CN113372927A - Liquid crystal composition containing polymerizable compound and liquid crystal display device - Google Patents
Liquid crystal composition containing polymerizable compound and liquid crystal display device Download PDFInfo
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Classifications
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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
-
- 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
- C09K19/38—Polymers
- C09K19/3833—Polymers with mesogenic groups in the side chain
- C09K19/3842—Polyvinyl derivatives
- C09K19/3852—Poly(meth)acrylate derivatives
- C09K19/3857—Poly(meth)acrylate derivatives containing at least one asymmetric carbon atom
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- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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- Liquid Crystal Substances (AREA)
Abstract
The invention provides a liquid crystal composition containing a polymerizable compound and a liquid crystal display device containing the liquid crystal composition. Compared with the prior art, the liquid crystal composition has better low-temperature storage stability, higher polymerization speed, lower residual amount of polymerizable compounds and better pre-tilt angle stability, so that a liquid crystal display device comprising the liquid crystal composition has higher response speed, effectively solves the problems of 'image retention', 'image sticking' or 'display unevenness' and the like of the liquid crystal display device, and has higher practical application value.
Description
Technical Field
The invention relates to the field of liquid crystal, in particular to a liquid crystal composition containing a polymerizable compound and a liquid crystal display device thereof.
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 mode is to fix the orientation of liquid crystal molecules by adding a small amount (e.g., 0.3 wt%, more typically < 1 wt%) of one or more polymerizable compounds to a liquid crystal composition and polymerizing or crosslinking it in situ (typically by UV photopolymerization) in a state where the liquid crystal molecules have an initial orientation with or without applying a voltage between electrodes after filling the liquid crystal composition into a liquid crystal cell. The polymerization is carried out at a temperature at which the liquid-crystalline composition exhibits a liquid-crystalline phase (generally at room temperature). It has been confirmed that the addition of a polymerizable liquid crystal compound to a liquid crystal composition is particularly suitable because the tilt angle of liquid crystal molecules can be well controlled by the polymer structure formed in the cell, and the PSA type liquid crystal display element also has the effects of high-speed response and high contrast.
Accordingly, a PSA type liquid crystal display element is continuously developed, and the PSA principle is also used in various conventional liquid crystal displays such as known PSA-VA, PSA-OCB, PSA-IPS, PSA-FFS and PSA-TN type liquid crystal displays. In the PSA type liquid crystal display, the liquid crystal composition containing the polymerizable compound is located between two substrates, each of which is provided with an electrode structure, or both electrode structures are disposed on only one of the substrates. In addition, either or both of the two substrates may contain an alignment layer disposed on the substrate or electrode structure (if present) so as to be in contact with the liquid crystal composition 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 or passive matrix displays. In the case of active matrix displays the individual pixels are typically 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 multiplexing methods 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 compound phase separates from the other compounds in the liquid crystal composition and forms a polymer layer 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, UV photopolymerization in the production process of PSA type liquid crystal displays is achieved in two steps. In a first step (hereinafter referred to as the "UV 1 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; in the second step (hereinafter referred to as the "UV 2 step"), the liquid crystal composition is exposed to UV radiation without applying a voltage to the electrode structure to ensure complete polymerization of any residual polymerizable compounds that were not polymerized in the UV1 step. As described above, thorough polymerization is important because residual unpolymerized polymerizable compounds may cause undesirable effects such as reduced reliability in displays, reduced tilt angle stability, or image sticking. Furthermore, it is important to ensure that the polymerization in the UV2 step is completed within an acceptable time, so that the beat time is significantly shorter than 2 h. Furthermore, the UV radiation intensity in the UV2 step should be reduced compared to the UV1 step to avoid or reduce negative effects (such as reduced reliability or image sticking).
However, the PSA type liquid crystal display element also has some cases of poor display (such as image retention). Studies have shown that such problems are mostly caused by the presence of impurities and by the variation of the orientation of the liquid crystal molecules (variation of the pretilt angle), which is controlled by the polymer network formed after polymerization of the polymerizable compound. If the structural rigidity of the polymerizable compound constituting the polymer network is insufficient, there is a possibility that the structure of the polymer network changes when the PSA type liquid crystal display element continuously displays the same pattern for a long time, which in turn causes a change in the pretilt angle of the liquid crystal molecules. Therefore, it is generally necessary to select a polymerizable compound having a rigid structure.
The prior art widely uses polymerizable compounds of the following formulae (a) and (b):
wherein, P1And P2Both represent polymerizable groups, typically acrylate or methacrylate groups.
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 panel manufacturing processes, the continuous development of liquid crystal materials is one of the solutions, and especially for PSA type liquid crystal displays, the improvement of the performance of various aspects of polymerizable compounds is a hot spot of research.
The more preferred polymerizable compounds should produce a smaller pretilt angle at the same exposure time or the same pretilt angle at a shorter UV exposure time during polymerization than existing Reactive Monomers (RMs). The use of such more preferred polymerizable compounds can save display production time, thereby increasing display production efficiency and reducing cost.
At present, problems common in the production of PSA type liquid crystal displays are 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 the polymerizable compounds that have not reacted all the time 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 over a number of addressing cycles in the switched-on display area, the transmittance may change accordingly, and the pretilt angle and transmittance may remain unchanged in the non-switched-on 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 plurality of addressing periods have elapsed.
Another problem observed in the operation of PSA type liquid crystal displays is display mura (mura). In the manufacturing process of the PSA type liquid crystal display, the action of external conditions such as light, heat, stress, and the like is required, and UV exposure is particularly an indispensable part thereof. As described above, UV photopolymerization requires two steps of UV1 and UV2, and the UV2 step affects the formed pretilt angle, and the larger the change of the pretilt angle is, the more susceptible the PSA type lcd is to UV process non-uniformity (non-uniformity of external conditions such as light, heat, stress, etc.) to cause corresponding display non-uniformity. Therefore, it is desirable to obtain a polymerizable compound with less pre-tilt angle change after two UV light irradiations, thereby being more beneficial to obtain a wider process margin and better display uniformity.
Another common problem of the PSA type liquid crystal display is the tendency to "shatter bright spots" due to the excessive size of a portion of the polymer particles formed by the polymerizable compound during the polymerization process. In addition, the polymer particles are not uniform in size, which causes uneven distribution of the polymer, and thus, uneven display. Therefore, it is desired to obtain a polymerizable compound capable of forming polymer particles having a small particle size and a uniform distribution, thereby improving the problems of "broken bright spots" and display unevenness.
On the other hand, the polymerizable liquid crystal composition applied to the PSA type liquid crystal display should have a lower rotational viscosity and better electrical properties. In particular, the polymerizable liquid crystal composition should have a high Voltage Holding Ratio (VHR), especially after UV light irradiation. PSA-type lcds are inevitably exposed to UV radiation both during the fabrication process and after fabrication is complete, and the use of liquid crystal media with a low VHR also produces a "blooming" effect in PSA-type lcds. Therefore, the polymerizable liquid crystal composition is inevitably required to have a high VHR.
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 object of the present invention is to provide a polymerizable compound-containing liquid crystal composition having better low-temperature storage stability, faster polymerization speed, lower residual amount of polymerizable compound, and better pre-tilt angle stability.
The invention also aims to provide a liquid crystal display device comprising the 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
at least one compound of the formula M
Wherein,
r and X1-X12Each independently represents-H, halogen, -CN, -Sp2-P2Or a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, wherein one or two of the linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms are not adjacent to each otherabove-CH2-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, wherein X is1-X12At least one of them represents-Cl;
P1and P2Each independently represents a polymerizable group;
Sp1and Sp2Each independently represents a spacer group or a single bond;
R1、R2、RM1and RM2Each 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 atoms2-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 of2May be replaced by-O-, one or more single bonds in the ring may be replaced by a double bond, whereMay be substituted by-F, -Cl or-CN, and one or more rings may be substituted by-CH-N ═ NReplacement;
ring (C)Ring (C)And ringEach independently represent WhereinOne or more-CH of2-may be replaced by-O-and one or more single bonds in the ring may be replaced by double bonds,at most one-H in (a) may be substituted by halogen;
Z1and Z2Each independently represents-O-, -S-, -CO-O-, -O-CO-O-, -CH2O-、-OCH2-、-CH2S-、-SCH2-、-CF2O-、-OCF2-、-CF2S-、-SCF2-、-(CH2)n-、-CF2CH2-、-CH2CF2-、-(CF2)n-、 -CH=CH-、-CF=CF-、-CH=CF-、-CF=CH-、-C≡C-、-CH=CH-CO-O-、-O-CO-CH=CH-、 -CH2CH2-CO-O-、-O-CO-CH2CH2-、-CR1R2-or a single bond, wherein R1And R2Each 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;
Z3represents-CO-O-, -O-CO-, -CH2O-、-OCH2-、-CH=CH-、-C≡C-、-CH2CH2-、-CF2CF2-、 -(CH2)4-、-CF2O-or-OCF2-;
Z4Represents a single bond, -CO-O-, -O-CO-, -CH2O-、-OCH2-、-CH=CH-、-C≡C-、-CH2CH2-、-CF2CF2-、 -(CH2)4-、-CF2O-or-OCF2-;
ZM1And ZM2Each independently represents a single bond, -CO-O-, -O-CO-, -CH2O-、-OCH2-、-C≡C-、-CH=CH-、 -CH2CH2-or- (CH)2)4-;
Y1And Y2Each independently represents-F or-Cl;
a represents an integer of 0 to 2, wherein, when a is 2, the ringMay be the same or different, Z2May be the same or different;
n2represents 0 or 1;
nMrepresents an integer of 0 to 3, wherein when nMWhen 2, ringMay be the same or different, ZM2May be the same or different.
In some embodiments of the invention, preferably, R represents-Sp2-P2。
In some embodiments of the invention, preferably, a represents 0 or 1.
In some embodiments of the present invention, preferably, the liquid crystal composition comprises one polymerizable compound of formula I wherein a ═ 0 and one polymerizable compound of formula I wherein a ═ 1.
In some embodiments of the invention, the compound of formula I is selected from the group consisting of:
wherein,
X1-X12each independently represents-F, -Cl, -Sp2-P2Or a linear, branched or cyclic alkyl or alkoxy group containing 1 to 5 carbon atoms.
In some embodiments of the invention, preferably, Z is1And Z2At least one represents a single bond; further preferably, Z1And Z2All represent single bonds.
The lower limit of the weight percentage of the compound of formula I relative to the total weight of the liquid crystal composition of the present invention is 0.001%, 0.005%, 0.01%, 0.04%, 0.08%, 0.1%, 0.2%, 0.25%, 0.28%, 0.3%, 0.32%, 0.35%, 0.5%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, or 3.5%; the upper limit of the weight percentage of the compound of formula I with respect to the total weight of the liquid crystal composition of the present invention is 5%, 4%, 3.5%, 3%, 2.5%, 2%, 1.5%, 1%, 0.8%, 0.5%, 0.35%, 0.3%, 0.28%, 0.2%, 0.15%, or 0.1%.
In some embodiments of the invention, the compound of formula I comprises 0.001% to 5% by weight of the liquid crystal composition; preferably, the compound of the general formula I accounts for 0.01-2% of the liquid crystal composition by weight; further preferably, the compound of the general formula I accounts for 0.25-0.35% of the liquid crystal composition by weight.
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-C ═ C-or-C ≡ C-are particularly preferred, and for ring-opening polymerization, for example oxetane or epoxy groups are particularly preferred.
In some embodiments of the invention, the polymerizable group P1And P2Each independently represent or-SH; preferably, the polymerizable group P1And P2Each independently represent or-SH; further preferably, the polymerizable group P1And P2Each independently represent
As used herein, the term "spacer" 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.tsciersk, g.pelzl, s.diele, angelw.chem.2004, 116, 6340-. 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)p1-、 -(CH2CH2O)q1-CH2CH2-、-(CH2CH2S)q1-CH2CH2-、-(CH2CH2NH)q1-CH2CH2-、 -CR0R00-(CH2)p1-or- (SiR)0R00-O)p1-, in which p1Represents an integer of 1 to 12, q1Represents an integer of 1 to 3, R0And R00Each independently represents-H or a linear, linear or cyclic alkyl group containing 1 to 12 carbon atoms. A particularly preferred spacer group is- (CH)2)p1-、-(CH2)p1-O-、-(CH2)p1-O-CO-、-(CH2)p1-CO-O-、-(CH2)p1-O-CO-O-or-CR0R00-(CH2)p1-。
The lower limit of the weight percentage of the compound of formula II with respect to the total weight of the liquid crystal composition of the present invention is 1%, 2%, 4%, 6%, 8%, 10%, 12%, 14%, 16%, 18%, 20%, 21.5%, 22%, 24%, 26%, 28%, 30%, 35% or 40%; the upper limit of the weight percentage of the compound of formula II with respect to the total weight of the liquid crystal composition of the present invention is 50%, 48%, 45%, 44%, 42%, 40%, 38%, 36%, 34%, 32%, 30%, 28%, 26%, 24%, 22%, 20%, 18%, 16%, or 15%.
In some embodiments of the invention, the compound of formula II comprises 1% to 50% by weight of the liquid crystal composition; preferably, the compound of the general formula II accounts for 15-50% of the liquid crystal composition by weight; further preferably, the compound of the general formula II accounts for 20-40% of the liquid crystal composition by weight.
In some embodiments of the present invention, Z is preferred when both good miscibility of the liquid crystal composition with the polymerizable compound and faster response speed of the liquid crystal display device need to be taken into account3represents-CH2O-or-OCH2-。
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, R1And R2Each 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, R1And R2Each 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, R1And R2Each independently represents a straight or branched chain containing 1 to 5 carbon atomsA linear alkyl group, 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.
The alkenyl group in the present invention is preferably a group represented by any one of formulae (V1) to (V9), and particularly preferably formula (V1), formula (V2), formula (V8), or (V9). The groups represented by formulae (V1) to (V9) are shown below:
wherein denotes the carbon atom in the ring structure to which it is bonded.
The alkenyloxy group in the present invention is preferably a group represented by any one of formulae (OV1) to (OV9), and particularly preferably formula (OV1), formula (OV2), formula (OV8) or (OV 9). The groups represented by formulae (OV1) to (OV9) are shown below:
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, preferably, RM1And RM2Each 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, RM1And RM2Each 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, RM1And RM2Each 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, RM1And RM2Preferably each independently a linear alkenyl group having 2 to 8 carbon atoms, and more preferably each independently a linear alkenyl group having 2 to 5 carbon atoms.
In some embodiments of the invention, preferably, RM1And RM2Any one of them 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, RM1And RM2Preferably each independently a linear alkyl group containing 1 to 8 carbon atoms, or a linear alkoxy group containing 1 to 7 carbon atoms; further preferred are each independently 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, RM1And RM2Either 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, RM1And RM2Each independently is a linear alkyl group containing 1 to 5 carbon atoms.
The lower limit of the weight percentage of the compound of formula M with respect to the total weight of the liquid crystal composition of the present invention is 5%, 8%, 10%, 15%, 20%, 22%, 24%, 26%, 28%, 30%, 35%, 38%, 40%, 45% or 50%; the upper limit of the weight percentage of the compound of formula M relative to the total weight of the liquid crystal composition of the present invention is 70%, 68%, 65%, 60%, 58%, 56%, 54%, 52%, 50%, 45%, 40%, 38%, 35%, 30%, 28%, 25%, 24%, 22%, or 20%.
In some embodiments of the invention, the compound of formula M comprises 5% to 70% by weight of the liquid crystal composition; preferably, the compound of the general formula M accounts for 30-70% of the liquid crystal composition by weight; further preferably, the compound of the general formula M accounts for 35-65% of the liquid crystal composition by weight.
The content of the compound of the formula M is preferably higher in the lower limit value and higher in the upper limit value 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 it is necessary to keep the clearing point of the liquid crystal composition of the present invention high and the temperature stability good, it is preferable that the lower limit value is high and the upper limit value is high; 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 is lowered and the upper limit value is lowered.
In the case where reliability is important, R is preferableM1And RM2Each independently is alkyl; in the case where importance is attached to reduction in volatility of the compound, R is preferablyM1And RM2Each independently is an alkoxy group; when importance is attached to the reduction in viscosity, R is preferably usedM1And RM2At least one of which is alkenyl.
In some embodiments of the present invention, preferably, the compound of formula M is selected from the group consisting of compounds of formula M-1, formula M-2, formula M-3, formula M-4, formula M-5, formula M-6, formula M-8, formula M-9, formula M-10, formula M-11, formula M-12, formula M-13, formula M-15, formula M-16, formula M-17, formula M-18, formula M-19, formula M-20, and formula M-22; further preferably, the compound of formula M is selected from the group consisting of compounds of formula M-1, formula M-2, formula M-3, formula M-6, formula M-8, formula M-9, formula M-12, formula M-13, formula M-15, formula M-16, formula M-18, formula M-19, formula M-20 and formula M-22; still further preferably, the compound of formula M is selected from the group consisting of compounds of formula M-1, formula M-2, formula M-3, formula M-8, formula M-12, formula M-13 or formula M-22.
In some embodiments of the invention, the liquid crystal composition further comprises at least one compound of formula III:
wherein,
R3and R4Each 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 atoms2-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 of2-may be replaced by-O-and one or more single bonds in the ring may be replaced by double bonds, whereinMay be substituted by-F, -Cl or-CN, and one or more rings-CH-may be replaced by-N;
Y3and Y4Each independently represents-F or-Cl; and is
The lower limit of the weight percentage of the compound of formula III with respect to the total weight of the liquid crystal composition of the present invention is 1%, 2%, 4%, 6%, 8%, 10%, 12%, 15%, 20%, 22%, 24%, 26%, 28% or 30%; the upper limit of the weight percentage of the compound of formula III with respect to the total weight of the liquid crystal composition of the present invention is 40%, 38%, 36%, 35%, 30%, 28%, 25%, 24%, 22% or 20%.
In some embodiments of the invention, the compound of formula III comprises 1% to 40% by weight of the liquid crystal composition; preferably, the compound of the general formula III accounts for 10-40% of the liquid crystal composition by weight.
In some embodiments of the invention, the compound of formula III is selected from the group consisting of:
in some embodiments of the invention, preferably, R3And R4Each 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, R3And R4Each 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, R3And R4Each 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 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 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:
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 present in an amount of 0.001% to 0.1% by weight of the total 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 used to impart a liquid crystal pretilt angle by polymerization of a polymerizable compound in the liquid crystal composition and control the amount of transmitted light in a liquid crystal display device 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. The polymerization is preferably carried out at a temperature close to room temperature (i.e., 15 to 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 is preferably used by blocking the ultraviolet light as necessary. The intensity of the ultraviolet ray to be irradiated is preferably 0.1mW/cm2-50 mW/cm2. When ultraviolet rays are irradiated, the intensity thereof may be changed, and the ultraviolet rays to be irradiated are appropriately selected according to the intensity of the ultraviolet rays to be irradiatedThe time of (3) is preferably 10 s to 600 s.
As used herein, the terms "tilt" and "tilt angle" will be understood as the tilted alignment of liquid crystal molecules with respect to the surface of a liquid crystal cell in a liquid crystal display device, preferably a PSA-type liquid crystal display device. 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 compound of formula I of the invention.
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 containing the polymerizable compound provided by the invention has better low-temperature storage stability, faster polymerization speed, lower polymerizable compound residual quantity and better pre-tilt angle stability, so that a liquid crystal display device containing the polymerizable compound has faster response speed, effectively improves the problems of 'image retention', 'image sticking' or 'display unevenness' and the like of the liquid crystal display device, 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 convenience of expression, in the following examples, the group structures of the liquid crystal compounds are represented by the codes listed in Table 1:
TABLE 1 radical structural code of liquid crystal 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 C atom number of the left alkyl, for example, n is 3, namely, the alkyl is-C3H 7; c in the code represents cyclohexane, G represents 2-fluoro-1, 4-phenylene, and F represents a fluorine substituent.
The abbreviated codes of the test items in the following examples are 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.)
γ1Rotational viscosity (mPa. multidot.s, 25 ℃ C.)
K11Elasticity constant of splay
K33Flexural elastic constant
KaveAverage elastic constant
t-20℃Storage time (day) at-20 deg.C
Stability of the PTA Pre-Tilt Angle (Pre-Tilt Angle Change after fixed time of applied Voltage) (°)
PTA Pre-tilt Angle (°)
T response time (ms)
Wherein,
clearing point 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: 25 ℃, 1KHz, and VA type test cell (cell thickness 6 μm).
Rotational viscosity gamma1: testing by using an LCM-2 type liquid crystal physical property evaluation system; and (3) testing conditions are as follows: the temperature was 25 ℃, the voltage was 240V, and the cell thickness was 20 μm.
K11And K33: C-V curves of the liquid crystal material were measured using an LCR meter and an antiparallel rubbing cassette, and calculated to obtain the test conditions: and a 7-micron antiparallel friction box, wherein V is 0.1-20V.
Low temperature storage time t-20℃: the glass bottle containing the liquid crystal composition was stored at a low temperature of-20 ℃ and observed for crystal precipitation at a fixed time.
Pre-tilt angle PTA: using a crystal rotation method, a liquid crystal is poured into a VA type test cell (cell thickness 3.5 μm), a voltage (16V, 60Hz) is applied while irradiation with ultraviolet light UV1 is performed, so that the polymerizable compound is polymerized to form a pre-tilt angle PTA1, and then the irradiation of ultraviolet light UV2 is continued to the liquid crystal composition having formed the pre-tilt angle PTA1, so as to eliminate the residual polymerizable compound in the PTA1 state, at which time the pre-tilt angle formed by the polymerizable compound is PTA 2. The present inventors examined the polymerization speed of the polymerizable compound by comparing the magnitude of the pretilt angle formed when UV1 was 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 time required, the faster the polymerization speed). The invention inspects the residual amount of the polymerizable compound by eluting the liquid crystal in the liquid crystal test box after applying UV2 with fixed irradiation time length and testing the concentration of the polymerizable compound by High Performance Liquid Chromatography (HPLC).
Pre-tilt angle stability Δ PTA: after a cassette used in a test of pre-tilt angle PTA is subjected to UV1 step and UV2 step to form a pre-tilt angle of 88 ± 0.2 °, a SW wave of 60Hz, an AC voltage of 20V, and a DC voltage of 2V are applied to the cassette, and after a fixed period of time in an environment of 40 ℃ and the presence of backlight, the pre-tilt angle of the cassette is measured, where Δ PTA (168h) ═ PTA (initial) -PTA (168h), and the smaller Δ PTA (168h) indicates the better stability of the pre-tilt angle.
Response time T: the test result is obtained by using a DMS505 tester at 25 ℃, and the test conditions are as follows: TN left-handed type test cell (cell thickness 3.7 μm), drive voltage 5.5V.
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 by conventional methods in the art, such as mixing in proportion by heating, ultrasonic wave, suspension, etc.
TABLE 2 structures and codes of polymerizable Compounds
Comparative examples 1-2 and examples 1-11 liquid crystal compositions Host-1 were prepared according to the compounds and weight percentages listed in Table 3, as shown in the following table:
TABLE 3 liquid crystal composition Host-1 formulation and Performance parameter test results
Polymerizable compounds RM-01 and RM-02 were added to 100 parts by weight of the liquid crystal composition Hsot-1 as comparative example 1-2, and polymerizable compounds RM-1, RM-2, RM-3, RM-4 and RM-5 were added to 100 parts by weight of the liquid crystal composition Host-1 as examples 1-11, and the specific parts by weight of the polymerizable compounds and the results of the relevant property tests are shown in Table 4 below:
as can be seen from the data in Table 4 above, in the case where the Host liquid crystal Host-1 is the same and only the polymerizable compound is different, the liquid crystal composition of the present invention has better low-temperature storage stability than the comparative example 1-2 (the liquid crystal composition in the prior art); as can be seen from the data of PTA1 formed after UV1 is applied to the liquid crystal composition for different times, the polymerization speed of the liquid crystal composition is faster, and the response speed is faster; as can be seen from the test results of the polymer residues, the liquid crystal composition of the invention has lower polymer residues and faster response speed; from the pre-tilt angle stability test results, the pre-tilt angle of the liquid crystal composition provided by the invention has smaller change under the driving of voltage after the pre-tilt angle is generated, and the liquid crystal composition has better pre-tilt angle stability.
Comparative examples 3 to 5 and examples 12 to 23
A liquid crystal composition Host-2 was prepared according to the compounds and weight percentages listed in Table 5, as shown in the following Table:
TABLE 5 liquid crystal composition Host-2 formulation and Performance parameter test results
Polymerizable compounds RM-01 and RM-02 were added to 100 parts by weight of the liquid crystal composition Hsot-2 as comparative examples 3-5, and polymerizable compounds RM-1, RM-2, RM-3, RM-4, RM-5, RM-6, RM-7, RM-8, RM-9, RM-10 and RM-11 were added to 100 parts by weight of the liquid crystal composition Host-2 as examples 12-23, and the specific parts by weight of the polymerizable compounds and the results of the relevant property tests are shown in Table 6 below:
as can be seen from the data of Table 6 above, in the case where the Host liquid crystal Host-2 is the same and only the polymerizable compound is different, the liquid crystal composition of the present invention has better low-temperature storage stability than the comparative examples 3-5 (liquid crystal composition of the prior art); as can be seen from the data of PTA1 formed after applying UV1 for various times to the liquid crystal composition, the polymerization speed of the liquid crystal composition of the present invention is faster, and thus the response speed is faster; as can be seen from the test results of the polymer residues, the liquid crystal composition of the invention has lower polymer residues and faster response speed; from the pre-tilt angle stability test results, the pre-tilt angle of the liquid crystal composition provided by the invention has smaller change under the driving of voltage after the pre-tilt angle is generated, and the liquid crystal composition has better pre-tilt angle stability.
In conclusion, the liquid crystal composition has good low-temperature storage stability, high polymerization speed, low residual amount of polymerizable compounds and good pre-tilt angle stability, so that a liquid crystal display device comprising the liquid crystal composition has good low-temperature storage stability and high response speed, the problems of 'image retention', 'image sticking' or 'display unevenness' of the liquid crystal display device can be effectively improved, and the liquid crystal composition has high 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 (10)
1. 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
at least one compound of the formula M
Wherein,
r and X1-X12Each independently represents-H, halogen, -CN, -Sp2-P2Or a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, wherein one or two or more-CH groups which are not adjacent to each other are contained in the linear, branched or cyclic alkyl group having 1 to 12 carbon atoms2-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, wherein X is1-X12At least one of them represents-Cl;
P1and P2Each independently represents a polymerizable group;
Sp1and Sp2Each independently represents a spacer group or a single bond;
R1、R2、RM1and RM2Each 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 atoms2-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 of2May be replaced by-O-, one or more single bonds in the ring may be replaced by a double bond, whereMay be substituted by-F, -Cl or-CN, and one or more rings-CH-may be replaced by-N;
ring (C)Ring (C)And ringEach independently represent WhereinOne or more-CH of2-may be replaced by-O-, and single bonds in one or more rings may be replaced by double bonds,At most one-H in (a) may be substituted by halogen;
Z1and Z2Each independently represents-O-, -S-, -CO-O-, -O-CO-O-, -CH2O-、-OCH2-、-CH2S-、-SCH2-、-CF2O-、-OCF2-、-CF2S-、-SCF2-、-(CH2)n-、-CF2CH2-、-CH2CF2-、-(CF2)n-、-CH=CH-、-CF=CF-、-CH=CF-、-CF=CH-、-C≡C-、-CH=CH-CO-O-、-O-CO-CH=CH-、-CH2CH2-CO-O-、-O-CO-CH2CH2-、-CR1R2-or a single bond, wherein R1And R2Each 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;
Z3represents-CO-O-, -O-CO-, -CH2O-、-OCH2-、-CH=CH-、-C≡C-、-CH2CH2-、-CF2CF2-、-(CH2)4-、-CF2O-or-OCF2-;
Z4Represents a single bond, -CO-O-, -O-CO-, -CH2O-、-OCH2-、-CH=CH-、-C≡C-、-CH2CH2-、-CF2CF2-、-(CH2)4-、-CF2O-or-OCF2-;
ZM1And ZM2Each independently represents a single bond, -CO-O-, -O-CO-, -CH2O-、-OCH2-、-C≡C-、-CH=CH-、-CH2CH2-or- (CH)2)4-;
Y1And Y2Each independently represents-F or-Cl;
a represents an integer of 0 to 2, wherein, when a is 2, the ringMay be the same or different, Z2May be the same or different;
n2represents 0 or 1;
2. The liquid crystal composition of claim 1, wherein R represents-Sp2-P2。
3. The liquid crystal composition according to claim 1, wherein a represents 0 or 1.
4. Liquid crystal composition according to any of claims 1 to 3, characterized in that the compound of formula I is selected from the group consisting of:
wherein,
X1-X12each independently represents-F, -Cl, -Sp2-P2Or a linear, branched or cyclic alkyl or alkoxy group containing 1 to 5 carbon atoms.
6. the liquid crystal composition of claim 1, wherein the compound of formula I accounts for 0.001-5 wt% of the liquid crystal composition, the compound of formula II accounts for 1-50 wt% of the liquid crystal composition, and the compound of formula M accounts for 5-70 wt% of the liquid crystal composition.
7. The liquid crystal composition of claim 1, further comprising at least one compound of formula III:
wherein,
R3and R4Each 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 atoms2-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 of2May be replaced by-O-, one or more single bonds in the ring may be replaced by a double bond, whereMay be substituted by-F, -Cl or-CN, and one or more rings-CH-may be replaced by-N;
Y3and Y4Each independently represents-F or-Cl; and is
9. the liquid crystal composition according to claim 7 or 8, wherein the compound of formula III accounts for 1 to 40 weight percent of the liquid crystal composition.
10. A liquid crystal display device comprising the liquid crystal composition of any one of claims 1 to 9.
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GB955127A (en) * | 1961-09-20 | 1964-04-15 | Electro Chimie Metal | Methacrylic and acrylic esters of halogenated polyphenols and polymers derived therefrom |
US4149008A (en) * | 1976-03-26 | 1979-04-10 | Dynamit Nobel Aktiengesellschaft | Halogen-containing unsaturated bis-esters |
JP2004157545A (en) * | 1993-02-15 | 2004-06-03 | Seiko Epson Corp | Liquid crystal device |
JP2004123829A (en) * | 2002-09-30 | 2004-04-22 | Seiko Epson Corp | Liquid crystal composition, liquid crystal element and projection display device |
US20140346399A1 (en) * | 2011-10-12 | 2014-11-27 | Jnc Corporation | Polymerizable compound, liquid crystal composition, and liquid crystal display device |
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