TW201905182A - Polymerizable liquid crystal composition and liquid crystal display device thereof - Google Patents

Abstract

Provided are a polymerized liquid crystal composition and a liquid crystal display device thereof. The polymerized liquid crystal composition comprises at least one compound of general formula I, at least one compound of general formula II and at least one compound of general formula III. The polymerized liquid crystal composition does not exhibit or exhibits less problems existing in the prior art, has a lower polymerizable compound residue and has good stability and higher reliability, wherein same are specifically shown as being a good UV-resistant stability, and also has a higher voltage holding ratio. At the same time, a liquid crystal display device comprising the polymerized liquid crystal composition has little or almost no residual image effects.

Description

Polymerizable liquid crystal composition and liquid crystal display device

The invention relates to a polymerizable liquid crystal composition, in particular to a polymerizable liquid crystal composition having good stability and high reliability and a liquid crystal display device thereof.

The liquid crystal display element can be used in various household appliances such as clocks and electronic calculators, measuring devices, automobile panels, word processing agents, computers, printers, and televisions. In its typical display mode, the liquid crystal display device may include: PC (phase change), TN (twist nematic), STN (super twisted nematic), and ECB (electrically controlled birefringence, electronically controlled birefringence), OCB (optically compensated bend), IPS (in-plane switching), VA (vertical alignment), CSH (color super homeotropic), color super homeotropic )Wait. According to the driving method of the device, the liquid crystal display device is divided into a PM (passive matrix, passive matrix) type and an AM (active matrix, active matrix) type. PM is divided into static (static) and multiplex (multiplex) types. AM is divided into TFT (thin film transistor, thin film transistor), MIM (metal insulator metal, metal-insulating layer-metal) and other types. The types of TFTs are amorphous silicon and polycrystal silicon. The latter is divided into high-temperature type and low-temperature type according to the manufacturing process. Liquid crystal display elements are classified into a reflective type using natural light, a transmissive type using backlight, and a semi-transmissive type using two light sources of natural light and backlight according to the type of light source.

Among these display modes, the IPS mode, the ECB mode, the VA mode, or the CSH mode are different from the TN mode or the STN mode commonly used now in that the former uses a liquid crystal material having negative dielectric anisotropy. Among these display modes, especially the VA type display driven by AM is used in display elements requiring high speed and wide viewing angle, and the most anticipated is the application in liquid crystal elements such as televisions.

The VA mode and the IPS mode are always black, but the difference is that the liquid crystal molecules in the liquid crystal layer of the VA mode panel use negative dielectric anisotropic liquid crystal materials, and the transparent electrodes are provided on the upper and lower substrates to form an electric field perpendicular to the substrates. When power is not applied, the long axis of the liquid crystal molecules is perpendicular to the substrate, and a dark state is formed; when power is applied, the long axis of the liquid crystal molecules falls parallel to the direction of the substrate. The initial alignment also needs to rub the substrate, resulting in problems such as pollution and static electricity. The pre-tilt angle is also difficult to control. To solve the initial alignment problem of the VA mode, there are various derivative modes, such as multi-domain vertical alignment. , MVA), Image Vertical Alignment (PVA), Polymer Sustained Alignment (PSA) and Polymer Stabilized Vertical Alignment (PSVA). Among them, PSA mode and PSVA mode have gradually become mainstream due to their high penetration rate, high contrast and fast response.

The Polymer Sustained Alignment (PSA) liquid crystal display device is a device that forms a polymer structure in a cell in order to control the pretilt angle of liquid crystal molecules. Due to its fast response and high contrast characteristics, It is used as a liquid crystal display element.

PSA type liquid crystal display elements are manufactured as follows:

The polymerizable composition composed of the liquid crystal compound and the polymerizable compound is injected between the substrates, a voltage is applied, and the polymerizable compound is polymerized in a state where the liquid crystal molecules are aligned, and the alignment of the liquid crystal molecules is fixed.

In the display device, due to the effect of the electric field and the alignment layer, the charged particles in the liquid crystal molecules will be separated according to polarity and distributed on the two substrates to form an internal electric field. When driving the display, it will weaken the ability of the electric field to control the liquid crystal molecules; when the driving is cancelled, the internal electric field will still have an effect on the liquid crystal molecules, thereby affecting the arrangement of the liquid crystal molecules. After driving for a long time, the internal electric field will gradually become larger. When the driving is cancelled, the internal electric field can still maintain a certain degree of rotation of the liquid crystal molecules, so that the liquid crystal molecules cannot be restored to the initial state, which causes the phenomenon of image retention.

For liquid crystal displays, it is necessary to avoid the occurrence of image retention as much as possible.

In order to improve the phenomenon of image sticking in liquid crystal displays, it is necessary to reduce the content of impurities in the liquid crystal composition as much as possible and increase the voltage retention rate (ie, VHR) of the liquid crystal composition.

The PSVA liquid crystal composition is composed of a stable liquid crystal compound and an optically active polymerizable compound at the same time. During the use of the liquid crystal display, the remaining polymerizable compound inevitably needs to be irradiated with backlight, the longer the time, The more easily the structure changes, ions are generated, and an internal electric field is formed, which affects the arrangement of liquid crystal molecules and causes a display defect of image retention. Therefore, reducing the residue of polymerizable compounds as much as possible can effectively improve the image retention phenomenon of PSVA liquid crystal displays.

PSVA uses a polymerizable compound to control the alignment direction of liquid crystal molecules: the liquid crystal is placed in a desired alignment state by applying an electric field. While maintaining this state, UV exposure is performed to polymerize the polymerizable compound in the mixed liquid crystal, thereby "curing" "Live the ideal arrangement of the LCD.

The PSVA mode does not require a friction alignment process, so it can avoid problems such as static electricity and pollution caused by friction in the TN and IPS modes.

Unfortunately, the current polymerizable liquid crystal monomers still have many defects. For example, the melting point of the polymerizable liquid crystal monomer described in US Pat. No. 6,136,225 is too high, and the actual production needs to be operated at a temperature of 80 to 90°C. This greatly increases energy consumption, and it is also easy to cause defects such as uneven alignment and abnormal polymerization that seriously affect the optical quality at high temperatures.

Therefore, attempts have been made to improve the performance of polymerizable liquid crystals by the method of preparing polymerizable liquid crystal compositions. Japanese Patent JP2003193053 provides a polymerizable liquid crystal composition with a lower melting point, but there is a serious problem of uneven alignment. The US patent US6090308 provides a polymerizable liquid crystal composition with a relatively low melting point, but it has the problems of poor stability and easy crystallization at low temperature.

In the prior art, generally used polymerizable liquid crystal compositions have various problems, such as: slower or faster polymerization speed, difficult to control, large change in pretilt angle, excessive residual amount after polymerization, poor UV stability, and poor reliability High, and there will be various display defects, such as afterimages and uneven display.

Therefore, there is a great need for a new type of polymerizable liquid crystal composition that can reduce or largely reduce the above disadvantages.

Object of the invention: The object of the present invention is to provide a polymerizable liquid crystal composition which exhibits no or little performance problems in the technology, the polymerizable liquid crystal composition has good stability and The higher reliability is specifically manifested as good UV stability, higher voltage retention, and the liquid crystal display device containing the polymerizable liquid crystal composition has little or no image sticking effect.

Another object of the present invention is a liquid crystal display device containing the polymerizable liquid crystal composition.

Technical Solution: In order to accomplish the above object of the invention, the present invention provides a polymerizable liquid crystal composition, the polymerizable liquid crystal composition comprising: at least one compound of general formula I Ⅰ; at least one compound of general formula II Ⅱ; at least one compound of general formula III Ⅲ; wherein, P ₁ and P _{2 are the} same or different, each independently represents a polymerizable group; Y ₁ and Y _{2 are the} same or different, each independently represents a straight chain or branch of 1-20 carbon atoms Chain alkyl; the R ₁ , R ₂ , R ₃ and R _{4 are the} same or different, and each independently represents a linear or branched alkyl or alkoxy group of carbon number -H, 1 to 12 or carbon Alkenyl or alkenyloxy having 2 to 12 atoms, wherein one or more of -CH ₂ -in the linear or branched alkyl or alkoxy of 1 to 12 may be substituted by -O-, One or more -CH ₂ -in the alkenyl group or alkenoxy group having 2 to 12 carbon atoms may be substituted with -O-, provided that -O- is not directly connected; the ring A represents or , Where the ring One or more -CH ₂ -may be replaced by -O- or -S-; ring One or more of -H may be substituted by -F or -CH ₃ ; Ring B, Ring C and Ring D are the same or different, and each represents independently or ,among them, One or more -H can be replaced by -F, One or more of -CH ₂ -may be substituted by -O-; ring E, ring F, ring G and ring H are the same or different, and each represents independently or ,among them, One or more -H can be replaced by -F, provided that the substitution sites are not adjacent, One or more -CH ₂ -may be substituted by -O-; the L ₁ -L _{12 are the} same or different, each independently represents -H, -F, or -CH ₃ ; The Z and Z ^{1 are the} same or Different, each independently represents a single bond, -CH ₂ O-, -OCH ₂ -, -CH ₂ CH ₂ -, -COO-, -OCO-, -CF ₂ O-, or -OCF ₂ -; the Z ² Same as Z ³ or different, each independently represents a single bond, -O-, -OCO-, -COO- or -O-COO-; the Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ and Z _{6 The} same or different, each independently represents a single bond, -CH ₂ O-, -OCH ₂ -, -CH ₂ CH ₂ -, -COO-, -OCO-, -CF ₂ O-, or -OCF ₂ -; Said n, n ₁ and n _{2 are the} same or different and each independently represents 0 or 1; said b, c and d are the same or different, each independently represents 0, 1 or 2; and said e, f, g and h The same or different, each independently represents 0, 1, or 2, where e+f+g+h≥2.

In some embodiments of the invention, Z and Z ^{1 are} not single bonds at the same time.

In some embodiments of the invention, only one of Z and Z ¹ is a single bond.

In some embodiments of the present invention, P ₁ and P _{2 are the} same or different, and each represents independently , , , , , , , , , , , , or .

In some embodiments of the present invention, preferably, P ₁ and P _{2 are the} same or different, each independently representing , , , , , , , , or .

In some embodiments of the present invention, it is further preferred that P ₁ and P _{2 are the} same or different, each independently representing , , , , , , , , or .

In some embodiments of the present invention, it is further preferred that P ₁ and P _{2 are the} same or different, each independently representing , , , , , , or .

In some embodiments of the present invention, the compound of formula I accounts for 0.01-30% of the total weight of the polymerizable liquid crystal composition.

In some embodiments of the present invention, the compound of formula I accounts for 0.01-10% of the total weight of the polymerizable liquid crystal composition.

In some embodiments of the present invention, the compound of general formula I accounts for 0.05-5% of the total weight of the polymerizable liquid crystal composition.

In some embodiments of the present invention, the compound of formula I accounts for 0.1-5% of the total weight of the polymerizable liquid crystal composition.

In some embodiments of the present invention, the compound of formula I accounts for 0.1-3% of the total weight of the polymerizable liquid crystal composition.

In some embodiments of the present invention, the compound of formula I accounts for 0.1-1% of the total weight of the polymerizable liquid crystal composition.

In some embodiments of the invention, the compound of general formula I is selected from one or more of the compounds of general formula I-1 to I-3: Ⅰ-1; Ⅰ-2; and Ⅰ-3.

In some embodiments of the present invention, at least one of L ₁ -L ₁₆ is -F or -CH ₃ .

In some embodiments of the present invention, the Z represents -CH ₂ O-, -OCH ₂ -, -CH ₂ CH ₂ -, -COO-, or -OCO-.

In some embodiments of the present invention, at least one of L ₅ -L ₈ and/or L ₁₃ -L ₁₆ in the general formula 1-1 is -F or CH ₃ .

In some embodiments of the present invention, in the general formula I-1 and the general formula I-2, at least two of L ₁ -L ₁₆ are -F or CH ₃ .

In some embodiments of the invention, the compound of general formula 1-1 is selected from one or more of the following compounds: Ⅰ-1-1; Ⅰ-1-2; Ⅰ-1-3; Ⅰ-1-4; Ⅰ-1-5; Ⅰ-1-6; Ⅰ-1-7; Ⅰ-1-8; Ⅰ-1-9; Ⅰ-1-10; Ⅰ-1-11; Ⅰ-1-12; Ⅰ-1-13; Ⅰ-1-14; Ⅰ-1-15; Ⅰ-1-16; Ⅰ-1-17; Ⅰ-1-18; Ⅰ-1-19; Ⅰ-1-20; Ⅰ-1-21; Ⅰ-1-22; Ⅰ-1-23; Ⅰ-1-24; Ⅰ-1-25; Ⅰ-1-26; Ⅰ-1-27; Ⅰ-1-28; Ⅰ-1-29; Ⅰ-1-30; Ⅰ-1-31; Ⅰ-1-32; Ⅰ-1-33; Ⅰ-1-34; Ⅰ-1-35; Ⅰ-1-36; Ⅰ-1-37; Ⅰ-1-38; Ⅰ-1-39; Ⅰ-1-40; and Ⅰ-1-41, wherein X ₁ and X _{2 are the} same or different and each independently represents -H or -CH ₃ ; Z and Z ^{1 are the} same or different and each independently represents -CH ₂ O-, -OCH ₂ -, -CH ₂ CH ₂ -, -COO- or -OCO-.

In some embodiments of the present invention, the compound of general formula 1-1 is further preferably selected from one or more of the following compounds: Ⅰ-1-1-1; Ⅰ-1-1-2; Ⅰ-1-1-3; Ⅰ-1-1-4; Ⅰ-1-2-1; Ⅰ-1-2-2; Ⅰ-1-3-1; Ⅰ-1-3-2; Ⅰ-1-4-1; Ⅰ-1-4-2; Ⅰ-1-5-1; Ⅰ-1-5-2; Ⅰ-1-6-1; Ⅰ-1-6-2; Ⅰ-1-7-1; Ⅰ-1-7-2; Ⅰ-1-8-1; Ⅰ-1-8-2; Ⅰ-1-9-1; Ⅰ-1-9-2; Ⅰ-1-10-1; Ⅰ-1-10-2; Ⅰ-1-11-1; Ⅰ-1-11-2; Ⅰ-1-12-1; Ⅰ-1-12-2; Ⅰ-1-13-1; Ⅰ-1-13-2; Ⅰ-1-14-1; Ⅰ-1-14-2; Ⅰ-1-15-1; Ⅰ-1-15-2; Ⅰ-1-16-1; Ⅰ-1-16-2; Ⅰ-1-17-1; Ⅰ-1-17-2; Ⅰ-1-18-1; Ⅰ-1-18-2; Ⅰ-1-19-1; Ⅰ-1-19-2; Ⅰ-1-20-1; Ⅰ-1-20-2; Ⅰ-1-21-1; Ⅰ-1-21-2; Ⅰ-1-22-1; Ⅰ-1-22-2; Ⅰ-1-23-1; Ⅰ-1-23-2; Ⅰ-1-24-1; Ⅰ-1-24-2; Ⅰ-1-25-1; Ⅰ-1-25-2; Ⅰ-1-26-1; Ⅰ-1-26-2; Ⅰ-1-27-1; Ⅰ-1-27-2; Ⅰ-1-28-1; Ⅰ-1-28-2; Ⅰ-1-29-1; Ⅰ-1-29-2; Ⅰ-1-30-1; Ⅰ-1-30-2; Ⅰ-1-31-1; Ⅰ-1-31-2; Ⅰ-1-32-1; Ⅰ-1-32-2; Ⅰ-1-33-1; Ⅰ-1-33-2; Ⅰ-1-34-1; Ⅰ-1-34-2; Ⅰ-1-35-1; Ⅰ-1-35-2; Ⅰ-1-36-1; Ⅰ-1-36-2; Ⅰ-1-37-1; Ⅰ-1-37-2; Ⅰ-1-38-1; Ⅰ-1-38-2; Ⅰ-1-39-1; Ⅰ-1-39-2; Ⅰ-1-40-1; Ⅰ-1-40-2; Ⅰ-1-41-1; and Ⅰ-1-41-2.

In some embodiments of the present invention, the compound of the general formula 1-2 is selected from one or more of the following compounds: Ⅰ-2-1; Ⅰ-2-2; Ⅰ-2-3; Ⅰ-2-4; Ⅰ-2-5; Ⅰ-2-6; wherein, X ₁ and X _{2 are the} same or different, and each independently represents -H or -CH ₃ ; Z represents -CH ₂ O-, -OCH ₂ -, -CH ₂ CH ₂ -, -COO- or -OCO-.

In some embodiments of the invention, the compound of general formula 1-2 is further preferably selected from one or more of the following compounds: Ⅰ-2-1-1; Ⅰ-2-2-1; Ⅰ-2-3-1; Ⅰ-2-4-1; Ⅰ-2-5-1; Ⅰ-2-6-1.

In some embodiments of the invention, the compound of general formula 1-3 is selected from one or more of the following compounds: Ⅰ-3-1; Ⅰ-3-2; Ⅰ-3-3; Ⅰ-3-4; Ⅰ-3-5; Ⅰ-3-6; Ⅰ-3-7; Ⅰ-3-8; Ⅰ-3-9; and Ⅰ-3-10, wherein X ₁ and X _{2 are the} same or different, and each independently represents -H or -CH ₃ ; Z represents -CH ₂ O-, -OCH ₂ -, -CH ₂ CH ₂ -, -COO- or -OCO-.

In some embodiments of the invention, the compound of general formula 1-3 is further preferably selected from one or more of the following compounds: Ⅰ-3-1-1; Ⅰ-3-2-1; Ⅰ-3-3-1; Ⅰ-3-4-1; Ⅰ-3-5-1; Ⅰ-3-6-1; Ⅰ-3-7-1; Ⅰ-3-8-1; Ⅰ-3-9-1; Ⅰ-3-10-1.

In some embodiments of the invention, the compound of general formula II is selected from one or more of the following compounds: Ⅱ-1; Ⅱ-2; Ⅱ-3; Ⅱ-4; Ⅱ-5; Ⅱ-6; Ⅱ-7; Ⅱ-8; Ⅱ-9; Ⅱ-10; Ⅱ-11; Ⅱ-12; Ⅱ-13; Ⅱ-14; Ⅱ-15; Ⅱ-16; Ⅱ-17; Ⅱ-18; Ⅱ-19; Ⅱ-20; Ⅱ-21; Ⅱ-22; Ⅱ-23; Ⅱ-24; Ⅱ-25; and Ⅱ-26.

In some embodiments of the present invention, the compound of Formula II accounts for 20-80% of the total weight of the polymerizable liquid crystal composition.

In some embodiments of the present invention, the compound of formula II accounts for 20-70% of the total weight of the polymerizable liquid crystal composition.

In some embodiments of the present invention, the compound of formula II accounts for 20-65% of the total weight of the polymerizable liquid crystal composition.

In some embodiments of the present invention, the compound of general formula II accounts for 25-60% of the total weight of the polymerizable liquid crystal composition.

In some embodiments of the present invention, the compound of formula II accounts for 20-55% of the total weight of the polymerizable liquid crystal composition.

In some embodiments of the present invention, the compound of formula II accounts for 30-55% of the total weight of the polymerizable liquid crystal composition.

In some embodiments of the invention, the compound of general formula III is selected from one or more of the following compounds: Ⅲ-1; Ⅲ-2; Ⅲ-3; Ⅲ-4; Ⅲ-5; Ⅲ-6; Ⅲ-7; Ⅲ-8; Ⅲ-9; Ⅲ-10; Ⅲ-11; Ⅲ-12; Ⅲ-13; Ⅲ-14; Ⅲ-15; Ⅲ-16; Ⅲ-17; Ⅲ-18; Ⅲ-19; Ⅲ-20; Ⅲ-21; and Ⅲ-22.

In some embodiments of the present invention, the compound of Formula III accounts for 20-80% of the total weight of the polymerizable liquid crystal composition.

In some embodiments of the present invention, the compound of Formula III accounts for 20-70% of the total weight of the polymerizable liquid crystal composition.

In some embodiments of the present invention, the compound of formula III accounts for 20-60% of the total weight of the polymerizable liquid crystal composition.

In some embodiments of the present invention, the compound of formula III accounts for 25-50% of the total weight of the polymerizable liquid crystal composition.

In some embodiments of the present invention, the compound of formula III accounts for 25-45% of the total weight of the polymerizable liquid crystal composition.

In some embodiments of the invention, the compound of general formula II is preferably selected from the following compounds: I-1-8-1, I-1-21-1, I-1-29-1 and I-1-34 -2 group.

In some embodiments of the invention, the compound of general formula II is preferably selected from the following compounds: II-1, II-2, II-4, II-7, II-8, II-13 and II-15 group.

In some embodiments of the invention, the compound of general formula III is preferably selected from the group consisting of III-1, III-2, III-3, III-7, III-10 and III-13.

The polymerizable liquid crystal composition of the present invention further contains one or more additives known to those skilled in the art and described in the literature. For example, 0-15% polychromatic dyes and/or chiral dopants can be added.

The following shows possible dopants which are preferably added to the mixture according to the invention. ; ; ; ; ; ; ; ; ; ; ; ; ;as well as .

Mentioned as follows are stabilizers which can be added to the mixture according to the invention

Preferably, the stabilizer is selected from stabilizers shown below.

In the embodiment of the present invention, preferably, the stabilizer accounts for 0-5% of the total weight of the liquid crystal composition; more preferably, the stabilizer accounts for 0-1% of the total weight of the liquid crystal composition; as In a particularly preferred solution, the stabilizer accounts for 0-0.1% of the total weight of the liquid crystal composition.

Another aspect of the present invention provides a liquid crystal display device including the polymerizable liquid crystal composition of the present invention.

Another aspect of the present invention provides an application of the polymerizable liquid crystal composition of the present invention in PSVA and PVA display modes.

Beneficial effect: Compared with other polymerizable liquid crystal compositions in the prior art, the polymerizable liquid crystal composition provided by the present invention does not exhibit or exhibits few problems due to technical problems. It is found in repeated experiments that under the same experimental conditions, the polymerizable liquid crystal composition of the present invention can have lower polymerizable compound residues, has good stability and higher reliability, and is specifically expressed as good UV stability, has a high voltage retention rate, and the liquid crystal display device containing the polymerizable liquid crystal composition has little or no image sticking effect.

Generally, the higher the ring number of biphenyl, the faster the polymerization rate, and the better the improvement of the residual image of the liquid crystal display device. However, as the number of rings increases, the lower the content of the polymerizable compound that can be incorporated into the liquid crystal.

After a lot of repeated experiments in the present invention, it was found that adding a spacer group between different rings can effectively improve the solubility problem of the polymerizable compound, and at the same time, the polymerizable liquid crystal composition of the present invention can have a lower The residual polymerizable compound has better UV stability and better reliability, which can effectively improve the image retention phenomenon of liquid crystal display devices.

The present invention will be described below in conjunction with specific embodiments. It should be noted that the following embodiments are examples of the present invention, which are only used to illustrate the present invention, but not to limit the present invention. Other combinations and various improvements within the concept of the present invention can be made without departing from the gist or scope of the present invention.

The liquid crystal displays used in the following embodiments are all VA mode display devices, with a cell thickness d=4 μm, and are composed of polarizers (polarizers), electrode substrates, and the like. The display device is in the normally white mode, that is, when no voltage difference is applied between the row and column electrodes, the observer observes the white primitive color. The axes of the upper and lower polarizers on the substrate are at 90 degrees to each other. The space between the two substrates is filled with optical liquid crystal material.

For ease of expression, in the following examples, the group structure of the liquid crystal composition is represented by the codes listed in Table 1: Table 1 The group structure of liquid crystal compounds

Take the following structural formula as an example:

If the structural formula is expressed by the codes listed in Table 1, it can be expressed as: nCGUF, n in the code represents the number of carbon atoms of the left terminal alkyl group, for example, n is "2", which means that the alkyl group is -C ₂ H ₅ ; C in the code represents "1,4-cyclohexylene", G in the code represents "2-fluoro-1,4-phenylene", and U in the code represents "2,5-difluoro-1, 4-phenylene", F in the code stands for "fluoro substituent". If the structural formula is expressed by the codes listed in Table 1, it can be expressed as: V(1)EPGE(1)V.

The abbreviated codes of the test items in the following embodiments are as follows:

Among them, the refractive index anisotropy was measured using an Abbe refractometer under a sodium light (589 nm) light source at 25°C; the dielectric test box was TN90 type, and the box thickness was 7 μm.

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: 25℃, 1KHz, test box is TN90 type, box thickness 7 μm.

C. Use high performance liquid chromatography to test the initial content of polymerizable compounds.

C _UV uses high performance liquid chromatography to test the content of polymerizable compounds after UV light irradiation for 180 seconds.

Test condition of VHR ₁ voltage retention rate: VHR is tested using TOY06254 type liquid crystal physical property evaluation system; using TN type test cell, cell thickness 9μm, 5V6Hz, 60℃.

Test condition of VHR ₂ voltage retention rate: VHR was tested using TOY06254 type liquid crystal physical property evaluation system; using TN type test cell, cell thickness 9 μm, and test after irradiating 6000 mJ with 365 nm light.

Example 1

The polymerizable liquid crystal composition of Example 1 was prepared according to the compounds and weight percentages listed in Table 2, and it was filled between two substrates of a liquid crystal display for performance testing. The test data is shown in the following table: Table 2 Liquid crystal composition Formulation and test performance

Under the condition that other components remain unchanged, the compound of formula 1 is substituted for compound I-1-29-1 to form a polymerizable liquid crystal composition RM-1, and the voltage retention rate before and after UV light irradiation is tested, and the test result of Example 1 For comparison, as shown in Table 3 below: Equation 1 Table 3

Example 2

The polymerizable liquid crystal composition of Example 2 was prepared according to the compounds and weight percentages listed in Table 4, and filled between two substrates of a liquid crystal display for performance testing. The test data is shown in the following table: Table 4 Liquid crystal composition Formulation and test performance

Under the condition that other components remain unchanged, the compound of formula 1 is substituted for compound I-1-8-1 to form a polymerizable liquid crystal composition RM-2, and the voltage retention rate before and after UV light irradiation is tested, and the test result of Example 2 For comparison, as shown in Table 5 below: Equation 1 Table 5

Example 3

The polymerizable liquid crystal composition of Example 3 was prepared according to the compounds and weight percentages listed in Table 6, which was filled between the two substrates of the liquid crystal display for performance testing. The test data is shown in the following table: Table 6 Liquid crystal combination Formulation and test performance

Under the condition that other components remain unchanged, the compound of formula 1 is substituted for compound I-1-34-2 to form a polymerizable liquid crystal composition RM-3, and the voltage retention rate before and after UV light irradiation is tested, and the test result of Example 3 For comparison, as shown in Table 7 below: Equation 1 Table 7

Example 4

The polymerizable liquid crystal composition of Example 4 was prepared according to the compounds and weight percentages listed in Table 8, which was filled between the two substrates of the liquid crystal display for performance testing. The test data is shown in the following table: Table 8 Liquid Crystal Combination Formulation and test performance

Under the condition that other components remain unchanged, the compound of formula 1 is substituted for compound I-1-21-1 to form a polymerizable liquid crystal composition RM-4, and the voltage retention rate before and after UV light irradiation is tested, and the test result of Example 4 For comparison, as shown in Table 9 below: Equation 1 Table 9

It can be seen from the data of Examples 1-4 that the polymerizable liquid crystal composition of the present invention has good stability and high reliability, which is specifically manifested as having lower polymerizable compound residues and having higher The voltage retention rate makes the liquid crystal display device containing the polymerizable liquid crystal composition have little or no image sticking effect.

The above is only the preferred embodiments of the present invention, and does not limit the present invention in any form. Although the present invention has been disclosed in the preferred embodiments as above, it is not intended to limit the present invention. Anyone familiar with the profession Technical personnel, without departing from the scope of the technical solution of the present invention, when the technical contents disclosed above can be used to make some modifications or modifications to equivalent equivalent embodiments, but any technical solutions based on the present invention without departing from the technical solution content of the present invention In essence, any simple modifications, equivalent changes and modifications made to the above embodiments still fall within the scope of the technical solution of the present invention.

Claims (11)

A polymerizable liquid crystal composition comprising: at least one compound of general formula I Ⅰ; at least one compound of general formula II Ⅱ; at least one compound of general formula III Ⅲ; wherein, P ₁ and P _{2 are the} same or different, each independently represents a polymerizable group; Y ₁ and Y _{2 are the} same or different, each independently represents a linear or branched alkyl group of 1-20 carbon atoms; R ₁ , R ₂ , R ₃ and R _{4 are the} same or different, and each independently represents a linear or branched alkyl or alkoxy group having a carbon number of -H, 1 to 12, and a carbon number of 2 to 12 Alkenyl group or alkenyloxy group, wherein one or more -CH ₂ -in a linear or branched alkyl or alkoxy group of 1 to 12 may be substituted by -O-, and the number of carbon atoms is 2 to 12 One or more -CH ₂ -in the alkenyl group or alkenyloxy group may be substituted by -O-, provided that -O- is not directly connected; Ring A represents or , Where the ring One or more -CH ₂ -may be replaced by -O- or -S-; ring One or more of -H may be substituted by -F or -CH ₃ ; Ring B, Ring C and Ring D are the same or different, and each represents independently or ,among them, One or more -H can be replaced by -F, One or more of -CH ₂ -may be substituted by -O-; ring E, ring F, ring G and ring H are the same or different, and each represents independently or ,among them, One or more -H can be replaced by -F, provided that the substitution sites are not adjacent, One or more -CH ₂ -may be substituted by -O-; L ₁ -L _{12 are the} same or different, each independently represents -H, -F, or -CH ₃ ; Z and Z ^{1 are the} same or different, each independently Ground represents a single bond, -CH ₂ O-, -OCH ₂ -, -CH ₂ CH ₂ -, -COO-, -OCO-, -CF ₂ O- or -OCF ₂ -; Z ² and Z ^{3 are the} same or different , Each independently represents a single bond, -O-, -OCO-, -COO-, or -O-COO-; Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ and Z _{6 are the} same or different, each independently Represents a single bond, -CH ₂ O-, -OCH ₂ -, -CH ₂ CH ₂ -, -COO-, -OCO-, -CF ₂ O- or -OCF ₂ -; n, n ₁ and n _{2 are the} same or Different, each independently represents 0 or 1; b, c and d are the same or different, each independently represents 0, 1 or 2; e, f, g and h are the same or different, each independently represents 0, 1 or 2, Among them, e+f+g+h≥2. The polymerizable liquid crystal composition as described in item 1 of the patent application, wherein P ₁ and P _{2 are the} same or different, and each independently represents , , , , , , , , , , , , or . The polymerizable liquid crystal composition as described in item 2 of the patent application scope, wherein the compound of the general formula I is selected from one or more of the compounds of the general formula I-1 to I-3: Ⅰ-1; Ⅰ-2; and Ⅰ-3. The polymerizable liquid crystal composition as described in item 3 of the patent application range, wherein at least one of L ₁ -L ₁₆ is -F or -CH ₃ . The polymerizable liquid crystal composition as described in item 3 of the patent application, wherein Z represents -CH ₂ O-, -OCH ₂ -, -CH ₂ CH ₂ -, -COO-, or -OCO-. The polymerizable liquid crystal composition as described in item 3 of the patent application scope, wherein the compound of the general formula 1-1 is selected from one or more of the following compounds: Ⅰ-1-1; Ⅰ-1-2; Ⅰ-1-3; Ⅰ-1-4; Ⅰ-1-5; Ⅰ-1-6; Ⅰ-1-7; Ⅰ-1-8; Ⅰ-1-9; Ⅰ-1-10; Ⅰ-1-11; Ⅰ-1-12; Ⅰ-1-13; Ⅰ-1-14; Ⅰ-1-15; Ⅰ-1-16; Ⅰ-1-17; Ⅰ-1-18; Ⅰ-1-19; Ⅰ-1-20; Ⅰ-1-21; Ⅰ-1-22; Ⅰ-1-23; Ⅰ-1-24; Ⅰ-1-25; Ⅰ-1-26; Ⅰ-1-27; Ⅰ-1-28; Ⅰ-1-29; Ⅰ-1-30; Ⅰ-1-31; Ⅰ-1-32; Ⅰ-1-33; Ⅰ-1-34; Ⅰ-1-35; Ⅰ-1-36; Ⅰ-1-37; Ⅰ-1-38; Ⅰ-1-39; Ⅰ-1-40; and Ⅰ-1-41, wherein X ₁ and X _{2 are the} same or different, and each independently represents -H or -CH ₃ ; Z and Z ^{1 are the} same or different, each independently represents -CH ₂ O-, -OCH _2- , -CH ₂ CH ₂ -, -COO- or -OCO-. The polymerizable liquid crystal composition as described in item 3 of the patent application scope, wherein the compound of the general formula I-2 is selected from one or more of the following compounds: Ⅰ-2-1; Ⅰ-2-2; Ⅰ-2-3; Ⅰ-2-4; Ⅰ-2-5; Ⅰ-2-6; wherein, X ₁ and X _{2 are the} same or different, and each independently represents -H or -CH ₃ ; Z represents -CH ₂ O-, -OCH ₂ -, -CH ₂ CH ₂ -, -COO -Or-OCO-. The polymerizable liquid crystal composition as described in item 3 of the patent application scope, wherein the compound of the general formula I-3 is selected from one or more of the following compounds: Ⅰ-3-1; Ⅰ-3-2; Ⅰ-3-3; Ⅰ-3-4; Ⅰ-3-5; Ⅰ-3-6; Ⅰ-3-7; Ⅰ-3-8; Ⅰ-3-9; and I-3-10, wherein X ₁ and X _{2 are the} same or different, and each independently represents -H or -CH ₃ ; Z represents -CH ₂ O-, -OCH ₂ -, -CH ₂ CH ₂ -, -COO- or -OCO-. The polymerizable liquid crystal composition as described in item 1 of the patent application scope, wherein the compound of the general formula II is selected from one or more of the following compounds: Ⅱ-1; Ⅱ-2; Ⅱ-3; Ⅱ-4; Ⅱ-5; Ⅱ-6; Ⅱ-7; Ⅱ-8; Ⅱ-9; Ⅱ-10; Ⅱ-11; Ⅱ-12; Ⅱ-13; Ⅱ-14; Ⅱ-15; Ⅱ-16; Ⅱ-17; Ⅱ-18; Ⅱ-19; Ⅱ-20; Ⅱ-21; Ⅱ-22; Ⅱ-23; Ⅱ-24; Ⅱ-25; and Ⅱ-26. The polymerizable liquid crystal composition as described in item 1 of the patent application scope, wherein the compound of the general formula III is selected from one or more of the following compounds: Ⅲ-1; Ⅲ-2; Ⅲ-3; Ⅲ-4; Ⅲ-5; Ⅲ-6; Ⅲ-7; Ⅲ-8; Ⅲ-9; Ⅲ-10; Ⅲ-11; Ⅲ-12; Ⅲ-13; Ⅲ-14; Ⅲ-15; Ⅲ-16; Ⅲ-17; Ⅲ-18; Ⅲ-19; Ⅲ-20; Ⅲ-21; and Ⅲ-22. A liquid crystal display device comprising the polymerizable liquid crystal composition according to any one of items 1 to 10 of the patent application.