Patent Grant
11359142
The present invention includes novel compounds, novel liquid crystalline media, in particular for use in liquid crystal displays, and to these liquid-crystal displays, particularly to liquid-crystal displays which use the IPS (in-plane switching) or, preferably, the FFS (fringe field switching) effect using dielectrically positive liquid crystals.
The media are distinguished by a particularly high transmission and reduced response time in respective displays, which is brought about by their unique combination of physical properties, especially by their high values of the elastic constant(s), in particular by high k11 and their excellent, low ratio (γ1/k11) of the rotational viscosity (γ1) and the elastic constant (k11). This also leads to their excellent performance in the displays according to the invention.
IPS and FFS displays using dielectrically positive liquid crystals are well known in the field and have been widely adopted for various types of displays, e.g., note books, desk top monitors and TV sets, but also for mobile applications.
However, recently, IPS and in particular FFS displays using dielectrically negative liquid crystals are widely adopted. The latter ones are sometimes also called UB-FFS (ultra-bright FFS). Such displays are disclosed, e.g., in US 2013/0207038 A1. These displays are characterized by a markedly increased transmission compared to the previously used IPS- and FFS displays, which have been dielectrically positive liquid crystals. These displays using dielectrically negative liquid crystals, however, have the severe disadvantage of requiring a higher operation voltage than the respective displays using dielectrically positive liquid crystals. Liquid crystalline media used for UB-FFS have a dielectric anisotropy of −0.5 or less and preferably of −1.5 or less.
According to the present application, however, the IPS or the FFS effect with dielectrically positive liquid crystalline media in a homogeneous alignment are preferred.
Industrial application of this effect in electro-optical display elements requires LC phases which have to meet a multiplicity of requirements. Particularly important here are chemical resistance to moisture, air and physical influences, such as heat, radiation in the infrared, visible and ultraviolet regions, and direct (DC) and alternating (AC) electric fields.
Furthermore, LC phases which can be used industrially are required to have a liquid-crystalline mesophase in a suitable temperature range and low viscosity.
None of the series of compounds having a liquid-crystalline mesophase that have been disclosed hitherto includes a single compound which meets all these requirements. Mixtures of two to 25, preferably three to 18, compounds are therefore generally prepared in order to obtain substances which can be used as LC phases.
Matrix liquid-crystal displays (MLC displays) are known. Non-linear elements which can be used for individual switching of the individual pixels are, for example, active elements (i.e. transistors). The term “active matrix” is then used, where in general use is made of thin-film transistors (TFTs), which are generally arranged on a glass plate as substrate.
A distinction is made between two technologies: TFTs comprising compound semiconductors, such as, for example, CdSe, or metal oxides like ZnO or TFTs based on polycrystalline and, inter alia, amorphous silicon. The latter technology currently has the greatest commercial importance worldwide.
The TFT matrix is applied to the inside of one glass plate of the display, while the other glass plate carries the transparent counter electrode on its inside. Compared with the size of the pixel electrode, the TFT is very small and has virtually no adverse effect on the image. This technology can also be extended to fully colour-capable displays, in which a mosaic of red, green and blue filters is arranged in such a way that a filter element is located opposite each switchable pixel.
The TFT displays most used hitherto usually operate with crossed polarisers in transmission and are backlit. For TV applications, ECB (or VAN) cells or FFS cells are used, whereas monitors usually use IPS cells or TN (twisted nematic) cells, and notebooks, laptops and mobile applications usually use TN, VA or FFS cells.
The term MLC displays here encompasses any matrix display having integrated non-linear elements, i.e., besides the active matrix, also displays with passive elements, such as varistors or diodes (MIM=metal-insulator-metal).
MLC displays of this type are particularly suitable for TV applications, monitors and notebooks or for displays with a high information density, for example in automobile manufacture or aircraft construction. Besides problems regarding the angle dependence of the contrast and the response times, difficulties also arise in MLC displays due to insufficiently high specific resistance of the liquid-crystal mixtures [TOGASHI, S., SEKIGUCHI, K., TANABE, H., YAMAMOTO, E., SORIMACHI, K., TAJIMA, E., WATANABE, H., SHIMIZU, H., Proc. Eurodisplay 84, September 1984: A 210-288 Matrix LCD Controlled by Double Stage Diode Rings, pp. 141 ff., Paris; STROMER, M., Proc. Eurodisplay 84, September 1984: Design of Thin Film Transistors for Matrix Addressing of Television Liquid Crystal Displays, pp. 145 ff., Paris]. With decreasing resistance, the contrast of an MLC display deteriorates. Since the specific resistance of the liquid-crystal mixture generally drops over the life of an MLC display owing to interaction with the inside surfaces of the display, a high (initial) resistance is very important for displays that have to have acceptable resistance values over a long operating period.
In general form, the technologies are compared, for example, in Souk, Jun, SID Seminar 2004, Seminar M-6: “Recent Advances in LCD Technology”, Seminar Lecture Notes, M-6/1 to M-6/26, and Miller, Ian, SID Seminar 2004, Seminar M-7: “LCD-Television”, Seminar Lecture Notes, M-7/1 to M-7/32. Although the response times of modern ECB displays have already been significantly improved by addressing methods with overdrive, for example: Kim, Hyeon Kyeong et al., Paper 9.1: “A 57-in. Wide UXGA TFT-LCD for HDTV Application”, SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book I, pp. 106 to 109, the achievement of video-compatible response times, in particular in the switching of grey shades, is still a problem which has not yet been solved to a satisfactory extent.
In liquid-crystal displays of this type, the liquid crystals are used as dielectrics, whose optical properties change reversibly on application of an electrical voltage.
Since in displays in general, i.e., also in displays in accordance with these mentioned effects, the operating voltage should be as low as possible, use is made of liquid-crystal media which are generally predominantly composed of liquid-crystal compounds, all of which have the same sign of the dielectric anisotropy and have the highest possible value of the dielectric anisotropy. In general, at most relatively small proportions of neutral compounds and if possible, no compounds having a sign of the dielectric anisotropy which is opposite to that of the medium are employed. In the case of liquid-crystal media having negative dielectric anisotropy, e.g., for ECB or UB-FFS displays, predominantly compounds having negative dielectric anisotropy are thus employed. The respective liquid-crystalline media employed generally consist predominantly and usually even essentially of liquid-crystal compounds having negative dielectric anisotropy.
In the media used in accordance with the present application, significant amounts of dielectrically positive liquid-crystal compounds and generally only very small amounts of dielectrically compounds or even none at all are typically employed, since in general the liquid-crystal displays are intended to have the lowest possible addressing voltages. At the same time small amounts of dielectrically neutral compounds may be beneficially used in some cases.
Liquid crystalline media having a positive dielectric anisotropy for IPS and FFS displays have already been disclosed. In the following some examples will be given.
Laid open DE 102016003902.3, EP 3 081 620 and EP 3 095 834 are related to liquid crystal compounds respectively liquid crystalline media for application in respective displays.
Pending, not yet published Applications EP 17164891.8, EP 16190393.5, EP 16194162.0, EP 16197206.2 and EP 16199580.8 of the applicant of the instant application are also related to liquid crystal compounds respectively liquid crystalline media for application in respective displays.
The compound of formula
is disclosed in DE 10 2010 027 099 A1.
EP Appln. No. 19185360.5, which is not yet published, discloses a liquid crystalline medium comprising the compound of formula
(PUS-n-T with n=3) and the compound of formula
(CLP-V-n with n=1) and another one additionally comprising
(CLP-n-T with n=3).
Obviously, the range of the nematic phase of the liquid-crystal mixture must be sufficiently broad for the intended application of the display.
The response times of the liquid-crystal media in the displays also have to be improved, i.e., reduced. This is particularly important for displays for television or multimedia applications and for gaming both for monitors and for note books. In order to improve the response times, it has repeatedly been proposed in the past to optimise the rotational viscosity of the liquid-crystal media (γ1), i.e., to achieve media having the lowest possible rotational viscosity. However, the results achieved here are inadequate for many applications and therefore make it appear desirable to find further optimisation approaches.
Adequate stability of the media to extreme loads, in particular to UV exposure and heating, is very particularly important. In particular in the case of applications in displays in mobile equipment, such as, for example, mobile telephones, this may be crucial.
Besides their relatively poor transmission and their relatively long response times, the MLC displays disclosed hitherto, have further disadvantages. These are, e.g., their comparatively low contrast, their relatively high viewing-angle dependence and the difficulty in the reproduction of grey scales in these displays, especially when observed from an oblique viewing angle, as well as their inadequate VHR and their inadequate lifetime. The desired improvements of the transmission of the displays and of their response times are required in order to improve their energy efficiency, respectively their capacity to render rapidly moving pictures.
There thus continues to be a great demand for MLC displays having very high specific resistance at the same time as a large working-temperature range, short response times and a low threshold voltage, with the aid of which various grey shades can be produced and which have, in particular, a good and stable VHR.
The invention has an object of providing MLC displays, not only for monitor and TV applications, but also for gaming and for mobile applications such as, e.g., telephones and navigation systems, which are based on the ECB, IPS or FFS effect, do not have the disadvantages indicated above, or only do so to a lesser extent, and at the same time have very high specific resistance values. In particular, it must be ensured for mobile telephones and navigation systems that they also work at extremely high and extremely low temperatures.
Surprisingly, it has been found that it is possible to achieve liquid-crystal displays which have, in particular in IPS and FFS displays, a low threshold voltage with short response times, a sufficiently broad nematic phase, favourable, relatively high birefringence (Δn) and, at the same time, a high transmission, good stability to decomposition by heating and by UV exposure, and a stable, high VHR if use is made in these display elements of nematic liquid-crystal mixtures which comprise at least one compound, preferably two or more compounds of formula T, preferably selected from the group of the compounds of the sub-formulae T-1 and T-2 and one or more compounds of formula L, preferably selected from the group of the compounds of the sub-formulae L-1 and L-2, and preferably additionally at least one compound, preferably two or more compounds, selected from the group of the compounds of the formulae II and III, the former preferably of formula II-1 and/or II-2, and/or at least one compound, preferably two or more compounds selected from the group of formulae IV and/or V (all formulae as defined herein below).
Media of this type can be used, in particular, for electro-optical displays having active-matrix addressing for IPS- or FFS displays.
The media according to the present invention preferably additionally comprise a one or more compounds selected from the group of compounds of formulae II and III, preferably one or more compounds of formula II, more preferably in addition one or more compounds of formula III and, most preferably, additionally one or more compounds selected from the group of the compounds of formulae IV and V and, again preferably, one or more compounds selected from the group of compounds of formulae VI to IX (all formulae as defined below).
The mixtures according to the invention exhibit very broad nematic phase ranges with clearing points ≥70° C., very favourable values for the capacitive threshold, relatively high values for the holding ratio and at the same time good low-temperature stabilities at −20° C. and −30° C., as well as very low rotational viscosities. The mixtures according to the invention are furthermore distinguished by a good ratio of clearing point and rotational viscosity and by a relatively high positive dielectric anisotropy.
Now, it has been found surprisingly that LCs of the FFS type using liquid crystals with positive dielectric anisotropy may be realised using specially selected liquid crystalline media. These media are characterised by a particular combination of physical properties. Most decisive amongst these are their high values of the elastic constant(s), in particular by high k11 and their excellent, low ratio (γ1/k11) of the rotational viscosity (γ1) and the elastic constant. (k11).
The liquid crystalline media according to the present invention preferably have a positive dielectric anisotropy, preferably in the range from 1.5 or more to 20.0 or less, more preferably in the range from 2.0 or more to 8.0 or less and, most preferably in the range from 2.5 or more to 7.0. or less.
The liquid crystalline medium of the present invention, preferably has a dielectric anisotropy (Δε) of 0.5 or more and comprises
in which
in which
in which
occurs twice,
to
preferably
preferably
denotes
and, if present,
preferably denotes
Throughout this application 1,3-cyclopentenylene is a moiety selected from the group of the formulae
preferably
most preferably
The liquid-crystalline media in accordance with the present application preferably have a nematic phase.
The present invention also concerns the simultaneous use of the compounds of formulae T and L, as shown above, wherein the parameters have the respective meanings, including the respective preferred meanings, given above and below.
Preferably the compounds of formula T, which are used in the liquid crystalline media according to the present application, are selected from the group of compounds of formulae T-1 and T-2, preferably of formula T-1:
wherein the parameters have the respective meanings given under formula T above, with the exception that RS2 in formula T-1 may not denote XS, and
in which
Preferably the compounds of formula T-1, which are used in the liquid crystalline media according to the present application, are selected from the group of compounds of formulae T-1-1 to T-1-3, preferably from formulae T-1-2 and T-1-3, most preferably from formula T-1-3:
wherein the parameters have the respective meanings, including the respective preferred meanings, given above.
Preferably the compounds of formula T-2, which are used in the liquid crystalline media according to the present application, are selected from the group of compounds of formulae T-2-1 to T-2-3, preferably from formulae T-2-2 and T-2-3, most preferably from formula T-2-3:
wherein the parameters have the respective meanings, including the respective preferred meanings, given above.
The compounds of formula T, e.g., of formulae PPS-n-m, PGS-n-m, PUS-n-m, PPS-n-X, PGS-n-X and PUS-n-X (these formulae being defined below), wherein X is F, CF3 or OCF3, are prepared according to known synthetic routes.
Preferably the compounds of formula L, which are used in the liquid crystalline media according to the present application, are selected from the group of compounds of formulae L-1 and L-2, preferably of formula L-1, more preferably both of formula L-1 and of formula L-2:
wherein the parameters have the respective meanings given under formula L above, with the exception that RL2 in formula L-1 may not denote XL, and
in which
Preferably the compounds of formula L-1, which are used in the liquid crystalline media according to the present application, are selected from the group of compounds of formulae L-1-1 to L-1-3, preferably from formulae L-1-1 and L-1-2, most preferably of formula L-1-1:
wherein the parameters have the respective meanings, including the respective preferred meanings, given above.
Preferably the compounds of formula L-2, which are used in the liquid crystalline media according to the present application, are selected from the group of compounds of formulae L-2-1 to L-2-3, preferably from formulae L-2-2 and L-2-3, most preferably of formula L-2-3:
wherein the parameters have the respective meanings including the respective preferred meanings, given above and preferably
The compounds of formula L, e.g. of formulae CLP-V-n, CLP-1V-n and CLP-n-T (these formulae being defined below), are prepared according to known synthetic routes.
The invention furthermore relates to a liquid-crystal display containing a liquid-crystalline medium according to the invention, in particular an IPS or FFS display, particularly preferably a FFS or SG-FFS display.
The invention furthermore relates to a liquid-crystal display of the IPS or FFS type comprising a liquid-crystal cell consisting of two substrates, where at least one substrate is transparent to light and at least one substrate has an electrode layer, and a layer, located between the substrates, of a liquid-crystalline medium comprising a polymerised component and a low-molecular-weight component, where the polymerised component is obtainable by polymerisation of one or more polymerisable compounds in the liquid-crystalline medium between the substrates of the liquid-crystal cell, preferably with application of an electrical voltage and where the low-molecular-weight component is a liquid-crystal mixture according to the invention as described above and below.
The displays in accordance with 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 be used in an advantageous manner in displays having other known addressing means.
The invention furthermore relates to a process for the preparation of a liquid-crystalline medium according to the invention by mixing one or more compounds of formulae T and L, preferably selected from the group of compounds of formulae T-1 and/or T-2 with one or more compounds of formulae L-1 and/or L-2 with one or more low-molecular-weight liquid-crystalline compounds, or a liquid-crystal mixture and optionally with further liquid-crystalline compounds and/or additives.
The following meanings apply above and below:
The term “mesogenic group” is known to the person skilled in the art and is described in the literature, and denotes a group which, due to the anisotropy of its attracting and repelling interactions, essentially contributes to causing a liquid-crystalline (LC) phase in low-molecular-weight or polymeric substances. Compounds containing mesogenic groups (mesogenic compounds) do not necessarily have to have a liquid-crystalline phase themselves. It is also possible for mesogenic compounds to exhibit liquid-crystalline phase behaviour only after mixing with other compounds and/or after polymerisation. Typical mesogenic groups are, for example, rigid rod- or disc-shaped units. An overview of the terms and definitions used in connection with mesogenic or liquid-crystalline compounds is given in Pure Appl. Chem. 73(5), 888 (2001) and C. Tschierske, G. Pelzl, S. Diele, Angew. Chem. 2004, 116, 6340-6368.
The term “spacer group” or “spacer” for short, also referred to as “Sp” above and below, is known to the person skilled in the art and is described in the literature, see, for example, Pure Appl. Chem. 73(5), 888 (2001) and C. Tschierske, G. Pelzl, S. Diele, Angew. Chem. 2004, 116, 6340-6368. Unless indicated otherwise, the term “spacer group” or “spacer” above and below denotes a flexible group which connects the mesogenic group and the polymerisable group(s) to one another in a polymerisable mesogenic compound.
For the purposes of this invention, the term “liquid-crystalline medium” is intended to denote a medium which comprises a liquid-crystal mixture and one or more polymerisable compounds (such as, for example, reactive mesogens). The term “liquid-crystal mixture” (or “host mixture”) is intended to denote a liquid-crystalline mixture which consists exclusively of unpolymerisable, low-molecular-weight compounds, preferably of two or more liquid-crystalline compounds and optionally further additives, such as, for example, chiral dopants or stabilisers.
Particular preference is given to liquid-crystal mixtures and liquid-crystalline media which have a nematic phase, in particular at room temperature.
In a preferred embodiment of the present invention, the liquid-crystal medium comprises one or more, preferably dielectrically positive, compounds preferably having a dielectric anisotropy of 3 or more, selected from the group of the compounds of the formulae II-1 and 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 formulae II-1 and II-2, X2 preferably denotes F or OCF3, particularly preferably F, and, in the case of formula II-2, and
independently of one another, preferably denote
and/or selected from the group of the compounds of the formulae III-1 and III-2:
in which the parameters have the meanings given under formula III,
and the media in accordance with the present invention may comprise, alternatively or in addition to the compounds of the formulae III-1 and/or III-2, one or more compounds of the formula III-3
in which the parameters have the respective meanings indicated above, and the parameters L31 and L32, independently of one another and of the other parameters, denote H or F.
The liquid-crystal medium preferably comprises compounds selected from the group of the compounds of the formulae II-1 and II-2 in which L21 and L22 and/or L23 and L24 both denote F.
In a preferred embodiment, the liquid-crystal medium comprises compounds selected from the group of the compounds of the formulae II-1 and II-2 in which L21, L22, L23 and L24 all denote F.
The liquid-crystal medium preferably comprises 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-1e, preferably one or more compounds of formulae II-1a and/or II-1b and/or II-1d, preferably of formula II-1a and/or II-1d or II-1b and/or II-1d, most preferably of formula II-1d:
in which the parameters have the respective meanings indicated above, and L25 and L26, independently of one another and of the other parameters, denote H or F, and preferably
in the formulae II-1a and II-1b,
L21 and L22 both denote F,
in the formulae II-1c and II-1 d,
L21 and L22 both denote F and/or L23 and L24 both denote F, and
in formula II-1e,
L21, L22 and L23 denote F.
The liquid-crystal medium preferably comprises 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-2k, preferably one or more compounds each of formulae II-2a and/or II-2h and/or II-2j:
in which the parameters have the respective meanings indicated above, and L25 to L28, independently of one another, denote H or F, preferably L27 and L28 both denote H, particularly preferably L26 denotes H.
The liquid-crystal medium preferably comprises compounds selected from the group of the compounds of the formulae II-1a to II-1e in which L21 and L22 both denote F and/or L23 and L24 both denote F.
In a preferred embodiment, the liquid-crystal medium comprises compounds selected from the group of the compounds of the formulae II-2a to II-2k 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, particularly preferred of formulae II-2a-1 and/or II-2h-1 and/or II-2k-2:
in which R2 and X2 have the meanings indicated above, and X2 preferably denotes F.
The liquid-crystal medium preferably comprises one or more compounds of the formula III-1. The compounds of the formula III-1 are preferably selected from the group of the compounds of the formulae III-1a to III-1j, preferably from formulae III-1c, III-1f, III-1g and III-1j:
in which the parameters have the meanings given above and preferably in which the parameters have the respective meanings indicated above, the parameters L35 and L36, independently of one another and of the other parameters, denote H or F, and the parameters L35 and L36, independently of one another and of the other parameters, denote H or F.
The liquid-crystal medium preferably comprises one or more compounds of the formula III-1c, which are preferably selected from the group of the compounds of the formulae III-1c-1 to III-1c-5, preferably of formulae III-1c-1 and/or III-1c-2, most preferably of formula III-1c-1:
in which R3 has the meaning indicated above.
The liquid-crystal medium preferably comprises one or more compounds of the formula III-1f, which are preferably selected from the group of the compounds of the formulae III-1f-1 to III-1f-6, preferably of formulae
III-1f-1 and/or III-1f-2 and/or III-1f-3 and/or III-1f-6, more preferably of formula III-1f-3 and/or III-1f-6, more preferably of formula III-1f-6:
in which R3 has the meaning indicated above.
The liquid-crystal medium preferably comprises one or more compounds of the formula III-1g, which are preferably selected from the group of the compounds of the formulae III-1g-1 to III-1g-5, preferably of formula III-1g-3:
in which R3 has the meaning indicated above.
The liquid-crystal medium preferably comprises one or more compounds of the formula III-1h, which are preferably selected from the group of the compounds of the formulae III-1h-1 to III-1h-3, preferably of the formula III-1h-3:
in which the parameters have the meanings given above, and X3 preferably denotes F.
The liquid-crystal medium preferably comprises one or more compounds of the formula III-1i, which are preferably selected from the group of the compounds of the formulae III-1i-1 and III-1i-2, preferably of the formula III-1i-2:
in which the parameters have the meanings given above, and X3 preferably denotes F.
The liquid-crystal medium preferably comprises one or more compounds of the formula III-1j, which are preferably selected from the group of the compounds of the formulae III-1j-1 and III-1j-2, preferably of the formula III-1j-1:
in which the parameters have the meanings given above.
The liquid-crystal medium preferably comprises one or more compounds of the formula III-2. The compounds of the formula III-2 are preferably selected from the group of the compounds of the formulae III-2a and III-2b, preferably of formula III-2b:
in which the parameters have the respective meanings indicated above, and the parameters L33 and L34, independently of one another and of the other parameters, denote H or F.
The liquid-crystal medium preferably comprises one or more compounds of the formula III-2a, which are preferably selected from the group of the compounds of the formulae III-2a-1 to III-2a-6:
in which R3 has the meaning indicated above.
The liquid-crystal medium preferably comprises one or more compounds of the formula III-2b, which are preferably selected from the group of the compounds of the formulae III-2b-1 to III-2b-4, preferably
in which R3 has the meaning indicated above.
Alternatively or in addition to the compounds of the formulae III-1 and/or III-2, the media in accordance with the present invention may comprise one or more compounds of the formula III-3
in which the parameters 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.
The liquid-crystalline media in accordance with the present invention preferably comprise one or more dielectrically neutral compounds, preferably having a dielectric anisotropy in the range from −1.5 to 3, preferably selected from the group of the compounds of the formulae VI, VII, VIII and IX.
In the present application, the elements all include their respective isotopes. In particular, one or more H in the compounds may be replaced by D. and this is also particularly preferred in some embodiments. A correspondingly high degree of deuteration of the corresponding compounds enables, for example, detection and recognition of the compounds. This is very helpful in some cases, in particular in the case of the compounds of formula I.
In the present application,
In a further preferred embodiment, the medium comprises one or more compounds of formula IV, preferably
one or more compounds of formula IV-A
in which
In a particularly preferred embodiment, the medium comprises one or more compounds of formula IV-A selected from the group of the compounds of the formulae IV-1 to IV-4, preferably of formula IV-1,
in which
In a particularly preferred embodiment, the media according to the invention comprise one or more compounds of formula IV-1 and/or one or more compounds of formula IV-2.
In a further preferred embodiment, the medium comprises one or more compounds of formula V.
The media according to the invention preferably comprise the following compounds in the total concentrations indicated:
The latter condition is preferred for all media according to the present application.
In a further preferred embodiment, the media in accordance with the present invention in addition to the compounds of formula T or the preferred sub-formulae thereof, preferably comprise one or more, preferably dielectrically neutral, compounds selected from the group of compounds of formulae IV and V preferably in a total concentration in the range from 5% or more to 90% or less, preferably from 10% or more to 80% or less, particularly preferably from 20% or more to 70% or less.
The medium according to the invention in a particularly preferred embodiment comprises one or more compounds of formula II in a total concentration in the range from 5% or more to 50% or less, preferably in the range from 10% or more to 40% or less.
Preferably the concentration of the compounds of formula T in the media according to the invention is in the range from 1% or more to 60% or less, more preferably from 5% or more to 50% or less, most preferably from 8% or more to 45% or less.
Preferably the concentration of the compounds of formula L in the media according to the invention is in the range from 1% or more to 60% or less, more preferably from 5% or more to 40% or less, most preferably from 8% or more to 35% or less.
In a preferred embodiment of the present invention the concentration of the compounds of formula II in the media is in the range from 3% or more to 60% or less, more preferably from 5% or more to 55% or less, more preferably from 10% or more to 50% or less and, most preferably, from 15% or more to 45% or less.
The present invention also relates to electro-optical displays or electro-optical components which contain liquid-crystalline media according to the invention. Preference is given to electro-optical displays which are based on the VA, ECB, IPS or FFS effect, preferably on the VA; IPS or FFS effect, and in particular those which are addressed by means of an active-matrix addressing device.
Accordingly, the present invention likewise relates to the use of a liquid-crystalline medium according to the invention in an electro-optical display or in an electro-optical component, and to a process for the preparation of the liquid-crystalline media according to the invention, characterised in that one or more compounds of formula T preferably of the sub-formulae T-1 and/or T-2, are mixed with one or more compounds of formula L, preferably with one or more compounds of the sub-formulae L-1 and/or L-2 and/or with one or more compounds selected from of formulae IV and V, and or with one or more compounds of formulae II-1, II-2 and one or more further compounds, preferably selected from the group of the compounds of the formulae IV and V, more preferably with one or more compounds both of formula IV and of formula V.
In a further preferred embodiment, the medium comprises one or more compounds of formula IV, selected from the group of the compounds of the formulae IV-2 and IV-3,
in which
In a further preferred embodiment, the medium comprises one or more compounds of formula V selected from the group of the compounds of the formulae V-1 and V-2, preferably of formulae V-1,
in which the parameters have the meanings given above under formula V, and preferably
In a further preferred embodiment, the medium comprises one or more compounds of formula V-1 selected from the group of the compounds of the formulae V-1a and V-1b,
in which
In addition, the present invention relates to a method for the reduction of the wavelength dispersion of the birefringence of a liquid-crystalline medium which comprises one or more compounds of formula II, optionally one or more compounds selected from the group of the compounds of formula IV and/or one or more compounds of formula V, characterised in that one or more compounds each of formulae T and L are used in the medium.
Besides compounds of the formulae T, L and II to V, other constituents may also be present, for example in an amount of up to 35%, but preferably up to 25%, in particular up to 10%, of the mixture as a whole.
The media according to the invention may optionally also comprise a dielectrically positive component, whose total concentration is preferably 20% or less, more preferably 10% or less, based on the entire medium.
In a preferred embodiment, the liquid-crystal media according to the invention comprise in total, based on the mixture as a whole,
1% or more to 50% or less, preferably 2% or more to 35% or less, particularly preferably 3% or more to 25% or less, of the compounds of formula T,
1% or more to 20% or less, preferably 2% or more to 15% or less, particularly preferably 3% or more to 12% or less, of the compound of formula L.
20% or more to 50% or less, preferably 25% or more to 45% or less, particularly preferably 30% or more to 40% or less, of compounds of formulae II and/or III, and
0% or more to 35% or less, preferably 2% or more to 30% or less, particularly preferably 3% or more to 25% or less, of compounds of formulae IV and/or V, and
The liquid-crystal media in accordance with the present invention may comprise one or more chiral compounds.
Particularly preferred embodiments of the present invention meet one or more of the following conditions,
where the acronyms (abbreviations) are explained in Tables A to C and illustrated by examples in Table D.
In a preferred embodiment of the present application the compounds of formula T, which are preferred as such and are used preferably in the liquid crystalline media, wherein YS1 is F and YS2 is H, and, alternatively, compounds of formula T, wherein both YS1 and YS2 are F.
Preferably the media according to the present invention fulfil one or more of the following conditions.
The invention furthermore relates to an electro-optical display having active-matrix addressing based on the VA, ECB, IPS, FFS or UB-FFS effect, characterised in that it contains, as dielectric, a liquid-crystalline medium in accordance with the present invention.
The liquid-crystal mixture preferably has a nematic phase range having a width of at least 70 degrees.
The rotational viscosity γ1 is preferably 200 mPa·s or less, preferably 150·s or less and, in particular, 120 mPa·s or less.
The mixtures according to the invention are suitable for all IPS and FFS-TFT applications using dielectrically positive liquid crystalline media.
The liquid-crystalline media according to the invention preferably virtually completely consist of 4 to 18, in particular 5 to 15, and particularly preferably 12 or less, compounds. These are preferably selected from the group of the compounds of the formulae T, L, II, III, IV and V.
The liquid-crystalline media according to the invention may optionally also comprise more than 18 compounds. In this case, they preferably comprise 18 to 25 compounds.
In a preferred embodiment, the liquid-crystal media according to the invention predominantly consist of, preferably essentially consist of and, most preferably, virtually completely consist of compounds which do not comprise a cyano group.
In a preferred embodiment, the liquid-crystal media according to the invention comprise compounds selected from the group of the compounds of the formulae T, L, II and III, IV and V, preferably selected from the group of the compounds of the formulae T, preferably selected from T-1 and T-2, L, preferably selected from L-1 and L-2, II, preferably selected from II-1 and II-2, III, preferably selected from III-1 and III-2, IV and V. They preferably consist predominantly, particularly preferably essentially and very particularly preferably virtually completely of the compounds of the said formulae.
The liquid-crystal media according to the invention preferably have a nematic phase from in each case at least −10° C. or less to 70° C. or more, particularly preferably from −20° C. or less to 80° C. or more, very particularly preferably from −30° C. or less to 85° C. or more and most preferably from −40° C. or less to 90° C. or more.
The expression “have a nematic phase” here means on the one hand that no smectic phase and no crystallisation are observed at low temperatures at the corresponding temperature and on the other hand that no clearing occurs on heating out of the nematic phase. The investigation at low temperatures is carried out in a flow viscometer at the corresponding temperature and checked by storage in test cells having a cell thickness corresponding to the electro-optical application for at least 100 hours. If the storage stability at a temperature of −20° C. in a corresponding test cell is 1000 h or more, the medium is regarded as stable at this temperature. At temperatures of −30° C. and −40° C., the corresponding times are 500 h and 250 h respectively. At high temperatures, the clearing point is measured in capillaries by conventional methods.
The liquid-crystal media according to the invention preferably have relatively low values for the threshold voltage (Vol in the range from 1.0 V or more to 2.7 V or less, preferably from 1.2 V or more to 2.5 V or less, particularly preferably from 1.3 V or more to 2.2 V or less.
In addition, the liquid-crystal media according to the invention have high values for the VHR in liquid-crystal cells.
In freshly filled cells at 20° C. in the cells, these values of the VHR are greater than or equal to 95%, preferably greater than or equal to 97%, particularly preferably greater than or equal to 98% and very particularly preferably greater than or equal to 99%, and after 5 minutes in the oven at 100° C. in the cells, these are greater than or equal to 90%, preferably greater than or equal to 93%, particularly preferably greater than or equal to 96% and very particularly preferably greater than or equal to 98%.
In general, liquid-crystal media having a low addressing voltage or threshold voltage here have a lower VHR than those having a higher addressing voltage or threshold voltage, and vice versa.
These preferred values for the individual physical properties are preferably also in each case maintained by the media according to the invention in combination with one another.
In the present application, the term “compounds”, also written as “compound(s)”, means both one and also a plurality of compounds, unless explicitly indicated otherwise.
In a preferred embodiment, the liquid-crystalline media according to the invention comprise:
one or more compounds of formula T-1 and
one or more compounds of formula T-2, and/or
one or more compounds of formulae L-1 and/or L-2 preferably one or compounds of formulae L-1 and L-2 and/or
one or more compounds of formula II, preferably selected form the group of formulae
PUQU-n-F, CDUQU-n-F, APUQU-n-F and PGUQU-n-F, and/or
one or more compounds of formula III, preferably selected form the group of formulae
CCP-n-OT, CLP-n-T, CGG-n-F, and CGG-n-OD, and/or
one or more compounds of formula IV, preferably selected form the group of formulae
CC-n-V, CC-n-Vm, CC-n-m, and CC-V-V and/or
one or more compounds of formula V, preferably selected form the group of formulae
CCP-n-m, CCP-V-n, CCP-V2-n, CLP-V-n, CCVC-n-V, and CGP-n-m and/or
optionally, preferably obligatorily, one or more compounds of formula IV, preferably selected from the group of the compounds of the formulae CC-n-V, CC-n-Vm and CC-nV-Vm, preferably CC-3-V, CC-3-V1, CC-4-V, CC-5-V and CC-V-V, particularly preferably selected from the group of the compounds CC-3-V, CC-3-V1, CC-4-V and CC-V-V, very particularly preferably the compound CC-3-V, and optionally additionally the compound(s) CC-4-V and/or CC-3-V1 and/or CC-V-V, and/or
optionally, preferably obligatorily, one or more compounds of formula V, preferably of the formulae CCP-V-1 and/or CCP-V2-1.
For the present invention, the following definitions apply in connection with the specification of the constituents of the compositions, unless indicated otherwise in individual cases:
This applies both to the media as compositions with their constituents, which can be components and compounds, and also to the components with their constituents, the compounds. Only in relation to the concentration of an individual compound relative to the medium as a whole does the term comprise mean: the concentration of the compound in question is preferably 1% or more, particularly preferably 2% or more, very particularly preferably 4% or more.
For the present invention, “≤” means less than or equal to, preferably less than, and “≥” means greater than or equal to, preferably greater than.
For the present invention,
denote trans-1,4-cyclohexylene,
denotes 1,4-cyclohexylene, preferably trans-1,4-cyclohexylene,
denote 1,4-phenylene.
For the present invention, the expression “dielectrically positive compounds” means compounds having a Δε of >1.5, the expression “dielectrically neutral compounds” generally means those where −1.5≤Δε≤1.5 and the expression “dielectrically negative compounds” means those where Δε<−1.5. The dielectric anisotropy of the compounds is determined here by dissolving 10% of the compounds in a liquid-crystalline host and determining the capacitance of the resultant mixture in each case in at least one test cell having a cell thickness of 20 μm with homeotropic and with homogeneous surface alignment at a temperature of 20° C. and at a frequency of 1 kHz. The measurement voltage is typically 1.0 V, but is always lower than the capacitive threshold of the respective liquid-crystal mixture investigated.
The host mixture used for dielectrically positive and dielectrically neutral compounds is ZLI-4792 and that used for dielectrically negative compounds is ZLI-2857, both from Merck KGaA, Germany. The values for the respective compounds to be investigated are obtained from the change in the dielectric constant of the host mixture after addition of the compound to be investigated and extrapolation to 100% of the compound employed. The compound to be investigated is dissolved in the host mixture in an amount of 10%. If the solubility of the substance is too low for this purpose, the concentration is halved in steps until the investigation can be carried out at the desired temperature.
The liquid-crystal media according to the invention may, if necessary, also comprise further additives, such as, for example, stabilisers and/or pleochroic, e.g. dichroitic, dyes and/or chiral dopants in the usual amounts. The amount of these additives employed is preferably in total 0% or more to 10% or less, based on the amount of the entire mixture, particularly preferably 0.1% or more to 6% or less. The concentration of the individual compounds employed is preferably 0.1% or more to 3% or less. The concentration of these and similar additives is generally not taken into account when specifying the concentrations and concentration ranges of the liquid-crystal compounds in the liquid-crystal media.
In a preferred embodiment, the liquid-crystal media according to the invention comprise a polymer precursor which comprises one or more reactive compounds, preferably reactive mesogens, and, if necessary, also further additives, such as, for example, polymerisation initiators and/or polymerisation moderators, in the usual amounts. The amount of these additives employed is in total 0% or more to 10% or less, based on the amount of the entire mixture, preferably 0.1% or more to 2% or less. The concentration of these and similar additives is not taken into account when specifying the concentrations and concentration ranges of the liquid-crystal compounds in the liquid-crystal media.
The compositions consist of a plurality of compounds, preferably 3 or more to 30 or fewer, particularly preferably 6 or more to 20 or fewer and very particularly preferably 10 or more to 16 or fewer compounds, which are mixed in a conventional manner. In general, the desired amount of the components used in lesser amount is dissolved in the components making up the principal constituent of the mixture. This is advantageously carried out at elevated temperature. If the selected temperature is above the clearing point of the principal constituent, completion of the dissolution operation is particularly easy to observe. However, it is also possible to prepare the liquid-crystal mixtures in other conventional ways, for example using pre-mixes or from a so-called “multi-bottle system”.
The mixtures according to the invention exhibit very broad nematic phase ranges having clearing points of 65° C. or more, very favourable values for the capacitive threshold, relatively high values for the voltage holding ratio (VHR) and at the same time very good low-temperature stabilities at −30° C. and −40° C. Furthermore, the mixtures according to the invention are distinguished by low rotational viscosities γ1.
It goes without saying to the person skilled in the art that the media according to the invention for use in VA, IPS, FFS or PALC displays may also comprise compounds in which, for example, H, N, O, Cl, F have been replaced by the corresponding isotopes.
The structure of the liquid-crystal displays according to the invention corresponds to the usual geometry, as described, for example, in EP-A 0 240 379.
The liquid-crystal phases according to the invention can be modified by means of suitable additives in such a way that they can be employed in any type of, for example, IPS and FFS LCD display that has been disclosed to date.
Table E below indicates possible dopants which can be added to the mixtures according to the invention. If the mixtures comprise one or more dopants, it is (they are) employed in amounts of 0.01% to 4%, preferably 0.1% to 1.0%.
Stabilisers which can be added, for example, to the mixtures according to the invention, preferably in amounts of 0.01% to 6%, in particular 0.1% to 3%, are shown below in Table F.
For the purposes of the present invention, all concentrations are, unless explicitly noted otherwise, indicated in percent by weight and relate to the corresponding mixture as a whole or to the respective mixture component, again as a whole, unless explicitly indicated otherwise. In this context the term “the mixture” describes the liquid crystalline medium.
All temperature values indicated in the present application, such as, for example, the melting point T(C,N), the smectic (S) to nematic (N) phase transition T(S,N) and the clearing point T(N,I), are indicated in degrees Celsius (° C.) and all temperature differences are correspondingly indicated in differential degrees (° or degrees), unless explicitly indicated otherwise.
For the present invention, the term “threshold voltage” relates to the capacitive threshold (V0), also known as the Freedericks threshold, unless explicitly indicated otherwise.
All physical properties are and have been determined in accordance with “Merck Liquid Crystals, Physical Properties of Liquid Crystals”, status November 1997, Merck KGaA, Germany, and apply for a temperature of 20° C., and Δn is determined at 436 nm, 589 nm and at 633 nm, and Δε at 1 kHz, unless explicitly indicated otherwise in each case.
The electro-optical properties, for example the threshold voltage (V0) (capacitive measurement), are, as is the switching behaviour, determined in test cells produced at Merck Japan. The measurement cells have soda-lime glass substrates and are constructed in an ECB or VA configuration with polyimide alignment layers (SE-1211 with diluent **26 (mixing ratio 1:1), both from Nissan Chemicals, Japan), which have been rubbed perpendicularly to one another and effect homeotropic alignment of the liquid crystals. The surface area of the transparent, virtually square ITO electrodes is 1 cm2.
Unless indicated otherwise, a chiral dopant is not added to the liquid-crystal mixtures used, but the latter are also particularly suitable for applications in which doping of this type is necessary.
The rotational viscosity is determined using the rotating permanent magnet method and the flow viscosity in a modified Ubbelohde viscometer. For liquid-crystal mixtures ZLI-2293, ZLI-4792 and MLC-6608, all products from Merck KGaA, Darmstadt, Germany, the rotational viscosity values determined at 20° C. are 161 mPa·s, 133 mPa·s and 186 mPa·s respectively, and the flow viscosity values (v) are 21 mm2·s−1, 14 mm2·s−1 and 27 mm2·s−1, respectively.
The dispersion of the refractive index of the materials may for practical purposes be conveniently characterized in the following way, which is used throughout this application unless explicitly stated otherwise. The values of the birefringence are determined at a temperature of 20° C. at several fixed wavelengths using a modified Abbé refractometer with homeotropically aligning surfaces on the sides of the prisms in contact with the material. The birefringence values are determined at the specific wavelength values of 436 nm (respective selected spectral line of a low pressure mercury lamp), 589 nm (sodium “D” line) and 633 nm (wavelength of a HE-Ne laser (used in combination with an attenuator/diffusor in order to prevent damage to the eyes of the observers. In the following table Δn is given at 589 nm and Δ(Δn) is given as Δ(Δn)=Δn(436 nm)−Δn(633 nm).
The following symbols are used, unless explicitly indicated otherwise:
The following examples explain the present invention without limiting it. However, they show the person skilled in the art preferred mixture concepts with compounds preferably to be employed and the respective concentrations thereof and combinations thereof with one another. In addition, the examples illustrate the properties and property combinations that are accessible.
For the present invention and in the following examples, the structures of the liquid-crystal compounds are indicated by means of acronyms, with the transformation into chemical formulae taking place in accordance with Tables A to C below. All radicals CnH2n+1, CmH2m+1 and ClH2l+1 or CnH2n, CmH2m and ClH2l are straight-chain alkyl radicals or alkylene radicals, in each case having n, m and l C atoms respectively. Preferably n, m and l are independently of each other 1, 2, 3, 4, 5, 6, or 7. Table A shows the codes for the ring elements of the nuclei of the compound, Table B lists the bridging units, and Table C lists the meanings of the symbols for the left- and right-hand end groups of the molecules. 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 are each integers, and the three dots “ . . . ” are place-holders for other abbreviations from this table.
Besides the compounds of formula T and L, the mixtures according to the invention preferably comprise one or more compounds of the compounds mentioned below.
The following abbreviations are used:
(n, m and l are, independently of one another, each an integer, preferably 1 to 6, l possibly also 0 and preferably 0 or 2).
PGS-n-F
PUS-n-F
PPS-n-T
PGS-n-T
PUS-n-T
PGS-n-OT
PUS-n-OT
PUS-n-m
PGS-n-T
PGS-n-m
CCS-n-T
CLS-n-T
CPS-n-T
CGS-n-T
CYS-n-T
CUS-n-T
LGS-n-T
CLP-n-T
CLP-n-OT
CB(S)-n-F
CB(S)-n-T
CB(S)-n-OT
LB(S)-n-F
LB(S)-n-T
LB(S)-n-OT
DB(S)-n-T
DB(S)-n-OT
B(S)-n-Om
B(S)-nO-Om
B(S)-n-F
B(S)-nO-F
B(S)-n-T
B(S)-nO-T
B(S)-n-OT
B(S)-nO-OT
YG-n-F
YG-nO-F
YG-nO-OD
YG-n-OD
YG-n-T
YG-nO-T
YG-n-OT
YG-nO-OT
CK-n-F
B-n-m
B-n-Om
B-nO-Om
B-n-F
B-nO-F
B-n-T
B-nO-T
B-n-OT
B-nO-OT
CP-n-F
CP-n-CL
GP-n-F
GP-n-CL
CCP-n-OT
CCG-n-OT
CCG-n-F
CCG-V-F
CCG-nV-F
CCU-n-F
CCEP-n-F
CCEG-n-F
CCEU-n-F
CDU-n-F
CPG-n-F
CPU-n-F
CPU-n-OXF
CGG-n-F
CGG-n-OD
CGU-n-F
PGU-n-F
GGP-n-F
GGP-n-CL
PGIGI-n-F
PGIGI-n-CL
CCPU-n-F
CCGU-n-F
CPGU-n-F
CPGU-n-OT
PPGU-n-F
DPGU-n-F
CCZU-n-F
PUZU-n-F
CCOC-n-m
CCQG-n-F
CCQU-n-F
PUQU-n-F
CDUQU-n-F
CPUQU-n-F
CGUQU-n-F
PGUQU-n-F
APUQU-n-F
DPUQU-n-F
DGUQU-n-F
CPU-n-F
DAUQU-n-F
CLUQU-n-F
ALUQU-n-F
DLUQU-n-F
LGPQU-n-F
CC-n-m
CC-n-Om
CC-n-V
CC-n-Vm
CC-n-mV
CC-n-mVI
CC-V-V
CC-V-mV
CC-V-Vm
CC-Vn-mV
CC-nV-mV
CC-nV-Vm
CC-n-VV
CC-n-VVm
CVC-n-V
CVC-n-Vm
CP-n-m
CP-n-Om
PP-n-m
PP-n-Om
PP-n-mV
PP-n-mVI
CCP-n-m
CCP-n-Om
CCP-V-m
CCP-nV-m
CCP-Vn-m
CCP-nVm-I
CLP-V-n
CLP-n-mV
CLP-nV-m
CPP-n-m
CPG-n-F
CGP-n-m
PGP-n-m
PGP-n-mV
PGP-n-mVI
CCVC-n-V
CCZPC-n-m
CPPC-n-m
CGPC-n-m
CPGP-n-m
Table E shows chiral dopants which are preferably employed in the mixtures according to the invention.
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 from Table E.
Table F shows stabilisers which can preferably be employed in the mixtures according to the invention in addition to the compounds of formula I. The parameter n here denotes an integer in the range from 1 to 12. In particular, the phenol derivatives shown can be employed as additional stabilisers since they act as antioxidants.
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 from Table F, in particular one or more compounds selected from the group of the compounds of the following formulae
The following examples explain the present invention without restricting it in any way. However, the physical properties make it clear to 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.
Compounds of formula T are e.g.
This compound (PGS-3-T) has a melting point of 61° C., a clearing point of 172° C., a phase range of K 61° C. SB 98° C. N 172° C. l and a Δε of +13.7.
This compound (PUS-3-T) has a melting point of 67° C., a clearing point of 102° C., a phase range of K 67° C. N 102° C. l and a Δε of +17.4.
This compound (PUS-3-F) has a melting point of 67° C., a clearing point of 102° C., a phase range of K 67° C. Sa 76° C. N 102° C. l and a Δε of +10.6.
Analogously the following compounds of formula T-2-2 are prepared
Analogously the following compounds of formula T-2-3 are prepared
In the following are exemplary mixtures disclosed.
The following mixture (M-1) is prepared and investigated.
This mixture, mixture M-1, is characterized by low switching parameter γ1/k11(20° C.) of 3.11 mPa·s/pN.
The following mixture (M-2) is prepared and investigated.
This mixture, mixture M-2, shows short response times.
The following mixture (M-3) is prepared and investigated.
This mixture, mixture M-3, shows short response times.
The following mixture (M-4) is prepared and investigated.
This mixture, mixture M-4, shows short response times.
The following mixture (M-5) is prepared and investigated.
This mixture, mixture M-5, shows short response times.
The following mixture (M-6) is prepared and investigated.
This mixture, mixture M-6, shows short response times.
The following mixture (M-7) is prepared and investigated.
This mixture, mixture M-7, shows short response times.
The following mixture (M-8) is prepared and investigated.
This mixture, mixture M-8, is characterized by good properties, like those of the previous examples.
The following mixture (M-9) is prepared and investigated.
This mixture, mixture M-9, is characterized by good properties, like those of the previous examples.
The following mixture (M-10) is prepared and investigated.
This mixture, mixture M-10, is characterized by good properties, like those of the previous examples.
The following mixture (M-11) is prepared and investigated.
This mixture, mixture M-11, is characterized by good properties, like those of the previous examples.
The following mixture (M-12) is prepared and investigated.
This mixture, mixture M-12, is characterized by good properties, like those of the previous examples.
The following mixture (M-13 is prepared and investigated.
This mixture, mixture M-13, is characterized by good properties, like those of the previous examples.
The following mixture (M-14) is prepared and investigated.
This mixture, mixture M-14, is characterized by good properties, like those of the previous examples.
The following mixture (M-15) is prepared and investigated.
This mixture, mixture M-15, is characterized by good properties, like those of the previous examples.
The following mixture (M-16) is prepared and investigated.
This mixture, mixture M-16, is characterized by good properties, like those of the previous examples.
The following mixture (M-17) is prepared and investigated.
This mixture, mixture M-17, is characterized by good properties, like those of the previous examples.
The following mixture (M-18) is prepared and investigated.
This mixture, mixture M-18, is characterized by good properties, like those of the previous examples.
The following mixture (M-19) is prepared and investigated.
This mixture, mixture M-19, is characterized by rather short response times and shows a high clearing point.
The following mixture (M-20) is prepared and investigated.
This mixture, mixture M-20, is characterized by good properties, like those of the previous examples.
500 ppm of the compound of the formula
wherein the two O atoms bonded to the N atoms indicate radicals, are added to the mixture M-20 of the previous example. The resultant mixture, mixture M-21, is investigated. It is exhibiting good stability against exposure to illumination by light, while, at the same time, the other physical properties are maintained.
The following mixture (M-22) is prepared and investigated.
This mixture, mixture M-22, is characterized by good properties, like those of the previous examples.
The following mixture (M-23) is prepared and investigated.
This mixture, mixture M-23, is characterized by good properties, like those of the previous examples and shows high elastic constant(s) (i.e. k11).
The following mixture (M-24) is prepared and investigated.
This mixture, mixture M-24, is characterized by good properties, like those of the previous examples and shows high elastic constant(s) (i.e. k11).
The following mixture (M-25) is prepared and investigated.
This mixture, mixture M-25, is characterized by good properties, like those of the previous examples.
The following mixture (M-26) is prepared and investigated.
This mixture, mixture M-26, is characterized by good properties, like those of the previous examples.
The following mixture (M-27) is prepared and investigated.
This mixture, mixture M-27, is characterized by good properties, like those of the previous examples and shows high elastic constant(s) (i.e. k11).
The following mixture (M-28) is prepared and investigated.
This mixture, mixture M-28, is characterized by good properties, like those of the previous examples.
The following mixture (M-29) is prepared and investigated.
This mixture, mixture M-29, is characterized by good properties, like those of the previous examples.
The following mixture (M-30) is prepared and investigated.
This mixture, mixture M-30, is characterized by good properties, like those of the previous examples.
The following mixture (M-31) is prepared and investigated.
This mixture, mixture M-31, is characterized by good properties, like those of the previous examples.
The following mixture (M-32) is prepared and investigated
This mixture, mixture M-32, is characterized by good properties, like those of the previous examples.
The following mixture (M-33) is prepared and investigated.
This mixture, mixture M-33, is characterized good properties, like those of the previous examples.
The following mixture (M-34) is prepared and investigated.
This mixture, mixture M-34, is characterized by good properties, like those of the previous examples.
The following mixture (M-35) is prepared and investigated.
This mixture, mixture M-35, is characterized by good properties, like those of the previous examples.
The following mixture (M-36) is prepared and investigated
This mixture, mixture M-36, is characterized by good properties, like those of the previous examples.
The following mixture (M-37) is prepared and investigated.
This mixture, mixture M-37, is characterized by good properties, like those of the previous examples.
The following mixture (M-38) is prepared and investigated.
This mixture, mixture M-38, is characterized by good properties, like those of the previous examples.
The following mixture (M-39) is prepared and investigated.
This mixture, mixture M-39, is characterized by good properties, like those of the previous examples.
The following mixture (M-40) is prepared and investigated.
This mixture, mixture M-40, is characterized by good properties, like those of the previous examples.
The following mixture (M-41) is prepared and investigated.
This mixture, mixture M-41, is characterized by good properties, like those of the previous examples.
The following mixture (M-42) is prepared and investigated.
This mixture, mixture M-42, is characterized by good properties, like those of the previous examples.
The following mixture (M-43) is prepared and investigated.
This mixture, mixture M-43, is characterized by good properties, like those of the previous examples.
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.
The entire disclosure[s] of all applications, patents and publications, cited herein and of corresponding EP Patent application No. 19218466.1, filed Dec. 20, 2019, is [are] incorporated by reference herein.
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.
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| 3526308 | Aug 2019 | EP |
| 3299438 | Jan 2020 | EP |
| 3081620 | Apr 2020 | EP |
| 3541892 | Oct 2020 | EP |
| 3763802 | Jan 2021 | EP |
| 20002401 | Jan 2020 | WO |
| Entry |
|---|
| Search report in corresponding EP application 20215274.0 dated May 25, 2021 (pp. 1-6). |
| Number | Date | Country | |
|---|---|---|---|
| 20210189241 A1 | Jun 2021 | US |
