CN115216306A - Liquid crystal composition and liquid crystal display device thereof - Google Patents
Liquid crystal composition and liquid crystal display device thereof Download PDFInfo
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- CN115216306A CN115216306A CN202110406655.9A CN202110406655A CN115216306A CN 115216306 A CN115216306 A CN 115216306A CN 202110406655 A CN202110406655 A CN 202110406655A CN 115216306 A CN115216306 A CN 115216306A
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- 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
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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 larger absolute value of dielectric anisotropy, larger K value, longer low-temperature storage time, smaller roughness of the surface of a polymer layer, smaller pretilt angle, faster angular velocity, lower polymer residue, higher VHR and good stability of the pretilt angle under the condition of maintaining proper clearing point, optical anisotropy and rotational viscosity, so that a liquid crystal display device has wider temperature use range, better low-temperature intersolubility, lower threshold voltage and better contrast, the production process of a PSA type liquid crystal display is effectively accelerated, the production efficiency is improved, the problems of image sticking, uneven display and broken bright point existing in the PSA type liquid crystal display are effectively improved, and the application value is higher.
Description
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 in portable electronic information products in particular. 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, which is achieved 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 method of the PSA type liquid crystal display, UV photopolymerization is achieved by the following two steps:
in a first step (hereinafter referred to as "UV1 step"), the liquid crystal composition is exposed to UV radiation emitted by a radiation source (hereinafter referred to as "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 (i.e., faster angular velocity) in a shorter UV1 irradiation time to improve production efficiency, shorten tact time (tact time) in mass production, and reduce costs, and 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 cause 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 condition of poor display is caused.
However, with the development of technology, the LCD industry has more strict requirements on the display quality of the LCD, and particularly in the TV industry, the size of the TV 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 panel manufacturing process, the continuous development of liquid crystal materials is one of the solutions, especially for PSA type liquid crystal display, the selection of liquid crystal composition used in combination with polymerizable compound is a hot research.
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 polymerizable compounds by applying UV1 radiation and UV2 radiation to produce a 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. 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 over a number of addressing cycles in the switched-on display area, while the pretilt angle and transmittance remain unchanged in the non-switched-on display area, resulting in an "image sticking" effect. It is therefore desirable that during the production of liquid crystal displays of the PSA type the polymerizable compounds polymerize as completely as possible and the residual polymerizable compounds can react in a controlled manner, the faster the polymerization speed, the more favourable it is to achieve this desire. Furthermore, it is also desirable that the change in the pre-tilt angle is small after a plurality of addressing periods have elapsed.
In addition, the polymerizable compounds of the prior art generally have high melting points and show only limited solubility in many of the existing commonly used liquid crystal compositions, often precipitating out of the liquid crystal composition. In addition, the polymerizable compound has a possibility of self-polymerization, which further deteriorates its solubility in the liquid crystal composition. Therefore, it is generally necessary to introduce a liquid crystal composition having a polymerizable compound dissolved therein at a low temperature in order to reduce the risk of self-polymerization of the polymerizable compound, which puts higher demands on the solubility of the polymerizable compound in the liquid crystal composition, especially its solubility at a low temperature.
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 present invention provides a liquid crystal composition having a large absolute value of dielectric anisotropy, a large K value, a long low-temperature storage time, a small surface roughness of a polymer layer, a small pre-tilt angle, a fast angle forming speed, a small polymer residue, a high VHR, and a good pre-tilt angle stability while maintaining a proper clearing point, a proper optical anisotropy, and a proper rotational viscosity.
It is a further object of the present invention to provide 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
at least one compound of the formula II
Wherein, the first and the second end of the pipe are connected with each other,
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, In which a linear or branched alkyl radical having 1 to 12 carbon atoms,Or two or more-CHs that are not adjacent to each other 2 -may each independently be replaced by-CH = CH-, -C ≡ C-, -O-, -CO-O-, or-O-CO-, and one or more-H may each independently be substituted by-F or-Cl;
R 3 and R 4 Each independently represents a linear or branched alkyl group having 1 to 12 carbon atoms, 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 And L 2 Each independently represents-H or halogen;
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 and r 3 Each independently represents 0, 1, 2 or 3, when r 1 、r 2 And r 3 Each independently represents 2 or 3, L may be the same or different; and is
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,may be the same or different, when n 2 When the expression (2) is used, the expression,may be the same or different.
In some embodiments of the invention, R 1 Denotes straight-chain alkyl having 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 from the group consisting of a larger absolute value of dielectric anisotropy, a larger K value, a longer low temperature storage time, a smaller surface roughness of the polymer layer, a smaller pre-tilt angle, a faster angle-forming rate, a lower polymer residue, a higher VHR, and a 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 independentlyRepresents a single bond.
In some embodiments of the invention, R 2 denotes-Sp 2 -P 2 。
In some embodiments of the invention, the compound of formula I is selected from the group consisting of:
wherein the content of the first and second substances,
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 compounds of formula I-1, compounds of formula I-2, compounds of formula I-4, and compounds of formula I-8 in order to obtain a larger absolute value of dielectric anisotropy, a larger K value, a longer low temperature storage time, a smaller surface roughness of the polymer layer, a smaller pre-tilt angle, a faster angular rate, 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, for ring-opening polymerization, for example oxetane or epoxy groups are particularly preferred.
The term "polymerizable groups" each independently means or-SH; preferably, the "polymerizable groups" each independently represent or-SH; further preferably, each of the "polymerizable groups" independently represents
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 connects 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 Denotes an integer of 1 to 3, e.g. 2,R 0 And R 00 Each independently represents-H or containsStraight-chain or branched alkyl having 1 to 12 carbon atoms,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 the present invention, the expression method in which a straight line crosses a ring structure represents that the access bond of the group is at any bondable position of the ring structure.
In some embodiments of the invention, the compound of formula II is selected from the group consisting of:
in some embodiments of the invention, preferably, R 3 And R 4 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 alkoxy group having 2 to 10 carbon atomsStraight or branched chain alkenyl of carbon atoms; further preferably, R 3 And R 4 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 3 And R 4 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 3 Represents a linear or branched alkyl group having 1 to 5 carbon atoms, R 4 Represents a linear or branched alkoxy group having 1 to 4 carbon atoms.
In some embodiments of the invention, R is R for greater absolute value of dielectric anisotropy, greater K, longer low temperature storage time, less surface roughness of polymer layer, smaller pre-tilt angle, faster angular rate, lower polymer residue, higher VHR, and better pre-tilt angle stability 4 Represents a linear or branched alkoxy group having 1 to 4 carbon atoms.
In some embodiments of the present invention, the compound of formula II is selected from the group consisting of compounds of formula II-1 and compounds of formula II-4 in order to obtain a larger absolute value of dielectric anisotropy, a larger K value, a longer low temperature storage time, a smaller surface roughness of the polymer layer, a smaller pre-tilt angle, a faster angular rate, a lower polymer residue, a higher VHR, and a better pre-tilt angle stability.
In some embodiments of the present invention, the content of the compound of formula II is preferably adjusted to obtain a larger absolute value of dielectric anisotropy, a larger K-value, a longer low temperature storage time, 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 compound of formula II is present in an amount of 0.1% to 25% by weight of the liquid crystal composition, e.g., 0.1%, 1%, 2%, 4%, 6%, 8%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 20%, 22%, 24%, 25%; preferably, the compound of formula II accounts for 1% -20% of the liquid crystal composition by weight.
In some embodiments of the present invention, the liquid crystal composition of the present invention further comprises at least one compound of formula M:
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, 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)Ring (C)And ringEach independently represent WhereinOf 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 whereinAt 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, ringMay 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:
wherein denotes a carbon atom in the bonded ring structure.
The alkenyloxy group in the present invention is preferably selected from the group 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 as follows:
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:
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-2, 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, a compound of formula M-24, a compound of formula M-26, and a compound of formula M-30.
In some embodiments of the present invention, the compound of formula M is selected from the group consisting of compounds of formula M-1, compounds of formula M-2, compounds of formula M-6, and compounds of formula M-16 in order to achieve a larger absolute value of dielectric anisotropy, a larger K value, a longer low temperature storage time, a smaller surface roughness of the polymer layer, a smaller pre-tilt angle, a faster angular rate, 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 larger absolute value of dielectric anisotropy, a larger K value, a longer low-temperature storage time, a smaller surface roughness of the polymer layer, a smaller pre-tilt angle, a faster angle-forming speed, 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 maintain a high clearing point and good temperature stability, it is preferable that the lower limit of the content is high and the upper limit of the content is 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, having 1 to 7 carbonsLinear or branched alkoxy of an atom, or linear or branched alkenyl containing 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 them is an alkenyl group.
In some embodiments of the invention, the liquid crystal composition of the invention further comprises at least one compound of formula N:
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, In which one or more than two non-adjacent-CH groups in the linear or branched alkyl group containing 1-12 carbon atoms 2 -may be independently replaced by-CH = CH-, -C ≡ C-, -O-, -CO-O-, or-O-CO-, respectively;
ring (C)And ringEach independently representWhereinOne 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, whereinMay each be independently substituted with-F, -Cl, or-CN, and one or more rings-CH = may be replaced by-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 ringMay be the same or different, Z N1 May be the same or different; and is provided with
When n is N1 +n N2 In the case of =2, the compound of the general formula N does not contain a terphenyl structure.
In some embodiments of the invention, the compound of formula N is selected from the group consisting of:
in some embodiments of the invention, the compound of formula N is selected from the group consisting of a compound of formula N-1, 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-14, a compound of formula N-20, and a compound of formula N-22.
In some embodiments of the present invention, the compound of formula N is selected from the group consisting of compounds of formula N-2 and compounds of formula N-5 in order to obtain a larger absolute value of dielectric anisotropy, a larger K value, a longer low temperature storage time, a smaller surface roughness of the polymer layer, a smaller pre-tilt angle, a faster angle formation rate, 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 selected from the group consisting of compounds of formula N-3 and compounds of formula N-6 in order to obtain a larger absolute value of dielectric anisotropy, a larger K value, a longer low temperature storage time, a smaller surface roughness of the polymer layer, a smaller pre-tilt angle, a faster angle formation rate, 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 selected from the group consisting of compounds of formula N-10 and compounds of formula N-13 in order to obtain a larger absolute value of dielectric anisotropy, a larger K value, a longer low temperature storage time, a smaller surface roughness of the polymer layer, a smaller pre-tilt angle, a faster angular rate, 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 obtain a larger absolute value of dielectric anisotropy, a larger K value, a longer low-temperature storage time, a smaller surface roughness of the polymer layer, a smaller pre-tilt angle, a faster angle-forming speed, 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 65%, 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 1-60% 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 invention, preferably, 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:
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, In which one or more than two non-adjacent-CH groups in the linear or branched alkyl group containing 1-12 carbon atoms 2 -linear or branched alkyl which may be independently replaced by-CH = CH-, -C.ident.C-, -O-, -CO-O-or-O-CO-and which contains from 1 to 12 carbon atoms,Each of which may be independently substituted with-F or-Cl;
ring (C)Ring (C)Ring (C)And ringEach independently representWherein One or more-CH of 2 -may each be independently replaced by-O-,and one or more of the ring single bonds may each be independently replaced by a double bond, whereinMay each be independently substituted with-F, -Cl, or-CN, and one or more rings-CH = 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, a ringMay be the same or different, Z A11 May be the same or different;
n A2 Represents 0, 1, 2 or 3, wherein when n is A2 When =2 or 3, ringMay 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:
wherein, the first and the second end of the pipe are connected with each other,
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-H 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 denotes-F, -CF 3 or-OCF 3 (ii) a And is provided with
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%.
Regarding 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:
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 the linear or branched alkyl group has 1 to 8 carbon atomsOne or more-CH groups not adjacent to each other in the alkyl group of (A) 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 set the lower limit of the content to be slightly higher and the upper limit of the content to be 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:
wherein the content of the first and second substances,
R B1 and R B2 Each independently represents-H, halogen, straight or branched chain containing 1-12 carbon atomsChain alkyl, in which one or more than two-CH of linear or branched 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-), And one or more-H of the foregoing groups may each be independently substituted with-F or-Cl;
ring(s)And a ringEach independently represent WhereinOne 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, whereinCan 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, halogenated or non-halogenated alkyl 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, ringMay be the same or different, Z B1 May be the same or different, wherein when n B2 When =2, ringMay 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:
wherein the content of the first and second substances,
Y B3 and Y B4 Each independently represents-H, -F, -Cl, -CN, -CH 3 or-OCH 3 (ii) a And is
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 larger absolute value of dielectric anisotropy, a larger K-value, a longer low temperature storage time, a smaller surface roughness of the polymer layer, a smaller pre-tilt angle, a faster angle-forming speed, a lower polymer residue, a higher VHR, and a better pre-tilt angle stability.
In some embodiments of the present invention, the content of the compound of formula B is preferably adjusted to obtain a larger absolute value of dielectric anisotropy, a larger K-value, a longer low temperature storage time, 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 compound of formula B comprises 0.1% to 30% by weight of the liquid crystal composition, for example, 0.1%, 1%, 2%, 4%, 6%, 8%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 20%, 22%, 24%, 25%, 26%, 28% or 30%.
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:
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,In which one or more than two non-adjacent-CH groups in the linear or branched alkyl group containing 1-12 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,Each of which may be independently substituted with-F or-Cl;
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;
Ring (C)And ringEach independently representWhereinOf 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,In which one or more than two non-adjacent-CH groups in the linear or branched alkyl group containing 1-12 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,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 is s2 When the compound is represented by 2 or 3,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:
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:
wherein the content of the first and second substances,
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, or the like.
Possible dopants which are preferably added to the liquid-crystal composition according to the invention are shown below:
in some embodiments of the invention, the dopant comprises 0% to 5% by weight of the liquid crystal composition; preferably, the dopant is present in an amount of 0.01% to 1% by weight of the liquid crystal composition.
Further, additives such as an antioxidant and a light stabilizer used in the liquid crystal composition of the present invention are preferably as follows:
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:
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 a method for polymerizing a polymerizable compound, a method of polymerizing by irradiating active energy rays such as ultraviolet rays or electron beams is preferable because it is desired that polymerization proceeds rapidly. 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 for 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 the ultraviolet rays are irradiated, the intensity thereof may be changed, and the time for irradiating the 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 advantages that: compared with the prior art, the liquid crystal composition has larger absolute value of dielectric anisotropy, larger K value, longer low-temperature storage time, smaller roughness of the surface of a polymer layer, smaller pretilt angle, faster angular velocity, lower polymer residue, higher VHR and better pretilt angle stability under the condition of maintaining proper clearing point, proper optical anisotropy and proper rotational viscosity, so that a liquid crystal display device comprising the liquid crystal composition has wider temperature use range, better low-temperature intersolubility, lower threshold voltage and better contrast, 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 point' in the conventional PSA type liquid crystal display, and has higher practical application value.
Detailed Description
The invention will be illustrated below 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:
TABLE 1 radical Structure code for Compounds
Compounds of the following formula are exemplified:
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", i.e., -C 3 H 7 (ii) a C in the code represents 1, 4-cyclohexylene, G represents 2-fluoro-14-phenylene and F represents a fluorine 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
t -20℃ Storage at-20 ℃ for a prolonged period of time (days)
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 content of the first and second substances,
cp: obtained by melting point apparatus testing.
Δ n: obtained by testing at 25 deg.C with Abbe refractometer under sodium lamp (wavelength 589 nm).
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: at 25 deg.C, 160V-260V, and the thickness of the test box is 20 μm.
K 11 And K 33 : the LCR instrument and the VA type test box are used for testing the C-V curve of the liquid crystal material, and the calculation is carried out to obtain the following test conditions: 6 μm VA-type test cell, V =0.1-20V.
t -20℃ : placing nematic liquid crystal medium in a glass bottle, storing at-20 deg.C, andthe time recorded when crystal precipitation was observed.
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, filling a liquid crystal into a VA type test cell (cell thickness 3.5 μm), applying a voltage (15v, 60hz), and simultaneously irradiating with ultraviolet light UV1 to polymerize the polymerizable compound to form a pre-tilt angle PTA1, and then continuously irradiating ultraviolet light UV2 to the liquid crystal composition having formed the pre-tilt angle PTA1 to remove the residual polymerizable compound in the state of PTA1, wherein the pre-tilt angle formed by the polymerizable compound 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 ° was 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 were applied to the test cell, and the pre-tilt angle of the test cell was tested after a fixed period of time in an environment of 40 ℃ and the presence of backlight, Δ PTA (168 h) = PTA (initial) -PTA (168 h), and the smaller Δ PTA (168 h) indicates the better stability of the pre-tilt angle.
Polymer residue: after applying UV2 for 50min, 60min and 70min, respectively, the liquid crystals eluted from the liquid crystal test cell were examined by High Performance Liquid Chromatography (HPLC) and the content of the polymerizable compounds therein was 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 examples below can be synthesized by known methods 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 by 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 structures and codes of polymerizable Compounds
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 formulations and performance parameter test results
The polymerizable compounds RM-01, RM-02, RM-03, and RM-1 were added to 100 parts by weight of the liquid crystal composition control Host-1, respectively, as comparative examples 1-3, the polymerizable compound RM-01 was added to 100 parts by weight of the liquid crystal composition Host-1, as comparative example 4, the polymerizable compounds RM-1 and RM-2 were added to 100 parts by weight of the liquid crystal composition Host-1, respectively, as examples 1-2, the polymerizable compounds RM-1, RM-2, RM-3, and RM-4 were added to 100 parts by weight of the liquid crystal composition Host-2, respectively, as examples 3-5, the specific parts by weight of the polymerizable compounds and the results of the relevant performance tests are shown in the following Table 4:
as can be seen from the comparison of comparative examples 1 to 4 and examples 1 to 5, the liquid crystal composition of the present invention has a larger absolute value of dielectric anisotropy, a larger K value, a longer low-temperature storage time, a smaller surface roughness of the polymer layer, a smaller pre-tilt angle in a shorter time under the action of UV1, a faster angular velocity, a lower polymer residue in a shorter time under the action of UV2, a higher VHR after the action of UV2 for 90min, and a better stability of the pre-tilt angle, while maintaining a proper clearing point, a proper optical anisotropy, 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 their weight percentages listed in Table 5, and filled between two substrates of a liquid crystal display for performance test.
TABLE 5 liquid crystal composition formulations and performance parameter test results
Polymerizable compounds RM-01, RM-02, RM-03 and RM-1 were added to 100 parts by weight of the liquid crystal composition control Host-2, respectively, as comparative examples 5-7, the polymerizable compound RM-01 was added to 100 parts by weight of the liquid crystal composition Host-3, as comparative example 8, the polymerizable compounds RM-1 and RM-2 were added to 100 parts by weight of the liquid crystal composition Host-3, respectively, as examples 6-7, the polymerizable compounds RM-1, RM-2, RM-3 and RM-4 were added to 100 parts by weight of the liquid crystal composition Host-4, respectively, as examples 8-10, and the specific parts by weight of the polymerizable compounds and the results of the relevant performance tests are shown in Table 6 below:
as can be seen from the comparison of comparative examples 5 to 8 and examples 6 to 10, the liquid crystal composition of the present invention has a larger absolute value of dielectric anisotropy, a larger K value, a longer low-temperature storage time, a smaller roughness of the surface of the polymer layer, a smaller pre-tilt angle in a shorter time under the action of UV1, a faster angle-forming speed, a lower polymer residue in a shorter time under the action of UV2, a higher VHR after the action of UV2 for 90min, and a better stability of the pre-tilt angle while maintaining a proper clearing point, a proper optical anisotropy, and a proper rotational viscosity.
Example 11
0.6 part by weight of a compound of SA-2-1
To 100 parts by weight of Host-1, and 0.6 part by weight of RM-1 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-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 12
0.6 part by weight of a compound of SA-4-1
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 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-4-1, 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 13
0.5 part by weight of a compound of SA-4-2
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, 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 14
A liquid crystal composition of Host-5 was prepared according to the respective compounds and their weight percentages listed in Table 7, and filled between two substrates of a liquid crystal display to conduct a performance test.
TABLE 7 liquid crystal composition formulations and performance parameter test results
0.03 parts by weight of a stabilizer of the formula was added to 100 parts by weight of the liquid crystal composition of Host-5
And 0.3 parts by weight of RM-1 polymerizable compound was added as example 14, 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.
In summary, the liquid crystal composition of the present invention has a larger absolute value of dielectric anisotropy, a larger K value, a longer low-temperature storage time, a smaller surface roughness of the polymer layer, a smaller pre-tilt angle, a faster angle-forming speed, a lower polymer residue, a higher VHR, and a better stability of the pre-tilt angle while maintaining a proper clearing point, a proper optical anisotropy, and a proper rotational viscosity, so that the liquid crystal display device including the liquid crystal composition has a wider temperature application range, a better low-temperature intersolubility, a lower threshold voltage, and a better contrast, 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, "broken bright points" 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 (11)
1. A liquid crystal composition, comprising:
at least one compound of formula I:
at least one compound of formula II:
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, Wherein said linear or branched alkyl group having 1 to 12 carbon atoms, Or two or more-CHs that are 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 independently represents a linear or branched alkyl group having 1 to 12 carbon atoms, 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-O-not directlyLinked in a manner independently replaced by-CH = CH-, -C ≡ C-, -O-, -CO-O-or-O-CO-;
l each independently represents halogen, -CN or-Sp 2 -P 2 ;
L 1 And L 2 Each independently represents-H or halogen;
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-, -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 and r 3 Each independently represents 0, 1, 2 or 3, when r 1 、r 2 And r 3 Each independently represents 2 or 3, L may be the same or different; and is provided with
4. the liquid crystal composition of claim 1, further comprising at least one compound of formula M:
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, 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 (C)Ring (C)And ringEach independently represent WhereinOne 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 whereinAt 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
5. The liquid crystal composition of claim 1, further comprising at least one compound of formula N:
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, Wherein one or two or more non-adjacent-CH groups of a 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-;
ring (C)And ringEach independently representWhereinOne 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, whereinMay 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 ringMay be the same or different, Z N1 May be the same or different; and is provided with
When n is N1 +n N2 In the case of =2, the compound of the general formula N does not contain a terphenyl structure.
6. The liquid crystal composition of claim 1, further comprising at least one compound of formula B:
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 of the straight or branched chain alkyl containing 1-12 carbon atoms-CH 2 May be independently bound by-CH = CH-respectively in a manner not directly bound to-O-) -C.ident.C-, -O-, -S-, -CO-O-, -O-CO-, and one or more-H of the foregoing groups may each be independently substituted with-F or-Cl;
ring(s)And a ringEach independently represent WhereinOf one or more-CH 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, whereinCan be independently substituted by-F, -Cl, -CN, -CH 3 or-OCH 3 Is substituted, and one or more-CH = in the 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, 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
7. The liquid crystal composition of claim 1, further comprising at least one self-aligning agent of the general formula SA:
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,Wherein said compound containsOne or two or more non-adjacent-CH groups selected from straight-chain or branched-chain alkyl groups of 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,Each of one or more-H may be independently substituted with-F or-Cl;
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 non-halogenated 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;
Ring (C)And ringEach independently representWhereinOne 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;
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,Wherein one or two or more non-adjacent-CH groups of a 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,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,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 provided with
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 having 1 to 12 carbon atoms, and n represents an integer of 1 to 4.
8. 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.
9. The liquid crystal composition of claim 3, wherein the compound of formula II is present in an amount of 0.1% to 25% by weight of the liquid crystal composition.
10. Liquid crystal composition according to any of claims 1 to 9, characterized in that it further comprises at least one additive.
11. A liquid crystal display device comprising the liquid crystal composition of any one of claims 1 to 10.
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US20190390112A1 (en) * | 2018-06-21 | 2019-12-26 | Merck Patent Gmbh | Liquid-crystalline medium |
CN110872519A (en) * | 2018-09-03 | 2020-03-10 | Dic株式会社 | Liquid crystal composition and liquid crystal display element |
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US20190390112A1 (en) * | 2018-06-21 | 2019-12-26 | Merck Patent Gmbh | Liquid-crystalline medium |
CN110872519A (en) * | 2018-09-03 | 2020-03-10 | Dic株式会社 | Liquid crystal composition and liquid crystal display element |
JP2020052305A (en) * | 2018-09-28 | 2020-04-02 | Dic株式会社 | Method for manufacturing liquid crystal display element |
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