Patent Application
20180195002
The present invention relates to liquid-crystalline media and to liquid-crystal displays containing these media, especially to displays addressed by an active matrix and in particular to displays of the in-plane switching (IPS) or fringe-field switching (FFS) type. The invention further relates to a process for the fabrication of liquid crystal displays.
Liquid-crystal displays (LCDs) are used in many areas for the display of information. LCDs are used both for direct-view displays and for projection-type displays. The electro-optical modes used are, for example, the twisted nematic (TN), super twisted nematic (STN), optically compensated bend (OCB) and electrically controlled birefringence (ECB) modes together with their various modifications, as well as others. All these modes utilize an electric field which is substantially perpendicular to the substrates or the liquid-crystal layer. Besides these modes, there are also electro-optical modes that utilize an electric field which is substantially parallel to the substrates or the liquid-crystal layer, such as, for example, the in-plane switching (IPS) mode (as disclosed, for example, in DE 40 00 451 and EP 0 588 568) and the fringe field switching (FFS) mode, in which a strong “fringe field” is present, i.e. a strong electric field close to the edge of the electrodes and, throughout the cell, an electric field which has both a strong vertical component and a strong horizontal component. These latter two electro-optical modes in particular are used for LCDs in modern desktop monitors and displays for TV sets and multimedia applications. The liquid crystals according to the present invention are preferably used in displays of this type. In general, dielectrically positive liquid-crystalline media having rather lower values of the dielectric anisotropy are used in FFS displays, but in some cases liquid-crystalline media having a dielectric anisotropy of only about 3 or even less are also used in IPS displays.
For these displays, novel liquid-crystalline media having improved properties are required. The addressing times in particular have to be improved for many types of applications. Thus, liquid-crystalline media having lower viscosities (η), especially having lower rotational viscosities (γ1), are required. Besides these viscosity parameters, the media must have a nematic phase range of suitable width and position and an appropriate birefringence (Δn), and the dielectric anisotropy (Δε) should be sufficiently high to allow a reasonably low operating voltage.
The displays according to the present invention are preferably addressed by an active matrix (active matrix LCDs, AMDs for short), preferably by a matrix of thin film transistors (TFTs). However, the liquid crystals according to the invention can also advantageously be used in displays having other known addressing means.
Liquid-crystal compositions which are suitable for LCDs and especially for IPS displays are known, for example, from JP 07-181 439 (A), EP 0 667 555, EP 0 673 986, DE 195 09 410, DE 195 28 106, DE 195 28 107, WO 96/23 851 and WO 96/28 521. However, these compositions have certain disadvantages. Amongst other deficiencies, most of them result in disadvantageously long addressing times, have inadequate values of the resistivity and/or require excessively high operating voltages. In addition, there is a demand for improving the low-temperature behavior of LCDs. Both an improvement in the operating properties and also in the shelf life are necessary here.
A special problem arises during the manufacture of a display panel. An LCD display is typically produced by adhesively bonding a first substrate having a pixel electrode, a thin-film transistor (TFT) and other components to a second substrate which contains a common electrode, using a sealant. The space enclosed by the substrates is filled with the liquid crystal via a fill opening by means of capillary force or vacuum; the fill opening is subsequently sealed using a sealant. With the increase in the size of liquid-crystal displays in recent years, the so-called “one drop filling” process (ODF process) has been proposed as a process for the mass production of liquid-crystal displays (see, for example, JPS63-179323 and JPH10-239694) in order to shorten the cycle times during production. This is a process for the production of a liquid-crystal display in which one or a plurality of drops of the liquid crystal is applied to the substrate, which is fitted with electrodes and is provided with a sealant round the edges. The second substrate is subsequently mounted in vacuo and the sealant is cured.
However, the one drop filling bears the risk of causing display defects referred to as “ODF mura” or “drop mura” where symmetrical patterns related to the arrangement of the individual drops that had been dispensed in the ODF process remain visible after assembly of the panel. Depending on their size and shape, small circular spots (“dotting mura”) or larger, rather square areas (chess pattern mura) can be visible.
Thus, there is a considerable need for liquid-crystalline media having suitable properties for practical applications, such as a broad nematic phase range, suitable optical anisotropy Δn corresponding to the display type used, a high Δε and particularly low viscosities for particularly short response times. In addition, it is important to provide mixture concepts that enable a flexible adaptation of ODF-process relevant parameters in order to avoid display defects such as drop mura.
Surprisingly, it was found that it is possible to achieve liquid-crystalline media having a suitably high Δε, a suitable phase range and Δn which do not exhibit the disadvantages of the materials from the prior art, or at least only do so to a significantly lesser extent, and that allow for a flexible adjustment of the contact angle in order to influence the spreading behaviour of the liquid crystal medium during the ODF process which unexpectedly proved useful for the at least partial or complete avoidance of drop mura.
These improved liquid-crystalline media according to the present invention comprise
one or more compounds selected from the compounds of formula I
and
a compound of the formula CV
and
one or more, preferably one, compound(s) of the formula OT
and
a compound of the formula PV
In a preferred embodiment the medium according to the invention further comprises one or more compounds selected from the group of compounds of the formulae IA, IB and IC
independently of one another, denote
denotes
In a preferred embodiment of the present invention, the medium comprises one or more compounds selected from the group of the compounds of the formulae II and III:
in which
and
in the case where X2 does not denote F, m may also denote 2,
and where the compounds of formula OT are excluded from compounds of formula III and its sub-formulae.
In a preferred embodiment of the present invention, the medium comprises one or more compounds of the formula IV
in which
occurs twice, also these independently of one another, denote
and where the compounds CV and PV are excluded from the compounds of formula IV and its subformulae.
The compounds of the formula IV are preferably dielectrically neutral compounds, preferably having a dielectric anisotropy in the range from −1.5 to 3.
In a preferred embodiment of the present invention, the media according to the invention in each case comprise one or more compounds of the formula IA selected from the group of the compounds of the formulae IA-1 to IA-12, preferably of the formula IA-2:
in which R1 has the meaning indicated above under formula I.
In a preferred embodiment of the present invention, the media according to the invention in each case comprise one or more compounds of the formula IB selected from the group of the compounds of the formulae IB-1 to IB-12, preferably of the formulae IB-1 and/or IB-2 and/or IB-6 and/or IB-12:
in which R1 has the meaning indicated above under formula IB.
In a preferred embodiment of the present invention, the media according to the invention in each case comprise one or more compounds of the formula IC selected from the group of the compounds of the formulae IC-1 to IC-4:
in which R1 has the meaning indicated above under formula IC.
In addition to the compounds selected from the group of the compounds of the formulae I, CV, OT, PV, and IA to IC, or preferred sub-formulae thereof, the media according to the present invention preferably comprise one or more dielectrically positive compounds having a dielectric anisotropy of greater than 3, selected from the group of the formulae II and III.
In a preferred embodiment of the present invention, the media according to the invention comprise one or more compounds selected from the group of the compounds of the formulae II-1 to II-4, preferably of the formulae II-1 and/or II-2:
in which the parameters have the respective meanings indicated above under formula II, and L23 and L24, independently of one another, denote H or F, preferably L23 denotes F, and
has one of the meanings given for
and, in the case of the formulae II-1 and II-4, X2 preferably denotes F or OCF3, particularly preferably F, and, in the case of the formula II-3,
independently of one another, preferably denote
where the compounds of the formulae I, IA, IB and IC are excluded,
and/or selected from the group of the compounds of the formulae III-1 and III-2:
in which the occurring groups and parameters, R3, X3, L31, L32,
and n have the meanings given under formula III.
In a preferred embodiment, the media according to the present invention alternatively or in addition to the compounds of the formulae III-1 and/or III-2 comprise one or more compounds of the formula III-3
in which the parameters R3, X3,
and n have the respective meanings indicated above for formula III, and the parameters L31 and L32, independently of one another and of the other parameters, denote H or F.
The media according to the invention preferably comprise one or more compounds selected from the group of the compounds of the formulae II-1 to II-4 in which L21 and L22 and/or L23 and L24 both denote F.
In a preferred embodiment, the media comprise one or more compounds which are selected from the group of the compounds of the formulae II-2 and II-4 in which L21, L22, L23 and L24 all denote F.
The media preferably comprise one or more compounds of the formula II-1. The compounds of the formula II-1 are preferably selected from the group of the compounds of the formulae II-1a to II-1f:
in which the parameters R2, X2, L21 and L22 have the respective meanings indicated above for formula II, and L23, L24, L25 and L26, independently of one another and of the other parameters, denote H or F, and preferably
in formulae II-1a, II-1b and II-1c
L21 and L22 both denote F,
in formulae II-1d and II-1e
L21 and L22 both denote F and/or L23 and L24 both denote F, and in formula II-1f
L21, L22 and L25 denote F and L26 denotes H.
Especially preferred compounds of the formula II-1 are
in which R2 has the meaning indicated above for formula II.
The media preferably comprise one or more compounds of the formula II-2, which are preferably selected from the group of the compounds of the formulae II-2a to II-2j:
in which the parameters R2, X2, L21 and L22 have the respective meanings indicated above for formula II, and L23 to L28, independently of one another, denote H or F, preferably L27 and L28 both denote H, particularly preferably L26 denotes H, and where the compounds of the formulae IA, IB and IC are excluded.
The media according to the invention preferably comprise one or more compounds selected from the group of the compounds of the formulae II-1a to II-1j in which L21 and L22 both denote F and/or L23 and L24 both denote F.
In a preferred embodiment, the media according to the invention comprise one or more compounds selected from the group of the compounds of the formulae II-2a to II-2j in which L21, L22, L23 and L24 all denote F.
Especially preferred compounds of the formula II-2 are the compounds of the following formulae:
in which R2 and X2 have the meanings indicated above for formula II, and X2 preferably denotes F, and where the compounds of the formulae IA, IB and IC are excluded.
The media according to the invention preferably comprise one or more compounds of the formula II-3, preferably selected from the group of the compounds of the formulae II-3a to II-3c:
in which the parameters R2, X2, L21 and L22 have the respective meanings indicated above for formula II, and L21 and L22 preferably both denote F, and where the compounds of the formulae IA, IB and IC are excluded.
In a preferred embodiment, the media according to the invention comprise one or more compounds of the formula II-4, preferably of the formula II-4a,
in which the parameters R2 and X2 have the meanings given above for formula II, and X2 preferably denotes F or OCF3, particularly preferably F.
The media according to the invention preferably comprise one or more compounds of the formula III-1, preferably selected from the group of the compounds of the formulae III-1a and III-1b:
in which the parameters R2, X2, L31 and L32 have the respective meanings indicated above for formula III, and the parameters L33 and L34, independently of one another and of the other parameters, denote H or F.
The media according to the invention preferably comprise one or more compounds of the formula III-1a, preferably selected from the group of the compounds of the formulae III-1a-1 to III-1a-6:
in which R3 has the meaning indicated above for formula III.
The media according to the invention preferably comprise one or more compounds of the formula III-1b, preferably selected from the group of the compounds of the formulae III-1b-1 to III-1b-4, preferably of the formula III-1b-4:
in which R3 has the meaning indicated above for formula III.
The media according to the invention preferably comprise one or more compounds of the formula III-2, preferably selected from the group of the compounds of the formulae III-2a to III-2j:
in which the parameters R3, X3, L31 and L32 have the meaning given above for formula III, and the parameters L33, L34, L35 and L36, independently of one another and of the other parameters, denote H or F.
The media according to the invention preferably comprise one or more compounds of the formula III-2a, preferably selected from the group of the compounds of the formulae III-2a-1 to III-2a-5:
in which R3 has the meaning indicated above for formula III.
The media according to the invention preferably comprise one or more compounds of the formula III-2b, preferably selected from the group of the compounds of the formulae III-2b-1 and III-2b-2, preferably of the formula III-2b-2:
in which R3 has the meaning indicated above for formula III.
The media according to the invention preferably comprise one or more compounds of the formula III-2c, preferably selected from the group of the compounds of the formulae III-2c-1 to III-2c-4:
in which R3 has the meaning indicated above for formula III.
The media according to the invention preferably comprise one or more compounds selected from the group of the compounds of the formulae III-2d and III-2e, preferably selected from the group of the compounds of the formulae III-2d-1 and III-2e-1:
in which R3 has the meaning indicated above for formula III.
The media according to the invention preferably comprise one or more compounds of the formula III-2f, preferably selected from the group of the compounds of the formulae III-2f-1 to III-2f-5:
in which R3 has the meaning indicated above for formula III.
The media according to the invention preferably comprise one or more compounds of the formula III-2g, preferably selected from the group of the compounds of the formulae III-2g-1 to III-2g-5:
in which R3 has the meaning indicated above for formula III.
The media according to the invention preferably comprise one or more compounds of the formula III-2h, preferably selected from the group of the compounds of the formulae III-2h-1 to III-2h-3, preferably of the formula III-2h-3:
in which the parameters R3 and X3 have the meanings given above for formula III, and X3 preferably denotes F.
The media according to the invention preferably comprise one or more compounds of the formula III-2i, preferably selected from the group of the compounds of the formulae III-2i-1 and III-2i-2, preferably of the formula III-2i-2:
in which the parameters R3 and X3 have the meanings given above for formula III, and X3 preferably denotes F.
The media according to the invention preferably comprise one or more compounds of the formula III-2j, preferably selected from the group of the compounds of the formulae III-2j-1 and III-2j-2, preferably of the formula III-2j-1:
in which the parameters R3 and X3 have the meanings given above for formula III.
The media according to the invention preferably comprise one or more compounds of the formula III-2k, preferably selected from the compounds of the formula III-2k-1:
in which the parameters R3 and X3 have the meanings given above for formula III and X3 preferably denotes F.
Alternatively or in addition to the compounds of the formulae III-1 and/or III-2, the media according to the present invention may comprise one or more compounds of the formula III-3
in which the parameters R3, X3, L31, L32
and n have the respective meanings indicated above under formula III.
These compounds are preferably selected from the group of the formulae III-3a and III-3b:
in which R3 has the meaning indicated above for formula III.
The liquid-crystalline media according to the present invention preferably comprise a dielectrically neutral component, component C. This component has a dielectric anisotropy in the range from −1.5 to 3. It preferably comprises, more preferably predominantly consists of, even more preferably essentially consists of and especially preferably entirely consists of dielectrically neutral compounds having a dielectric anisotropy in the range from −1.5 to 3. This component preferably comprises, more preferably predominantly consists of, even more preferably essentially consists of and very preferably entirely consists of one or more dielectrically neutral compounds of the formula IV having a dielectric anisotropy in the range from −1.5 to 3.
The dielectrically neutral component, component C, preferably comprises one or more compounds selected from the group of the compounds of the formulae IV-1 to IV-6:
in which R41 and R42 have the respective meanings indicated above under formula IV, and in formulae IV-1, IV-5 and IV-6 R41 preferably denotes alkyl or alkenyl, preferably alkenyl, and R42 preferably denotes alkyl or alkenyl, preferably alkyl, in formula IV-2 R41 and R42 preferably denote alkyl, and in formula IV-4 R41 preferably denotes alkyl or alkenyl, more preferably alkyl, and R42 preferably denotes alkyl or alkoxy, more preferably alkoxy.
The dielectrically neutral component, component C, preferably comprises one or more compounds selected from the group of the compounds of the formulae IV-1, IV-4, IV-5 and IV-6, preferably one or more compounds of the formula IV-1 and one or more compounds selected from the group of the formulae IV-4 and IV-5, more preferably one or more compounds of each of the formulae IV-1, IV-4 and IV-5 and very preferably one or more compounds of each of the formulae IV-1, IV-4, IV-5 and IV-6.
In a preferred embodiment, the media according to the invention comprise one or more compounds of the formula IV-5, more preferably selected from the respective sub-formulae thereof of the formulae CCP-V-n and/or CCP-nV-m and/or CCP-Vn-m, more preferably of the formulae CCP-V-n and/or CCP-V2-n and very preferably CCP-V2-1. The definitions of these abbreviations (acronyms) are indicated below in Table D or are evident from Tables A to C.
In a likewise preferred embodiment, the media according to the invention comprise one or more compounds of the formula IV-1, more preferably selected from the respective sub-formulae thereof of the formulae CC-n-m, CC-n-V, CC-n-Vm, CC-V-V, CC-V-Vn and/or CC-nV-Vm, more preferably of the formulae CC-n-V and/or CC-n-Vm and very preferably selected from the group of the formulae CC-4-V, CC-5-V, CC-3-V1, CC-4-V1, CC-5-V1, CC-3-V2 and CC-V-V1. The definitions of these abbreviations (acronyms) are likewise indicated below in Table D or are evident from Tables A to C.
In a further preferred embodiment of the present invention, which may be the same as the previous one or a different one, the liquid-crystal mixtures according to the present invention comprise component C which comprises, preferably predominantly consists of and very preferably entirely consists of compounds of the formula IV selected from the group of the compounds of the formulae IV-1 to IV-6 as shown above and optionally of the formulae IV-7 to IV-13:
in which
In a preferred embodiment, the media according to the invention comprise one or more compounds of the formula IV-8, more preferably selected from the respective sub-formulae thereof of the formulae CPP-3-2, CPP-5-2 and CGP-3-2, more preferably of the formulae CPP-3-2 and/or CGP-3-2 and very particularly preferably of the formula CPP-3-2. The definitions of these abbreviations (acronyms) are indicated below in Table D or are evident from Tables A to C.
The liquid-crystalline media according to the present invention preferably comprise one or more compounds of the formula V
in which
and, if it occurs twice, independently of one another on each occurrence, denotes
denote
The compounds of the formula V are preferably dielectrically neutral compounds having a dielectric anisotropy in the range from −1.5 to 3.
The media according to the invention preferably comprise one or more compounds selected from the group of the compounds of the formulae V-1 and V-2:
in which R51 and R52 have the respective meanings indicated above under formula V, and R51 preferably denotes alkyl, and in formula V-1 R52 preferably denotes alkenyl, preferably —(CH2)2—CH═CH—CH3, and in formula V-2 R52 preferably denotes alkyl or alkenyl, preferably —(CH2)2—CH═CH2 or —(CH2)2—CH═CH—CH3.
The media according to the invention preferably comprise one or more compounds selected from the group of the compounds of the formulae V-1 and V-2 in which R51 preferably denotes n-alkyl, and in formula V-1 R52 preferably denotes alkenyl, and in formula V-2 R52 preferably denotes n-alkyl.
In a preferred embodiment, the media according to the invention comprise one or more compounds of the formula V-1, more preferably of the sub-formula PP-n-2Vm thereof, even more preferably of the formula PP-1-2V1. The definitions of these abbreviations (acronyms) are indicated below in Table D or are evident from Tables A to C.
In a preferred embodiment, the media according to the invention comprise one or more compounds of the formula V-2, more preferably of the sub-formulae PGP-n-m, PGP-n-2V and PGP-n-2Vm thereof, even more preferably of the sub-formulae PGP-3-m, PGP-n-2V and PGP-n-V1 thereof, very preferably selected from the formulae PGP-3-2, PGP-3-3, PGP-3-4, PGP-3-5, PGP-1-2V, PGP-2-2V and PGP-3-2V. The definitions of these abbreviations (acronyms) are likewise indicated below in Table D or are evident from Tables A to C.
Alternatively or in addition to the compounds of the formulae II and/or III, the media according to the present invention may comprise one or more dielectrically positive compounds of the formula VI
in which
independently of one another, denote
The media according to the present invention preferably comprise one or more compounds of the formula VI, preferably selected from the group of the compounds of the formulae VI-1 and VI-2:
in which the parameters have the respective meanings indicated above for formula VI, and the parameters L63 and L64, independently of one another and of the other parameters, denote H or F, and Z6 preferably denotes —CH2—CH2—.
The compounds of the formula VI-1 are preferably selected from the group of the compounds of the formulae VI-1a and VI-1b:
in which R6 has the meaning indicated above for formula VI.
The compounds of the formula VI-2 are preferably selected from the group of the compounds of the formulae VI-2a to VI-2d:
in which R6 has the meaning indicated above for formula VI.
In addition, the liquid-crystal media according to the present invention may comprise one or more compounds of the formula VII
in which
one of
which is present denotes
preferably
and the others have the same meaning or, independently of one another, denote
The compounds of the formula VII are preferably dielectrically positive compounds.
In addition, the liquid-crystal media according to the present invention may comprise one or more compounds of the formula VIII
in which
denotes
preferably
denotes
The compounds of the formula VIII are preferably dielectrically negative compounds.
The media according to the invention preferably comprise one or more compounds of the formula VIII, preferably selected from the group of the compounds of the formulae VIII-1 to VIII-3:
in which
In formulae VIII-1 to VIII-3, R81 preferably denotes n-alkyl or 1-E-alkenyl and R82 preferably denotes n-alkyl or alkoxy.
The liquid-crystalline media according to the present invention preferably comprise one or more compounds selected from the group of the compounds of the formulae I, IA, IB, IC and II to VIII, preferably of the formulae I, IA, IB, IC and II to VII and more preferably of the formulae I, IA, IB, IC and II, III and/or IV and/or VI. They particularly preferably predominantly consist of, even more preferably essentially consist of and very preferably entirely consist of these compounds.
In this context, “predominantly consist of” means that the relevant entity comprises 55% or more, preferably 60% or more and very preferably 70% or more of the component or components or the compound or compounds indicated.
In this context, “essentially consist of” means that the relevant entity comprises 80% or more, preferably 90% or more and very preferably 95% or more of the component or components or the compound or compounds indicated.
In this context, “virtually completely consist of” or “entirely consist of” means that the relevant entity comprises 98% or more, preferably 99% or more and very preferably 100.0% of the component or components or the compound or compounds indicated.
The liquid-crystalline media according to the present application preferably comprise in total
1 to 20%, preferably 2 to 15%, and particularly preferably 3 to 8% of compounds of the formula I,
5 to 30%, preferably 10 to 25% and particularly preferably 15 to 20% of the compound of formula CV,
1 to 15%, preferably 2 to 12% and particularly preferably 3 to 8% of compounds of the formula OT,
1 to 15%, preferably 2 to 12% and particularly preferably 3 to 10% of the compound of the formula PV.
In a preferred embodiment of the present invention, the medium comprises one or more compounds of formula IA in a total concentration of 1 to 25%, preferably 5 to 20%, and particularly preferably 10 to 20%.
In a preferred embodiment of the present invention, the medium comprises one or more compounds of formula IB in a total concentration of 1 to 20%, preferably 2 to 15%, and particularly preferably 3 to 10%.
In a preferred embodiment of the present invention, the medium comprises one or more compounds of formula IC in a total concentration of 1 to 20%, preferably 5 to 15%, and particularly preferably 7 to 12%.
Preferably, the medium comprises one or more compounds of formula I and/or IA and/or IB and/or IC in a total concentration of 10 to 50%, preferably 20 to 40% and particularly preferably 25 to 35%.
The compounds selected from the group of the formulae II and III are preferably used in a total concentration of 2% to 60%, more preferably 3% to 35%, even more preferably 4% to 30% and very preferably 5% to 20% of the mixture as a whole.
The compounds of the formula IV are preferably used in a total concentration of 1% to 20%, more preferably 2% to 15%, even more preferably 3% to 12% and very preferably 5% to 10% of the mixture as a whole.
The compounds of the formula V are preferably used in a total concentration of 0% to 30%, more preferably 0% to 15% and very preferably 1% to 10% of the mixture as a whole.
The compounds of the formula VI are preferably used in a total concentration of 0% to 50%, more preferably 1% to 40%, even more preferably 5% to 30% and very preferably 10% to 20% of the mixture as a whole.
The media according to the invention may optionally comprise further liquid-crystal compounds in order to adjust the physical properties. Such compounds are known to the person skilled in the art. Their concentration in the media according to the present invention is preferably 0% to 30%, more preferably 0.1% to 20% and very preferably 1% to 15%.
The liquid-crystal media preferably comprise in total 50% to 100%, more preferably 70% to 98% and very preferably 80% to 95% and in particular 90% to 92% of the compounds of the formulae I, CV, CP, OT, IA, IB, IC and II to VII, preferably selected from the group of the compounds of the formulae I, CV, CP, OT, IA and/or IB and/or IC and II to VI, particularly preferably of the formulae I, CV, CP, OT, IA and/or IB and/or IC and II to V, in particular of the formulae I, CV, CP, OT, IA and/or IB and/or IC and/or II, III, IV, V and VII and very particularly preferably of the formulae I, CV, CP, OT, IA and/or IB and/or IC and/or II, III, IV and V. They preferably predominantly consist of and very preferably virtually completely consist of these compounds. In a preferred embodiment, the liquid-crystal media in each case comprise one or more compounds of each of these formulae.
Preferably, the medium comprises one or compounds of formula CCQU-n-F in a total concentration of 5 to 20%, preferably 8 to 18%, particularly preferably 10 to 15%.
Preferably, the medium comprises one or compounds of formula DPGU-n-F in a total concentration of 1 to 10%, preferably 2 to 8%, particularly preferably 3 to 6%.
Preferably, the medium comprises one or compounds of formula CPGU-n-OT in a total concentration of 1 to 10%, preferably 2 to 8%, particularly preferably 3 to 6%.
The acronyms used above and below are explained in tables A to D below.
Other mesogenic compounds which are not explicitly mentioned above can optionally and advantageously also be used in the media according to the present invention. Such compounds are known to the person skilled in the art.
The liquid-crystal media according to the present invention preferably have a clearing point of 90° C. or more, more preferably 95° C. or more, even more preferably 100° C. or more, particularly preferably 105° C. or more and very particularly preferably 110° C. or more.
For the present invention a broad nematic phase range is advantageous and it preferably extends at least from −15° C. or less to 80° C. or more, more preferably at least from −20° C. or less to 90° C. or more, very preferably at least from −30° C. or less to 100° C. or more and in particular at least from −40° C. or less to 105° C. or more.
The Δε of the liquid-crystal medium according to the invention, at 1 kHz and 20° C., is preferably 2 or more, more preferably 4 or more and very preferably 6 or more. Δε is particularly preferably 25 or less and in some preferred embodiments 20 or less.
The Δn of the liquid-crystal media according to the present invention, at 589 nm (NaD) and 20° C., is preferably in the range from 0.070 or more to 0.150 or less, more preferably in the range from 0.080 or more to 0.140 or less, even more preferably in the range from 0.090 or more to 0.135 or less and very particularly preferably in the range from 0.100 or more to 0.130 or less.
In a preferred embodiment of the present application, the Δn of the liquid-crystal media according to the present invention is preferably 0.080 or more, more preferably 0.090 or more.
In this preferred embodiment of the present invention, the Δn of the liquid-crystal media is preferably in the range from 0.090 or more to 0.120 or less, more preferably in the range from 0.095 or more to 0.115 or less and very particularly preferably in the range from 0.100 or more to 0.110 or less, while Δε is preferably in the range of from 7 to 25, preferably in the range of from 10 to 22, more preferably in the range of from 13 to 20 and particularly preferably in the range of from 15 to 18.
The present invention further relates to a process for the fabrication of a liquid crystal display using the ODF process, the process comprising at least the steps: forming a sealant on a first panel; dropping liquid crystal on the first panel to form a plurality of liquid crystal dots; and assembling a second panel with the first panel, wherein the first and the second panels have a plurality of pixel areas.
It was found that the appearance of drop mura can be avoided by fine tuning the contact angle of the individual drops of liquid crystal media according to the invention, on the substrate.
In particular, the contact angle of a liquid crystal droplet on the display surface changes with the individual concentrations of the mixture components of the formulae CV, PV and OT.
For the avoidance of drop mura it was observed that it is beneficial to keep the concentration of the compound of formula CV at 30% or less.
The contact angle will be higher with increasing concentrations of the compound of formula PV and decreasing concentrations of compounds of the formula OT.
The contact angle will be lower with decreasing concentrations of the compound of formula CP and increasing concentrations of compounds of formula OT in the medium.
Hence, the contact angle can be either decreased or increased by variation of the concentration of the mixture components of the formulae CV, PV and OT depending on the particular requirements of the process.
In a preferred embodiment of the present invention, the concentration of the compound of formula IV-5-1 in the medium used is 8% or more.
It is further preferred that the concentration of the compound of formula OT in the medium used is 6% or less.
In another preferred embodiment of the present invention, the concentration of the compound of formula OT in the medium used is 4% or more and the concentration of IV-5-1 is 9% or less.
Further preferred embodiments of the present invention are as follows (the compounds are abbreviated using the acronyms explained below in tables A to D):
Preferably,
APUQU-n-F in a total concentration in the range of from 2% to 25%, more preferably from 8% to 20% and particularly preferably from 12% to 16%,
The present invention further relates to a liquid crystal display obtainable by the process described above using a medium according to the present invention.
Preferable, the display according to the invention is addressed by an active matrix.
In the present application, the expression dielectrically positive describes compounds or components where Δε>3.0, dielectrically neutral describes those where −1.5≤Δε≤3.0 and dielectrically negative describes those where Δε<−1.5. Δε is determined at a frequency of 1 kHz and at 20° C. The dielectric anisotropy of the respective compound is determined from the results of a solution of 10% of the respective individual compound in a nematic host mixture. If the solubility of the respective compound in the host mixture is less than 10%, the concentration is reduced to 5%. The capacitances of the test mixtures are determined both in a cell having homeotropic alignment and in a cell having homogeneous alignment. The cell thickness of both types of cells is approximately 20 μm. The voltage applied is a rectangular wave having a frequency of 1 kHz and an effective value of typically 0.5 V to 1.0 V, but it is always selected to be below the capacitive threshold of the respective test mixture.
Δε is defined as (ε∥−ε⊥), while εav. is (ε∥+2ε⊥)/3.
The host mixture used for dielectrically positive compounds is mixture ZLI-4792 and that used for dielectrically neutral and dielectrically negative compounds is mixture ZLI-3086, both from Merck KGaA, Germany. The absolute values of the dielectric constants of the compounds are determined from the change in the respective values of the host mixture on addition of the compounds of interest. The values are extrapolated to a concentration of the compounds of interest of 100%.
Components having a nematic phase at the measurement temperature of 20° C. are measured as such, all others are treated like compounds.
The expression threshold voltage in the present application refers to the optical threshold and is quoted for 10% relative contrast (V10), and the expression saturation voltage refers to the optical saturation and is quoted for 90% relative contrast (V90), in both cases unless expressly stated otherwise. The capacitive threshold voltage (V0), also called the Freedericks threshold (VFr), is only used if expressly mentioned.
The ranges of the parameters indicated in this application all include the limit values, unless expressly stated otherwise.
The different upper and lower limit values indicated for various ranges of properties in combination with one another give rise to additional preferred ranges.
Throughout this application, the following conditions and definitions apply, unless expressly stated otherwise. All concentrations are indicated in percent by weight and relate to the respective mixture as a whole, all temperatures are quoted in degrees Celsius and all temperature differences are quoted in differential degrees. All physical properties are determined in accordance with “Merck Liquid Crystals, Physical Properties of Liquid Crystals”, Status November 1997, Merck KGaA, Germany and are quoted for a temperature of 20° C., unless expressly stated otherwise. The optical anisotropy (Δn) is determined at a wavelength of 589.3 nm. The dielectric anisotropy (Δε) is determined at a frequency of 1 kHz. The threshold voltages, as well as all other electro-optical properties, are determined using test cells produced at Merck KGaA, Germany. The test cells for the determination of Δε have a cell thickness of approximately 20 μm. The electrode is a circular ITO electrode having an area of 1.13 cm2 and a guard ring. The orientation layers are SE-1211 from Nissan Chemicals, Japan, for homeotropic orientation (ε∥) and polyimide AL-1054 from Japan Synthetic Rubber, Japan, for homogeneous orientation (ε⊥). The capacitances are determined using a Solatron 1260 frequency response analyser using a sine wave with a voltage of 0.3 Vrms. The light used in the electro-optical measurements is white light. A set-up using a commercially available DMS instrument from Autronic-Melchers, Germany, is used here. The characteristic voltages have been determined under perpendicular observation. The threshold (V10), mid-grey (V50) and saturation (V90) voltages have been determined for 10%, 50% and 90% relative contrast, respectively.
The liquid-crystal media according to the present invention may comprise further additives and chiral dopants in the usual concentrations. The total concentration of these further constituents is in the range from 0% to 10%, preferably 0.1% to 6%, based on the mixture as a whole. The concentrations of the individual compounds used are each preferably in the range from 0.1% to 3%. The concentration of these and similar additives is not taken into consideration when quoting the values and concentration ranges of the liquid-crystal components and compounds of the liquid-crystal media in this application.
The liquid-crystal media according to the invention consist of a plurality of compounds, preferably 3 to 30, more preferably 4 to 20 and very preferably 4 to 16 compounds. These compounds are mixed in a conventional manner. In general, the desired amount of the compound used in the smaller amount is dissolved in the compound used in the larger amount. If the temperature is above the clearing point of the compound used in the higher concentration, it is particularly easy to observe completion of the dissolution process. It is, however, also possible to prepare the media in other conventional ways, for example using so-called pre-mixes, which can be, for example, homologous or eutectic mixtures of compounds, or using so-called “multibottle” systems, the constituents of which are themselves ready-to-use mixtures.
By addition of suitable additives, the liquid-crystal media according to the present invention can be modified in such a way that they can be used in all known types of liquid-crystal displays, either using the liquid-crystal media as such, such as TN, TN-AMD, ECB-AMD, VAN-AMD, IPS-AMD, FFS-AMD LCDs, or in composite systems, such as PDLC, NCAP, PN LCDs and especially in ASM-PA LCDs.
All temperatures, such as, for example, the melting point T(C,N) or T(C,S), the transition from the smectic (S) to the nematic (N) phase T(S,N) and the clearing point T(N,I) of the liquid crystals, are quoted in degrees Celsius. All temperature differences are quoted in differential degrees.
In the present invention and especially in the following examples, the structures of the mesogenic compounds are indicated by means of abbreviations, also called acronyms. In these acronyms, the chemical formulae are abbreviated as follows using Tables A to C below. All groups CnH2n+1, CmH2m+1 and ClH2l+1 or CnH2n−1, CmH2m−1 and ClH2l−1 denote straight-chain alkyl or alkenyl, preferably 1E-alkenyl, each having n, m and I C atoms respectively. Table A lists the codes used for the ring elements of the core structures of the compounds, while Table B shows the linking groups. Table C gives the meanings of the codes for the left-hand or right-hand end groups. The acronyms are composed of the codes for the ring elements with optional linking groups, followed by a first hyphen and the codes for the left-hand end group, and a second hyphen and the codes for the right-hand end group. Table D shows illustrative structures of compounds together with their respective abbreviations.
in which n and m each denote integers, and the three dots “ . . . ” are placeholders for other abbreviations from this table.
The following table shows illustrative structures together with their respective abbreviations. These are shown in order to illustrate the meaning of the rules for the abbreviations. They furthermore represent compounds which are preferably used.
The following table, Table E, shows illustrative compounds which can be used as stabiliser in the mesogenic media according to the present invention.
In a preferred embodiment of the present invention, the mesogenic media comprise one or more compounds selected from the group of the compounds from Table E.
The following table, Table F, shows illustrative compounds which can preferably be used as chiral dopants in the mesogenic media according to the present invention.
In a preferred embodiment of the present invention, the mesogenic media comprise one or more compounds selected from the group of the compounds from Table F.
The mesogenic media according to the present application preferably comprise two or more, preferably four or more, compounds selected from the group consisting of the compounds from the above tables.
The liquid-crystal media according to the present invention preferably comprise
Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The preceding preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.
In the foregoing and in the examples, all temperatures are set forth uncorrected in degrees Celsius and, all parts and percentages are by weight, unless otherwise indicated.
The entire disclosures of all applications, patents and publications, cited herein and of corresponding European application No. 17150727, filed Jan. 9, 2017 are incorporated by reference herein.
The examples below illustrate the present invention without limiting it in any way.
However, the physical properties show the person skilled in the art what properties can be achieved and in what ranges they can be modified. In particular, the combination of the various properties which can preferably be achieved is thus well defined for the person skilled in the art.
Liquid-crystal mixtures having the composition and properties as indicated in the following tables are prepared.
The contact angle is the angle where a liquid-vapor interface meets a solid surface. For each of the mixtures described above the contact angle of the liquid crystal is measured on Parafilm-M®.
Parafilm-M® is available from Bemis Company, Inc., Oshkosh, Wis., U.S.A., having the following characteristics:
Parafilm M® All-Purpose Laboratory Film, (#PM996),
Permeability Characteristics:
Oxygen (ASTM 1927-98): 150 cc/m2d at 23° C. and 50% RH
Carbon Dioxide (Modulated IR Method): 1200 cc/m2d at 23° C. and 0% RH
Water Vapour (ASTM F1249-01): Flat: 1 g/m2 d at 38° C. and 90% RH.
The contact angle (αcon) is measured using a “Drop Shape Analyzer”, Model DSA100 (Krüss GmbH, Hamburg, Germany). A small droplet of liquid crystal is dispensed onto the substrate (Parafilm) by means of a syringe and the contact angle is measured with the circle fitting method.
The following results are obtained for the comparative mixture examples CM1 and CM2, and the mixture examples M1 and M2, all of which contain the compound of formula CV (CC-3-V), the compound of formula PV (CCP-V-1) and a compound of formula OT (CCP-3-OT):
As can be seen, for the comparative mixture examples CM1 and CM2, containing both 8% of CCP-V-1 and 2.5% of CCP-3-OT and a very similar amount of CC-3-V of 31.5% and 33%, respectively, the contact angle is the same (αcon=43.8°). Both mixtures CM1 and CM2 show drop mura (chess pattern) in test panels. The reduction of the amount of CC-3-V to 26% and increase of the concentration of CCP-V-1 to 10% in mixture M1 results in an increase of the contact angle by almost 1° to 44.7° (αcon=44.7° for mixture M1). Mixture M1 does not show drop mura (chess pattern) in a test panel as used with CM1 or CM2.
A lower contact angle can be achieved by significantly reducing the amount of CCP-V-1 to 2.5% in combination with a significant increase in the concentration of CCP-3-OT (αcon=43° for mixture M2). This effect is useful for the avoidance of drop mura of the dotting mura type.
A precise adjustment of the contact angle is a prerequisite for the control of the behaviour of a liquid crystal mixture in the ODF process and has a significant influence in the avoidance of display defects such as ODF mura.
The examples show that it is possible to adjust the contact angle of the mixtures according to the invention by keeping the other relevant parameters sufficiently constant for applications.
The preceding examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples.
From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention and, without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.
| Number | Date | Country | Kind |
|---|---|---|---|
| 17150727.0 | Jan 2017 | EP | regional |
