阅读说明：本技术 化合物、液晶组合物、液晶显示元件及液晶显示器 (Compound, liquid crystal composition, liquid crystal display element and liquid crystal display ) 是由 李明 孟劲松 员国良 郭民生 程建明 赵磊 于 2018-08-04 设计创作，主要内容包括：本发明涉及化合物、液晶组合物、液晶显示元件及液晶显示器。所述化合物为下述的式I所示的化合物。本发明的液晶组合物含有式I所示的化合物。本发明提供的式I所示化合物具有与其他化合物互溶性好、紫外线耐受能力好等优点。作为反应性介晶(RM)具有互溶性良好、电荷保持率(VHR)高、聚合活性高(单体残留少)等优点,不仅可以单独作为液晶组合物的自配向剂,也可以于作为垂直配向材料与其他RM共聚用于PSA(聚合物支持的配向)、PS(聚合物稳定的)型模式的液晶组合物的自配向剂,可以避免PI制程,使液晶显示元件或液晶显示器的制程得到简化,提高生产效率。<Image he="115" wi="558" file="DDA0001754385020000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention relates to a compound, a liquid crystal composition, a liquid crystal display element and a liquid crystal display. The compound is shown in the formula I. The liquid crystal composition contains a compound shown in a formula I. The compound shown in the formula I has the advantages of good intersolubility with other compounds, good ultraviolet ray tolerance and the like. The Reactive Mesogen (RM) has the advantages of good intersolubility, high charge retention rate (VHR), high polymerization activity (less monomer residue) and the like, and not onlyThe self-aligning agent can be used as the self-aligning agent of the liquid crystal composition alone or used as a vertical alignment material and other RM copolymerized for the liquid crystal composition of PSA (polymer supported alignment) and PS (polymer stabilized) modes, can avoid PI (polyimide) process, simplifies the process of a liquid crystal display element or a liquid crystal display and improves the production efficiency.)

1. A compound of formula I:

wherein R is₀Represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, and R is₀Any one or more of the radicals indicated being unconnected-CH₂-may each independently be replaced by-O-or cycloalkylene;

q represents 1, 2 or 3;

K₁、K₂each independently represents an aromatic ring, a heteroaromatic ring, an aliphatic ring, a fused ring, a spiro ring or a bridged ring, any of which-CH₂Optionally substituted by-O-, -S-, K₁、K₂Optionally one or more H on the ring of (a) is substituted by L or-Sp¹-P₅Substitution;

l represents F, -Sp²-X₁An alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, and any of-CH₂-optionally substituted by cyclopentylene, cyclobutyl, cyclopropylene;

P₅represents H or a polymerizable group;

Sp¹、Sp²each independently representA single bond or a spacer;

X₁each independently represents an alkyl-substituted sulfone having 1 to 10 carbon atoms, a cyclic sulfone, an alkyl-substituted sulfoxide having 1 to 10 carbon atoms, or a cyclic sulfoxide; hydroxy, ester, carbonyl or mercapto, at least one of which is X₁Represents an alkyl-substituted sulfone or cyclic sulfone having 1 to 10 carbon atoms; C1-C10 alkyl substituted sulfoxide or cyclic sulfoxide; any one H in said alkyl group being optionally substituted by F, any one or more unconnected-CH₂-optionally substituted by-O-, -S-;

Z₀represents a single bond, -O-, -S-, -CO-, -COO-, -OCO-, -OCOO-, -OCH₂-、-CH₂O-、-SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂-、-(CH₂)n₁-、-CF₂CH₂-、-CH₂CF₂-、-(CF₂)n₂-、-CH＝CH-、-C≡C-、-CF＝CF-、-CH＝CH-COO-、-OCO-CH＝CH-、-(CR_YR_Z)n₃-、-CH(-Sp-P₆)-、-CH₂CH(-Sp-P₆) -, or, -CH (-Sp-P)₆)CH(-Sp-P₆)-；

n₁、n₂、n₃Each independently represents 1, 2, 3 or 4;

R_Y、R_Zeach independently represents H or an alkyl group having 1 to 5 carbon atoms, and R_Y、R_ZAt least one of which is an alkyl group having 1 to 5 carbon atoms;

sp represents a single bond or a spacer;

P₆represents H or a polymerizable group;

R_xrepresents (a), (b) or (c):

m₁represents 1, 2, 3 or 4;

Sp³、Sp⁴、Sp⁵each independently represents a single bond or a spacer;

P₄represents H or a polymerizable group;

L₁represents F, -Sp³-X₂An alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, and any of-CH₂-optionally substituted by cyclopentylene, cyclobutyl, cyclopropylene;

X₂each independently represents an alkyl-substituted sulfone having 1 to 10 carbon atoms, a cyclic sulfone, an alkyl-substituted sulfoxide having 1 to 10 carbon atoms, or a cyclic sulfoxide; hydroxy, ester, carbonyl or mercapto, at least one of which is X₁Represents an alkyl-substituted sulfone or cyclic sulfone having 1 to 10 carbon atoms; C1-C10 alkyl substituted sulfoxide or cyclic sulfoxide; any one H in said alkyl group being optionally substituted by F, any one or more unconnected-CH₂-optionally substituted by-O-, -S-;

S¹represents a trivalent radical, S²Represents a tetravalent group.

2. The compound of claim 1, selected from the group consisting of compounds represented by formula I1 to formula I37,

3. a liquid crystal composition comprising one or more compounds of claim 1 or claim 2.

4. The liquid crystal composition according to claim 3, further comprising one or more compounds represented by the following formula II and one or more compounds represented by the following formula III,

in the formula II, R₁、R₂Each independently represents a carbon atomA sub-number of 1 to 10 of an alkyl group, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, a carbon-1 to 10 alkoxy group, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, a carbon-2 to 10 alkenyl group, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, a carbon-3 to 8 alkenyloxy group or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms,

In the formula III, R₃、R₄Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, and R₃、R₄Any one or more of unconnected-CH₂Optionally substituted by cyclopentylene, cyclobutyl or cyclopropylene,

Z₁、Z₂each independently represents a single bond, -CH₂CH₂-or-CH₂O-，

m represents 1 or 2; n represents 0, 1 or 2.

5. The liquid crystal composition of claim 4, wherein the one or more compounds of formula II are selected from the group consisting of compounds of formulae II 1-II 14; the one or more compounds shown in the formula III are selected from compounds shown in formulas III 1-III 11;

in the formulae III1 to III11, R₃、R₄Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, and R₃、R₄Any one or more of unconnected-CH₂-optionally substituted by cyclopentylene, cyclobutyl or cyclopropylene.

6. The liquid crystal composition according to any one of claims 3 to 5, wherein the liquid crystal composition is a negative dielectric anisotropy liquid crystal composition further comprising one or more compounds represented by formula IV,

wherein R is₅、R₆Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a substituted alkyl group having 1 to 10 carbon atoms, a substituted alkoxy group having a fluorine-substituted alkyl group having a fluorine-,A fluorine-substituted alkenyl group having 2 to 10 carbon atoms, a carbon-3-8 alkenyloxy group or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, and R₅、R₆Any one of-CH₂-optionally substituted by cyclopentylene, cyclobutyl or cyclopropylene; w represents-O-, -S-or-CH₂O-。

7. The liquid crystal composition of any one of claims 3 to 6, wherein the liquid crystal composition is a negative dielectric anisotropy liquid crystal composition, and further comprises one or more compounds represented by formula V,

wherein R is₇、R₈Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms;

8. The liquid crystal composition of any one of claims 3 to 7, further comprising one or more compounds of formula VI,

9. A liquid crystal display element or a liquid crystal display comprising the compound of claim 1 or 2, or the liquid crystal composition of any one of claims 3 to 8, which is an active matrix display element or a display or a passive matrix display element or a display.

10. The liquid crystal display element or the liquid crystal display according to claim 9, characterized in that: the active matrix display element or the active matrix display is a PSVA-TFT liquid crystal display element or a PSVA-TFT liquid crystal display without a PI alignment layer.

Technical Field

The invention belongs to the technical field of liquid crystal display, and particularly relates to a compound, a liquid crystal composition containing the compound, and a liquid crystal display element or a liquid crystal display containing the compound or the liquid crystal composition.

Background

The liquid crystal medium used for display elements of active matrix addressing type such as VA mode is not perfect, and for example, the image sticking level is significantly inferior to that of display elements of positive dielectric anisotropy, and the liquid crystal medium has disadvantages of relatively slow response time, relatively high driving voltage, and the like. At this time, some of the novel VA display technologies are silent but are still living: the PSVA technology realizes a wide-field-angle display mode similar to MVA/PVA, and simplifies the CF process, thereby reducing the CF cost, improving the aperture opening ratio, obtaining higher brightness and further obtaining higher contrast. In addition, because the liquid crystal of the whole surface has the pretilt angle and does not have domino delay phenomenon, the liquid crystal can obtain faster response time under the condition of keeping the same driving voltage, and the afterimage level can not be influenced. Like UVVA technique, on the basis of keeping PSVA technical advantage, because do not have Slit structure on TFT side, the uneven problem of display that the uneven pixel electrode width arouses has still been improved. Despite the continuous development of display devices, there is a continuing effort to develop new liquid-crystalline compounds which lead to a continuous development of liquid-crystalline media and their properties for use in display devices.

The polymerizable mesogenic unit (RMs) is currently a very popular and important topic in the display industry, and the possible applications include Polymer Sustained Alignment (PSA) liquid crystal display, polymer sustained blue phase (PS-BP) liquid crystal display, and patterned Retarder Film (Pattern recorder Film).

The PSA principle is being applied in different typical LC displays, such as PSA-VA, PSA-OCB, PS-IPS/FFS and PS-TN liquid crystal displays. Taking the PSA-VA display, which is currently most widely used, as an example, the pretilt angle of the liquid crystal cell can be obtained by the PSA method, which has a positive effect on the response time. For PSA-VA displays, standard MVA or PVA pixel and electrode designs can be used, but if the electrode design on one side is specially patterned and the other side is not raised, the production can be significantly simplified, while achieving very good contrast and very high light transmission of the display.

Disclosure of Invention

The invention provides a compound capable of realizing a self-alignment function, a liquid crystal composition containing the compound, a liquid crystal display element or a liquid crystal display comprising the compound or the liquid crystal composition, and a PSVA liquid crystal composition especially suitable for display or TV application.

The compound has the advantages of good intersolubility with other compounds and good ultraviolet ray tolerance. The Reactive Mesogen (RM) has the advantages of high charge retention rate (VHR) and high polymerization activity (less monomer residue), can be used as a self-alignment agent of the liquid crystal composition alone, can also be used as a self-alignment agent of a vertical alignment material copolymerized with other RMs and used for liquid crystal compositions in PSA and PS modes, can avoid a PI process and improve the production efficiency.

The liquid crystal composition contains one or more compounds shown in the formula I, a layer of polymer with rough surface is spontaneously formed through polymerization of the compounds shown in the formula I, the effects of PI insulation and vertical alignment of liquid crystal molecules can be achieved, the PI manufacturing process can be avoided, the manufacturing process of a liquid crystal display element or a liquid crystal display is simplified, and the production efficiency is improved. In addition, the liquid crystal composition has lower viscosity, can realize quick response, and simultaneously has moderate dielectric anisotropy delta epsilon, moderate optical anisotropy delta n and high stability to heat and light. The liquid crystal display element or the liquid crystal display comprising the liquid crystal composition has the properties of wide nematic phase temperature range, proper or higher birefringence anisotropy delta n, very high resistivity, good ultraviolet resistance, high charge retention rate, low vapor pressure and the like.

In order to achieve the above object, the present invention provides a compound represented by the following formula I:

wherein R is₀Represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, and R is₀Any one or more of the radicals indicated being unconnected-CH₂-may each independently be replaced by-O-or cycloalkylene;

examples of the cycloalkylene group include a cyclopentylene group, a cyclobutyl group and a cyclopropylene group, that is, a cycloalkylene group having 3 to 5 carbon atoms;

q represents 1, 2 or 3;

K₁、K₂each independently represents an aromatic ring, a heteroaromatic ring, an aliphatic ring, a condensed ring, a spiro ring or a bridged ring, any of which is-CH₂-optionally substituted by-O-, -S-, one or more H on the ring optionally being replaced by L or-Sp¹-P₅Substitution;

l represents F, -Sp²-X₁Alkyl group having 1 to 10 carbon atoms, fluorine-substituted alkyl group having 1 to 10 carbon atomsA group which is a group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, and any of-CH₂-may be replaced by cyclopentylene, cyclobutyl, cyclopropylene;

P₅represents H or a polymerizable group;

Sp¹、Sp²each independently represents a single bond or a spacer;

X₁each independently represents an alkyl-substituted sulfone having 1 to 10 carbon atoms, a cyclic sulfone, an alkyl-substituted sulfoxide having 1 to 10 carbon atoms, a cyclic sulfoxide, a hydroxyl group, an ester group, a carbonyl group or a mercapto group, wherein at least one X₁Represents an alkyl-substituted sulfone having 1 to 10 carbon atoms, a cyclic sulfone, an alkyl-substituted sulfoxide having 1 to 10 carbon atoms or a cyclic sulfoxide; wherein any H in said alkyl as a substituent is optionally substituted by F, any one or more unconnected-CH₂-optionally substituted by-O-, -S-;

Z₀represents a single bond, -O-, -S-, -CO-, -COO-, -OCO-, -OCOO-, -OCH₂-、-CH₂O-、-SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂-、-(CH₂)n₁-、-CF₂CH₂-、-CH₂CF₂-、-(CF₂)n₂-、-CH＝CH-、-C≡C-、-CF＝CF-、-CH＝CH-COO-、-OCO-CH＝CH-、-(CR_YR_Z)n₃-、-CH(-Sp-P₆)-、-CH₂CH(-Sp-P₆)-、-CH(-Sp-P₆)CH(-Sp-P₆)-，

n₁、n₂、n₃Each independently represents 1, 2, 3 or 4;

R_Y、R_Zeach independently represents H or an alkyl group having 1 to 5 carbon atoms, and at least one is an alkyl group having 1 to 5 carbon atoms;

sp represents a single bond or a spacer;

P₆represents H or a polymerizable group;

R_xrepresents (a), (b) or (c):

m₁represents 1, 2, 3 or 4;

represents an aromatic, aliphatic or fused ring, any of which is-CH₂-optionally substituted by-O-, -S-, one or more H on the ring optionally being replaced by L₁or-Sp⁵-P₄Substitution;

Sp³、Sp⁴、Sp⁵each independently represents a single bond or a spacer;

P₄represents H or a polymerizable group;

L₁represents F, -Sp³-X₂An alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, and any of-CH₂-optionally substituted by cyclopentyl, cyclobutyl, cyclopropyl;

X₂each independently represents an alkyl-substituted sulfone having 1 to 10 carbon atoms, a cyclic sulfone, an alkyl-substituted sulfoxide having 1 to 10 carbon atoms, or a cyclic sulfoxide; hydroxy, ester, carbonyl or mercapto, at least one of which is X₁Represents an alkyl-substituted sulfone or cyclic sulfone having 1 to 10 carbon atoms; C1-C10 alkyl substituted sulfoxide or cyclic sulfoxide; any one H in said alkyl group being optionally substituted by F, any one or more unconnected-CH₂-optionally substituted by-O-, -S-;

S¹represents a trivalent radical, S²Represents a tetravalent group;

as the trivalent group, S may be mentioned¹Represents the case of a trivalent group of carbon or silicon; as the tetravalent group, S may be mentioned²Represents the case of a tetravalent group of phosphorus.

The compound shown in the formula I has better solubility in the liquid crystal composition, the adding amount of the compound in the liquid crystal composition is generally between 0.5 and 5 percent, preferably between 1 and 2 percent, and the compound shown in the formula I is easy to absorb UV and is polymerized rapidly to form a polymer with an alignment function.

X₁、X₂Denotes an anchor group, X₁、X₂Each independently represents an alkyl-substituted sulfone having 1 to 10 carbon atoms, a cyclic sulfone, an alkyl-substituted sulfoxide having 1 to 10 carbon atoms, or a cyclic sulfoxide; hydroxyl, ester, carbonyl; wherein at least one X₁、X₂Represents an alkyl-substituted sulfone having 1 to 10 carbon atoms, a cyclic sulfone, an alkyl-substituted sulfoxide having 1 to 10 carbon atoms or a cyclic sulfoxide. After the liquid crystal composition is subjected to an ODF process, the compound shown in the formula I is spontaneously and vertically arranged on the surface of a panel (glass surface, ITO or polyimide), and a stable pretilt angle is formed after UV illumination polymerization under the condition of voltage application.

Anchoring group X₁、X₂Each independently is preferably selected from the group consisting of:

P₄、P₅、P₆when representing a polymerizable group, a methacrylate group, an acrylate group, a vinyl group or an ethylene oxide group is preferable.

The "spacer" in the present invention means a chain-like group, preferably a branched or straight-chain alkyl group having 1 to 10 carbon atoms, wherein-CH is optionally disconnected in the alkyl group₂-optionally substituted by-O-, optionally-CH₂-optionally substituted by cyclopropylene, cyclobutylene or cyclopentylene.

K₁、K₂Each independently represents an aromatic ring, a heteroaromatic ring, an aliphatic ring, or a fused ringA ring, spiro or bridged ring, any of which is-CH₂-optionally substituted by-O-, -S-, one or more H on the ring optionally being replaced by L or-Sp¹-a P substitution. The aromatic ring is preferably a benzene ring or a naphthalene ring; the heteroaromatic ring is preferably a benzene or naphthalene ring in which at least one-CH-is substituted by-N-; the aliphatic ring is preferably cyclohexane, cyclohexene, at least one-CH₂Cyclohexane substituted by-O-or-S-, and at least one-CH₂-cyclohexene substituted by-O-or-S-; fused rings are preferably indane, indene, indane substituted by-O-or-S-, and indene substituted by-O-or-S-; the spiro ring or bridged ring is preferably bicyclo (1,1,1) pentane, bicyclo (2,2,2) octane, bicyclo (3,3,0) octane, spiro (3,3) heptane, decahydronaphthalene or tetrahydronaphthalene, etc.

Optionally, the compound of formula I is selected from the group consisting of compounds of formula I1 through formula I37, described below.

The invention also provides a liquid crystal composition which comprises one or more compounds shown in the formula I.

Optionally, the liquid crystal composition of the present invention may further comprise one or more compounds of formula II, and one or more compounds of formula III,

in the formula II, R₁、R₂Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms,

each independently represent

In the formula III, R₃、R₄Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, and R₃、R₄Any one or more of unconnected-CH₂Optionally substituted by cyclopentylene, cyclobutyl or cyclopropylene,

Z₁、Z₂each independently represents a single bond, -CH₂CH₂-or-CH₂O-，

Each independently represent

m represents 1 or 2; n represents 0, 1 or 2.

Optionally, the one or more compounds represented by formula II are selected from compounds represented by formulas II 1-II 14; the one or more compounds shown in the formula III are selected from compounds shown in formulas III 1-III 11;

in the formulae III1 to III11, R₃、R₄Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, and R₃、R₄Any one or more of unconnected-CH₂-may be replaced by cyclopentylene, cyclobutyl or cyclopropylene.

In the liquid crystal composition, in the compound shown in the formula I, X₁、X₂The anchor functional group, X₁、X₂Each independently an anchoring functional group having a sulfone or sulfoxide structure, or an anchoring functional group which may be a hydroxyl, carbonyl or ester structure. After the panel is processed by the ODF process, due to the acting force between the anchoring functional group and the molecules on the surface of the panel (glass surface, ITO electrode surface), the liquid crystal molecules close to the compound shown in the formula I are spontaneously vertically arranged on the upper surface of the panel glass or the ITO transparent electrode substrate, so that the liquid crystal molecules are vertically arranged. Under the irradiation of UV light, the compound shown in the formula I can be polymerized on a substrate to form a layer of polymer with rough surface, and the effect of insulating PI and vertically aligning liquid crystal molecules is achieved. The thickness of PI is usually 50nm to 120nm, and the amount of the compound represented by formula I added is preferably 1% or more in order to form a thin film having a thickness equivalent to that of PI after polymerization of the compound represented by formula I. In this case, the compound of the formula I is added in a relatively large amount, and therefore, a high demand is placed on its storage stability at low temperatures.

Since hydroxyl groups are likely to form hydrogen bonds and have a strong anchoring ability, however, since hydrogen atoms of hydroxyl groups are almost exposed protons, excessive use of the liquid crystal composition tends to cause a drop in VHR of the liquid crystal composition after heat and UV irradiation, which adversely affects the display effect of a liquid crystal display element or a liquid crystal display, for example, a problem of display afterimage of the liquid crystal display. The compound shown in the formula I provided by the invention uses less or no hydroxyl functional group as an anchoring functional group, but uses a functional group with a more stable sulfone or sulfoxide structure and a hydroxyl group or other functional groups (ester group and carbonyl group) with anchoring effect to be combined as the anchoring functional group of the compound shown in the formula I, so that the liquid crystal composition can show better stability to heat and UV, and VHR is kept from being reduced.

The compound shown in the formula I has the advantages of good intersolubility with other compounds, good ultraviolet ray tolerance and the like. The Reactive Mesogen (RM) has the advantages of good intersolubility, high charge retention rate (VHR), high polymerization activity (little monomer residue) and the like, can be used as a self-alignment agent of a liquid crystal composition independently, and can also be used as a self-alignment agent of a liquid crystal composition for copolymerization of a vertical alignment material and other RMs and used for PSA (polymer-supported alignment) and PS (polymer-stabilized) mode liquid crystal compositions, so that a PI (polyimide) process can be avoided, the process of a liquid crystal display element or a liquid crystal display is simplified, and the production efficiency is improved.

In addition, a liquid crystal composition or an optically anisotropic body of a liquid crystal composition comprising a compound represented by formula I also belongs to the protection scope of the present invention:

the compounds shown in the formula I have slightly different solubility in the liquid crystal composition due to different substituents, but can be added into the liquid crystal composition in an amount of 0.5-5% by mass. Since a certain thickness of the polymer formed by the compound of formula I is necessary to function as an insulator for PI, the compound of formula I should have sufficient solubility.

The compound shown in the formula I can be added into the liquid crystal composition in an amount of 0.5-5 wt%, preferably 1-3 wt%.

The amount (mass percentage) of the compound represented by the formula II added to the liquid crystal composition may be 15 to 60%, preferably 20 to 40%.

The amount (mass percentage) of the compound represented by the formula III added to the liquid crystal composition may be 20 to 60%, preferably 30 to 50%.

Optionally, the liquid crystal composition of the invention can also comprise one or more compounds shown as a formula IV

Wherein R is₅、R₆Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, and R₅、R₆Any one of-CH₂-may be replaced by cyclopentylene, cyclobutyl or cyclopropylene; w represents-O-, -S-or-CH₂O-。

Optionally, the one or more compounds of formula iv are selected from the group consisting of compounds of formulae iv 1-iv 6:

wherein R is₆₁Represents an alkyl group having 2 to 6 carbon atoms.

The amount (mass percentage) of the compound represented by the formula IV added to the liquid crystal composition may be 1 to 15%, preferably 2 to 10%.

Optionally, the liquid crystal composition of the invention may further comprise one or more compounds represented by formula V

Wherein R is₇、R₈Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms;

each independently represent

Optionally, the one or more compounds of formula v are selected from the group consisting of compounds of formulae v 1-v 4:

wherein R is₇₁、R₈₁Each independently represents an alkyl group having 2 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms; r₈₂Represents an alkoxy group having 1 to 5 carbon atoms; among them, examples of the alkenyl group having 2 to 6 carbon atoms include a vinyl group, a 2-propenyl group, or a 3-pentenyl group.

The amount (mass%) of the compound represented by the formula V added to the liquid crystal composition may be 1 to 40%, preferably 5 to 30%.

Optionally, the liquid crystal composition of the invention may further comprise one or more polymerizable compounds of formula VI,

each independently represent

P₁、P₂、P₃Each independently represents a methacrylate group or an acrylate group.

Optionally, the one or more compounds of formula VI are selected from the group consisting of compounds of formulae VI 1-VI 3:

the compounds of formula VI are slightly less sensitive to UV and polymerize at a slower rate than the compounds of formula I, and are relatively superficial when the polymer is actually formed. When the compound shown in the formula VI and the compound shown in the formula I are added for copolymerization, the display effect can be improved, the polymer layer provides continuous and stable pretilt, and the pretilt of liquid crystal molecules is very favorable for improving the response speed of liquid crystals under an electric field. In the case of copolymerization of the compound of the formula VI with the compound of the formula I, the compound of the formula VI may be added in an amount of 0.1 to 1% by mass, preferably 0.2 to 0.5% by mass.

The liquid crystal composition of the present invention does not contain a particular amount of the componentsMeanwhile, the liquid crystal composition shows slightly different properties such as dielectric anisotropy Delta epsilon, optical anisotropy Delta n, transition temperature point Cp of a nematic phase of liquid crystal converted into liquid and stability at low temperature, but has the same characteristic that the rotational viscosity gamma₁Lower. The liquid crystal display device can realize quick response. The liquid crystal composition has high stability to heat and light. The liquid crystal display element or the liquid crystal display comprising the liquid crystal composition has the properties of wide nematic phase temperature range, proper or higher birefringence anisotropy delta n, very high resistivity, good ultraviolet resistance, high charge retention rate, low vapor pressure and the like. PSVA liquid crystal compositions suitable for display or TV applications, in particular after long run, have no or significantly reduced image sticking.

The liquid crystal composition of the present invention may further comprise various functional dopants, preferably in an amount of 0.01 to 1% by mass, and the dopants are mainly antioxidants, ultraviolet absorbers, and chiral agents.

Examples of the antioxidant and ultraviolet absorber include:

s represents an integer of 1 to 10.

The invention also provides a liquid crystal display element or a liquid crystal display comprising any one of the liquid crystal compounds or the liquid crystal composition; the display element or display is an active matrix display element or display or a passive matrix display element or display.

Optionally, the liquid crystal display element or liquid crystal display is preferably an active matrix addressed liquid crystal display element or liquid crystal display.

Optionally, the active matrix display element or display is a PSVA-TFT liquid crystal display element or display without a PI alignment layer.

Drawings

FIG. 1 is a mass spectrum of compound I37.

Detailed Description

The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.

The progress of the reaction is generally monitored by TLC, and the post-treatment after the completion of the reaction is generally water washing, extraction, combination of organic phases, drying, evaporation of the solvent under reduced pressure, recrystallization, and column chromatography, and those skilled in the art can implement the present invention as described below.

The percentages in the specification are mass percentages, the temperature is centigrade (DEG C), and the specific meanings and test conditions of other symbols are as follows:

cp represents a liquid crystal clearing point (DEG C), and is measured by a DSC quantitative method;

Δ n represents optical anisotropy, and Δ n ═ n_e-n_o，n_oRefractive index of ordinary light, n_eThe refractive index of the extraordinary ray is measured under the conditions of 25 +/-2 ℃ and 589nm, and the Abbe refractometer is used for testing;

Δ ε represents dielectric anisotropy, and Δ ε_∥-ε_⊥Wherein, epsilon_∥Is a dielectric constant parallel to the molecular axis,. epsilon_⊥Dielectric constant perpendicular to the molecular axis, at 25 + -0.5 deg.C, 20 μm parallel box, INSTEC: ALCT-IR1 test;

γ 1 represents rotational viscosity (mPa. multidot.s) at 25. + -. 0.5 ℃ in a 20 μm parallel cell INSTEC: ALCT-IR1 test;

VHR represents the voltage holding ratio (%), and the test conditions are 20 +/-2 ℃, voltage +/-5V, pulse width 10ms and voltage holding time 16.7 ms. The testing equipment is a TOYO Model6254 liquid crystal performance comprehensive tester.

The preparation method of the liquid crystal composition comprises the following steps: weighing each liquid crystal monomer according to a certain proportion, putting the liquid crystal monomers into a stainless steel beaker, putting the stainless steel beaker filled with each liquid crystal monomer on a magnetic stirring instrument for heating and melting, adding a magnetic rotor into the stainless steel beaker after most of the liquid crystal monomers in the stainless steel beaker are melted, uniformly stirring the mixture, and cooling to room temperature to obtain the liquid crystal composition.

The liquid crystal monomer structure of the embodiment of the invention is represented by codes, and the code representation methods of the liquid crystal ring structure, the end group and the connecting group are shown in the following table (I) and table (II).

Table (one): corresponding code of ring structure

Table (ii): corresponding codes for end groups and linking groups

Examples are:

the compounds of formula I can be prepared by the following schematic synthetic route:

the first scheme is as follows: chain (sulfoxide) sulfone structure without polymerizable functional group

Scheme II: chain (sulfoxide) sulfone structure containing one polymerizable functional group

The third scheme is as follows: cyclic sulfone structure containing two polymerizable functional groups

And the scheme is as follows: bis (sulfoxide) sulfone structure containing two polymerizable functional groups

And a fifth scheme: alcohol + (sulfoxide) structure containing two polymerizable functional groups

Scheme six: bis-alcohol + (ene) sulfone structure containing two polymerizable functional groups

Wherein k represents 0 to 20; j represents 1 or 2; r_iRepresents an alkyl or alkenyl group of 1 to 10 carbon atoms, wherein any hydrogen may be substituted by fluorine, and any one methylene group or a plurality of methylene groups not directly connected may be substituted by oxygen;

represents 1, 4-cyclohexylene or 1, 4-cyclohexylene in which any methylene group or methylene groups not directly connected are replaced by oxygen, 1, 4-phenylene, and H in the 1, 4-phenylene may be replaced by L_iSubstitution; l is_iRepresents H, or an alkyl, branched alkyl, cycloalkyl, alkenyl group having 1 to 20 carbon atoms, wherein any one methylene group or a plurality of methylene groups not directly connected are optionally replaced by oxygen, and any hydrogen atom is optionally substituted by fluorine.