TW202134412A - Polymerizable compound, liquid crystal composition, and liquid crystal display device - Google Patents

Abstract

A polymerizable compound has a chemical formula as formula (I):

, wherein ring A, ring B, Z₁ , Z₂ , R, P, n, and m are described in the specification and the claims. A liquid crystal composition and a liquid crystal display device containing thereof have a good pretilt angle stability and a good low temperature storage property.

Description

Polymerizable compound, liquid crystal composition and liquid crystal display device

The present invention relates to the field of display technology, in particular to a polymerizable compound, a liquid crystal composition and a liquid crystal display device.

With the widespread use of liquid crystal display devices, compounds used in liquid crystal display devices are also required to have various properties (such as low voltage drive, high-speed response time, high voltage retention, low rotational viscosity, wide operating temperature range, etc.). Therefore, At present, the industry continues to search for novel compounds and mixtures suitable for various applications.

In recent years, Polymer Sustained Alignment (PSA) technology has been widely used for mass production of liquid crystal display devices. The principle of this technology is to add one or more polymerizable compounds to the liquid crystal medium, mix them evenly and inject them into the conductive substrate of the display element, and irradiate the polymerizable compound monomers with the appropriate wavelength of ultraviolet light. The substrate is polymerized into a polymer structure, allowing the liquid crystal to form a stable pre-tilt arrangement along the polymer structure to achieve the alignment of the liquid crystal. Through the above-mentioned technology, PSA-VA, PSA-TN, PSA-IPS, PSA-FFS and PSA-OCB display devices have been extensively studied. In addition, Polymer-Dispersed Liquid Crystal (PDLC) is a composite film in which anisotropic liquid crystal droplets are uniformly dispersed in a polymer. It adjusts the arrangement of the liquid crystal by changing the electric field between the upper and lower substrates to control the relationship between the refractive index between the liquid crystal and the polymer to achieve an optical display effect between the fog state and the transparent state. PDLC can be applied not only to liquid crystal display devices, but also to smart glass. Therefore, the industry is also actively developing novel compounds with better characteristics.

Therefore, the object of the present invention is to provide a novel polymerizable compound.

(I) 其中 環A和環B各自獨立地為未經取代或至少一個碳上的氫被氟、C₁ ~C₅ 直鏈伸烷基或C₃ ~C₅ 支鏈伸烷基所取代的1,4-伸環己基、1,4-伸苯基、萘-2,6-二基、茚滿-1,5-二基、茚滿-2,5-二基或1,2,3,4-四氫萘-2,6-二基，其中該伸烷基為未經取代或至少一個−CH₂ −被−O−或−C=C−所取代； Z₁ 和Z₂ 各自獨立為C₁ ~C₄ 直鏈伸烷基、−CF₂ O−、−OCF₂ −或單鍵，其中該伸烷基為未經取代或至少一個−CH₂ −被−O−、−C=C−或−C≡C−所取代； n和m各自為0、1、2、3或4，且n+m=1~4；當n+m≥2時，該複數個環A和環B為彼此相同或彼此不同， Z₁ 和Z₂ 為彼此相同或彼此不同； R為C₁ ~C₁₂ 烷基、C₁ ~C₁₂ 烷氧基、C₂ ~C₁₂ 烯基或P，其中，該烯基為未經取代或是至少一個碳上的氫被氟取代；且 P為

、

、

、

、

、

、

、

或

。In one embodiment of the present invention, the above-mentioned polymerizable compound has a chemical formula as shown in formula (I):

(I) where ring A and ring B are each independently unsubstituted or at least one hydrogen on carbon is substituted by fluorine, C ₁ ~C ₅ linear alkylene or C ₃ ~C ₅ branched alkylene 1,4-cyclohexyl, 1,4-phenylene, naphthalene-2,6-diyl, indane-1,5-diyl, indane-2,5-diyl or 1,2,3 ,4-Tetrahydronaphthalene-2,6-diyl, where the alkylene is unsubstituted or at least one −CH ₂ − is substituted by −O− or −C=C−; Z ₁ and Z ₂ are each independent C ₁ ~C ₄ straight chain alkylene, −CF ₂ O−, −OCF ₂ − or single bond, where the alkylene is unsubstituted or at least one −CH ₂ −by −O−, −C= C− or −C≡C−; n and m are 0, 1, 2, 3 or 4 respectively, and n+m=1~4; when n+m≥2, the plural rings A and rings B is the same or different from each other, Z ₁ and Z ₂ are the same or different from each other; R is C ₁ ~C ₁₂ alkyl, C ₁ ~C ₁₂ alkoxy, C ₂ ~C ₁₂ alkenyl or P, wherein , The alkenyl is unsubstituted or at least one hydrogen on the carbon is replaced by fluorine; and P is

,

,

,

,

,

,

,

or

.

Another object of the present invention is to provide a liquid crystal composition. The liquid crystal composition includes one or more of the above-mentioned polymerizable compounds.

Another object of the present invention is to provide a liquid crystal display device. The liquid crystal display device includes the above-mentioned liquid crystal composition.

Before describing in detail at least one embodiment of the present invention, it should be understood that the present invention is not necessarily limited to its application in the multiple details illustrated in the multiple examples in the following description, for example, the number of embodiments or the use of them Specific mixing ratio, etc. The present invention can be implemented or realized in other embodiments or in various ways.

[Polymerizable compound]

The invention provides a polymerizable compound that can be used in PSA-VA, PSA-TN, PSA-IPS, PSA-FFS, PSA-OCB and PDLC. The liquid crystal composition and the liquid crystal display device containing the polymerizable compound have good pretilt angle stability and low-temperature storage properties.

(I) 其中 環A和環B各自獨立地為未經取代或至少一個碳上的氫被氟、C₁ ~C₅ 直鏈伸烷基或C₃ ~C₅ 支鏈伸烷基所取代的1,4-伸環己基、1,4-伸苯基、萘-2,6-二基、茚滿-1,5-二基、茚滿-2,5-二基或1,2,3,4-四氫萘-2,6-二基，其中該伸烷基為未經取代或至少一個−CH₂ −被−O−或−C=C−所取代； Z₁ 和Z₂ 各自獨立為C₁ ~C₄ 直鏈伸烷基、−CF₂ O−、−OCF₂ −或單鍵，其中該伸烷基為未經取代或至少一個−CH₂ −被−O−、−C=C−或−C≡C−所取代； n和m各自為0、1、2、3或4，且n+m=1~4；當n+m≥2時，該複數個環A和環B為彼此相同或彼此不同， Z₁ 和Z₂ 為彼此相同或彼此不同； R為C₁ ~C₁₂ 烷基、C₁ ~C₁₂ 烷氧基、C₂ ~C₁₂ 烯基或P，其中，該烯基為未經取代或是至少一個碳上的氫被氟取代；且 P為

、

、

、

、

、

、

、

或

。The polymerizable compound has a chemical formula as shown in formula (I):

(I) where ring A and ring B are each independently unsubstituted or at least one hydrogen on carbon is substituted by fluorine, C ₁ ~C ₅ linear alkylene or C ₃ ~C ₅ branched alkylene 1,4-cyclohexyl, 1,4-phenylene, naphthalene-2,6-diyl, indane-1,5-diyl, indane-2,5-diyl or 1,2,3 ,4-Tetrahydronaphthalene-2,6-diyl, where the alkylene is unsubstituted or at least one −CH ₂ − is substituted by −O− or −C=C−; Z ₁ and Z ₂ are each independent C ₁ ~C ₄ straight chain alkylene, −CF ₂ O−, −OCF ₂ − or single bond, where the alkylene is unsubstituted or at least one −CH ₂ −by −O−, −C= C− or −C≡C−; n and m are 0, 1, 2, 3 or 4 respectively, and n+m=1~4; when n+m≥2, the plural rings A and rings B is the same or different from each other, Z ₁ and Z ₂ are the same or different from each other; R is C ₁ ~C ₁₂ alkyl, C ₁ ~C ₁₂ alkoxy, C ₂ ~C ₁₂ alkenyl or P, wherein , The alkenyl is unsubstituted or at least one hydrogen on the carbon is replaced by fluorine; and P is

,

,

,

,

,

,

,

or

.

In one of the embodiments of the present invention, Z ₁ and Z ₂ are each independently −OCH ₂ −, −CH ₂ O−, −O(CH ₂ ) ₃ −, −(CH ₂ ) ₃ O−, −OC ₂ H ₄ O−, −C=C−, −C≡C−, −CF ₂ O−, −OCF ₂ − or single bond.

In one embodiment of the present invention, the ring A and the ring B are each independently unsubstituted or at least one hydrogen on the carbon is _{branched by fluorine, a C 1} ~C ₅ linear alkylene group, or a C ₃ ~C ₅ 1,4-phenylene or naphthalene-2,6-diyl substituted by chain alkylene; said Z ₁ and Z ₂ are each independently −OCH ₂ −, −CH ₂ O− or a single bond; n+ m=1~3.

In one embodiment of the present invention, the ring A is unsubstituted or the hydrogen on at least one carbon is substituted by fluorine, C ₁ ~C ₅ straight chain alkylene or C ₃ ~C ₅ branched alkylene Z ₁ is a single bond, n=1~2, m=0, R is P, and the definition of P is the same as above.

In one embodiment of the present invention, the ring A and ring B are unsubstituted or at least one hydrogen on the carbon is fluorine, C ₁ ~C ₅ straight chain alkylene or C ₃ ~C ₅ branched alkylene The 1,4-phenylene group substituted by the group, Z ₁ and Z ₂ are each independently −OCH ₂ −, −CH ₂ O− or a single bond, n=0~3, m=0~3, n+m= 3. R is P, and the definition of P is the same as above.

(I-1)、

(I-2)、

(I-3)、

(I-4)、

(I-5)、

(I-6)、

(I-7)、

(I-8)、

(I-9)、

(I-10)、

(I-11)。Specific examples of formula (I) of the present invention are formula (I-1) ~ formula (I-11):

(I-1),

(I-2),

(I-3),

(I-4),

(I-5),

(I-6),

(I-7),

(I-8),

(I-9),

(I-10),

(I-11).

[Liquid crystal composition]

The liquid crystal composition provided by the present invention includes the polymerizable compound represented by the above formula (I). The liquid crystal composition of the present invention can make the display device have good pretilt angle stability by containing the polymerizable compound represented by the above formula (I) through a photocuring process, and the polymerizable compound has good properties in the liquid crystal composition. Low temperature storage.

Specifically, the polymerizable compound represented by formula (I) is based on the total content of the liquid crystal compound as 100%, and the external addition ratio ranges from 0.01 to 10% by weight, preferably 0.02 to 2% by weight, and more preferably 0.05~1% by weight.

(II)The liquid crystal composition provided by the present invention may further include liquid crystal compounds with other characteristics. Preferably, the liquid crystal composition further comprises one or more compounds of formula (II):

(II)

Wherein R ²¹ and R ²² are each independently hydrogen, a halogen atom, a C ₁ to C ₁₅ alkyl group or a C ₂ to C ₁₅ alkenyl group, and wherein the C ₁ to C ₁₅ alkyl group or the C ₂ to C ₁₅ alkenyl group Is unsubstituted or at least one hydrogen atom is replaced by a halogen atom, and/or at least one −CH ₂ − is replaced by −O−, and −O− is not directly connected to −O−;

Rings B ¹ , B ² and B ³ are each independently 1,4-phenylene, 1,4-cyclohexylene, 2,5-benzofuranyl, 1,3-dioxane-2,5 -Diyl, 2,5-tetrahydropyranyl, divalent dioxa-bicyclo[2.2.2] octane functional group, divalent trioxa-bicyclo[2.2.2] octane functional group, four Hydronaphthalene-2,6-diyl or indan-2,5-diyl. Wherein the 1,4-phenylene, the 1,4-cyclohexylene, the 1,3-dioxane-2,5-diyl, the 2,5-benzofuranyl, The tetralin-2,6-diyl, the indan-2,5-diyl or the 2,5-tetrahydropyranyl is unsubstituted or at least one hydrogen atom is a halogen atom or −CN substitution, and/or at least one −CH ₂ − is substituted by −O−, −N−, or −S−, and the −O−, −N−, and −S− substitution atoms are not directly connected to each other;

Z ²¹ and Z ²² are each independently a single bond, C ₁ to C ₄ alkylene, C ₂ to C ₄ alkenylene, C ₂ to C ₄ alkynylene, and wherein the C ₁ to C ₄ alkylene Group, the C ₂ ~C ₄ alkenylene group or the C ₂ ~C ₄ alkynylene group is unsubstituted or at least one hydrogen atom is substituted by a halogen atom or −CN, and/or at least one −CH ₂ − is substituted −O− or −S− is substituted, and −O− is not directly connected to −O− or −S−, −S− is not directly connected to −S−; and n ²¹ is 0, 1, or 2, and when n ²¹ When it is 2, the two B ¹ groups may be the same or different from each other.

Specifically, the ratio of the compound of the formula (II) to the overall liquid crystal compound ranges from 40 to 100% by weight, preferably from 50 to 100% by weight, and more preferably from 60 to 100% by weight.

(II-1)

(II-2) 其中Preferably, the compound of formula (II) is a compound of the following formula (II-1) or formula (II-2):

(II-1)

(II-2) where

R ²¹ and R ²² are each independently hydrogen, a halogen atom, a C ₁ to C ₁₅ alkyl group or a C ₂ to C ₁₅ alkenyl group, and wherein the C ₁ to C ₁₅ alkyl group or the C ₂ to C ₁₅ alkene group The group is unsubstituted or at least one hydrogen atom is replaced by a halogen atom, and/or at least one −CH ₂ − is replaced by −O−, and −O− is not directly connected to −O−;

Rings B ¹ and B ² are each independently 1,4-phenylene, 1,4-cyclohexylene, 2,5-benzofuranyl, 1,3-dioxane-2,5-diyl , 2,5-tetrahydropyranyl, divalent dioxa-bicyclo[2.2.2] octane functional group, divalent trioxa-bicyclo[2.2.2] octane functional group, tetralin- 2,6-diyl or indan-2,5-diyl, wherein the 1,4-phenylene, the 1,4-cyclohexylene, the 1,3-dioxane-2, 5-diyl, the 2,5-benzofuranyl, the tetralin-2,6-diyl, the indan-2,5-diyl, or the 2,5-tetralin Hydropyranyl is unsubstituted or at least one hydrogen atom is replaced by a halogen atom or -CN, and/or at least one -CH ₂ -is replaced by -O-, -N- or -S-, and where -O-, −N− and −S− substituted atoms are not directly connected to each other;

Z ^{22 is} independently a single bond, C ₁ to C ₄ alkylene, C ₂ to C ₄ alkenylene, C ₂ to C ₄ alkynylene, and wherein the C ₁ to C ₄ alkylene, the The C ₂ ~C ₄ alkenylene group or the C ₂ ~C ₄ alkynylene group is unsubstituted or at least one hydrogen atom is substituted by a halogen atom or −CN, and/or at least one −CH ₂ − is −O− or −S− is replaced, and −O− is not directly connected to −O− or −S−, and −S− is not directly connected to −S−;

n ²¹ is 0, 1, or 2, and when n ²¹ is 2, the two B ¹ groups may be the same as or different from each other.

Specifically, the ratio of the compound of the formula (II-1) to the overall liquid crystal compound ranges from 5 to 60% by weight, preferably from 10 to 50% by weight, more preferably from 15 to 40% by weight; The proportion of the compound of II-2) in the overall liquid crystal compound ranges from 20 to 90% by weight, preferably 25 to 80% by weight, and more preferably 30 to 70% by weight.

Specifically, the above-mentioned liquid crystal compounds may be exemplified as follows, including but not limited to:

(II-1-1)

(II-1-1)

(II-1-2)

(II-1-2)

(II-1-3)

(II-1-3)

(II-2-1)

(II-2-1)

(II-2-2)

(II-2-2)

(II-2-3)

(II-2-3)

(II-2-4)

(II-2-4)

(II-2-5)

(II-2-5)

(II-2-6)

(II-2-6)

(II-2-7)

(II-2-7)

Where n and m are each independently 1, 2, 3, 4, or 5.

More specifically, the above-mentioned liquid crystal compounds may be exemplified as follows, including but not limited to:

(II-1-1-1)

(II-1-1-1)

(II-1-1-2)

(II-1-1-2)

(II-2-1-1)

(II-2-1-1)

(II-2-3-1)

(II-2-3-1)

(II-2-3-2)

(II-2-3-2)

(II-2-4-1)

(II-2-4-1)

(II-2-5-1)

(II-2-5-1)

(II-2-5-2)

(II-2-5-2)

(II-2-7-1)。

(II-2-7-1).

(III)

(IV)

(V) 其中The liquid crystal composition provided by the present invention may further include one or more other polymerizable compounds. Preferably, the other polymerizable compounds include, but are not limited to, compounds represented by formula (III), formula (IV) or formula (V):

(III)

(IV)

(V) where

K ²¹ , K ²² , K ²³ and K ²⁴ are each independently hydrogen or methyl; Z ²³ and Z ²⁴ are each independently a single bond, C ₁ to C ₁₅ linear alkylene, C ₃ to C ₁₅ branch A chain alkylene group, a C ₂ to C ₁₅ straight chain alkenylene group, or a C ₃ to C ₁₅ branched chain alkenylene group, and wherein the C ₁ to C ₁₅ straight chain alkylene group, the C ₃ ~C ₁₅ branched alkylene group, the C ₂ ~C ₁₅ linear alkenylene group or the C ₃ ~C ₁₅ branched chain alkenylene group is unsubstituted or at least one hydrogen atom is substituted by a halogen atom , And/or at least one of −CH ₂ − is replaced by −O−, −CO−, −COO−, or −OCO−, and the −O−, −CO−, −COO−, and −OCO− are not directly connected to each other ；

Z ²⁵ , Z ²⁶ , Z ²⁷ and Z ²⁸ are each independently a single bond, −C≡C−, C ₁ ~C ₁₅ linear alkylene, C ₃ ~C ₁₅ branched alkylene, C ₂ ~C ₁₅ straight chain alkenylene group or C ₃ ~C ₁₅ branched chain alkenylene group, and wherein the C ₁ ~C ₁₅ straight chain alkylene group and the C ₃ ~C ₁₅ branched chain alkylene group Group, the C ₂ to C ₁₅ linear alkenylene group or the C ₃ to C ₁₅ branched chain alkenylene group is unsubstituted or at least one hydrogen atom is substituted by a halogen atom, and/or at least one −CH ₂ − is replaced by −SiR ^e ₂ −, −S −, −O −, −CO −, −COO −, −OCO −, −CO −NR ^e − or −NR ^e −CO −, and the −SiR ^e ₂ −, −S −, −O −, −CO −, −COO −, −OCO −, −CO −NR ^e − and −NR ^e −CO − are not directly connected to each other, where R ^e is hydrogen, C ₁ ~ C ₄ straight-chain alkyl or C ₃ ~ C ₄ branched alkyl, and Si bonded to the same two R ^e groups may be the same or different from each other;

Rings B ⁴ , B ⁵ , B ⁶ and B ⁷ are each independently an unsubstituted 1,4-phenylene, 1,4-cyclohexylene, benzofuran-2,5-diyl, 1,3 -Dioxane-2,5-diyl, tetrahydropyran-2,5-diyl, divalent dioxa-bicyclo[2.2.2] octane functional group, divalent trioxa-bicyclo[2.2 .2] Octane functional group, tetralin-2,6-diyl or indan-2,5-diyl, or 1,4-phenylene, 1,4-phenylene substituted with at least one substituent Cyclohexyl, benzofuran-2,5-diyl, 1,3-dioxane-2,5-diyl, tetrahydropyran-2,5-diyl, divalent dioxa-bicyclo[2.2 .2] octane functional group, divalent trioxa-bicyclo[2.2.2] octane functional group, tetralin-2,6-diyl or indan-2,5-diyl, wherein the at least A substituent is selected from F, Cl, CN, C ₁ ~C ₁₂ linear alkyl, C ₃ ~C ₁₂ branched alkyl, C ₂ ~C ₁₂ linear alkenyl, C ₂ ~ C ₁₂ linear alkynyl, C ₄ to C ₁₂ branched alkenyl or C ₄ to C ₁₂ branched alkynyl, and wherein the C ₁ to C ₁₂ linear alkyl, the C ₃ to C ₁₂ branched alkyl, the C ₂ to C ₁₂ linear alkenyl, the C ₂ to C ₁₂ linear alkynyl, the C ₄ to C ₁₂ branched alkenyl, or the C ₄ ~C ₁₂ branched alkynyl is unsubstituted or at least one hydrogen atom is substituted by a halogen atom, and/or at least one −CH ₂ − is substituted by −O−, −CO−, −COO− or −OCO−, And the -O-, -CO-, -COO- and -OCO- are not directly connected to each other;

M ¹ is a single bond, −CH ₂ O−, −OCH ₂ −, −CH ₂ CH ₂ −, −CH=CH−, −C≡C−, −CH ₂ −, −C(CH ₃ ) ₂ −, −C(CF ₃ ) ₂ −, −SiH ₂ −, −Si(CH ₃ ) ₂ − or −Si(CF ₃ ) ₂ −;

R ²³ and R ²⁴ are each independently a C ₁ to C ₃₀ linear alkyl group or a C ₃ to C ₃₀ branched chain alkyl group, and wherein the C ₁ to C ₃₀ linear alkyl group or the C ₃ to C ₃₀ A branched alkyl group is unsubstituted or at least one hydrogen atom is substituted by a halogen atom, and/or at least one −CH ₂ − is substituted by −Si−, −O−, −CO−, −COO−, or −OCO−, and The said −Si−, −O−, −CO−, −COO− and −OCO− are not directly connected to each other; and

n ²² and n ²³ are each independently an integer between 0 and 3, and when n ²² is 2 or more, two or more B ⁴ groups and M ¹ groups are the same or different from each other, and when n ^{When 23} is 2 or more, two or more B ⁶ groups and Z ²⁷ groups are the same or different from each other.

Preferably, the compound represented by the formula (III) can be further defined as ring B ⁴ and ring B ⁵ are each independently unsubstituted or at least one hydrogen is substituted by fluorine or methyl substituted 1,4- ring extension Hexyl, 1,4-phenylene, indane-1,5-diyl or indane-2,5-diyl; K ²¹ and K ²² are each independently hydrogen or methyl; Z ²³ and Z ²⁴ are Single bond; M ¹ is a single bond, -CH ₂ O- or -OCH ₂ -; and n ²² is 1, 2 or 3, when n ²² ≥ 2, plural B ⁴ and B ⁵ are the same or different from each other , The plurality of M ¹ may be the same or different from each other.

Specifically, the compound represented by the above formula (III) can be exemplified as follows, including but not limited to:

(III-1)。

(III-1).

The content of other polymerizable compounds that can be contained in the liquid crystal composition of the present invention is based on the total content of the liquid crystal compound as 100%, and the external addition ratio ranges from 0.01 to 10% by weight, preferably 0.02 to 2% by weight, more preferably It is 0.05~1% by weight, but the amount can be adjusted according to the actual situation, and it is not limited to this.

The liquid crystal composition of the present invention may further include additives. The additives include, but are not limited to: chiral dopants, UV stabilizers, antioxidants, free radical scavengers, nanoparticles and the like.

[Liquid crystal display device]

The present invention further provides a liquid crystal display device. The display device includes any one of the above-mentioned liquid crystal compositions.

[Preparation example]

The preparation process of the polymerizable compound formula (I-1) and formula (I-6) is taken as an example to illustrate the preparation process of the polymerizable compound of the present invention.

The synthesis process of the polymerizable compound formula (I-1) (namely PPcMA described later) is shown below. The following will describe the compounds 1 to 5 and the polymerizable compound formula (I-1) (namely PPcMA described later) in sequence. ) Synthesis steps:

Place 4-Bromophenol (5.02g, 29 mmol), imidazole (Imidazole, 2.37 g, 34.8 mmol) and solvent dichloromethane (dichloromethane, 50 mL) in a 250 mL double-necked flask, and stir at room temperature To dissolve. Add tert-Butyldimethylsilyl chloride (4.35 g, 29 mmol) in an ice bath, and react at room temperature for 2 hours. After the reaction is completed, extraction is performed with ethyl acetate (Ethyl acetate) and water, and the organic layer is collected after drying with magnesium sulfate (Megnesium sulfate). A rotary concentrator was used to remove the solvent of the collected organic layer, and then column chromatography was performed to obtain compound 1 as a colorless liquid.

Put compound 1 (8.03 g, 28 mmol) and anhydrous tetrahydrofuran (Anhydrous Tetrahydrofuran, 60 mL) into a 250 mL two-neck flask filled with nitrogen. Cool down to -78°C, take a 2.2M n-Butyllithium solution (n-Butyllithium solution 2.2 M in hexane, 13.44 mL) slowly into a double-necked flask with a syringe, and maintain the temperature at -60°C and -80° React between C for 1 hour, then add triisopropyl borate (Triisopropyl borate, 6.25 mL, 33.6 mmol), heat to room temperature and stir for 1 hour, add 1N aqueous hydrochloric acid (HCl 33.6 mL) to terminate the reaction, use ethyl acetate and water After extraction, the organic layer was collected after drying with magnesium sulfate. A rotary concentrator was used to remove the solvent of the collected organic layer, and then column chromatography was performed to obtain compound 2 as a white solid.

Compound 2 (6.80g, 27mmol), 6-Bromo-2-Tetralone (6-Bromo-2-Tetralone, 4.05g, 18mmol), potassium carbonate (9.32g, 67.5mmol), tetrahydrofuran (tetrahydrofuran, THF (100mL) and water (22.5mL) were placed in a 250mL reaction flask and stirred. Fill with nitrogen to remove oxygen, and stir vigorously for 1 hour. Tetrakis (triphenyl-phosphine) palladium (0), 0.52g, 0.45mmol) was added and stirred at 70°C under reflux for 8 hours. After the reaction was completed, extraction was performed with ethyl acetate and water, and the organic layer was collected after drying with magnesium sulfate. A rotary concentrator was used to remove the solvent of the collected organic layer, and then column chromatography was performed to obtain compound 3 as a pale yellow solid.

Take compound 3 (7.04, 20 mmol) and methanol (Methanol, 60 mL) into a 250 mL double-necked flask and stir to dissolve. Sodium borohydirde (Sodium borohydirde, 30 mmol) was added to the double-necked flask in batches under ice bath, and stirred at room temperature for 1 hour. After the reaction was completed, extraction was performed with ethyl acetate and water, and the organic layer was collected after drying with magnesium sulfate. A rotary concentrator was used to remove the solvent of the collected organic layer, and then column chromatography was performed to obtain compound 4 as a brown liquid.

Dissolve compound 4 (7.08g, 20mmol) and tetrahydrofuran (50 mL) in a 250mL reaction flask and cool to 0°C. Slowly add 1M Tetrabutylammonium fluoride solution in THF (26 ml, 26 mmol), return to room temperature and stir for 2 hours. After the reaction is complete, extract with ethyl acetate and water, and dry with magnesium sulfate After that, the organic layer was collected. A rotary concentrator was used to remove the solvent of the collected organic layer, and then column chromatography was performed to obtain compound 5 as a yellow solid.

Compound 5 (3.60 g, 15 mmol), methacrylic acid (Methacrylic acid, 0.77g, 9 mmol), 4-Dimethylaminopyridine (4-Dimethylaminopyridine, 1.10g, 9 mmol) and tetrahydrofuran (tetrahydrofuran, 50 mL) Stir and dissolve in a 250mL reaction flask. Reduce the reaction to 0°C, and slowly add N,N'-dicyclohexylcarbodiimide (N,N'-dicyclohexylcarbodiimide, 12.38g, 60 mmol) in tetrahydrofuran (20 mL), slowly and dropwise, at 0°C After stirring for 30 minutes, returning to room temperature and stirring for 8 hours. After the reaction was completed, the white precipitate was filtered by suction, extracted with ethyl acetate and water, dried with magnesium sulfate, and the organic layer was collected. A rotary concentrator was used to remove the solvent of the collected organic layer, and then column chromatography was performed to obtain the compound PPcMA as a white solid.

The polymerizable compound PPcMA was analyzed by nuclear magnetic resonance spectroscopy, and the spectral information obtained is as follows: ¹ H NMR (CDCl ₃ , 400 MHz): 1.94(s,1H), 2.08(s,1H), 1.98-2.16(m,2H), 2.89- 3.22(m,4H), 5.28-5.34(m, 1H), 5.55(t, J =1.6Hz, 1H), 5.77(t, J =1.6Hz, 1H), 6.09(s, 1H), 6.37 (s, 1H), 7.14(d, J =3.8Hz, 1H),7.14-7.18(m, 2H), 7.32(s, 1H), 7.35(q, J =3Hz, 1H), 7.58(m, 2H) ).

The synthesis process of the polymerizable compound formula (I-6) (that is, PPcO1PPMA described later) is shown below. The following will describe compounds 6 to 8 and the polymerizable compound formula (I-6) (that is, the PPcO1PPMA described later) in sequence. ) Synthesis steps:

Put 6-Bromo-2-Tetralone (6-Bromo-2-Tetralone, 4g, 22 mmol), methanol (100 mL) and tetrahydrofuran (30 mL) into a 250 mL double-necked flask and stir until dissolved. Add sodium borohydride into the double-necked flask in batches under ice bath, and stir at room temperature for 1 hour. After the reaction was completed, extraction was performed with ethyl acetate and water, and after drying with magnesium sulfate, the organic layer was collected. A rotary concentrator was used to remove the solvent of the collected organic layer, and then column chromatography was performed to obtain compound 7 as a brown liquid.

Put compound 7 (4.54 g, 20 mmol) and tetrahydrofuran (60 mL) into a 250 mL double-necked flask and stir to dissolve. Add 60% sodium hydride (60% NaH, 4 g, 100 mmol) in an ice bath, and stir for 1 hour in an ice bath. Add 4-Bromobenzyl bromide (6.00 g, 24 mmol) dissolved in tetrahydrofuran (20 mL), and stir at room temperature for 8 hours. The reaction solution was poured into ice cubes to terminate the reaction. After the reaction was completed, extraction was performed with ethyl acetate and water, and after drying with magnesium sulfate, the organic layer was collected. A rotary concentrator was used to remove the solvent of the collected organic layer, and then column chromatography was performed to obtain compound 8 as a brown solid.

Compound 8 (7.09g, 18mmol), 4-Hydroxyphenylboronic acid (4-Hydroxyphenylboronic acid, 12.42g, 90mmol), potassium carbonate (7.45 g, 54 mmol), tetrahydrofuran (tetrahydrofuran, 150 mL) and water ( 30mL) was placed in a 500mL reaction flask and stirred. Fill with nitrogen to remove oxygen, and stir vigorously for 1 hour. Tetrakis (triphenyl-phosphine) palladium (0), 0.751g, 0.65mmol) was added and stirred at 70°C under reflux for 8 hours. After the reaction was completed, extraction was performed with ethyl acetate and water, and after drying with magnesium sulfate, the organic layer was collected. A rotary concentrator was used to remove the solvent of the collected organic layer, and then column chromatography was performed to obtain compound 9 as a pale yellow solid.

Compound 9 (5.32 g, 12.6 mmol), methacrylic acid (Methacrylic acid, 6.50 g, 75.6 mmol), 4-Dimethylaminopyridine (4-Dimethylaminopyridine, 0.77 g, 6.3 mmol) and dichloromethane (dichloromethane, 100mL ) Put it in a 250mL reaction flask. The reaction was reduced to 0°C, and N,N'-dicyclohexylcarbodiimide (N,N'-dicyclohexylcarbodiimide, 6.50 g, 31.5 mmol) was slowly added dropwise to dichloromethane (dichloromethane, 20 mL), Stir at 0°C for 30 minutes, return to room temperature and stir for 3 hours. After the reaction is completed, the white precipitate is filtered by suction, extracted with ethyl acetate and water, dried with magnesium sulfate, and the organic layer is collected. A rotary concentrator was used to remove the solvent of the collected organic layer, and then column chromatography was performed to obtain a white solid polymerizable compound PPcO1PPMA.

The liquid crystal compound PPcO1PPMA was analyzed by nuclear magnetic resonance spectroscopy, and the spectral information obtained is as follows: ¹ H NMR (CDCl ₃ , 400 MHz): 1.91-2.00(m, 1H), 2.08(d, J =0.4Hz, 6H), 2.13- 2.16 (m, 1H), 2.82-3.17(m, 4H), 3.90-3.96(m, 1H), 4.70(q, J =2Hz, 2H), 5.77(q, J =6.4Hz, 2H), 6.37(s , 2H), 7.15-7.20(m, 2H), 7.30-7.34(m, 2H), 7.45(d, J = 4Hz, 2H), 7.54-7.61(m, 6H).

The liquid crystal structures used in the preparation examples and examples in this specification are represented by the codes in Table 1:

Table 1:

為3CPO2，

為1.3PPcMA。E.g:

Is 3CPO2,

It is 1.3PPcMA.

The following embodiments respectively use the following methods to carry out property tests:

Dielectric anisotropy (Δε): Put the liquid crystal composition into a liquid crystal cell, and apply a voltage of 0 V to 30 V to the liquid crystal cell at a temperature of 25°C, measured in the direction parallel to the long axis of the liquid crystal molecules The average dielectric constant is ε _‖ , the average dielectric constant measured perpendicular to the long axis of the liquid crystal molecule is ε _⊥ , and the dielectric anisotropy (Δε) = ε _‖ -ε _⊥ .

Refractive index anisotropy (Δn): Use an Abbe refractometer (manufacturer: ATAGO; model: DR-M2) with a polarizer mounted on an eyepiece to measure the liquid crystal composition (or liquid to be measured) . First, wipe the main surface of the Abbe refractometer in a single direction, then drop a small amount of liquid crystal composition (or liquid to be tested) on the main beam, and then use a wavelength of 589 nm at a test temperature of 25°C. The optical filter measures the refractive index anisotropy. When the polarization direction is parallel to the wiping direction, the measured refractive index is n _‖ ; when the polarization direction is perpendicular to the wiping direction, the measured refractive index is n _⊥ ; refractive index anisotropy (Δn) = n _‖ －n _⊥ .

Clearing point temperature (Tni): Using a differential scanning calorimeter (DSC) system, the liquid crystal composition is placed on an aluminum plate to finely weigh 0.5 to 10 mg, and the endothermic and exothermic peaks of the liquid crystal composition due to phase changes The starting point to determine the phase change temperature. The expression of the phase change is as follows: the crystalline phase is marked as C, the smectic phase is marked as S, the nematic phase is marked as N, and the liquid is marked as I. Among them, the phase transition temperature from the nematic phase to the liquid is the clearing point temperature (Tni).

Low temperature stability (LTS): Take 0.5g of liquid crystal composition in a 7ml sample bottle and place it in a freezer at -20°C. Observe the crystal precipitation condition every day, and record the number of days without solid precipitates, which is LTS The number of days.

Stable polymer alignment process time: Prepare liquid crystal composition as mother liquor. With the total weight of the liquid crystal mother liquor being 100 parts by weight, the corresponding parts by weight of the polymerizable compound were added, vacuum-filled into the test box, and then the polymer stabilized alignment (PSA) process step was carried out to make the polymerizable The compound is polymerized. The conditions of the above PSA process steps are that the test strip is applied with a voltage of 12V and ^{irradiated under a UV lamp (0.1 mW/cm 2} ) to confirm that the Ton of the test box falls within 10 ms, and the required time is the process time.

Polymer Stable Alignment UV Process: After the aforementioned polymer stabilization process is completed, put the test box under a UV lamp and ^{irradiate it at 0.5 mW/cm 2 for} 120 minutes.

Pretilt angle stability: The test box after the polymer stabilized alignment UV process is placed in a high-temperature 60°C oven, and 20V 60Hz alternating current is applied for 72 hours to compare the pretilt angle of the test box before and after the electric field.

[Example]

The composition of the mother liquor of LC-1 is shown in Table 2 below:

Table 2: The composition of the mother liquor of LC-1: LC-1 wt% 3CC2 24.5 3CC5 4.25 3CPO2 2.75 3CCP1 3.5 3CPP2 9 3CP2YO2 7 2CPYO2 4.25 3CPYO2 11 3C1OYO1 3.75 3C1OYO2 3.75 3CYO2 17.25 3CCYO2 9 Tni 73.87 Δε -3.02 Δn 0.0962 LTS (-20 ^o C) 24D

The polymerizable compound of the present invention is added to LC-1 to form the liquid crystal composition of the present invention.

Table 3: Example 1 & Comparative Examples 1~3: Example 1 Comparative example 1 Comparative example 2 Comparative example 3 LC-1 (%) 100 100 100 100 PPcMA (%) 0.3 - - - PRIMA (%) - 0.3 - - PNMA (%) - - 0.3 - 1.3PPcMA (%) - - - 0.3 Process time (s) 205 210 110 210 Initial PTA ( ^o ) 89.91 89.9 89.9 89.92 PTA after Stress ( ^o ) 89.85 89.55 89.81 89.71 ΔPTA ( ^o ) 0.06 0.35 0.09 0.21 LTS (-20 ^o C) 19D 15D 8D 12D

Table 4: Example 2 & Comparative Example 4: Example 2 Comparative example 4 LC-1 (%) 100 100 PPPcMA (%) 0.3 - PGRIMA (%) - 0.3 Process time (s) 60 70 Initial PTA ( ^o ) 89.89 89.91 PTA after Stress ( ^o ) 89.74 88.97 ΔPTA ( ^o ) 0.15 0.94 LTS (-20 ^o C) 9D 10D

Table 5: Examples 3~6: Example 3 Example 4 Example 5 Example 6 LC-1 (%) 100 100 100 100 PPcMA (%) - - - 0.3 PPcO1PPMA (%) 0.2 0.15 0.15 - PPcO1G'PMA (%) - - 0.15 - PG1OGPMA (%) - 0.15 - 0.25 Process time (s) 160 180 190 180 Initial PTA ( ^o ) 89.89 89.92 89.9 89.88 PTA after Stress ( ^o ) 89.82 89.85 89.84 89.86 ΔPTA ( ^o ) 0.07 0.07 0.06 0.02 LTS (-20 ^o C) 12D 12D 10D 8D

It can be seen from Table 3 that in the liquid crystal composition, PPcMA, PRIMA, and PNMA have the best pretilt angle stability and low-temperature storage stability compared with 1.3PPcMA among the polymerizable compounds with two rings; 4 It can be seen that among the polymerizable compounds with 3 rings, PPPcMA also has better pretilt angle stability than PGRIMA; from Table 5, it can be seen that PPcO1PPMA with 4 ring structure also has excellent pretilt angle stability and low temperature Storage stability, and the liquid crystal composition containing the polymerizable compound of the present invention and other polymerizable compounds can also achieve better pretilt angle stability and low-temperature storage stability.

[Application field]

The polymerizable compound and liquid crystal composition of the present invention can be applied to various types of liquid crystal display devices such as VA, TN, IPS, FFS, OCB and PDLC, as well as the application of smart glass.

Although the present invention has been disclosed in a number of preferred embodiments, it is not intended to limit the present invention, but only to enable those with ordinary knowledge to clearly understand the implementation content of this specification. Anyone in the field who is familiar with this technique can make various changes, substitutions and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention shall be defined as the scope of the attached patent application. allow.

without

without

Claims (11)

A polymerizable compound having the chemical formula shown in formula (I):

(I) where ring A and ring B are each independently unsubstituted or at least one hydrogen on carbon is substituted by fluorine, C ₁ ~C ₅ linear alkylene or C ₃ ~C ₅ branched alkylene 1,4-cyclohexyl, 1,4-phenylene, naphthalene-2,6-diyl, indane-1,5-diyl, indane-2,5-diyl or 1,2,3 ,4-Tetrahydronaphthalene-2,6-diyl, where the alkylene is unsubstituted or at least one −CH ₂ − is substituted by −O− or −C=C−; Z ₁ and Z ₂ are each independent C ₁ ~C ₄ straight chain alkylene, −CF ₂ O−, −OCF ₂ − or single bond, where the alkylene is unsubstituted or at least one −CH ₂ −by −O−, −C= C− or −C≡C−; n and m are 0, 1, 2, 3 or 4 respectively, and n+m=1~4; when n+m≥2, the plural rings A and rings B is the same or different from each other, Z ₁ and Z ₂ are the same or different from each other; R is C ₁ ~C ₁₂ alkyl, C ₁ ~C ₁₂ alkoxy, C ₂ ~C ₁₂ alkenyl or P, wherein , The alkenyl is unsubstituted or at least one hydrogen on the carbon is replaced by fluorine; and P is

,

,

,

,

,

,

,

or

. Such as the polymerizable compound of claim 1, where Z ₁ and Z ₂ are each independently −OCH ₂ −, −CH ₂ O−, −O(CH ₂ ) ₃ −, − (CH ₂ ) ₃ O−, −OC ₂ H ₄ O−, −C=C−, −C≡C−, −CF ₂ O−, −OCF ₂ − or single bond. The polymerizable compound of claim 1, wherein the ring A and the ring B are each independently unsubstituted or at least one hydrogen on the carbon is _{branched by fluorine, a C 1} to C ₅ linear alkylene group, or a C ₃ to C ₅ 1,4-phenylene or naphthalene-2,6-diyl substituted by chain alkylene; Z ₁ and Z ₂ are each independently −OCH ₂ −, −CH ₂ O− or a single bond; n+m= 1~3. The polymerizable compound of claim 1, wherein the ring A is unsubstituted or at least one hydrogen on carbon is substituted by fluorine, C ₁ ~C ₅ straight chain alkylene or C ₃ ~C ₅ branched alkylene Z ₁ is a single bond, n=1~2, m=0, R is P, and the definition of P is the same as that of claim 1. The polymerizable compound of claim 1, wherein the ring A and ring B are unsubstituted or at least one hydrogen on the carbon is fluorine, C ₁ ~C ₅ linear alkylene or C ₃ ~C ₅ branched alkylene The 1,4-phenylene group substituted by the group, Z ₁ and Z ₂ are each independently −OCH ₂ −, −CH ₂ O− or a single bond, n=0~3, m=0~3, n+m= 3. R is P, and the definition of P is the same as that of claim 1. A liquid crystal composition comprising one or more polymerizable compounds as described in claim 1. Such as the liquid crystal composition of claim 6, which further comprises one or more compounds of formula (II):

(II) wherein R ²¹ and R ²² are each independently hydrogen, a halogen atom, a C ₁ to C ₁₅ alkyl group or a C ₂ to C ₁₅ alkenyl group, and wherein the C ₁ to C ₁₅ alkyl group or the C ₂ to C ₁₅ Alkenyl is unsubstituted or at least one hydrogen atom is substituted by a halogen atom, and/or at least one −CH ₂ − is substituted by −O−, and −O− is not directly connected to −O−; B ¹ , B ² and B ^{3 is} each independently 1,4-phenylene, 1,4-cyclohexylene, 2,5-benzofuranyl, 1,3-dioxane-2,5-diyl, 2,5 -Tetrahydropyranyl, divalent dioxa-bicyclo[2.2.2]octane functional group, divalent trioxa-bicyclo[2.2.2]octane functional group, tetralin-2,6- Diyl or indan-2,5-diyl, wherein the 1,4-phenylene, the 1,4-cyclohexylene, the 1,3-dioxane-2,5-diyl, the 2 ,5-benzofuranyl, the tetralin-2,6-diyl, the indan-2,5-diyl or the 2,5-tetrahydropyranyl is unsubstituted or at least one The hydrogen atom is replaced by a halogen atom or -CN, and/or at least one -CH ₂ -is replaced by -O-, -N- or -S-, and the -O-, -N- and -S- substituted atoms are not mutually exclusive Directly connected; Z ²¹ and Z ²² are each independently a single bond, C ₁ to C ₄ alkylene, C ₂ to C ₄ alkenylene, C ₂ to C ₄ alkynylene, and wherein the C ₁ to C ₄ The alkylene group, the C ₂ ~C ₄ alkenylene group or the C ₂ ~C ₄ alkynylene group is unsubstituted or at least one hydrogen atom is substituted by a halogen atom or −CN, and/or at least one −CH ₂ − is substituted −O− or −S− is substituted, and −O− is not directly connected to −O− or −S−, −S− is not directly connected to −S−; and n ²¹ is 0, 1, or 2, and when n ²¹ When it is 2, the two B ¹ groups are the same or different from each other. Such as the liquid crystal composition of claim 6, which further comprises one or more compounds of formula (II-1) or formula (II-2):

(II-1)

(II-2) wherein R ²¹ and R ²² are each independently hydrogen, a halogen atom, a C ₁ to C ₁₅ alkyl group or a C ₂ to C ₁₅ alkenyl group, and wherein the C ₁ to C ₁₅ alkyl group or the C ₂ ~C ₁₅ alkenyl is unsubstituted or at least one hydrogen atom is substituted by a halogen atom, and/or at least one −CH ₂ − is substituted by −O−, and −O− is not directly connected to −O−; B ¹ and B ² Each independently is 1,4-phenylene, 1,4-cyclohexylene, 2,5-benzofuranyl, 1,3-dioxane-2,5-diyl, 2,5- Tetrahydropyranyl, divalent dioxa-bicyclo[2.2.2] octane functional group, divalent trioxa-bicyclo[2.2.2] octane functional group, tetralin-2,6-di Group or indan-2,5-diyl, wherein the 1,4-phenylene, the 1,4-cyclohexylene, the 1,3-dioxane-2,5-diyl, the 2, 5-benzofuranyl, the tetralin-2,6-diyl, the indan-2,5-diyl or the 2,5-tetrahydropyranyl is unsubstituted or at least one hydrogen Atoms are substituted by halogen atoms or −CN, and/or at least one −CH ₂ − is substituted by −O−, −N−, or −S−, and the substituted atoms of −O−, −N−, and −S− are not directly each other Connected; Z ^{22 is} independently a single bond, C ₁ to C ₄ alkylene, C ₂ to C ₄ alkenylene, C ₂ to C ₄ alkynylene, and wherein the C ₁ to C ₄ alkylene, the The C ₂ ~C ₄ alkenylene group or the C ₂ ~C ₄ alkynylene group is unsubstituted or at least one hydrogen atom is substituted by a halogen atom or −CN, and/or at least one −CH ₂ − is −O− or − S− is substituted, and −O− is not directly connected to −O− or −S−, −S− is not directly connected to −S−; and n ²¹ is 0, 1, or 2, and when n ²¹ is 2, the The two B ¹ groups are the same as or different from each other. For example, the liquid crystal composition of any one of claims 6 to 8, which further comprises one or more compounds represented by formula (III), formula (IV) or formula (V):

(III)

(IV)

(V) wherein K ²¹ , K ²² , K ²³ and K ²⁴ are each independently hydrogen or methyl; Z ²³ and Z ²⁴ are each independently a single bond, C ₁ ~C ₁₅ linear alkylene, C ₃ ~C ₁₅ branched alkylene, C ₂ ~C ₁₅ linear alkenylene or C ₃ ~C ₁₅ branched alkenylene, and wherein the C ₁ ~C ₁₅ linear alkylene, the The C ₃ ~C ₁₅ branched alkylene group, the C ₂ ~C ₁₅ straight chain alkenylene group or the C ₃ ~C ₁₅ branched chain alkenylene group is unsubstituted or at least one hydrogen atom is substituted by a halogen atom , And/or at least one of −CH ₂ − is replaced by −O −, −CO −, −COO − or −OCO −, and the −O −, −CO −, −COO − and −OCO − are not directly connected to each other; Z ²⁵ , Z ²⁶ , Z ²⁷ and Z ²⁸ are each independently a single bond, −C≡C−, C ₁ ~C ₁₅ linear alkylene, C ₃ ~C ₁₅ branched alkylene, C ₂ ~C ₁₅ linear alkenylene group or C ₃ ~C ₁₅ branched alkenylene group, and wherein the C ₁ ~C ₁₅ linear alkylene group, the C ₃ ~C ₁₅ branched alkylene group, The C ₂ ~C ₁₅ linear alkenylene group or the C ₃ ~C ₁₅ branched chain alkenylene group is unsubstituted or at least one hydrogen atom is substituted by a halogen atom, and/or at least one −CH ₂ − is − SiR ^e ₂ −, −S −, −O −, −CO −, −COO −, −OCO −, −CO −NR ^e − or −NR ^e −CO − substituted, and the −SiR ^e ₂ −, −S −, −O−, −CO−, −COO−, −OCO−, −CO−NR ^e − and −NR ^e −CO− are not directly connected to each other, where R ^e is hydrogen, C ₁ ~C ₄ linear alkane group or a C ₃ ~ C ₄ branched alkyl, and Si bonded to the same two R ^e groups are the same or different from each ^{other; B 4, B 5, B} 6 and B ⁷ each independently without Substituted 1,4-phenylene, 1,4-cyclohexyl, benzofuran-2,5-diyl, 1,3-dioxane-2,5-diyl, tetrahydropyran-2 ,5-Diyl, divalent dioxa-bicyclo[2.2.2]octane functional group, divalent trioxa-bicyclo[2.2.2]octane functional group, tetralin-2,6-diyl Or indane-2,5-diyl, or 1,4-phenylene, 1,4-cyclohexylene, benzofuran-2,5-diyl, 1,3-substituted with at least one substituent Dioxane-2,5-diyl, tetrahydropyran-2,5-diyl, divalent dioxa-bicyclo[2.2.2] octane functional group, divalent trioxa-bicyclo[2.2. 2] Octane functional group, tetralin-2,6-diyl or indan-2,5-diyl, wherein the at least one substituent is selected from F, Cl, CN, C ₁ ~C ₁₂ Linear alkyl, C ₃ ~ C ₁₂ branched alkyl, C ₂ ~C ₁₂ linear alkenyl, C ₂ ~C ₁₂ linear alkynyl, C ₄ ~C ₁₂ branched alkenyl or C ₄ ~C ₁₂ branched alkyne Group, and wherein the C ₁ ~C ₁₂ linear alkyl group, the C ₃ ~C ₁₂ branched alkyl group, the C ₂ ~C ₁₂ linear alkenyl group, the C ₂ ~C ₁₂ linear alkyne Group, the C ₄ ~C ₁₂ branched alkenyl group or the C ₄ ~C ₁₂ branched alkynyl group is unsubstituted or at least one hydrogen atom is substituted by a halogen atom, and/or at least one −CH ₂ − is − O−, −CO−, −COO− or −OCO− are substituted, and the −O−, −CO−, −COO−, and −OCO− are not directly connected to each other; M ¹ is a single bond, −CH ₂ O−, −OCH ₂ −, −CH ₂ CH ₂ −, −CH=CH−, −C≡C−, −CH ₂ −, −C(CH ₃ ) ₂ −, −C(CF ₃ ) ₂ −, −SiH ₂ −, −Si(CH ₃ ) ₂ − or −Si(CF ₃ ) ₂ −; R ²³ and R ²⁴ are each independently a C ₁ ~C ₃₀ linear alkyl group or a C ₃ ~C ₃₀ branched chain alkyl group, and Wherein the C ₁ ~C ₃₀ linear alkyl group or the C ₃ ~C ₃₀ branched chain alkyl group is unsubstituted or at least one hydrogen atom is substituted by a halogen atom, and/or at least one −CH ₂ − is −Si−, −O−, −CO−, −COO−, or −OCO− is replaced, and the −Si−, −O−, −CO−, −COO−, and −OCO− are not directly connected to each other; and n ²² and n ²³ are respectively It is independently an integer between 0 and 3, and when n ²² is 2 or more, the two or more B ⁴ groups and M ¹ groups are the same or different from each other, and when n ²³ is 2 or more , The two or more B ⁶ groups and Z ²⁷ groups are the same as or different from each other. The liquid crystal composition of claim 9, wherein the compound represented by formula (III) is further defined as: B ⁴ and B ⁵ are each independently 1,4- unsubstituted or at least one hydrogen substituted by fluorine or methyl Cyclohexyl, 1,4-phenylene, indan-1,5-diyl or indan-2,5-diyl; K ²¹ and K ²² are each independently hydrogen or methyl; Z ²³ and Z ²⁴ is a single bond; M ¹ is a single bond, -CH ₂ O- or -OCH ₂ -; and n ²² is 1, 2 or 3, when n ²² ≥ 2, plural B ⁴ and B ⁵ are the same as each other or Different from each other, the plural M ¹ are the same as or different from each other. A liquid crystal display device comprising a liquid crystal composition according to any one of Claims 6 to 8.