CN115029142B - Liquid crystal composition and application thereof - Google Patents

Liquid crystal composition and application thereof Download PDF

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CN115029142B
CN115029142B CN202110238795.XA CN202110238795A CN115029142B CN 115029142 B CN115029142 B CN 115029142B CN 202110238795 A CN202110238795 A CN 202110238795A CN 115029142 B CN115029142 B CN 115029142B
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general formula
compound represented
liquid crystal
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crystal composition
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CN115029142A (en
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王杰
戴雄
李伟
熊立刚
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Beijing Bayi Space LCD Technology Co Ltd
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Priority to TW111107406A priority patent/TWI820620B/en
Priority to PCT/CN2022/078825 priority patent/WO2022184098A1/en
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00Liquid crystal materials
    • C09K19/04Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/42Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • C09K19/46Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing esters
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices 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
    • G02F1/01Devices 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 
    • G02F1/13Devices 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
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1334Constructional arrangements; Manufacturing methods based on polymer dispersed liquid crystals, e.g. microencapsulated liquid crystals

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Abstract

The invention provides a liquid crystal composition and application thereof, wherein the liquid crystal composition comprises compounds represented by general formulas I-IX. When nine liquid crystal compounds of the general formulas I-IX are combined according to a specific proportion, the obtained liquid crystal composition has lower voltage change rate and higher clear point, can realize ultra-wide temperature operation, is particularly suitable for PDLC displays, can overcome the technical defects of narrow working temperature, particularly difficult driving at low temperature, of the existing PDLC displays, and widens the application range of the liquid crystal composition.

Description

Liquid crystal composition and application thereof
Technical Field
The invention relates to the technical field of liquid crystal materials, in particular to a liquid crystal composition and application thereof.
Background
Liquid crystal is an organic substance with certain order between solid and liquid, and has the characteristic of photoelectric dynamic scattering. The liquid crystal has a plurality of liquid crystal phases, such as cholesteric phase, various smectic phases, nematic phase, etc. At present, the application field of liquid crystal compounds has 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. Liquid crystal displays use liquid crystal mixtures having desired material properties such as operating temperature range, thermal stability, light stability, switching time, and contrast.
The polymer dispersed liquid crystal (Polymer Dispersed Liquid Crystal, PDLC) is a material which is prepared by mixing low molecular liquid crystal with prepolymer, carrying out polymerization reaction under certain conditions to form micron-sized liquid crystal microdroplets which are uniformly dispersed in a high molecular network, and utilizing the dielectric anisotropy of liquid crystal molecules to obtain the material with electro-optic response characteristics, wherein the material mainly works between a scattering state and a transparent state. Compared with the traditional liquid crystal device, the polymer dispersion display has a plurality of advantages, such as no need of a polaroid and an orientation layer, simple preparation process, easy manufacture of large-area flexible display and the like. In recent years, as PDLC is applied more and more in various fields, the corresponding requirements on liquid crystal materials are also higher and higher. Various characteristic parameters of the liquid crystal material, such as optical anisotropy (Δn), dielectric anisotropy (Δε), clearing point (Cp) and the like, affect the overall operation of the PDLC. The voltage change rate (dv/dt) is a parameter representing the change of the driving voltage of the liquid crystal device along with the temperature, and good voltage change rate at low temperature can ensure the liquid crystal display to work normally at low temperature.
Therefore, research on liquid crystal materials with high-wide temperature performance has important application value.
Disclosure of Invention
The invention provides a liquid crystal composition and application thereof, wherein the liquid crystal composition has good voltage change rate (dv/dt) characteristic at low temperature, and simultaneously has high clear point, so that ultra-wide temperature working can be realized.
The invention provides a liquid crystal composition, which comprises the following components in percentage by weight:
3 to 9 percent of compound represented by a general formula I;
41 to 47 percent of compound represented by a general formula II;
1 to 5 percent of compound represented by a general formula III;
5 to 10 percent of compound represented by a general formula IV;
10 to 15 percent of compound represented by a general formula V;
1 to 5 percent of compound represented by a general formula VI;
10 to 15 percent of compound represented by a general formula VII;
1 to 5 percent of compound represented by a general formula VIII;
2 to 7 percent of compound represented by a general formula IX,
the structures of the general formulas I to IX are as follows:
wherein R is 1 、R 21 、R 22 、R 31 、R 32 、R 41 、R 42 、R 5 、R 61 、R 62 、R 71 、R 72 、R 81 、R 82 、R 91 And R is 92 Identical or different, each independently represents C 1 ~C 12 Straight chain alkyl of (a).
Further, the R 1 、R 21 、R 22 、R 31 、R 32 、R 41 、R 42 、R 5 、R 61 、R 62 、R 71 、R 72 、R 81 、R 82 、R 91 And R is 92 Identical or different, each independently represents C 2 ~C 5 Straight chain alkyl groups such as ethyl, n-propyl, n-butyl, n-pentyl.
Further, the compound represented by the general formula I is selected from one or two of the formulas I-1 to I-2:
and/or the number of the groups of groups,
the compound represented by the general formula II is selected from one or more of the formulas II-1 to II-4:
and/or the number of the groups of groups,
the compound represented by the general formula III is selected from one or two of the formulas III-1 to III-2:
and/or the number of the groups of groups,
the compound represented by the general formula IV is selected from one or two of the formulas IV-1 to IV-2:
and/or the number of the groups of groups,
the compound represented by the general formula V is selected from one or more of the formulas V-1 to V-4:
and/or the number of the groups of groups,
the compound represented by the general formula VI is selected from one or more of the formulas VI-1 to VI-4:
and/or the number of the groups of groups,
the compound represented by the general formula VII is selected from one or more of formulas VII-1 to VII-4:
and/or the number of the groups of groups,
the compound represented by the general formula VIII is selected from one or more of the formulas VIII-1 to VIII-4:
and/or the number of the groups of groups,
the compound represented by the general formula IX is selected from one or more of the formulas IX-1 to IX-4:
further, the liquid crystal composition comprises the following components in percentage by weight:
5 to 7 percent of compound represented by a general formula I;
43 to 46 percent of compound represented by a general formula II;
2 to 3 percent of compound represented by a general formula III;
6 to 9 percent of compound represented by a general formula IV;
12 to 14 percent of compound represented by a general formula V;
3 to 5 percent of compound represented by a general formula VI;
13 to 15 percent of compound represented by a general formula VII;
3 to 5 percent of compound represented by a general formula VIII;
4% -5% of a compound represented by the general formula IX.
Further, in order to improve the stability of the liquid crystal composition to heat and light, particularly ultraviolet light, the liquid crystal composition further comprises one or more of an ultraviolet absorber, a hindered amine light stabilizer and a hindered phenol antioxidant; preferably, the ultraviolet absorber is selected from one or more of benzotriazoles, benzophenones, triazines and benzoates.
Further, in order to improve the display effect of the liquid crystal display device, the liquid crystal composition may further include one or more dichroic dyes; preferably, the dichroism dye is selected from one or more of azo and anthraquinone.
The liquid crystal composition has good low-temperature voltage change rate (dv/dt) and high clearing point, can be used for various display mode devices, and can widen the working temperature range of the liquid crystal display device. The display mode device is preferably a PDLC type liquid crystal display device or a dye PDLC type liquid crystal display device.
The method for producing the liquid crystal composition of the present invention is not particularly limited, and two or more compounds may be mixed by a conventional method for production, such as a method of mixing different components at high temperature and dissolving each other, wherein the liquid crystal composition is dissolved in a solvent for the compounds and mixed, and then the solvent is distilled off under reduced pressure; alternatively, the liquid crystal composition of the present invention may be prepared by a conventional method, such as dissolving the component having a smaller content in the main component having a larger content at a higher temperature, or dissolving each of the components in an organic solvent such as acetone, chloroform or methanol, etc., and then mixing the solutions to remove the solvent.
The compounds referred to in the present invention are all known compounds and are commercially available or available from Beijing eight hundred million space time liquid crystal technologies Co.
In the present invention, compounds represented by the general formulae I to IX:
the compound represented by the general formula I has high dielectric anisotropy (delta epsilon) and moderate intersolubility; the compound represented by the general formula II has large optical anisotropy (delta n), moderate clear point (Cp), good intersolubility and excellent comprehensive performance; the compound represented by the general formula III has larger optical anisotropy (delta n) and high clear point (Cp); the compound represented by the general formula IV has high clear point (Cp) and high optical anisotropy (delta n); the compound represented by the general formula V has high dielectric anisotropy (delta epsilon), moderate optical anisotropy (delta n), and excellent low-temperature intersolubility; the compound represented by the general formula VI has good low-temperature intersolubility and moderate optical anisotropy (delta n); the compound represented by the general formula VII has excellent low-temperature intersolubility, and can obviously improve the low-temperature performance of the liquid crystal composition; the compound represented by the general formula VIII has moderate clear point (Cp), moderate optical anisotropy (delta n) and good low-temperature intersolubility; the compound represented by the general formula IX has very high clearing point (Cp) and moderate optical anisotropy (Deltan).
The invention has the following beneficial effects:
the inventor performs a great deal of researches on the photoelectric property and physical property of the existing liquid crystal compounds, and unexpectedly discovers that when nine liquid crystal compounds of the general formulas I to IX selected from the liquid crystal compounds are combined according to a specific proportion, the obtained liquid crystal composition has lower voltage change rate and higher clear point, can realize ultra-wide temperature work, is particularly suitable for a PDLC display, can overcome the technical defects of narrower working temperature, particularly difficult driving at low temperature, of the existing PDLC display, and widens the application range of the PDLC display.
Detailed Description
The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
Unless otherwise indicated, percentages in the present invention are weight percentages; the temperature unit is in degrees celsius; Δn represents optical anisotropy (25 ℃); epsilon And epsilon Represents parallel and perpendicular dielectric constants (25 ℃,1000 Hz), respectively; delta epsilon represents dielectric anisotropy (25 ℃,1000 Hz); cp represents the clearing point (. Degree. C.) of the liquid crystal composition; vth25 represents a threshold voltage (V) at 25 ℃; vth-20 represents a threshold voltage (V) at-20deg.C; dv/dt represents the ratio of the threshold voltage variation to the temperature variation (mV/. Degree.C.) of-20 ℃ to 25 ℃.
In the following examples, the group structures in the liquid crystal compounds are represented by codes shown in Table 1.
TABLE 1
Taking the following compound structure as an example:
expressed as: 3DUCN
Expressed as: 3CCZPC2
In the following examples, the liquid crystal composition was prepared by a thermal dissolution method, which comprises the following steps: weighing the liquid crystal compound by a balance according to weight percentage, wherein the weighing and adding sequence has no specific requirement, generally weighing and mixing the liquid crystal compound in sequence from high melting point to low melting point, heating and stirring the liquid crystal compound at 60-100 ℃ to enable each component to be melted uniformly, filtering, steaming in a rotary mode, 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 examples below, all components referred to are known liquid-crystalline compounds, which are available from Beijing eight hundred million space-time.
Example 1
TABLE 2
Example 2
TABLE 3 Table 3
Category(s) Compound code Weight percent (%) Performance parameters Parameter value
I 2DUCN 2 Cp 129
I 3DUCN 5 △n 0.242
II 2UTPP3 22 △ε 12.8
II 5UTPP3 22 Vth25 1.81
III 3CPTP2 3 Vth-20 2.68
IV 3CGPC3 3 dv/dt 15.8
IV 5CGPC3 5
V 3PZUCN 7
V 5PZUCN 6
VI 3PZP5 4
VII 5CZPO2 8
VII 3CZPO2 4
VIII 3CPZP3 4
IX 3CCZPC3 5
Example 3
TABLE 4 Table 4
Example 4
TABLE 5
Example 5
TABLE 6
Example 6
TABLE 7
Category(s) Compound code Weight percent (%) Performance parameters Parameter value
I 2DUCN 8 Cp 131
II 2UTPP3 20 △n 0.241
II 4UTPP3 10 △ε 12.8
II 5UTPP3 17 Vth25 1.82
III 3CPTP2 1 Vth-20 2.89
IV 3CGPC3 4 dv/dt 19.5
IV 7CGPC3 4
V 3PZUCN 6
V 5PZUCN 6
VI 3PZP5 1
VII 2CZPO3 3
VII 3CZPO2 4
VII 4CZPO2 4
VII 7CZPO2 4
VIII 2CPZP5 1
IX 3CCZPC3 1
IX 5CCZPC3 2
IX 3CCZPC4 2
IX 3CCZPC5 2
Comparative example 1
The liquid crystal composition of this comparative example differs from example 1 only in that the group I compound 2DUCN in example 1 is replaced with an equivalent amount of the group V compound 5PZUCN. The weight percentages of the respective compounds in the liquid crystal compositions of this comparative example and the performance parameters of the liquid crystal compositions are shown in Table 8.
TABLE 8
Category(s) Compound code Weight percent (%) Performance parameters Parameter value
II 2UTPP3 20 Cp 132
II 4UTPP3 10 △n 0.248
II 5UTPP3 14 △ε 13.5
III 3CPTP2 3 Vth25 1.73
IV 3CGPC3 4 Vth-20 3.23
IV 5CGPC3 4 dv/dt 27.3
V 3PZUCN 7
V 5PZUCN 12
VI 3PZP5 4
VII 5CZPO2 13
VIII 3CPZP5 4
IX 3CCZPC3 5
Comparative example 2
The liquid crystal composition of this comparative example differs from example 1 only in that the V-group compounds 3PZUCN and 5PZUCN in example 1 are replaced with the same amount of the I-group compound 2DUCN. The weight percentages of the components in the liquid crystal composition of this comparative example and the performance parameters of the liquid crystal composition are shown in Table 9.
TABLE 9
The results of comparing the respective performance parameters of the liquid crystal compositions obtained in example 1, comparative example 1 and comparative example 2 together are shown in Table 10.
Table 10
Performance parameters CP △n △ε Vth25 Vth-20 dv/dt
Example 1 129 0.242 12.6 1.82 2.69 15.8
Comparative example 1 132 0.248 13.5 1.73 3.23 27.3
Comparative example 2 121 0.231 10.5 1.99 3.47 26.9
The comparison shows that: the low temperature voltage change rate of the liquid crystal composition containing no class I compound and the liquid crystal composition containing no class V compound are both significantly higher than that of example 1, indicating that the combination of the class I compound and the class V compound can significantly improve the low temperature voltage change rate (dv/dt) characteristics of the liquid crystal composition.
Comparative example 3
The liquid crystal composition of this comparative example is different from example 1 in that the compounds represented by the group IV, the group VII and the group VIII in example 1 are replaced with other types of liquid crystal compounds.
TABLE 11
The results of comparing the respective performance parameters of the liquid crystal compositions obtained in example 1 and comparative example 3 together are shown in Table 12.
Table 12
Performance parameters CP △n △ε Vth25 Vth-20 dv/dt
Example 1 129 0.242 12.6 1.82 2.69 15.8
Comparative example 3 133 0.244 12.7 1.83 2.83 18.2
The comparison shows that: the increase in the low temperature voltage change rate of the liquid crystal composition of comparative example 3 compared with example 1 indicates that the compounds represented by group IV, group VII and group VIII have a synergistic optimizing effect on the low temperature voltage change rate of the liquid crystal composition.
Comparative example 4
The liquid crystal composition of this comparative example is different from that of example 1 in the content of the compound represented by each category.
TABLE 13
The results of comparing the respective performance parameters of the liquid crystal compositions obtained in example 1 and comparative example 4 together are shown in Table 14.
TABLE 14
Performance parameters CP △n △ε Vth25 Vth-20 dv/dt
Example 1 129 0.242 12.6 1.82 2.69 15.8
Comparative example 4 138 0.231 9.1 2.43 3.79 24.7
The comparison shows that: the low temperature voltage change rate of the liquid crystal composition of comparative example 4 was significantly increased as compared with example 1.
Comparative example 5
The weight percentages of the components in the liquid crystal composition of this comparative example and the performance parameters of the liquid crystal composition are shown in Table 15.
TABLE 15
The results of comparing the respective performance parameters of the liquid crystal compositions obtained in example 1 and comparative example 5 together are shown in Table 16.
Table 16
Performance parameters CP △n △ε Vth25 Vth-20 dv/dt
Example 1 129 0.242 12.6 1.82 2.69 15.8
Comparative example 5 129 0.241 12.4 1.98 3.60 29.5
The comparison shows that: the liquid crystal composition provided in example 1 has low voltage change rate characteristics with the same level of dielectric anisotropy, optical anisotropy and clear point as comparative example 5, and is more easily driven at low temperature (-20 ℃).
While the invention has been described in detail in the foregoing general description, embodiments and experiments, it will be apparent to those skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.

Claims (12)

1. A liquid crystal composition characterized in that the liquid crystal composition comprises the following components in percentage by weight:
3 to 9 percent of compound represented by a general formula I;
41 to 47 percent of compound represented by a general formula II;
1 to 5 percent of compound represented by a general formula III;
5 to 10 percent of compound represented by a general formula IV;
10 to 15 percent of compound represented by a general formula V;
1 to 5 percent of compound represented by a general formula VI;
10 to 15 percent of compound represented by a general formula VII;
1 to 5 percent of compound represented by a general formula VIII;
2 to 7 percent of compound represented by a general formula IX,
the structures of the general formulas I to IX are as follows:
wherein R is 1 、R 21 、R 22 、R 31 、R 32 、R 41 、R 42 、R 5 、R 61 、R 62 、R 71 、R 72 、R 81 、R 82 、R 91 And R is 92 Identical or different, each independently represents C 1 ~C 12 Straight chain alkyl of (a).
2. The liquid crystal composition according to claim 1, wherein R is 1 、R 21 、R 22 、R 31 、R 32 、R 41 、R 42 、R 5 、R 61 、R 62 、R 71 、R 72 、R 81 、R 82 、R 91 And R is 92 Identical or different, each independently represents C 2 ~C 5 Straight chain alkyl of (a).
3. The liquid crystal composition according to claim 1 or 2, wherein the compound represented by the general formula I is selected from one or two of the formulas I-1 to I-2:
and/or the number of the groups of groups,
the compound represented by the general formula II is selected from one or more of the formulas II-1 to II-4:
and/or the number of the groups of groups,
the compound represented by the general formula III is selected from one or two of the formulas III-1 to III-2:
4. the liquid crystal composition according to claim 1 or 2, wherein the compound represented by the general formula IV is selected from one or two of the formulas IV-1 to IV-2:
and/or the number of the groups of groups,
the compound represented by the general formula V is selected from one or more of the formulas V-1 to V-4:
and/or the number of the groups of groups,
the compound represented by the general formula VI is selected from one or more of the formulas VI-1 to VI-4:
5. the liquid crystal composition according to claim 1 or 2, wherein the compound represented by the general formula VII is selected from one or more of the formulas VII-1 to VII-4:
and/or the number of the groups of groups,
the compound represented by the general formula VIII is selected from one or more of the formulas VIII-1 to VIII-4:
and/or the number of the groups of groups,
the compound represented by the general formula IX is selected from one or more of the formulas IX-1 to IX-4:
6. the liquid crystal composition according to claim 1 or 2, characterized in that it comprises the following components in weight percent:
5 to 7 percent of compound represented by a general formula I;
43 to 46 percent of compound represented by a general formula II;
2 to 3 percent of compound represented by a general formula III;
6 to 9 percent of compound represented by a general formula IV;
12 to 14 percent of compound represented by a general formula V;
3 to 5 percent of compound represented by a general formula VI;
13 to 15 percent of compound represented by a general formula VII;
3 to 5 percent of compound represented by a general formula VIII;
4% -5% of a compound represented by the general formula IX.
7. The liquid crystal composition according to claim 1, further comprising one or more of an ultraviolet absorber, a hindered amine light stabilizer, and a hindered phenol antioxidant.
8. The liquid crystal composition according to claim 7, wherein the ultraviolet absorber is one or more selected from the group consisting of benzotriazoles, benzophenones, triazines, and benzoates.
9. The liquid crystal composition of claim 1, further comprising a dichroic dye.
10. The liquid crystal composition according to claim 9, wherein the dichroic dye is one or more selected from azo dyes and anthraquinone dyes.
11. Use of a liquid crystal composition according to any one of claims 1 to 10 in a display mode device.
12. The use according to claim 11, wherein the display mode device is a PDLC type liquid crystal display device or a dye PDLC type liquid crystal display device.
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