are required to show switching.
By using additives like the compounds of formula SA-4-2, VA, PM-VA, PVA, MVA, HT-VA, VA-IPS and other similar display technologies no longer require alignment layers (e.g. no PI coating) based on a combination of Δ ε < 0 and vertical alignment.
Example 16
A liquid crystal composition of Host-5 was prepared according to the compounds listed in Table 7 and the weight percentages thereof, and filled between two substrates of a liquid crystal display to perform a performance test.
TABLE 7 liquid crystal composition formulations and performance parameter test results
Figure BDA0003022486870000461
0.03 parts by weight of a stabilizer of the following formula was added to 100 parts by weight of the liquid crystal composition of Host-5,
Figure BDA0003022486870000462
and 0.3 parts by weight of RM-1 polymerizable compound was added as example 16, which was examined to have less polymer layer surface roughness, less pre-tilt angle, faster angulation speed, lower polymer residue, higher VHR, and better pre-tilt angle stability.
Example 17
A liquid crystal composition of Host-6 was prepared according to the respective compounds and their weight percentages listed in Table 8, and filled between two substrates of a liquid crystal display to conduct a performance test.
TABLE 8 liquid crystal composition formulations and performance parameter test results
Figure BDA0003022486870000471
RM-2 was added in an amount of 0.3 parts by weight to 100 parts by weight of the liquid crystal composition Host-6 as example 17, which was examined to have a smaller polymer layer surface roughness, a smaller pretilt angle, a faster angular velocity, a lower polymer residue, a higher VHR and a better pretilt angle stability.
In summary, the liquid crystal composition of the present invention has a higher clearing point, a larger absolute value of dielectric anisotropy, a smaller threshold voltage, a smaller surface roughness of the polymer layer, a smaller pre-tilt angle, a faster angular velocity, a lower polymer residue, a higher VHR, and a better stability of the pre-tilt angle while maintaining a proper optical anisotropy, a proper K value, and a proper rotational viscosity, so that the liquid crystal display device including the liquid crystal composition has a wider temperature application range and a smaller threshold voltage, can effectively accelerate the production process of the PSA type liquid crystal display, accelerate the production efficiency, and can effectively improve the problems of "image sticking", display unevenness, and "broken bright spots" in the existing PSA type liquid crystal display, and has a higher practical application value.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the present invention is not limited thereto, and equivalent changes and modifications made according to the spirit of the present invention should be covered thereby.

Claims (12)

1. A liquid crystal composition, comprising:
at least one compound of formula I:
Figure FDA0003022486860000011
and
at least one compound of formula II:
Figure FDA0003022486860000012
wherein the content of the first and second substances,
R 1 represents a linear or branched, halogenated or non-halogenated alkyl group containing from 1 to 5 carbon atoms;
R 2 represents-H, halogen, -CN, -Sp 2 -P 2 Or a linear or branched alkyl group having 1 to 12 carbon atoms,
Figure FDA0003022486860000013
Figure FDA0003022486860000014
Wherein said linear or branched alkyl group having 1 to 12 carbon atoms,
Figure FDA0003022486860000015
Figure FDA0003022486860000016
One or more-CH's not adjacent to each other 2 -can be independently replaced by-CH = CH-, -C ≡ C-, -O-, -CO-O-, or-O-CO-, respectively, one or more-H can be independently substituted by-F or-Cl, respectively;
R 3 and R 4 Each is independentRepresents a straight-chain or branched alkyl group having 1 to 12 carbon atoms,
Figure FDA0003022486860000017
Figure FDA0003022486860000018
Wherein one or two or more non-adjacent-CH groups in the linear or branched alkyl group having 1 to 12 carbon atoms 2 -can be independently replaced by-CH = CH-, -C ≡ C-, -O-, -CO-O-or-O-CO-, respectively, in such a way that-O-is not directly linked;
l each independently represents halogen, -CN or-Sp 2 -P 2 ；
L 1 、L 2 And L 3 Each independently represents halogen or-CN;
P 1 and P 2 Each independently represents a polymerizable group;
Sp 1 and Sp 2 Each independently represents a spacer group or a single bond;
Z 1 and Z 2 Each independently represents-O-, -S-, -CO-) -CO-O-, -O-CO-) -O-CO-O-, -CH 2 O-、-OCH 2 -、-CH 2 S-、-SCH 2 -、-CF 2 O-、-OCF 2 -、-CF 2 S-、-SCF 2 -、-(CH 2 ) n -、-CF 2 CH 2 -、-CH 2 CF 2 -、-(CF 2 ) n -、-CH＝CH-、-CF＝CF-、-CH＝CF-、-CF＝CH-、-C≡C-、-CH＝CH-CO-O-、-O-CO-CH＝CH-、-CH 2 CH 2 -CO-O-、-O-CO-CH 2 CH 2 -、-CR 1 R 2 -or a single bond, wherein R 1 And R 2 Each independently represents-H or a linear or branched alkyl group containing 1 to 12 carbon atoms, and n represents an integer of 1 to 4;
r 1 、r 2 、r 3 and r 4 Each independently represents 0, 1, 2 or 3, when r 1 、r 2 And r 3 When each independently represents 2 or 3, L may be the same or different, and when r is 4 When represents 2 or 3, L 3 May be the same or different; and is provided with
n 1 And n 2 Each independently represents 0, 1 or 2, and n 1 +n 2 Not less than 1, when n 1 When the expression is shown in the figure 2,
Figure FDA0003022486860000019
may be the same or different when n 2 When the expression is shown in the figure 2,
Figure FDA0003022486860000021
may be the same or different.
2. The liquid crystal composition of claim 1, wherein the compound of formula I is selected from the group consisting of:
Figure FDA0003022486860000022
Figure FDA0003022486860000031
and
Figure FDA0003022486860000032
wherein the content of the first and second substances,
l 'and L' each independently represent-F, -Cl, -CN or-Sp 2 -P 2 。
3. The liquid crystal composition of claim 1, wherein the compound of formula II is selected from the group consisting of:
Figure FDA0003022486860000033
Figure FDA0003022486860000034
and
Figure FDA0003022486860000035
4. the liquid crystal composition of claim 1, further comprising at least one compound of formula M:
Figure FDA0003022486860000036
wherein the content of the first and second substances,
R M1 and R M2 Each independently represents a linear or branched alkyl group having 1 to 12 carbon atoms,
Figure FDA0003022486860000037
Figure FDA0003022486860000038
Wherein one or two or more non-adjacent-CH groups in the linear or branched alkyl group having 1 to 12 carbon atoms 2 -may be independently replaced by-CH = CH-, -C ≡ C-, -O-, -CO-O-, or-O-CO-, respectively;
ring(s)
Figure FDA0003022486860000041
Ring(s)
Figure FDA0003022486860000042
And ring
Figure FDA0003022486860000043
Each independently represent
Figure FDA0003022486860000044
Figure FDA0003022486860000045
Wherein
Figure FDA0003022486860000046
One or more-CH of 2 -may be replaced by-O-and one or more single bonds in the ring may be replaced by double bonds, and wherein
Figure FDA0003022486860000047
At most one-H in (a) 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 -; and is
n M Represents 0, 1 or 2, wherein when n M When =2, ring
Figure FDA0003022486860000048
May be the same or different, Z M2 May be the same or different.
5. The liquid crystal composition of claim 1, further comprising at least one compound of formula N:
Figure FDA0003022486860000049
wherein, the first and the second end of the pipe are connected with each other,
R N1 and R N2 Each independently represents a linear or branched alkyl group having 1 to 12 carbon atoms, a linear or branched alkoxy group having 1 to 11 carbon atoms, a linear or branched alkenyl group having 2 to 12 carbon atoms,
Figure FDA00030224868600000410
Figure FDA00030224868600000411
Ring(s)
Figure FDA00030224868600000412
And ring
Figure FDA00030224868600000413
Each independently represent
Figure FDA00030224868600000414
Wherein
Figure FDA00030224868600000415
One or more-CH of 2 -may be replaced by-O-and one or more single bonds in the ring may be replaced by a double bond, wherein
Figure FDA00030224868600000416
May each be independently substituted with-F, -Cl, or-CN, and one or more rings-CH = may be replaced with-N =;
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, an alkyl group containing 1 to 3 carbon atoms or halogen;
n N1 represents 0, 1, 2 or 3,n N2 Represents 0 or 1, and 0. Ltoreq. N N1 +n N2 Is less than or equal to 3, wherein when n is N1 When =2 or 3, ring
Figure FDA00030224868600000417
May be the same or different, Z N1 May be the same or different; and is
When n is more than or equal to 0 N1 +n N2 When the compound with the general formula N is not more than 1 and the structure of the biphenyl is R N1 And R N2 Not simultaneously alkoxy.
6. The liquid crystal composition of claim 1, further comprising at least one compound of formula B:
Figure FDA0003022486860000051
wherein the content of the first and second substances,
R B1 and R B2 Each independently represents-H, halogen, straight or branched chain alkyl containing 1 to 12 carbon atoms, wherein one or more than two of the straight or branched chain alkyl containing 1 to 12 carbon atoms is-CH 2 May be independently represented by-CH = CH-in a manner not directly connected to-O-, respectively-C.ident.C-, -O-, -S-, -CO-O-, -O-CO-,
Figure FDA0003022486860000052
Figure FDA0003022486860000053
and one or more-H of the foregoing groups may each be independently substituted with-F or-Cl;
ring (C)
Figure FDA0003022486860000054
And ring
Figure FDA0003022486860000055
Each independently represent
Figure FDA0003022486860000056
Figure FDA0003022486860000057
Wherein
Figure FDA0003022486860000058
One or more-CH of 2 -may each independently be replaced by-O-, and one or more single bonds in the ring may each independently be replaced by a double bond, wherein
Figure FDA0003022486860000059
Can be independently substituted by-F, -Cl, -CN, -CH 3 or-OCH 3 Substituted, and-CH = in one or more rings may each be independently replaced by-N =;
X B represents-O-) -S-, -CO-, -CF 2 -, -NH-or-NF-;
Y B1 and Y B2 Each independently represents-H, halogen, halogenated or non-halogenated alkyl having 1 to 3 carbon atoms, or halogenated or non-halogenated alkoxy having 1 to 3 carbon atoms;
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 -; and is
n B1 And n B2 Each independently represents 0, 1 or 2, wherein when n is B1 When =2, ring
Figure FDA00030224868600000510
May be the same or different, Z B1 May be the same or different, wherein when n is B2 When =2, ring
Figure FDA00030224868600000511
May be the same or different, Z B2 May be the same or different.
7. The liquid crystal composition of claim 1, further comprising at least one self-aligning agent of the general formula SA:
Figure FDA00030224868600000512
wherein the content of the first and second substances,
R S1 represents Sp-P, a linear or branched alkyl group having 1 to 12 carbon atoms,
Figure FDA00030224868600000513
Wherein one or two or more non-adjacent-CH groups in the linear or branched alkyl group having 1 to 12 carbon atoms 2 -said linear or branched alkyl radical containing from 1 to 12 carbon atoms which may be independently replaced by-CH = CH-, -C.ident.C-, -O-, -CO-O-or-O-CO-, respectively,
Figure FDA0003022486860000061
Each of which may be independently substituted with-F or-Cl;
R S2 represents an anchoring group:
Figure FDA0003022486860000062
p represents 1 or 2, when p represents 2, -Sp d -X 2 May be the same or different;
o represents 0 or 1;
X 1 and X 2 Each independently represents-H, -OH, -SH, -NH 2 、-NHR 11 、-NR 11 2 、NHC(O)-R 11 、-OR 11 -C (O) OH, -CHO or a linear or branched, halogenated or unhalogenated alkyl group containing 1 to 12 carbon atoms;
wherein, X 1 And X 2 At least one of them is selected from-OH, -SH, -NH 2 、-NHR 11 -C (O) OH or-CHO;
Sp a 、Sp c and Sp d Each independently represents a spacer group or a single bond;
Sp b each independently represent
Figure FDA0003022486860000063
Ring (C)
Figure FDA0003022486860000064
And a ring
Figure FDA0003022486860000065
Each independently represent
Figure FDA0003022486860000066
Wherein
Figure FDA0003022486860000067
Of one or more-CH 2 -may be replaced by-O-and one or more single bonds in the ring may be replaced by double bonds;
ls independently represent-F, -Cl, -CN, -NO 2 、-NCO、-NCS、-OCN、-SCN、-C(O)N(R 0 ) 2 、-C(O)R 0 A straight or branched alkyl group having 1 to 12 carbon atoms,
Figure FDA0003022486860000068
Wherein one or two or more non-adjacent-CH groups in the linear or branched alkyl group having 1 to 12 carbon atoms 2 -said linear or branched alkyl radical containing 1 to 12 carbon atoms which may be independently replaced by-CH = CH-, -C ≡ C-, -O-, -CO-O-or-O-CO-, respectively,
Figure FDA0003022486860000069
Each of one or more-H may be independently substituted with-F;
R 0 and R 11 Each independently represents a linear or branched alkyl group having 1 to 12 carbon atoms;
p represents a polymerizable group;
sp represents a spacer group or a single bond;
n s1 represents 0 or 1;
n s2 represents 0, 1, 2 or 3, when n s2 When the compound is represented by 2 or 3,
Figure FDA00030224868600000610
may be the same or different;
p s1 、p s2 、p s3 and p s4 Each independently represents 0, 1 or 2, wherein 1. Ltoreq. P s1 +p s2 ≤2；
p s5 And p s6 Each independently represents 0 or 1; and is
Z 1 And Z 2 Each independently represents-O-, -S-, -CO-, -CO-O-, -O-CO-O-, -CH 2 O-、-OCH 2 -、-CH 2 S-、-SCH 2 -、-CF 2 O-、-OCF 2 -、-CF 2 S-、-SCF 2 -、-(CH 2 ) n -、-CF 2 CH 2 -、-CH 2 CF 2 -、-(CF 2 ) n -、-CH＝CH-、-CF＝CF-、-CH＝CF-、-CF＝CH-、-C≡C-、-CH＝CH-CO-O-、-O-CO-CH＝CH-、-CH 2 CH 2 -CO-O-、-O-CO-CH 2 CH 2 -、-CR 1 R 2 -or a single bond, wherein R 1 And R 2 Each independently represents-H or a linear or branched alkyl group having 1 to 12 carbon atoms, and n represents an integer of 1 to 4.
8. The liquid crystal composition of claim 1, wherein the liquid crystal composition comprises at least two compounds of formula II.
9. The liquid crystal composition of claim 2, wherein the compound of formula I is present in an amount of 0.001% to 5% by weight of the liquid crystal composition.
10. The liquid crystal composition of claim 3, wherein the compound of formula II is present in an amount of 0.1% to 30% by weight of the liquid crystal composition.
11. Liquid crystal composition according to any of claims 1 to 10, characterized in that it further comprises at least one additive.
12. A liquid crystal display device comprising the liquid crystal composition of any one of claims 1 to 11.
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