TWI681041B - Liquid crystal display device and liquid crystal composition used therefor - Google Patents

Abstract

A liquid crystal display device comprises a first substrate, a second substrate which faces the first substrate, an electrode part which is provided on at least one of the first substrate and the second substrate, and a liquid crystal layer which comprises a liquid crystal composition and is provided between the first substrate and the second substrate. The liquid crystal composition includes a liquid crystal compound of Formula 1.

Description

Liquid crystal display and liquid crystal composite used therefor

Cross-reference of related applications

This application claims the priority and benefits of Korean Patent Application No. 10-2015-0053223 filed with the Korean Intellectual Property Office on April 15, 2015, and No. 10-2015-018292 filed on December 21, 2015 , The entire content of which is used as a reference in this manual.

The present invention relates to a liquid crystal display (LCD) and the liquid crystal composition used therefor.

The liquid crystal display device may include a first substrate having a plurality of pixels, a second substrate, and a liquid crystal layer interposed between the first and second substrates. The liquid crystal display device changes the light transmittance of light in the liquid crystal layer according to the electric field generated between each pixel electrode and the common electrode, thereby displaying an image. The liquid crystal display device may include a plurality of pixels, and each pixel may include a pixel electrode.

Recently, it has been found that in addition to displaying flat images (2D), liquid crystal display devices can also display stereoscopic images (3D), and solutions that require more image information are provided to users. Therefore, compared with the conventional liquid crystal display device, a liquid crystal display device with high speed and high durability is required.

Exemplary embodiments provide a single liquid crystal compound having high dielectric anisotropy and high refractive index anisotropy and having good low temperature stability (LTS), and liquid crystal synthesis including the same Thing.

Another exemplary embodiment provides a liquid crystal display device including a liquid crystal composition having high dielectric anisotropy and high refractive index anisotropy and improving low-temperature stability.

According to an embodiment, a liquid crystal display device includes a first substrate, a second substrate facing the first substrate, an electrode portion located on at least one of the first substrate and the second substrate, and a liquid crystal composition and located on the first substrate and The liquid crystal layer between the second substrates.

According to an embodiment, the liquid crystal composition includes at least one liquid crystal compound, as shown in Formula 1. Formula 1

In Formula 1, R ₁ represents hydrogen or an alkyl group having 1 to 15 carbon atoms, in which at least one -CH ₂ -group can be independently -C≡C-, -CF ₂ O when oxygen-free atoms are connected to each other -, -CH=CH-, -O-, -CO-O-, -O-CO-, or -O-CO-O-, and 1 to 3 hydrogen atoms can be replaced by halogen atoms.

R ₂ represents -F, -Cl, -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₃ , -CN, -NCS, or an alkane having 1 to 5 carbon atoms substituted with one to three -F Group, and the -CH ₂ -group selectivity is independently substituted by an oxygen atom without two oxygen atoms being connected to each other.

、

、

、

、

、

、

、

、

、

、

、

、

、

、

、或

。 Z₁₁ 、Z₁₂ 、Z₁₃ 、Z₂₁ 、及Z₂₂ 可各自獨立地為單鍵、-CH₂ CH₂ -、-CH=CH-、-CH₂ O-、-OCH₂ -、-C≡C-、-CH₂ CF₂ -、-CHFCHF-、-CF₂ CH₂ -、-CH₂ CHF-、-CHFCH₂ -、-C₂ F₄ -、-COO-、-OCO-、-CF₂ O-、或-OCF₂ -，a、b、c、d、及e係各自獨立地為0~3的整數，且a+b+c+d+e小於或等於5。(F) indicates that the hydrogen atom is selectively substituted with -F, and A ₁₁ , A ₁₂ , A ₁₃ , A ₂₁ , and A ₂₂ are each independently represented by the following structures:

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,or

. Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₂₁ , and Z ₂₂ may each independently be a single bond, -CH ₂ CH ₂ -, -CH=CH-, -CH ₂ O-, -OCH ₂ -, -C≡ C-, -CH ₂ CF ₂ -, -CHFCHF-, -CF ₂ CH ₂ -, -CH ₂ CHF-, -CHFCH ₂ -, -C ₂ F ₄ -, -COO-, -OCO-, -CF ₂ O-, or -OCF ₂ -, a, b, c, d, and e are each independently an integer of 0 to 3, and a+b+c+d+e is less than or equal to 5.

According to an embodiment, at least one of Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₂₁ , and Z ₂₂ may be -CF ₂ O-.

According to an embodiment, d and e are 0, and R ₂ may be -F, -OCF ₃ , or -CF ₃ .

According to an embodiment, Z ₁₃ is -CF ₂ O-, d and e are 0, and R ₂ may be -F, -OCF ₃ , or -CF ₃ .

According to the embodiment, the liquid crystal compound of Formula 1 may be represented by Formula 1-1.

Formula 1-1

R ₁ , R ₂ , A ₁₁ , A ₁₂ , Z ₁₁ , Z ₁₂ , a, and b are the same as defined in Formula 1.

According to the embodiment, the liquid crystal compound of Formula 1-1 may be represented by Formula 1-2.

Formula 1-2

R ₁ is the same as defined in Formula 1, and o is 0 or 1.

According to an embodiment, the liquid crystal composition may further include at least one liquid crystal compound as shown in Formula 2.

Formula 2

、

、

、

、

、或

。 ₁ and the same system as defined in Formula 1 R R _11, in addition to the definition of R 1 of formula _1, R ₂₁ represents -F, -Cl, -CF3, or -OCF _3, A ₃ and A ₄ independently of one another by F-substituted or unsubstituted 1,4-cyclohexylene (1,4-cyclohexylene) or F-substituted or unsubstituted 1,4-phenylene (1,4-phenylene), and A ₅ represents the following One of the structures:

,

,

,

,

,or

.

According to an embodiment, the liquid crystal composition further includes a liquid crystal compound represented by Formula 3.

Formula 3

R ₁₁ and R _{12 are} independently the same as the definition of R ₁ in Formula 1, and A ₃ and A _{4 are} independently 1,4-cyclohexyl substituted by F- or unsubstituted or 1 substituted or unsubstituted by F ,4-phenylene.

According to an embodiment, the liquid crystal composition may further include a liquid crystal compound as shown in Formula 4.

Formula 4

In Formula 4, R ₁ and R _{2 are the} same as the definitions of R ₁ and R ₂ in Formula 1, A ₁₁ , A ₁₂ , A ₁₃ , Z ₁₁ , Z ₁₂ , Z ₁₃ and (F) are also the same as in Formula 1 In the definitions of A ₁₁ , A ₁₂ , A ₁₃ , Z ₁₁ , Z ₁₂ , Z ₁₃ and (F), f, g and h are each independently 0 or 1, and f+g+h is 2 or 3.

According to an embodiment, the liquid crystal composition may further include at least one liquid crystal compound, which is any one of Formulas 5-7.

Formula 5

Formula 6

Formula 7

R ₁ and A ₁₁ are the same as defined in Formula 1, p is 0 or 1, R ₃ represents hydrogen, oxygen radical, or an alkyl group having 1 to 15 carbon atoms, of which at least one -CH2- group may be In the case where no two oxygen atoms are connected to each other, they are independently -C≡C-, -CF ₂ O-, -CH=CH-, -O-, -CO-O-, -O-CO-, or -O- CO-O- substitution, and 1 to 3 hydrogen atoms can be replaced by halogen atoms, n is an integer of 1 to 12, and m is an integer of 0 to 12.

According to an embodiment, the liquid crystal composition further includes a pitch modifier as shown in Formula 8.

Formula 8

R ₁ is the same as defined in Formula 1.

According to the liquid crystal composition prepared by the present invention, a liquid crystal composition having improved LTS, high dielectric constant and high refractive index can be manufactured.

In addition, the liquid crystal composition prepared according to the present invention can provide a liquid crystal composition optimized for various forms of liquid crystal display devices, such as twisted nematic (TN), super twisted nematic (STN), in-plane switching, IPS), fringe electric field switching (FFS), or plane-to-line switching (PLS), etc.

The present invention can be implemented in various changes and various shapes, and in this section, a specific embodiment will be described in detail with reference to the drawings. On the other hand, the drawings are not intended to limit the present invention to the described embodiments, but are interpreted to include all changes, equivalents, and alternatives that conform to the spirit and scope of the present invention. For clarity, the size of layers and regions can be enlarged in the drawings.

Although the words "first", "second", etc. may be used herein to describe various elements, these elements should not be limited to these words. These words can be used to distinguish one element from another. Therefore, the so-called first element in the present invention may be named as the second element without departing from the teachings of the one or more embodiments. The description of an element as a "first" element may not require or imply the presence of a second element or other elements. You can also use words such as "first" and "second" to distinguish between different categories or component groups. For ease of description, the words "first", "second", etc. may mean "first type (or first group)", "second type (or second group)", etc., respectively.

When it is mentioned that the first element is located "on", "connected" or "coupled" to the second element, the first element may be directly located on the second element, directly connected or coupled to the second element, or may There are one or more intermediate elements. Conversely, when it is mentioned that the first component is "directly" located "on", "directly connected" or "directly coupled" to the second component, there is no intermediate component between the first component and the second component. When element A is "between" the other two elements B and C, element A may be directly on element B and directly on element C, or there may be other intermediate layers between A and B, A and C, Or between A and B and A and C. Throughout the specification, the same symbol may indicate the same element. The word "and/or" includes any and all combinations of one or more related items. "Or" means "and/or".

This text may use spatial relative terms such as "below", "below", "below", "above", "above", etc. in order to explain the relationship between one element or feature and another element or feature shown in the drawings. In addition to explaining the orientations depicted in the drawings, spatial relative word systems will cover different orientations of the devices used or in operation. For example, if the device shown in the figure is turned over, the so-called "below" or "below" other elements or features will be oriented "above" the other elements or features.

The vocabulary used herein is for the purpose of describing particular embodiments only and is not limiting. Throughout the specification, unless clearly stated otherwise, the singular expression "a" and "the" are intended to include both the plural expressions. It will be further understood that when the words "include" and/or "include" are used in this document, they refer to the existence of listed features, integers, steps, operations, elements, and/or components, but do not exclude one or more There are other features, integers, steps, operations, elements, components, and/or combinations of the above.

This document describes the embodiments with reference to the cross-sectional views of the embodiments (and intermediate structures). Therefore, for example, differences in manufacturing techniques and/or tolerances are expected to result in different schematic shapes. Also, the embodiments should not be construed as being limited to the shapes of specific blocks depicted herein, but should include, for example, shape distortions caused by manufacturing. For example, the edges of the implanted area depicted as a rectangle may have rounded or curved features and/or implant concentration gradients, not just the binary changes implanted into the non-implanted area. Similarly, the embedding area formed by the implantation method can pass through the place where the implantation occurs to cause the implantation to act on the block between the implantation and the surface. Therefore, the blocks shown in the drawings are schematic diagrams, and the shape is not intended to illustrate the actual shape of the device block, nor to limit the scope of the embodiments.

Considering the measurement errors related to the measurement and the related specific quantity (ie, the limitation of the measurement system), "approximately" or "approximately" as used herein shall include the listed values and represent the specific values determined by those of ordinary knowledge in the field. Accept the deviation. For example, "about" may mean within one or more standard deviations, or within ±30%, ±20%, ±10%, or ±5% of the listed values.

As used herein, "alkyl" refers to a linear or branched, saturated, monovalent hydrocarbon group (eg, methyl or hexyl) having a specific number of carbon atoms.

Unless otherwise defined, all terms (including technical and scientific terms) used in this text have the same meaning as those of ordinary knowledge in the field to which the present invention belongs. As generally defined in dictionaries, these terms will be further understood and interpreted to have a meaning consistent with the literature in the relevant field, and should not be interpreted as an over-ideal or formal meaning unless otherwise defined herein.

The following will explain the preferred embodiment in more detail.

The present invention relates to a liquid crystal display device using a liquid crystal compound as a material, and a composition containing the liquid crystal compound.

The single liquid crystal compound constituting the liquid crystal product may be an organic substance with a molecular weight of 200 to 600 g/mol and has a long bond molecular structure. The liquid crystal molecular structure can be divided into a core group that maintains a straight-chain characteristic, a flexible end group, and a special-purpose chain group. Without being bound by theory, the terminal groups at one or both ends have flexible chain formation (alkyl, alkoxy, alkenyl, etc.) to maintain flexibility, and polar groups (-F, -CN,-are inserted at the other end) OCF ₃ ) to adjust the physical characteristics of liquid crystal such as dielectric constant.

According to the characteristics and application methods of the liquid crystal display panel (LCD), the LCD can have various modes, such as twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), and fringe electric field switching ( FFS) etc. In these different liquid crystal display devices, it is difficult to meet the product requirements with only one or two liquid crystal compounds, such as clearing point (Clearing Point, Tc) temperature, dielectric anisotropy, refractive index anisotropy, rotational viscosity (rotational viscosity), etc., so 7 to 20 kinds of single liquid crystal compounds can be mixed to make liquid crystal composites.

The general characteristics of the main components required for the liquid crystal composition are listed in Table 1. Table 1

As shown in Table 1, regardless of the application method of the LCD panel, low rotational viscosity is preferred, and the refractive index anisotropy is preferably greater than or equal to 0.07, although its optimal value will vary according to the crystal gap of the LCD. At the same time, the specific resistance required for an active matrix liquid crystal display (AM-LCD) is greater than or equal to 10 ¹³ Ωm. There is a need to manufacture a mixture that meets these characteristics and can operate LCDs even at low temperatures of -25°C or less.

When mixing no less than 10 single liquid crystal compounds, although most of the eutectic points are not higher than -20℃, high melting point single liquid crystal compounds may occur when the mixture is kept at a low temperature for a long time re-crystallize. Therefore, in order to avoid this recrystallization, it is appropriate to mix alkyl homologues with different alkyl derivatives. On the other hand, single liquid crystal compounds tend to have long alkyl chains to increase refractive index anisotropy or dielectric anisotropy, and the long alkyl chains can increase rotational viscosity and reduce elastic modulus. The increased rotational viscosity and reduced elastic modulus can increase the reaction time.

For example, as shown in Table 2, compound No. 2 with two more methylene units (methylene, -CH ₂ -) than compound No. 1 has a low melting point, making it a better LTS; however, rotational viscosity (γ1 ) An increase of more than 20 mPas increases the LCD response time ( Hiraoka, H, (2009), Mol. Cryst. Liq. Cryst., Vol 509, pp 89 ). Table 2

Therefore, a single liquid crystal compound having high dielectric anisotropy, high refractive index anisotropy, low rotational viscosity, and low melting point is desired, and the single liquid crystal compound provided by the present invention has high dielectric anisotropy and high refractive index anisotropy Anisotropy, low rotational viscosity and low melting point.

The liquid crystal compound system according to the embodiment is represented as Formula 1.

Formula 1

In Formula 1, R ₁ represents hydrogen or an alkyl group having 1 to 15 carbon atoms, wherein at least one -CH ₂ -group can be independently -C≡C-, -CF ₂ without two oxygen atoms connected to each other O-, -CH=CH-, -O-, -CO-O-, -O-CO-, or -O-CO-O-, and 1 to 3 hydrogen atoms can be replaced by halogen atoms.

Meanwhile, for R ₁ , when at least one -CH ₂ -group in R ₁ having an even number of carbon atoms is substituted with a double bond, the double bond may be inserted into the end of the double carbon. For example, when a double bond is inserted into R ₁ , it may be CH ₂ =CH- or CH ₂ =CH-CH ₂ -CH ₂ -. When the number of carbon atoms of R ₁ is odd and greater than or equal to 3, the double bond can be inserted between the double-numbered carbon counted from the terminal and the single-numbered carbon next to it. For example, when a double bond is inserted into R ₁ , it can be CH ₃ -CH=CH- or CH ₃ -CH=CH-CH ₂ -CH ₂ -. Without being bound by theory, by inserting a double bond in R ₁ , the rotational viscosity can be reduced, the clarification point can be increased, and the elastic modulus can be controlled. R ₂ may be a polar group, -F, -Cl, -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₃ , -CN, -NCS, or an alkyl group substituted with one to three -F, which The -CH ₂ -group is independently replaced by an oxygen atom without two oxygen atoms being connected to each other. According to an embodiment, R ₂ may be -F, -Cl, -CF ₃ , or -OCF ₃ .

、

、

、

、

、

、

、

、

、

、

、

、

、

、

、或

。(F) indicates that the hydrogen atom is selectively substituted with -F, and A ₁₁ , A ₁₂ , A ₁₃ , A ₂₁ , and A _{22 are} each independently represented by the following structures:

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,or

.

According to the embodiments and not being bound by theory, 1,4-phenylene can be used for A ₁₁ , A ₁₂ , A ₁₃ , A ₂₁ , and A ₂₂ for high refractive index anisotropy, and ring structures containing fluorine or oxygen are available To improve the dielectric anisotropy.

Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₂₁ , and Z ₂₂ are independently a single bond, -CH ₂ CH ₂ -, -CH=CH-, -CH ₂ O-, -OCH ₂ -, -C≡C- , -CH ₂ CF ₂ -, -CHFCHF-, -CF ₂ CH ₂ -, -CH ₂ CHF-, -CHFCH2-, -C ₂ F ₄ -, -COO-, -OCO-, -CF ₂ O-, Or -OCF ₂ -.

In consideration of dielectric anisotropy, rotational viscosity, refractive index anisotropy, etc., Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₂₁ , and Z ₂₂ can be selectively combined. According to an embodiment, at least one of Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₂₁ , and Z ₂₂ may be -CF ₂ O-. When at least one of Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₂₁ , and Z ₂₂ is -CF ₂ O-, the liquid crystal compound may have high dielectric anisotropy. In particular, when Z ₁₃ is -CF ₂ O-, the dielectric anisotropy can be improved and the decrease in the clear point of the liquid crystal compound can be minimized. According to an embodiment, Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₂₁ , and Z ₂₂ may each be a single bond, and in this case, the compound may have a low rotational viscosity.

a, b, c, d, and e independently represent the values 0 to 3, and a+b+c+d+e is less than or equal to 5.

The liquid crystal compound of Formula 1 may have a higher dielectric constant than other types of liquid crystal, and it is considered that the rotational viscosity may be relatively low under a high dielectric constant. Meanwhile, the liquid crystal compound of Formula 1 may have a relatively lower melting point than other types of liquid crystal compounds corresponding to molecular weight.

In an embodiment, when the ring between multiple rings is substituted with a methyl group, the methyl substituted ring increases the angle between the multiple rings. Without being bound by theory, when the angle between multiple rings increases due to the methyl-substituted ring, the packing density between liquid crystal molecules decreases and the melting point decreases. In Formula 1, the third position of 1,4-phenylene is substituted with a methyl group, and thus the bulk density of the liquid crystal compound of Formula 1 is reduced and the melting point is lowered. Without being limited by theory, when two or more alkyl groups having 2 carbon atoms exist between the polycyclic rings, the ratio between the long axis and the short axis of the liquid crystal molecule decreases, and the clearing point decreases greatly. At the same time, when the ring between multiple rings is substituted with fluorine, the ring behaves essentially the same as the methyl-substituted ring. On the other hand, since fluorine reduces the positive dielectric anisotropy, it is difficult to obtain the expected amount of high dielectric anisotropy. In order to increase the positive dielectric anisotropy, fluorine groups can be inserted in the second and sixth positions of the ring.

The liquid crystal compound of Formula 1 may include a compound represented by Formula 1A, and in Formula 1A, R ₁ is the same as Formula 1.

[1]、

[2]、

[3]、

[4]、

[5]、

[6]、

[7]、

[8]、

[9]、

[10]、

[11]、

[12]、

[13]、

[14]、

[15]、

[16]、

[17]、

[18]、

[19]、

[20]、

[21]、

[22]、

[23]、

[24]、

[25]、

[26]、

[27]、

[28]、

[29]、

[30]、

[31]、

[32]、

[33]、

[34]。Formula 1A

[1],

[2],

[3],

[4],

[5],

[6],

[7],

[8],

[9],

[10],

[11],

[12],

[13],

[14],

[15],

[16],

[17],

[18],

[19],

[20],

[twenty one],

[twenty two],

[twenty three],

[twenty four],

[25],

[26],

[27],

[28],

[29],

[30],

[31],

[32],

[33],

[34].

For example, in some embodiments, the liquid crystal compound may be a liquid crystal compound represented by Formula 1, wherein at least one of Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₂₁ , and Z ₂₂ is -CF ₂ O-. According to another embodiment, the liquid crystal compound may be a liquid crystal compound in which d and e are 0, and R ₂ is -F, -OCF ₃ , or -CF ₃ . According to another embodiment, the liquid crystal compound may be a liquid crystal compound in which Z ₁₃ is -CF ₂ O-, d and e are 0, and R ₂ is -F, -OCF ₃ , or -CF ₃ .

More specifically, according to the embodiment, the liquid crystal compound of Formula 1 may be one of the structural compounds represented by Formula 1-1.

Formula 1-1

R ₁ , R ₂ , A ₁₁ , A ₁₂ , Z ₁₁ , Z ₁₂ , (F), a, and b are the same as defined in Formula 1.

According to an embodiment, the liquid crystal compound of Formula 1 may be at least one of the structural compounds represented by Formula 1-2.

Formula 1-2

Where o is 0 or 1

R ₁ is the same as Formula 1. The liquid crystal compound of Formula 1-2 may be at least one of the structural compounds represented by Formula 1-2-1, 1-2-2, and 1-2-3.

Formula 1-2-1

Formula 1-2-2

Formula 1-2-3

In another embodiment, the liquid crystal composition includes or consists of the liquid crystal compound of Formula 1.

As in the liquid crystal composition according to the embodiment, the liquid crystal compound of Formula 1 contains 1% or more by weight (wt%) corresponding to the total weight of the liquid crystal composition.

The liquid crystal composition according to the embodiment may include the liquid crystal compound of Formula 1 in a weight percentage of 1% or more, or in the range of 1-40%, or in the range of 1-30%. When the weight percentage of the liquid crystal compound of Formula 1 is less than 1%, it is difficult to obtain a high dielectric constant and ensure LTS, and when the weight percentage is higher than 40%, for example, the durability of the display device may be caused by low direct current (DC) Degraded in the display device.

The liquid crystal composition according to the embodiment may preferably include one or two or more liquid crystal compounds of the structure of Formula 1-2, and in this case, LTS can be maintained for a long time.

In particular, the liquid crystal composition according to the embodiment may include the liquid crystal compound of Formula 1-2-1. For Formula 1-2-1, it is a material with a dielectric anisotropy of 20 and a rotational viscosity of 114 mPas. Therefore, when the dielectric anisotropy of the liquid crystal composition is about 3~6, in order to effectively obtain a liquid crystal composition with low rotational viscosity, the liquid crystal compound of Formula 1-2-1 may be included in a weight percentage of about 3~7%. In the case of a liquid crystal composition with a dielectric anisotropy of 10 or higher, when a single substance of formula 1-2-2 and/or 1-2-3 with a dielectric anisotropy of 30 or higher When the weight percentage of the material is about 10% or higher, the dielectric anisotropy can be easily adjusted.

According to an embodiment, in addition to the liquid crystal compound of Formula 1, a liquid crystal composition mixed with one or more of the following additional liquid crystal compounds can improve LTS, high dielectric anisotropy, and low rotational viscosity.

In the liquid crystal composition according to the embodiment, the liquid crystal composition may further include at least one liquid crystal compound of Formula 2.

Formula 2

、

、

、

、

、

。The same as R ₁₁ defined in Formula 1 R _1, in addition to the definition of R ₁₁ in the formula, R ₂₁ represents -F, -Cl, -CF _3, or -OCF _3, A ₃ and A ₄ independently of one another by F-substituted or unsubstituted 1,4-cyclohexyl, or F-substituted or unsubstituted 1,4-phenylene, and A ₅ may have the following structure:

,

,

,

,

,

.

According to the embodiment, the liquid crystal compound of Formula 2 is a compound having the structure shown in Formula 2-1.

Formula 2-1

R ₁₁ , R ₂₁ , and A ₅ are the same as in Formula 2. The liquid crystal compound of Formula 2-1 can be used at a higher temperature than the liquid crystal compound of Formula 1, and when the compound of Formula 1 and the compound of Formula 2-1 are combined, high-temperature stability and low rotational viscosity can be compensated. When the compound of Formula 2-1 and the compound of Formula 1 are mixed, the preferred weight percentage of the liquid crystal compound of Formula 2-1 is 5 to 35%. When the weight percentage of the liquid crystal compound of Formula 2-1 is not more than 5%, the clearing point rise effect can be reduced, and when its weight is more than 35%, a smectic liquid phase can be developed to reduce LTS.

The liquid crystal compound of Formula 2-1 may have a structure as shown in Formula 2-1-1a or Formula 2-1-1b.

Formula 2-1-1a

Formula 2-1-1b

R ₁₁ and R ₂₁ are the same as in Formula 2.

The liquid crystal compound of Formula 2-1-1a or Formula 2-1-1b may be at least one compound of the structure represented by Formula 2-1-1-1 and/or Formula 2-1-1-2.

Formula 2-1-1

Formula 2-1-1-2

According to an embodiment, the liquid crystal compound of Formula 2 may be a compound of the structure shown in Formula 2-2.

Formula 2-2

R ₁₁ and R ₂₁ are the same as defined in Formula 2, X ₁ to X _{5 are} independently -H or -F, and at least one X ₃ or X ₄ is -F.

The liquid crystal compound of Formula 2-2 has higher refractive index anisotropy and higher clear point than the liquid crystal compound of Formula 1. Therefore, when combining the liquid crystal composition of Formula 1, the liquid crystal compound of Formula 2-2 can compensate for the refractive index anisotropy and low clearing point of the liquid crystal composition. When the compounds of Formula 1 and Formula 2-2 are mixed, the liquid crystal compound of Formula 2-2 may be included in the total composition by 1 to 20% by weight. When 20% by weight or more of the liquid crystal compound of Formula 2-2 is included, the refractive index anisotropy may become too high to be used in a liquid crystal display device. In addition, when the weight percentage is less than 1%, it may be difficult to control the refractive index anisotropy in the composition.

The liquid crystal compound of Formula 2-2 may be a liquid crystal compound having at least one structure of Formula 2-2-1.

、

。Formula 2-2-1

,

.

R ₁₁ and R ₂₁ are the same as in Formula 2. The liquid crystal compound of Formula 2-2-1 may have the structure of Formula 2-2-1-1 as follows: Formula 2-2-1-1

In the liquid crystal composition according to the embodiment, the liquid crystal composition may further include at least one compound of the liquid crystal compound of Formula 3.

Formula 3

R ₁₁ and R _{12 are} independently the same as the definition of R ₁ in Formula 1, and A ₃ and A _{4 are} independently 1,4-cyclohexyl substituted or unsubstituted by F- or substituted or unsubstituted by F- 1,4-phenylene. According to the embodiment, the liquid crystal compound of Formula 3 is a compound of the structure shown in Formula 3-1 or 3-2.

Formula 3-1

Formula 3-2

R ₁₁ and R ₁₂ are the same as in Formula 3.

The liquid crystal compound of Formula 3-1 may have the structure of Formula 3-1-1 or Formula 3-1-2 as follows:

Formula 3-1-1

Formula 3-1-2

The liquid crystal compound shown in Formula 3, especially Formula 3-1-1, has a rotational viscosity lower than that of Formula 1. Therefore, when combined with the liquid crystal compound of Formula 1, the rotational viscosity of the liquid crystal composition can be compensated. In particular, when the liquid crystal compound of Formula 1 is mixed with the liquid crystal compound of Formula 3-1-1, the liquid crystal compound of Formula 3-1-1 may correspond to 15 to 45% by weight of the entire liquid crystal composition. When the weight percentage of the liquid crystal compound of Formula 3-1-1 is less than 15%, it is difficult to obtain a liquid crystal composition having a low rotation density for dynamic images. However, when its weight percentage is higher than 45%, it is excessive use of a single substance and can reduce LTS.

In the liquid crystal composition according to the embodiment, the liquid crystal composition includes at least one liquid crystal compound of Formula 1, at least one liquid crystal compound of Formula 2, and at least one liquid crystal compound of Formula 3.

In the liquid crystal composition according to the embodiment, the liquid crystal composition may further include at least a liquid crystal compound of Formula 4.

Formula 4

In Formula 4, R ₁ and R _{2 are} independently the same as the definitions of R ₁ and R ₂ in Formula 1, and A ₁₁ , A ₁₂ , A ₁₃ , Z ₁₁ , Z ₁₂ , Z ₁₃ and (F) are also the same as the formula In the definitions of A ₁₁ , A ₁₂ , A ₁₃ , Z ₁₁ , Z ₁₂ , Z ₁₃ and (F) in 1, f, g and h are each independently 0 or 1, and f+g+h is 2 or 3.

The liquid crystal composition of Formula 4 may include at least one liquid crystal compound of the structure shown in Formula 4-1, and the definitions of R ₁ , R ₂ , and (F) in Formula 4-1 are the same as their definitions in Formula 1.

、

、

、

、

、

、

、

、

、

、

、

、

、

、

、

、

、

。Formula 4-1

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

.

According to an embodiment, the liquid crystal compound of Formula 4-1 includes at least one liquid crystal compound of the structure represented by Formula 4-1-1 and 4-1-2.

Formula 4-1-1

Formula 4-1-2

、

、

、

、

、或

。A represents one of the following structures:

,

,

,

,

,or

.

The liquid crystal compound shown in Formula 4 is used to optimize the physical properties of the liquid crystal composition of the liquid crystal display device, and especially the compound of Formula 4-1-1 can simultaneously increase the clear point and dielectric constant of the liquid crystal. Also, when the liquid crystal composition including Formula 1 has a low dielectric anisotropy not greater than 6, LTS can be reduced; however, when the weight percentage of the compound of Formula 4-1-1 relative to the total liquid crystal composition is 1 to 10 %, can increase LTS.

The liquid crystal compound represented by Formula 4-1-1 may have a structure of Formula 4-1-1-1.

Formula 4-1-1-1

Meanwhile, the liquid crystal composition embodiment may further include various additives, such as antioxidants and/or ultraviolet (UV) stabilizers.

The liquid crystal composition may further include one or more compounds selected from Formulae 5 to 7 as antioxidants or UV stabilizers.

Formula 5

R ₁ and A ₁₁ are the same as defined in Formula 1, and p is 0 or 1.

Formula 6

Formula 7

In formulas 6 and 7, R ₃ represents hydrogen, an oxygen radical, or an alkyl group having 1 to 15 carbon atoms, in which at least one -CH2- group can be independently-without two oxygen atoms connected to each other- C≡C-, -CF ₂ O-, -CH=CH-, -O-, -CO-O-, -O-CO-, or -O-CO-O-, and 1 to 3 hydrogen atoms It can be substituted by halogen atom, n is an integer from 1 to 12, and m is an integer from 0 to 12.

The content of the compound selected from formulas 5 to 7 may be about 1 to 2000 ppm, and preferably 200 to 500 ppm based on the total weight of the composition.

The compound of Formula 5 can capture impurities generated by UV in the liquid crystal composition, such as ions and free radicals.

The compound of Formula 5 may be the compound of Formula 5-1.

Formula 5-1

Where (O) is O or CH ₂ .

The compounds of formulas 6 and 7 can capture impurities such as ions and free radicals generated in the liquid crystal composition due to thermal energy. The liquid crystal composition according to the embodiment includes at least one liquid crystal compound of Formula 1 and at least one compound of Formula 5-7, and in this case, the compound containing at least one Formula 5-7 is used to improve the thermal stability and UV stability of the liquid crystal composition Sex.

Meanwhile, in the liquid crystal composition according to the embodiment, the liquid crystal composition further includes the distance modification compound of Formula 8. R ₁ has the same definition as in Formula 1.

Formula 8

When the liquid crystal has a twisted spiral structure, the pitch indicates the distance traveled by the liquid crystal director within 360 degrees of rotation in the spiral structure. The spacing value can be adjusted according to the composition ratio of the spacing modifier.

When the liquid crystal composition with a relative weight percentage of 100% contains the compound represented by Formula 8 in an amount of about 0.01 to 5% by weight, the desired pitch can be obtained more easily.

According to an embodiment, the liquid crystal composition includes various compositions of one of the liquid crystal compounds of formulae 1 to 4 and/or one of the compounds of formulae 5 to 8.

For example, the liquid crystal composition according to the embodiment may include the liquid crystal compound of Formula 1-2 and the liquid crystal compound of Formula 2-1.

The liquid crystal composition according to another embodiment includes the liquid crystal compound of Formula 1-2 and the liquid crystal compound of Formula 2-2.

The liquid crystal composition according to still another embodiment includes the liquid crystal compound of Formula 1-2 and the liquid crystal compound of Formula 4-1.

The liquid crystal composition according to still another embodiment additionally includes the liquid crystal compound of Formula 3. For example, the liquid crystal composition according to the embodiment may include the liquid crystal compound of Formula 1-2, the liquid crystal compound of Formula 2-2, and the liquid crystal compound of Formula 3.

The liquid crystal composition according to still another embodiment additionally includes the liquid crystal compound of Formula 4.

The liquid crystal composition according to still another embodiment additionally includes at least one liquid crystal compound of formula 5-7. For example, the liquid crystal composition according to the embodiment may include the liquid crystal compound of Formula 1-2 and the additives of Formula 5-7.

The liquid crystal composition according to still another embodiment further includes the compound of formula 8.

According to the embodiment, the liquid crystal composition may have various synthesis ratios without violating the concept of the present invention.

According to an embodiment, the liquid crystal composition includes a liquid crystal compound of Formula 1-2, a liquid crystal compound of Formula 3-1-1, and a compound of Formula 5.

For example, the liquid crystal composition according to the embodiment may include 3 to 35 parts by weight of the liquid crystal compound as shown in Formula 1-2-1, and 15 to 45 parts by weight of the liquid crystal as shown in Formula 3-1-1 The compound and 0.01 to 0.05 parts by weight of the liquid crystal compound represented by Formula 5.

Meanwhile, the liquid crystal composition according to the embodiment may include a liquid crystal compound as shown in Formula 1-2-1, and a liquid crystal compound as shown in Formula 1-2-3, and in this case, Formula 1-1-2 The weight ratio between the liquid crystal compound and the liquid crystal compound of Formula 1-2-3 may be 1:0.5 to 1:2.0.

According to an embodiment, the liquid crystal composition includes a liquid crystal compound of formula 1-2, a liquid crystal compound of formula 2-1-1-1, a liquid crystal compound of formula 2-1-1-2, and a formula of 4-1-1 Liquid crystal compound.

Meanwhile, the liquid crystal compound according to the embodiment includes at least one 5 to 20 parts by weight of the liquid crystal compound represented by Formula 1-2-1 and the formula 2-1-1-1, and 5 to 20 parts by weight of Formula 2 Liquid crystal compound represented by -1-1-2, and 2 to 10 parts by weight of the liquid crystal compound represented by Formula 4-1-1-1.

According to an embodiment, the liquid crystal composition includes a liquid crystal compound of Formula 1-2, a liquid crystal compound of Formula 3-1-1, a liquid crystal compound of Formula 2-2-1-1, and a liquid crystal compound of Formula 4-1-2.

Meanwhile, the liquid crystal composition according to the embodiment includes 1 to 40 parts by weight of the liquid crystal compound represented by Formula 1-2, 15 to 45 parts by weight of the liquid crystal compound represented by Formula 3-1-1, and 2 to 15 parts by weight One part is a liquid crystal compound represented by Formula 2-2-1-1, and 3 to 35 parts by weight is a liquid crystal compound represented by Formula 4-1-2.

In this way, a liquid crystal composition with positive dielectric anisotropy can be obtained, and the resulting liquid crystal composition has a dielectric anisotropy of 2.0 or higher, a clear point of 70 degrees or higher, and 0.09 or higher The refractive index anisotropy. Liquid crystal composites can be used in liquid crystals to do active array AM-LCD or passive array PM-LCD. And the liquid crystal composition can be applied to the liquid crystal display of vertical electric field mode or horizontal electric field mode, and more specifically applied to various LCD modes, such as twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS) , Edge electric field switching (FFS), plane-to-line switching (PLS), advanced high-efficiency IPS (AH-IPS), polymer sustained alignment (PSA), etc.

The liquid crystal display using the liquid crystal composition according to the embodiment may have a vertical electric field mode or a horizontal electric field mode. Liquid crystal display device

FIG. 1 is a schematic diagram of a liquid crystal display device according to an exemplary embodiment.

The liquid crystal display device according to the embodiment may be implemented in various types, such as twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), fringe electric field switching (FFS), and plane-to-line switching (PLS) , Advanced high-performance IPS (AH-IPS), polymer stable alignment (PSA), etc.

In the embodiment, the TN mode is explained as an example, and the shape and layout of each component can be changed according to the individual mode.

According to an embodiment, the liquid crystal display device 100 includes a first substrate 110, a second substrate 120, and a liquid crystal layer 130 interposed between the first substrate 110 and the second substrate 120. A plurality of pixel areas are defined on the second substrate 120, and a plurality of pixels are provided on each pixel area.

The first substrate 110 may include an upper base substrate 111, a photomask layer 112, a filter 113, an upper insulating film 114, a common electrode 115, and an upper alignment film 101. The photomask layer 112 is formed on the upper base substrate 111 and may contain a toner of a light-transmitting material with a low light transmission rate (such as carbon black, etc.).

The filter 113 is formed on the upper base substrate 111 and may be formed to partially overlap the photomask layer 112 or other adjacent filters 113.

The upper insulating film 113 protects the photomask layer 112 and the filter 113, and can fill in the step difference generated by the photomask layer 112 and the filter 113, so that the surface of the first substrate 110 is flat.

The common electrode 115 can be made of, for example, indium tin oxide (ITO) or indium zinc oxide (IZO). A preset common voltage is applied to the common electrode 115.

The upper alignment film 101 contacts the liquid crystal layer 130 so that the liquid crystal molecules 131 in the liquid crystal layer 130 are initially aligned or tilted along the preset direction.

The second substrate 120 includes a plurality of thin film transistors provided for pixels. More specifically, the second substrate 120 may include a lower substrate 121, a gate electrode 122, a gate insulating film 123, a semiconductor layer 124a, an ohmic contact layer 124b, a source electrode 125, a drain electrode 126, a protective layer 127, a pixel electrode 128, and Lower alignment film 102.

The gate electrode 122 is formed on the lower base substrate 121 and receives a gate signal (not shown) from the gate line. The gate insulating film 123 covers the gate electrode 122.

The semiconductor layer 124a is formed on the gate insulating film 123 to overlap the gate electrode 122, and a pair of ohmic contact layers 124b are formed on the semiconductor layer 124a to face each other.

The source electrode 125 and the drain electrode 126 are formed on the ohmic contact layer 124b. The source electrode 125 is provided to be separated from the drain electrode 126 to expose part of the semiconductor layer 124a. Part of the drain electrode 126 is electrically connected to the pixel electrode 128 through the contact hole CH.

The protective layer 127 covers the source electrode 125, the drain electrode 126, and the exposed semiconductor layer 124a.

The contact hole CH is formed in the protective layer 127 so that the drain electrode 126 is electrically connected to the pixel electrode 128 through the contact hole CH.

The pixel electrode 128 is formed on the protective layer 127, and the lower alignment film 102 is formed on the pixel electrode 128. The predetermined data voltage sent from the drain electrode 126 is applied to the pixel electrode 128.

The voltage difference between the data voltage applied to the common electrode 115 and the common voltage generates an electric field, and the electric field can be used to adjust the arrangement of the liquid crystal molecules 131 in the liquid crystal layer 130.

According to an embodiment, although the mask layer and the filter are shown as being formed on the upper base substrate, the present invention is not limited thereto, and the mask layer and/or the filter may be formed on the lower base substrate.

Meanwhile, according to the embodiment, when the electrode portion serves as an electrode to provide an electric field to the liquid crystal layer, that is, the pixel electrode and the common electrode, the electrode portion may be provided in different ways. For example, although in the foregoing embodiments, the common electrode is shown to be formed on the upper base substrate, the present invention is not limited thereto, and in other embodiments, the common electrode may be formed on the lower base substrate. FIG. 2 is a schematic diagram of a liquid crystal display device according to another exemplary embodiment. In the embodiment, the common electrode 115 is provided on the lower substrate 121. In the embodiment, the common electrode 115 and the pixel electrode 128 are located on the same layer, but it is not limited thereto. The common electrode 115 and the pixel electrode 128 may be disposed on different layers, and may overlap the pixel electrode 128 in other embodiments.

The liquid crystal layer 130 includes a liquid crystal composition containing the liquid crystal compound of Formula 1. Since the liquid crystal composition is essentially the same as the liquid crystal composition of the above embodiment, no further explanation will be provided.

In order to increase the viewing angle, pixels can be divided into multiple fields, and the liquid crystal composition can be aligned along two or more different directions within a pixel area. A protrusion or the like may be formed in each pixel to divide the pixel into a plurality of areas, and the pixel electrode and the common electrode may include cutouts.

The liquid crystal composition applied to the liquid crystal display device according to the embodiment may have various modes, such as a vertical electric field mode (eg, TN, STN, VA, etc.), and a horizontal electric field mode (eg, IPS, PLS, FFS, etc.).

Hereinafter, the embodiment will be described in detail. Synthesis of Liquid Crystal Compound of Formula 1

The liquid crystal compound of Formula 1 can be synthesized using the following preparation method, and it is relatively important for the corresponding preparation method to insert a methyl group next to fluorine.

Reaction 1

Reaction 2

Reaction 3

As shown in Equation 1, by gradually dropping lithium diisopropylamide (LDA) and titrating methyl iodide, 1-bromo-2-fluoro-4-iodobenzene (1- bromo-2-fluoro-4-iodobenzene) hydrogen at the third position and connect the methyl group to the third position of the phenylene group. For the reaction, refer to the literature ((a) Schlosser, M. 2001 Eur. J. Org. Chem. , pp 3975; (b) Schlosser, M. (2005) Angew. Chem. Int. Ed. , vol 44, pp 376).

On the other hand, according to Reaction Formula 3, the method of Reaction Formula 1 is applied to 2-substituted-1,3-difluoro-5-iodobenzene to produce a compound having one or two methyl substituents. Since this compound has no polarity, it cannot be divided, and thus the desired compound cannot be obtained.

The most efficient method, as in Equation 2, the alcohol part is protected in the ring structure, and then butyllithium is added so that the methyl group is only inserted in a single position. This alcohol ring structure protection reaction is achieved using a known method, and according to the present invention, 1.5 equivalents of 2,3-dihydropyran (2,3-dihydropyran) and alcoholate are mixed, and then hydrochloric acid is used as a catalyst to obtain alcohol Ring structure protection material.

Therefore, the following liquid crystal composition can be produced by Reaction Formulas 1 and 2, and R ₂ in Reaction Formulas 2 and ₃ can be -F, -Cl, or -Br.

[1]、

[2]、

[3]、

[4]、

[5]、

[6]、

[7]、

[8]、

[9]、

[10]、

[11]、

[12]、

[13]、

[14]、

[15]、

[16]、

[17]、

[18]、

[19]、

[20]、

[21]、

[22]、

[23]、

[24]、

[25]、

[26]、

[27]、

[28]、

[29]、

[30]、

[31]、

[32]、

[33]、

[34]。A detailed example of the liquid crystal composition manufactured using the above reaction formula according to the embodiment is shown below, and R ₁ is the same as Formula 1.

[1],

[2],

[3],

[4],

[5],

[6],

[7],

[8],

[9],

[10],

[11],

[12],

[13],

[14],

[15],

[16],

[17],

[18],

[19],

[20],

[twenty one],

[twenty two],

[twenty three],

[twenty four],

[25],

[26],

[27],

[28],

[29],

[30],

[31],

[32],

[33],

[34].

In the following, the functions and benefits of the present invention will be explained in detail through detailed embodiments. However, these embodiments are only examples and do not limit the scope of the present invention. Synthesis Example 1: Synthesis of Compound A1 of the liquid crystal

Reaction 4

Under a nitrogen atmosphere, alcoholate (A1-2) (2.3g, 14.2 mmol), tetrabutylammonium bromide (0.42g, 1.29 mmol), and potassium carbonate (3.6g, 25.9 mmol) was dissolved in dimethylformamide (50 ml), and the product was stirred at 40°C for 1 hour. The bromide (A1-1) (5.4 g, 15 mmol) was dissolved in dimethylformamide (50 ml), the solution was added dropwise and then the product was refluxed at 90° C. for 2 hours. After the reaction, the reaction solution was diluted with water and toluene to separate the phases. The organic layer was extracted, washed with sodium bicarbonate solution and distilled water, and then dried over magnesium sulfate. The product was washed on a silica gel column, and then recrystallized (solvent n-hexane: ethyl acetate) until the product (A1) (4.5 g, 10.3 mmol) was formed. (Yield 73%) Mass spectrum: 252, 281, 442 [M ⁺ ], phase transition temperature (T _Cr-l ): 67.3°C. Synthesis Example 2: Synthesis of liquid crystal compound A2

Reaction 5

Under a nitrogen atmosphere, the boric acid compound (A2-1) (4.9 g, 20 mmol), bromide (A2-2) (7.8 g, 20 mmol), and (PPh ₃ ) ₄ Pd (0.1 g) were dissolved in dimethoxy Ethane (100ml), and then added 2M potassium carbonate solution (30ml). Warm to 60°C and reflux the product for 6 hours. After cooling, the reaction solution was diluted with water and dichloromethane to separate phases. Next, the organic layer was extracted, washed with distilled water, and dried over magnesium sulfate. The product was washed on a silica gel column, and then recrystallized (n-hexane: ethyl acetate) until the product (A2) (4.8 g, 8.9 mmol) was formed. (Yield 45%) Mass spectrum: 360, 389, 536 [M ⁺ ], phase transition temperature (T _Cr-l ): 53.1°C. Synthesis Example 3: Synthesis of liquid crystal compound A3

Reaction 6

Under a nitrogen atmosphere, alcoholate (A3-2) (4.1g, 25.6mmol), tetrabutylammonium bromide (0.75g, 2.3mmol), and potassium carbonate (6.4g, 46.6mmol) were dissolved in dimethyl formaldehyde In acetamide (70 ml), the product was stirred at 40°C for 1 hour. The bromide (A3-1) (12.2 g, 27 mmol) was dissolved in dimethylformamide (70 ml), the solution was dropped and then the product was refluxed at 90° C. for 2 hours. After the reaction, the reaction solution was diluted with water and toluene to separate the phases. The organic layer was extracted, washed with sodium bicarbonate solution and distilled water, and then dried over magnesium sulfate. The product was washed on a silica gel column, and then recrystallized (solvent n-hexane: ethyl acetate) until the product (A3) (9.7 g, 18.1 mmol) was formed. (Yield 71%) Mass spectrum: 346, 375, 536 [M ⁺ ], phase transition temperature (T _Cr-N ): 70.2°C, phase transition temperature (T _Nl ): 126.3°C. Synthesis Example 4: Synthesis of Compound A4 of the liquid crystal

Reaction 7

Under a nitrogen atmosphere, alcoholate (A4-2) (3.20g, 19.7mmol), tetrabutylammonium bromide (0.64g, 2.0mmol), and potassium carbonate (5.46g, 39.5mmol) were dissolved in dimethyl formaldehyde In acetamide (50 ml), the product was stirred at 40°C for 1 hour. The bromide (A4-1) (8.23 g, 21.7 mmol) was dissolved in dimethylformamide (50 ml), the solution was added dropwise and the product was then refluxed at 90° C. for 2 hours. After the reaction, the reaction solution was diluted with water and toluene to separate the phases. The organic layer was extracted, washed with sodium bicarbonate solution and distilled water, and then dried over magnesium sulfate. The product was washed on a silica gel column, and then recrystallized (solvent n-hexane: ethyl acetate) until the product (A4) (5.91 g, 12.8 mmol) was formed. (65% yield) Mass spectrum: 271, 299, 460 [M ⁺ ], phase transition temperature (T _Cr-l ): 72.2°C. Synthesis Example 5: Synthesis of liquid crystal compound A5

Reaction 8

Under a nitrogen atmosphere, alcoholate (A5-2) (3.70 g, 22.8 mmol), tetrabutylammonium bromide (0.74 g, 2.3 mmol), and potassium carbonate (6.31 g, 45.6 mmol) were dissolved in dimethyl formaldehyde In acetamide (50 ml), the product was stirred at 40°C for 1 hour. The bromide (A5-1) (11.08 g, 25.1 mmol) was dissolved in dimethylformamide (50 ml), the solution was dropped and then the product was refluxed at 90°C for 2 hours. After the reaction, the reaction solution was diluted with water and toluene to separate the phases. The organic layer was extracted, washed with sodium bicarbonate solution and distilled water, and then dried over magnesium sulfate. The product was washed on a silica gel column, and then recrystallized (solvent n-hexane: ethyl acetate) until the product (A5) (8.59 g, 16.4 mmol) was formed. (Yield 72%) Mass spectrum: 347, 361, 522 [M ⁺ ], phase transition temperature (T _Cr-N ): 89°C, phase transition temperature (T _Nl ): 123.0°C. Synthesis Example 6: Synthesis of Compound A6 of the liquid crystal

Reaction 9

Under a nitrogen atmosphere, alcoholate (A6-2) (2.27 g, 14.0 mmol), tetrabutylammonium bromide (0.46 g, 1.4 mmol), and potassium carbonate (3.87 g, 28.0 mmol) were dissolved in dimethyl methyl In acetamide (50 ml), the product was stirred at 40°C for 1 hour. Bromide (A6-1) (6.64 g, 15.4 mmol) was dissolved in dimethylformamide (50 ml), the solution was added dropwise and the product was then refluxed at 90°C for 2 hours. After the reaction, the reaction solution was diluted with water and toluene to separate the phases. The organic layer was extracted, washed with sodium bicarbonate solution and distilled water, and then dried over magnesium sulfate. The product was washed on a silica gel column, and then recrystallized (solvent n-hexane: ethyl acetate) until the product (A6) (4.23 g, 8.3 mmol) was formed. (Yield 59%) Mass spectrum: 351, 512 [M ⁺ ], phase transition temperature (T _Cr-N ): 82.4°C, phase transition temperature (T _Nl ): 94.5°C. Synthesis Example 7: Synthesis of liquid crystal compound of A7

Reactive 10

Under a nitrogen atmosphere, alcoholate (A7-2) (3.25 g, 20.0 mmol), tetrabutylammonium bromide (0.65 g, 2.0 mmol), and potassium carbonate (5.54 g, 40.1 mmol) were dissolved in dimethyl formaldehyde In acetamide (50 ml), the product was stirred at 40°C for 1 hour. The bromide (A7-1) (9.82 g, 22.1 mmol) was dissolved in dimethylformamide (50 ml), the solution was added dropwise and then the product was refluxed at 90°C for 2 hours. After the reaction, the reaction solution was diluted with water and toluene to separate the phases. The organic layer was extracted, washed with sodium bicarbonate solution and distilled water, and then dried over magnesium sulfate. The product was washed on a silica gel column, and then recrystallized (solvent n-hexane: ethyl acetate) until the product (A7) (6.44 g, 12.2 mmol) was formed. (Yield 61%) Mass spectrum: 365, 526 [M ⁺ ], phase transition temperature (T _Cr-N ): 65.7°C, phase transition temperature (T _Nl ): 121.8°C. Synthesis Example 8: Synthesis of liquid crystal compound A8

Reaction 11

Under a nitrogen atmosphere, alcoholate (A8-2) (2.74 g, 16.9 mmol), tetrabutylammonium bromide (0.55 g, 1.7 mmol), and potassium carbonate (4.67 g, 33.8 mmol) were dissolved in dimethyl formaldehyde In amide (50 ml), the product was stirred at 40°C for 1 hour. The bromide (A8-1) (8.32 g, 18.6 mmol) was dissolved in dimethylformamide (50 ml), the solution was added dropwise and the product was then refluxed at 90°C for 2 hours. After the reaction, the reaction solution was diluted with water and toluene to separate the phases. The organic layer was extracted, washed with sodium bicarbonate solution and distilled water, and then dried over magnesium sulfate. The product was washed on a silica gel column, and then recrystallized (solvent n-hexane: ethyl acetate) until the product (A8) (6.07 g, 11.5 mmol) was formed. (Yield 68%) Mass spectrum: 367, 528 [M ⁺ ], phase transition temperature (T _Cr-N ): 67.3°C. Evaluation method of liquid crystal compound and liquid crystal compound

Evaluate the physical properties of LTS, liquid crystal compounds and liquid crystal compounds according to the following methods: (1) LTS

First, place 2g of liquid crystal compound in a 10 ml bottle, place it in a freezer at -25°C, and check for recrystallization every other day. If recrystallization occurs from the OOth day after storage in the freezer, it is marked as "OO day, failure", and if the liquid crystal phase is maintained for 20 days or more, it is marked as "20 day, success". (2) Clarification point (Tc)

The liquid crystal composition to be clarified is dropped on a glass slide and covered with a cover glass to obtain a sample for measuring the clarification point.

The sample was placed in a METTLER TOLEDO FP90 (METTLER TOLEDO FP90) temperature regulator device, and the change of the sample was observed while increasing the temperature at a rate of 3°C per minute during the FP82 heating stage (FP82 HT Hot Stage). Record the temperature of the hole formed in the sample and repeat this process 3 times to obtain the average value. Next, this temperature value is defined as the clear point of the liquid crystal composition. (3) Refractive index anisotropy (n)

Using an Abbe refractometer equipped with a polarizing plate in the eyepiece, the refractive index (n) of the liquid crystal composition was measured at 20°C with light having a wavelength of 589 nm. Rub the surface of the main prism in one direction, and drop the liquid crystal composition to be measured on the main prism. Next, the refractive index (n∥) whose polarization direction is parallel to the rubbing direction and the refractive index (n⊥) whose polarizing direction is perpendicular to the rubbing direction are measured. In addition, this refractive index value is substituted into Equation 1 to calculate the refractive index anisotropy (n).

Equation 1 n = n∥-n⊥ (4) Dielectric anisotropy (Δε)

Substitute the measured ε∥ and ε⊥ in Equation 2 to calculate the dielectric anisotropy (ε) of the liquid crystal composition.

Equation 2 Δε = ε∥-ε⊥

1. Measurement of the dielectric constant ε∥: apply a vertical alignment agent on the surface of the two slides formed by the ITO pattern to form a vertical alignment film. The spacer was stuck to one of the two slides so that the vertical alignment films were opposed to each other, and the interval (crystal gap) between the two slides was 4 μm. And then mount the two slides on a component. The liquid crystal composition to be measured is injected into this device, sealed with an adhesive, and then hardened with UV. Next, the dielectric constant (ε∥) of the device was measured using an instrument manufactured by Agilent 4294A at 1 kHz, 0.3 V, and 20°C.

2. Measurement of the dielectric constant ε⊥: apply a horizontal alignment agent to the surface of the two slides formed by the ITO pattern to form a horizontal alignment film. Stick the spacer to one of the two slides so that the horizontal alignment films are opposed to each other, and the interval (crystal gap) between the two slides is 4 μm. And then mount the two slides on a component. The liquid crystal composition to be measured is injected into this device, sealed with an adhesive, and then hardened with UV. Next, the dielectric constant (ε∥) of the device was measured using an instrument manufactured by Agilent 4294A at 1 kHz, 0.3 V, and 20°C. (5) Rotating viscosity (γ1)

The horizontal alignment agent is coated on the surface of the two slides formed by the ITO pattern to form a horizontal alignment film. Stick the spacer to one of the two slides so that the horizontal alignment films are opposed to each other, and the interval (crystal gap) between the two slides is 20 μm. And then mount the two slides on a component. The liquid crystal composition to be measured is injected into this device and sealed with an adhesive. Next, the rotational viscosity of the element was measured at 20°C using an instrument model 6254 manufactured by Toyo Corp., which was equipped with a temperature controller (model SU-241) manufactured by ESPEC Corp. ). (6) Voltage retention rate (VHR)

The horizontal alignment agent is coated on the surface of the two slides formed by the ITO pattern to form a horizontal alignment film. Stick the spacer to one of the two slides so that the horizontal alignment films are opposed to each other, and the interval (crystal gap) between the two slides is 4 μm. And then mount the two slides on a component. The liquid crystal composition is injected and closed. The device injected with liquid crystal was heated at 100° C. for 24 hours, and irradiated with UV with a wavelength of 365 nm at an energy of 20 Joules (J). Next, the voltage retention rate of the device was measured at 100°C using an instrument model 6254 manufactured by Toyo Corp. The instrument was equipped with a temperature controller (model SU) manufactured by ESPEC Corp. -241). Examples of evaluation of physical properties of liquid crystal compounds

The physical properties of the liquid crystal compounds according to the aforementioned synthesis examples were compared with known materials (contained in WO1996-011897 and JP1997-176645, M3) and the results are shown in Table 3. table 3

It can be seen from Table 3 that the melting point when the temperature drops affects LTS, and it can be seen that the melting points of A2 and A3 are lower than the known material M3 having the same molecular length according to the present invention by about 20°C or more. It can be seen that the A2 and A3 liquid crystals have greatly improved LTS compared to the conventional liquid crystal M3 of the same molecular length.

At the same time, when the methyl group is present at a specific position as shown in A3, the dielectric anisotropy can be increased by about 15% compared with the liquid crystal M3. Although A5 has lower LTS than A1, A2, and A3 in all materials, it still has better rotational viscosity compared to the dielectric anisotropy of traditional material M3. As shown above, liquid crystal compounds have better LTS and better dielectric anisotropy than traditional liquid crystals, and can be used as liquid crystal compounds for various devices that use liquid crystal media. Comparative Examples and Examples Evaluation of physical properties of liquid crystal

The conventional material M3 compound and the compounds of formulas 2 to 4 were mixed into a composite as shown in Tables 5 to 9 to evaluate the physical properties and LTS of the liquid crystal composite according to the comparative example.

The compound of Formula 1 and the compounds of Formula 2 to 4 were mixed into a composition as shown in Tables 10 to 39 to evaluate the physical properties and LTS of the liquid crystal composition according to the examples.

The structures of the core groups, chain groups, and terminal groups of the compounds composed of Comparative Examples 1 to 5 and Examples 1 to 30, and the compounds composed of Comparative Examples 1 to 2 and their symbols are shown in Table 4. In the following embodiments, A1 to A7 represent material symbols in the aforementioned synthesis examples. Table 4

＊There is no separating symbol between core group and chain group.

＊The core/chain group and terminal group are distinguished by "-".

＊The terminal and terminal are distinguished by ".", the number indicates the number of carbon atoms in the alkyl group (in this case, the terminal is an alkyl group), and the terminal is written at the end.

A. ACE-3.F

ACEXE-3.F

B. BB-3.V

BB-3.U1For example, the symbol will look like this:

A. ACE-3.F

ACEXE-3.F

B. BB-3.V

BB-3.U1

In the following examples, the comparative examples 1 to 2 using the conventional material M3 are compared with the examples 1 to 2 using A2 and A3 derived from formula 1, the LTS of the liquid crystal composition of examples 1 to 2 is higher than Comparative Examples 1-2. At the same time, it can be seen that the dielectric anisotropy and rotational viscosity of the liquid crystal compositions of Examples 1 to 2 can be easily adjusted.

In addition, for Examples 3 to 30, it can be seen that the liquid crystal composition in the example using the liquid crystal compound derived from Formula 1 has high dielectric anisotropy and different refractive index anisotropy. Specifically, Examples 10 to 15 are liquid crystal compositions including a liquid crystal compound of Formula 1 and a liquid crystal compound of Formula 2, Examples 16 to 21 are liquid crystal compounds including a liquid crystal compound of Formula 1, a liquid crystal compound of Formula 2, and a liquid crystal of Formula 3 The liquid crystal composition of the compound, and Examples 22 to 27 are the liquid crystal compound of Formula 1 and the liquid crystal compound of Formula 4, it can be seen that the liquid crystal compositions of various compositions including the liquid crystal compound of Formula 1 show superior performance under low temperature environment Characteristics, and can form liquid crystal composites to meet various standards of liquid crystal display devices.

In addition, the compositions of Examples 28 to 30 are formed by additionally mixing the heat/UV stabilizers of Formulae 5 to 7 to the liquid crystal composition containing the liquid crystal compound of Formula 1. In the table, "additive of formula 5" means that R _{1 in} the compound of formula 5 is C ₇ H ₁₅ and p is 0; and "additive of formula 6" means a compound where R ₃ is hydrogen and n is 8. When the liquid crystal compositions of Comparative Examples 3 to 5 are compared with the liquid crystal compositions of Examples 28 to 30, it can be seen that the voltage retention rate of the mixture added with the heat/UV stabilizer is more than 10% higher. Comparative example 1

比較例 2 table 5

Comparative example 2

比較例 3 Table 6

Comparative Example 3

比較例 4 Table 7

Comparative Example 4

比較例 5 Table 8

Comparative example 5

實施例 1 Table 9

Example 1

實施例 2 Table 10

Example 2

實施例 3 Table 11

Example 3

實施例 4 Table 12

Example 4

實施例 5 Table 13

Example 5

實施例 6 Table 14

Example 6

實施例 7 Table 15

Example 7

實施例 8 Table 16

Example 8

實施例 9 Table 17

Example 9

實施例 10 Table 18

Example 10

實施例 11 Table 19

Example 11

實施例 12 Table 20

Example 12

實施例 13 Table 21

Example 13

實施例 14 Table 22

Example 14

實施例 15 Table 23

Example 15

實施例 16 Table 24

Example 16

實施例 17 Table 25

Example 17

實施例 18 Table 26

Example 18

實施例 19 Table 27

Example 19

實施例 20 Table 28

Example 20

實施例 21 Table 29

Example 21

實施例 22 Table 30

Example 22

實施例 23 Table 31

Example 23

實施例 24 Table 32

Example 24

實施例 25 Table 33

Example 25

實施例 26 Table 34

Example 26

實施例 27 Table 35

Example 27

實施例 28 Table 36

Example 28

實施例 29 Table 37

Example 29

實施例 30 Table 38

Example 30

Table 39

Although the present invention has been specifically shown and described with reference to its embodiments, those of ordinary skill in the art will understand that various modifications in form and details can be made to the present invention without departing from the spirit and scope of the invention as defined in the following patent applications category.

100‧‧‧Liquid crystal display device 101‧‧‧Upper alignment film 102‧‧‧Lower alignment film 110‧‧‧First substrate 111‧‧‧Upper substrate 112‧‧‧Photomask layer 113‧‧‧ Filter 114‧‧‧ Upper insulating film 115‧‧‧ Common electrode 120‧‧‧Second substrate 121‧‧‧Lower substrate 122‧‧‧ Gate electrode 123‧‧‧ Gate insulating film 124a‧‧‧Semiconductor layer 124b‧‧‧ Ohmic contact layer 125‧‧‧ source electrode 126‧‧‧ drain electrode 127‧‧‧ protective layer 128‧‧‧ pixel electrode 130‧‧‧ liquid crystal layer 131‧‧‧ liquid crystal molecules CH‧‧‧ contact hole

The above and other advantages and features of the present invention will be more apparent through the exemplary embodiments described in further detail and the drawings referred to therein, in which:

FIG. 1 is a schematic diagram of a liquid crystal display device according to an exemplary embodiment.

FIG. 2 is a schematic diagram of a liquid crystal display device according to another exemplary embodiment.

100‧‧‧LCD display device

101‧‧‧Upper alignment film

102‧‧‧Lower alignment film

110‧‧‧The first substrate

111‧‧‧Top board

112‧‧‧ Mask layer

113‧‧‧ filter

114‧‧‧Upper insulating film

115‧‧‧Common electrode

120‧‧‧Second substrate

121‧‧‧Lower base board

122‧‧‧Gate electrode

123‧‧‧Gate insulating film

124a‧‧‧Semiconductor layer

124b‧‧‧ohm contact layer

125‧‧‧Source electrode

126‧‧‧Drain electrode

127‧‧‧Protective layer

128‧‧‧Pixel electrode

130‧‧‧Liquid crystal layer

131‧‧‧ liquid crystal molecules

CH‧‧‧Contact hole

Claims (24)

A liquid crystal display device includes: a first substrate; a second substrate facing the first substrate; an electrode portion disposed on at least one of the first substrate and the second substrate; and a liquid crystal layer , Disposed between the first substrate and the second substrate, the liquid crystal layer includes a liquid crystal composition (Liquid Crystal Composition), wherein the liquid crystal composition includes at least one liquid crystal compound as shown in Formula 1 and as shown in Formula 2 At least one liquid crystal compound shown:

Where R ₁ represents hydrogen or an alkyl group having 1 to 15 carbon atoms, in which at least one -CH ₂ -group is selectively independently -C≡C-, -CF without two oxygen atoms connected to each other ₂ O-, -CH=CH-, -O-, -CO-O-, -O-CO-, or -O-CO-O-, and 1 to 3 hydrogen atoms are selectively substituted by halogen atoms , Where R ₂ represents -F, -Cl, -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₃ , or an alkyl group having 1 to 5 carbon atoms substituted with one to three -F, Where -CH ₂ -groups are selectively substituted independently by oxygen atoms without two oxygen atoms being connected to each other, wherein (F) represents that a hydrogen atom is selectively substituted by -F, where A ₁₁ and A ₁₂ , A ₁₃ , A ₂₁ , and A ₂₂ each independently represent one of the following structures:

,

,or

; And wherein Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₂₁ , and Z ₂₂ are each independently a single bond, -CH ₂ CH ₂ -, -CH=CH-, -CH ₂ O-, -OCH ₂ -, -C≡C-, -CH ₂ CF ₂ -, -CHFCHF-, -CF ₂ CH ₂ -, -CH ₂ CHF-, -CHFCH ₂ -, -C ₂ F ₄ -, -COO-, -OCO-, -CF ₂ O-, or -OCF ₂ -; a, b, c, d, and e are each independently an integer of 0 to 3, and a+b+c+d+e is less than or equal to 5,

Wherein, R ₁₁ the same lines as defined in formula R _1, in addition to the definition of R ₁₁ in the formula, R ₂₁ represents -F, -Cl, -CF _3, or -OCF _3, A ₃ and A ₄ independently from each other The ground is 1,4-cyclohexylene or 1,4-phenylene, and A ₅ represents one of the following structures:

A liquid crystal composition (Liquid Crystal Composition) comprising at least one liquid crystal compound as shown in Formula 1 and at least one liquid crystal compound as shown in Formula 2:

Where R ₁ represents hydrogen or an alkyl group having 1 to 15 carbon atoms, in which at least one -CH ₂ -group is selectively independently -C≡C-, -CF without two oxygen atoms connected to each other ₂ O-, -CH=CH-, -O-, -CO-O-, -O-CO-, or -O-CO-O-, and 1 to 3 hydrogen atoms are selectively substituted by halogen atoms , Where R ₂ represents -F, -Cl, -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₃ , or an alkyl group having 1 to 5 carbon atoms substituted with one to three -F , Wherein -CH ₂ -groups are selectively substituted by oxygen atoms independently without two oxygen atoms being connected to each other, wherein (F) represents that a hydrogen atom is selectively substituted by -F, wherein, A ₁₁ , A ₁₂ , A ₁₃ , A ₂₁ , and A ₂₂ each independently represent one of the following structures:

,

,or

; And wherein Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₂₁ , and Z ₂₂ are each independently a single bond, -CH ₂ CH ₂ -, -CH=CH-, -CH ₂ O-, -OCH ₂ -, -C≡C-, -CH ₂ CF ₂ -, -CHFCHF-, -CF ₂ CH ₂ -, -CH ₂ CHF-, -CHFCH ₂ -, -C ₂ F ₄ -, -COO-, -OCO-, -CF ₂ O-, or -OCF ₂ -; a, b, c, d, and e are each independently an integer of 0 to 3, and a+b+c+d+e is less than or equal to 5,

Wherein, R ₁₁ the same lines as defined in formula R _1, in addition to the definition of R ₁₁ in the formula, R ₂₁ represents -F, -Cl, -CF _3, or -OCF _3, A ₃ and A ₄ independently from each other The ground is 1,4-cyclohexylene or 1,4-phenylene, and A ₅ represents one of the following structures:

The liquid crystal composition as described in item 2 of the patent application scope, wherein at least one of Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₂₁ , and Z ₂₂ is -CF ₂ O-. The liquid crystal composition as described in item 2 of the patent application, wherein d and e are 0, and R ₂ is -F, -OCF ₃ , or -CF ₃ . The liquid crystal composition according to item 2 of the patent application scope, wherein Z ₁₃ is -CF ₂ O-, d and e are 0, and R ₂ is -F, -OCF ₃ , or -CF ₃ . The liquid crystal composition as described in item 2 of the patent application scope, wherein the liquid crystal compound of formula 1 is represented by formula 1-1:

Among them, R ₁ , R ₂ , A ₁₁ , A ₁₂ , Z ₁₁ , Z ₁₂ , (F), a and b are the same as defined in Formula 1. The liquid crystal composition as described in item 6 of the patent application scope, wherein the liquid crystal compound of formula 1-1 is represented by formula 1-2:

Wherein, o is 0 or 1 and R ₁ system and the same as defined in Formula 1. The liquid crystal composition as described in item 2 of the patent application scope further includes a liquid crystal compound represented by Formula 2-1 or Formula 2-2:

Among them, R ₁₁ , R ₂₁ , and A ₅ are independently the same as defined in Formula 2, X ₁ to X _{5 are} independently -H or -F, and at least one of X ₃ and X ₄ is -F. The liquid crystal composition as described in item 2 of the scope of the patent application further includes a liquid crystal compound as shown in Formula 3:

Wherein R ₁₁ and R ₂₁ are independently the same as R ₁ defined in Formula 1, and A ₃ and A ₄ are independently F-substituted or unsubstituted 1,4-cyclohexyl or substituted by F or Unsubstituted 1,4-phenylene. The liquid crystal composition as described in item 9 of the patent application scope, wherein the liquid crystal compound represented by Formula 3 is represented by Formula 3-1 or Formula 3-2:

However, R ₁₁ and R ₂₁ are independently the same as R ₁ defined in Formula 1. The liquid crystal composition as described in item 9 of the patent application scope, wherein the liquid crystal compound represented by Formula 2 is represented by Formula 2-1:

However, R ₁₁ , R ₂₁ , and A ₅ are the same as defined in Formula 2. The liquid crystal composition as described in item 9 of the patent application scope, wherein the liquid crystal compound represented by Formula 2 is represented by Formula 2-2: Formula 2-2

Wherein R ₁₁ and R ₂₁ are the same as defined in Formula 2, X ₁ to X ₅ are independently -H or -F, and at least one of X ₃ and X ₄ is -F. The liquid crystal composition as described in item 2 of the patent application scope further includes a liquid crystal compound as shown in Formula 4:

Among them, R ₁ and R ₂ are the same as R ₁ and R ₂ defined in Formula 1, and A ₁₁ , A ₁₂ , A ₁₃ , Z ₁₁ , Z ₁₂ , Z ₁₃ and (F) are also defined as in Formula 1. A ₁₁ , A ₁₂ , A ₁₃ , Z ₁₁ , Z ₁₂ , Z ₁₃ and (F) are the same, f, g and h are each independently 0 or 1, and f+g+h is 2 or 3. The liquid crystal composition as described in item 2 of the patent application scope further comprises at least one compound represented by formulae 5 to 7:

Formula 7

Wherein, R ₁ and A ₁₁ are the same as defined in Formula 1, p is 0 or 1, R ₃ represents hydrogen, oxygen radical, or an alkyl group having 1 to 15 carbon atoms, of which at least one is -CH ₂ -The group is independently selected by -C≡C-, -CF ₂ O-, -CH=CH-, -O-, -CO-O-, -O-CO- without two oxygen atoms being connected to each other , Or -O-CO-O-, and 1 to 3 hydrogen atoms are selectively substituted by halogen atoms, n is an integer of 1 to 12, and m is an integer of 0 to 12. The liquid crystal composition as described in item 2 of the patent application scope further includes a pitch modifier as shown in Formula 8:

Here, R ₁ is the same as defined in Formula 1. The liquid crystal composition as described in item 2 of the patent application scope, wherein the liquid crystal compound of formula 1 is represented by formula 1-2:

Wherein, R ₁ is the same as defined in Formula 1, o is 0 or 1, and wherein the liquid crystal composition further includes at least one liquid crystal compound as shown in Formula 2-1-1- One liquid crystal compound shown in 1-2, and one liquid crystal compound shown in Formula 4-1-1:

The liquid crystal composition as described in Item 16 of the patent application range, wherein the liquid crystal composition includes at least one of the liquid crystal compounds 5 to 20 as shown in Formula 1-2 and as shown in Formula 2-1-1-1 The parts by weight, 5 to 20 parts by weight of the liquid crystal compound shown by Formula 2-1-1-2, and 2 to 10 parts by weight of the liquid crystal compound shown by Formula 4-1-1. The liquid crystal composition as described in item 2 of the patent application scope, wherein the liquid crystal compound of formula 1 is represented by formula 1-2:

The liquid crystal composition further includes a liquid crystal compound as shown in Formula 3-1-1, a liquid crystal compound as shown in Formula 2-2-1-1, and a liquid crystal as shown in Formula 4-1-2 Compound: Formula 3-1-1

Among them, A represents one of the following structures:

or

, And wherein R ₁ is the same as defined in Formula 1, and o is 0 or 1. The liquid crystal composition as described in item 18 of the patent application range, wherein the liquid crystal compound contains 15 to 45 parts by weight of the liquid crystal compound as shown in Formula 3-1-1, as shown in Formula 2-2-1-1 2 to 15 parts by weight of the liquid crystal compound, and 3 to 35 parts by weight of the liquid crystal compound as shown in Formula 4-1-2. The liquid crystal composition as described in item 2 of the patent application scope, wherein the liquid crystal compound of Formula 1 is one of the compounds of the following structures:

A liquid crystal composition comprising at least one liquid crystal compound as shown in Formula 1:

Where R ₁ represents hydrogen or an alkyl group having 1 to 15 carbon atoms, in which at least one -CH ₂ -group is selectively independently -C≡C-, -CF without two oxygen atoms connected to each other ₂ O-, -CH=CH-, -O-, -CO-O-, -O-CO-, or -O-CO-O-, and 1 to 3 hydrogen atoms are selectively substituted by halogen atoms , Where R ₂ represents -F, -Cl, -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₃ , or an alkyl group having 1 to 5 carbon atoms substituted with one to three -F , Wherein -CH ₂ -groups are selectively substituted by oxygen atoms independently without two oxygen atoms being connected to each other, wherein (F) represents that a hydrogen atom is selectively substituted by -F, wherein, A ₁₁ , A ₁₂ , A ₁₃ , A ₂₁ , and A ₂₂ each independently represent one of the following structures:

,

,or

; And wherein Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₂₁ , and Z ₂₂ are each independently a single bond, -CH ₂ CH ₂ -, -CH=CH-, -CH ₂ O-, -OCH ₂ -, -C≡C-, -CH ₂ CF ₂ -, -CHFCHF-, -CF ₂ CH ₂ -, -CH ₂ CHF-, -CHFCH ₂ -, -C ₂ F ₄ -, -COO-, -OCO-, -CF ₂ O-, or -OCF ₂ -; a, b, c, d, and e are each independently an integer of 0 to 3, and a+b+c+d+e is less than or equal to 5, where the formula The liquid crystal compound of 1 is shown in Formula 1-2:

And the liquid crystal composition further includes a liquid crystal compound shown in Formula 3-1-1 and a liquid crystal compound shown in Formula 5:

Formula 5

Wherein, o is 0 or 1, R ₁ and A ₁₁ have the same definitions as in Formula 1, and p is 0 or 1. The liquid crystal composition as described in item 21 of the patent application range, wherein the liquid crystal composition contains 3 to 35 parts by weight of the liquid crystal compound as shown in Formula 1-2, and 15 to 15 as shown in Formula 3-1-1 45 parts by weight of the liquid crystal compound, and 0.01 to 0.05 parts by weight of the liquid crystal compound as shown in Formula 5. A liquid crystal composition comprising at least one liquid crystal compound as shown in Formula 1:

Where R ₁ represents hydrogen or an alkyl group having 1 to 15 carbon atoms, in which at least one -CH ₂ -group is selectively independently -C≡C-, -CF without two oxygen atoms connected to each other ₂ O-, -CH=CH-, -O-, -CO-O-, -O-CO-, or -O-CO-O-, and 1 to 3 hydrogen atoms are selectively substituted by halogen atoms , Where R ₂ represents -F, -Cl, -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₃ , or an alkyl group having 1 to 5 carbon atoms substituted with one to three -F , Wherein -CH ₂ -groups are selectively substituted by oxygen atoms independently without two oxygen atoms being connected to each other, wherein (F) represents that a hydrogen atom is selectively substituted by -F, wherein, A ₁₁ , A ₁₂ , A ₁₃ , A ₂₁ , and A ₂₂ each independently represent one of the following structures:

,

,or

; And wherein Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₂₁ , and Z ₂₂ are each independently a single bond, -CH ₂ CH ₂ -, -CH=CH-, -CH ₂ O-, -OCH ₂ -, -C≡C-, -CH ₂ CF ₂ -, -CHFCHF-, -CF ₂ CH ₂ -, -CH ₂ CHF-, -CHFCH ₂ -, -C ₂ F ₄ -, -COO-, -OCO-, -CF ₂ O-, or -OCF ₂ -; a, b, c, d, and e are each independently an integer of 0 to 3, and a+b+c+d+e is less than or equal to 5, where the formula The liquid crystal compound of 1 includes a liquid crystal compound shown in Formula 1-2-1 and a liquid crystal compound shown in Formula 1-2-3:

The liquid crystal composition as described in item 23 of the patent application range, wherein the weight ratio between the liquid crystal compound of Formula 1-2-2 and the liquid crystal compound of Formula 1-2-3 is 1:0.5 to 1:2.0.

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