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 梁志安 王国芳 王会芳 张兴 温刚 舒克伦 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="250" wi="700" file="DDA0001754382970000011.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 as the formula IThe compounds shown are shown. 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 (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.)

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 any one of-CH₂-optionally substituted by cycloalkylene; any one or more unconnected-CH₂-optionally substituted by-O-;

q represents 1, 2 or 3; r represents 0, 1, 2 or 3;

K₁represents an aromatic ring, a heteroaromatic ring, an aliphatic ring or a condensed ring, wherein any one of-CH's on the ring₂-optionally substituted by-O-, -S-; k₁One or more of H in (a) is optionally substituted by L₁Substitution;

L、L₁each independently represents-Sp¹-P₄、-Sp²-X₁F, C1-10 alkyl, fluorine-substituted C1-10 alkylAn 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 L, L₁Any one of-CH₂-optionally substituted by cyclopentylene, cyclobutyl, cyclopropylene;

P₄represents H or a polymerizable group;

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

X₁represents a hydroxyl group, an ester group or a carbonyl group;

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-P₅)-、-CH₂CH(-Sp-P₅) -, or, -CH (-Sp-P)₅)CH(-Sp-P₅)-；

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;

P₅represents H or a polymerizable group;

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

m₁represents 1, 2, 3 or 4;

Sp³、Sp⁴each independently represents a single bond or a spacer;

X₂represents a hydroxyl group, an ester group or a carbonyl group;

L₂represents-Sp³-X₂F, an alkyl group having 1 to 10 carbon atoms, 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, and any of-CH₂-optionally substituted by cyclopentylene, cyclobutyl, cyclopropylene;

S¹represents a trivalent radical, S²Represents a tetravalent group.

2. The compound of claim 1, wherein the compound of formula I is selected from the group consisting of compounds of formula I1 through formula I21,

3. a liquid crystal composition comprising one or more compounds of claim 1 or 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 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-CH₂-optionally 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 of formula III are selected from the group consisting of compounds of formulae 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 of any one of claims 3 to 5, wherein the liquid crystal composition is a negative dielectric anisotropy liquid crystal composition, and the liquid crystal composition further comprises 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 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 or more 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. A liquid-crystalline composition according to any one of claims 3 to 5, further comprising one or more polymerizable compounds of the formula VI,

P₁、P₂、P₃each independently represents a methacrylate group or an acrylate group.

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; the display element or display is an active matrix display element or display or a passive matrix display element or 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 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 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 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 specifically provides the following compounds 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 any one of-CH₂-optionally substituted by cycloalkylene; any one or more unconnected-CH₂-optionally substituted by-O-;

as the cycloalkylene group, a cyclopentylene group, a cyclobutyl group or a cyclopropylene group;

q represents 1, 2 or 3; r represents 0, 1, 2 or 3;

K₁represents an aromatic, heteroaromatic, aliphatic or condensed ring wherein any of-CH's on the ring₂-optionally substituted by-O-, -S-; k₁One or more of H in (a) is optionally substituted by L₁Substitution;

L、L₁each independently represents-Sp¹-P₄、-Sp²-X₁F, 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 alkenyl group having 3 to 8 carbon atomsAn alkoxy group or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, and any one of CH₂Optionally substituted with cyclopentylene, cyclobutyl, cyclopropylene;

P₄represents H or a polymerizable group,

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

X₁represents a hydroxyl group, an ester group or a carbonyl group;

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-P₅)-、-CH₂CH(-Sp-P₅) -, or, -CH (-Sp-P)₅)CH(-Sp-P₅)-；

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;

P₅represents H or a polymerizable group;

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

m₁represents 1, 2, 3 or 4;

represents an aromatic ring, an aliphatic ring or a condensed ring, wherein any of-CH's on the ring₂-is optionally substituted by-O-, -S-substitution;

one or more of H in (a) is optionally substituted by L₂Substitution;

Sp³、Sp⁴each independently represents a single bond or a spacer;

X₂represents a hydroxyl group, an ester group or a carbonyl group;

L₂represents-Sp³-X₂F, an alkyl group having 1 to 10 carbon atoms, 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, and any of-CH₂-optionally substituted by cyclopentyl, cyclobutyl, cyclopropyl;

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, and when the addition amount of the compound in the liquid crystal composition is generally between 0.5 and 5 percent, preferably between 1 and 2 percent, and is in the range, the compound is easy to absorb UV and is rapidly polymerized to form a polymer with an alignment function.

The compounds of the formula I having an anchoring group X₁、X₂，X₁、X₂Selected from hydroxyl, ester or carbonyl groups, preferably hydroxyl. 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 or ITO or polyimide), and a stable pretilt angle is formed after UV illumination polymerization under the condition of voltage application.

P₄、P₅When representing a polymerizable group, a methacrylate group, an acrylate group, a vinyl group or an ethylene oxide group is preferable.

The spacer represents a chain-like group, preferably a branched or straight-chain alkyl group having 1 to 10 carbon atoms, and optionally-CH in the alkyl group₂-optionally substituted by-O-, optionally-CH₂-optionally substituted by cyclopropylene, cyclobutylene or cyclopentylene.

K₁Represents an aromatic, heteroaromatic, aliphatic or condensed ring, any of which is-CH₂-optionally substituted by-O-, -S-; k₁One or more of H in (a) is optionally substituted by L₁And (4) substitution. The aromatic ring is preferably a benzene ring or a naphthalene ring, the heteroaromatic ring is preferably a benzene ring or a naphthalene ring in which at least one-CH-is substituted by-N-, and the aliphatic ring is preferably cyclohexane or cyclohexene, at least one-CH₂-cyclohexane substituted by-O-or-S-, and, at least one-CH₂Cyclohexene, K substituted by-O-or-S-₁It may also represent a spiro ring or bridged ring, preferably bicyclo (1,1,1) pentane, bicyclo (2,2,2) octane, bicyclo (3,3,0) octane, spiro (3,3) heptane, decahydronaphthalene, tetrahydronaphthalene, etc. The fused ring is preferably an indane ring, an indene ring, an indane ring in which at least one C on the ring is replaced by-O-or-S-, and an indene ring in which at least one C on the ring is replaced by-O-or-S-.

Anchoring group X₁preferably-OH.

R_xPreferably:

optionally, the compound of formula I is selected from the group consisting of compounds of formula I1 through formula I21, 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 invention may further comprise one or more compounds represented by formula II, and one or more compounds represented by 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-CH₂-optionally substituted by cyclopentylene, cyclobutyl or cyclopropylene;

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

Each of which isIndependently represent

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

Optionally, 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 of formula III are selected from the group consisting of compounds of formulae III1 to III11,

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.

In the liquid crystal composition, in the compound shown in the formula I, X₁、X₂The anchor functional group, X₁、X₂Independently, the functional group is an anchoring functional group with a hydroxyl, carbonyl or ester structure, and after the panel ODF manufacturing process, the anchoring functional group can be spontaneously vertically arranged on the panel glass due to the intermolecular force between the anchoring functional group and the panel surface (glass surface, ITO electrode surface)Or the upper surface of the ITO transparent electrode substrate promotes the liquid crystal molecules close to the compound shown in the formula I to be vertically arranged, and under the irradiation of UV light, the compound shown in the formula I can be polymerized on the substrate to form a layer of polymer with rough surface, thereby playing the roles of insulating PI and vertically aligning the liquid crystal molecules. 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.

The compound of the formula I provided by the invention is used as a Reactive Mesogen (RM), a cinnamic acid structure is used as a main structure of the compound, and the cinnamic acid structure has a polymerizable function, so that no polymerizable functional group is required or less additional polymerizable functional groups are added, the synthesis process is simple, the cost is low, and the molecular structure of the compound is simple. In addition, as the cinnamic acid structure has the function of lengthening the molecular length, compared with the existing RM, one ring structure is reduced, so that the synthesis route is simpler, the molecular weight is smaller, and the low-temperature storage property is better.

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 mixture which is used for the copolymerization of a vertical alignment material and RM and is used for PSA (polymer-supported alignment) and PS (polymer-stabilized) mode, so that the PI 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 containing the compound shown in the formula I or an optical anisotropic body of the liquid crystal composition also belongs to the protection scope of the invention.

The solubility of the compound of formula I in liquid crystal is slightly different due to different substituents, but the addition amount of 0.5-5% by mass in the liquid crystal composition can be realized. 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 of formula I may be added to the liquid crystal composition in an amount (mass%) of 0.5% to 5%, preferably 1% to 3%.

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、R₆In any of-CH₂-optionally substituted 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 represents a 1, 4-phenylene group, a 1, 4-cyclohexylene group or a 1, 4-cyclohexenylene group.

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 and a 3-pentenyl group.

The amount (mass percentage) 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 represents phenylene, fluorinated phenylene or indanyl;

P₁、P₂、P₃each independently represents a methacrylate group or an acrylate group.

Optionally, one or more of the compounds of formula VI above is 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. When the compound shown in the formula VI is added to be copolymerized with the compound shown in the formula I, the compound shown in the formula VI can be added in an amount of 0.1-1% by mass, and preferably 0.2-0.5% by mass.

The liquid crystal composition of the present invention shows slightly different properties such as dielectric anisotropy Δ ∈, optical anisotropy Δ n, transition temperature point CP of liquid crystal from nematic phase to liquid, and stability at low temperature according to different proportions of the components, but has the same characteristic that rotational viscosity γ thereof is different₁Lower. 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 compound provided by the invention can also be added with dopants with various functions, the content of the dopants is preferably 0.01-1% by mass, and the dopants can be an antioxidant, an ultraviolet absorbent and a chiral agent.

Examples of the antioxidant and ultraviolet absorber include:

s represents an integer of 1 to 10.

The invention also relates to a liquid crystal display element or a liquid crystal display comprising any one of the liquid crystal compositions; 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.

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;

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 expressed by codes, and the code expression methods of the liquid crystal ring structure, the end group and the connecting group are shown in the following tables (I) and (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:

when L is a polymerizable group:

for the product obtained by the above illustrative synthetic route, the reaction product was precipitated as a solid by adding ice water and the obtained product was determined by HPLC.