CN107267156B - Liquid crystal composition and application thereof - Google Patents
Liquid crystal composition and application thereof Download PDFInfo
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- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
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- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
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- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
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- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
- C09K19/3405—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a five-membered ring
- C09K2019/3408—Five-membered ring with oxygen(s) in fused, bridged or spiro ring systems
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- G—PHYSICS
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- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/137—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
- G02F1/13712—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering the liquid crystal having negative dielectric anisotropy
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Abstract
Hair brushThe invention relates to a liquid crystal composition and application thereof, wherein the liquid crystal composition comprises at least one of compounds represented by a general formula I and at least one of compounds represented by a general formula II:
Description
Technical Field
The invention relates to the technical field of liquid crystal materials, in particular to a liquid crystal composition, specifically a nematic liquid crystal composition, and specifically provides a liquid crystal composition with negative dielectric anisotropy and faster response time.
Background
Liquid crystals are currently widely used in the field of information display, and have been used in optical communications (s.t.wu, d.k.yang.reflective Liquid Crystal display. wiley, 2001). In recent years, the application fields of liquid crystal compounds have been remarkably widened to various display devices, electro-optical devices, electronic components, sensors, and the like, and nematic liquid crystal compounds have been most widely used in flat panel displays, particularly in systems of TFT active matrix.
Liquid crystal display has experienced a long development route along with the discovery of liquid crystals. In 1888, the first liquid crystal material, cholesterol benzoate, was discovered by the austria phytologist Friedrich reintzer. In 1917, Manguin invented rubbing alignment method to make single domain liquid crystal and study optical anisotropy. The theory of scraping (Swarm) was established by e.bose in 1909 and supported by l.s.ormstein and f.zernike et al (1918), which were later discussed as statistical fluctuations by De Gennes. G.w.oseen and h.zocher created continuum theory in 1933 and was perfected by f.c.frank (1958). M.born (1916) and k.lichtennecker (1926) discovered and studied the dielectric anisotropy of liquid crystals. In 1932, w.kast accordingly classified the nematic phase into two main classes, positive and negative. In 1927, v.freedericksz and v.zolonao found that nematic liquid crystals deformed and had a voltage threshold (freedericksz transition) under the action of an electric or magnetic field. This finding provides the basis for the fabrication of liquid crystal displays.
In 1968, R.Williams, RCA corporation in America, discovered that nematic liquid crystals form fringe domains under the action of an electric field and have a light scattering phenomenon. The g.h.heilmeir was subsequently developed into a dynamic scattering display mode and made the first Liquid Crystal Display (LCD) in the world. In the early seventies, Helfrich and Schadt invented the TN principle, and people made them into display devices (TN-LCD) by using the combination of TN photoelectric effect and integrated circuit, thus developing a broad prospect for the application of liquid crystal. Since the seventies, the application of liquid crystal in display has been developed in a breakthrough due to the development of large-scale integrated circuits and liquid crystal materials, and the Super Twisted Nematic (STN) mode proposed by t.scheffer et al in 1983-1985 and the Active Matrix (AM) mode proposed by p.brody in 1972 were adopted again. Conventional TN-LCD technology has been developed into STN-LCD and TFT-LCD technology, and although the number of scan lines of STN can reach 768 lines or more, problems of response speed, viewing angle, gray scale and the like still exist when the temperature rises, so that the active matrix display mode is mostly adopted for large-area, high-information content and color display. TFT-LCD has been widely used in direct view televisions, large screen projection televisions, computer terminal displays and some military instrument displays, and TFT-LCD technology is believed to have wider application prospects. Where "active matrix" includes two types: 1. OMS (metal oxide semiconductor) or other diodes on a silicon chip as a substrate. 2. A Thin Film Transistor (TFT) on a glass plate as a substrate. The use of single crystal silicon as a substrate material limits the display size because of the many problems that arise with the assembly of parts of the display device and even the modules at their junctions. Thus, the second type of thin film transistor is a promising type of active matrix, and the photoelectric effect utilized is typically the TN effect. TFTs include compound semiconductors, such as CdSe, or TFTs based on polycrystalline or amorphous silicon.
At present, the technology of LCD products has matured, and the technical problems of viewing angle, resolution, color saturation and the like are successfully solved, and the display performance of the LCD products is close to or exceeds that of CRT displays. Large-sized and medium-sized LCDs have gradually occupied the mainstream position of flat panel displays in their respective fields.
The response speed is an important evaluation index of the LCD, and the phenomenon of picture smear can occur when the response speed is too slow. Factors that affect the response speed of an LCD include the thickness of the LCD cell, the driving method, and the hybrid liquid crystal selected.
Disclosure of Invention
The liquid crystal composition containing benzofuran provided by the invention has lower rotational viscosity, can effectively improve the response speed of a liquid crystal display, improves the phenomenon of image smear, and achieves better display effect.
One of the technical schemes of the invention is as follows: a liquid crystal composition comprising at least one of the compounds represented by formula I, and at least one of the compounds represented by formula II:
in the general formula I, R1Represents a H atom or C1~C10Linear alkyl radical of (2), R2Represents C1~C10Linear alkyl or linear alkoxy of (a); a. the1Represents 1, 4-phenylene, 1, 4-cyclohexylene or 1, 4-phenylene in which 1 to 4 hydrogen atoms are replaced by fluorine atoms; n is 0 or 1;
in the general formula II, R3、R4Each independently represents C1~C12Or one or more non-adjacent CH therein2A group substituted with O, S or CH ═ CH; a. the2、A3Each independently represents trans-1, 4-cyclohexyl or 1, 4-phenylene.
The compound represented by the general formula I provided by the invention is a dibenzofuran compound, and the structure has large negative dielectric anisotropy.
Preferably, the compound represented by the general formula I is selected from one or more compounds represented by the following formula:
wherein R is1Represents a H atom or C1~C10Linear alkyl radical of (2), R2Represents C1~C10Linear alkyl or linear alkoxy of (a); preferably, R1Represents a H atom or C1~C7The linear alkyl group of (1); r2Represents C1~C7Linear alkyl or linear alkoxy of (a); further preferably, R1Represents a H atom, R2Represents C1~C5Linear alkyl or linear alkoxy groups of (1).
More preferably, the compound represented by the general formula I is one or more compounds selected from the group consisting of compounds represented by the formulae IA1 to IF 10:
in the liquid crystal composition, the compound represented by the general formula I preferably adopts one or more of IA 7-IA 10, ID 7-ID 10 and F7-IF 10 compounds.
In the liquid crystal composition, the compound represented by the general formula I is added in an amount of 1 to 30%, or 1 to 11%, or 12 to 30%, or 5 to 25%, or 1 to 15%, or 2 to 25%, or 2 to 14%, or 15 to 25%, preferably 2 to 25%, and more preferably 2 to 14%, based on 100%.
The compound represented by the general formula II provided by the invention is a bicyclic structure, and the structure has extremely low rotational viscosity.
Preferably, the compound represented by the general formula II is selected from one or more of the following compounds:
wherein R is3、R4Each independently represents C1~C12Wherein one or more non-adjacent CH2May be substituted with O, S or CH ═ CH; preferably, R3Represents C1~C7The linear alkyl group of (1); r4Represents C1~C7Linear alkyl, linear alkoxy or C2~C7A linear alkenyl group of (a); further preferably, R3Represents C2~C5The linear alkyl group of (1); r4Represents C2~C5Straight chain alkyl group of (1), C1~C4Linear alkoxy of (5) or C2~C5Linear alkenyl groups of (a).
More preferably, the compound represented by the general formula II is one or more compounds selected from the group consisting of compounds represented by the formulae IIA1 to IIC 24:
in the liquid crystal composition, the compound represented by the general formula II preferably adopts one or more of compounds IIA 1-IIA 4, IIA 14-IIA 18, IIB 18-IIB 24, IIC 2-IIC 4 and IIC 15-IIC 16.
In the liquid crystal composition, the compound represented by the general formula II is added in an amount of 20 to 50%, or 27 to 40%, or 20 to 60%, or 27 to 53%, or 20 to 40%, or 27 to 36%, or 40 to 53%, preferably 27 to 53%, more preferably 27 to 36%, still more preferably 27 to 32%, based on 100%.
The compound represented by the general formula I in the liquid crystal composition provided by the invention is a compound with a dibenzofuran structure, has great negative dielectric anisotropy, and can effectively increase the dielectric anisotropy of the liquid crystal composition; the compound represented by the general formula II is a two-ring structure, has extremely low rotational viscosity, and is the best choice for reducing the rotational viscosity of the liquid crystal composition; the liquid crystal composition provided by the invention increases the dielectric anisotropy of the liquid crystal composition by adding the compound represented by the general formula I, so that the use of polar monomers is reduced, and the purpose of reducing the rotational viscosity of the liquid crystal composition is achieved by increasing the compound represented by the general formula II.
Preferably, the liquid crystal composition provided by the invention further comprises one or more compounds selected from the structures of the general formula III, so as to help improve the elastic constant and clearing point of the liquid crystal composition:
R5、R6each independently represents C1~C12Wherein one or more non-adjacent CH2May be substituted by O or CH ═ CH.
A4One selected from the following structures:
preferably, the compound represented by formula III is selected from one or more of formulae IIIA to IIIC:
wherein R is5、R6Each independently represents C1~C12Wherein one or more non-adjacent CH2May be substituted by O or CH ═ CH, preferably, R5Represents C2~C10A linear alkyl or linear alkenyl group of (a); r6Represents C1~C8The linear alkyl group of (1); further preferably: r5Represents C2~C5A linear alkyl or linear alkenyl group of (a); r6Represents C1~C5Linear alkyl group of (1).
More preferably, the compound represented by formula III is selected from one or more of the structures of formulae IIIA1 to IIIC 29:
in the liquid crystal composition, the compound represented by the general formula III preferably adopts one or more of compounds IIIA 1-IIIA 4, IIIA 14-IIIA 18, IIIB 1-IIIB 3 and IIIB 12-IIIB 16.
In the liquid crystal composition, the compound represented by the general formula III is an optional component, and the addition amount of the compound represented by the general formula III is 0-10%, or 0-15%, or 0-25% in terms of 100%, and when the compound represented by the general formula III is added, the addition amount is 5-25%, or 6-21%, or 6-11%, or 18-21%.
Further, the liquid crystal composition provided by the invention also comprises one or more compounds selected from the compounds represented by the general formula IV, wherein the compounds represented by the general formula IV have a negative group structure, and when the compounds are added into the liquid crystal composition, the compounds are helpful for improving dielectric anisotropy of the liquid crystal composition.
Wherein R is7、R8Each independently represents C1~C12Linear alkyl, alkoxy or C2~C12A linear alkenyl group of (a); a. the5Represents 1, 4-cyclohexylene or 1, 4-phenylene; z1Represents a single bond, CH2CH2Or CH2O。
Preferably, the compound represented by formula IV is selected from one or more of the following compounds:
wherein R is7、R8Each independently represents C1~C12Linear alkyl, alkoxy or C2~C12Preferably, R is7Represents C1~C7Straight chain alkyl or C2~C7A linear alkenyl group of (a); r8Represents C1~C7Linear alkyl or linear alkoxy of (a); further preferably, R7Represents C2~C5Straight chain alkyl or C2~C4A linear alkenyl group of (a); r8Represents C1~C4Linear alkyl or linear alkoxy groups of (1).
More preferably, the compound of formula IV is selected from one or more of formulae IVA1 to formula IVD 16;
in the liquid crystal composition, the compound represented by the general formula IV preferably adopts one or more of IVA 22-IVA 30, IVB 6-IVB 8, IVC 18-IVC 20 and IVD 6-IVD 8 compounds.
In the liquid crystal composition, the compound represented by the general formula IV is an optional component in the liquid crystal composition, and the adding amount of the compound represented by the general formula IV is 0-10%, or 0-16%, or 0-2%, or 0-30% in terms of 100%, and when the compound is added, the adding amount is 3-20%, or 5-16%, or 2-14%, and the preferable adding amount is 2-14%.
In order to further increase the optical anisotropy of the liquid crystal composition, the liquid crystal composition provided by the present invention preferably further comprises one or more compounds represented by the general formula V:
wherein R is9、R10Each independently represents C1~C12Preferably, R9、R10Each independently represents C1~C5Linear alkyl group of (1).
Preferably, the compound represented by formula V is selected from one or more of the following structures:
in the liquid crystal composition, the compound represented by the general formula V preferably adopts one or more compounds from V3 to V5.
In the liquid crystal composition, the compound represented by the general formula V is an optional component in the liquid crystal composition, the addition amount of the compound represented by the general formula V is 0-30%, or 0-20%, or 0-10% in terms of 100%, and when the compound is added, the preferable addition amount is 6-25%.
Preferably, the liquid crystal composition provided by the invention further comprises one or more compounds represented by a general formula VI, wherein the compounds represented by the general formula VI have a terphenyl structure and are added into the liquid crystal composition to help to improve the refractive index of the composition.
Wherein R is11、R12Each independently represents C1~C12Straight chain alkyl, straight chain alkoxy; l is1Represents H or F.
Preferably, the compound represented by formula VI is selected from one or more of VIA and VIB:
wherein R is11、R12Each independently represents C1~C12Straight chain alkyl, straight chain alkoxy, preferably, R11、R12Each independently represents C1~C7Straight chain alkyl, straight chain alkoxy; further preferably, R11、R12Each independently represents C1~C5Linear alkyl or linear alkoxy groups of (1).
In the liquid crystal composition, the compound represented by the general formula VI is an optional component in the liquid crystal composition, the addition amount of the compound represented by the general formula VI is 0-15% or 0-10% in terms of 100%, and when the compound is added, the preferred addition amount is 10%.
The liquid crystal composition provided by the invention also comprises one or more compounds represented by the general formula VII:
wherein R is13、R14Each independently represents C1~C12Linear alkyl, linear alkoxy or C2~C12A linear alkenyl group of (a); a. the6One selected from the following structures:
A7one selected from the following structures:
preferably, the compound represented by formula VII is selected from one or more of the following structures:
wherein R is13Represents C1~C7Straight chain alkyl or C2~C7Linear olefins ofRadical, R14Represents C1~C7Linear alkyl or alkoxy of, preferably, R13Represents C2~C5A linear alkyl or linear alkenyl group of (a); r14Represents C1~C5Linear alkyl or linear alkoxy groups of (1).
In the liquid crystal composition, the compound represented by the general formula VII is an optional component in the liquid crystal composition, the addition amount of the compound represented by the general formula VII is 0-60%, or 0-45%, or 0-29% in terms of 100%, and when the compound is added, the preferable addition amount is 7-48%, preferably 29-48%.
More preferably, the liquid crystal composition provided by the invention further comprises one or more compounds represented by the general formula VIII, wherein the compounds have a tetracyclic structure, and the compounds are added into the liquid crystal composition and are helpful for improving the clearing point of the composition.
Wherein R is15、R16Each independently represents C1~C12The linear alkyl group of (1); l is2、L3Each independently represents H or F; a. the8Represents 1, 4-cyclohexyl or 1, 4-phenylene.
Preferably, the compound represented by formula VIII is selected from one or more of the following structures:
wherein R is15、R16Each independently represents C1~C12Linear alkyl radical of (1), preferably C1~C7Further preferred is C2~C5Linear alkyl group of (1).
In the liquid crystal composition, the compound represented by the general formula VIII is an optional component in the liquid crystal composition, the addition amount of the compound represented by the general formula VIII is 0-12%, or 0-8%, or 0-4% in terms of 100%, and when the compound is added, the preferable addition amount is 4-12%.
In addition, the liquid crystal composition provided by the invention also comprises one or more compounds represented by the general formula IX:
wherein R is17Represents C1~C12Linear alkyl, linear alkoxy or C2~C12Linear alkenyl of (A), R18Represents C1~C7Linear alkyl or linear alkoxy of (a); preferably, R17Represents C2~C7Linear alkenyl or linear alkyl of, R18Represents C1~C5Linear alkyl or linear alkoxy of (a); further preferably, R17Represents C2~C5Linear alkyl or linear alkenyl of (1).
In the liquid crystal composition, the compound represented by the general formula IX is an optional component in the liquid crystal composition, the addition amount of the compound represented by the general formula IX is 0-40%, or 0-33%, or 0-20% in terms of 100%, and when the compound is added, the preferable addition amount is 23-33%.
The liquid crystal composition has the following beneficial effects that except that the compounds represented by the general formulas I and II are optional components, other components (such as the compounds shown in the general formulas III to IX) are optional components, and optional modes can be selected in any combination mode, for example, only one, a plurality of or all of the other components are added into the optional components.
In particular, in order to make the liquid crystal composition meet different requirements, the liquid crystal composition provided by the invention further preferably limits the content range of each component in the composition.
The liquid crystal composition comprises the following components in percentage by weight of 100 percent: 1 to 11% of one or more compounds represented by formula I, 20 to 50% of one or more compounds represented by formula II, 0 to 15% of one or more compounds represented by formula III, 3 to 20% of one or more compounds represented by formula IV, 0 to 30% of one or more compounds represented by formula V, 0 to 15% of one or more compounds represented by formula VI, 5 to 50% of one or more compounds represented by formula VII, and 0 to 40% of one or more compounds represented by formula IX.
Preferably, the liquid crystal composition provided by the invention comprises the following components: 2 to 11% of one or more compounds represented by formula I, 27 to 40% of one or more compounds represented by formula II, 0 to 10% of one or more compounds represented by formula III, 5 to 16% of one or more compounds represented by formula IV, 0 to 25% of one or more compounds represented by formula V, 0 to 10% of one or more compounds represented by formula VI, 7 to 48% of one or more compounds represented by formula VII, and 0 to 33% of one or more compounds represented by formula IX.
Or the liquid crystal composition provided by the invention comprises the following components: 12-30% of one or more compounds represented by formula I, 20-60% of one or more compounds represented by formula II, 0-25% of one or more compounds represented by formula III, 0-10% of one or more compounds represented by formula IV, 0-20% of one or more compounds represented by formula V, 0-60% of one or more compounds represented by formula VII, 0-10% of one or more compounds represented by formula VIII, and 0-25% of one or more compounds represented by formula IX.
Preferably, the liquid crystal composition provided by the invention comprises the following components: 12-25% of one or more compounds represented by formula I, 29-53% of one or more compounds represented by formula II, 0-21% of one or more compounds represented by formula III, 0-2% of one or more compounds represented by formula IV, 0-10% of one or more compounds represented by formula V, 0-54% of one or more compounds represented by formula VII, 0-8% of one or more compounds represented by formula VIII, and 0-20% of one or more compounds represented by formula IX.
Or the liquid crystal composition provided by the invention comprises the following components: 3 to 30% of one or more compounds represented by formula I, 20 to 55% of one or more compounds represented by formula II, 5 to 25% of one or more compounds represented by formula III, 0 to 20% of one or more compounds represented by formula IV, 0 to 15% of one or more compounds represented by formula V, 0 to 45% of one or more compounds represented by formula VII, 0 to 10% of one or more compounds represented by formula VIII, and 0 to 40% of one or more compounds represented by formula IX.
Preferably, the liquid crystal composition provided by the invention comprises the following components: 5 to 25% of one or more compounds represented by formula I, 29 to 53% of one or more compounds represented by formula II, 6 to 21% of one or more compounds represented by formula III, 0 to 16% of one or more compounds represented by formula IV, 0 to 10% of one or more compounds represented by formula V, 0 to 40% of one or more compounds represented by formula VII, 0 to 8% of one or more compounds represented by formula VIII, and 0 to 33% of one or more compounds represented by formula IX.
Or the liquid crystal composition provided by the invention comprises the following components: 1-15% of one or more compounds represented by a general formula I, 20-40% of one or more compounds represented by a general formula II, 1-20% of one or more compounds represented by a general formula IV, 0-30% of one or more compounds represented by a general formula V, 0-15% of one or more compounds represented by a general formula VI and 25-60% of one or more compounds represented by a general formula VII.
Preferably, the liquid crystal composition provided by the invention comprises the following components: 2-14% of one or more compounds represented by formula I, 27-36% of one or more compounds represented by formula II, 2-15% of one or more compounds represented by formula IV, 0-25% of one or more compounds represented by formula V, 0-10% of one or more compounds represented by formula VI, and 29-54% of one or more compounds represented by formula VII.
Or the liquid crystal composition provided by the invention comprises the following components: 2-25% of one or more compounds represented by formula I, 27-53% of one or more compounds represented by formula II, 0-21% of one or more compounds represented by formula III, 0-16% of one or more compounds represented by formula IV, 0-25% of one or more compounds represented by formula V, and 0-10% of one or more compounds represented by formula VI; 0 to 48% of one or more compounds represented by formula VII, 0 to 12% of one or more compounds represented by formula VIII, and 0 to 33% of one or more compounds represented by formula IX.
And, the more ideal formulation is: 2-14% of one or more compounds represented by formula I, 27-36% of one or more compounds represented by formula II, 2-14% of one or more compounds represented by formula IV, 6-25% of one or more compounds represented by formula V, and 29-48% of one or more compounds represented by formula VII.
Preferably, in any one of the liquid crystal compositions, the weight percentage of the liquid crystal composition is 100%.
Within the above range, a negative dielectric anisotropic liquid crystal composition having a low rotational viscosity and a large elastic constant can be obtained, and a liquid crystal display using the liquid crystal composition has a fast response time.
The method for producing the liquid crystal composition of the present invention is not particularly limited, and it can be produced by mixing two or more compounds by a conventional method, such as a method of mixing the different components at a high temperature and dissolving each other, wherein the liquid crystal composition is dissolved and mixed in a solvent for the compounds, and then the solvent is distilled off under reduced pressure; alternatively, the liquid crystal composition of the present invention can be prepared by a conventional method, for example, by dissolving the component having a smaller content in the main component having a larger content at a higher temperature, or by dissolving each of the components in an organic solvent, for example, acetone, chloroform or methanol, and then mixing the solutions to remove the solvent.
The second technical scheme of the invention is as follows: use of any one of the above liquid crystal compositions in a liquid crystal display device.
The negative liquid crystal composition has low rotary viscosity, large elastic constant, good low-temperature intersolubility and high response speed, can be used for fast response liquid crystal display of various display modes, and is preferably suitable for IPS, FFS or VA type liquid crystal display devices. The composition of the invention can obviously improve the display effect of the liquid crystal display when used in the liquid crystal display device, in particular to VA type liquid crystal display devices such as MVA, PVA, PS-VA and the like.
When the liquid crystal composition of the present invention is applied to a PS-VA type liquid crystal display device, in order to set a desired pretilt angle, it is preferable that the liquid crystal composition further includes a polymer obtained by polymerizing one or more of the following polymerizable compounds:
preferably, the polymerizable compound is used in an amount of 0.01 to 5% by weight of the liquid crystal composition.
The preparation method of the liquid crystal composition applied to the PS-VA liquid crystal display device comprises the following steps: adding 0.1-5% of a mixture of a polymerizable compound and a photoinitiator into the nematic liquid crystal composition, then polymerizing by UV light irradiation, and continuously applying a voltage during the irradiation. The polymerizable compound in the liquid crystal composition is polymerized under the irradiation of an initiator and UV light to generate a network structure.
Suitable initiators and polymerization conditions for the polymerization reaction are known to the person skilled in the art and are described in the literature. Suitable for free-radical polymerization are, for example, the commercially available photoinitiators Irgacure 651, Irgacure 184 or Darocure 1173. The amount of initiator is 1-3% by weight of the polymerizable compound.
The compounds referred to in the present invention are all known compounds and are commercially available or available from the company Beijing Baybigos space-time liquid Crystal technology, Inc.
On the basis of the common knowledge in the field, the above preferred conditions can be combined with each other to obtain the preferred embodiments of the invention.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
In the present invention, the percentages are by weight, the temperature is given in degrees Celsius, △ n represents the optical anisotropy (25 ℃), △ ε represents the dielectric anisotropy (25 ℃, 1000Hz), V10Represents a threshold voltage, which is a characteristic voltage (V, 25 ℃) at which the relative transmittance changes by 10%; γ 1 represents rotational viscosity (mpa.s, 25 ℃); cp represents the clearing point (. degree. C.) of the liquid crystal composition; k11、K22、K33Respectively representing the splay, twist and bend elastic constants (pN, 25 ℃).
In the following examples, the group structures in the liquid crystal compounds are represented by codes shown in Table 1.
Table 1: radical structure code of liquid crystal compound
Take the following compound structure as an example:
expressed as: 1EGIBO5
Expressed as: 3CPWO1
In the following examples, the liquid crystal composition was prepared by a thermal dissolution method, comprising the steps of: weighing the liquid crystal compound by a balance according to the weight percentage, wherein the weighing and adding sequence has no specific requirements, generally weighing and mixing the liquid crystal compound in sequence from high melting point to low melting point, heating and stirring at 60-100 ℃ to uniformly melt all the components, filtering, performing rotary evaporation, and finally packaging to obtain the target sample.
In the following examples, the weight percentages of the components in the liquid crystal composition and the performance parameters of the liquid crystal composition are shown in the following tables.
In the following examples, all the components referred to are known liquid-crystalline compounds, which are available from the company of the Beijing Bay space-time liquid Crystal technology, Inc.
Example 1
Table 2: the weight percentage and performance parameters of each component in the liquid crystal composition
Example 2
Table 3: the weight percentage and performance parameters of each component in the liquid crystal composition
Example 3
Table 4: the weight percentage and performance parameters of each component in the liquid crystal composition
Example 4
Table 5: the weight percentage and performance parameters of each component in the liquid crystal composition
Example 5
Table 6: the weight percentage and performance parameters of each component in the liquid crystal composition
Example 6
Table 7: the weight percentage and performance parameters of each component in the liquid crystal composition
Example 7
Table 8: the weight percentage and performance parameters of each component in the liquid crystal composition
Example 8
Table 9: the weight percentage and performance parameters of each component in the liquid crystal composition
Example 9
Table 10: the weight percentage and performance parameters of each component in the liquid crystal composition
Example 10
Table 11: the weight percentage and performance parameters of each component in the liquid crystal composition
Example 11
Table 12: the weight percentage and performance parameters of each component in the liquid crystal composition
Example 12
Table 13: the weight percentage and performance parameters of each component in the liquid crystal composition
Example 13
Table 14: the weight percentage and performance parameters of each component in the liquid crystal composition
Example 14
Table 15: the weight percentage and performance parameters of each component in the liquid crystal composition
Example 15
A liquid crystal composition comprising 99.7% of the liquid crystal composition of example 4, and 0.3% of a polymerizable compound of the formula
Example 16
A liquid crystal composition comprising 99.8% of the liquid crystal composition of example 5, and 0.2% of a polymerizable compound of the formula
Example 17
A liquid crystal composition comprising 99.7% of the liquid crystal composition of example 11, and 0.3% of a polymerizable compound of the formula
Comparative example 1
Table 16: the weight percentage and performance parameters of each component in the liquid crystal composition
The liquid crystal compositions obtained in example 1 and comparative example 1 were compared together for each of their performance parameter values, see table 16.
Table 17: comparison of Performance parameters of liquid Crystal compositions
△n | △ε | Cp | γ1 | K11 | K22 | K33 | |
Example 1 | 0.104 | -2.6 | 82 | 51 | 13.9 | 6.9 | 14.3 |
Comparative example 1 | 0.105 | -2.6 | 82 | 69 | 12.3 | 6.2 | 13.9 |
By comparison, it can be seen that: example 1 provides a liquid crystal composition having a low rotational viscosity, i.e., having a faster response time, compared to comparative example 1.
As can be seen from the above examples, the liquid crystal composition containing a liquid crystal compound of dibenzofuran provided by the present invention has low viscosity, high resistivity, suitable optical anisotropy, good low-temperature mutual solubility, large elastic constant, and excellent light stability and thermal stability, and can reduce the response time of a liquid crystal display, thereby solving the problem of slow response speed of the liquid crystal display. Therefore, the liquid crystal composition provided by the invention is suitable for fast-response IPS and FFS and VA type liquid crystal display devices such as MVA, PVA, PS-VA and the like, and is particularly suitable for fast-response liquid crystal display devices.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (35)
1. A liquid crystal composition characterized by: consisting of compounds represented by the essential component general formulas I to II and compounds represented by the optional component general formulas III to IX:
in the general formula I, R1Represents a H atom or C1~C10Linear alkyl radical of (2), R2Represents C1~C10Linear alkyl or linear alkoxy of (a); a. the1Represents 1, 4-phenylene or 1, 4-phenylene in which 1 to 4 hydrogen atoms are substituted by fluorine atoms; n is 0 or 1;
in the general formula II, R3、R4Each independently represents C1~C12Or one or more non-adjacent CH therein2A group substituted with O, S or CH ═ CH; a. the2、A3Each independently represents trans-1, 4-cyclohexyl or 1, 4-phenylene;
optionally, one or more of the compounds represented by formulas III-IX may be added:
wherein R is5、R6Each independently represents C1~C12Or one or more non-adjacent CH therein2A group substituted with O or CH ═ CH;
A4one selected from the following structures:
wherein R is7、R8Each independently represents C1~C12Linear alkyl, alkoxy or C2~C12A linear alkenyl group of (a); a. the5Represents 1, 4-cyclohexylene or 1, 4-phenylene; z1Represents a single bond, CH2CH2Or CH2O;
Wherein R is9、R10Each independently represents C1~C12The linear alkyl group of (1);
wherein R is11、R12Each independently represents C1~C12Straight chain alkyl, straight chain alkoxy; l is1Represents H or F;
wherein R is13、R14Each independently represents C1~C12Linear alkyl, linear alkoxy or C2~C12A linear alkenyl group of (a); a. the6One selected from the following structures:
A7one selected from the following structures:
wherein R is15、R16Each independently represents C1~C12The linear alkyl group of (1); l is2、L3Each independently represents H or F; a. the8Represents 1, 4-cyclohexyl or 1, 4-phenylene;
wherein R is17Represents C1~C12Linear alkyl, linear alkoxy or C2~C12Linear alkenyl of (A), R18Represents C1~C7Linear alkyl or linear alkoxy groups of (1).
2. The liquid crystal composition according to claim 1, wherein: the compound represented by the general formula I is selected from one or more compounds represented by the following formula:
wherein R is1Represents a H atom or C1~C10Linear alkyl radical of (2), R2Represents C1~C10Linear alkyl or linear alkoxy groups of (1).
3. The liquid crystal composition according to claim 2, characterized in that: r1Represents a H atom or C1~C7The linear alkyl group of (1); r2Represents C1~C7Linear alkyl or linear alkoxy groups of (1).
4. The liquid crystal composition according to claim 3, wherein: r1Represents a H atom, R2Represents C1~C5Linear alkyl or linear alkoxy groups of (1).
6. the liquid crystal composition according to claim 5, wherein: the compound represented by the general formula I is selected from one or more of IA 7-IA 10, ID 7-ID 10 and IF 7-IF 10.
7. The liquid crystal composition according to claim 1, wherein: the compound represented by the general formula II is selected from one or more of the following compounds:
wherein R is3、R4Each independently represents C1~C12Or one or more non-adjacent CH therein2Groups substituted with O, S or CH ═ CH.
8. The liquid crystal composition according to claim 7, wherein: r3Represents C1~C7The linear alkyl group of (1); r4Represents C1~C7Linear alkyl, linear alkoxy or C2~C7Linear alkenyl groups of (a).
9. The liquid crystal composition according to claim 8, wherein: r3Represents C2~C5The linear alkyl group of (1); r4Represents C2~C5Straight chain alkyl group of (1), C1~C4Linear alkoxy of (5) or C2~C5Linear alkenyl groups of (a).
11. the liquid crystal composition according to claim 10, wherein: the compound represented by the general formula II is selected from one or more of IIA 1-IIA 4, IIA 14-IIA 18, IIB 18-IIB 24, IIC 2-IIC 4 and IIC 15-IIC 16.
12. The liquid crystal composition according to any one of claims 1 to 11, wherein: the liquid crystal composition comprises at least one of compounds represented by a general formula I, at least one of compounds represented by a general formula II, at least one of compounds represented by a general formula IV, at least one of compounds represented by a general formula V and at least one of compounds represented by a general formula VII.
13. The liquid crystal composition according to claim 1, wherein: the compound represented by the general formula III is selected from one or more of formulas IIIA to IIIC:
wherein R is5、R6Each independently represents C1~C12Or one or more non-adjacent CH therein2A group substituted with O or CH ═ CH;
the compound represented by formula IV is selected from one or more of the following compounds:
wherein R is7、R8Each independently represents C1~C12Linear alkyl, alkoxy or C2~C12A linear alkenyl group of (a);
the compound represented by formula V is selected from one or more of the following structures:
the compound represented by formula VI is selected from one or more of VIA and VIB:
wherein R is11、R12Each independently represents C1~C12Straight chain alkyl, straight chain alkoxy;
the compound represented by formula VII is selected from one or more of the following structures:
wherein R is13Represents C1~C7Straight chain alkyl or C2~C7Linear alkenyl of (A), R14Represents C1~C7Linear alkyl or linear alkoxy of (a);
the compound represented by formula VIII is selected from one or more of the following structures:
wherein R is15、R16Each independently represents C1~C12The linear alkyl group of (1);
the compound represented by formula IX is selected from one or more of the following structures:
wherein R is17Represents C2~C7Linear alkenyl or linear alkyl of, R18Represents C1~C5Linear alkyl or linear alkoxy groups of (1).
14. The liquid crystal composition according to claim 13, wherein: r5Represents C2~C10A linear alkyl or linear alkenyl group of (a); r6Represents C1~C8Linear alkyl group of (1).
15. The liquid crystal composition according to claim 14, wherein: r5Represents C2~C5A linear alkyl or linear alkenyl group of (a); r6Represents C1~C5Linear alkyl group of (1).
17. the liquid crystal composition of claim 16, wherein: the compound represented by the general formula III is selected from one or more of IIIA 1-IIIA 4, IIIA 14-IIIA 18, IIIB 1-IIIB 3 and IIIB 12-IIIB 16.
18. The liquid crystal composition according to claim 13, wherein: in the general formula IV, R7Represents C1~C7Straight chain alkyl or C2~C7A linear alkenyl group of (a); r8Represents C1~C7Linear alkyl or linear alkoxy groups of (1).
19. The liquid crystal composition of claim 18, wherein: r7Represents C2~C5Straight chain alkyl or C2~C4A linear alkenyl group of (a); r8Represents C1~C4Linear alkyl or linear alkoxy groups of (1).
21. the liquid crystal composition of claim 20, wherein: the compound represented by the general formula IV is selected from one or more of IVA 22-IVA 30, IVB 6-IVB 8, IVC 18-IVC 20 and IVD 6-IVD 8.
22. The liquid crystal composition according to claim 13, wherein: the compound represented by the general formula V is selected from one or more of V3-V5.
23. The liquid crystal composition according to claim 13, wherein: in the general formula VI, R11、R12Each independently represents C1~C7Straight chain alkyl, straight chain alkoxy.
24. The liquid crystal composition of claim 23, wherein: r11、R12Each independently represents C1~C5Linear alkyl or linear alkoxy groups of (1).
25. The liquid crystal composition according to claim 13, wherein: in the general formula VII, R13Represents C2~C5A linear alkyl or linear alkenyl group of (a); r14Represents C1~C5Linear alkyl or linear alkoxy groups of (1).
26. The liquid crystal composition according to claim 13, wherein: in the general formula VIII, R15、R16Each independently represents C1~C7Linear alkyl group of (1).
27. The liquid crystal composition of claim 26, wherein: r15、R16Each independently represents C2~C5Linear alkyl group of (1).
28. The liquid crystal composition according to claim 13, wherein: in the general formula IX, R17Represents C2~C5Linear alkyl or linear alkenyl of (1).
29. The liquid crystal composition according to any one of claims 1 to 11 and 13 to 28, wherein: the composite material comprises the following components in percentage by weight:
(1) 1-11% of one or more compounds represented by general formula I;
20-50% of one or more compounds represented by the general formula II;
0-15% of one or more compounds represented by general formula III;
3-20% of one or more compounds represented by the general formula IV;
0-30% of one or more compounds represented by the general formula V;
0-15% of one or more compounds represented by general formula VI;
5-50% of one or more compounds represented by the general formula VII;
0-40% of one or more compounds represented by general formula IX;
or (2) 12-30% of one or more compounds represented by the general formula I;
20-60% of one or more compounds represented by general formula II;
0-25% of one or more compounds represented by general formula III;
0-10% of one or more compounds represented by general formula IV;
0-20% of one or more compounds represented by the general formula V;
0-60% of one or more compounds represented by general formula VII;
0-10% of one or more compounds represented by general formula VIII;
0-25% of one or more compounds represented by general formula IX;
or (3) 3-30% of one or more compounds represented by the general formula I;
20-55% of one or more compounds represented by the general formula II;
5-25% of one or more compounds represented by the general formula III;
0-20% of one or more compounds represented by general formula IV;
0-15% of one or more compounds represented by general formula V;
0-45% of one or more compounds represented by general formula VII;
0-10% of one or more compounds represented by general formula VIII;
0-40% of one or more compounds represented by general formula IX;
or (4) 1-15% of one or more compounds represented by the general formula I;
20-40% of one or more compounds represented by the general formula II;
1-20% of one or more compounds represented by the general formula IV;
0-30% of one or more compounds represented by the general formula V;
0-15% of one or more compounds represented by general formula VI;
25-60% of one or more compounds represented by general formula VII;
or (5) 2-25% of one or more compounds represented by the general formula I;
27-53% of one or more compounds represented by general formula II;
0-21% of one or more compounds represented by general formula III;
0-16% of one or more compounds represented by general formula IV;
0-25% of one or more compounds represented by general formula V;
0-10% of one or more of the compounds represented by formula VI;
0-48% of one or more compounds represented by general formula VII;
0-12% of one or more compounds represented by general formula VIII;
0-33% of one or more compounds represented by general formula IX;
or (6) 2-14% of one or more compounds represented by the general formula I;
27-36% of one or more compounds represented by general formula II;
2-14% of one or more compounds represented by the general formula IV;
6-25% of one or more compounds represented by the general formula V;
29-48% of one or more compounds represented by the general formula VII.
30. The liquid crystal composition according to any one of claims 1 to 11 and 13 to 28, wherein: the composite material comprises the following components in percentage by weight: (1) 2-11% of one or more compounds represented by the general formula I;
27-40% of one or more compounds represented by general formula II;
0-10% of one or more compounds represented by general formula III;
5-16% of one or more compounds represented by the general formula IV;
0-25% of one or more compounds represented by general formula V;
0-10% of one or more compounds represented by general formula VI;
7-48% of one or more compounds represented by the general formula VII;
0-33% of one or more compounds represented by general formula IX;
or (2) 12-25% of one or more compounds represented by the general formula I;
29-53% of one or more compounds represented by general formula II;
0-21% of one or more compounds represented by general formula III;
0-2% of one or more compounds represented by general formula IV;
0-10% of one or more compounds represented by the general formula V;
0-54% of one or more compounds represented by the general formula VII;
0-8% of one or more compounds represented by general formula VIII;
0-20% of one or more compounds represented by general formula IX;
or (3) 5-25% of one or more compounds represented by the general formula I;
29-53% of one or more compounds represented by general formula II;
6-21% of one or more compounds represented by the general formula III;
0-16% of one or more compounds represented by general formula IV;
0-10% of one or more compounds represented by the general formula V;
0-40% of one or more compounds represented by general formula VII;
0-8% of one or more compounds represented by general formula VIII;
0-33% of one or more compounds represented by general formula IX;
or (4) 2-14% of one or more compounds represented by the general formula I;
27-36% of one or more compounds represented by general formula II;
2-15% of one or more compounds represented by general formula IV;
0-25% of one or more compounds represented by general formula V;
0-10% of one or more compounds represented by general formula VI;
29-54% of one or more compounds represented by the general formula VII.
31. Use of the liquid crystal composition of any of claims 1 to 30 in a liquid crystal display device.
32. Use according to claim 31, wherein the liquid crystal display device is an IPS, FFS or VA liquid crystal display device.
33. The use according to claim 32, wherein the VA mode liquid crystal display device is MVA, PVA, or PS-VA.
35. use according to claim 34, characterized in that: the amount of the polymerizable compound is 0.1-5% of the weight of the liquid crystal composition.
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DE102018004237A1 (en) * | 2017-06-14 | 2018-12-20 | Merck Patent Gmbh | Dibenzofuran and dibenzothiophene derivatives |
JP2019077792A (en) * | 2017-10-25 | 2019-05-23 | Jnc株式会社 | Liquid crystal composition and liquid crystal display element |
CN107794057B (en) * | 2017-10-31 | 2021-03-23 | 晶美晟光电材料(南京)有限公司 | Negative liquid crystal compound, liquid crystal mixture and application thereof |
CN109913238A (en) * | 2017-12-12 | 2019-06-21 | 北京八亿时空液晶科技股份有限公司 | A kind of positive and negative mixed liquid crystal composition containing dibenzofurans compound and its application |
CN110016353A (en) * | 2018-01-10 | 2019-07-16 | 北京八亿时空液晶科技股份有限公司 | A kind of liquid-crystal composition and its application |
CN108531196B (en) * | 2018-05-25 | 2020-11-06 | 石家庄晶奥量新材料有限公司 | Liquid crystal compound containing dibenzofuran ring and preparation method and application thereof |
CN110117277B (en) * | 2019-01-24 | 2022-12-30 | 河北迈尔斯通电子材料有限公司 | Negative liquid crystal monomer and preparation method thereof |
CN112980460A (en) * | 2019-12-13 | 2021-06-18 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal compound and preparation method and application thereof |
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CN113512428A (en) * | 2020-04-09 | 2021-10-19 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal composition with negative dielectric anisotropy and application thereof |
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