CN108611103B - Liquid crystal composition containing polymerizable compound and application thereof - Google Patents

Liquid crystal composition containing polymerizable compound and application thereof Download PDF

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CN108611103B
CN108611103B CN201611128729.2A CN201611128729A CN108611103B CN 108611103 B CN108611103 B CN 108611103B CN 201611128729 A CN201611128729 A CN 201611128729A CN 108611103 B CN108611103 B CN 108611103B
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carbon atoms
liquid crystal
alkyl
group
coo
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CN108611103A (en
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马文阳
徐海彬
韩文明
陈昭远
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Jiangsu Hecheng Display Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • C09K19/44—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing compounds with benzene rings directly linked
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL 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
    • G02F1/00—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
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods

Abstract

The invention discloses a liquid crystal composition containing polymerizable compounds, which comprises a polymerizable component A and a liquid crystal component B, wherein the polymerizable component A contains one or more polymerizable compounds; the liquid crystal component B comprises at least one compound of the general formula I. The invention also discloses a liquid crystal display device comprising the liquid crystal composition. The liquid crystal composition provided by the invention has larger optical anisotropy and larger dielectric anisotropy, can form a lower pretilt angle after RM is added,

Description

Liquid crystal composition containing polymerizable compound and application thereof
Technical Field
The invention belongs to the field of liquid crystal materials, and particularly relates to a liquid crystal composition containing a polymerizable compound and application thereof in a PSA (pressure sensitive adhesive) display.
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. Types according to the display mode are classified into PC (phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), IPS (in-plane switching), FFS (fringe field switching), VA (vertical alignment), and PSA (polymer stable alignment).
Among these, the PSA mode is a mode in which a small amount (e.g., 0.3 wt%, more typically < 1 wt%) of one or more polymerizable compounds is added to a liquid crystal composition and polymerized or crosslinked in situ (typically by UV photopolymerization) with or without voltage applied between electrodes after charging a liquid crystal cell. The polymerization is carried out at a temperature at which the liquid-crystalline composition exhibits a liquid-crystalline phase, generally at room temperature. It has proved to be particularly suitable to add polymerizable liquid-crystalline compounds to the liquid-crystalline composition.
Meanwhile, the PSA principle is being used in various conventional liquid crystal displays such as known PSA-VA, PSA-OCB, PSA-IPS, PSA-FFS and PSA-TN displays. PSA displays can operate as either active matrix or passive matrix displays, as conventional liquid crystal displays. In the case of active matrix displays the individual pixels are usually addressed by integrated non-linear active elements, such as transistors, whereas in the case of passive matrix displays the individual pixels are usually addressed according to multiplexing methods known in the art.
In the prior art, polymerizable compounds of the formula:
Figure GDA0003141483320000011
wherein P represents a polymerizable group, typically an acrylate or methacrylate group, as described in US 7169449.
However, not all combinations of liquid crystal composition + polymerizable component (RM) are suitable for PSA displays, since, for example, no tilt at all or no sufficient tilt can be established. Furthermore, it has been found that the previously known liquid crystal compositions and RMs still have some disadvantages when used in PSA displays. Thus, not every known RM soluble in liquid crystal compositions is suitable for use in PSA displays. Furthermore, in addition to directly measuring the pretilt angle in PSA displays, it is often difficult to find a suitable selection criterion for the RM. If it is desired to carry out the polymerization by means of UV light without addition of photoinitiators, the choice of suitable RMs becomes smaller.
In addition, the selected liquid crystal composition/RM combination should have as low rotational viscosity as possible and as good electrical properties as possible, in particular it should have as high a VHR as possible. In PSA displays, a high VHR after irradiation with UV light is particularly required, since UV exposure is an essential part of the display production process, and also the normal exposure during operation of the finished display.
For PSA displays it is preferable to produce a particularly small pretilt angle, where preferred materials should be able to produce a smaller pretilt angle than hitherto known materials during polymerization at the same exposure time and/or achieve the pretilt angle achievable with known materials also at shorter exposure times. Thus, the production time of the display can be shortened and the cost can be reduced.
Another problem in the production of PSA displays is the presence of residual amounts of unpolymerized RM, which may polymerize in an uncontrolled manner after the display has been made, and which negatively affect the properties of the display, such as that known PSA displays often show "image sticking" or "image burn", i.e. the image produced by the short addressing of individual pixels is still visible after the electric field in these pixels has been switched off or after other pixels have been addressed.
Disclosure of Invention
The purpose of the invention is as follows: in view of the drawbacks of the prior art, the present invention aims to provide a liquid crystal composition that can be polymerized rapidly and can establish a lower pretilt angle while having greater optical anisotropy, greater dielectric anisotropy, and the like, and the use of the liquid crystal composition comprising a polymerizable compound in PSA-type displays.
The technical scheme of the invention is as follows:
a liquid crystal composition containing polymerizable compounds comprises a polymerizable component A and a liquid crystal component B, wherein the polymerizable component A contains one or more polymerizable compounds;
the liquid crystal component B comprises at least one compound of the general formula I
Figure GDA0003141483320000021
Wherein the content of the first and second substances,
R1and R2Are identical to each otherOr different, each independently represents H, alkyl with 1-12 carbon atoms or halogenated alkyl with 1-12 carbon atoms, and one or two non-adjacent CH in the alkyl with 1-12 carbon atoms or the halogenated alkyl with 1-12 carbon atoms2A group may be replaced by-O-, -CH ═ CH-, -CO-, -OCO-, or-COO-;
m represents 1 or 2.
Preferably, the compound of formula i is selected from one or more compounds of the group consisting of:
Figure GDA0003141483320000022
Figure GDA0003141483320000031
Figure GDA0003141483320000041
and
Figure GDA00031414833200000414
further, the liquid crystal component B further comprises at least one compound of the general formula II:
Figure GDA0003141483320000042
and/or
At least one compound of the formula III
Figure GDA0003141483320000043
Wherein the content of the first and second substances,
ring (C)
Figure GDA0003141483320000044
Identical or different, each independently of the other
Figure GDA0003141483320000045
Figure GDA0003141483320000046
And when
Figure GDA0003141483320000047
To represent
Figure GDA0003141483320000048
When the temperature of the water is higher than the set temperature,
Figure GDA0003141483320000049
the upper tertiary hydrogen may be substituted by-CN or-CF3Substitution;
ring (C)
Figure GDA00031414833200000410
Identical or different, each independently of the other
Figure GDA00031414833200000411
Figure GDA00031414833200000412
R3And R4The same or different, each independently represent H, F, CN or alkyl with 1-12 carbon atoms, one or two non-adjacent CH in the alkyl with 1-12 carbon atoms2A group may be replaced by-O-, -CH ═ CH-, -CO-, -OCO-, or-COO-;
R5and R6The same or different, each independently represents H, alkyl with 1-12 carbon atoms or halogenated alkyl with 1-12 carbon atoms, and one or two non-adjacent CH in the alkyl with 1-12 carbon atoms or the halogenated alkyl with 1-12 carbon atoms2A group may be replaced by-O-, -CH ═ CH-, -CO-, -OCO-, or-COO-;
n represents 0 or 1;
q represents 1 or 2, and when q is 2, two rings
Figure GDA0003141483320000051
Can be connected withEither the same or different.
Preferably, the compound of formula ii is selected from one or more compounds of the group consisting of:
Figure GDA0003141483320000052
wherein, R is31And R41The same or different, each independently represent H, F or alkyl with 1-8 carbon atoms, and one or two non-adjacent CH in the alkyl with 1-8 carbon atoms2A group may be replaced by-O-, -CH ═ CH-, -CO-, -OCO-, or-COO-;
the compound of formula iii is selected from one or more compounds of the group consisting of:
Figure GDA0003141483320000053
wherein R is51And R61The same or different, each independently represents H, alkyl with 1-8 carbon atoms or halogenated alkyl with 1-8 carbon atoms, and one or two non-adjacent CH in the alkyl with 1-8 carbon atoms or the halogenated alkyl with 1-8 carbon atoms2A group may be replaced by-O-, -CH ═ CH-, -CO-, -OCO-, or-COO-.
Further preferably, the compound of formula II-1 is one or more compounds selected from the group consisting of:
Figure GDA0003141483320000061
and
Figure GDA0003141483320000062
the compound of the general formula II-2 is selected from one or more compounds of the group consisting of:
Figure GDA0003141483320000063
Figure GDA0003141483320000071
and
Figure GDA0003141483320000072
the compound of the general formula II-3 is one or more compounds selected from the group consisting of:
Figure GDA0003141483320000073
Figure GDA0003141483320000081
Figure GDA0003141483320000082
and
Figure GDA0003141483320000083
the compound of formula II-4 is selected from one or more compounds of the group consisting of:
Figure GDA0003141483320000084
and
Figure GDA0003141483320000085
the compound of formula II-5 is selected from one or more compounds of the group consisting of:
Figure GDA0003141483320000086
Figure GDA0003141483320000091
Figure GDA0003141483320000101
and
Figure GDA0003141483320000102
the compound of the general formula II-6 is one or more compounds selected from the group consisting of:
Figure GDA0003141483320000103
Figure GDA0003141483320000104
and
Figure GDA0003141483320000105
the compound of the general formula II-7 is selected from one or more compounds of the group consisting of:
Figure GDA0003141483320000111
and
Figure GDA0003141483320000112
the compound of the general formula II-8 is selected from one or more compounds of the group consisting of:
Figure GDA0003141483320000113
Figure GDA0003141483320000121
and
Figure GDA0003141483320000122
the compounds of the general formulae II-9 are selected from one or more compounds from the group consisting of:
Figure GDA0003141483320000123
and
Figure GDA0003141483320000124
the compounds of the general formulae II to 10 are selected from one or more compounds from the group consisting of:
Figure GDA0003141483320000125
Figure GDA0003141483320000131
and
Figure GDA0003141483320000132
the compounds of the general formulae II to 11 are selected from one or more compounds from the group consisting of:
Figure GDA0003141483320000133
Figure GDA0003141483320000141
Figure GDA0003141483320000142
and
Figure GDA0003141483320000143
the compound of the general formula III-1 is selected from one or more compounds of the group consisting of:
Figure GDA0003141483320000144
Figure GDA0003141483320000145
and
Figure GDA0003141483320000146
the compound of the general formula III-2 is selected from one or more compounds of the group consisting of:
Figure GDA0003141483320000147
Figure GDA0003141483320000151
Figure GDA0003141483320000152
and
Figure GDA0003141483320000153
the compound of the general formula III-3 is selected from one or more compounds of the group consisting of:
Figure GDA0003141483320000154
Figure GDA0003141483320000155
and
Figure GDA0003141483320000156
the compound of the general formula III-4 is selected from one or more compounds of the group consisting of:
Figure GDA0003141483320000157
Figure GDA0003141483320000161
Figure GDA0003141483320000162
and
Figure GDA0003141483320000163
the compound of the general formula III-5 is selected from one or more compounds of the group consisting of:
Figure GDA0003141483320000164
Figure GDA0003141483320000165
and
Figure GDA0003141483320000166
further, the liquid crystal component B further comprises at least one compound of the general formula IV:
Figure GDA0003141483320000167
and/or at least one compound of formula v:
Figure GDA0003141483320000168
wherein the content of the first and second substances,
R7and R8The same or different, each independently represents H, an alkyl group of 1 to 12 carbon atoms or a haloalkyl group of 1 to 12 carbon atoms, the 1 to 12 carbonsOne or two non-adjacent CH in alkyl or haloalkyl of 1 to 12 carbon atoms2A group may be replaced by-O-, -CH ═ CH-, -CO-, -OCO-, or-COO-;
R9and R10The same or different, each independently represents H or alkyl with 1-12 carbon atoms, and one or two non-adjacent CH in the alkyl with 1-12 carbon atoms2A group may be replaced by-O-, -CH ═ CH-, -CO-, -OCO-, or-COO-;
Z1represents a double bond, a triple bond, -CH2O-or-COO-;
Z2represents a single bond, -CH2O-or-COO-;
p represents 0 or 1;
ring (C)
Figure GDA0003141483320000171
Are the same or different and each independently represents
Figure GDA0003141483320000172
And when it is looped
Figure GDA0003141483320000173
To represent
Figure GDA0003141483320000174
Wherein one or more H may be substituted by F.
Preferably, the compound of formula iv is selected from one or more compounds of the group consisting of:
Figure GDA0003141483320000175
Figure GDA0003141483320000176
and
Figure GDA0003141483320000177
wherein R is71And R81Is the same as orDifferent from each other, independently represent H, alkyl with 1 to 6 carbon atoms or halogenated alkyl with 1 to 6 carbon atoms, and one or two non-adjacent CH in the alkyl with 1 to 6 carbon atoms or the halogenated alkyl with 1 to 6 carbon atoms2A group may be replaced by-O-, -CH ═ CH-, -CO-, -OCO-, or-COO-.
Further preferably, the compound of the general formula IV-1 is one or more compounds selected from the group consisting of:
Figure GDA0003141483320000178
Figure GDA0003141483320000179
and
Figure GDA00031414833200001710
the compound of the general formula IV-2 is selected from one or more compounds of the group consisting of:
Figure GDA0003141483320000181
Figure GDA0003141483320000182
and
Figure GDA0003141483320000183
the compound of the general formula IV-3 is one or more compounds selected from the group consisting of:
Figure GDA0003141483320000184
Figure GDA0003141483320000191
Figure GDA0003141483320000192
and
Figure GDA0003141483320000193
the compound of the general formula IV-4 is one or more compounds selected from the group consisting of:
Figure GDA0003141483320000194
Figure GDA0003141483320000195
and
Figure GDA0003141483320000196
preferably, said compound of formula v is a compound selected from one or more of the group consisting of:
Figure GDA0003141483320000197
Figure GDA0003141483320000198
and
Figure GDA0003141483320000201
wherein the content of the first and second substances,
the R is91And R101The same or different, each independently represents H or alkyl with 1-6 carbon atoms, and one or two non-adjacent CH in the alkyl with 1-6 carbon atoms2A group may be replaced by-O-, -CH ═ CH-, -CO-, -OCO-, or-COO-in such a manner that O atoms are not directly linked to each other.
Further preferably, said compound of formula v-1 is selected from one or more compounds of the group consisting of:
Figure GDA0003141483320000202
Figure GDA0003141483320000203
and
Figure GDA0003141483320000204
the compound of formula V-2 is selected from one or more compounds of the group consisting of:
Figure GDA0003141483320000205
Figure GDA0003141483320000211
and
Figure GDA0003141483320000212
the compound of formula V-3 is selected from one or more compounds of the group consisting of:
Figure GDA0003141483320000213
Figure GDA0003141483320000221
and
Figure GDA0003141483320000222
the compound of formula V-4 is selected from one or more compounds of the group consisting of:
Figure GDA0003141483320000223
Figure GDA0003141483320000231
Figure GDA0003141483320000232
and
Figure GDA0003141483320000233
the compound of formula v-5 is selected from one or more compounds of the group consisting of:
Figure GDA0003141483320000234
Figure GDA0003141483320000241
Figure GDA0003141483320000242
and
Figure GDA0003141483320000243
the compound of formula V-6 is selected from one or more compounds of the group consisting of:
Figure GDA0003141483320000244
Figure GDA0003141483320000245
and
Figure GDA0003141483320000246
the compound of formula v-7 is selected from one or more compounds of the group consisting of:
Figure GDA0003141483320000251
Figure GDA0003141483320000252
and
Figure GDA0003141483320000253
further, the polymerizable component a is selected from one or more compounds of the group consisting of compounds of the following general formula vi:
Figure GDA0003141483320000254
wherein the content of the first and second substances,
P1to represent
Figure GDA0003141483320000255
Figure GDA0003141483320000256
or-SH;
Sp1represents a single bond or C1～C20Wherein one or more of said alkylene groups is not adjacent-CH2-groups may be replaced independently of each other by-O-, -S-, -COO-, -OCO-O-, -S-CO-, -CO-S-, -CH ═ CH-, or-C ≡ C-, the hydrogen in the alkylene group being substituted by 1 or more halogen or CN;
Qp1selected from the group consisting of a single bond, -O-, -S-, -NH-, -NHCOO-, -OCONH-, -CF2O-、-OCF2-、-CF2S-、-SCF2-、-CH2CH2-、-CF2CH2-、-CH2CF2-、-CF2CF2-、-CF＝CH-、-CH＝CF-、-CF＝CF-、-CO-、-COO-、-OCO-、-OCOO-、-CH2-、-OCH2-、-SCH2-、-CH2S-、-CH＝CH-、-C≡C-、-CH-COO-and-OCO-CH-;
r1 and r2 are the same or different and each independently represents 1,2 or 3;
MGprepresents a mesogenic group or a mesogenic support group;
Rp1represents halogen, nitrile group or C1～C20Alkylene of (a), one or more of said alkylene not being adjacent-CH2The radicals-may be independently of one another-O-, -S-, -NH-, -NCH3-, -CO-, -COO-, -OCO-O-, -S-CO-, -CO-S-, -CH-or-C.ident.C-substitution, or Rp1Can be P2-Sp2-Qp2-, in which P2、Sp2、Qp2Are respectively defined with P1、Sp1、Qp1The same is true.
Further, the MGpTo represent
Figure GDA0003141483320000261
Wherein A is1、A2And A3The same or different, each independently selected from the group consisting of 1, 4-cyclohexyl, 1, 4-cyclohexenyl, piperidine-1, 4-diyl, 1, 4-bicyclo [2,2 ]]Octyl, 1, 4-phenyl, pyridine-2, 5-diyl, pyrimidine-2, 5-diyl, naphthalene-2, 6-diyl, trans-decahydronaphthalene-2, 6-diyl, tetrahydronaphthalene-2, 6-diyl and 1, 2-indane, wherein one or two of said 1, 4-cyclohexyl groups are not directly attached CH2Can be replaced independently of one another by O or S, one or more H of the 1, 4-phenyl radicals can be replaced independently of one another by halogen, CN or C1～C4Alkyl or alkoxy substitution of (a);
Zp1and Zp2The same or different, each independently selected from the group consisting of a single bond, -O-, -S-, -NH-, -NHCOO-, -OCONH-, -CF-2O-、-OCF2-、-CF2S-、-SCF2-、-CH2CH2-、-CF2CH2-、-CH2CF2-、-CF2CF2-、-CF＝CH-、-CH＝CF-、-CF＝CF-、-CO-、-COO-、-OCO-、-OCOO-、-CH2-、-OCH2-、-SCH2-、-CH2S-, -CH ═ CH-, -C ≡ C-, -CH ═ CH-COO-, and-OCO-CH ═ CH-;
r3 represents 0, 1 or 2.
Preferably, the compound of formula vi is selected from one or more of the group consisting of:
Figure GDA0003141483320000262
Figure GDA0003141483320000271
wherein the content of the first and second substances,
r4 represents 1,2 or 3;
r5 represents 0, 1,2, 3 or 4.
Further, P1And P2Identical or different, each independently of the other
Figure GDA0003141483320000272
Figure GDA0003141483320000273
Still further, Sp in the above formula is preferable1、Sp2、Qp1And Qp2All of which are single-bond polymerizable compounds.
Still further, compounds containing a biphenyl and/or terphenyl structure are preferred.
Still further, the polymerizable component A is 0.01 to 5% by weight of the total composition.
In another aspect, the present invention also provides a liquid crystal display comprising one of the above-described liquid crystal compositions comprising a polymerizable compound.
Preferably, the liquid crystal display is a PSA type display.
The liquid-crystal compositions according to the invention may optionally also comprise further additives known to the person skilled in the art and described in the literature, such as polymerization initiators, inhibitors, stabilizers, surfactants or chiral dopants. These additives may or may not be polymerizable. Accordingly, polymerizable additives are classified into polymerizable component a, and non-polymerizable additives are classified into the remaining components other than component a and component B.
The term "mesogenic group" or "mesogenic support group" as used in the present invention is known to the person skilled in the art and described in the literature and will be understood to mean an anisotropic group due to an attractive and repulsive interaction, which substantially contributes to the creation of a liquid crystalline phase in a low molecular weight or polymeric substance, the compound comprising the mesogenic group (mesogenic compound) not necessarily having a liquid crystalline phase per se. It is also possible for mesogenic compounds to exhibit liquid-crystalline phase behavior only after mixing of the other compounds and/or after polymerization. Typical mesogenic groups are for example rigid rodlike or discotic units. Reviews of the terms and definitions used in relation to mesogenic or liquid crystal compounds are given in Pure appi.chem.73(5), 888(2001) and c.tschierske, g.peizi, s.dieie., angelw.chem.2004, 116, 6340-6368.
The term "halogen" as used herein will be understood to mean F, Cl, Br or I.
Has the advantages that:
the liquid crystal composition provided by the invention has larger optical anisotropy and larger dielectric anisotropy, can form a lower pretilt angle compared with the prior art after RM is added, and is particularly suitable for PSA type displays.
In some embodiments of the present invention, through extensive experimental screening and optimization, the liquid crystal composition of the present invention is obtained, which has a clearing point Cp between 70-85 ℃; the optical anisotropy Deltan is between 0.09 and 0.130(20 ℃); the absolute value of the dielectric anisotropy | Δ ∈ | is between 3.0 and 5.0.
Detailed Description
The invention will be illustrated below with reference to specific embodiments. It should be noted that the following examples are illustrative of the present invention, and are not intended to limit the present invention. Other combinations and various modifications within the spirit or scope of the present invention may be made without departing from the spirit or scope of the present invention.
For convenience of expression, in the following examples, the group structure of the liquid crystal composition is represented by the code listed in Table 1:
TABLE 1 radical structural code of liquid crystal compounds
Figure GDA0003141483320000281
Figure GDA0003141483320000291
Compounds of the following formula are exemplified:
Figure GDA0003141483320000292
the structural formula is represented by the code listed in Table 1, and can be expressed as: nCCGF, wherein n in the code represents the number of C atoms of the left alkyl group, for example, n is 3, namely, the alkyl group is-C3H7(ii) a C in the code represents cyclohexane, G represents 2-fluoro-1, 4-phenylene and F represents fluorine.
The abbreviated codes of the test items in the following examples are as follows:
cp (. degree. C.) clearing Point (nematic-isotropic phase transition temperature)
Δ n refractive index anisotropy (589nm, 25 ℃ C.)
Delta epsilon dielectric anisotropy (1KHz, 25 ℃ C.)
Wherein, the refractive index anisotropy is obtained by testing an Abbe refractometer under a sodium lamp (589nm) light source at 25 ℃;
Δ ∈/∈ · - ∈ ·, where ∈/, is the dielectric constant parallel to the molecular axis, ∈ · is the dielectric constant perpendicular to the molecular axis, test conditions: the test box is VA type at 25 deg.C and 1KHz, and the thickness of the test box is 6 μm.
Pretilt Angle test Using the crystal rotation method, liquid crystal was poured into a VA type test cell, 6 μm thick, and 16V 60HZ voltage was applied while irradiating with 6500mJ @365nm UV light, so that RM polymerized to form a pretilt angle.
The components used in the following examples can be synthesized by a known method or obtained commercially. These synthesis techniques are conventional, and the resulting liquid crystal compounds were tested to meet the standards for electronic compounds.
Liquid crystal compositions were prepared according to the compounding ratios of the liquid crystal compositions specified in the following examples. The liquid crystal composition is prepared according to the conventional method in the field, such as heating, ultrasonic wave, suspension and the like, and is mixed according to the specified proportion.
Liquid crystal compositions given in the following examples were prepared and studied. The composition of each liquid crystal composition and the results of the performance parameter test thereof are shown below.
Comparative example 1
The liquid crystal composition of comparative example 1, which was filled between two substrates of a liquid crystal display and subjected to a performance test, was prepared with each compound and weight percentage as listed in table 2, and the test data are shown in the following table:
TABLE 2 liquid crystal composition formulations and their test properties
Figure GDA0003141483320000301
To the above formulation was added 0.5% V (1) EPPE (1) V and after mixing was complete the pretilt angle was tested and the magnitude was: and 83.2 degrees.
Example 1
The liquid crystal composition of example 1 was prepared according to the compounds and weight percentages listed in table 3, and filled between two substrates of a liquid crystal display for performance testing, and the test data are shown in the following table:
TABLE 3 liquid crystal composition formula and its test performance
Figure GDA0003141483320000302
Figure GDA0003141483320000311
To the above formulation was added 0.5% V (1) EPPE (1) V and after mixing was complete the pretilt angle was tested and the magnitude was: 81.5 degrees.
Comparative example 2
The liquid crystal composition of comparative example 2, which was filled between two substrates of a liquid crystal display and subjected to a performance test, was prepared with each compound and weight percentage as listed in table 4, and the test data are shown in the following table:
TABLE 4 liquid crystal composition formula and its test performance
Figure GDA0003141483320000312
To the above formulation, 0.2% V (1) EPGE (1) V and 0.2% V (1) EPPE (1) V were added and the pretilt angle was measured after mixing was complete and was: 84.7 degrees.
Example 2
The liquid crystal composition of example 2 was prepared according to the compounds and weight percentages listed in table 5, and filled between two substrates of a liquid crystal display for performance testing, and the test data are shown in the following table:
TABLE 5 liquid crystal composition formulations and their test properties
Figure GDA0003141483320000321
To the above formulation, 0.2% V (1) EPGE (1) V and 0.2% V (1) EPPE (1) V were added and the pretilt angle was measured after mixing was complete and was: 83.1 degrees.
Comparative example 3
The liquid crystal composition of comparative example 3, which was filled between two substrates of a liquid crystal display and subjected to a performance test, was prepared with each compound and weight percentage as listed in table 6, and the test data are shown in the following table:
TABLE 6 liquid crystal composition formula and its test performance
Figure GDA0003141483320000322
Figure GDA0003141483320000331
To the above formulation was added 0.3% V (1) E3PGPE (1) V, and after mixing was complete the pretilt angle was tested and the magnitude: 85.2 degrees.
Example 3
The liquid crystal composition of example 3 was prepared according to the compounds and weight percentages listed in table 7, and filled between two substrates of a liquid crystal display for performance testing, and the test data are shown in the following table:
TABLE 7 liquid crystal composition formulations and their test properties
Figure GDA0003141483320000332
To the above formulation was added 0.3% V (1) E3PGPE (1) V, and after mixing was complete the pretilt angle was tested and the magnitude: and 83.4 degrees.
Comparative example 4
The liquid crystal composition of comparative example 4, which was filled between two substrates of a liquid crystal display and subjected to a performance test, was prepared with each compound and weight percentage as listed in table 8, and the test data are shown in the following table:
TABLE 8 liquid crystal composition formulations and their test properties
Figure GDA0003141483320000341
To the above formulation, 0.2% V (1) EPGE (1) V and 0.1% V (1) EPGPE (1) V were added, and after mixing was complete the pretilt angle was tested and the magnitude: 82.7 degrees.
Example 4
The liquid crystal composition of example 4 was prepared according to the compounds and weight percentages listed in table 9, and filled between two substrates of a liquid crystal display for performance testing, and the test data are shown in the following table:
TABLE 9 liquid crystal composition formulations and their test properties
Figure GDA0003141483320000342
Figure GDA0003141483320000351
To the above formulation, 0.2% V (1) EPGE (1) V and 0.1% V (1) EPGPE (1) V were added, and after mixing was complete the pretilt angle was tested and the magnitude: 80.3 degrees.
In order to highlight the beneficial effects of the liquid crystal composition of the present invention, the inventors selected a comparative example similar to the system of the embodiment of the present invention. As can be seen from the above comparative examples 1,2, 3, 4, 1,2, 3 and 4, the liquid crystal composition provided by the present invention has greater optical anisotropy and greater dielectric anisotropy, can form a lower pretilt angle after RM is added, and is more suitable for PSA displays, and the composition of the present invention, in which no unpolymerized RM is found, can clearly display images when applied to PSA displays.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (8)

1. A liquid crystal composition comprising a polymerizable compound, comprising a polymerizable component a and a liquid crystal component B, wherein the polymerizable component a is selected from one or more compounds of the group consisting of compounds of the following general formula vi:
Figure FDA0003141483310000011
wherein the content of the first and second substances,
P1to represent
Figure FDA0003141483310000012
Sp1Represents a single bond or C1～C20Wherein one or more of said alkylene groups is not adjacent-CH2-groups may be replaced independently of each other by-O-, -S-, -COO-, -OCO-O-, -S-CO-, -CO-S-, -CH ═ CH-, or-C ≡ C-, the hydrogen in the alkylene group being substituted by 1 or more halogen or CN;
Qp1selected from the group consisting of a single bond, -O-, -S-, -NH-, -NHCOO-, -OCONH-, -CF2O-、-OCF2-、-CF2S-、-SCF2-、-CH2CH2-、-CF2CH2-、-CH2CF2-、-CF2CF2-、-CF＝CH-、-CH＝CF-、-CF＝CF-、-CO-、-COO-、-OCO-、-OCOO-、-CH2-、-OCH2-、-SCH2-、-CH2S-, -CH ═ CH-, -C ≡ C-, -CH ═ CH-COO-, and-OCO-CH ═ CH-;
r1 and r2 are the same or different and each independently represents 1,2 or 3;
MGpto represent
Figure FDA0003141483310000013
Wherein the content of the first and second substances,
A1、A2and A3The same or different, and the same or different,each independently selected from the group consisting of 1, 4-cyclohexyl, 1, 4-cyclohexenyl, piperidin-1, 4-diyl, 1, 4-bicyclo [2,2 ]]Octyl, 1, 4-phenyl, pyridine-2, 5-diyl, pyrimidine-2, 5-diyl, naphthalene-2, 6-diyl, trans-decahydronaphthalene-2, 6-diyl, tetrahydronaphthalene-2, 6-diyl and 1, 2-indane, wherein one or two of said 1, 4-cyclohexyl groups are not directly attached CH2Can be replaced independently of one another by O or S, one or more H of the 1, 4-phenyl radicals can be replaced independently of one another by halogen, CN or C1～C4Alkyl or alkoxy substitution of (a);
Zp1and Zp2The same or different, each independently selected from the group consisting of a single bond, -O-, -S-, -NH-, -NHCOO-, -OCONH-, -CF-2O-、-OCF2-、-CF2S-、-SCF2-、-CH2CH2-、-CF2CH2-、-CH2CF2-、-CF2CF2-、-CF＝CH-、-CH＝CF-、-CF＝CF-、-CO-、-COO-、-OCO-、-OCOO-、-CH2-、-OCH2-、-SCH2-、-CH2S-, -CH ═ CH-, -C ≡ C-, -CH ═ CH-COO-, and-OCO-CH ═ CH-;
r3 represents 0, 1 or 2;
Rp1represents halogen, nitrile group or C1～C20Alkylene of (a), one or more of said alkylene not being adjacent-CH2The radicals-may be independently of one another-O-, -S-, -NH-, -NCH3-, -CO-, -COO-, -OCO-O-, -S-CO-, -CO-S-, -CH-or-C.ident.C-; or Rp1Is P2-Sp2-Qp2-, in which P2、Sp2、Qp2Are respectively defined with P1、Sp1、Qp1The same;
the polymerizable component A accounts for 0.01 to 5 percent of the total weight of the liquid crystal composition;
the liquid crystal component B comprises at least one compound of the general formula I
Figure FDA0003141483310000014
And at least one compound of the general formula II:
Figure FDA0003141483310000021
wherein the content of the first and second substances,
R1and R2The same or different, each independently represents H, alkyl with 1-12 carbon atoms or halogenated alkyl with 1-12 carbon atoms, and one or two non-adjacent CH in the alkyl with 1-12 carbon atoms or the halogenated alkyl with 1-12 carbon atoms2A group may be replaced by-O-, -CH ═ CH-, -CO-, -OCO-, or-COO-;
m represents 1 or 2;
ring (C)
Figure FDA0003141483310000022
Identical or different, each independently of the other
Figure FDA0003141483310000023
Figure FDA0003141483310000024
And when
Figure FDA0003141483310000025
To represent
Figure FDA0003141483310000026
When the temperature of the water is higher than the set temperature,
Figure FDA0003141483310000027
the upper tertiary hydrogen may be substituted by-CN or-CF3Substitution;
ring (C)
Figure FDA0003141483310000028
To represent
Figure FDA0003141483310000029
R3And R4The same or different, each independently represent H, F, CN or alkyl with 1-12 carbon atoms, one or two non-adjacent CH in the alkyl with 1-12 carbon atoms2The groups may be replaced by-O-, -CO-, -OCO-or-COO-;
n represents 0 or 1.
2. A liquid crystal composition comprising a polymerizable compound according to claim 1, wherein the compound of the general formula i is one or more compounds selected from the group consisting of:
Figure FDA00031414833100000210
Figure FDA0003141483310000031
Figure FDA0003141483310000041
Figure FDA0003141483310000042
and
Figure FDA0003141483310000043
3. the liquid crystal composition comprising the polymerizable compound as claimed in claim 1, wherein the liquid crystal component B further comprises
At least one compound of the formula III
Figure FDA0003141483310000044
Wherein the content of the first and second substances,
ring (C)
Figure FDA0003141483310000045
To represent
Figure FDA0003141483310000046
R5And R6The same or different, each independently represents H, alkyl with 1-12 carbon atoms or halogenated alkyl with 1-12 carbon atoms, and one or two non-adjacent CH in the alkyl with 1-12 carbon atoms or the halogenated alkyl with 1-12 carbon atoms2A group may be replaced by-O-, -CH ═ CH-, -CO-, -OCO-, or-COO-;
q represents 1 or 2, and when q is 2, two rings
Figure FDA0003141483310000051
May be the same or different.
4. The liquid crystal composition of claim 3, wherein the compound of formula II is selected from one or more compounds of the group consisting of:
Figure FDA0003141483310000052
wherein, R is31And R41The same or different, each independently represent H, F or alkyl with 1-8 carbon atoms, and one or two non-adjacent CH in the alkyl with 1-8 carbon atoms2The groups may be replaced by-O-, -CO-, -OCO-or-COO-;
the compound of formula iii is selected from one or more compounds of the group consisting of:
Figure FDA0003141483310000053
Figure FDA0003141483310000061
wherein R is51And R61The same or different, each independently represents H, alkyl with 1-8 carbon atoms or halogenated alkyl with 1-8 carbon atoms, and one or two non-adjacent CH in the alkyl with 1-8 carbon atoms or the halogenated alkyl with 1-8 carbon atoms2A group may be replaced by-O-, -CH ═ CH-, -CO-, -OCO-, or-COO-in such a manner that O atoms are not directly linked to each other.
5. The liquid crystal composition comprising the polymerizable compound as claimed in claim 1, wherein the liquid crystal component B further comprises at least one compound of the general formula IV:
Figure FDA0003141483310000062
and/or at least one compound of formula v:
Figure FDA0003141483310000063
wherein the content of the first and second substances,
R7and R8The same or different, each independently represents H, alkyl with 1-12 carbon atoms or halogenated alkyl with 1-12 carbon atoms, and one or two non-adjacent CH in the alkyl with 1-12 carbon atoms or the halogenated alkyl with 1-12 carbon atoms2A group may be replaced by-O-, -CH ═ CH-, -CO-, -OCO-, or-COO-;
R9and R10The same or different, each independently represents H or alkyl with 1-12 carbon atoms, and one or two non-adjacent CH in the alkyl with 1-12 carbon atoms2The radicals may be substituted by-O-, -CH-, -CO-, -OCO-or-COO-substitution;
Z1represents a double bond, a triple bond, -CH2O-or-COO-;
Z2represents a single bond, -CH2O-or-COO-;
p represents 0 or 1;
ring (C)
Figure FDA0003141483310000064
Are the same or different and each independently represents
Figure FDA0003141483310000065
And when it is looped
Figure FDA0003141483310000066
To represent
Figure FDA0003141483310000067
Wherein one or more H may be substituted by F.
6. A liquid crystal composition comprising a polymerizable compound according to claim 5, wherein the compound of the general formula IV is one or more compounds selected from the group consisting of:
Figure FDA0003141483310000071
Figure FDA0003141483310000072
and
Figure FDA0003141483310000073
the compound of formula v is selected from one or more compounds of the group consisting of:
Figure FDA0003141483310000074
Figure FDA0003141483310000075
and
Figure FDA0003141483310000076
wherein R is71、R81、R91And R101The same or different, each independently represents H, alkyl with 1-6 carbon atoms or halogenated alkyl with 1-6 carbon atoms, and one or two non-adjacent CH in the alkyl with 1-6 carbon atoms or the halogenated alkyl with 1-6 carbon atoms2The radicals may be replaced by-O-, -CH ═ CH-, -CO-, -OCO-or-COO-.
7. A liquid crystal display comprising a liquid crystal composition containing a polymerizable compound as claimed in any one of claims 1 to 6.
8. The liquid crystal display of claim 7, wherein the liquid crystal display is a PSA type display.
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