Liquid crystal composition and liquid crystal display device containing the same

Abstract

The present invention provides a liquid crystal composition and a liquid crystal display device containing the same. The liquid crystal composition comprises at least one polymerizable compound (RM) and at least one self-aligning agent (SA). The liquid crystal composition exhibits a low haze value in the absence of an applied voltage, but exhibits a high haze value and a high VHR value after voltage is applied. This allows liquid crystal displays containing the composition to achieve vertical alignment of liquid crystal molecules without requiring a PI alignment layer, resulting in high reliability and a long service life. The composition is particularly suitable for use in R-PNLC display modes. #imgabs0#

Description

Technical Field

[0001] The present invention relates to the field of liquid crystals, and in particular to a liquid crystal composition and a polymer network liquid crystal display device comprising the liquid crystal composition. Background Art

[0002] Liquid crystal display devices contain a nematic liquid crystal composition with suitable properties. Improving the properties of the liquid crystal composition can yield an AM device with superior properties. The relationship between the properties of the liquid crystal composition and the AM device is summarized in Table A below. The properties of the liquid crystal composition are further explained based on commercially available AM ​​devices. The temperature range of the nematic phase correlates with the device's operating temperature range. The viscosity of the liquid crystal composition correlates with the device's response time. To enable the device to display dynamic images, a short response time is preferred.

[0003] Table A: Characteristics of liquid crystal compositions and AM devices

[0004] serial number Characteristics of liquid crystal compositions Characteristics of AM components 1 Nematic phase has a wide temperature range Wide temperature range 2 Low viscosity Short response time 3 Large optical anisotropy High contrast 4 Large absolute value of dielectric anisotropy Low threshold voltage, low power consumption, high contrast 5 Larger specific resistance High voltage holding rate and contrast 6 UV and heat stable Long lifespan 7 Large elastic constant High contrast, short response time, fast response speed

[0005] According to the formula (Wherein, γ1 is the rotational viscosity of the liquid crystal material, d is the liquid crystal cell spacing, V is the liquid crystal cell driving voltage, and Δε is the liquid crystal cell dielectric anisotropy) It can be seen that to reduce the response application, the rotational viscosity of the liquid crystal material can be reduced, the dielectric anisotropy can be increased, or the liquid crystal cell spacing can be reduced. However, the rotational viscosity of the liquid crystal material and the dielectric anisotropy of the liquid crystal material are directly related to the characteristics of the liquid crystal material itself. R&D personnel need to conduct repeated experiments and multi-faceted comparative tests to determine a liquid crystal material that is stable and can meet the low response time requirements. On the other hand, by improving the manufacturing process and reducing the thickness of the liquid crystal cell, the response time can be increased. This is also the most direct way for panel manufacturers to increase the response time. However, the delay amount (Δn×d) is usually fixed, so liquid crystal display devices with a smaller cell thickness often require the liquid crystal composition to have a larger optical anisotropy. How to make the liquid crystal composition take into account a larger optical anisotropy, a larger dielectric anisotropy and a suitable rotational viscosity is still a problem that needs to be solved in this field.

[0006] Polymer-dispersed liquid crystal (PDLC) displays are a recently developed type of flat-panel display device capable of displaying information. PDLC combines liquid crystals with a polymer matrix and, under certain conditions, undergoes a polymerization reaction to form micron-sized liquid crystal droplets uniformly dispersed within the matrix. The dielectric anisotropy of the liquid crystal molecules is then exploited to create a material with electro-optical response properties. Under the influence of an external field (such as an electric field or thermal field), it can exhibit two distinct optical states: transmission and scattering. In the absence of an applied voltage, the PDLs cannot form a regular electric field, resulting in a random and disordered optical axis orientation of the liquid crystal particles. Their effective refractive index does not match that of the polymer, strongly scattering incident light and rendering the display opaque or translucent. Upon application of an external voltage, the optical axes of the liquid crystal particles align perpendicular to the display surface, aligning with the direction of the electric field. The ordinary refractive index of the particles essentially matches that of the polymer, creating a largely homogeneous medium with no distinct interface. Consequently, incident light is not scattered, and the display appears transparent.

[0007] However, PDLC displays have problems such as high operating voltage (20-30V) and narrow viewing angle, resulting in high power consumption. In addition, the molecules of PDLC liquid crystals are large and not easy to drive using a horizontal electric field. Therefore, by increasing the proportion of liquid crystal in the mixture (usually the proportion of liquid crystal reaches more than 80%), during the phase separation process, the liquid crystal is no longer dispersed in the polymer in the form of droplets, but exists in a continuous phase form. At this time, the polymer is distributed in the liquid crystal in a network texture, that is, the polymer network liquid crystal (PNLC) display mode. In the PNLC liquid crystal display mode, in the absence of an external voltage, since the liquid crystal exists in a multi-domain state in the network, the distribution of the directivity of each liquid crystal domain is random, and the incident light is scattered at the interface between the domains due to the discontinuous change of refractive index, which appears opaque; when a voltage is applied, the electric field causes the directivity of all liquid crystal domains to be arranged into a single domain state along the direction of the electric field. For the incident light, it is a medium with a uniform refractive index and is therefore transparent. When the voltage applied to the PNLC is large enough, the vertical transmittance reaches its maximum and the film is in a transparent state.

[0008] The aforementioned PNLC display mode is a forward polymer network liquid crystal (PNLC), meaning it's "transparent when powered on, frosted when powered off." Currently, a reverse polymer network liquid crystal (R-PNLC) display mode has been developed, exhibiting both a transparent off-state and a light-scattering on-state. Because the R-PNLC display mode exhibits transparency in its off-state, it has broad application prospects, including applications in glass windows, e-readers, and transparent displays.

[0009] The electro-optical properties of the R-PNLC display mode are achieved by using nematic liquid crystals (LCs) with negative dielectric anisotropy or dual-frequency addressable nematic liquid crystals. In the absence of an applied voltage, the vertical alignment layer aligns the negative LC molecules with their long axes perpendicular to the electrodes. At this point, light only sees the refractive index along the short axis, which is close to that of the polymer, resulting in a transparent state. When an electric field is applied, the LC molecules are affected by the electric field, causing the LC directors to flip parallel to the substrate. This means that the LC molecules' short axes rotate parallel to the electric field, resulting in a tendency for the LC to lie flat. The LC molecules are distributed in a continuous phase within the polymer network and, influenced by the anchoring effect of the polymer network, the direction in which the LC falls is disordered, appearing as a scattered state. Furthermore, the degree of LC disorder varies depending on the process conditions, such as temperature and LC injection pressure. This can lead to differences in haze values ​​between samples when driven with voltage, ultimately resulting in inconsistent haze across the LC panel.

[0010] The current R-PNLC display mode usually uses a polyimide (PI) layer as the orientation layer. Limited by the physical properties of polyimide, the PI orientation layer in the R-PNLC display mode is generally light yellow. However, since transparent displays have high requirements for initial transparency, the process method of using PI liquid as the orientation layer can no longer adapt to the development trend of display technology. In addition, in the current R-PNLC display mode, since there is no chemical connection between the polymer matrix and the orientation layer or the orientation layer and the glass substrate, and they are closely bonded physically, the bonding force gradually weakens with the increase of years of use, so that the polymer matrix and the orientation layer or the orientation layer and the glass substrate peel off, resulting in a gap, which will affect the light transmittance and service life of the R-PNLC display mode.

[0011] Therefore, there is an urgent need for a liquid crystal composition suitable for the R-PNLC display mode, which does not require a PI alignment layer to achieve the purpose of reducing costs and simplifying the process, while having a better haze value, better reliability and longer service life, and can meet the high requirements of technological development for liquid crystal display devices. Summary of the Invention

[0012] Purpose of the invention: In view of the defects of the prior art, the purpose of the present invention is to provide a liquid crystal composition, which has a smaller haze value when no external voltage is applied, and has a larger haze value and a higher VHR value after voltage is applied.

[0013] Another object of the present invention is to provide a liquid crystal display device comprising the liquid crystal composition, in particular a liquid crystal display device in an R-PNLC display mode.

[0014] Technical solution: In order to achieve the above invention objectives, the present invention provides a liquid crystal composition, which comprises:

[0015] At least one polymerizable compound of the general formula RM

[0016] as well as

[0017] At least one self-aligning agent of the general formula SA

[0018]

[0019] in,

[0020] R1 represents -Sp2-P2, a linear or branched alkyl group containing 1-12 (for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11) carbon atoms, wherein one or two or more non-adjacent -CH2- in the linear or branched alkyl group containing 1-12 carbon atoms may be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O-, or -O-CO-, and one or more -H may be independently replaced by -F or -Cl;

[0021] R S1 Indicates -Sp 1 -P 1 , a linear or branched alkyl group containing 1 to 12 (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11) carbon atoms, wherein one or more non-adjacent -CH2- in a linear or branched alkyl group containing 1 to 12 carbon atoms may be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O- or -O-CO-, and wherein one or more non-adjacent -CH2- in a linear or branched alkyl group containing 1 to 12 carbon atoms, One or more -H in can be independently replaced by -F or -Cl;

[0022] ring ring and Ring Each independently expresses in One or more -CH2- in the ring may be replaced by -O-, and one or more single bonds in the ring may be replaced by double bonds, wherein wherein one or more -H in the ring may be independently replaced by -F, -Cl, -CN, -Sp3-P3, -KO, -CO-OKO-, -O-COKO-, or -O-CO-OKO-, and -CH= in one or more rings may be replaced by -N=, wherein K0 represents a halogenated or unhalogenated straight-chain alkylene group containing 1 to 6 carbon atoms, or a halogenated or unhalogenated straight-chain alkyleneoxy group containing 1 to 5 carbon atoms;

[0023] ring express in One or more -CH2- in the ring may be replaced by -O-, and one or more single bonds in the ring may be replaced by double bonds;

[0024] Ls1 and Ls3 each independently represent -F, -Cl, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(O)N(R S0 )2、-C(O)R S0 , a linear or branched alkyl group containing 1 to 12 (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11) carbon atoms, wherein one or more non-adjacent -CH2- in a linear or branched alkyl group containing 1 to 12 carbon atoms may be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O- or -O-CO-, and wherein one or more non-adjacent -CH2- in a linear or branched alkyl group containing 1 to 12 carbon atoms, One or more -H in the R S0 represents a straight or branched alkyl group containing 1 to 12 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12) carbon atoms;

[0025] Ls2 means -Sp 3 -P 2 or

[0026] R S2 and R S3 Each independently represents an anchoring group, the anchoring group is

[0027] Where * indicates the connection site in the bonded structure;

[0028] p represents 1 or 2, wherein when p represents 2, -Sp 8 -X 2 Can be the same or different;

[0029] o represents 0 or 1;

[0030] M S1 express

[0031] I S1 and J S1 Each independently represents -CH2-, -O- or -S-;

[0032] N S1 Indicates =O or =S;

[0033] V K1 、V K2 and V K3 Each independently represents -CH= or -N=;

[0034] X 1 and X 2 Each independently represents -H, -OH, -SH, -NH2, -NHR 11 、-N(R 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 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12) carbon atoms, wherein X 1 and X 2 At least one of -OH, -SH, -NH2, -NHR 11 , -C(O)OH and -CHO, where R 11 represents a straight or branched alkyl group containing 1 to 12 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12) carbon atoms;

[0035] P1, P2, P3, P 1 、P 2 and P 3 each independently represents a polymerizable group;

[0036] Sp1, Sp2, Sp3, Sp 1 、Sp 2 、Sp 3 、Sp 4 、Sp 5 、Sp 7 and Sp 8Each independently represents a spacer group or a single bond;

[0037] Sp 6 Each independently expresses

[0038] Z 1 and Z 2 Each independently represents -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CH2O-, -OCH2-, -CH2S-, -SCH2-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -(CH2) d -, -CF2CH2-, -CH2CF2-, -(CF2) d -, -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -C≡C-, -CH=CH-CO-O-, -O-CO-CH=CH-, -CH2CH2-CO-O-, -O-CO-CH2CH2-, -CHR 1 -、-CR 1 R 2 - or a single bond, where R 1 and R 2 Each independently represents a linear or branched alkyl group containing 1 to 12 carbon atoms, and d represents an integer of 1 to 4;

[0039] n s1 Indicates 1, 2, or 3, n s2 means 1, 2, 3 or 4, and n s1 +n s2 ≥3, where n s1 When it means 2 or 3, Can be the same or different, where n s2 When it means 2, 3 or 4, Can be the same or different;

[0040] p s1 、p s2 、p s3 and p s4 Each independently represents 0, 1 or 2, where p s1 When p represents 2, Ls2 can be the same or different. s2 When p represents 2, Ls1 can be the same or different; s3 When it means 2, -Sp 5 -R S3 can be the same or different; when p s4 When it represents 2, Ls3 can be the same or different;

[0041] Z1 and Z2 each independently represent -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CH2O-, -OCH2-, -CH2S-, -SCH2-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -(CH2) d -, -CF2CH2-, -CH2CF2-, -(CF2) d -, -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -C≡C-, -CH=CH-CO-O-, -O-CO-CH=CH-, -CH2CH2-CO-O-, or -O-CO-CH2CH2-; and

[0042] a represents 1 or 2, b represents 0 or 1, where a+b≥3. When a represents 2, the ring can be the same or different, and Z1 can be the same or different.

[0043] In some embodiments of the present invention, the polymerizable compound of formula RM is selected from the group consisting of:

[0044]

[0045]

[0046] in,

[0047] X1, X2 and X3 each independently represent -F, -Cl, -Sp3-P3, -KO, -CO-OK0-, -O-COKO-, -O-CO-OK0-;

[0048] ring express in One or more -CH2- in the ring may be replaced by -O-, and one or more single bonds in the ring may be replaced by double bonds, wherein One or more -H in the ring may be independently replaced by -F, -Cl, -CN, -Sp3-P3, -KO, -CO-OKO-, -O-COKO-, or -O-CO-OKO-, and -CH= in one or more rings may be replaced by -N=.

[0049] In some embodiments of the present invention, X1, X2 and X3 each independently represent -F, -Cl, -Sp3-P3, -CH3, -OCH3, -CO-OCH3, -CO-OCH2CH3, -O-COCH3, or -O-CO-OCH3.

[0050] In some embodiments of the present invention, preferably, Z1 and Z2 each independently represent -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CH2O-, -OCH2-, -CH2S-, -SCH2-, -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -C≡C-, -CH=CH-CO-O-, -O-CO-CH=CH-, -CH2CH2-CO-O- or -O-CO-CH2CH2-; further preferably, Z1 and Z2 each independently represent -CO-O-, -O-CO-, -O-CO-O-, CH=CH-, -C≡C-.

[0051] In some embodiments of the present invention, the polymerizable compound of formula RM-1 is selected from the group consisting of:

[0052]

[0053] as well as

[0054]

[0055] In some embodiments of the present invention, the polymerizable compound of formula RM-2 is selected from the group consisting of:

[0056]

[0057] as well as

[0058]

[0059] In some embodiments of the present invention, the polymerizable compound of formula RM-3 is selected from the group consisting of:

[0060]

[0061] as well as

[0062]

[0063] In some embodiments of the present invention, the polymerizable compound of formula RM-4 is selected from the group consisting of:

[0064]

[0065] as well as

[0066]

[0067] The polymerizable groups of the present invention are groups suitable for polymerization reactions (e.g., free radical or ionic polymerization, addition polymerization, or condensation polymerization), or groups suitable for addition or condensation onto the polymer backbone. For chain polymerization, polymerizable groups containing -C=C- or -C≡C- are particularly preferred, and for ring-opening polymerization, groups such as oxetane or epoxy groups are particularly preferred.

[0068] In some embodiments of the present invention, the polymerizable groups P1, P2, P3, P 1 、P 2 , and P 3 Each independently expresses Or -SH; Preferably, the polymerizable groups P1, P2, P3, P 1 、P 2 , and P 3 Each independently expresses Or -SH; Further preferably, the polymerizable groups P1, P2, P3, P 1 、P 2 , and P 3 Each independently expresses

[0069] 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. Tschierske, G. Pelzl, S. Diele, Angew. Chem. 2004, 116, 6340-6368). As used herein, the term "spacer group" refers to a flexible group that connects the mesogenic group and the polymerizable group in a polymerizable compound. Typical spacer groups are, for example, -(CH2)p1-, -(CH2CH2O)q1-CH2CH2-, -(CH2CH2S)q1-CH2CH2-, -(CH2CH2NH)q1-CH2CH2-, -CR 0 R 00 -(CH2) p1 -or-(SiR 0 R 00 -O)p1-, wherein p1 represents an integer from 1 to 12 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12), q1 represents an integer from 1 to 3 (e.g., 1, 2, 3), and R 0 and R 00Each independently represents -H, a linear or branched alkyl group containing 1 to 12 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12) carbon atoms, or a cyclic alkyl group containing 3 to 12 (e.g., 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12) carbon atoms. Particularly preferred spacer groups are -(CH2)p1-, -(CH2)p1-O-, -(CH2)p1-O-CO-, -(CH2)p1-CO-O-, -(CH2)p1-O-CO-O-, or -CR 0 R 00 -(CH2) p1 -.

[0070] In some embodiments of the present invention, Sp1, Sp2 and Sp3 each independently represent -(CH2)p1-O-, -(CH2)p1-O-CO-, -(CH2)p1-CO-O- or -(CH2)p1-O-CO-O-.

[0071] In some embodiments of the present invention, in order to obtain better haze value and higher VHR value, p1 preferably represents an integer of 2-8 (eg, 2, 3, 4, 5, 6, 7, 8).

[0072] In some embodiments of the present invention, the polymerizable compound of formula RM accounts for 0.001% to 15% by weight of the liquid crystal composition (including any value or sub-range between the ranges), for example, 0.001%, 0.002%, 0.004%, 0.005%, 0.006%, 0.008%, 0.01%, 0.02%, 0.04%, 0.06%, 0.08%, 0.1%, 0.2%, 0.25%, 0.26%, 0.27%, 0.28%, 0.29%, 0.3%, 0.32%, 0.33%, 0.34%, 0.35%, 0.4% %, 0.5%, 0.6%, 0.8%, 1%, 1.2%, 1.6%, 1.8%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.2%, 5.6%, 5.8%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%, or a range between any two values; preferably, the weight percentage of the polymerizable compound of general formula RM in the liquid crystal composition is 0.1%-10%.

[0073] In some embodiments of the present invention, Ls2 represents -Sp 3 -P 2 、

[0074] In some embodiments of the present invention, Sp 3 、Sp 4 and Sp 5 Each independently represents -(CH2)p1-, -(CH2)p1-O-, -(CH2)p1-O-CO-, -(CH2)p1-CO-O-, -(CH2)p1-O-CO-O- or -CR 0 R 00 -(CH2) p1 -, wherein p1 represents an integer from 1 to 10 (e.g., 2, 3, 4, 5, 6, 7, 8, or 9), R 0 and R 00 Each independently represents -H or a linear or branched alkyl group containing 1 to 10 carbon atoms; preferably, Sp 3 、Sp 4 and Sp 5 Each independently represents -(CH2)p1- or -(CH2)p1-O-.

[0075] In some embodiments of the present invention, the self-aligning agent of formula SA is selected from the group consisting of the following compounds:

[0076]

[0077]

[0078]

[0079] as well as

[0080]

[0081] in,

[0082] Ls 31 Indicates -F, -Cl, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(O)N(R S0 )2、-C(O)R S0 , a linear or branched alkyl group containing 1 to 12 (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11) carbon atoms, wherein one or more non-adjacent -CH2- in a linear or branched alkyl group containing 1 to 12 carbon atoms may be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O- or -O-CO-, and wherein one or more non-adjacent -CH2- in a linear or branched alkyl group containing 1 to 12 carbon atoms, One or more -H in the R S0 represents a straight-chain or branched alkyl group containing 1 to 12 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12) carbon atoms;

[0083] Ls 21 Indicates -Sp 3 -P 2 or and

[0084] Z 11 Represents -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CH2O-, -OCH2-, -CH2S-, -SCH2-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -(CH2) d -, -CF2CH2-, -CH2CF2-, -(CF2) d -, -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -C≡C-, -CH=CH-CO-O-, -O-CO-CH=CH-, -CH2CH2-CO-O-, -O-CO-CH2CH2-, -CHR 1 -、-CR 1 R 2 - or a single bond, where R 1 and R 2 Each independently represents a linear or branched alkyl group containing 1 to 12 carbon atoms, and d represents an integer of 1 to 4.

[0085] In some embodiments of the present invention, the compound of formula SA is selected from the group consisting of a compound of formula SA-1, a compound of formula SA-2, and a compound of formula SA-3.

[0086] In some embodiments of the present invention, preferably, Ls1, Ls3 and Ls 31 Each independently represents -F, -Cl, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(O)N(R S0 )2、-C(O)R S0 , a straight-chain or branched alkyl group containing 1 to 10 carbon atoms, a straight-chain or branched alkoxy group containing 1 to 9 carbon atoms, or a straight-chain or branched alkenyl group containing 2 to 10 carbon atoms; further preferably, Ls1, Ls3 and Ls 31 Each independently represents -F, -Cl, a linear or branched alkyl group containing 1 to 8 carbon atoms, a linear or branched alkoxy group containing 1 to 7 carbon atoms, or a linear or branched alkenyl group containing 2 to 8 carbon atoms.

[0087] In some embodiments of the present invention, preferably, R S1 Indicates -Sp 1 -P 1 , a straight-chain or branched alkyl group containing 1 to 10 carbon atoms, a straight-chain or branched alkoxy group containing 1 to 9 carbon atoms, or a straight-chain or branched alkenyl group containing 2 to 10 carbon atoms; further preferably, R S1 It represents a straight-chain or branched alkyl group containing 1 to 8 carbon atoms, a straight-chain or branched alkoxy group containing 1 to 7 carbon atoms, or a straight-chain or branched alkenyl group containing 2 to 8 carbon atoms.

[0088] In some embodiments of the present invention, R S2 and R S3 Each independently represents -OH, -SH, -NH2, -NHR 11 、-N(R 11 )2, -NHC(O)R 11 、-OR 11 、-C(O)OH、 or -X 1 .

[0089] In some embodiments of the present invention, R S2 and R S3 are each independently selected from the group consisting of:

[0090]

[0091]

[0092] as well as

[0093] in,

[0094] * indicates the attachment site in the bonded structure.

[0095] In some embodiments of the present invention, R S2 and R S3 are each independently selected from the group consisting of:

[0096] as well as Furthermore, R S2 and R S3 Each independently preferably is:

[0097] In some embodiments of the present invention, p s1 Indicates 1 or 2.

[0098] In some embodiments of the present invention, p s2 Indicates 0 or 1.

[0099] In some embodiments of the present invention, the weight percentage of the compound of general formula SA in the liquid crystal composition is 0.001% to 5% (including any value or sub-range between this range), for example, 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%, 5%, or a range between any two values ​​therein; preferably, the weight percentage of the compound of general formula SA in the liquid crystal composition is 0.1% to 2%.

[0100] In the present invention, when the compound of the general formula SA is added to the liquid crystal composition, the liquid crystal composition of the present invention can align the liquid crystal molecules without setting a PI alignment layer, so that the liquid crystal composition of the present invention does not require a PI alignment layer when applied to the R-PNLC display mode, simplifies the process, has a better haze value, and enables the liquid crystal display device to have higher reliability and longer service life, and has a better display effect.

[0101] In some embodiments of the present invention, the liquid crystal composition further comprises at least one compound of the general formula N:

[0102]

[0103] in,

[0104] R N1 and R N2 Each independently represents a straight or branched alkyl group containing 1 to 12 (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 11) carbon atoms, One or more non-adjacent -CH2- in the linear or branched alkyl group containing 1 to 12 carbon atoms may be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O- or -O-CO-;

[0105] ring and Ring Each independently expresses in One or more -CH2- in the ring may be replaced by -O-, and one or more single bonds in the ring may be replaced by double bonds, wherein One or more -H in the ring may be replaced by -F, -Cl or -CN, and one or more -CH= in the ring may be replaced by -N=;

[0106] Z N1 and Z N2 Each independently represents a single bond, -CO-O-, -O-CO-, -CH2O-, -OCH2-, -C≡C-, -CH=CH-, -CH2CH2- or -(CH2)4-;

[0107] L N1 and L N2 Each independently represents -H, an alkyl group containing 1 to 3 (e.g., 1, 2, 3) carbon atoms, or a halogen;

[0108] n N1 Indicates 0, 1, 2, or 3, n N2 Represents 0 or 1, and 0≤n N1 +n N2 ≤3, when n N1 =2 or 3, the ring Can be the same or different, Z N1 Can be the same or different.

[0109] In some embodiments of the present invention, L N1 and L N2 All represent -H.

[0110] In some embodiments of the present invention, the compound of formula N is selected from the group consisting of:

[0111]

[0112]

[0113]

[0114] as well as

[0115]

[0116] In some embodiments of the present invention, preferably, R N1 and R N2 Each independently represents a straight-chain or branched alkyl group containing 1 to 10 carbon atoms, a straight-chain or branched alkoxy group containing 1 to 9 carbon atoms, or a straight-chain or branched alkenyl group containing 2 to 10 carbon atoms; further preferably, R N1 and R N2Each independently represents a straight-chain or branched alkyl group containing 1 to 8 carbon atoms, a straight-chain or branched alkoxy group containing 1 to 7 carbon atoms, or a straight-chain or branched alkenyl group containing 2 to 8 carbon atoms.

[0117] In some embodiments of the present invention, in order to obtain a higher clearing point, a smaller low temperature storage phase transition point, a larger optical anisotropy (larger n e , smaller n0), larger absolute value of dielectric anisotropy, smaller volume viscosity, smaller haze value when no external voltage is applied, larger haze value after voltage is applied, the compound of general formula N is selected from the group consisting of compounds of general formula N-6, compounds of general formula N-7, compounds of general formula N-14, compounds of general formula N-18, compounds of general formula N-19, compounds of general formula N-20, compounds of general formula N-21, compounds of general formula N-23, compounds of general formula N-27, and compounds of general formula N-31.

[0118] In some embodiments of the present invention, in order to obtain a higher clearing point, a smaller low temperature storage phase transition point, a larger optical anisotropy (larger n e , smaller n0), larger absolute value of dielectric anisotropy, smaller volume viscosity, smaller haze value when no external voltage is applied, larger haze value after voltage is applied, the compound of general formula N is selected from the group consisting of compounds of general formula N-6, compounds of general formula N-7, compounds of general formula N-14, compounds of general formula N-19, compounds of general formula N-21, and compounds of general formula N-31.

[0119] In some embodiments of the present invention, in order to obtain a higher clearing point, a smaller low temperature storage phase transition point, a larger optical anisotropy (larger n e , smaller n0), larger absolute value of dielectric anisotropy, smaller volume viscosity, smaller haze value when no external voltage is applied, larger haze value after voltage is applied, the compound of general formula N is selected from the group consisting of compounds of general formula N-18, compounds of general formula N-20, compounds of general formula N-23, and compounds of general formula N-27.

[0120] In some embodiments of the present invention, it is preferred to adjust the content of the compound of formula N so that the liquid crystal composition of the present invention has a higher clearing point, a smaller low-temperature storage phase transition point, a larger optical anisotropy (larger n e , smaller n0), larger absolute value of dielectric anisotropy, smaller volume viscosity, smaller haze value when no external voltage is applied, and larger haze value after voltage is applied.

[0121] In some embodiments of the present invention, the weight percentage of the compound of formula N in the liquid crystal composition is 0.1%-99% (including any value or sub-range between the ranges), for example, 0.1%, 1%, 4%, 6%, 8%, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, 30%, 32%, 34%, 36%, 38%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 100%, 100%, 101%, 102%, 103%, 104%, 105%, 106%, 107%, 108%, 109%, 110%, 111%, 112%, 113%, 114%, 115%, 116%, 117%, 118%, 2%, 44%, 46%, 48%, 50%, 52%, 54%, 56%, 58%, 60%, 62%, 64%, 66%, 68%, 70%, 72%, 74%, 76%, 78%, 80%, 82%, 84%, 86%, 98%, 99%, or any range between two of these values; preferably, the weight percentage of the compound of formula N in the liquid crystal composition is 40%-98%.

[0122] In some embodiments of the present invention, the liquid crystal composition comprises at least one compound of the general formula M:

[0123]

[0124] in,

[0125] R M1 and R M2 Each independently represents a straight or branched alkyl group containing 1 to 12 (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 11) carbon atoms, One or more non-adjacent -CH2- in the linear or branched alkyl group containing 1 to 12 carbon atoms may be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O- or -O-CO-;

[0126] ring ring and Ring Each independently expresses in One or more -CH2- in the ring 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 may be replaced by halogen;

[0127] Z M1 and Z M2 Each independently represents a single bond, -CO-O-, -O-CO-, -CH2O-, -OCH2-, -C≡C-, -CH=CH-, -CH2CH2- or -(CH2)4-; and

[0128] n M represents 0, 1 or 2, where n M=2, the ring Can be the same or different, Z M2 Can be the same or different.

[0129] In some embodiments of the present invention, preferably, R M1 and R M2 Each independently represents a straight-chain or branched alkyl group containing 1 to 10 carbon atoms, a straight-chain or branched alkoxy group containing 1 to 9 carbon atoms, or a straight-chain or branched alkenyl group containing 2 to 10 carbon atoms; further preferably, R M1 and R M2 Each independently represents a straight-chain or branched alkyl group containing 1 to 8 carbon atoms, a straight-chain or branched alkoxy group containing 1 to 7 carbon atoms, or a straight-chain or branched alkenyl group containing 2 to 8 carbon atoms.

[0130] In some embodiments of the present invention, R M1 and R M2 Preferably, each independently represents a straight-chain alkenyl group containing 2 to 8 carbon atoms; R M1 and R M2 More preferably, each independently represents a straight-chain alkenyl group containing 2 to 5 carbon atoms.

[0131] In some embodiments of the present invention, preferably, R M1 and R M2 One of them is a straight-chain alkenyl group containing 2 to 5 carbon atoms, and the other is a straight-chain alkyl group containing 1 to 5 carbon atoms.

[0132] In some embodiments of the present invention, preferably, R M1 and R M2 Each independently represents a straight chain alkoxy group containing 1 to 8 carbon atoms; further preferably, R M1 and R M2 Each independently represents a straight-chain alkoxy group containing 1 to 5 carbon atoms.

[0133] In some embodiments of the present invention, preferably, R M1 and R M2 One of them is a straight-chain alkoxy group containing 1 to 5 carbon atoms, and the other is a straight-chain alkyl group containing 1 to 5 carbon atoms.

[0134] In some embodiments of the present invention, when reliability is important, R M1 and R M2 are all alkyl groups; when it is important to reduce the volatility of the compound, R M1 and R M2 are all alkoxy groups; when the viscosity reduction is important, R M1 and R M2At least one of them is an alkenyl group.

[0135] The alkenyl group in the present invention is preferably selected from the group represented by any one of formula (V1) to formula (V9), and is particularly preferably formula (V1), formula (V2), formula (V8), or (V9). The groups represented by formula (V1) to formula (V9) are as follows:

[0136]

[0137] Here, * represents the carbon atom in the ring structure to which it is bonded.

[0138] The alkenyloxy group in the present invention is preferably selected from the group represented by any one of Formula (OV1) to Formula (OV9), and is particularly preferably Formula (OV1), Formula (OV2), Formula (OV8), or (OV9). The groups represented by Formula (OV1) to Formula (OV9) are as follows:

[0139]

[0140] Here, * represents the carbon atom in the ring structure to which it is bonded.

[0141] In some embodiments of the present invention, the compound of formula M is selected from the group consisting of:

[0142]

[0143]

[0144]

[0145] as well as

[0146]

[0147] In some embodiments of the present invention, in order to obtain a higher clearing point, a smaller low temperature storage phase transition point, a larger optical anisotropy (larger n e , smaller n0), larger absolute value of dielectric anisotropy, smaller volume viscosity, smaller haze value when no external voltage is applied, larger haze value after voltage is applied, the compound of general formula M is selected from the group consisting of compounds of general formula M-1, compounds of general formula M-9, and compounds of general formula M-13.

[0148] In some embodiments of the present invention, it is preferred to adjust the content of the compound of formula M so that the liquid crystal composition of the present invention has a higher clearing point, a smaller low-temperature storage phase transition point, a larger optical anisotropy (larger n e, smaller n0), larger absolute value of dielectric anisotropy, smaller volume viscosity, smaller haze value when no external voltage is applied, and larger haze value after voltage is applied.

[0149] In some embodiments of the present invention, the weight percentage of the compound of formula M in the liquid crystal composition is 0.1%-50% (including any value or sub-range between this range), for example, 0.1%, 1%, 4%, 6%, 8%, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, 30%, 32%, 34%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, 50%, or a range between any two values.

[0150] In some embodiments of the present invention, the liquid crystal composition of the present invention further comprises at least one compound selected from the group consisting of compounds of formula A-1 and formula A-2

[0151]

[0152] in,

[0153] R A1 and R A2 Each independently represents a straight or branched alkyl group containing 1 to 12 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12) carbon atoms, One or more non-adjacent -CH2- in the linear or branched alkyl group containing 1 to 12 carbon atoms can be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O- or -O-CO-, and the linear or branched alkyl group containing 1 to 12 carbon atoms, One or more -H in can be independently replaced by -F or -Cl;

[0154] ring ring ring and Ring Each independently expresses in One or more -CH2- in the ring may be replaced by -O-, and one or more single bonds in the ring may be replaced by double bonds, wherein One or more -H in the ring may be replaced by -F, -Cl or -CN, and one or more -CH= in the ring may be replaced by -N=;

[0155] Z A11 , Z A21 and Z A22each independently represents a single bond, -CH2CH2-, -CF2CF2-, -CO-O-, -O-CO-, -O-CO-O-, -CH=CH-, -CF=CF-, -CH2O- or -OCH2-;

[0156] 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 a halogen;

[0157] X A1 and X A2 Each independently represents halogen, a haloalkyl or haloalkoxy group containing 1 to 5 carbon atoms, a haloalkenyl or haloalkenyloxy group containing 2 to 5 carbon atoms;

[0158] n A11 Represents 0, 1, 2, or 3. When n A11 =2 or 3, the ring Can be the same or different, Z A11 Can be the same or different;

[0159] n A12 represents 1 or 2, where n A12 =2, the ring may be the same or different; and

[0160] n A2 represents 0, 1, 2, or 3, where n A2 =2 or 3, the ring Can be the same or different, Z A21 Can be the same or different.

[0161] In some embodiments of the present invention, the compound of formula A-1 is selected from the group consisting of:

[0162]

[0163]

[0164]

[0165] as well as

[0166]

[0167] in,

[0168] R A1 represents a straight or branched alkyl group containing 1 to 8 carbon atoms, One or more non-adjacent -CH2- in the linear or branched alkyl group containing 1 to 8 carbon atoms may be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O- or -O-CO-, and one or more -H in these groups may be independently replaced by -F or -Cl;

[0169] R v and R w Each independently represents -CH2- or -O-;

[0170] L A11 、L A12 、L A11 '、L A12 '、L A14 、L A15 and L A16 Each independently represents -H or -F;

[0171] L A13 and L A13 'Each independently represents -H or -CH3;

[0172] X A1 represents -F, -CF3 or -OCF3; and

[0173] v and w each independently represent 0 or 1.

[0174] In some embodiments of the present invention, the weight percentage of the compound of general formula A-1 in the liquid crystal composition is 0.1%-50% (including any value or sub-range between this range), for example, 0.1%, 1%, 4%, 6%, 8%, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, 30%, 32%, 34%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, 50%, or a range between any two values.

[0175] In some embodiments of the present invention, the compound of formula A-2 is selected from the group consisting of:

[0176]

[0177]

[0178] as well as

[0179]

[0180] in,

[0181] R A2represents a straight-chain or branched alkyl group containing 1 to 8 carbon atoms, wherein one or two or more non-adjacent -CH2- groups in the straight-chain or branched alkyl group containing 1 to 8 carbon atoms may be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O- or -O-CO-, and one or more -H groups in these groups may be independently replaced by -F or -Cl;

[0182] L A21 、L A22 、L A23 、L A24 and L A25 each independently represents -H or -F; and

[0183] X A2 It represents -F, -CF3, -OCF3 or -CH2CH2CH=CF2.

[0184] In some embodiments of the present invention, the weight percentage of the compound of general formula A-2 in the liquid crystal composition is 0.1%-50% (including any value or sub-range between this range), for example, 0.1%, 1%, 4%, 6%, 8%, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, 30%, 32%, 34%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, 50%, or a range between any two values.

[0185] In order to achieve different display effects, the liquid crystal composition of the present invention may further include a dye molecule.

[0186] In some embodiments of the present invention, the dye may be a dichroic dye molecule.

[0187] In some embodiments of the present invention, the dichroic dye molecule is one or more dyes selected from the group consisting of azo, anthraquinone, phthalocyanine, cyanine, indigoid, arylmethane, nitro, and nitroso.

[0188] In some embodiments of the present invention, the dichroic dye molecules are selected from the group consisting of azo and anthraquinone.

[0189] In some embodiments of the present invention, the dichroic dye molecule is selected from the group consisting of:

[0190]

[0191]

[0192]

[0193] In some embodiments of the present invention, the dye accounts for 0.01%-10% by weight of the liquid crystal composition, for example, 0.1%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%.

[0194] In some embodiments of the present invention, the liquid crystal composition comprises at least one additive.

[0195] In addition to the above compounds, the liquid crystal composition of the present invention may also contain conventional nematic liquid crystals, smectic liquid crystals, cholesteric liquid crystals, dopants, antioxidants, ultraviolet absorbers, infrared absorbers, photoinitiators, polymerizable monomers or light stabilizers.

[0196] Possible dopants which are preferably added to the liquid crystal composition according to the invention are shown below:

[0197]

[0198] as well as

[0199]

[0200] In some embodiments of the present invention, the weight percentage of the dopant in the liquid crystal composition is 0%-5%; preferably, the weight percentage of the dopant in the liquid crystal composition is 0.01%-1%.

[0201] In addition, the additives such as antioxidants, light stabilizers, and ultraviolet absorbers used in the liquid crystal composition of the present invention are preferably the following:

[0202]

[0203]

[0204]

[0205] Here, n represents a positive integer from 1 to 12.

[0206] Preferably, the antioxidant is selected from the light stabilizers shown below:

[0207]

[0208] In some embodiments of the present invention, the additive accounts for 0%-5% of the total weight of the liquid crystal composition; preferably, the additive accounts for 0.01%-1% of the total weight of the liquid crystal composition.

[0209] In some embodiments of the present invention, the liquid crystal composition of the present invention comprises at least one photoinitiator as shown below:

[0210]

[0211] In yet another aspect, the present invention further provides a liquid crystal display device, comprising the above-mentioned liquid crystal composition; preferably, the liquid crystal display device is in R-PNLC display mode.

[0212] In some embodiments of the present invention, the liquid crystal display device includes: a first base layer, a first conductive layer, a liquid crystal medium layer, a second conductive layer, and a second base layer.

[0213] Beneficial effects: Compared with the prior art, the liquid crystal composition of the present invention has a smaller haze value in the absence of an external voltage, and a larger haze value after voltage is applied, and has a higher VHR value (VHR (initial), VHR (UV) and VHR (Ra)), so that the liquid crystal display device containing it can achieve vertical alignment of liquid crystal molecules without a PI alignment layer, produce better display effects, and has higher reliability and longer service life. DETAILED DESCRIPTION

[0214] The present invention will be described below in conjunction with specific embodiments. It should be noted that the following examples are illustrative of the present invention and are intended only to illustrate the present invention and are not intended to limit the present invention. Other combinations and various modifications within the scope of the present invention may be made without departing from the spirit or scope of the present invention.

[0215] For ease of expression, in the following examples, the group structures of the compounds are represented by the codes listed in Table 1:

[0216] Table 1. Group structure codes of compounds

[0217]

[0218]

[0219] Take the following compound as an example:

[0220]

[0221] If the structural formula is represented by the codes listed in Table 2, it can be expressed as: Nccgf, where n in the code represents the number of carbon atoms in the left-hand alkyl group. For example, if n is "3", it means that the alkyl group is -C3H7; C in the code represents 1,4-cyclohexylene, G represents 2-fluoro-1,4-phenylene, and F represents fluorine.

[0222] The abbreviated codes for the test items in the following embodiments are as follows:

[0223] Cp clearing point (nematic-isotropic phase transition temperature, °C)

[0224] n o Refractive index of ordinary light

[0225] n e Refractive index of extraordinary light

[0226] Δn optical anisotropy (589nm, 20℃)

[0227] Δε dielectric anisotropy (1KHz, 20℃)

[0228] T c Low-temperature storage phase transition point (i.e., nematic phase lower limit temperature, °C)

[0229] η Bulk viscosity (mm2·s-1, 20℃)

[0230] Haze (%)

[0231] VHR(initial) Initial voltage holding ratio (%)

[0232] VHR(UV) Voltage holding ratio after UV light irradiation (%)

[0233] VHR(Ra) Voltage holding ratio (%) after being kept at 60℃ for 1 hour

[0234] in,

[0235] Cp: ​​obtained by melting point test.

[0236] Δn: Δn=n e -n0 was measured using an Abbe refractometer under a sodium lamp (589 nm) at 20°C.

[0237] Δε: Δε=ε ∥ -ε ⊥ , where ε ∥ is the dielectric constant parallel to the molecular axis, ε ⊥ is the dielectric constant perpendicular to the molecular axis; test conditions: 20°C, 1 kHz, VA-type test cell with a cell thickness of 6 μm.

[0238] T c : Place the nematic liquid crystal material in a glass bottle and store it in a refrigerator at 0℃, -10℃, -20℃, -30℃, and -40℃ respectively. Then observe the low temperature conditions after 10 days. For example, if the sample is nematic at -20℃ and becomes crystalline or smectic at -30℃, then T c is less than -20℃.

[0239] H: measured using a Brookfield plate viscometer at a test temperature of 20°C.

[0240] Haze: measured using a WGT-S transmittance / haze tester at 20°C.

[0241] VHR(initial): initial voltage holding ratio, measured using the TOY06254 liquid crystal property evaluation system; the test temperature is 25°C, the test voltage is 5V, and the test frequency is 6Hz.

[0242] VHR (UV): Measured using the TOY06254 liquid crystal property evaluation system; wavelength: 365nm, energy: 6000mJ / cm 2 The test is conducted after the liquid crystal is irradiated with UV light, the test temperature is 25°C, the test voltage is 5V, and the test frequency is 6Hz.

[0243] VHR(Ra): measured using the TOY06254 liquid crystal property evaluation system; the liquid crystal is kept at 60°C for 1 hour, the test temperature is 25°C, the test voltage is 5V, and the test frequency is 6Hz.

[0244] Each component used in the following examples can be synthesized by known methods or obtained through commercial channels. These synthesis techniques are conventional, and the obtained liquid crystal compounds meet the standards of electronic compounds after testing.

[0245] Liquid crystal compositions were prepared according to the ratios of the liquid crystal compositions specified in the following examples. The preparation of the liquid crystal compositions was carried out according to conventional methods in the art, such as mixing in proportions by heating, ultrasonication, suspension, etc.

[0246] The structures of the polymerizable compounds used in the following examples are shown in Table 2 below:

[0247] Table 2. Structure, component number and code of polymerizable compounds

[0248]

[0249] The structures of the self-aligning agents used in the following examples are shown in Table 3:

[0250] Table 3. Structure, component number and code of self-aligning agent

[0251]

[0252]

[0253] A liquid crystal composition of Host-1 was prepared according to the compounds and their weight percentages listed in Table 4, and filled between two substrates of a liquid crystal display for performance testing.

[0254] Table 4 Formulation and performance parameter test results of liquid crystal composition

[0255]

[0256] The liquid crystal composition of Host-2 was prepared according to the compounds and their weight percentages listed in Table 5, and filled between two substrates of a liquid crystal display for performance testing.

[0257] Table 5 Formulation and performance parameter test results of liquid crystal composition

[0258]

[0259]

[0260] A liquid crystal composition of Host-3 was prepared according to the compounds and their weight percentages listed in Table 6, and filled between two substrates of a liquid crystal display for performance testing.

[0261] Table 6 Formulation and performance parameter test results of liquid crystal composition

[0262]

[0263] A liquid crystal composition of Host-4 was prepared according to the compounds and their weight percentages listed in Table 7, and filled between two substrates of a liquid crystal display for performance testing.

[0264] Table 7 Formulation and performance parameter test results of liquid crystal composition

[0265]

[0266] Comparative Example 1

[0267] 5.8 parts by weight of polymerizable compound RM-1 and 0.2 parts by weight of IE184 were added to 94 parts by weight of liquid crystal composition Host-1 to prepare the liquid crystal composition of Comparative Example 1. The obtained liquid crystal composition was filled into a liquid crystal cell (VA type test cell with a cell thickness d of 6 μm, including an alignment layer and a passivation layer). The liquid crystal cell was thermally aligned at 100° C. for 5 minutes, then taken out and cooled to room temperature (25° C.). The liquid crystal cell was then exposed to UV light (365 nm, 30 mW / cm 2 ) for 6 minutes, and the haze test of the prepared samples was carried out at voltages of 10V, 20V, 30V, 40V, and 50V, respectively. The test results are shown in Table B below. The voltage holding rate was also tested, and the test results are shown in Table B-1 below.

[0268] Table B Haze test results

[0269] Voltage / V 0 10 20 30 40 50 Haze / % 2.72 8.12 44.5 79 85 90

[0270] Table B-1 Voltage Holding Rate Test Results

[0271] VHR (initial) 85.6 VHR(UV) 78 VHR(Ra) 76.3

[0272] Example 1

[0273] 5.8 parts by weight of polymerizable compound RM-1, 0.4 parts by weight of Add-1 and 0.2 parts by weight of IE184 were added to 93.6 parts by weight of liquid crystal composition Host-1 to prepare the liquid crystal composition of Example 1. The obtained liquid crystal composition was filled into a "non-aligned" liquid crystal cell (cell thickness d was 13 μm, with ITO coating on both sides (structured ITO in the case of multi-domain switching), no alignment layer and no passivation layer), the liquid crystal cell was thermally aligned at 100° C. for 5 minutes, taken out and cooled to room temperature (25° C.), and then irradiated under UV (365 nm, 30 mW / cm 2 ) for 6 minutes, and the prepared samples were subjected to haze tests at voltages of 10V, 20V, 30V, 40V, and 50V, respectively. The test results are shown in Table 8 below, and the voltage holding rate was tested, and the test results are shown in Table 8-1 below.

[0274] Table 8 Haze test results

[0275] Voltage / V 0 10 20 30 40 50 Haze / % 2.7 8.24 45.68 80.2 85.6 90.6

[0276] Table 8-1 Voltage holding rate test results

[0277] VHR (initial) 88.5 VHR(UV) 85.4 VHR(Ra) 84.2

[0278] From the comparison between Example 1 and Comparative Example 1, it can be seen that the liquid crystal composition of the present invention has a smaller haze value when no external voltage is applied, and has a larger haze value after voltage is applied, and has a higher VHR value (VHR (initial), VHR (UV) and VHR (Ra)), so that the liquid crystal display device containing it can achieve vertical alignment of liquid crystal molecules without a PI alignment layer, produce a better display effect, and have higher reliability.

[0279] Example 2

[0280] 8 parts by weight of polymerizable compound RM-2, 0.3 parts by weight of Add-3 and 0.2 parts by weight of IE184 were added to 91.4 parts by weight of liquid crystal composition Host-2 to prepare the liquid crystal composition of Example 2. The obtained liquid crystal composition was filled into a "non-aligned" liquid crystal cell (cell thickness d was 13 μm, with ITO coating on both sides (structured ITO in the case of multi-domain switching), no alignment layer and no passivation layer), the liquid crystal cell was thermally aligned at 85° C. for 5 minutes, taken out and cooled to room temperature (25° C.), and then irradiated under UV (365 nm, 30 mW / cm2 ) for 6 minutes, and the prepared samples were subjected to haze tests at voltages of 10V, 20V, 30V, 40V, and 50V, respectively. The test results are shown in Table 9 below, and the voltage holding rate was tested, and the test results are shown in Table 9-1 below.

[0281] Table 9 Haze test results

[0282] Voltage / V 0 10 20 30 40 50 Haze / % 2.68 4.1 42.3 78.6 81.4 86.7

[0283] Table 9-1 Voltage holding rate test results

[0284] VHR (initial) 86.4 VHR(UV) 84 VHR(Ra) 83.5

[0285] Example 3

[0286] 4 parts by weight of polymerizable compound RM-3, 0.3 parts by weight of Add-4 and 0.2 parts by weight of IE184 were added to 95.5 parts by weight of liquid crystal composition Host-2 to prepare the liquid crystal composition of Example 3. The obtained liquid crystal composition was filled into a "non-aligned" liquid crystal cell (cell thickness d was 13 μm, with ITO coating on both sides (structured ITO in the case of multi-domain switching), no alignment layer and no passivation layer), the liquid crystal cell was thermally aligned at 100° C. for 5 minutes, taken out and cooled to room temperature (25° C.), and then irradiated under UV (365 nm, 30 mW / cm 2 ) for 6 minutes, and the prepared samples were subjected to haze tests at voltages of 10V, 20V, 30V, 40V, and 50V, respectively. The test results are shown in Table 10 below, and the voltage holding rate was tested, and the test results are shown in Table 10-1 below.

[0287] Table 10 Haze test results

[0288]

[0289]

[0290] Table 10-1 Voltage holding rate test results

[0291] VHR (initial) 89 VHR(UV) 87.6 VHR(Ra) 85.4

[0292] Example 4

[0293] 5 parts by weight of polymerizable compound RM-4, 0.3 parts by weight of Add-2 and 0.2 parts by weight of IE184 were added to 94.5 parts by weight of liquid crystal composition Host-3 to prepare the liquid crystal composition of Example 4. The obtained liquid crystal composition was filled into a "non-aligned" liquid crystal box (the box thickness d was 13 μm, with ITO coating on both sides (structured ITO in the case of multi-domain switching), no alignment layer and no passivation layer), the liquid crystal box was thermally aligned at 80° C. for 5 minutes, taken out and cooled to room temperature (25° C.), and then irradiated under UV (365 nm, 30 mW / cm 2 ) for 6 minutes, and the prepared samples were subjected to haze tests at voltages of 10V, 20V, 30V, 40V, and 50V, respectively. The test results are shown in Table 11 below, and the voltage holding rate was tested, and the test results are shown in Table 11-1 below.

[0294] Table 11 Haze test results

[0295] Voltage / V 0 10 20 30 40 50 Haze / % 2.01 8.02 78.5 85.4 89.4 92.5

[0296] Table 11-1 Voltage holding rate test results

[0297] VHR (initial) 88 VHR(UV) 85.7 VHR(Ra) 84.3

[0298] Example 5

[0299] 3 parts by weight of polymerizable compound RM-5, 0.3 parts by weight of Add-1 and 0.2 parts by weight of IE184 were added to 96.3 parts by weight of liquid crystal composition Host-4 to prepare the liquid crystal composition of Example 5. The obtained liquid crystal composition was filled into a "non-aligned" liquid crystal cell (cell thickness d was 13 μm, with ITO coating on both sides (structured ITO in the case of multi-domain switching), no alignment layer and no passivation layer), the liquid crystal cell was thermally aligned at 100° C. for 5 minutes, taken out and cooled to room temperature (25° C.), and then irradiated under UV (365 nm, 30 mW / cm 2 ) for 6 minutes, and the prepared samples were subjected to haze tests at voltages of 10V, 20V, 30V, 40V, and 50V, respectively. The test results are shown in Table 12 below, and the voltage holding rate was tested, and the test results are shown in Table 12-1 below.

[0300] Table 12 Haze test results

[0301] Voltage / V 0 10 20 30 40 50 Haze / % 1.5 12.5 60.2 88.6 90.1 92.6

[0302] Table 12-1 Voltage holding rate test results

[0303] VHR (initial) 88.9 VHR(UV) 85 VHR(Ra) 83.4

[0304] Example 6

[0305] 3 parts by weight of polymerizable compound RM-6, 0.8 parts by weight of Add-3 and 0.2 parts by weight of IE184 were added to 96.3 parts by weight of liquid crystal composition Host-1 to prepare the liquid crystal composition of Example 6. The obtained liquid crystal composition was filled into a "non-aligned" liquid crystal cell (cell thickness d was 13 μm, with ITO coating on both sides (structured ITO in the case of multi-domain switching), no alignment layer and no passivation layer), the liquid crystal cell was thermally aligned at 100° C. for 5 minutes, taken out and cooled to room temperature (25° C.), and then irradiated under UV (365 nm, 30 mW / cm 2 ) for 6 minutes, and the haze test of the prepared samples was carried out at voltages of 10V, 20V, 30V, 40V, and 50V, respectively. The test results are shown in Table 13 below, and the voltage holding rate was tested, and the test results are shown in Table 13-1 below.

[0306] Table 13 Haze test results

[0307] Voltage / V 0 10 20 30 40 50 Haze / % 0.8 8.02 61.06 80.38 85.5 88.6

[0308] Table 13-1 Voltage holding rate test results

[0309] VHR (initial) 88 VHR(UV) 85.4 VHR(Ra) 84.2

[0310] Example 7

[0311] 4 parts by weight of polymerizable compound RM-6, 0.2 parts by weight of Add-2 and 0.2 parts by weight of IE184 were added to 96.6 parts by weight of liquid crystal composition Host-2 to prepare the liquid crystal composition of Example 7. The obtained liquid crystal composition was filled into a "non-aligned" liquid crystal box (the box thickness d was 13 μm, with ITO coating on both sides (structured ITO in the case of multi-domain switching), no alignment layer and no passivation layer), the liquid crystal box was thermally aligned at 85° C. for 5 minutes, taken out and cooled to room temperature (25° C.), and then irradiated under UV (365 nm, 30 mW / cm 2 ) for 6 minutes, and the prepared samples were subjected to haze tests at voltages of 10V, 20V, 30V, 40V, and 50V, respectively. The test results are shown in Table 14 below, and the voltage holding rate was tested, and the test results are shown in Table 14-1 below.

[0312] Table 14 Haze test results

[0313] Voltage / V 0 10 20 30 40 50 Haze / % 1 8.02 65.06 80.38 86.5 88.6

[0314] Table 14-1 Voltage holding rate test results

[0315] VHR (initial) 88.7 VHR(UV) 85.3 VHR(Ra) 84.7

[0316] In summary, the liquid crystal composition of the present invention has a smaller haze value when no external voltage is applied, and has a larger haze value after voltage is applied, and has higher VHR values ​​(VHR (initial), VHR (UV) and VHR (Ra)), so that the liquid crystal display device containing it can achieve vertical alignment of liquid crystal molecules without a PI alignment layer, produce better display effects, better stability against ultraviolet rays and high temperatures, higher reliability and longer service life.

[0317] The above embodiments are only for illustrating the technical concept and features of the present invention. Its purpose is to enable people familiar with this technology to understand the content of the present invention and implement it. It cannot be used to limit the scope of protection of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of protection of the present invention.

Claims

1. A liquid crystal composition, characterized in that The liquid crystal composition comprises: At least one polymerizable compound of the general formula RM, the polymerizable compound of the general formula RM being selected from the group consisting of: At least one self-aligning agent of the general formula SA, wherein the self-aligning agent of SA is selected from the group consisting of the following compounds: and as well as At least one compound of formula N, wherein the compound of formula N is selected from the group consisting of the following compounds: and in, R S1 Indicates -Sp 1 -P 1 , a straight or branched alkyl group containing 1 to 12 carbon atoms, wherein one or more non-adjacent -CH2- in a linear or branched alkyl group containing 1 to 12 carbon atoms may be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O- or -O-CO-, and wherein one or more non-adjacent -CH2- in a linear or branched alkyl group containing 1 to 12 carbon atoms, One or more -H in can be independently replaced by -F or -Cl; ring and Ring Each independently expresses in One or more -CH2- in the ring may be replaced by -O-, and one or more single bonds in the ring may be replaced by double bonds, wherein wherein one or more -H in the ring may be independently replaced by -F, -Cl, -CN, -Sp3-P3, -KO, -CO-OKO-, -O-COKO-, or -O-CO-OKO-, and -CH= in one or more rings may be replaced by -N=, wherein K0 represents a halogenated or unhalogenated straight-chain alkylene group containing 1 to 6 carbon atoms, or a halogenated or unhalogenated straight-chain alkyleneoxy group containing 1 to 5 carbon atoms; ring express in One or more -CH2- in the ring may be replaced by -O-, and one or more single bonds in the ring may be replaced by double bonds, wherein One or more -H in the ring may be independently replaced by -F, -Cl, -CN, -Sp3-P3, -KO, -CO-OKO-, -O-COKO-, or -O-CO-OKO-, and -CH= in one or more rings may be replaced by -N=; Ls1 and Ls3 each independently represent -F, -Cl, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(O)N(R S0 )2、-C(O)R S0 , a straight or branched alkyl group containing 1 to 12 carbon atoms, wherein one or more non-adjacent -CH2- in a linear or branched alkyl group containing 1 to 12 carbon atoms may be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O- or -O-CO-, and wherein one or more non-adjacent -CH2- in a linear or branched alkyl group containing 1 to 12 carbon atoms, One or more -H in the R S0 represents a straight-chain or branched alkyl group containing 1 to 12 carbon atoms; Ls2 means -Sp 3 -P 2 or R S2 and R S3 Each independently represents an anchoring group, the anchoring group is Where * indicates the connection site in the bonded structure; p represents 1 or 2, wherein when p represents 2, -Sp 8 -X 2 Can be the same or different; o represents 0 or 1; M S1 express I S1 and J S1 Each independently represents -CH2-, -O- or -S-; N S1 Indicates =O or =S; V K1 、V K2 and V K3 Each independently represents -CH= or -N=; X 1 and X 2 Each independently represents -H, -OH, -SH, -NH2, -NHR 11 、-N(R 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 -OH, -SH, -NH2, -NHR 11 , -C(O)OH and -CHO, where R 11 represents a straight-chain or branched alkyl group containing 1 to 12 carbon atoms; P1, P2, P3, P 1 、P 2 and P 3 each independently represents a polymerizable group; Sp1, Sp2, Sp3, Sp 1 、Sp 2 、Sp 3 、Sp 4 、Sp 5 、Sp 7 and Sp 8 each independently represents a spacer group or a single bond; Sp 6 Each independently expresses Z 1 and Z 2 Each independently represents -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CH2O-, -OCH2-, -CH2S-, -SCH2-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -(CH2) d -, -CF2CH2-, -CH2CF2-, -(CF2) d -, -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -C≡C-, -CH=CH-CO-O-, -O-CO-CH=CH-, -CH2CH2-CO-O-, -O-CO-CH2CH2-, -CHR 1 -、-CR 1 R 2 - or a single bond, where R 1 and R 2 Each independently represents a linear or branched alkyl group containing 1 to 12 carbon atoms, and d represents an integer of 1 to 4; p s1 and p s2 Each independently represents 1 or 2, wherein when p s1 When p represents 2, Ls2 can be the same or different. s2 When it represents 2, Ls1 can be the same or different; p s3 represents 0, 1 or 2, where when p s3 When it means 2, -Sp 5 -R S3 Can be the same or different; Z1 and Z2 each independently represent -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CH2O-, -OCH2-, -CH2S-, -SCH2-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -(CH2) d -, -CF2CH2-, -CH2CF2-, -(CF2) d -, -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -C≡C-, -CH=CH-CO-O-, -O-CO-CH=CH-, -CH2CH2-CO-O- or -O-CO-CH2CH2-; Z1' has the same limited range as Z1; Z 11 Represents -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CH2O-, -OCH2-, -CH2S-, -SCH2-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -(CH2) d -, -CF2CH2-, -CH2CF2-, -(CF2) d -, -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -C≡C-, -CH=CH-CO-O-, -O-CO-CH=CH-, -CH2CH2-CO-O-, -O-CO-CH2CH2-, -CHR 1 -、-CR 1 R 2 - or a single bond, where R 1 and R 2 Each independently represents a linear or branched alkyl group containing 1 to 12 carbon atoms, and d represents an integer of 1 to 4, R N1 and R N2 Each independently represents a linear or branched alkyl group containing 1 to 12 carbon atoms, One or more non-adjacent -CH2- in the linear or branched alkyl group containing 1 to 12 carbon atoms may be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O- or -O-CO-; The self-aligning agent of the general formula SA accounts for 0.1% to 2% by weight of the liquid crystal composition.

2. The liquid crystal composition according to claim 1, wherein The liquid crystal composition comprises at least one compound of formula M in, R M1 and R M2 Each independently represents a linear or branched alkyl group containing 1 to 12 carbon atoms, One or more non-adjacent -CH2- in the linear or branched alkyl group containing 1 to 12 carbon atoms may be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O- or -O-CO-; ring ring and Ring Each independently expresses in One or more -CH2- in the ring 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 may be replaced by halogen; Z M1 and Z M2 Each independently represents a single bond, -CO-O-, -O-CO-, -CH2O-, -OCH2-, -C≡C-, -CH=CH-, -CH2CH2- or -(CH2)4-; and n M represents 0, 1 or 2, where n M =2, the ring Can be the same or different, Z M2 Can be the same or different.

3. The liquid crystal composition according to claim 2, wherein The compound of formula M is selected from the group consisting of the following compounds: as well as 4. The liquid crystal composition according to claim 1, wherein The weight percentage of the compound of the general formula RM in the liquid crystal composition is 0.001%-15%; the weight percentage of the compound of the general formula N in the liquid crystal composition is 0.1%-99%.

5. The liquid crystal composition according to claim 1, wherein The compound of formula RM-1 is selected from the group consisting of the following compounds: as well as The compound of formula RM-2 is selected from the group consisting of the following compounds: as well as The compound of formula RM-4 is selected from the group consisting of the following compounds: as well as 6. A liquid crystal display device comprising the liquid crystal composition according to any one of claims 1 to 5.

7. The liquid crystal display device according to claim 6, wherein: The liquid crystal display is in R-PNLC display mode.

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