USOO8399073B2
`
`(12) United States Patent
`Klasen-Memmer et al.
`
`(10) Patent N0.:
`(45) Date of Patent:
`
`US 8,399,073 B2
`Mar. 19, 2013
`
`(54) LIQUID-CRYSTAL MEDIUM
`
`(75) Inventors: Melanie Klasen-Memmer,
`Heuchelheim (DE); Matthias Bremer,
`Darmstadt (DE); Konstantin Schneider,
`Bad Camberg (DE); Detlef Pauluth,
`Ober-Ramstadt (DE)
`
`(73)
`
`Assignee:
`
`Merck Patent Gesellschaft mit
`Beschrankter Haftung, Darmstadt (DE)
`
`Notice:
`
`Subject to any disclaimer, the term of this
`patent is extended or adjusted under 35
`U.S.C. 154(b) by 0 days.
`
`8/2010 Klasen-Memmer et al.
`7,767,280 B2
`8/2001 Heckmeier et a1.
`2001/0010366 A1
`2003/ 0222245 A1 * 12/2003 Klasen-Memmer
`et a1. ...................... .. 252/29966
`2005/0230661 A1 10/2005 Hattori et a1.
`2006/0198967 A1
`9/2006 Saito et a1.
`2006/0198968 A1
`9/2006 Goto et a1.
`2008/0011984 A1
`1/2008 Fujita et a1.
`2008/0191167 A1
`8/2008 Klasen-Memmer et al.
`2008/0273160 A1 11/2008 Kim et a1.
`2008/0308768 A1* 12/2008 Klasen-Memmer
`et a1. ...................... .. 252/29961
`4/2010 Klasen-Memmer et al.
`9/2010 Klasen-Memmer et al.
`8/2011 Klasen-Memmer
`et a1. ...................... .. 252/29961
`
`2010/0102275 A1
`2010/ 0243958 A1
`2011/0193020 A1 *
`
`(21) App1.No.:
`
`13/141,132
`
`(22) PCT Filed:
`
`Dec. 17, 2009
`
`(86) PCT N0.:
`§ 371 (0X1)’
`(2), (4) Date:
`
`PCT/EP2009/009079
`
`Jun. 21, 2011
`
`(87) PCT Pub. No.: WO2010/072370
`
`PCT Pub. Date: Jul. 1, 2010
`
`Prior Publication Data
`
`(65)
`
`(30)
`
`EP
`EP
`EP
`JP
`JP
`
`FOREIGN PATENT DOCUMENTS
`0474062 A2
`3/1992
`1106671 A2
`6/2001
`1958999 A1
`8/2008
`11228966 A
`8/1999
`11236567 A
`8/1999
`
`OTHER PUBLICATIONS
`
`World IP Organization. International Search Report. PCT/EP2009/
`009079, Applicant: Merck Patent GMBH, Mailed: Mar. 19, 2010.
`ESPACENET. “English AbstractiLiquid Crystal Medium”. JP
`11228966 A, Applicant: Merck Patent GMBH, Aug. 24, 1999.
`ESPACENET. “English AbstractiLiquid Crystal Medium”. JP
`11236567 A, Applicant: Merck Patent GMBH, Aug. 31, 1999.
`
`Primary Examiner * Shean C Wu
`(74) Attorney, Agent, or Firm *Millen, White, Zelano &
`Branigan, PC.
`
`ABSTRACT
`(57)
`The invention relates to a liquid-crystalline medium having
`negative dielectric anisotropy Which comprises at least one
`compound of the formula I
`
`US 2011/0248216A1
`
`Oct. 13,2011
`
`* cited by examiner
`
`Foreign Application Priority Data
`
`Dec. 22, 2008 (DE) ....................... .. 10 2008 064 171
`
`(51) Int. Cl.
`(2006.01)
`C09K19/30
`(2006.01)
`C09K19/12
`(2006.01)
`C09K19/34
`(2006.01)
`C09K19/32
`(2006.01)
`C09K19/20
`US. Cl. ............. .. 428/1.1; 252/299.61; 252/299.62;
`252/299.63; 252/299.66; 252/299.67
`Field of Classi?cation Search ................. .. 428/1 .1;
`252/29961, 299.62, 299.63, 299.66, 299.67
`See application ?le for complete search history.
`
`(52)
`
`(58)
`
`(56)
`
`References Cited
`
`U.S. PATENT DOCUMENTS
`5,384,065 A
`1/1995 Geelhaar et a1.
`6,066,268 A
`5/2000 Ichinose et al.
`6,514,580 B2
`2/2003 Heckmeier et a1.
`
`in Which
`R1, R1* and a have the meanings indicated in Claim 1,
`and to the use thereof for an active-matrix display, in particu
`lar based on the VA, PS-VA, PALC, FFS or IPS effect.
`
`14 Claims, No Drawings
`
`1
`
`

`

`US 8,399,073 B2
`
`1
`LIQUID-CRYSTAL MEDIUM
`
`The invention relates to a liquid-crystalline medium having
`negative dielectric anisotropy which comprises at least one
`compound of the formula I
`
`ll
`
`2
`“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 signi?cantly 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 Sym
`posium, Digest of Technical Papers, XXXV, Book I, pp. 106
`to 109, the achievement of video-compatible response times,
`in particular on switching of grey shades, is still a problem
`which has not yet been satisfactorily solved.
`Industrial application of this effect in electro-optical dis
`play elements requires LC phases, which have to satisfy a
`multiplicity of requirements. Particularly important here are
`chemical resistance to moisture, air and physical in?uences,
`such as heat, infrared, visible and ultraviolet radiation and
`direct and alternating electric ?elds.
`Furthermore, industrially usable LC phases are required to
`have a liquid-crystalline mesophase in a suitable temperature
`range and low viscosity.
`None of the hitherto-disclosed series of compounds having
`a liquid-crystalline mesophase 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. However, it has not been possible to prepare
`optimum phases easily in this way since no liquid-crystal
`materials having signi?cantly negative dielectric anisotropy
`and adequate long-term stability were hitherto available.
`Matrix liquid-crystal displays (MLC displays) are known.
`Non-linear elements which can be used for individual switch
`ing of the individual pixels are, for example, active elements
`(i.e. transistors). The term “active matrix” is then used, where
`a distinction can be made between two types:
`1. MOS (metal oxide semiconductor) transistors on a silicon
`wafer as substrate
`2. thin-?lm transistors (TFTs) on a glass plate as substrate.
`In the case of type 1, the electro-optical effect used is
`usually dynamic scattering or the guest-host effect. The use of
`single-crystal silicon as substrate material restricts the dis
`play size, since even modular assembly of various part-dis
`plays results in problems at the joints.
`In the case of the more promising type 2, which is pre
`ferred, the electro-optical effect used is usually the TN effect.
`A distinction is made between two technologies: TFTs
`comprising compound semiconductors, such as, for example,
`CdSe, or TFTs based on polycrystalline or amorphous sili
`con. The latter technology is being worked on intensively
`worldwide.
`The TFT matrix is applied to the inside of one glass plate of
`the display, while the other glass plate carries the transparent
`counterelectrode 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 ?lters is arranged in such a way that a
`?lter element is opposite each switchable pixel.
`The TFT displays disclosed hitherto usually operate as TN
`cells with crossed polarisers in transmission and are back-lit.
`The term MLC displays here covers any matrix display
`with integrated non-linear elements, i.e. besides the active
`matrix, also displays With pass1ve elements, such as vanstors
`or diodes (MIMImetal-insulator-metal).
`MLC displays of this type are particularly suitable for TV
`applications (for example pocket TVs) or for high-informa
`tion displays in automobile or aircraft construction. Besides
`
`in which
`R1 and R1* each, independently of one another, denote an
`alkyl radical having 1-6 C atoms, and
`a denotes 0 or 1.
`Media of this type can be used, in particular, for electro
`optical displays having active-matrix addressing based on the
`ECB effect and for IPS (in-plane switching) displays or FFS
`(fringe ?eld switching) displays.
`The principle of electrically controlled birefringence, the
`ECB effect or also DAP (deformation of aligned phases)
`effect, was described for the ?rst time in 1971 (M. F.
`Schieckel and K. Fahrenschon, “Deformation of nematic liq
`uid crystals with vertical orientation in electrical ?elds”,
`Appl. Phys. Lett. 19 (1971), 3912). This was followed by
`papers by J. F. Kahn (Appl. Phys. Lett. 20 (1972), 1193) and
`G. Labrunie and J. Robert (J. Appl. Phys. 44 (1973), 4869).
`The papers by J. Robert and F. Clerc (SID 80 Digest Techn.
`Papers (1980), 30), J. Duchene (Displays 7 (1986), 3) and H.
`Schad (SID 82 DigestTechn. Papers (1982), 244) showedthat
`liquid-crystalline phases must have high values for the ratio
`of the elastic constants K3/Kl, high values for the optical
`anisotropy An and values for the dielectric anisotropy of
`Aeé—05 in order to be suitable for use in high-information
`display elements based on the ECB effect. Electro-optical
`display elements based on the ECB effect have a homeotropic
`edge alignment (VA technoloqu/ertically aligned). Dielec
`trically negative liquid-crystal media can also be used in
`displays which use the so-called IPS or FFS effect.
`Displays which use the ECB effect, as so-called VAN (ver
`tically aligned nematic) displays, for example in the MVA
`(multi-domain vertical alignment, for example: Yoshide, H. et
`al., paper 3.1: “MVA LCD for Notebook or Mobile PCs . .
`. ”,
`SID 2004 International Symposium, Digest of Technical
`Papers, XXXV, Book I, pp. 6 to 9, and Liu, C. T. et al., paper
`15.1: “A 46-inch TFT-LCD HDTV Technology .
`.
`. ”, SID
`2004 International Symposium, Digest of Technical Papers,
`XXXV, Book II, pp. 750 to 753), PVA (patterned vertical
`alignment, for example: Kim, Sang Soo, paper 15.4: “Super
`PVA Sets New State-of-the-Art for LCD-TV”, SID 2004
`International Symposium, Digest of Technical Papers,
`XXXV, Book II, pp. 760 to 763), ASV (advanced super view,
`for example: Shigeta, Mitzuhiro and Fukuoka, Hirofumi,
`paper 15.2: “Development of High Quality LCDTV”, SID
`2004 International Symposium, Digest of Technical Papers,
`XXXV, Book II, pp. 754 to 757) modes, have established
`themselves as one of the three more recent types of liquid
`crystal display that are currently the most important, in par
`ticular for television applications, besides IPS (in-plane
`switching) displays (for example: Yea, S. D., paper 15.3: “An
`LC D1splay for the 1V Application”, SID 2004 International
`Symposium, Digest of Technical Papers, XXXV, Book II, pp.
`758 & 759) and the long-known TN (twisted nematic) dis
`plays. The technologies are compared in general form, for
`example, in Souk, Jun, SID Seminar 2004, seminar M-6:
`
`20
`
`25
`
`30
`
`35
`
`40
`
`45
`
`50
`
`55
`
`60
`
`65
`
`2
`
`

`

`US 8,399,073 B2
`
`3
`problems regarding the angle dependence of the contrast and
`the response times, dif?culties also arise in MLC displays due
`to insuf?ciently high speci?c resistance of the liquid-crystal
`mixtures [TOGASHL S., SEKIGUCHI, K., TANABE, H.,
`YAMAMOTO, E., SORIMACHI, K., TAMA, E.,
`WATANABE, H., SHIMIZU, H., Proc. Eurodisplay 84, Sep
`tember 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 Tran
`sistors for Matrix Addressing of Television Liquid Crystal
`Displays, pp. 145 ff., Paris]. With decreasing resistance, the
`contrast of an MLC display deteriorates. Since the speci?c
`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.
`The disadvantages of the MLC-TN displays disclosed hith
`erto are their comparatively low contrast, the relatively high
`viewing-angle dependence and the dif?culty in producing
`grey shades in these displays.
`There thus continues to be a great demand for MLC dis
`plays having very high speci?c 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.
`For television applications in particular, it is very important
`to achieve short response times. In order to achieve this, the
`dielectrically neutral compounds used in ECB or VA appli
`cations are, in particular, compounds of the formulae
`
`R1 /
`
`where R1:H or CH3
`
`20
`
`25
`
`30
`
`35
`
`40
`
`45
`
`since these are distinguished by particularly low rotational
`viscosities and very good solubilities.
`In LCD television applications, reliability problems fre
`quently occur, such as, for example, image sticking, i.e.
`apparent “buming-in” of the image if the display has been
`addressed over an extended time.
`This problem frequently only occurs after extended oper
`ating times of the television sets. The cause is frequently
`regarded as being the long exposure time to the backlight at
`the same time as increased operating temperatures, which can
`result in still unexplained processes in the display, for
`example an interaction between alignment layer and a liquid
`crystal mixture. On the pad of the liquid-crystal mixture, the
`cause of the occurrence of image sticking problems is
`regarded as being the neutral alkenyl compounds frequently
`used, which are, for example, mentioned above.
`The invention is based on the object of providing liquid
`crystal mixtures, in particular for monitor and TV applica
`
`50
`
`55
`
`60
`
`65
`
`4
`tions, which are based on the ECB effect or on the IPS or FFS
`effect, which do not have the above-mentioned disadvantages
`or only do so to a reduced extent. In particular, it must be
`ensured for monitors and televisions that they also operate at
`extremely high and extremely low temperatures and at the
`same time have short response times and at the same time
`have improved reliability behaviour, in particular have no or
`signi?cantly reduced image sticking after long operating
`times.
`Surprisingly, it has now been found that this object can be
`achieved if nematic liquid-crystal mixtures which comprise at
`least one compound of the formula I
`
`ll
`
`in which
`R1 and R1* each, independently of one another, denote an
`alkyl radical having 1 to 6 C atoms, and
`a denotes 0 or 1,
`are used in these display elements.
`The use of the compounds of the formula I in VA mixtures
`is known, for example, from EP 0 474 062 B1, US. Pat. No.
`6,066,268, JP H11-228966, JP H11-236567, EP 1 106 671
`B1, US. 2005/0230661.
`In contrast to the prior art, the negative dielectric anisot
`ropy mixture concept according to the invention is distin
`guished by short response times at the same time as good
`low-temperature stability, in spite of the absence of neutral
`alkenyl compounds.
`The invention thus relates to a liquid-crystalline medium
`which comprises at least one compound of the formula I.
`The mixtures according to the invention preferably exhibit
`very broad sematic phase ranges having clearing points 260°
`C., preferably 265° C., in particular 270° C., very favour
`able values for the capacitive threshold, relatively high values
`for the holding ratio and at the same time very good low
`temperature stabilities at —30° C. and —40° C., as well as very
`low rotational viscosities and short response times. The mix
`tures according to the invention are furthermore distinguished
`by the fact that, in addition to the improvement in the rota
`tional viscosity y 1, an increase in the elastic constants K33 for
`improving the response times is observed, and they exhibit
`improved reliability behaviour.
`Some preferred embodiments of the mixtures according to
`the invention are indicated below:
`a) R1 and R1 * in the formula I denote straight-chain alkyl, in
`particular C2H5, n-C3H7, n-C4H9, furthermore n-C5Hl 1,
`n-C6Hl3. Particularly preferably, Rl denotes n-C3H7 and
`R1* denotes CH3, C2H5 or n-C3H7.
`b) Liquid-crystalline medium which comprises one, two,
`three, four or more, preferably one, two or three, com
`pounds of the formula I.
`c) Liquid-crystalline medium in which the proportion of com
`pounds of the formula I in the mixture as a whole is 23%
`by weight, preferably 210% by weight, particularly pref
`erably 215% by weight. Particular preference is given to
`liquid-crystalline media which comprise 3-50%, prefer
`ably 25-35%, of one or more compounds of the formula I.
`Compounds of the formula I where a:0 are preferably
`present in the mixture in amounts of 15-35%. Compounds
`of the formula I where a:1 are preferably present in the
`mixture in amounts of 3-30%.
`
`3
`
`

`

`5
`d) Preferred compounds of the formula I are the compounds
`of the formulae 1-1 to 1-6:
`
`US 8,399,073 B2
`
`1-2
`
`The compounds 1-2 and 1-3 are preferably present in the
`mixture in a concentration of 15-35%, particularly pref
`erably 15-25% and especially preferably 18-22%, based
`on the mixture as a Whole.
`Very particularly preferred mixtures comprise the folloW
`ing three compounds:
`
`1-2
`
`The compounds 1-1, 1-2 and 1-3 are preferably present in
`the mixture in a concentration of 15-35%, particularly
`preferably 15-25% and especially preferably 18-22%,
`based on the mixture as a Whole.
`e) Liquid-crystalline medium Which additionally comprises
`one or more compounds selected from the group of the
`compounds of the formulae TIA, IIB and 11C:
`
`20
`
`25
`
`30
`
`35
`
`45
`
`50
`
`Mixtures according to the invention preferably comprise
`the compounds of the formulae 1-1 and/ or 1-2, preferably
`in amounts of 5-30%.
`The medium according to the invention particularly pref
`erably comprises the tricyclic compounds of the formula
`1-1 and/ or of the formula 1-2 in combination With one or
`more bicyclic compounds of the formulae 1-3 to 1-6. The
`total proportion of the compounds of the formulae l-l
`and/or 1-2 in combination With one or more compounds
`selected from the bicyclic compounds of the formulae
`1-3 to 1-6 is preferably 5-40%, very particularly prefer
`ably l 5 -35%.
`Very particularly preferred mixtures comprise the com
`pounds l-l and 1-3:
`
`IIA
`
`IIB
`
`IIC
`
`H7C3 a o 6 CH3
`1-3 i
`
`L3
`
`R28 @ ZZ @ 22'
`
`55
`
`60
`
`The compounds 1-1 and 1-3 are preferably present in the
`mixture in a concentration of 15-35%, particularly pref
`erably 15-25% and especially preferably 18-22%, based
`on the mixture as a Whole.
`Very particularly preferred mixtures comprise the com
`pounds l-2 and 1-3:
`
`65
`
`in Which
`RM, R25 and RZC each, independently of one another,
`denote H, an alkyl radical having up to 15 C atoms Which
`is unsubstituted, monosubstituted by CN or CF3 or at
`
`4
`
`

`

`US 8,399,073 B2
`
`7
`least monosubstituted by halogen, Where, in addition,
`one or more CH2 groups in these radicals may be
`replaced by 40*, iSi,
`
`a»,
`
`%ECi, %F20i, ADCFZi, iOCADi or
`4OiCOi in such a way that O atoms are not linked
`directly to one another,
`Ll'4 each, independently of one another, denote F or Cl,
`Z2 and Z2' each, independently of one another, denote a
`single bond, iCHZCHZi, iCH:CHi, 4CF2Oi,
`ADCFZi, %H20i, ADCHZi, %OOi,
`ADCOi,
`%2F4i,
`%F:CFi,
`%H:CHCH20i,
`p denotes l or 2,
`q denotes 0 or 1, and
`V denotes l to 6.
`In the compounds of the formulae IIA and IIB, Z2 may have
`identical or different meanings. In the compounds of the
`formula IIB, Z2 and Z2 may have identical or different
`meanings.
`In the compounds of the formulae IIA, IIB and IIC, RZA,
`R25 and R20 each preferably denote alkyl having 1-6 C
`atoms, in particular CH3, CZHS, n-C3H7, n-C4H9,
`n-CSHU.
`In the compounds of the formulae IIA and IIB, L1, L2, L3
`and L4 preferably denote LIILZIF and L3IL4IF, fur
`thermore LIIF and LZICl, LIICl and L2IF, L3:F and
`L4:Cl, L3:Cl and L4IF. Z2 and Z2' in the formulae IIA
`and IIB preferably each, independently of one another,
`denote a single bond, furthermore a iC2H4i bridge.
`If in the formula IIB Z2:iC2H4i, Z2' is preferably a
`single bond or, if Z2 :iC2H4i, Z2 is preferably a
`single bond. In the compounds of the formulae IIA and
`IIB, (O)CVH2V+1 preferably denotes OCszvH, further
`more CVHZWI. In the compounds of the formula IIC,
`(O)CVH2V+1 preferably denotes CVHZWI. In the com
`pounds of the formula IIC, L3 and L4 preferably each
`denote F.
`Preferred compounds of the formulae IIA, IIB and IIC are
`indicated beloW:
`
`10
`
`20
`
`25
`
`30
`
`35
`
`40
`
`45
`
`alkyl
`
`alkyl
`
`alkyl
`
`alkyl
`
`alkyl
`
`alkyl
`
`alkyl
`
`F
`
`F
`
`IIA-l
`
`50
`
`alkyl
`
`F
`
`F
`
`alkyl 0 Q O_alkyl*
`
`Cl
`
`F
`
`55
`
`IIA-2
`
`IIA-3
`
`60
`
`65
`
`alkyl
`
`alkyl* é <<>I
`
`alky
`
`-continued
`
`Cl
`
`F
`
`F
`
`Cl
`
`F
`
`Cl
`
`O_alkyl*
`
`alky1*
`
`O_alkyl*
`
`F
`
`F
`
`F
`
`F
`
`Cl
`
`F
`
`Cl
`
`F
`
`F
`
`Cl
`
`F
`
`Cl
`
`IIA-4
`
`IIA-5
`
`IIA-6
`
`IIA-7
`
`alkyrg
`
`IIA-8
`
`O—alkyl*
`
`IIA-9
`
`alkyrg
`
`IIA- 10
`
`O_alkyl*
`
`IIA- II
`
`alkyrg
`
`IIA- 12
`
`O_alkyl*
`
`IIA- I3
`
`5
`
`

`

`US 8,399,073 B2
`
`-continued
`
`-continued
`
`alkyl*<E>>C2H4
`
`alkyl
`
`C2H4
`
`alkyl
`
`C2H4
`
`F
`
`C1
`
`C1
`
`F
`
`F
`
`F
`
`F
`
`F
`
`C1
`
`Cl
`
`IIA—14
`
`5
`
`10
`
`O-alkyl*
`
`HA— 15
`
`alkyl*
`
`alkyl
`
`HA— 1 6
`
`15
`
`alkyl
`
`HA—24
`
`(O)alkyl*
`
`HA—25
`
`F
`
`C1
`
`CF20
`
`C1
`
`F
`
`CF20
`
`(O)alkyl*
`
`P
`
`P
`
`O—alkyl*
`
`20
`
`F
`
`F
`
`alkyl\<E>>CH20
`
`HA—17
`
`HA— 1 8
`
`HA—26
`
`(O)alkyl*
`
`HA—27
`
`30
`
`alkyl
`
`0CH2
`
`(O)alkyl*
`
`F
`
`F
`
`HA—28
`
`alkyl
`
`C2H4
`
`O—alkyl*
`
`HA—19 35
`
`alkeny1 alW1*
`
`F
`
`F
`
`alkyl CF2O
`
`alkyl <E>>OCF2
`
`F
`
`F
`
`O—alkyl*
`
`HA_20
`
`O—alkyl*
`
`HA 21
`
`alkyl
`
`CF20
`
`F
`
`F
`
`F
`
`F
`
`(O)alkyl*
`
`HA—22
`
`alkyl46%OCF2 (O)alkyl*
`
`40
`
`45
`
`50
`
`55
`
`F
`
`C1
`
`C1
`
`F
`
`F
`
`F
`
`O-alkyl*
`
`alkyl*
`
`O-alkyl*
`
`alkenyl
`
`alkenyl
`
`alkenyl
`
`F
`
`C1
`
`alkenyl*8»alkyl*
`
`“-23 60
`
`F
`
`F
`
`F
`
`C1
`
`alkyl CH:CHCH2O (O)alky1* 65
`
`P
`
`alkeHyl Oalkyl¥
`
`HA—29
`
`HA—30
`
`HA—31
`
`HA—32
`
`HA—33
`
`6
`
`

`

`US 8,399,073 B2
`
`11
`-continued
`
`HA-34
`
`-continued
`
`HB-3
`
`alkenyl
`
`alkenyl
`
`alkenyl
`
`alkenyl
`
`alkyl
`
`alkyl
`
`alkyl{ CZH4
`
`HA—35
`
`0-alk}/1*
`
`HA—3 6
`
`HA—37
`
`0-alk}/1*
`
`HA—3 8
`
`10
`
`15
`
`20
`
`25
`
`30
`
`HA—39
`
`35
`
`0-alk}/1*
`
`IIA—40
`
`HA—41
`
`alkyl
`
`alkyl
`
`40
`
`45
`
`50
`
`55
`
`Cl
`
`Cl
`
`F
`
`F
`
`F
`
`F
`
`Cl
`
`Cl
`
`F
`
`F
`
`F
`
`F
`
`HB-4
`
`O_alkyl*
`
`HB-5
`
`HB-6
`
`O_alkyl*
`
`HB-7
`
`HB—8
`
`O_alkyl*
`
`HB-9
`
`F
`
`F
`
`OCF2 j(O)a1kyl*
`
`HB- 10
`
`F
`
`F
`
`CF20 }(O)alkyl*
`
`HB-11
`
`mkeny1 C2m
`
`"11
`
`"11
`
`3<1
`
`0-alkyl*
`
`IIB—1
`
`F
`
`F
`
`a1kyl 0-3-1kyl*
`
`F
`
`F
`
`0
`
`alkyl a1ky1¥
`
`60
`
`HB—2
`
`F
`
`F
`
`Cl
`
`F
`
`dky1 O_alkyl*
`
`65 a1kyl 0-3-1kyl*
`
`HB- 12
`
`HB- 13
`
`7
`
`

`

`13
`-continued
`
`F
`
`Cl
`
`alkyl—<: :3 E>—O-alkyl*
`
`F
`
`F
`
`US 8,399,073 B2
`
`llB—l4
`
`llB—lS
`
`alkyl*
`
`HB-16
`
`5
`
`10
`
`14
`
`:
`
`:
`
`denotes
`
`:
`
`:
`
`0
`
`O
`
`or
`
`alkenyl
`
`alkenyl
`
`alkyl
`
`F
`
`F
`
`O_alkyl*
`
`Hc_1 20
`
`alkyl*,
`
`25
`
`Z3 denotes a single bond, 4CH2CH2i, iCH:CHi,
`4CF2Oi, 4OCF2i, 4CH20i, iOCHZi,
`iC2F4i, 4C4H8i,
`
`4CF:CFi.
`Preferred compounds of the formula III are indicated
`beloW:
`
`in Which alkyl and alkyl* each, independently of one
`another, denote a straight-chain alkyl radical having 1-6
`C atoms.
`Particularly preferred mixtures according to the invention
`comprise one or more compounds of the formulae TIA-2,
`TIA-8, TIA-14, TIA-29, TIA-35, llB-2, llB-l l, llB- l 6 and
`llC-l.
`The proportion of compounds of the formulae IIA and/or
`IIB in the mixture as a Whole is preferably at least 20%
`by weight.
`Particularly preferred media according to the invention
`.
`compr1se a compound of the formula llC-l
`
`alkylwalky?
`
`30
`
`35
`
`alkyl
`
`alkyl
`
`40
`
`alkyl
`
`O_alkyl*
`
`alkyl*
`
`*
`alkyl
`
`Illa
`
`mb
`
`1110
`
`IIId
`
`F
`
`F
`
`alkyl
`
`alkyl},
`’
`
`45
`
`in Which alkyl and alkyl* have the meanings indicated 50
`above,preferab1yin amounts of >3% by weight, in par-
`ticular >5% by weight and panicu1ar1y preferably
`5-2 5% by weight,
`f) Liquid-crystalline medium Which additionally comprises
`one or more compounds of the formula III
`
`55
`
`in Which
`alkyl and
`alkyl* each, independently of one another, denote a
`straight-chain alkyl radical having 1-6 C atoms.
`The medium according to the invention preferably com
`prises at least one compound of the formula Illa and/or
`fOI'mI?a Inb
`The proportion of compounds of the formula III in the
`mixture as a whole is preferably at least 5% by we1ght.
`g) Liquid-crystalline medium additionally comprising a com
`pound of the formula
`
`R31
`
`23
`
`R32
`
`HI
`
`60
`
`H7C34®<E>—\ and / or
`
`H9C44@@_\ and / or
`
`1n Whlch
`R31 and R32 each, independently of one another, denote a 65
`straight-chain alkyl, alkoxyalkyl or alkoxy radical hav
`ing up to 12 C atoms, and
`
`H1105
`
`H
`
`H
`
`,
`\
`
`8
`
`

`

`US 8,399,073 B2
`
`1 5
`preferably in total amounts of <20% by weight, in particu
`lar <10% by weight.
`Preference is furthermore given to mixtures according to
`the invention comprising the compound
`
`1 6
`
`F
`
`F
`
`h) Liquid-crystalline medium which additionally comprises
`one or more tetracyclic compounds of the formulae
`
`5
`
`10
`
`15
`
`20
`
`F
`
`F
`
`R15 a ‘ OCH=CH2
`
`F
`
`F
`
`RIGOCHZCH=CH2
`
`Y—l
`
`Y—Z
`
`Y—3
`
`Y-4
`
`R17
`
`25
`
`C2H4
`
`30
`
`R18
`
`F
`
`F
`
`F
`
`F
`
`W
`
`O—C=CH2
`
`Y—5
`
`OCH=CH2
`
`Y—6
`
`F
`
`F
`
`35
`
`40
`
`45
`
`50
`
`55
`
`60
`
`65
`
`in which
`R7'lo each, independently of one another, have one of the
`meanings indicated for RM in Claim 2, and
`W and X each, independently of one another, denote l to 6.
`i) Liquid-crystalline medium which additionally comprises
`one or more compounds of the formulae Y-l to Y-6:
`
`R190CH2CH=CH2
`
`in which Rl‘l-R19 each, independently of one another,
`denote an alkyl or alkoxy radical having 1-6 C atoms; Z
`and m each, independently of one another, denote 1-6; X
`denotes 0, l, 2 or 3.
`The medium according to the invention particularly pref
`erably comprises one or more compounds of the formula
`Y-l, preferably in amounts of 25% by weight.
`j) Liquid-crystalline medium additionally comprising one or
`more ?uorinated terphenyls of the formulae T-l to T-20:
`
`R
`
`F
`
`T—l
`
`T—Z
`
`9
`
`

`

`1 7
`-continued
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`US 8,399,073 B2
`
`T—3
`
`T-4
`
`T—5
`
`1 8
`-continued
`
`F
`
`CHFZ
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`CF3
`
`F
`
`CF3
`
`T—6
`
`T—7
`
`20
`
`25
`
`30
`
`T—S
`
`35
`
`40
`
`T—9
`
`T— 10
`
`45
`
`50
`
`T— 11
`
`55
`
`60
`
`T— 12
`
`65
`
`T— 13
`
`T— 14
`
`T— 15
`
`T— 1 6
`
`T— 17
`
`T— 1 8
`
`T— 19
`
`T—ZO
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`in Which
`R denotes a straight-chain alkyl or alkoxy radical having
`1-7 C atoms, and m is 1-6.
`R preferably denotes methyl, ethyl, propyl, butyl, pentyl,
`hexyl, methoxy, ethoxy, propoxy, butoxy, pentoxy.
`The medium according to the invention preferably com
`prises the terphenyls of the formulae T-l to T-20 in
`amounts of 2-30% by weight, in particular 5-20% by
`weight.
`Particular preference is given to compounds of the formu
`lae T-l, T-2 and T-20. In these compounds, R preferably
`denotes alkyl, furthermore alkoxy, each having 1-5 C
`atoms.
`
`10
`
`

`

`US 8,399,073 B2
`
`19
`The terphenyls are preferably employed in the mixtures
`according to the invention if the An value of the mixture
`is to be 20.1. Preferred mixtures comprise 2-20% by
`weight of one or more terphenyl compounds selected
`from the group of the compounds T-l to T-20.
`k) Liquid-crystalline medium additionally comprising one or
`more biphenyls of the formulae B-l to B-3:
`
`alkyl
`
`alkyl*
`
`alkylalkenyl*
`
`alkenyl
`
`alkeny1*
`
`B-l
`
`B-Z
`
`B-3
`
`20
`
`in which
`alkyl and alkyl* each, independently of one another,
`denote a straight-chain alkyl radical having 1-6 C atoms,
`and
`alkenyl and alkenyl* each, independently of one another,
`denote a straight-chain alkenyl radical having 2-6 C
`atoms.
`The proportion of the biphenyls of the formulae B-l to B-3
`in the mixture as a whole is preferably at least 3% by
`weight, in particular 5% by weight.
`Of the compounds of the formulae B-l to B-3, the com
`pounds of the formula B-2 are particularly preferred.
`Particularly preferred biphenyls are
`
`in which alkyl* denotes an alkyl radical having 1-6 C
`atoms. The medium according to the invention particu
`larly preferably comprises one or more compounds of
`the formulae B-la and/or B-2c.
`l) Liquid-crystalline medium comprising at least one com
`pound of the formulae Z-l to Z-7:
`
`20
`
`F
`
`F
`
`o
`
`F
`
`F
`
`o
`
`R
`
`R
`
`(O)alkyl
`
`(O)alkyl
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`0
`
`11000112
`
`0
`
`11000112
`
`o
`
`R4<l>iCFZO
`
`0
`
`11001120
`
`(O)alkyl
`
`(O)alkyl
`
`(O)alkyl
`
`(O)alkyl
`
`2-1
`
`2-2
`
`2-3
`
`2-4
`
`2-5
`
`Z-6
`
`2-7
`
`25
`
`30
`
`35
`
`40
`
`é
`
`in which R and alkyl have the meanings indicated above,
`m) Liquid-crystalline medium comprising at least one com
`pound of the formulae 0-1 to O-l8:
`
`50
`
`55
`
`R1
`
`RIM
`
`60
`
`R1
`
`65
`
`RKEH} O o 9 R2
`
`11
`
`

`

`-continued
`
`R1
`
`US 8,399,073 B2
`
`22
`-continued
`
`0—5
`
`R2
`
`0—6
`
`0—7
`
`0—8
`
`0— l 8
`
`woooow
`
`10
`
`in which R1 and R2 have the meanings indicated for RM, R1
`and R2 preferably each, independently of one another,
`denote straight-chain alkyl.
`Preferred media comprise one or more compounds of the
`formulae 0-1, 0-3, 0-4, 0-9, 0-13, 0-14, 0-15, 0-16,
`0-17 and/or O-l8.
`n) Preferred liquid-crystalline media according to the inven
`tion comprise one or more substances Which contain a
`tetrahydronaphthyl or naphthyl unit, such as, for example,
`the compounds of the formulae N-l to N-5:
`
`20
`
`0—9
`
`O— 10
`
`30
`
`0— ll
`
`35
`
`O— 12
`
`40
`
`O— 13
`
`O— 14
`
`50
`
`55
`
`F
`
`F
`
`F
`
`RIN@ZI@ZZ Q
`
`F
`
`N.
`
`in Which RW and R2N each, independently of one another,
`have the meanings indicated for RZA, preferably denote
`straight-chain alkyl, straight-chain alkoxy or straight
`chain alkenyl, and
`Z1 and Z2 each, independently of one another, denote
`4C2H4i> iCH:CHis *(CH2)4*, *(CH2)3O*,
`
`%F:CHi, %H:CFi, iCF2Oi, iOCin,
`4CH2i or a single bond.
`
`12
`
`

`

`US 8,399,073 B2
`
`23
`0) Preferred mixtures comprise one or more compounds
`selected from the group of the di?uorodibenzochroman
`compounds of the formula BC, chromans of the formula
`CR, ?uorinated phenanthrenes of the formulae PH-l and
`PH-2, ?uorinated dibenzofurans of the formula BF:
`
`F
`
`O
`
`F
`
`BC
`
`CR
`
`F
`
`F
`
`O
`
`O
`
`Rch W RCRZ
`
`C
`
`F
`
`F
`
`PH—l
`
`20
`
`25
`
`R1
`
`R2
`
`PH—Z
`
`30
`
`-continued
`
`F
`
`O
`
`F
`
`alkyl—O Q Q O—alkyl*
`
`F
`
`O
`
`F
`
`alkyl Q Q O—alkyl*
`
`F
`
`O
`
`F
`
`alkenyl Q Q alkenyl*
`
`F
`
`O
`
`F
`
`alkyl
`
`alkenyl
`
`F
`
`O
`
`F
`
`alkenyl G G alkyl
`
`F
`
`F
`
`BC-3
`
`BC-4
`
`BC-5
`
`BC-6
`
`BC-7
`
`CR-l
`
`F
`
`F
`
`F
`
`F
`
`F
`
`O
`
`F
`
`35
`
`BF
`
`alky14<E>_/
`
`o
`
`a1ky1-04<E>_/
`
`o
`
`F
`
`F
`
`o
`
`alkyl*
`
`CR- 2
`
`o
`
`alkyl*
`
`CR- 3
`
`F
`
`F
`
`o
`
`0
`
`C
`
`in Which
`RB 1, R52, RCRI, RCRZ, R1, R2 each, independently of one
`another, have the meaning of RZA. c is 0, l or 2.
`The mixtures according to the invention preferably com
`prise the compounds of the formulae BC, CR, PH-l,
`PH-2 and/or BF in amounts of 3 to 20% by weight, in
`particular in amounts of 3 to 15% by weight. Particularly
`preferred compounds of the formulae BC and CR are the
`compounds BC-l to BC-7 and CR-l to CR-5:
`
`F
`
`o
`
`F
`
`F
`
`o
`
`F
`
`BC-2
`
`40
`
`45
`
`50
`
`55
`
`60
`
`alkyl W alkyl *
`
`CR-4
`
`F
`
`F
`
`o
`
`0
`
`alkyl— 0 W alkyl *
`CR- 5
`
`F
`
`F
`
`o
`
`o
`
`Mklealkyl’“
`
`alkenyl W alkyl*
`
`13
`
`

`

`US 8,399,073 B2
`
`25
`
`26
`
`in Which
`alkyl and alkyl* each, independently of one another,
`denote a straight-chain alkyl radical having 1-6 C atoms,
`and
`alkenyl and
`alkenyl* each, independently of one another, denote a
`straight-chain alkenyl radical having 2-6 C atoms.
`Very particular preference is given to mixtures comprising
`one, two or three compounds of the formula BC-2.
`
`p) Preferred mixtures comprise one or more indane com
`pounds of the formula In
`
`in which
`11
`12
`R 5R 5
`R13 each, independently of one another, denote a straight
`chain alkyl, alkoxy, alkoxyalkyl or alkenyl radical hav
`ing 1-6 C atoms,
`R12 and R13 additionally denote halogen, preferably F,
`
`5?
`
`denotes
`
`A AC “T” V
`
`20
`
`25
`
`35
`
`40
`
`45
`
`50
`
`55
`
`60
`
`i denotes 0, l or 2.
`Preferred compounds of the formula In are the compounds
`of the formulae ln-l to ln-l6 indicated beloW:
`
`65
`
`CH3
`
`6 i0
`0 0 a
`6 i0
`0 0 a
`6 :0
`6 :0
`6 i0
`RI 6 i0
`6 i0
`6 ii.
`
`Csz
`
`Csz
`
`14
`
`

`

`US 8,399,073 B2
`
`2 8
`-continued
`
`F
`
`Cl
`
`L—Z
`
`L—3
`
`L-4
`
`L—5
`
`L—6
`
`R
`
`R
`
`Cl
`
`F
`
`(O)—alkyl
`
`(O)_alkyl
`
`F
`
`F
`
`F
`
`Cl
`
`Cl
`
`F
`
`R o O 0 (O)_alkyl
`
`L—7
`
`L—S
`
`L—9
`
`(O)—alkyl
`
`L— 10
`
`F
`
`F
`
`F
`
`Cl
`
`Cl
`
`F
`
`R
`
`F
`
`F
`
`F
`
`R1 Q Q
`
`F
`
`F
`
`L— ll
`
`20
`
`25
`
`30
`
`35
`
`40
`
`R11 0 o I
`
`C3H7—H
`
`F
`
`45
`
`F
`
`F
`
`F
`
`Particular preference is given to the compounds of the
`formulae ln-l, ln-2 and ln-3.
`The compounds of the formula In and the sub-formulae
`ln-l to ln-l6 are preferably employed in the mixtures
`according to the invention in concentrations 25% by
`weight, in particular 5-30% by weight and very particu
`larly preferably 5-25% by weight.
`q) Preferred mixtures additionally comprise one or more
`compounds of the formulae L-l to L-l l:
`
`50
`
`55
`
`F
`
`F
`
`60
`
`L-l
`
`R Q Q (O)—alkyl
`
`65
`
`R
`
`/5 O
`
`R2
`
`15
`
`

`

`US 8,399,073 B2
`
`29
`
`in which
`R, R1 and R2 each, independently of one another, have the
`meanings indicated for R2A in Claim 2, and alkyl denotes
`an alkyl radical having 1-6 C atoms. s denotes l or 2.
`Particular preference is given to the compounds of the
`formulae L-l and L-4, in particular L-4.
`The compounds of the formulae L-l to L-ll are preferably
`employed in concentrations of 5-50% by weigh