CN112824498B - Liquid crystal composition and application thereof - Google Patents
Liquid crystal composition and application thereof Download PDFInfo
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- CN112824498B CN112824498B CN201911150212.7A CN201911150212A CN112824498B CN 112824498 B CN112824498 B CN 112824498B CN 201911150212 A CN201911150212 A CN 201911150212A CN 112824498 B CN112824498 B CN 112824498B
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Abstract
The invention provides a liquid crystal composition and application thereof, wherein the liquid crystal composition comprises at least one compound shown as a formula I and at least one compound shown as a formula II. The liquid crystal composition provided by the invention can maintain low-temperature stability (better than the prior art) on the premise of proper optical anisotropy and dielectric anisotropy, higher clearing point and lower rotational viscosity, has high voltage retention rate under high temperature and ultraviolet rays, low liquid crystal conductivity, high ion dissipation speed, obviously improved liquid crystal reliability and obviously improved ghost shadow, is a liquid crystal material with high reliability and good stability, is suitable for a liquid crystal display device with high display performance, can meet the application requirements of the liquid crystal material in various display modes, and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of liquid crystal materials, and particularly relates to a liquid crystal composition and application thereof.
Background
Liquid Crystal Displays (LCDs) have been rapidly developed due to their small size, light weight, low power consumption and excellent Display quality, and are widely used particularly in portable electronic information products. As the size of liquid crystal screens for portable computers, office applications, and video applications increases, liquid crystal displays can be used for large screen displays and eventually replace Cathode Ray Tube (CRT) displays. Liquid crystals are mainly used as dielectrics in liquid crystal display devices, and optical properties of such substances can be changed by applying a voltage, so that liquid crystal materials must have good chemical and thermal stability, and good stability against electric fields and electromagnetic radiation, and the like.
Compared with the traditional display device and display material, the liquid crystal display material has obvious advantages, such as low driving voltage, small power consumption, high reliability, large display information amount, color display, no flicker, no harm to human bodies, automation of production process, low cost, capability of being manufactured into liquid crystal displays of various specifications and types, convenience in carrying and the like. Due to these advantages, the liquid crystal display technology has a profound effect on the display and development field, and the development of the microelectronic technology and the optoelectronic information technology is promoted. The liquid crystal material is widely applied to various display occasions by virtue of good optical performance and photoelectric effect.
Liquid crystal display elements can be classified into various modes such as a Twisted Nematic (TN) mode, a Super Twisted Nematic (STN) mode, an in-plane (IPS) mode, and a Vertical Alignment (VA) mode, according to a display mode of liquid crystal. Among them, the Vertical Alignment (VA) mode display has advantages of wide viewing angle, high contrast, no rubbing alignment, etc., has been widely used, and has become a liquid crystal display technology with great prospect. For the liquid crystal material used in the VA mode, it is necessary to realize low driving voltage, fast response, and high reliability, wherein the high reliability requires the liquid crystal to have the characteristics of high voltage holding ratio, low conductance, excellent high temperature stability, and strict requirements for stability against UV light or irradiation by conventional backlight illumination.
Because of the sensitivity of liquid crystal materials to ultraviolet rays, finished liquid crystals generally need to be matched with additives with an anti-UV function for use, wherein hindered amine light stabilizers are most widely applied. The hindered amine compound has good physical and chemical stability and excellent UV tolerance as an ultraviolet absorbent most commonly used in the field of liquid crystal materials at present, but the known hindered amine compound has the problem of poor compatibility after being mixed and dissolved with the liquid crystal materials, and particularly when the hindered amine compound is applied to a low-temperature environment, the phenomenon of solid precipitation often occurs. Therefore, developing a liquid crystal material with better mutual solubility to meet the demand of increasingly wide application environments is an urgent problem to be solved in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a liquid crystal composition, which has better low-temperature intersolubility through the matching use of specific components, has lower liquid crystal conductance, higher ion dissipation speed and higher voltage retention rate on the basis, obviously improves the reliability, and is suitable for display modes such as IPS, NFFS, VA, PSVA and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a liquid crystal composition comprising:
at least one compound of the formula I
at least one compound of the formula II
Wherein R is N Represents hydrogen, hydroxyl, C1-C15 straight chain or branched chain alkyl, or-CH in which one or at least two (for example, 2, 3, etc.) of the C1-C15 straight chain or branched chain alkyl are not adjacent 2 -groups substituted by-O-, -CO-, -NH-.
The C1-C15 can be C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14 or C15.
R x To represent
Or the said
Or at least two (e.g., 2, 3, etc.) non-adjacent-CH(s) 2 -a group substituted by-O-, -CO-, the dotted line representing the radical with-CH in the six-membered ring of formula I 2 The connecting site of (A) and the wavy line represents the group with S p The attachment site of (c).
Y 1 、Y 2 、Y 3 、Y 4 Each independently represents hydrogen or a C1 to C4 (e.g. C1, C2, C3 or C4) straight chain alkyl group.
t is 0 or 1, and when t is 1, R x Is different from
r is an integer from 1 to 4, for example r is 1, 2, 3 or 4.
When r is 1, S p Having a radical of formula (I) with R N The same limits apply.
When r is an integer of 2 to 4, S p Represents a C1-C15 linear or branched alkylene group, a C3-C7 cycloalkylene group, a C6-C15 arylene group, or one or at least two non-adjacent-CH groups in the C1-C15 linear or branched alkylene group 2 -substituted by-O-, -CO-O-, -O-CO-or-NH-, or-CH in said C1-C15 linear or branched alkylene, said C3-C7 cycloalkylene 2 -CH 2 -a group substituted by-CH = CH-or-C ≡ C-, or a group in which one or at least two CH of said C6 to C15 arylene radicals are substituted by N.
The C1-C15 can be C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14 or C15.
The C3-C7 can be C3, C4, C5, C6 or C7.
The C6-C15 can be C6, C7, C8, C9, C10, C11, C12, C13, C14 or C15.
R 1 、R 2 Each independently represents hydrogen, halogen, a halogenated or non-halogenated C1 to C10 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10) linear alkyl group, a halogenated or non-halogenated C1 to C10 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10) linear alkoxy group, a halogenated or non-halogenated C2 to C10 (e.g., C2, C3, C4, C5, C6, C7, C8, C9 or C10) alkenyl group, a halogenated or non-halogenated C2 to C10 (e.g., C2, C3, C4, C5, C6, C7, C8, C9 or C10) alkenyloxy group, or one or at least two (e.g., 2, 3, etc.) of the foregoing groups adjacent-CH 2 -a group substituted by a C3-C5 (e.g. C3, C4 or C5) cycloalkylene group.
Ring A 1 And ring A 2 Each independently represents 1, 4-cyclohexylene, 1, 4-cyclohexenylene, oxacyclohexylene, substituted or unsubstituted 1, 4-phenylene; when present, the substituent is halogen (e.g., fluorine, chlorine, etc.) or methyl.
Z 1 、Z 2 Each independently represents a single bond, -O-, or-S-, -COO-) -OCO-, -CH 2 O-、-OCH 2 -、-CF 2 O-、-OCF 2 -or-CH 2 CH 2 -。
X 1 、X 2 Each independently represents hydrogen, fluorine or chlorine.
G represents-O-, -S-or
n 1 、n 2 Each independently represents an integer of 0 to 2, such as 0, 1 or 2; and when n is 1 When 2, ring A 1 Same or different, Z 1 The same or different; when n is 2 When 2, ring A 2 Same or different, Z 2 The same or different.
Preferably, the compound of formula I has any one of the following structures:
wherein R is N 、Y 1 、Y 2 、Y 3 、Y 4 、r、S p Each independently having the same ranges as defined above.
As a further preferred technical scheme of the invention, the compound of the formula I has a structure shown in any one of a formula I-1, a formula I-2, a formula I-3 or a formula I-4, and is further preferably any one of the following structures:
wherein R is N Represents hydrogen, a C1-C15 linear or branched alkyl group, or a C1-C15 linear or branched alkoxy group.
In the formula I-2-1, the formula I-3-1 and the formula I-4-1, S p Represents hydrogen, hydroxyl, C1-C15 straight chain or branched chain alkyl, or one or at least two non-adjacent-CH of the C1-C15 straight chain or branched chain alkyl 2 -groups substituted by-O-, -CO-, -NH-.
In the formula I-2-2, the formula I-3-2 and the formula I-4-2, S p Represents a C1-C15 linear or branched alkylene group, a C3-C7 cycloalkylene group, a C6-C15 arylene group, or one or at least two non-adjacent-CH in the C1-C15 linear or branched alkylene group 2 -substituted by-O-, -CO-O-, -O-CO-or-NH-, or-CH in said C1-C15 linear or branched alkylene, said C3-C7 cycloalkylene 2 -CH 2 -a group substituted by-CH = CH-or-C ≡ C-, or a group in which one or at least two CH of said C6 to C15 arylene radicals are substituted by N.
The C1-C15 can be C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14 or C15.
The C3-C7 can be C3, C4, C5, C6 or C7.
The C6-C15 can be C6, C7, C8, C9, C10, C11, C12, C13, C14 or C15.
Preferably, said R is N Represents hydrogen or a C1-C8 (e.g., C1, C2, C3, C4, C5, C6, C7, or C8) straight chain alkyl group.
Preferably, said Y is 1 、Y 2 、Y 3 、Y 4 Are all methyl.
Preferably, r is 1 or 2.
Preferably, said S p Represents hydrogen, a hydroxyl group, C1 to C10 (for example, C1, C2, C3, C4,C5, C6, C7, C8, C9 or C10) straight-chain alkyl, C1-C10 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10) straight-chain alkylene, or one of said C1-C10 straight-chain alkyl, said C1-C10 straight-chain alkylene, or at least two non-adjacent-CH 2 -a group substituted by-O-, -CO-or-NH-.
Preferably, the compound of formula II has any one of the following structures:
wherein R is 1 、R 2 Each independently represents a C1-C6 (e.g., C1, C2, C3, C4, C5, or C6) linear alkyl group, a C1-C6 (e.g., C1, C2, C3, C4, C5, or C6) linear alkoxy group, a C3-C5 (e.g., C3, C4, or C5) cycloalkyl group, or a C3-C5 (e.g., C3, C4, or C5) cycloalkyloxy group.
Ring A 1 Ring A 2 Each independently represents a 1, 4-cyclohexylene group, a 1, 4-cyclohexenylene group, an oxacyclohexylene group, a substituted or unsubstituted 1, 4-phenylene group; when present, the substituent is halogen (e.g., fluorine or chlorine, etc.) or methyl.
G is-O-or-S-.
In the technical solution of the present invention, the content of the compound of formula I in the liquid crystal composition is 0.001 to 1% by mass, for example, 0.003%, 0.005%, 0.008%, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.08%, 0.1%, 0.3%, 0.5%, 0.7%, or 0.9%, and the specific values between the above-mentioned values are limited by space and for brevity, and the present invention does not exhaust the specific values included in the range, preferably 0.001 to 0.05%, and more preferably 0.001 to 0.2%.
In the technical solution of the present invention, the content of the compound of formula II in the liquid crystal composition is 1 to 25% by mass, for example, 2%, 4%, 6%, 8%, 10%, 12%, 14%, 16%, 18%, 20%, 22% or 24%, and specific values between the above values are limited by space and for simplicity, and the present invention does not exhaustive list the specific values included in the range, preferably 1 to 20%, and more preferably 1 to 15%.
In the technical scheme of the invention, the liquid crystal composition also comprises at least one compound of formula III-1 to formula III-3:
wherein R is 3 -R 8 Each independently represents hydrogen, a halogenated or non-halogenated C1 to C7 (e.g., C1, C2, C3, C4, C5, C6 or C7) linear alkyl group, a halogenated or non-halogenated C1 to C7 (e.g., C1, C2, C3, C4, C5, C6 or C7) linear alkoxy group, a halogenated or non-halogenated C2 to C7 (e.g., C2, C3, C4, C5, C6 or C7) alkenyl group, a halogenated or non-halogenated C2 to C7 (e.g., C2, C3, C4, C5, C6 or C7) alkenyloxy group.
Z 3 、Z 4 、Z 5 Each independently represents a single bond, -COO-, -OCO-, -CH 2 O-、-OCH 2 -or-CH 2 CH 2 -。
Ring A 3 -A 11 Each independently represents 1, 4-cyclohexylene, 1, 4-cyclohexenylene, a halogenated or non-halogenated 1, 4-phenylene group.
Preferably, the compound of formula III-1 has any one of the following structures:
wherein R is 3 、R 4 Each independently represents a C1 to C5 (e.g., C1, C2, C3, C4, or C5) straight chain alkyl group, a C1 to C5 (e.g., C1, C2, C3, C4, or C5) straight chain alkoxy group, or a C2 to C7 (e.g., C2, C3, C4, C5, C6, or C7) alkylene group.
The compound of formula III-2 has any one of the following structures:
wherein R is 5 、R 6 Each independently represents a C1 to C5 (e.g., C1, C2, C3, C4, or C5) straight chain alkyl group, a C1 to C5 (e.g., C1, C2, C3, C4, or C5) straight chain alkoxy group, or a C2 to C7 (e.g., C2, C3, C4, C5, C6, or C7) alkylene group.
The compound of formula III-3 has any one of the following structures:
wherein R is 7 、R 8 Each independently is a C1 to C7 (e.g., C1, C2, C3, C4, C5, C6, or C7) straight chain alkyl group.
In the technical solution of the present invention, the mass percentage content of the compounds of formulae III-1 to III-3 in the liquid crystal composition is 40 to 85%, for example, 41%, 43%, 45%, 47%, 50%, 53%, 55%, 57%, 60%, 62%, 65%, 68%, 70%, 72%, 75%, 78%, 80%, 82%, or 84%, and specific values therebetween are not exhaustive, and for brevity and conciseness, the present invention does not list specific values included in the range, preferably 50 to 85%.
In the technical solution of the present invention, the liquid crystal composition further comprises at least one compound of formula IV:
wherein R is 9 、R 10 Each independently represents hydrogen, halogen, C3-C5 cycloalkyl (including cyclopropane, cyclobutane or cyclopentane), halogenated or non-halogenated C1-C10 (e.g. C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10) straight chain alkyl, halogenated or non-halogenated C1-C10 (e.g. C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10) straight chain alkoxy, halogenated or non-halogenated C2-C10 (e.g. C2, C3, C4, C5, C6, C7, C8, C9 or C10) alkenyl, halogenated or non-halogenated C2-C10 (e.g. C2, C3, C4, C5, C6, C7, C8, C9 or C10) alkenyloxy.
Z 6 、Z 7 Each independently represents a single bond, -COO-, -OCO-, -CH 2 O-、-OCH 2 -or-CH 2 CH 2 -。
Ring A 12 Ring A 13 Each independently represents a 1, 4-cyclohexylene group1, 4-cyclohexenylene, a halogenated or non-halogenated 1, 4-phenylene group, or one or at least two non-adjacent-CH's in the 1, 4-cyclohexylene group 2 -is replaced by-O-.
n 3 、n 4 Each independently represents an integer of 0 to 2, such as 0, 1 or 2; and when n is 3 When 2, ring A 12 Same or different, Z 6 The same or different; when n is 4 When 2, ring A 13 Same or different, Z 7 The same or different.
Preferably, the compound of formula IV has any one of the following structures:
wherein R is 9 、R 10 Each independently represents a C1 to C5 (e.g., C1, C2, C3, C4, or C5) linear alkyl group or a C1 to C5 (e.g., C1, C2, C3, C4, or C5) linear alkoxy group.
In the technical solution of the present invention, the mass percentage of the compound of formula IV in the liquid crystal composition is 1 to 45%, for example, 2%, 4%, 6%, 8%, 10%, 13%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 33%, 35%, 38%, 40%, 42% or 44%, and specific values therebetween are not exhaustive, and for brevity, the present invention does not list the specific values included in the range, preferably 1 to 40%, more preferably 1 to 35%, and still more preferably 1 to 30%.
In the liquid crystal composition provided by the invention, the compounds in each component can be obtained commercially, the synthesis method is the prior art, and the source of the compounds is not described in detail in the invention.
The liquid crystal composition provided by the invention is prepared by mixing the components according to the above-defined proportion, and the mixing conditions exemplarily include but are not limited to: stirring, heating, ultrasonic wave, suspension, etc.
In another aspect, the present invention provides a liquid crystal display device comprising the liquid crystal composition as described above.
Compared with the prior art, the invention has the following beneficial effects:
the liquid crystal composition provided by the invention can maintain low-temperature stability (even better than the prior art) on the premise of proper optical anisotropy and dielectric anisotropy, higher clearing point and lower rotational viscosity, has high voltage retention rate under high temperature and ultraviolet rays, is low in liquid crystal conductivity, high in ion dissipation speed, remarkably improved in liquid crystal reliability and obviously improved in ghost, is a liquid crystal material with high reliability and good stability, is suitable for a liquid crystal display device with high display performance, can meet the application requirements of the liquid crystal material in various display modes, and has wide application prospect.
Drawings
FIG. 1 is a comparative graph showing the DC residual potential of the liquid crystal compositions provided in examples 1 to 5 and comparative example 1;
FIG. 2 is a comparative graph showing the DC residual potential of the liquid crystal compositions provided in examples 6 to 8 and comparative example 2;
FIG. 3 is a comparative graph showing the DC residual potential of the liquid crystal compositions provided in examples 9 to 11 and comparative example 3;
FIG. 4 is a comparative graph showing the DC residual potential of the liquid crystal compositions provided in examples 12 to 14 and comparative example 4;
FIG. 5 is a comparative graph showing the DC residual potential of the liquid crystal compositions provided in examples 15 to 17 and comparative example 5;
FIG. 6 is a comparative graph showing the DC residual potential of the liquid crystal compositions provided in examples 18 to 20 and comparative example 6;
FIG. 7 is a comparative graph showing the DC residual potential of the liquid crystal compositions provided in examples 20 to 25 and comparative example 6.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The compounds used in the following examples of the present invention can be synthesized by the prior art or can be obtained commercially, and the present invention is not described in detail with respect to the source of the raw materials.
For convenience of description, in the following examples and comparative examples of the present invention, the compounds of the components of the liquid crystal composition are represented by the codes listed in Table 1:
TABLE 1
Compounds of the following formula are exemplified:
the compound is represented by the code in Table 1, and is referred to as "mC1OWPV", wherein m is an integer of 1 or more and represents the number of C atoms in the left-end alkyl group.
In the following examples and comparative examples of the present invention, the method for testing the properties of the liquid crystal composition was as follows:
(1) Optical anisotropy Δ n: measured by Abbe refractometer under sodium lamp (589 nm) light source at 25 + -2 deg.C.
(2) Dielectric anisotropy Δ ∈: Δ ε = ε ∥ -ε ⊥ Wherein epsilon ∥ Is a dielectric constant parallel to the molecular axis,. Epsilon ⊥ Is the dielectric constant perpendicular to the molecular axis; and (3) testing conditions are as follows: 25 +/-0.5 ℃,1KHz, VA test box, and the box thickness is 7 mu m.
(3) Clearing point T ni : nematic phase-isotropic phase transition temperature in units of; the measurement was carried out by a melting point apparatus quantitative method.
(4) Rotational viscosity gamma 1 : the unit is mPa.s; and (3) testing conditions are as follows: 25 +/-0.5 ℃,20 mu m parallel box, INSTEC: ALCTIR 1.
(5) Voltage holding ratio under ultraviolet ray VHR-UV: the unit is%; and (3) testing conditions are as follows: the TOYO 6254 liquid crystal physical property evaluation system was tested at 5V, 6Hz and 60 ℃ under UV conditions of 365nm and 3000mJ.
(6) Voltage holding ratio at high temperature VHR-heat: the unit is%; and (3) testing conditions are as follows: after the liquid crystal is kept at high temperature of 150 ℃ for 1h, the liquid crystal is tested at 5V, 6Hz and 60 ℃ by utilizing a TOYO 6254 type liquid crystal physical property evaluation system;
(7) Conductivity I/V: the unit is Ghom -1 (ii) a And (3) testing conditions are as follows: in a 9 μm twisted nematic liquid crystal cell (TN cell) cell, a liquid crystal was filled, and applied with electricity at 10V/0.01Hz, and the I/V value was obtained by a test using TOYO 6254 (liquid crystal physical property evaluation system).
(8) Low temperature storage time t -20℃ : the observation was carried out daily in a low-temperature incubator at-20 ℃ to see whether crystals precipitated.
(9) RDC curve of dc residual potential: the test condition is 25 + -0.5 deg.C, the TOYO 6254 type liquid crystal physical property evaluation system cuts off the power supply after applying DC voltage 5V and 3600s, and continuously tests the residual potential 3600s of the liquid crystal, and records the potential variation curve.
Examples 1 to 5 and comparative example 1
The composition of the parent Host-1 is shown in Table 2:
TABLE 2
By adding different amounts of the compound Guest-1 of formula I as in Table 3 below to Host-1:
comparative example 1 and examples 1 to 5 constituting the present invention.
TABLE 3
The results of the performance test of the liquid crystal compositions provided in examples 1 to 5 and comparative example 1 are shown in Table 4, and the comparative test chart of the DC residual potential values is shown in FIG. 1:
TABLE 4
As can be seen from the data in Table 4, compared with comparative example 1 which does not include the compound Guest-1 of formula I, the liquid crystal compositions provided in examples 1 to 5 have the advantages of no reduction in low-temperature storage time, even prolongation, higher voltage holding ratio and lower ionic dissipation coefficient I/V, and prove that the liquid crystal compositions provided in examples 1 to 5 of the present invention can achieve both low-temperature mutual solubility and reliability.
Fig. 1 is a comparison graph of dc residual potential tests of the liquid crystal compositions provided in examples 1 to 5 and comparative example 1, and it can be seen from fig. 1 that the content of the compound of formula I has a significant effect on the RDC curve of the dc residual potential, and the dissipation rate of ions is increased when the content is in the range of 0.01% to 0.2%, wherein the dissipation rate of ions is fastest when the content is in the range of 0.05% to 0.1%.
Examples 6 to 8 and comparative example 2
The composition of the parent Host-2 is shown in Table 5:
TABLE 5
By adding different amounts of the compound Guest-2 of formula I as shown in Table 6 below to Host-2:
comparative example 2 and examples 6 to 8 constituting the present invention.
TABLE 6
| Example 6 | Example 7 | Example 8 | Comparative example 2 | |
| Guest-2 content (%) | 0.04 | 0.08 | 0.12 | 0 |
The results of the performance tests of the liquid crystal compositions provided in examples 6 to 8 and comparative example 2 are shown in Table 7, and the comparative test chart of the DC residual potential values is shown in FIG. 2:
TABLE 7
| Example 6 | Example 7 | Example 8 | Comparative example 2 | |
| Δn | 0.109 | 0.109 | 0.109 | 0.109 |
| Δε | -1.3 | -1.3 | -1.3 | -1.3 |
| T ni (℃) | 82 | 82 | 82 | 82 |
| γ 1 | 88 | 88 | 88 | 88 |
| VHR-UV | 92.3 | 92.3 | 91.9 | 84.1 |
| VHR-heat | 92.1 | 92.2 | 92.1 | 90.3 |
| I/V | 94.8 | 40.1 | 65.2 | 744.7 |
| t -20℃ | 7 days | 8 days | 8 days | 7 days |
As can be seen from the data in Table 7, compared with comparative example 2 which does not include the compound Guest-2 of formula I, the liquid crystal compositions provided in examples 6 to 8 have the advantages of no reduction in low-temperature storage time, even prolongation, higher voltage holding ratio and lower ionic dissipation coefficient I/V, and the liquid crystal compositions provided in examples 6 to 8 of the present invention are proved to have both low-temperature mutual solubility and reliability.
FIG. 2 is a comparison graph of DC residual potential tests of the liquid crystal compositions provided in examples 6-8 and comparative example 2, and it can be seen from FIG. 2 that the content of the compound of formula I has a significant effect on the DC residual potential RDC curve, and when the content is in the range of 0.04-0.12%, the dissipation rate of ions is increased.
Examples 9 to 11 and comparative example 3
The composition of the parent Host-3 is shown in Table 8:
TABLE 8
| Liquid crystal molecules | Mass fraction/% |
| 3CCV | 46 |
| 3CCV1 | 9 |
| VCCP1 | 6 |
| 3CPP2 | 5 |
| |
3 |
| |
3 |
| 2PWP3 | 5 |
| 2PWP4 | 5 |
| 2PPW3 | 5 |
| 2PPW4 | 5 |
| 3OB(O)O4 | 4 |
| 3OB(S)O4 | 4 |
| Small counter | 100 |
By adding different amounts of the compound Guest-3 of formula I as in Table 9 below to Host-3:
comparative example 3 and examples 9 to 11 constituting the present invention.
TABLE 9
| Example 9 | Example 10 | Example 11 | Comparative example 3 | |
| Guest-3 content (%) | 0.02 | 0.05 | 0.1 | 0 |
The results of the performance tests of the liquid crystal compositions provided in examples 9 to 11 and comparative example 3 are shown in Table 10, and the comparative test chart of the DC residual potential values is shown in FIG. 3:
TABLE 10
As can be seen from the data in Table 10, the liquid crystal compositions provided in examples 9 to 11 have not shortened or even prolonged low-temperature storage time, higher voltage holding ratio and lower ion dissipation factor I/V, compared with comparative example 3 which does not include the compound Guest-3 of formula I, and the liquid crystal compositions provided in examples 9 to 11 of the present invention are proved to have both low-temperature mutual solubility and reliability.
FIG. 3 is a comparison graph of DC residual potential tests of the liquid crystal compositions provided in examples 9-11 and comparative example 3, and it can be seen from FIG. 3 that the content of the compound of formula I has a significant effect on the DC residual potential RDC curve, and when the content is in the range of 0.02% -0.1%, the dissipation rate of ions is increased.
Examples 12 to 14 and comparative example 4
The composition of the parent Host-4 is shown in Table 11:
TABLE 11
| Liquid crystal molecules | Mass fraction/%) |
| 3CCV | 44 |
| 3CCV1 | 10 |
| VCCP1 | 5 |
| 3CPP1 | 4 |
| 3CPP2 | 4 |
| |
3 |
| |
3 |
| 2PWP3 | 5 |
| 2PWP4 | 5 |
| 3PPWO2 | 5 |
| 4PPWO2 | 5 |
| 2COB(O)O4 | 3.5 |
| 3COB(O)O4 | 3.5 |
| Small counter | 100 |
By adding different amounts of the compound Guest-4 of formula I as in Table 12 below to Host-4:
comparative example 4 and examples 12 to 14 constituting the present invention.
TABLE 12
| Example 12 | Example 13 | Example 14 | Comparative example 4 | |
| Guest-4 content (%) | 0.02 | 0.05 | 0.1 | 0 |
The results of the performance tests of the liquid crystal compositions provided in examples 12 to 14 and comparative example 4 are shown in Table 13, and the comparative test chart of the DC residual potential values is shown in FIG. 4:
watch 13
| Example 12 | Example 13 | Example 14 | Comparative example 4 | |
| Δn | 0.112 | 0.112 | 0.112 | 0.112 |
| Δε | -1.6 | -1.6 | -1.6 | -1.6 |
| T ni (℃) | 84 | 84 | 84 | 84 |
| γ 1 | 98 | 98 | 98 | 98 |
| VHR-UV | 92.9 | 93.7 | 93.4 | 84.8 |
| VHR-heat | 93.4 | 93.6 | 93.6 | 90.7 |
| I/V | 68.2 | 33.0 | 31.8 | 612.2 |
| t -20℃ | 7 days | 8 days | 8 days | 7 days |
As can be seen from the data in Table 13, the liquid crystal compositions provided in examples 12 to 14 have a shorter or even longer low temperature storage time, a higher voltage holding ratio and a lower ion dissipation factor I/V than comparative example 4 which does not include Guest-4, which is a compound of formula I, and thus it is proved that the liquid crystal compositions provided in examples 12 to 14 according to the present invention can achieve both low temperature mutual solubility and reliability.
FIG. 4 is a comparison of DC residual potential tests of the liquid crystal compositions provided in examples 12 to 14 and comparative example 4, and it can be seen from FIG. 4 that the addition of the compound of formula I has a significant effect on the RDC curve, and the content thereof in the range of 0.02% to 0.1% increases the dissipation rate of ions.
Examples 15 to 17 and comparative example 5
The composition of the parent Host-5 is shown in Table 14:
TABLE 14
By adding varying amounts of a compound of formula I Guest-5 as in Table 15 below to Host-5:
comparative example 5 and examples 15 to 17 constituting the present invention.
Watch 15
| Example 15 | Example 16 | Example 17 | Comparative example 5 | |
| Guest-5 content (%) | 0.03 | 0.06 | 0.09 | 0 |
The results of the performance tests of the liquid crystal compositions provided in examples 15 to 17 and comparative example 5 are shown in table 16, and the comparative test chart of the dc residual potential values is shown in fig. 5:
TABLE 16
As can be seen from the data in Table 16, compared with comparative example 5 which does not include the compound Guest-5 of formula I, the liquid crystal compositions provided in examples 15 to 17 have no short or even prolonged low-temperature storage time, and the voltage holding ratio is obviously increased, and the ion dissipation coefficient I/V is obviously reduced, which proves that the liquid crystal compositions provided in examples 15 to 17 of the present invention can achieve both low-temperature mutual solubility and reliability.
Fig. 5 is a comparison graph of dc residual potential tests of the liquid crystal compositions provided in examples 15 to 17 and comparative example 5, and it can be seen from fig. 5 that the addition of the compound Guest-5 of formula I has a significant effect on the RDC curve of the dc residual potential, and when the content thereof is in the range of 0.03% to 0.09%, the dissipation rate of ions can be significantly increased.
Examples 18 to 20 and comparative example 6
The composition of the parent Host-6 is shown in Table 17:
TABLE 17
By adding varying amounts of a compound of formula I Guest-6 as shown in Table 18 below to Host-6:
comparative example 6 and examples 18 to 20 constituting the present invention.
Watch 18
| Example 18 | Example 19 | Example 20 | Comparative example 6 | |
| Guest-6 content (%) | 0.02 | 0.05 | 0.08 | 0 |
The results of the performance tests of the liquid crystal compositions provided in examples 18 to 20 and comparative example 6 are shown in Table 19, and the comparative test chart of the DC residual potential values is shown in FIG. 6:
watch 19
| Example 18 | Example 19 | Example 20 | Comparative example 6 | |
| Δn | 0.095 | 0.095 | 0.095 | 0.095 |
| Δε | -2.6 | -2.6 | -2.6 | -2.6 |
| T ni (℃) | 90 | 90 | 90 | 90 |
| γ 1 | 109 | 109 | 109 | 109 |
| VHR-UV | 90.5 | 92.3 | 92.4 | 84.8 |
| VHR-heat | 93 | 93.1 | 93.3 | 90.7 |
| I/V | 68.2 | 33.0 | 31.8 | 612.2 |
| t -20℃ | 8 days | 9 days | 9 days | 8 days |
As can be seen from the data in Table 19, the liquid crystal compositions provided in examples 18 to 20 have no shorter or even longer low-temperature storage time, higher voltage holding ratio and significantly lower ion dissipation factor I/V compared to comparative example 6 which does not include Guest-6, a compound of formula I, and thus, the liquid crystal compositions provided in examples 18 to 20 of the present invention can achieve both low-temperature miscibility and reliability.
FIG. 6 is a comparison graph of DC residual potential tests of the liquid crystal compositions provided in examples 18 to 20 and comparative example 6, and it can be seen from FIG. 6 that the addition of Guest-6 compound of formula I has a significant effect on the RDC curve of DC residual potential, and when the content is in the range of 0.03% to 0.09%, the ion dissipation rate is significantly increased.
Example 21
This example provides a liquid crystal composition which differs from example 20 in that Guest-6 is replaced with an equal amount of Guest-1.
Example 22
This example provides a liquid crystal composition which differs from example 20 in that Guest-6 is replaced with an equal amount of Guest-2.
Example 23
This example provides a liquid crystal composition which differs from example 20 in that Guest-6 is replaced with an equal amount of Guest-3.
Example 24
This example provides a liquid crystal composition which differs from example 20 in that Guest-6 is replaced with an equal amount of Guest-4.
Example 25
This example provides a liquid crystal composition which differs from example 20 in that Guest-6 is replaced with an equal amount of Guest-5.
Comparative example 7
Comparative example 7 differs from example 20 in that Guest-6 was mixed with an equal amount of the comparative compound Guest-DZ:
and (6) replacing.
The results of the performance tests of the liquid crystal compositions provided in examples 20 to 25 and comparative example 6 are shown in Table 20, and the comparative DC residual potential test chart is shown in FIG. 7:
watch 20
It can be known from the composition information and the test data in the above tables 2 to 20 that the low temperature storage time of the liquid crystal composition provided by the present invention is not shortened, even prolonged, and in addition, the liquid crystal composition has higher VHR-UV and VHR-heat and lower liquid crystal conductance, as can be seen from fig. 1 to 7, the liquid crystal composition of the present invention also has faster ion dissipation speed, the reliability of the liquid crystal is significantly improved, the improvement of the ghost shadow is significant, and the optimal content range of the compound of formula I in the liquid crystal composition is 0.05 to 0.1%.
The applicant states that the present invention is illustrated by the above examples to the liquid crystal composition and its application, but the present invention is not limited to the above process steps, i.e. it does not mean that the present invention must rely on the above process steps to be carried out. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (10)
1. A liquid crystal composition, comprising:
at least one compound of formula I having any one of the following structures I-1, I-3, I-4:
at least one compound of the formula II
at least one compound selected from the group consisting of formula III-1 to formula III-3:
wherein R is N Represents hydrogen, hydroxyl, C1-C15 straight chain or branched chain alkyl, or one or at least two non-adjacent-CH in the C1-C15 straight chain or branched chain alkyl 2 -a group substituted by-O-, -CO-, -NH-;
Y 1 、Y 2 、Y 3 、Y 4 each independently represents hydrogen or a C1-C4 linear alkyl group;
r is 1 or 2;
when r is 1, S p Having a radical of formula (I) with R N The same limitations apply;
when r is 2, S p Represents a C1-C15 linear or branched alkylene group, a C3-C7 cycloalkylene group, a C6-C15 arylene group, or one or at least two non-adjacent-CH in the C1-C15 linear or branched alkylene group 2 -substituted by-O-, -CO-O-, -O-CO-or-NH-, or-CH in said C1-C15 linear or branched alkylene, said C3-C7 cycloalkylene 2 -CH 2 -a group substituted by-CH = CH-or-C ≡ C-, or a group in which one or at least two CH of said C6 to C15 arylene radicals are substituted by N;
R 1 、R 2 each independently represents hydrogen, halogen, halogenated or non-halogenated C1-C10 linear alkyl, halogenated or non-halogenated C1-C10 linear alkoxy, halogenated or non-halogenated C2-C10 alkenyl, halogenated or non-halogenated C2-C10 alkenyloxy, or one or at least two non-adjacent-CH 2 -a group substituted by a C3-C5 cycloalkylene group;
ring A 1 And ring A 2 Each independently represents 1, 4-cyclohexylene, 1, 4-cyclohexenylene, oxacyclohexylene, substituted or unsubstituted 1, 4-phenylene; when a substituent is present, the substituent is halogen or methyl;
Z 1 、Z 2 each independently represents a single bond, -O-, or-S-, -COO-) -OCO-, -CH 2 O-、-OCH 2 -、-CF 2 O-、-OCF 2 -or-CH 2 CH 2 -；
X 1 、X 2 Each independently represents hydrogen, fluorine or chlorine;
g represents-O-, -S-or
n 1 、n 2 Each independently represents an integer of 0 to 2; and when n is 1 When 2, ring A 1 Same or different, Z 1 The same or different; when n is 2 When 2, ring A 2 Same or different, Z 2 The same or different;
R 3 -R 8 each independently represents hydrogen, halogenated or non-halogenated C1-C7 straight-chain alkyl, halogenated or non-halogenated C1-C7 straight-chain alkoxy, halogenated or non-halogenated C2-C7 alkenyl, and halogenated or non-halogenated C2-C7 alkenyloxy;
Z 3 、Z 4 、Z 5 each independently represents a single bond, -COO-, -OCO-, -CH 2 O-、-OCH 2 -or-CH 2 CH 2 -；
Ring A 3 -A 11 Each independently represents 1, 4-cyclohexylene, 1, 4-cyclohexenylene, a halogenated or non-halogenated 1, 4-phenylene group;
the liquid crystal composition comprises 0.001-1% of a compound in a formula I, 1-25% of a compound in a formula II and 40-85% of compounds in a formula III-1-III-3 by mass.
2. The liquid crystal composition according to claim 1, wherein R is N Represents hydrogen or a C1-C8 linear alkyl group.
3. The liquid crystal composition according to claim 1, wherein Y is 1 、Y 2 、Y 3 、Y 4 Are all methyl.
4. The liquid crystal composition according to claim 1, wherein S is p Represents hydrogen, hydroxyl, C1-C10 linear alkyl, C1-C10 linear alkylene, or one or at least two non-adjacent-CH in the C1-C10 linear alkyl, the C1-C10 linear alkylene 2 -a group substituted by-O-, -CO-or-NH-.
5. The liquid crystal composition of claim 1, wherein the compound of formula II has any one of the following structures:
wherein R is 1 、R 2 Each independently represents a C1-C6 linear alkyl group, a C1-C6 linear alkoxy group, a C3-C5 cycloalkyl group or a C3-C5 cycloalkyloxy group;
ring A 1 Ring A 2 Each independently represents 1, 4-cyclohexylene, 1, 4-cyclohexenylene, oxacyclohexylene, substituted or unsubstituted 1, 4-phenylene; when a substituent is present, the substituent is halogen or methyl;
g represents-O-or-S-.
6. The liquid crystal composition of claim 1, wherein the compound of formula III-1 has any one of the following structures:
wherein R is 3 、R 4 Each independently represents C1-C5 straightAn alkyl group, a C1-C5 linear alkoxy group or a C2-C7 alkenyl group;
the compound of formula III-2 has any one of the following structures:
wherein R is 5 、R 6 Each independently represents a C1-C5 linear alkyl group, a C1-C5 linear alkoxy group or a C2-C7 alkylene group;
the compound of formula III-3 has any one of the following structures:
wherein R is 7 、R 8 Each independently is a C1-C7 straight chain alkyl group.
7. The liquid crystal composition of claim 1, further comprising at least one compound of formula IV:
wherein R is 9 、R 10 Each independently represents hydrogen, halogen, C3-C5 cycloalkyl, halogenated or non-halogenated C1-C10 straight-chain alkyl, halogenated or non-halogenated C1-C10 straight-chain alkoxy, halogenated or non-halogenated C2-C10 alkenyl, halogenated or non-halogenated C2-C10 alkenyloxy;
Z 6 、Z 7 each independently represents a single bond, -COO-, -OCO-, -CH 2 O-、-OCH 2 -or-CH 2 CH 2 -；
Ring A 12 、A 13 Each independently represents 1, 4-cyclohexylene, 1, 4-cyclohexenylene, a halogenated or non-halogenated 1, 4-phenylene group, or one or at least two non-adjacent-CH's in the 1, 4-cyclohexylene group 2 -is replaced by-O-;
n 3 、n 4 each independently represents an integer of 0 to 2; and when n is 3 When 2, ring A 12 Same or different, Z 6 The same or different; when n is 4 When 2, ring A 13 Same or different, Z 7 The same or different.
8. The liquid crystal composition of claim 7, wherein the compound of formula IV has any one of the following structures:
wherein R is 9 、R 10 Each independently represents a C1-C5 linear alkyl group or a C1-C5 linear alkoxy group.
9. The liquid crystal composition according to claim 7 or 8, wherein the mass percentage of the compound of formula IV in the liquid crystal composition is 1-45%.
10. A liquid crystal display device comprising the liquid crystal composition according to any one of claims 1 to 9.
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| US3899464A (en) * | 1972-10-26 | 1975-08-12 | Sankyo Co | Piperidine derivative and use thereof as stabilizers |
| US4336183A (en) * | 1979-07-12 | 1982-06-22 | Adeka Argus Chemical Co., Ltd. | 2,2,6,6-Tetramethyl-4-piperidyl carboxylic acid esters and amides of mono and poly alcohols, phenols and amines as stabilizers for synthetic polymers |
| WO2017018513A1 (en) * | 2015-07-29 | 2017-02-02 | 新日鐵住金株式会社 | Titanium composite material, and titanium material for use in hot rolling |
| CN107709522A (en) * | 2015-08-07 | 2018-02-16 | Dic株式会社 | Liquid-crystal composition and use its liquid crystal display cells |
| WO2018212059A1 (en) * | 2017-05-18 | 2018-11-22 | Dic株式会社 | Liquid-crystal composition and liquid-crystal display element employing same |
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2019
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3899464A (en) * | 1972-10-26 | 1975-08-12 | Sankyo Co | Piperidine derivative and use thereof as stabilizers |
| US4336183A (en) * | 1979-07-12 | 1982-06-22 | Adeka Argus Chemical Co., Ltd. | 2,2,6,6-Tetramethyl-4-piperidyl carboxylic acid esters and amides of mono and poly alcohols, phenols and amines as stabilizers for synthetic polymers |
| WO2017018513A1 (en) * | 2015-07-29 | 2017-02-02 | 新日鐵住金株式会社 | Titanium composite material, and titanium material for use in hot rolling |
| CN107709522A (en) * | 2015-08-07 | 2018-02-16 | Dic株式会社 | Liquid-crystal composition and use its liquid crystal display cells |
| WO2018212059A1 (en) * | 2017-05-18 | 2018-11-22 | Dic株式会社 | Liquid-crystal composition and liquid-crystal display element employing same |
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