WO2005112540A2 - Liquid crystal compounds, liquid crystal medium and liquid crystal display - Google Patents

Abstract

The instant invention relates to mesogenic compounds which comprise at least one mesogenic group and at least one discotic-like group, the discotic-like group preferably being a phenyl ring, which is bearing at least four alkoxy groups or modified alkoxy groups in positions 1, 2, 4 and 5 and at least one mesogenic group in one of the remaining positions, preferably a compound of formula (I) wherein the parameters are as specified in the text:. The instant invention further relates to mesogenic media, preferably liquid crystal media showing a blue phase and their use in electro-optical light modulation elements and their respective use in displays, as well as to such devices.

Description

Liquid Crystal Compounds, Liquid Crystal Medium and Liquid Crystal Display

Field of the invention

The present invention relates to mesogenic compounds, mesogenic media and to electro-optical displays comprising these mesogenic media as light modulation media, in particular to displays which are operated at a temperature at which the mesogenic modulation media are in an optically isotropic phase, preferably in a blue phase.

Problem to be solved and state of the art

Electro-optical displays and mesogenic light modulation media, which are in the isotropic phase when being operated in the display are described in DE 102 17 273 A. Electro-optical displays, and mesogenic light modulation media, which are in the optically isotropic blue phase, when being operated in the display are described in DE 103 13 979.6, which is not yet laid open.

The mesogenic media and displays described in these references provide several significant advantages compared to well-known and widely used displays using liquid crystals in the nematic phase, like for example liquid crystal displays (LCDs) operating in the twisted nematic (TN)-, the super twisted nematic (STN)-, the electrically controlled birefringence (ECB)- mode with its various modifications and the in-pjane switching (IPS)-mode. Amongst these advantages the most pronounced are their much faster switching times, and significantly wider optical viewing angle.

Whereas, compared to displays using mesogenic media in another liquid crystalline phase, as e.g. in the smectic phase in surface stabilized ferroelectric liquid crystal displays (SSF LCDs), the displays of DE 102 17 273.0 and DE 103 13 979 are much easier to be produced. For example, they do not require a very thin cell gap in the first place and the electro-optical effect is not very sensitive to small variations of the cell gap as well. However, the liquid crystal media described in these mentioned patent applications still require operating voltages, which are not low enough for some applications. Further the operating voltages of these media vary with temperature, and it is generally observed, that at a certain temperature the voltage dramatically increases with increasing temperature. This limits the applicability of liquid crystal media in the blue phase for display applications. A further disadvantage of the liquid crystal media described in these patent applications is their moderate reliability which is insufficient for very demanding applications. This moderate reliability may be for example expressed in terms of the voltage holding ratio parameter (VHR), which in liquid crystal media as described above may be below 90%.

Some compounds and compositions have been reported which possess a blue phase between the cholesteric phase and the isotropic phase and can usually be observed by optical microscopy. These compounds or compositions for which the blue phases are observed are typically single mesogenic compounds or mixtures showing a high chirality. However, generally the blue phases observed only extend over a very small temperature range, which is typically less than 1 degree centigrade (Kelvin) wide.

EP 03 018 708.2 (still unpublished) shows a general formula

which also encompasses compounds with four or five alkoxy groups bound to the phenyl ring shown, however, no specific compounds of this type are given, only compounds with a phenyl ring which is substituted by three alkoxy groups are exemplified, whereas EP 03 018 707.4 (still unpublished) shows the use of compounds covered by general formula I of EP 03 018 708.2 with a phenyl ring which is substituted by three alkoxy groups in displays with a light modulation medium which is in the optically isotropic, blue phase In order to operate the novel fast switching display mode of DE 103 13 979.6 the light modulation medium to be used has to be in the blue phase over a broad range of temperatures encompassing ambient temperature, however. Thus, a light modulation medium possessing a blue phase which is as wide as possible and conveniently located is required.

Therefore there is a strong need for a modulation medium with a blue phase with a wide phase range, which may be achieved either by an appropriate mixture of mesogenic compounds themselves or, preferably by mixing a host mixture with appropriate mesogenic properties with a single dopant or a mixture of dopants that stabilises the blue phase over a wide temperature range.

Summarizing, there is a need for liquid crystal media, which can be operated in liquid crystal displays which are operated at temperatures where the media is in the blue phase, which provide the following technical improvements:

- a reduced operating voltage, - a reduced temperature dependency of the operating voltage and

- an improved reliability, e.g. VHR.

Present invention

Surprisingly, it now has been found that mesogenic compounds with a molecular structure comprising at least one mesogenic group and at least one discotic-like group, which is preferably a phenyl ring, which is bearing for alkoxy groups or modified alkoxy groups in positions 1 , 2, 4 and 5 and at least one mesogenic group in one of the remaining positions, are suitable to considerably enhance the range of temperatures over which the blue phase is stable or even induce a blue phase in respective mesogenic hosts, which do not show such a phase on their own. Preferably the mesogenic hosts are liquid crystalline hosts. The mesogenic groups present do each contain at least one ring element, which is preferably selected from the group of four -, five -, six - or seven -, preferably of five - or six -, membered rings, which optionally are linked to one or more ring elements selected from this group of ring elements by a direct bond or a linking group. In a preferred embodiment the mesogenic compounds according to the present invention comprise two discotic-like groups, which are linked by a mesogenic group.

In a preferred embodiment the compounds according to the present invention are chiral compounds, preferably they comprise at least one chiral substituted atom and most preferably a chiral substituted C-atom.

Preferably these compounds are of formula I

wherein

Ft¹¹ to R¹⁶ are, independently of each other, H, F, Cl, CN, NCS, SF₅ , S0₂CF₃ or alkyl, which is straight chain, branched, cyclic or contains a cyclic moiety, preferably has 1 to 20 C-atoms, is unsubstituted, mono- or poly-substituted by F, Cl, or CN, and in which one or more non-adjacent CH₂ groups are optionally replaced, in each case independently from one another, by -0-, -S-, -NH-, -

NR -.0^U1 -, -SiR _Ϊ0^u1'R02 -, -CO-, -COO-, -OCO-, -OCO-0-, -S- CO-, -CO-S-, -CY⁰¹=CY⁰²-, -C≡C- or an aromatic biradical, which optionally may be substituted, preferably by halogen or alkyl and in which one or more CH groups may be replaced by N atoms, in such a manner that O and/or S atoms are not linked directly to one another, and in which one or more non-adjacent CH groups, when present, may optionally be replaced by N, preferably H, n-alkyl or n-alkoxy with 1 to 9 C-atoms preferably 2 to 5 C-atoms, alkenyl, alkenyloxy or alkoxyalkyl with 2 to 9 C-atoms, preferably with 2 to 5 C- atoms, cycloalkyl or CN, NCS or halogen, preferably F, Cl, halogenated alkyl, alkenyl or alkoxy, preferably mono-, di fluorinated or oligofluorinated alkyl, alkenyl or alkoxy, especially preferred CF₃, OCF₂H or OCF₃, or, alternatively, one or more of R¹¹ to R¹² may be -SP-PG and /or at least one of R¹¹ and R¹² may be

R¹³ to R¹⁶ preferably are, independently of each other, and in case they are occurring twice, also in these occurrences independently of each other, alkyl, which is straight chain, branched, cyclic or contains a cyclic moiety, preferably has 1 to 20 C-atoms, is unsubstituted, mono- or poly-substituted by halogen or CN, preferably by F, and in which one or more non-adjacent CH₂ groups are optionally replaced, in each case independently from one another, by -0-, or -S-, -NH-, -NR⁰¹-, -SiR⁰¹R⁰²-, -CY°¹=CY⁰²- or -C≡C- in such a manner that O and/or S atoms are not linked directly to one another, and in which one or more non-adjacent CH groups, when present, are optionally replaced by N, preferably n-alkyl with 1 to 9 C-atoms preferably 1 to 5 C-atoms, alkenyl or alkoxyalkyl with 2 to 9 C-atoms, preferably with 1 to 5 C-atoms halogenated alkyl or alkenyl, preferably mono-, di- or oligofluorinated alkyl or alkenyl,

R is which is straight chain, branched, cyclic or contains a cyclic moiety, preferably has 1 to 20 C-atoms, is unsubstituted, mono- or poly-substituted by halogen or

CN, preferably by F, and in which one or more non- adjacent CH₂ groups are optionally replaced, in each case independently from one another, by -0-, or -S-, -CY⁰¹=CY°²- or -C≡C- in such a manner that O and/or S atoms are not linked directly to one another, preferably n-alkyl with 1 to 9 C-atoms preferably 1 to 5 C-atoms, alkenyl or alkoxyalkyl with 2 to 9 C-atoms, preferably with 1 to 5 C-atoms halogenated alkyl or alkenyl, preferably mono-, di- or oligofluorinated alkyl or alkenyl,

PG is a polymerisable or reactive group,

SG is a spacer group or a single bond, and

occurring more than once, also these are in each occurrence independently of each other, an aromatic and/or alicyclic ring, or a group comprising two or more fused aromatic or alicyclic rings, wherein these rings optionally contain one or more hetero atoms selected from N, O and/or S, and are optionally monosubstituted or polysubstituted by R, wherein

Z¹¹ and Z¹² are, independently of each other, and in case Z¹¹ and/or

Z¹² are occurring more than once, also these are in each occurrence independently of each other, -CO-0-, -0-CO-, -S-CO-, -CO-S-, -CO-NR⁰ -, -NR⁰¹-CO-, -OCH₂-, -CH₂0-, -SCH₂-, -CH₂S-, -CF₂0-, -OCF₂-, -CF₂S-, -SCF₂-, -CH₂CH₂-, -CF₂CH₂-, -CH₂CF₂-, -CF₂CF₂-, -CH=N-, -N=CH-, -N=N-, -CH=CR⁰¹-, -CR⁰¹=CH-, -CY°¹=CY⁰²-, -C≡C-, -(CH₂) ₄-, -CH=CH-CO-0-, -0-CO-CH=CH- or a single bond, Y⁰¹ and Y⁰² are, independently of each other, F, Cl or CN, and alternatively one of them may be H,

R⁰¹ and R⁰² are, independently of each other, H or alkyl with 1 to 12

C-atoms,

n and m are, independently of each other, 0, 1 , 2, 3 or 4, while

n + m is 1 , 2, 3, 4, 5 or 6, preferably 1 , 2, 3, or 4 and

n is preferably 0,1 , or 2, most preferably 0 or 1.

in a preferred embodiment the discotic-like group is

wherein the parameters have the meaning given under formula I above.

In a preferred embodiment one or more of R¹¹ to R¹⁶ in the molecules of formula I is an alicyclic, an alicycloalkyl an aromatic (aryl) or an arylalkyl group, preferably, independently of each other in each occurrence, selected from

wherein the rings optionally may be substituted, preferably by alkyl, preferably by n-alkyl, most preferably by methyl or isopropyl, and, preferably the aromatic, rings optionally additionally or alternatively by halogen, CN or NCS, preferably by F.

Preferably these compounds are selected from the group of compounds of formulae I' and I"

wherein the parameters have the respective meanings given above.

In a further preferred embodiment the discotic-like group is selected from the group of partial formulae DG-1 to DG-7, preferably DG-1 to DG-4, in particular of DG-1 , DG-3 and DG-4

wherein

is an integer from 1 to 20, preferably from 1 to 10 and most preferably from 1 to 7 and the rings optionally may be substituted, preferably by alkyl and the aromatic rings also additionally or alternatively by halogen, CN or NCS, preferably by F.

In a further preferred embodiment the discotic-like group is selected from the group of partial formulae DG-8 to DG-19

Particularly preferred are compounds of formula I, wherein

at least one of Z¹¹ and Z¹², preferably at least one each of Z¹¹ and Z¹² and most preferably one each of Z¹¹ and Z¹², is -CO-0-, -0-CO-, -CH₂-0-, -0-CH₂-, -CF₂-0-, -0-CF₂- or -CH=CH-, most preferably -CF₂-0- or -O-CF2-, preferably -0-CH₂- or -CF₂-0-, and/or one or more of the rings A¹¹ and/or A¹², which are present, is, respectively are, phenylene, that is optionally substituted by one or more groups R and/or F-atoms and/or

R¹³ to R¹⁶ are alkyl with 1 to 12, preferably 1 to 8 C-atoms, or alkenyl or alkynyl with 2 to 12, preferably 2 to 7 C-atoms and/or n + m is 2 or 3 and/or n is 0 and/or one or more of the groups R¹¹ to R¹⁶, which are present, is, respectively are cycloalkyl, cycloalkylalkyl, alkylcycloalkyl or alkylcycloalkylalkyl and/or

identical to each other and, optionally, at the same time, preferably, a illssoo RR¹¹¹¹ aanndd RR¹¹²² aarree identical to each other, and/or

R is PG-SG- and/or

R is alkyl or alkoxy with 1 to 12, preferably 1 to 8 C-atoms, or alkenyl, alkenyloxy or alkynyl with 2 to 12, preferably 2 to 7 C-atoms and/or

SG is alkylene with 1 to 12 C atoms which is optionally mono- or polysubstituted by F and wherein one or more non-adjacent CH₂ may be replaced, in each case independently from one another, by -0-,

-CH=CH- or -C≡C-, and that is linked to a ring, preferably to ring A¹ via a group selected from -0-, -CO-O-, -O-CO-, -O-CO-0- and a single bond and/or

SG is a single bond.

In a preferred embodiment of the present invention rings A¹¹ to A¹³ are, independently of each other, an aromatic or alicyclic ring, preferably a 5-, 6- or 7-membered ring, or a group comprising two or more, preferably two or three, fused aromatic or alicyclic rings, wherein these rings optionally contain one or more hetero atoms selected from N, O and/or S, and are optionally mono- or polysubstituted with L, wherein L is F, Cl, Br, CN, OH, N0₂, and/or an alkyl, alkoxy, alkylcarbonyl or alkoxycarbonyl group with 1 to 12 C atoms, wherein one or more H atoms are optionally replaced by F or CI.

L is preferably F, Cl, CN, OH, N0₂, CH₃, C₂H₅, OCH₃, OC₂H₅, COCH₃,

COC₂H₅, COOCH3, COOC2H₅, CF₃, OCF₃, OCHF₂ or OC₂F₅, in particular F, Cl, CN, CH₃, C₂H₅, OCH₃, COCH₃ or OCF₃, most preferably F, Cl, CH₃, OCH₃ or COCH3.

Preferred rings A¹¹ and A¹² are for example furane, pyrrol, thiophene, oxazole, thiazole, thiadiazole, imidazoie, phenylene, cyclohexylene, cyclohexenylene, pyridine, pyrimidine, pyrazine, azulene, indane, naphthalene, tetrahydronaphthalene, decahydronaphthalene, tetrahydropyrane, anthracene, phenanthrene and fluorene.

Particularly preferably one or more of these rings A¹¹ and A¹² is, respectively are, selected from furane-2,5-diyl, thiophene-2,5-diyl, thienothiophene-2,5-diyl, dithienothiophene-2,6-diyl, pyrrol-2,5-diyl, 1 ,4- phenylene, azulene-2,6-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, 1 ,2,3,4-tetrahydro-naphthalene-2,6-diyl, indane-2,5- diyl, or 1 ,4-cyclohexylene wherein one or two non-adjacent CH₂ groups are optionally replaced by O and/or S, wherein these groups are unsubstituted, mono- or polysubstituted by L as defined above.

Preferably

and

, independently of each other in each occurrence, are

wherein

R is alkyl with 1 to 12 C-atoms, preferably with 1 to 7 C- atoms, or alkenyl or alkynyl with 2 to 12 C-atoms, preferably with 2 to 7 C-atoms, in both of which one or more non-adjacent -CH₂- groups, not adjacent to the phenyl ring, may be replaced by -O- and/or -CH=CH- and/or one or more H-atoms may be replaced by halogen, preferably by F and preferably is alkyl, preferably methyl, ethyl or propyl, preferably methyl,

or their mirror images

and most preferably at least one of them, in particular at least one each of them, is

In a preferred embodiment of the present invention at least one of the groups

preferably both of them, contains only monocyclic rings A¹¹ and A¹². Very preferably this is a group containing one or two 5- and/or 6-membered rings.

Preferred sub-formulae for this group are listed below. For reasons of simplicity, Phe in these groups is 1 ,4-phenylene, PheL is a 1 ,4-phenylene group which is substituted by 1 to 4 groups L as defined above, Cyc is 1 ,4- cyclohexylene, Pyd is pyridine-2,5-diyl and Pyr is pyrimidine-2,5-diyl. The following list of preferred groups is comprising the sub formulae A-1 to A-20 as well as their mirror images,

-Phe- A-1

-Pyd- A-2

-Pyr- A-3

-PheL- A-4

-Cyc- A-5

-Phe-Z-Cyc- A-6

-Cyc-Z-Cyc- A-7

-PheL-Cyc- A-8

-Phe-Z-Phe- A-9

-Phe-Z-Pyd- A-10

-Pyd-Z-Phe- A-11

-Phe-Z-Pyr- A-12

-Pyr-Z-Phe- A-13 -PheL-Z-Phe- A-14

-PheL-Z-Pyd- A-15

-PheL-Z-Pyr- A-16

-Pyr-Z-Pyd- A-17

-Pyd-Z-Pyd- A-18

-Pyr-Z-Pyr- A-19

•PheL-Z-PheL- A-20

In these preferred groups Z has the meaning of Z¹¹ as given in formula I. Preferably Z is -CF₂-0- or -0-CF₂- or a single bond.

Very preferably, at least one of the groups

preferably both of them, are selected from the following formulae la to Ir and their respective mirror images

wherein L has the meaning given above and r and s are independently of each other, 0, 1 , 2, 3 or 4, preferably 0, 1 or 2.

in these preferred formulae is very preferably

f^urthermore -

L- with L having each independently one of the meanings given above. Especially preferred compounds of formula I comprise at least one group each in rings A¹¹ and A¹² of the formula

- y— wherein r is 1 or 2.

Further preferred compounds of formula I comprise at least one group each in rings A¹¹ and A¹² of the formula

(L)r

—fr y— wherein r is 2 and/or at least one group each of the formula

—fr y— wherein r is 0, 1 or 2.

Very preferably, at least one of the groups

preferably both of them, are selected from

35

or their respective mirror images,

wherein the 1 ,4-phenylene rings may optionally be substituted by R or L, preferably by alkyl, preferably by methyl, and/or by alkoxy and/or by halogen, preferably F.

More preferably at least one of the groups

preferably both of them, are selected from

35

or their respective mirror images.

An alkyl or an alkoxy radical, i.e. an alkyl where the terminal CH group is replaced by -0-, in this application may be straight-chain or branched. It is preferably straight-chain, has 1 , 2, 3, 4, 5, 6, 7 or 8 carbon atoms and accordingly is preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, or octoxy, furthermore nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy or tetradecoxy, for example.

Oxaalkyl, i.e. an alkyl group in which one non-terminal CH₂ group is replaced by -0-, is preferably straight-chain 2-oxapropyl (= methoxy- methyl), 2- (= ethoxymethyl) or 3-oxabutyl (= 2-methoxyethyl), 2-, 3-, or 4- oxapentyl, 2-, 3-, 4-, or 5-oxahexyl, 2-, 3-, 4-, 5-, or 6-oxaheptyl, 2-, 3-, 4-, 5-, 6- or 7-oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanonyl or 2-, 3-, 4- 5-, 6-,7-, 8- or 9-oxadecyl, for example.

A cycloalkyl group is preferably cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, a cycloalkylalkyl group is preferably cyclopropylmethyl, cyclobutylmethyl or cyclopentylmehtyl.

An alkylcycloalkylalkyl group is preferably methylcyclopropylmethyl, ethylcyclopropylmethyl or methylcyclobutylmethyl.

An alkenyl group, i.e. an alkyl group wherein one or more CH₂ groups are replaced by -CH=CH-, may be straight-chain or branched. It is preferably straight-chain, has 2 to 10 C atoms and accordingly is preferably vinyl, prop-1-, or prop-2-enyl, but-1-, 2- or but-3-enyl, pent-1 -, 2-, 3- or pent- 4-enyl, hex-1-, 2-, 3-, 4- or hex-5-enyl, hept-1 -, 2-, 3-, 4-, 5- or hept-6-enyl, oct-1-, 2-, 3-, 4-, 5-, 6- or oct-7-enyl, non-1-, 2-, 3-, 4-, 5-, 6-, 7- or non- 8-enyl, dec-1 -, 2-, 3-, 4-, 5-, 6-, 7-, 8- or dec-9-enyl.

Especially preferred alkenyl groups are C2-C7-I E-alkenyl, C₄-C -3E- alkenyl, C₅-C₇-4-alkenyl, C₆-C₇-5-alkenyl and C₇-6-alkenyl, in particular C₂-C₇-I E-alkenyl, C₄-C₇-3E-alkenyl and C₅-C₇-4-alkenyl. Examples for particularly preferred alkenyl groups are vinyl, 1 E-propenyl, 1 E-butenyl, 1 E-pentenyl, 1 E-hexenyl, 1 E-heptenyl, 3-butenyl, 3E-pentenyl, 3E-hexenyl, 3E-heptenyl, 4-pentenyl, 4Z-hexenyl, 4E-hexenyl, 4Z-heptenyl, 5-hexenyl, 6-heptenyl and the like. Groups having up to 5 C atoms are generally preferred.

In an alkyl group, wherein one CH₂ group is replaced by -O- and one by -CO-, these radicals are preferably neighboured. Accordingly these radicals together form a carbonyloxy group -CO-O- or an oxycarbonyl group -O-CO-. Preferably such an alkyl group is straight-chain and has 2 to 6 C atoms.

It is accordingly preferably acetyloxy, propionyloxy, butyryloxy, pentanoyloxy, hexanoyloxy, acetyloxymethyl, propionyloxymethyl, butyryloxymethyl, pentanoyloxymethyl, 2-acetyloxyethyl, 2-propionyloxy- ethyl, 2-butyryloxyethyl, 3-acetyloxypropyl, 3-propionyloxypropyl, 4-acetyloxybutyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, methoxycarbonylmethyl, ethoxy- carbonylmethyl, propoxycarbonylmethyl, butoxycarbonylmethyl, 2-(methoxycarbonyl)ethyl, 2-(ethoxycarbonyl)ethyl, 2-(propoxy- carbonyl)ethyl, 3-(methoxycarbonyl)propyl, 3-(ethoxycarbonyl)propyl, 4-(methoxycarbonyl)-butyl.

An alkyl group wherein two or more CH₂ groups are replaced by -0- and/or -COO-, it can be straight-chain or branched. It is preferably straight-chain and has 3 to 12 C atoms. Accordingly it is preferably bis-carboxy-methyl, 2,2-bis-carboxy-ethyl, 3,3-bis-carboxy-propyl, 4,4-bis-carboxy-butyl, 5,5-bis-carboxy-pentyl, 6,6-bis-carboxy-hexyl, 7,7-bis-carboxy-heptyl, 8,8-bis-carboxy-octyl, 9,9-bis-carboxy-nonyl, 10,10-bis-carboxy-decyl, bis- (methoxycarbonyl)-methyl, 2,2-bis-(methoxycarbonyl)-ethyl, 3,3-bis- (methoxycarbonyl)-propyl, 4,4-bis-(methoxycarbonyl)-butyl, 5,5-bis- (methoxycarbonyl)-pentyl, 6,6-bis-(methoxycarbonyl)-hexyl, 7,7-bis- (methoxycarbonyl)-heptyl, 8,8-bis-(methoxycarbonyl)-octyl, bis- (ethoxycarbonyl)-methyl, 2,2-bis-(ethoxycarbonyl)-ethyl, 3,3-bis- (ethoxycarbonyl)-propyl, 4,4-bis-(ethoxycarbonyl)-butyl, 5,5-bis- (ethoxycarbonyl)-hexyl.

A alkyl or alkenyl group that is monosubstituted by CN or CF₃ is preferably straight-chain. The substitution by CN or CF₃ can be in any desired position.

An alkyl or alkenyl group that is at least monosubstituted by halogen, it is preferably straight-chain. Halogen is preferably F or Cl, in case of multiple substitution preferably F. The resulting groups include also perfluorinated groups. In case of monosubstitution the F or Cl substituent can be in any desired position, but is preferably in ω-position. Examples for especially preferred straight-chain groups with a terminal F substituent are fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl and 7-fluoroheptyl. Other positions of F are, however, not excluded.

Halogen means F, Cl, Br and I and is preferably F or Cl, most preferably F. Each of R¹¹ to R¹⁶ may be a polar or a non-polar group. In case of a polar group, it is preferably selected from CN, SF₅, halogen, OCH₃, SCN, COR⁵, COOR⁵ or a mono- oligo- or polyfluorinated alkyl or alkoxy group with 1 to 4 C atoms. R⁵ is optionally fluorinated alkyl with 1 to 4, preferably 1 to 3 C atoms. Especially preferred polar groups are selected of F, Cl, CN, OCH₃, COCH₃₎ COC₂H₅, COOCH₃, COOC₂H₅, CF₃, CHF₂, CH₂F, OCF₃, OCHF₂, OCH₂F, C₂F₅ and OC2F5, in particular F, Cl, CN, CF₃, OCHF₂ and OCF₃. In case of a non-polar group, it is preferably alkyl with up to 15 C atoms or alkoxy with 2 to 15 C atoms.

Each of R¹¹ to R¹⁶ may be an achiral or a chiral group. In case of a chiral group it is preferably of formula I^*:

*

-Q¹-CH-Q² I Q³ I_*

wherein

Q¹ is an alkylene or alkylene-oxy group with 1 to 9 C atoms or a single bond,

Q² is an alkyl or alkoxy group with 1 to 10 C atoms which may be unsubstituted, mono- or polysubstituted by F, Cl, Br or CN, it being also possible for one or more non-adjacent CH₂ groups to be replaced, in each case independently from one another, by -C≡C-, -0-, -S-, -NH-, -N(CH₃)-, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO- or -CO-S- in such a manner that oxygen atoms are not linked directly to one another,

Q _N3 is F, Cl, Br, CN or an alkyl or alkoxy group as defined for Q but being different from Q².

In case Q¹ in formula I^* is an alkylene-oxy group, the O atom is preferably adjacent to the chiral C atom. Preferred chiral groups of formula I^* are 2-alkyl, 2-alkoxy, 2-methylalkyl, 2- methylalkoxy, 2-fluoroalkyl, 2-fluoroalkoxy, 2-(2-ethin)-alkyl, 2-(2-ethin)-alkoxy, 1 ,1 ,1 -trif luoro-2-alkyl and 1 ,1 ,1 -trifluoro-2-alkoxy.

Particularly preferred chiral groups I^* are 2-butyl (=1-methylpropyl), 2- methylbutyl, 2-methylpentyl, 3-methylpentyl, 2-ethylhexyl, 2-propylpentyl, in particular 2-methylbutyl, 2-methylbutoxy, 2-methylpentoxy, 3- methylpentoxy, 2-ethylhexoxy, 1-methylhexoxy, 2-octyloxy, 2-oxa-3- methylbutyl, 3-oxa-4-methylpentyl, 4-methylhexyl, 2-hexyl, 2-octyl, 2-nonyl, 2-decyl, 2-dodecyl, 6-methoxyoctoxy, 6-methyloctoxy, 6- methyloctanoyloxy, 5-methylheptyloxycarbonyl, 2-methylbutyryloxy, 3- methylvaleroyloxy, 4-methylhexanoyloxy, 2-chlorpropionyloxy, 2-chloro-3- methylbutyryloxy, 2-chloro-4-methylvaleryloxy, 2-chloro-3-methylvaleryloxy, 2-methyl-3-oxapentyl, 2-methyl-3-oxahexyl, 1 -methoxypropyl-2-oxy, 1- ethoxypropyl-2-oxy, 1-propoxypropyl-2-oxy, 1 -butoxypropyl-2-oxy, 2- fluorooctyloxy, 2-fluorodecyloxy, 1 ,1 ,1 -trif luoro-2-octyloxy, 1 ,1 ,1 -trif luoro-2- octyl, 2-fluoromethyloctyloxy for example. Very preferred are 2-hexyl, 2- octyl, 2-octyloxy, 1 ,1 ,1 -trif luoro-2-hexyl, 1 ,1 ,1 -trif luoro-2-octyl and 1 ,1 ,1- trifluoro-2-octyloxy.

In addition, compounds containing an achiral branched alkyl group may occasionally be of importance, for example, due to a reduction in the tendency towards crystallization. Branched groups of this type generally do not contain more than one chain branch. Preferred achiral branched groups are isopropyl, isobutyl (= methylpropyl), isopentyl (= 3-methylbutyl), isopropoxy, 2-methyI-propoxy and 3-methylbutoxy.

In a preferred embodiment of the present invention one or more of R >11 to R¹⁶ are -SG-PG.

The polymerisable or reactive group PG is preferably selected from

CH₂=CW²-(0)_k1-, CH₃-CH=CH-0-, (CH₂=CH)₂CH-OCO-,

(CH₂=CH-CH₂)₂CH-OCO-, (CH₂=CH)₂CH-0-, (CH₂=CH-CH₂)₂N-, HO-CW²W³-, HS-CW²W³-, HW²N-, HO-CW²W³-NH-, CH₂=CW¹-CO-NH-, CH₂=CH-(COO)_k Phe-(0)_k2-, Phe-CH=CH-, HOOC-, OCN-, and W⁴W⁵W⁶Si-, with W¹ being H, Cl, CN, phenyl or alkyl with 1 to 5 C-atoms, in particular H, Cl or CH₃, W² and W³ being independently of each other H or alkyl with 1 to 5 C-atoms, in particular methyl, ethyl or n- propyl, W⁴, W⁵ and W⁶ being independently of each other Cl, oxaalkyl or oxacarbonylalkyl with 1 to 5 C-atoms, Phe being 1 ,4-phenylene and ki and k₂ being independently of each other 0 or 1.

Especially preferably PG is a vinyl group, an acrylate group, a methacrylate group, an oxetane group or an epoxy group, especially preferably an acrylate or methacrylate group.

As for the spacer group SG all groups can be used that are known for this purpose to those skilled in the art. The spacer group SG is preferably of formula SG'-X, such that PG-SG- is PG-SG'-X-, wherein

SG' is alkylene with up to 20 C atoms which may be unsubstituted, mono- or poly-substituted by F, Cl, Br, I or CN, it being also possible for one or more non-adjacent CH₂ groups to be replaced, in each case independently from one another, by -0-, -S-, -NH-, -NR⁰¹-, -SiR⁰¹R⁰²-, -CO-, -COO-, -OCO-, -OCO-0-, -S-, -CO-, -CO-S-, -CH=CH- or -C≡C- in such a manner that O and/or S atoms are not linked directly to one another,

X is -0-, -S-, -CO-, -COO-, -OCO-, -0-COO-, -CO-NR⁰¹-, -NR⁰¹-CO-, - OCH₂-, -CH₂0-, -SCH₂-, -CH₂S-, -CF₂0-, -OCF₂-, -CF₂S-, -SCF₂-, -CF₂CH₂-, -CH₂CF₂-, -CF₂CF₂-, -CH=N-, -N=CH-, -N=N-, -CH=CR⁰¹-, -CY°¹=CY°²-, -C≡C-, -CH=CH-COO-, -OCO-, -CH=CH- or a single bond, and

R⁰¹, R⁰², Y⁰¹ and Y⁰² have one of the respective meanings given above.

X is preferably -0-, -S-, -OCH₂-, -CH₂0-, -SCH₂-, -CH₂S-, -CF₂0-, -OCF₂-, -CF₂S-, -SCF₂-, _:CH₂CH₂-, -CF₂CH₂-, -CH₂CF₂-, -CF₂CF₂-,

-CH=N-, -N=CH-, -N=N-, -CH=CR⁰-, -CY°²=CY°²-, -C≡C- or a single bond, in particular -0-, -S-, -C≡C-, -CY⁰ =CY⁰²- or a single bond, very preferably a group that is able to from a conjugated system, such as -C≡C- or -CY⁰¹=CY°²-, or a single bond.

Typical groups SG' are, for example, -(CH₂)_P-, -(CH₂CH₂0)_q -CH₂CH₂-,

-CH₂CH₂-S-CH₂CH₂- or -CH₂CH₂-NH-CH₂CH₂- or -(SiR°R⁰⁰-O)_p-, with p being an integer from 2 to 12, q being an integer from 1 to 3 and R°, R⁰⁰ and the other parameters having the meanings given above.

Preferred groups SG' are ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylene-thioethylene, ethylene-N-methyl-iminoethylene, 1 -methylalkylene, ethenylene, propenylene and butenylene for example.

In another preferred embodiment SG' is a chiral group of formula

-Q¹-CH-Q⁴-

Q^J

wherein

Q¹ and Q³ have the meanings given in formula I^*, and

Q⁴ is an alkylene or alkylene-oxy group with 1 to 10 C atoms or a single bond, being different from Q¹,

with Q¹ being linked to the polymerisable group PG.

Further preferred are compounds with one or two groups PG-SG- wherein SG is a single bond. In case of compounds with two groups PG-SG, each of the two polymerisable groups PG and the two spacer groups SG can be identical or different.

Preferably the liquid crystalline media according to the instant invention contain a compound A comprising, preferably predominantly consisting of and most preferably entirely consisting of compounds of formula I.

The precursors of the compounds of formula I with four or five alkoxy groups bound to one phenyl ring preferably are prepared according to the following schemes (schemes I to IV)

Scheme I

^F

Scheme

RONa, tetraglyme,

cat. 18-crown-6, 140°C

Scheme III

RONa, tetraglyme, cat. 18-crown-6, 140°C

ϊcheme IV

2. 4-alkylcyclo exanone

3. cat. TsOH, - H₂0

4. H₂ , Pd-R , THF

RONa, tetraglyme, cat. 18-crown-6, 140°C

The compounds of formula I with four alkoxy groups and two identical mesogenic groups bound to one phenyl ring preferably are prepared according to the following schemes (scheme V).

Scheme V

RONa, tetraglyme,

cat. 18-crown-6, 140°C

The compounds of formula I with five alkoxy groups and one mesogenic group bound to one phenyl ring preferably are prepared according to the following schemes (scheme VI).

Scheme VI

The compounds of formula I with four alkoxy groups, one alkyl group and one mesogenic group bound to one phenyl ring preferably are prepared according to the following schemes (scheme VII).

Scheme VII

The compounds of formula I with four alkoxy groups and two mesogenic groups, which are different from each other, bound to one phenyl ring preferably are prepared according to the following schemes (scheme VIII). Scheme VIII

In schemes I to VIII the parameters have the respective meanings given above, in particular

has the meaning given for R 13

R' is alkyl or alkenyl, preferably alkyl,

MG¹ has the meaning given for

and MG and MG have, independently of each other, one of the meanings given for

wherein the parameters have the respective meanings given above and the boronates with the mesogenic moieties are obtainable by conventional methods.

MG' preferably is e.g.

or alkylbiphenyl, e.g.

35

Comprising in this application means in the context of compositions that the entity referred to, e.g. the medium or the component, contains the compound or compounds in question, preferably in a total concentration of 10 % or more and most-preferably of 20 % or more.

Predominantly consisting, in this context, means that the entity referred to contains 80 % or more, preferably 90 % or more and most preferably 95 % or more of the compound or compounds in question.

Entirely consisting, in this context, means that the entity referred to contains 98 % or more, preferably 99 % or more and most preferably 100.0 % of the compound or compounds in question.

The concentration of the compounds according to the present application are contained in the media according to the present application preferably is in the range from 0.5% or more to 30% or less, more preferably in the range from 1 % or more to 20% or less and most preferably in the range from 5% or more to 12% or less.

The compounds of formula I are preferably selected from the group of sub- formulae 1-1 to I-6

wherein the parameters have the respective meanings given under above and preferably R¹¹ and R¹² are, independently of each other, F, Cl, CN, NCS, CF₃, OCF₃, SF₅, alkyl, alkoxy, alkenyl or alkynyl, preferably F, Cl, CF₃, SF₅, alkyl or alkoxy, and most preferably F, CF₃, or SF₅,

R¹³ to R¹⁶ are, preferably identical to each other,

R' and R are, independently of each other, alkyl, alkoxy, alkenyl or alkynyl and in case they are linked to a C-atom also may be H, preferably they are alkyl or H, R' preferably is R¹³, R" preferably is CH₃,

L¹¹ to L¹⁴ are, independently of each other, H or F, preferably two or more, most preferably three or more of them are F,

and chiral compounds of these compounds are encompassed too.

In another preferred embodiment of the present invention the compounds of formula I are preferably selected from the group of sub-formulae I-7 to 1-1 1

wherein the parameters have the respective meanings given under above and preferably

,12 is F, Cl, CN, NCS, CF₃, OCF₃, SF₅, alkyl, alkoxy, alkenyl or alkynyl, preferably F, Cl, CF₃, SF₅, alkyl or alkoxy, and most preferably F, CF₃, or SF₅,

R have, independently of each other, one of the meanings given for R¹³, preferably they identical to each other,

R' and R are, independently of each other, alkyl, alkoxy, alkenyl or alkynyl and in case they are linked to a C-atom also may be H, preferably they are alkyl, R' preferably is R, R" preferably is CH₃,

L¹¹ to L¹⁶ are, independently of each other, H or F, preferably two or more, most preferably four or more of them are F,

and chiral compounds of these compounds are encompassed too.

In still another preferred embodiment of the present invention the compounds of formula I are preferably selected from the group of sub- formulae 1-12 to I-22, preferably 1-12 to 1-16,

wherein the methylene spacers or oligomethylene spacers in the molecules shown are exemplary only and in all formulae and especially in formulae 1-12, 1-15 and 1-17 to I-22, in particular in 1-12 and 1-15, may consist of any number of from 0 to 6 CH₂ groups, independently of each other, in each single occurrence and the phenyl rings may optionally be substituted, respectively ^'further substituted by F atoms or the F atoms shown may be replaced independently of each other by CN groups or preferably by H atoms,

and chiral compounds of these compounds are encompassed too. In a preferred embodiment the mesogenic modulation media according to the instant invention comprise

- a component A, preferably in a concentration of 1 % to 25 % by weight, comprising, preferably predominantly consisting of and most preferably entirely consisting of, one compound or more compounds of the formula I given above and

- optionally a dielectrically positive component B comprising, preferably predominantly consisting of and most preferably entirely consisting of one compound or of more compounds of formula II

wherein

R² has the meaning given under formula I for R¹¹,

A²¹, A²² and A²³ are, each independently of each other,

whereby each of A²¹ and A²² may have the same or a different meaning if present twice,

Z²¹ and Z²² are, each independently of each other, a single bond,

-(CH₂)₄)-, -CH₂CH₂-, -CF₂-CF₂-, -CF₂-CH₂-, -CH₂-CF₂-, -CH=CH-, -CF=CF-, -CF=CH-, -(CH₂)₃0-, -0(CH₂)₃-, -CH=CF-, -C≡C-, -CH₂0-, -OCH₂-, -CF₂0-, -OCF₂-, -CO-O- or -0-CO-, whereby each of Z²¹ and Z²² may have the same or a different meaning if present twice,

X² is halogen, -CN, -NCS, -SF₅, -S0₂CF₃, alkyl, alkenyl, alkenyloxy or alkylalkoxy or alkoxy radical each mono- or polysubstituted by CN and/or halogen,

L²¹ and L²² are, each independently of each other, H or F, and

m is 0, 1 or 2,

n is O, 1 , 2 or 3,

o is 0, 1 or 2, preferably 0 or 1 and

m + n + o is 3 or less, preferably 2 or less,

- optionally a component C, preferably in a concentration of 1 % to 25 %, preferably of 1 % to 10 % by weight, comprising, preferably predominantly consisting of and most preferably entirely consisting of one compound or of more compounds of formula III

wherein

a, b, c and d are each independently of each other 0, 1 or 2, whereby

a + b + c + d is 4 or less,

A³¹, A³², A³³ and A³⁴ are, each independently of each other,

whereby each of A³¹, A , A and A may have the same or a different meaning if present twice,

_z3_{1 j Z}32_{| Z}33

and Z³⁴ are, each independently of each other, a single bond,

-(CH₂)₄)-, -CH₂CH₂-, -CF₂-CF₂-, -CF₂-CH₂-, -CH₂-CF₂-, -CH=CH-, -CF=CF-, -CF=CH-, -(CH₂)₃0-, -0(CH₂)₃-, -CH=CF-, -C≡D-, -CH₂0-, -OCH₂-, -CF₂0-, -OCF₂-,

-CO-O- or -0-CO-, whereby each of Z³¹, Z³², Z³³ and Z³⁴ may have the same or a different meaning if present twice,

R³ is an alkyl or alkoxy radical having from 1 to 15 carbon atoms, wherein one or more methylene groups of said alkyl or alkoxy radical may be replaced independently of each other by -0-, -S-, -SiR^xR^y-, -CH=CH-, -C≡D-, -CO-O- and/or -O-CO- such that oxygen and/or sulfur atoms are not linked directly to each other, said alkyl or alkoxy radical being unsubstituted or mono-substituted with a -CN group or mono- or poly-substituted with halogen, preferably R¹¹ is a straight-chain alkyl, alkoxy, alkenyl, alkenyloxy or -O-alkylene-O-alkyl radical with up to 10 carbon atoms, said radicals being unsubstituted or mono- or poly-substituted with halogen,

L³¹, L³², L³³ and L³⁴ are each independently of each other hydrogen, halogen, a CN group, an alkyl or alkoxy radical having from 1 to 15 carbon atoms wherein one or more methylene groups of said alkyl or alkoxy radical may be replaced independently of each other by -0-, -S-, -SiR^xR^y-, -CH=CH-, -C≡D-, -CO-O- and/or -O-CO- such that oxygen and/or sulfur atoms are not linked directly to each other, said alkyl or alkoxy radical being unsubstituted or mono-substituted with a -CN group or mono- or poly-substituted with halogen, with the proviso that at least one of L³¹, L³², L³³ and L³⁴ is not hydrogen,

X /3^J is F, Cl, CF₃, OCF₃, CN, NCS, -SF₅ or -S0₂-R^z,

R^x and R^y are independently of each other hydrogen or an alkyl radical having from 1 to 7 carbon atoms; preferably R^x and R^y are both methyl, ethyl, propyl or butyl, and

R^z is an alkyl radical having from 1 to 7 carbon atoms, said alkyl radical being unsubstituted or mono- or polysubstituted with halogen; preferably R^z is CF₃, C₂F₅ or

From which compounds of formula I are excluded and

- 1-20 % by weight of component D comprising one chiral compound or more chiral compounds with a HTP of > 20 μ .

The inventive mixtures contain 1-25 wt.%, preferably 2-20 wt.% and most preferably 3-15 wt.% of component A.

Preferred compounds of formula II are compounds selected of the group of formulae 11-1 to II-8, preferably of formulae II-4 and/or II-5:

and in particular of formula ll-8a

wherein the parameters have the respective meanings given under formula II and preferably

is straight chain alkyl or alkoxy with up to six carbon atoms and

X is F, CN, NCS, CF₃, SF₅ or OCF₃, preferably F or CN.

Especially preferred are compounds of the formulae II-5 and II-8.

The inventive mixtures contain 20-80 wt.% of the pyrane compounds of the formulae II, preferably 25-70 wt.% and especially preferred 30-60 wt.%.

In a preferred embodiment of the present invention the compounds of formula III are selected from the group of compounds of the formulae 111-1 to III-7

wherein the parameters have the respective meanings given under formula III and preferably

is 0 or 1 , d is 0, 1 or 2, preferably 0 or 1 , especially preferred 1 ;

R³ is an alkyl or alkoxy radical having from 1 to 15 carbon atoms or an alkenyl or alkenyloxy or -0-alkylene-O-alkyl radical having from 2 to 15 carbon atoms, wherein one or more methylene groups of each of said radicals may be replaced independently of each other by -S-, -SiR^xR^y-, -C≡D-, -CO-O- and/or -O-CO- such that oxygen and/or sulfur and/or Si atoms are not linked directly to each other, said radicals being unsubstituted or mono-substituted with a -CN group or mono- or polysubstituted with halogen, preferably R³ is a straight- chain alkyl, alkoxy, alkenyl, alkenyloxy or -O-alkylene-O- alkyl radical with up to 10 carbon atoms, said radicals being unsubstituted or mono- or poly-substituted with halogen,

L³¹ , independently, has one of the meanings given for R³ and preferably is a straight-chain alkyl, alkoxy, alkenyl, alkenyloxy or -O-alkylene-O-alkyl radical with up to 10 carbon atoms, said radicals being unsubstituted or mono- or poly-substituted with halogen,

L³² , independently, has one of the meanings given for R³ or alternatively is hydrogen, halogen and preferably is

H, F, a straight-chain alkyl, alkoxy, alkenyl, alkenyloxy or -O-alkylene-O-alkyl radical with up to 10 carbon atoms, said radicals being unsubstituted or mono- or polysubstituted with halogen,

. 35 . 36

L³⁷, L³⁸

1 39 ■ 39a . 39b - i 1— 1₁ L. , and L^39c are, independently of each other, H or F and in formulae 111-1 to III-4 preferably at least L³⁵ is F and in formulae III-3 and III-4 preferably additionally L³⁸ is F, whereas in formula III-7 preferably additionally L³⁶ is F and in formulae 111-5 and 111-6 preferably at least both L³⁷ and L^39b are F,

X³ is F, Cl, -CN, -NCS, -SF₅, -S0₂-R^z, an alkyl or alkoxy radical having from 1 to 15 carbon atoms, wherein one or more methylene groups of said alkyl or alkoxy radical may be replaced independently of each other by -0-, -S-, -SiR^xR^y-, -CH=CH-, -C≡C-, -CO-O- and/or -O-CO- such that oxygen and/or sulfur atoms are not linked directly to each other, said alkyl or alkoxy radical being unsubstituted or mono-substituted with a -CN group or mono- or poly-substituted with halogen; preferably X³ is F, Cl, CF₃, OCF₃, OCHF₂, NCS, SF₅ or -S0₂-R^z,

Y³¹ is an alkyl or alkoxy radical having from 1 to 15 carbon atoms or an alkenyl or alkenyloxy or -O-alkylene-O-alkyl radical having from 2 to 15 carbon atoms, wherein one or more methylene groups of each of said radicals may be replaced independently of each other by -S-, -SiR^xR^y-, -C≡C-, -CO-O- and/or -O-CO- such that oxygen and/or sulfur atoms are not linked directly to each other, said radicals being unsubstituted or mono- substituted with a -CN group or mono- or polysubstituted with halogen, preferably Y³¹ is an alkoxy, alkenyloxy or -O-alkylene-O-alkyl radical with up to 10 carbon atoms, said radicals being unsubstituted or mono- or poly-substituted with halogen; in particular Y³¹ has the same meaning as L³¹,

Y³² is hydrogen, halogen, an alkyl or alkoxy radical having from 1 to 15 carbon atoms or an alkenyl or alkenyloxy or -O-alkylene-O-alkyl radical having from 2 to 15 carbon atoms, wherein one or more methylene groups of each of said radicals may be replaced independently of each other by -S-, -SiR^xR^y-, -C≡C-, -CO-O- and/or -O-CO- such that oxygen and/or sulfur atoms are not linked directly to each other, said radicals being unsubstituted or mono-substituted with a -CN group or mono- or polysubstituted with halogen, preferably Y³² is H,

Z³³ and Z³⁴ are, independently of each other, a single bond,

-CH₂CH₂-, (-CH₂CH₂-)₂, -CF₂-CF₂-, -CF₂-CH₂-, -CH₂-CF₂-, -CH=CH-, -CF=CF-, -CF=CH-, -CH=CF-, -C≡D-, -CH₂0-, -OCH₂-, -CF₂0-, -OCF₂-, -CO-O- or -0-CQ-, preferably Z³⁴ is a single bond, -C≡C-, -CF₂0- or -C0₂-, in particular a single bond or -CF₂0-, and in formulae III-3 and III-4 preferably one or both of Z³³ and Z is a single bond, more preferably Z and Z are both a single bond or one of Z³³ and Z³⁴ alternatively is

-CF₂0- or -C0₂-,

R^x and R^y are independently of each other hydrogen or an alkyl radical having from 1 to 7 carbon atoms; preferably both R^x and R^y are methyl, ethyl, propyl or butyl;

R^z is an alkyl radical having from 1 to 7 carbon atoms, said alkyl radical being unsubstituted or mono- or polysubstituted with halogen; preferably R^z is CF₃, C₂F₅ or n-C₄F₉,

whereby it is further preferred that at least one of R³, L³¹ and L³² is one of said straight-chain alkyl, alkoxy, alkenyl, alkenyloxy or -O-alkylene-O-alkyl radicals.

Suitable chiral compounds of component D are those, which have an absolute value of the helical twisting power of 20 μm or more, preferably of 40 μ or more and most preferably of 60 μm or more. The HTP is measured in MLCD-6260 at a temperature of 20°C.

The chiral component D comprises preferably one or more chiral compounds which have a mesogenic structure und exhibit preferably one or more mesophases themselves, particularly at least one cholesteric phase. Preferred chiral compounds being comprised in the chiral component D are, inter alia, well known chiral dopants like cholesteryl- nonanoate (CN), R/S-811 , R/S-1011 , R/S-2011 , R/S-3011 , R/S-4011 , R/S-5011 , CB-15 (Merck KGaA, Darmstadt, Germany). Preferred are chiral dopants having one or more chiral moieties and one or more mesogenic groups or having one or more aromatic or alicyclic moieties forming, together with the chiral moiety, a mesogenic group. More preferred are chiral moieties and mesogenic chiral compounds disclosed in DE 34 25 503, DE 35 34 777, DE 35 34 778, DE 35 34 779, DE 35 34 780, DE 43 42 280, EP 01 038 941 and DE 195 41 820 that disclosure is incorporated within this application by way of reference. Particular preference is given to chiral binaphthyl derivatives as disclosed in EP 01 111 954.2, chiral binaphthol derivatives as disclosed in WO 02/34739, chiral TADDOL derivatives as disclosed in WO 02/06265 as well as chiral dopants having at least one fluorinated linker and one end chiral moiety or one central chiral moiety as disclosed in WO 02/06196 and WO 02/06195.

The controlling medium of the present invention has a characteristic temperature, preferably a clearing point, in the range from about -30 °C to about 80 °C, especially up to about 55 °C.

Preferred chiral compounds of the component D are selected from the group of the compounds D-l to D-lll.

wherein

pa11 pa12 are each independently from each other alkyl, oxalkyl, pa21 pa22 alkoxy or alkenyl with up 9 carbon atoms with the

R^a31 and R a32 provisos that

a) R^a11 + R^a12 b) R^a21 + R^a22

Preferably R^a11, R^a12, R^a21, R^a22, R^a31 and R^a32 are an alkyl group, especially a straight chain alkyl group.

Especially preferred are chiral binaphthyl derivates of the formulae D-IV,

Especially preferred are binaphthyl derivatives of the formulae D-IV-1a to D-IV-lc,

wherein

is single bond, -CH₂CH₂-, -COO-, -OCO-, -CF₂0-, -OCF₂-, -CH2O-, -OCH₂-, -CF₂CF₂-, -CH=CH-, -C≡D- or -CF=CF-,

is 0, 1 or 2

R^u is hydrogen, an alkyl or alkoxy radical having from 1 to 15 carbon atoms wherein one or more methylene groups of said alkyl or alkoxy radical may be replaced independently of each other by -0-. -S-, -SiR x_B RY -, -CH=CH-, -C≡D-, -CO-O- and/or -O-CI- such that oxygen and/or sulfur atoms are not linked directly to each other, said alkyl or alkoxy radical being unsubstituted or mono- or poly-substituted with halogen,

Furthermore chiral binaphthyl derivates of the formulae D-V and D-VI are preferred

wherein Z and b have the above given meanings and X is

H, F, Cl, CN or has the meaning of R°^*. R^2* and R are each independently is F, Cl, OCF₃, CF₃, CN and L , L², L³ and L⁴ are each H or F. Z°^" denotes single bond, -C₂H₄-, -COO-, -OCO-, CH₂0-, -OCH₂-, -C₂F₄, -CH=CH-, -C≡D- or -CF=CF Especially preferred are chiral binaphthyl derivatives of the formulae D- V-2a to D-V-2f :

The inventive mixtures contain one ore more (two, three, four or more) chiral compounds in the range of 1 -25 wt.%, preferably 2-20 wt.%. Especially preferred are mixtures containing 3-15 wt.% of a chiral compound.

Preferred embodiments are indicated below:

The medium comprises one, two or more compounds of formula I;

Component B preferably contains besides one compound ore more compounds of formula II one ester compound or more ester compounds of the formula Z

wherein R^z has the meaning given under formula I for R¹ ,

X' is F, Cl, CN, NCS, OCF₃, CF₃ or SF₅.

Preferred compounds of the formula Z are selected from the group of compounds of formulae Z-1 to Z-14

35

wherein R has the meaning given under formula Z for R Especially preferred are mixtures containing 5 % to 35 %, preferably 10 % to 30 % and especially preferred 10 % to 20 % of compounds of formula Z, preferably selected from the group of formulae Z-1 to Z-14.

The component B preferably contains additionally one or more compounds selected from the group of ester compounds of formulae N-1 to N-10

Alkyl-C≡C— ( O )— COO- - O )— CN N-1

Alkyl-C≡C— ( O )— COO- O -CN

N-4

F

F

Alkyl-C≡C— O )— COO — O )— CN N-5

F

N-6

wherein

R has the meaning given under formula I for R11 and

"Alkyl" is alkyl with 1 to 7 C-atoms, preferably n-alkyl.

The medium component B additionally comprises one or more compounds selected from the group consisting of the general formulae IV to VIII

wherein

R^u is n-alkyl, alkoxy, oxaalkyl, fluoroalkyl or alkenyl, each having up to 9 carbon atoms,

X^u is CN, SF₅, NCS, S0₂CF₃, F, Cl, halogenated alkyl, halogenated alkenyl, halogenated alkenyloxy or halogenated alkoxy having up to 6 carbon atoms,

is -C₂F₄-, -CF=CF-, -C₂H₄-, -(CH₂)₄-, -OCH₂- -CH₂0- -CH=CH-, -CF₂0- or -OCF₂-, -C₂F₄-,

Y¹ to Y⁴ are each, independently of one another, H or F and r is 0 or 1 and

wherein further compounds of formula VII are excluded from formula VIM.

The compounds of the formula VI are preferably selected from the group of compounds of formulae VI-1 to VI-5, preferably of VI-1 and/or VI-2 and /or VI-4, most preferably of VI-2 and/or VI-4,

wherein the parameters have the respective meanings given under formula VI above. The component B preferably additionally comprises one compound or more compounds with four six-membered rings selected from the group consisting of the general formulae IX to XVI:

in which R°, X° and Y¹ to Y⁴ have the respective meanings given under formulae IV to VIM and preferably

X° is F, Cl, CF₃, OCF₃ or OCHF₂ ,

R° is alkyl, oxaalkyl, fluoroalkyl or alkenyl, each having up to 6 carbon atoms.

The component B preferably additionally comprises one or more compounds selected from the group of ester compounds of formulae E-1 to E-4

in which R° is as defined under formulae IV to VIII.

The proportion of the compounds of the formulae E-1 to E-4 is preferably 10-30% by weight, in particular 15 % to 25 %.

The proportion of compounds of the formulae III to VIII in the mixture as a whole is preferably from 1 % to 30 %.

F,

r r

-<θ)-OCF₃. -^OCF_3>- >-OCF₃, ^~ θ)-CF₃,

F F F F

- o^CF_g, -(o^-CF_g, -@-OCHF₂,- θ OCHF₂, — (o Vci, — (oVci or — ( oVci.

The medium comprises compounds of the formulae II, III, IV, V, VI, VII and/or VIM.

R° preferably is straight-chain alkyl or alkenyl having from 2 to 7 carbon atoms.

Component B preferably comprises further compounds, preferably selected from the following group consisting of the general formulae XVII to XXI:

wherein R° and X° are as defined under formulae IV to VII and the 1 ,4-phenylene rings optionally may additionally be substituted by CN, Cl or Fluorine, preferably by F. The 1 ,4-phenylene rings are preferably monosubstituted or polysubstituted by F atoms.

The medium preferably additionally comprises one compound, two, three or more, preferably two or three, compounds selected from the group of compounds of the formulae 0-1 and 0-2

wherein "Alkyl" and "Alkyl ' ", independently of each other, are as defined under formulae N-1 to N-6.

The proportion of the compounds of the formulae 0-1 and/or 0-2 in the mixtures according to the invention is preferably 5 % to 10 % by weight.

The medium preferably comprises one compound, two or three compounds of formula VII-4 in which X° is F or OCF₃.

The medium preferably comprises one compound or more compounds of the formulae IV-1 to IV-7

wherein R° has the meaning given under formula IV and preferably is methyl, ethyl, n-propyl, n-butyl, n-pentyl or vinyl.

The medium preferably comprises one compound or more compounds selected from the group of formulae Q-1 to Q-10

wherein R° has the meaning given under formulae IV to VIII.

The proportion of the compounds of the formula VI-1 and/or VI-12, in which X° preferably is fluorine, and R° preferably is CH₃, C₂H₅, n-C₃H₇, n-C₄H₉, n-C₅Hn or vinyl, in the mixture as a whole is from 2 % to 20 %, in particular from 2 % to 15 %.

The medium preferably comprises one compound or more compounds selected from the group of compounds of formulae II to VII in which R° is methyl.

The medium particularly preferably comprises one compound or more compounds selected from the group of compounds of formulae IV-1 a, IV-2a Q-2a, Q-3a and Q-7a

The medium preferably comprises one dioxane compound, two or more dioxane compounds, preferably one dioxane compound or two dioxane compounds, selected from the group of formulae Dx-1 and Dx-2

The medium preferably additionally comprises one, two or more compounds with two cyclohexane rings selected from the group of formulae Z-1 to Z-6

Alkyl- H -(O)-Alkyl ' Z-1

wherein R° has the meaning given under formulae IV to VIII, "Alkyl" and "Alkyl ' " have the respective meanings given under formulae 0-1 and 0-2 and

R^1a and R^2a are, each independently of each other, H, CH₃,

C₂H₅ or n-C₃H_7,

The medium preferably comprises one, two or more compounds with two cyclohexane rings selected from the group of formulae Z-1 , Z-2, Z-5 and Z-6. The medium preferably additionally comprises one, two or more compounds having fused rings, of the formulae AN-1 to AN-11

wherein R has the meaning given under formulae IV to VIM.

It has been found that even a relatively small proportion of compounds of the formulae I mixed with conventional liquid-crystal materials, but in particular with one or more compounds of the formulae II, III, IV, V, VI VII and/or VIM, results in a lower operating voltage and a broader operating temperature range. Preference is given, in particular, to mixtures which, besides one or more compounds of the formulae I, comprise one or more compounds of the formula II, in particular compounds of the formula II-5 and II-7 in which X² is F, Cl, CN, NCS, CF₃ or OCF₃. The compounds of the formulae I to VIM are colourless, stable and readily miscible with one another and with other liquid-crystalline materials.

The optimum mixing ratio of the compounds of the formulae I and II + III + IV + V + VI + VII + VIM depends substantially on the desired properties, on the choice of the components of the formulae I, II, III, IV, V, VI, VII and/or VIM, and on the choice of any other components that may be present. Suitable mixing ratios within the range given above can easily be determined from case to case.

The total amount of compounds of the formulae I to XXI in the mixtures according to the invention is not crucial. The mixtures can therefore comprise one or more further components for the purposes of optimisation of various properties. However, the observed effect on the operating voltage and the operating temperature range is generally greater, the higher the total concentration of compounds of the formulae I to XXI.

In a particularly preferred embodiment, the media according to the invention comprise compounds of the formulae III to VIM in which X° is F, OCF₃, OCHF₂, OCH=CF₂, OCF=CF₂ or OCF₂-CF₂H. A favourable synergistic effect with the compounds of the formulae I results in particularly advantageous properties. In particular, mixtures comprising compounds of formula I and of formula II and of formula III are distinguished by their low operating voltages.

The individual compounds of the formulae II to XXI and their respective sub-formulae, which can be used in the media according to the invention, are either known or can be prepared analogously to the known compounds.

The construction of the MLC display according to the invention from polarisers, electrode base plates and surface-treated electrodes corresponds to the conventional construction for displays of this type. The term conventional construction is broadly drawn here and also covers all derivatives and modifications of the MLC display, in particular including matrix display elements based on poly-Si TFT or MIM, however, particularly preferred are displays, which have electrodes on just one of the substrates, i.e. so called interdigital electrodes, as those used in IPS displays, preferably in one of the established structures.

A significant difference between the displays according to the invention and the conventional displays based on the twisted nematic cell consists, however, in the choice of the liquid-crystal parameters of the liquid-crystal layer.

The media according to the invention are prepared in a manner conventional per se. In general, the components are dissolved in one another, advantageously at elevated temperature. By means of suitable additives, the liquid-crystalline phases in accordance with the invention can be modified in such a way that they can be used in all types of liquid crystal display elements that have been disclosed hitherto. Additives of this type are known to the person skilled in the art and are described in detail in the literature (H. Kelker and R. Hatz, Handbook of Liquid Crystals, Verlag Chemie, Weinheim, 1980). For example, pleochroic dyes can be added for the preparation of coloured guest-host systems or substances can be added in order to modify the dielectric anisotropy, the viscosity and/or the alignment of the nematic phases. Furthermore, stabilisers and antioxidants can be added.

The mixtures according to the invention are suitable for TN, STN, ECB and IPS applications and isotropic switching mode (ISM) applications. Hence, there use in an electro-optical device and an electro-optical device containing liquid crystal media comprising at least one compound according to the invention are subject matters of the present invention.

The inventive mixtures are highly suitable for devices, which operate in an optically isotropic state. The mixtures of the invention are surprisingly found to be highly suitable for the respective use.

Electro-optical devices that are operated or operable in an optically isotropic state recently have become of interest with respect to video, TV, and multi-media applications. This is because conventional liquid crystal displays utilizing electro-optical effects based on the physical properties of liquid crystals exhibit a rather high switching time, which is undesired for, said applications. Furthermore most of the conventional displays show a significant viewing angle dependence of contrast that in turn makes necessary measures to compensate this undesired property.

With regard to devices utilizing electro-optical effects in an isotropic state the German Patent Application DE 102 17 273 A1 for example discloses light controlling (light modulation) elements in which the mesogenic controlling medium for modulation is in the isotropic phase at the operating temperature. These light controlling elements have a very short switching time and a good viewing angle dependence of contrast. However, the driving or operating voltages of said elements are very often unsuitably high for some applications.

German Patent Application DE 102 41 301 describes specific structures of electrodes allowing a significant reduction of the driving voltages. However, these electrodes make the process of manufacturing the light controlling elements more complicated.

Furthermore, the light controlling elements, for example, disclosed in both DE 102 17 273 A1 and DE 102 41 301 show a significant temperature dependence. The electro-optical effect that can be induced by the electrical field in the controlling medium being in an optical isotropic state is most pronounced at temperatures close to the clearing point of the controlling medium. In this range the light controlling elements have the lowest values of their characteristic voltages and, thus, require the lowest operating voltages. As temperature increases the characteristic voltages and hence the operating voltages increase remarkably. Typical values of the temperature dependence are in the range from about a few volts per centigrade up to about ten or more volts per centigrade. While DE 102 41 301 describes various structures of electrodes for devices operable or operated in the isotropic state, DE 102 17 273 A1 discloses isotropic media of varying composition that are useful in light controlling elements operable or operated in the isotropic state. The relative temperature dependence of the threshold voltage in these light controlling elements is at a temperature of 1 centigrade above the clearing point in the range of about 50%/centigrade. That temperature dependence decreases with increasing temperature so that it is at a temperature of 5 centigrade above the clearing point of about 10%/centigrade. However, for many practical applications of displays utilizing said light controlling elements the temperature dependence of the electro-optical effect is too high. To the contrary, for practical uses it is desired that the operating voltages are independent from the operating temperature over a temperature range of at least some centigrades, preferably of about 5 centigrades or more, even more preferably of about 10 centigrades or more and especially of about 20 centigrades or more.

Now it has been found that the use of the inventive mixtures are highly suitable as controlling media in the light controlling elements as described above and in DE 102 17 273 A1 , DE 10241 301 and DE 102 53606 and broaden the temperature range in which the operating voltages of said electro-optical operates. In this case the optical isotropic state or the blue phase is almost completely or completely independent from the operating temperature.

This effect is even more distinct if the mesogenic controlling media exhibit at least one so-called "blue phase" as described in yet unpublished DE 103 13 979. Liquid crystals having an extremely high chiral twist may have one or more optically isotropic phases. If they have a respective cholesteric pitch, these phases might appear bluish in a cell having a sufficiently large cell gap. Those phases are therefore also called "blue phases" (Gray and Goodby, "Smectic Liquid Crystals, Textures and Structures", Leonhard Hill, USA, Canada (1984)). Effects of electrical fields on liquid crystals existing in a blue phase are described for instance in H.S. Kitzerow, "The Effect of Electric Fields on Blue Phases", Mol. Cryst. Liq.

Cryst. (1991), Vol. 202, p. 51-83, as well as the three types of blue phases identified so far, namely BP I, BP II, and BP III, that may be observed in field-free liquid crystals. It is noteworthy, that if the liquid crystal exhibiting a blue phase or blue phases is subjected to an electrical field, further blue phases or other phases different from the blue phases I, II and III might appear. The inventive mixtures can be used in an electro-optical light controlling element, which comprises

one or more, especially two substrates; - an assembly of electrodes; one or more elements for polarizing the light; and said controlling medium;

whereby said light controlling element is operated (or operable) at a temperature at which the controlling medium is in an optically isotropic phase when it is in a non-driven state.

The controlling medium of the present invention has a characteristic temperature, preferably a clearing point, in the range from about -30 °C to about 80 °C, especially up to about 55 °C.

The operating temperature of the light controlling elements is preferably above the characteristic temperature of the controlling medium said temperature being usually the transition temperature of the controlling medium to the blue phase; generally the operating temperature is in the range of about 0.1 ° to about 50 °, preferably in the range of about 0.1 ° to about 10 ° above said characteristic temperature. It is highly preferred that the operating temperature is in the range from the transition temperature of the controlling medium to the blue phase up to the transition temperature of the controlling medium to the isotropic phase which is the clearing point. The light controlling elements, however, may also be operated at temperatures at which the controlling medium is in the isotropic phase.

For the purposes of the present invention the term "characteristic temperature" is defined as follows:

If the characteristic voltage as a function of temperature has a minimum, the temperature at this minimum is denoted as characteristic temperature. If the characteristic voltage as a function of temperature has no minimum and if the controlling medium has one or more blue phases, the transition temperature to the blue phase is denoted as characteristic temperature; in case there are more than one blue phase, the lowest transition temperature to a blue phase is denoted as characteristic temperature.

If the characteristic voltage as a function of temperature has no minimum and if the controlling medium has no blue phase, the transition temperature to the isotropic phase is denoted as c aracteristic temperature.

In the context of the present invention the term "alkyl" means, as long as it is not defined in a different manner elsewhere in this description or in the claims, straight-chain and branched hydrocarbon (aliphatic) radicals with 1 to 15 carbon atoms. The hydrocarbon radicals may be unsubstituted or substituted with one or more substituents being independently selected from the group consisting of F, Cl, Br, I or CN.

The dielectrics may also comprise further additives known to the person skilled in the art and described in the literature. For example, 0 to 5% of pleochroic dyes, antioxidants or stabilizers can be added.

C denotes a crystalline phase, S a smectic phase, Sc a smectic C phase, N a nematic phase, I the isotropic phase and BP the blue phase.

V_x denotes the voltage for X% transmission. Thus e.g. V₁₀ denotes the voltage for 10% transmission and V₁₀₀ denotes the voltage for 100% transmission (viewing angle perpendicular to the plate surface). τ_on denotes the switch-on time and τ_off the switch-off time at an operating voltage corresponding the value of V₁₀₀, respectively of V_max.

Δn denotes the optical anisotropy. Δε denotes the dielectric anisotropy (Δε = ε_(| - ε_x, where ε,, denotes the dielectric constant parallel to the longitudinal molecular axes and ε_x denotes the dielectric constant perpendicular thereto). The electro-optical data are measured in a TN cell at the 1^st minimum of transmission (i.e. at a (d ^• Δn) value of 0.5 μm) at 20°C, unless expressly stated otherwise. The optical data are measured at 20°C, unless expressly stated otherwise.

Optionally, the light modulation media according to the present invention can comprise further liquid crystal compounds in order to adjust the physical properties. Such compounds are known to the expert. Their concentration in the media according to the instant invention is preferably 0 % to 30 %, more preferably 0 % to 20 % and most preferably 5 % to15 %.

Preferably inventive media have a range of the blue phase or, in case of the occurrence of more than one blue phase, a combined range of the blue phases, with a width of 9° or more, preferably of 10° or more, more preferably of 15° or more and most preferably of 20° or more.

In a preferred embodiment this phase range at least from 10°C to 30°C, most preferably at least from 10°C to 40°C and most preferably at least from 0°C to 50°C, wherein at least means, that preferably the phase extends to temperatures below the lower limit and at the same time, that it extends to temperatures above the upper limit.

In another preferred embodiment this phase range at least from 20°C to 40°C, most preferably at least from 30°C to 80°C and most preferably at least from 30°C to 90°C. This embodiment is particularly suited for displays with a strong back light, dissipating energy and thus heating the display.

In the present application the term dielectrically positive compounds describes compounds with Δε > 1 ,5, dielectrically neutral compounds are compounds with -1 ,5 < Δε < 1 ,5 and dielectrically negative compounds are compounds with Δε < -1 ,5. The same holds for components. Δε is determined at 1 kHz and 20 °C. The dielectrical anisotropies of the compounds is determined from the results of a solution of 10 % of the individual compounds in a nematic host mixture. The capacities of these test mixtures are determined both in a cell with homeotropic and with homogeneous alignment. The cell gap of both types of cells is approximately 20 μ . The voltage applied is a rectangular wave with a frequency of 1 kHz and a root mean square value typically of 0.01 V to 1.0 V, however, it is always selected to be below the capacitive threshold of the respective test mixture.

For dielectrically positive compounds the mixture ZLI-4792 and for dielectrically neutral, as well as for dielectrically negative compounds, the mixture ZLI-3086, both of Merck KGaA, Germany are used as host mixture, respectively. The dielectric permittivities of the compounds are determined from the change of the respective values of the host mixture upon addition of the compounds of interest and are extrapolated to a concentration of the compounds of interest of 100 %.

Components having a nematic phase at the measurement temperature of 20 °C are measured as such, all others are treated like compounds.

The term threshold voltage refers in the instant application to the optical threshold and is given for 10 % relative contrast (V₁₀) and the term saturation voltage refers to the optical saturation and is given for 90 % relative contrast (V₉₀) both, if not explicitly stated otherwise. The capacitive threshold voltage (V₀, also called Freedericksz-threshold VF_Γ) is only used if explicitly mentioned.

The ranges of parameters given in this application are all including the limiting values, unless explicitly stated otherwise.

Throughout this application, unless explicitly stated otherwise, all concentrations are given in mass percent and relate to the respective complete mixture, all temperatures are given in degrees centigrade (Celsius) and all differences of temperatures in degrees centigrade. All physical properties have been and are determined according to "Merck Liquid Crystals, Physical Properties of Liquid Crystals", Status Nov. 1997, Merck KGaA, Germany and are given for a temperature of 20 °C, unless explicitly stated otherwise. The optical anisotropy (Δn) is determined at a wavelength of 589.3 nm. The dielectric anisotropy (Δε) is determined at a frequency of 1 kHz. The threshold voltages, as well as all other electro- optical properties have been determined with test cells prepared at Merck KGaA, Germany. The test cells for the determination of Δε had a cell gap of 22 μm. The electrode was a circular ITO electrode with an area of 1.13 cm² and a guard ring. The orientation layers were lecithin for homeotropic orientation (ε| |) and polyimide AL-1054 from Japan Synthetic Rubber for homogenous orientation (ε±). The capacities were determined with a frequency response analyser Solatron 1260 using a sine wave with a voltage of 0.3 or 0.1 V_rms. The light used in the electro-optical measurements was white light. The set up used was a commercially available equipment of Otsuka, Japan. The characteristic voltages have been determined under perpendicular observation. The threshold voltage (V₁₀), mid-grey voltage (V₅₀) and saturation voltage (V₉₀) have been determined for 10 %, 50 % and 90 % relative contrast, respectively. Mesogenic compounds are compounds which do not significantly deteriorate a mesogenic phase already present in a medium, preferably, they are compounds, which induce a mesophase in a medium which does not already have a mesophase or a respective mesophase or, most preferably, compounds, which have a mesophase of their own. Thus e.g. nematogenic compounds are compounds which have or inflict a nematic liquid crystalline phase, smectogenic compounds have or inflict a smectic phase, discogenic compounds have or inflict a discotic phase and the like.

The mesogenic modulation material has been filled into an electro optical test cell prepared at the respective facility of Merck KGaA. The test cells had inter-digital electrodes on one substrate side. The electrode width was 10 μm, the distance between adjacent electrodes was 10 μm and the cell gap was also 10 μm. This test cell has been evaluated electro-optically between crossed polarisers.

At low temperatures, the filled cells showed the typical texture of a chiral nematic mixture, with an optical transmission between crossed polarisers without applied voltage. Upon heating, at a first temperature (Ti) the mixtures turned optically isotropic, being dark between the crossed polarisers. This indicated the transition from the chiral nematic phase to the blue phase at that temperature. Up to a second temperature (T₂) the cell showed an electro-optical effect under applied voltage, typically of ^' some tens of volts, a certain voltage in that range leading to a maximum of the optical transmission. Typically at a higher temperature the voltage needed for a visible electro-optical effect increased strongly, indicating the transition from the blue phase to the isotropic phase at this second temperature (T₂).

The temperature range (ΔT(BP)), where the mixture can be used electro- optically in the blue phase, respectively in the bi-phasic region, most beneficially has been identified as ranging from Ti to T₂. This temperature range (ΔT(BP)) is the temperature range given in the examples of this application. The electro-optical displays can also be operated at temperatures beyond this range, i.e. at temperatures above T₂, albeit generally only at significantly increased operation voltages.

The liquid crystal media according to the present invention can contain further additives and chiral dopants in usual concentrations. The total concentration of these further constituents is in the range of 0 % to 10 %, preferably 0.1 % to 6 %, based in the total mixture. The concentrations of the individual compounds used each are preferably in the range of 0.1 to 3 %. The concentration of these and of similar additives is not taken into consideration for the values and ranges of the concentrations of the liquid crystal components and compounds of the liquid crystal media in this application.

The inventive liquid crystal media according to the present invention consist of several compounds, preferably of 3 to 30, more preferably of 5 to 20 and most preferably of 6 to 14 compounds. These compounds are mixed in conventional way. As a rule, the required amount of the compound used in the smaller amount is dissolved in the compound used in the greater amount. In case the temperature is above the clearing point of the compound used in the higher concentration, it is particularly easy to observe completion of the process of dissolution. It is, however, also possible to prepare the media by other conventional ways, e. g. using so called pre-mixtures, which can be e. g. homologous or eutectic mixtures of compounds or using so called multi-bottle-systems, the constituents of which are ready to use mixtures themselves. By addition of suitable additives, the liquid crystal media according to the instant invention can be modified in such a way, that they are usable in all known types of liquid crystal displays, either using the liquid crystal media as such, like TN-, TN-AMD, ECB-, VAN-AMD and in particular in composite systems, like PDLC-, NCAP- and PN-LCDs and especially in HPDLCs.

The melting point T(C,N), the transition from the smectic (S) to the nematic (N) phase T(S,N) and the clearing point T(N,I) of the liquid crystals are given in degrees centigrade.

In the present application and especially in the following examples, the structures of the liquid crystal compounds are represented by abbreviations also called acronyms. The transformation of the abbreviations into the corresponding structures is straight forward according to the following two tables A and B. All groups C_nH_2n+ι and

C_mH_2m+1 are straight chain alkyl groups with n respectively m D-atoms. The interpretation of table B is self evident. Table A does only list the abbreviations for the cores of the structures. The individual compounds are denoted by the abbreviation of the core followed by a hyphen and a code specifying the substituents Ri, R2, Li and l follows:

nO.m OC_nH_2n+1 C_mH_2m+ H H n C_nH_2n+ι CN H H nN.F C_nH_2n+ι - CN H F nN.F.F C_nH_2n+ι CN F F nF C_nH_2n+ι F H H nF.F C_nH_2n+ι F H F nF.F.F C_nH_2n+ι F F F nOF OC_nH_2n+ι F H H nCI C_nH_2n+ι Cl H H nCI.F C_πH_2n+ι Cl H F nCI.F.F C_nH_2π+ι Cl F F nCF₃ C_nH_2n+ι CF₃ H H nOCF₃ C_nH_2n+ι OCF₃ H H nOCF₃.F C_nH_2n+ι OCF₃ H F nOCF₃.F.F C_nH_2n+ι OCF₃ F F nOCF₂ C_nH_2n+ι OCHF₂ H H nOCF₂.F C_nH_2n+ι OCHF₂ H F nOCF₂.F.F C_nH_2n+ι OCHF₂ F F nS C_nH_2n+ι NCS H H nS.F C_nH_2n+ι NCS H F nS.F.F C_nH_2n+ι NCS F F rVsN CrH₂r₊rCH=CH-C₃H_2s- CN H H rEsN C_rH_2r+1-0-C₃H_2s- CN H H nAm C_nH_2n+1 COOC_mH_2m+1 H H nF.CI C_nH_2n+ι Cl H F

PCH EPCH

BCH CCP

CECP ECCP

BECH EBCH

PTP CPTP

CEPTP

CCH PDX

PYP PYRP

ME

HP CP

EHP

ET

FET

Table B:

CGP-n-X CGG-n-X

(X = F, CF3, OCHF2 or OCF3) (X = F, CF3, OCHF2 or OCF3)

CGU-n -X B-nO.FN

(X = F, CF3, OCHF2 or OCF3)

^■nm

CBC-nmF

K3 n M3 n

PG-n-AN

PU-n-AN

PPYRP-nN

PPYP-nN

PGP-n-N

PGIP-n-N

PVG-n-S

PVG-nO-S

PVG-V-S

PVG-nV-S

PVG-Vn-S

PPVU-n-S

CPVP-n-N

PTP-n(0)-S

PTG-n(0)-S

PTU-n(0)-S

GGP-n-CL

PGIGI-n-CL

CGU-n-F

PPU-n-S

PGU-n-S

BB3n

PPTUI-n-m

GZU-n-N

GZU-nO-N

GZU-nA-N

UZU-n-N

UZU-nO-N

UZU-nA-N

CUZU-n-N

CGP-n-m

CFU-n-F

CBC-nm

CBC-nmF

ECCP-nm

CCZU-n-F

T-nFm

CGG-n-F

CGU-n-F

F

CDU-n-F

DCU-n-F

CPZG-n-OT

CCP-Vn-m

CCG-V-F

CCP-nV-m

CC-n-V

CC-n-V1

CC-nV-Vm

CCQU-n-F

CQCU-n-F

Dec-U-n-F

CWCG-n-F

CWCU-n-F

CCOC-n-m

GPTU-n-F

PQU-n-F

PUQU-n-F

PUQU-n-S

PUQU-n-OT

PUQU-n-T

PUZU-n-F

PGU-n-F

AUZU-n-F

AUZU-n-N

CGZP-n-OT

CCGU-n-F

CCQG-n-F

CUQU-n-F

CCCQU-n-F

AGUQU-n-F

AUUQU-n-F

AUUQU-n-N

CUUQU-n-F

CUUQU-n-OT

GZU-nA-F

UZU-nA-N

AUUQU-n-OT

AUUQU-n-T

AUUQP-n-T

AUUQGU-n-F

AUUQPU-n-F

CUZU-n-N

GZU-nO-N

Particular preference is given to liquid-crystalline mixtures which, besides the compounds of the formula I, comprise at least one, two, three or four compounds from Table B.

Table C:

Table C shows possible dopants according to component D, which are generally added to the mixtures alone or in combination two, three or more) according to the invention.

C 15

CB 15

CM 21

0-CH-C₆H₁₃

CH,

R/S-811

CM 44

CM 45

CM 47

R/S-1011

R/S-3011

R/S-4011

R/S-5011

Table P

Stabilisers, which can be added, for example, to the mixtures according to the invention are mentioned below.

H₃₇C₁₈-COO-C₂H₄- θ -OH

25

30

35

The liquid crystal media according to the instant invention do contain preferably

four or more compounds selected from the group of compounds of tables A and B and/or five or more compounds selected from the group of compounds of table B and/or two or more compounds selected from the group of compounds of table A.

Examples

The examples given in the following are illustrating the present invention without limiting it in any way.

However, the physical data especially of the compounds illustrate to the expert which properties can be achieved in which ranges. Especially the combination of the various properties, which can be preferably achieved, is thus well defined.

Example 1

Preparation of

The compound (3) is prepared according to the following reaction scheme:

1.1 Preparation of (2)

A suspension of 0.1 mole of (1) in 300 ml of CH₂Cl₂ is cooled to temperature of -70°C and treated dropwise with a mixture of 0.15 mole of 3,4,5-trifluorophenole, 0,17 mol of N(C₂H₅)₃ and 100 ml of CH₂CI₂. After 5 min. first 0.5 mole of N(C₂H₅)₃-3HF are added dropwise, then, after 5 min. additionally 0.5 mol Br₂ are added also dropwise. After stirring for 1 h at a temperature of -70°C the mixture is allowed to warm up to ambient temperature of about 20°C and poured into ice-cold 0.1 N aqueous NaOH. The mixture is extracted three times with CH₂CI₂, the combined organic extracts are dried over Na₂S0₄ and subsequently evaporated to dryness. The crude product is dissolved in n-heptane, filtered over silicagel and crystallized at a temperature of -20°C from n-heptane. The yield of (2) is 78% of the theoretical yield.

1.2 Preparation of (3)

A mixture of 280 mmple of (2), 420 mmole of bis(pinacolato)boron, o 840 mmole of potassium acetate, 8.4 mmole of PdCI₂(dppf), 34 ml and 800 ml of dioxane is heated under reflux for 4 h under a nitrogen atmosphere. The usual aqueous work-up and chromatography in toluene over silica gel, followed by crystallisation from ethanole yielded (106 g, 87% of the theoretical yield) of the pure boronic ester (3). 5

1.3 Preparation of (5)

A mixture of 30 ml of π-propanole and 50 ml of triglyme is added dropwise to a suspension of 400 mmole of sodium hydride in 400 ml triglyme at a0 temperature of 30°C. After completion of the addition, the mixture is stirred for 30 min. at ambient temperature, the temperature is raised to 50°C and kept there for 1 h. After addition of 4.1 mmole of 18-crown-6, a solution of 40 mmol of (4) in 50 ml of triglyme is added at a temperature of 60°C. After the completion of the addition the mixture is stirred at 60°C for 1 h and5 subsequently heated first to 110°C, stirred for 1 h at this temperature and then to 170°C and stirred for 18 h at this temperature. After cooling down to ambient temperature 8.1 g (45% of the theoretical yield) of the bromide (5) is isolated by usual aqueous work-up, followed by chromatography in chlorobutane over silica gel being a viscous oil. 0

1.4 Preparation of (6)

A mixture of 40 mmole of the boronic ester (3), 40 mmole of the bromide (5), 1.1 mmole of PdCI₂(dppf), 120 ml of dioxane and 80 mmole of 5 K₃PO₄-3H20 is stirred for 18 h at 100°C under a nitogen atmosphere. After cooling down to ambient temperature the usual aqueous work-up and chromatography in n-heptane over silica gel, followed by crystallisation from ethanole yiels 63% of the theoretical yield of the final product (6).

The product has a phase sequence of T_g -63°C I.

Example 2

Analogously to example 1 the following compound is prepared:

The product has a phase sequence of T_g -50°C I.

Example 3

Analogously to example 1 the following compound is prepared:

The product has a phase sequence of C 73°C I.

Example 4

4.1 Preparation of 2", 3", 4", 5", 6"-pentakis-cyclopropylmethoxyphenyl bromide Cyclopropyl methanol (30.0 g, 416 mmol) is added slowly to a suspension of sodium hydride (60% suspension in oil) (18.0 g, 450 mmol) in triethylene glycol dimethyl ether (400 ml) and dibenzo-18-crown 6 ether (2.0 g), maintaining a temperature below 30 °C. Pentafluorophenyl bromide (10.0 g, 40.5 mmol) in triethylene glycol dimethyl ether (100 ml) is added at 60°C and subsequently the temperature is slowly raised to 150°C to avoid excess effervescence. After 16 hours, the mixture is cooled to ambient temperature, neutralized with dilute hydrochloric acid and extracted with ether. The organic phase is washed with water, dried and evaporated to give a brown oil which is purified on a flash master column to give a liquid (7.0 g, 34%). ¹H NMR shows expected signals and GCMS shows the mol- ion.

4.2 Preparation of 2,3,4,5,6-pentakis-cyclopropylmethoxy-4'-[1 ,1-difluoro- 1 -(3,4,5-trifluoro-phenoxy)-methyl]-3',5'-difluoro-biphenyl:

2", 3", 4", 5", 6"-Pentakis-cyclopropylmethoxyphenyl bromide (3.0 g, 5.9 mmol from 4.1 above), potassium phosphate dihydrate (4.2 g, 19.8 mmol), 3,5-difluoro-4[1 ,1 -difluoro-1-(3,4,5-trifluorophenoxy)methyl]-boronic acid (6.5 g, 18.2 mmol) and tetrakis(triphenylphosphine) palladium (0) are stirred under reflux in 1 ,4-dioxane for 16 hours. The mixture is partitioned between dichloromethane and water. The chlorinated layer is washed, dried over sodium sulphate and evaporated to dryness. Purification is achieved by preparative HPLC using acetonitrile/water as eluant to give a white solid (1.3 g, 20%). ¹H NMR shows the expected signals and GCMS the mol-ion. Example 5

Analogously to example 4 2", 3", 4", 5", 6"-pentakis-cyclopropylmethoxy- 4-heptyl-[1 ,1 ';4',1 "]terphenyl:

is prepared

2", 3", 4", 5", 6"-Pentakis-cyclopropylmethoxyphenyl bromide (3.0 g, 5.9 mmol, from example 4.1), 4'heptylbiphenylboronic acid (3.6 g, 12.2 mmol), potassium phosphate dihydrate (2.7 g, 12.7 mmol) and tetrakis triphenylphosphine palladium (0) (0.1 g) are stirred in 1 ,4-dioxane under reflux for 16 hours. The mixture is cooled and partitioned between water and dichloromethane. The chlorinated layer is removed, washed and dried over sodium sulphate, then evaporated to give an orange oil. Purification is achieved by flash column chromatography using petrol/DCM followed by recrystallisation from IPA to give 0.4 g, 10%. ¹H NMR shows the expected signals and GCMS the mol-peak.

Example 6

Analogously to example 1 the following compound is prepared:

The product has a phase sequence of C 85°C Example 7

Analogously to example 1 the following compound is prepared:

The product has a glass transition temperature of -45°C.

Examples 8 to 58

Analogously to example 1 the following compounds are prepared:

Jo. R L¹¹ L¹² _L13 L^{1 14} Phases (T/°C)

8 CH₃ H H H H

9 C₂H_δ H H H H

10 n-C₃H₇ H H H H

11 π-C₄H₉ H H H H

12 π-CsHn H H H H

14 n-C₇H₁₅ H H H H

15 n-C₈Hι₇ H H H H

16 n-CgHig H H H H

17 π-CιoH₂ι H H H H

18 CH₂=CH H H H H

19 CH₂=CH-CH₂ H H H H

20 CH₃-CH=CH H H H H

21 CH₃ H H F F

22 C₂H_δ H H F F

23 n-C₃H₇ H H F F

24 n-C₄H₉ H H F F

25 n-C₅Hn H H F F

27 n-C₇H₁₅ H H F F

28 n-C₈H₁₇ H H F F

30 n-CιoH₂ι H H F F R L¹¹ L¹² _L13 L¹⁴ Phases (T/°C)

CH₂=CH H H F F

CH₂=CH-CH₂ H H F F

CH₃-CH=CH H H F F

CH₃ H F H F

C₂H_δ H F H F n-C₃H₇ H F H F n-C₄H₉ H F H F n-C₅Hn H F H F

n-C₈Hι₇ H F H F n-CgHig H F H F n-CιoH₂ι H F H F

CH₂=CH H F H F

CH₂=CH-CH₂ H F H F

CH₃-CH=CH H F H F

CH₃ F F F F

C₂H_δ F F F F n-C₃H₇ F F F F T_g -63°C I n-C₄H₉ F F F F n-C₅Hn F F F F

n-C₇H₁₅ F F F F n-C₈Hι₇ F F F F n-CgHig F F F F n-C-ιoH₂ι F F F F

CH₂=CH F F F F

CH₂=CH-CH₂ F F F F

CH₃-CH=CH F F F F Examples 59 to 1 18

Analogously to example 1 the following compounds are prepared:

Jo. R L¹¹ L¹² _L13 L¹⁴ Phases (T/°C)

59 CH₃ H H H H

60 C₂H₅ H H H H

61 n-C₃H₇ H H H H

62 n-C₄H₉ H H H H

63 n-CsHn H H H H

64 -CeHι₃ H H H H

65 n-C₇H₁₅ H H H H

66 n-C₈H₁₇ H H H H

68 -CιoH₂ι H H H H

69 CH₂=CH H H H H

70 CH₂ ⁼CH-CH₂ H H H H

71 CH₃-CH=CH H H H H

72 CH₃ F H F H

73 C₂H_δ F H F H

74 n-C₃H₇ F H F H

75 n-C₄H₉ F H F H

76 n-C₅Hn F H F H

77 n-CeH₁₃ F H F H

78 n-C H ₅ F H F H

79 n-C₈H₁₇ F H F H

80 -CgHig F H F H

91 n-CιoH₂ι F H F H o. R L¹¹ L¹² L¹³ L¹⁴ Phases (T/°C)

92 CH₂=CH F H F H

93 CH₂=CH-CH₂ F H F H

94 CH₃-CH=CH F H F H 95 CH₃ H H F F

96 C₂H₅ H H F F

3 n-C₃H₇ H H F F C 73°C I

97 n-C₄H₉ H H F F

98 n-C₅Hn H H F F 99 n-C₆H₁₃ H H F F 00 n-C₇H₁₅ H H F F 01 n-C₈H₁₇ H H F F 02 n-CgHig H H F F 03 n-C₁₀H₂₁ H H F F 04 CH₂=CH H H F F 05 CH₂=CH-CH₂ H H F F 06 CH₃-CH=CH H H F F 07 CH₃ F F F F 08 C₂H₅ F F F F 2 n-C₃H₇ F F F F T_g -50°C I09 n-C₄H₉ F F F F 10 n-C₅Hn F F F F 1 1 n-C₆H₁₃ F F F F

13 n-C₈H_i7 F F F F 14 n-C₉H₁₉ F F F F 15 n-C₁₀H₂ι F F F F 16 CH₂=CH F F F F 17 CH₂=CH-CH₂ F F F F 18 CH₃-CH=CH F F F F Examples 1 19 to 170

Analogously to example 1 the following compounds are prepared:

No. R L¹¹ L¹² _L13 L¹⁴ Phases (T/°C)

119 CH₃ H H H H

120 C₂Hs H H H H

121 n-C₃H₇ H H H H

122 n-C₄H₉ H H H H

123 n-C₅Hn H H H H

126 n-C₈H₁₇ H H H H

127 n-CgHig H H H H

128 n-CιoH₂ι H H H H

129 CH₂=CH H H H H

130 CH₂=CH-CH₂ H H H H

131 CH₃-CH= :CH H H H H

132 CH₃ H H F F

133 C₂H_δ H H F F

134 n-C₃H₇ H H F F

135 n-C₄H₉ H H F F

136 n-C₅Hn H H F F

138 n-C₇H₁₅ H H F F

139 n-C₈H₁₇ H H F F

140 n-CgHig H H F F

141 n-CιoH₂ι H H F F No. R L¹¹ L¹² _L13 L¹⁴ Phases (T/°C)

142 CH₂=CH H H F F

143 CH₂=CH-CH₂ H H F F

144 CH₃-CH= CH H H F F

145 CH₃ H F H F

146 C₂H_δ H F H F

147 n-C₃H₇ H F H F

148 π-C₄H₉ H F H F

149 n-CsHn H F H F

151 n-C₇H₁₅ H F H F

152 n-C₈H₁₇ H F H F

154 π-CιoH₂ι H F H F

155 CH₂=CH H F H F

156 CH₂=CH-CH₂ H F H F

157 CH₃-CH= CH H F H F

158 CH₃ F F F F

159 C₂H_δ F F F F

160 n-C₃H₇ F F F F

161 n-C₄H₉ F F F F

162 n-C₅Hn F F F F

164 n-C₇H₁₅ F F F F

165 n-C₈Hι₇ F F F F

166 n-CgHig F F F F

167 -CιoH₂ι F F F F

168 CH₂=CH F F F F

169 CH₂=CH-CH₂ F F F F

170 CH₃-CH= CH F F F F Examples 171 to 222

Analogously to example 1 the following compounds are prepared:

No. R 11 12 13 14

Phases (T/°C)

171 CH₃ H H H H

172 C₂H_δ H H H H

173 n-C₃H₇ H H H H

174 n-C₄H H H H H

175 n-C₅Hn H H H H

177 n-C₇H₁₅ H H H H

178 n-C₈H₁₇ H H H H

180 n-CιoH₂ι H H H H

181 CH₂=CH H H H H

182 CH₂=CH-CH₂ H H H H

183 CH₃-CH=CH H H H H

184 CH₃ H H F F

185 C₂H_δ H H F F

186 n-C₃H₇ H H F F

187 n-C₄H₉ H H F F

188 n-C₅Hn H H F F

190 n-C₇H₁₅ H H F F

191 n-C₈H₁₇ H H F F

192 n-CgHig H H F F

193 n-CιoH₂ι H H F F No. R L¹¹ L¹² _L13 L¹⁴ Phases (T/°C)

194 CH₂=CH H H F F

195 CH₂=CH-CH₂ H H F F

196 CH₃-CH= CH H H F F

197 CH₃ H F H F

198 C₂H_δ H F H F

199 n-C₃H₇ H F H F

200 n-C₄H₉ H F H F

201 n-C₅Hn H F H F

203 n-C₇H₁₅ H F H F

204 n-C₈H₁₇ H F H F

205 -CgHig H F H F

206 -CιoH₂ι H F H F

207 CH₂=CH H F H F

208 CH₂=CH-CH₂ H F H F

209 CH₃-CH= CH H F H F

210 CH₃ F F F F

211 C₂Hs F F F F

212 n-C₃H₇ F F F F

213 n-C₄H₉ F F F F

214 n-C₅Hn F F F F

216 n-C₇Hι₅ F F F F

217 n-C₈H₁₇ F F F F

218 -CgHig F F F F

219 -CιoH₂ι F F F F

220 CH₂=CH F F F F

221 CH₂=CH-CH₂ F F F F ^'

222 CH₃-CH= :CH F F F F Examoles 223 to 274

Analogously to example 1 the following compounds are prepared:

No. R 11 12 13 14

Phases (T/°C)

223 CH₃ H H H H

224 C₂Hs H H H H

225 n-C₃H₇ H H H H

226 n-C₄H₉ H H H H

227 n-C₅Hn H H H H

229 n-C₇H₁₅ H H H H

230 n-C₈Hι₇ H H H H

232 n-CιoH₂ι H H H H

233 CH₂=CH H H H H

234 CH₂=CH-CH₂ H H H H

235 CH₃-CH=CH H H H H

236 CH₃ H H F F

237 C₂H₅ H H F F

238 n-C₃H₇ H H F F

239 n-C₄H₉ H H F F

240 n-C₅Hn H H F F

242 n-C₇H₁₅ H H F F

243 n-C₈H₁₇ H H F F

245 n-CιoH₂ι H H F F No. R _Lιι _L ¹² _L ¹³ _L ¹⁴ phases (T/°C)

246 CH₂=CH H H F F

247 CH₂=CH-CH₂ H H F F

248 CH₃-CH=CH H H F F 249 CH₃ H F H F

250 C₂H₅ H F H F

251 n-C₃H₇ H F H F

252 n-C₄H₉ H F H F

253 n-C₅Hn H F H F 254 n-C₆Hι₃ H F H F

255 n-C₇H₁₅ H F H F

256 n-C₈H₁₇ H F H F

257 n-C₉H₁₉ H F H F

258 n-Cι₀H₂₁ H F H F 259 CH₂=CH H F H F

260 CH₂=CH-CH₂ H F H F

261 CH₃-CH=CH H F H F

262 CH₃ F F F F

263 C₂H₅ F F F F 264 n-C₃H₇ F F F F

265 n-C₄H₉ F F F F

266 n-C₅Hn F F F F

267 n-C₆H₁₃ F F F F

268 n-C₇H₁₅ F F F F 269 n-C₈H₁₇ F F F F

270 n-C₉H₁₉ F F F F

271 n-Cι₀H₂₁ F F F F

272 CH₂=CH F F F F

273 CH₂=CH-CH₂ F F F F 274 CH₃-CH=CH F F F F Examples 275 to 326

Analogously to example 1 the following compounds are prepared:

No. R 11 12 13 14 Phases (T/°C)

275 CH₃ H H H H

276 C₂H₅ H H H H

277 n-C₃H₇ H H H H

278 n-C₄H H H H H

279 n-CsHn H H H H

281 n-C₇H₁₅ H H H H

282 n-C₈Hι₇ H H H H

283 n-CgHig H H H H

284 -CιoH₂ι H H H H

285 CH₂=CH H H H H

286 CH₂=CH-CH₂ H H H H

287 CH₃-CH=CH H H H H

228888 CCHH₃₃ H H F F

228899 CC₂₂HH_δδ H H F F

290 n-C₃H₇ H H F F

291 n-C₄H₉ H H F F

292 n-C₅Hn H H F F

294 n-C₇H₁₅ H H F F

295 n-C₈H₁₇ H H F F

297 n-CιoH₂ι H H F F No. R L¹¹ L¹² _L13 L¹⁴ Phases (T/°C)

298 CH₂=CH H H F F

299 CH₂=CH-CH₂ H H F F

300 CH₃-CH=CH H H F F

301 CH₃ H F H F

302 C₂H₅ H F H F

303 n-C₃H₇ H F H F

304 n-C₄H₉ H F H F

305 n-C₅Hn H F H F

307 n-C₇H₁₅ H F H F

308 n-C₈H₁₇ H F H F

309 -CgHig H F H F

310 -CιoH₂ι H F H F

311 CH₂=CH H F H F

312 CH₂=CH-CH₂ H F H F

313 CH₃-CH=CH H F H F

314 CH₃ F F F F

315 C₂H₅ F F F F

316 n-C₃H₇ F F F F

317 n-C₄H₉ F F F F

318 n-C₅Hn F F F F

320 n-C₇H₁₅ F F F F

321 n-C₈H₁₇ F F F F

322 n-CgHig F F F F

323 -CιoH₂ι F F F F

324 CH₂=CH F F F F

325 CH₂=CH-CH₂ F F F F

326 CH₃-CH=CH F F F F Examples 327 to 377

Analogously to example 1 the following compounds are prepared:

11 14

No. 12 13 Phases (T/°C)

327 CH₃ H H H H

328 C₂H_δ H H H H

329 n-C₃H₇ H H H H

330 n-C H₉ H H H H

331 n-C₅Hn H H H H

333 n-C₇H₁₅ H H H H

334 n-C₈Hι₇ H H H H

335 n-CgHig H H H H

336 -CιoH₂ι H H H H

337 CH₂=CH H H H H

338 CH₂=CH-CH₂ H H H H

339 CH₃-CH=CH H H H H

340 CH₃ H H F F

341 C₂H_δ H H F F

342 n-C₃H₇ H H F F

343 n-C₄H₉ H H F F

344 n-C₅Hn H H F F

346 n-C₇H₁₅ H H F F

347 n-C₈H₁₇ H H F F

348 n-CgHig H H F F

349 -CιoH₂ι H H F F No. R L¹¹ L¹² _L13 L¹⁴ Phases (T/°C)

350 CH₂=CH H H F F

351 CH₂=CH-CH₂ H H F F

352 CH₃-CH= CH H H F F

353 CH₃ H F H F

354 C₂H_δ H F H F

355 n-C₃H₇ H F H F

356 n-C₄H₉ H F H F

357 n-C₅Hn H F H F

359 n-C₇H₁₅ H F H F

360 n-C₈H₁₇ H F H F

361 n-CgHig H F H F

362 -CιoH₂ι H F H F

363 CH₂=CH H F H F

364 CH₂=CH-CH₂ H F H F

365 CH₃-CH= CH H F H F

366 CH₃ F F F F

367 C₂H_δ F F F F

7 n-C₃H₇ F F F F T_g -45°C I

368 n-C₄H₉ F F F F

369 n-C₅Hιι F F F F

372 n-C₈Hι₇ F F F F

373 n-CgHig F F F F

374 n-C-ιoH₂ι F F F F

375 CH₂=CH F F F F

376 CH₂=CH-CH₂ F F F F

377 CH₃-CH= CH F F F F Examples 378 to 429

Analogously to example 1 the following compounds are prepared:

11 12

No. R 13 14 Phases (T/°C)

378 CH₃ H H H H

379 C₂H_δ H H H H

380 n-C₃H₇ H H H H

381 n-C₄H₉ H H H H

382 n-C₅Hn H H H H

384 n-C H₁₅ H H H H

385 n-C₈H₁₇ H H H H

387 n-CιoH₂ι H H H H

388 CH₂=CH H H H H

389 CH₂=CH-CH₂ H H H H 390 CH₃-CH=CH H H H H 391 CH₃ H F F 339922 C₂Hs H F F 339933 n-C₃H₇ H F F

394 n-C₄H₉ H F F

395 n-C₅Hn H F F

397 n-C₇H₁₅ H F F

398 n-C₈Hι₇ H F F

400 n-CιoH₂ι H F F No. R L¹¹ L¹² _L13 L¹⁴ Phases (T/°C)

401 CH₂=CH H H F F

402 CH₂=CH-CH₂ H H F F

403 CH₃-CH=CH H H F F

404 CH₃ H F H F

405 C₂H_δ H F H F

406 π-C₃H₇ H F H F

407 n-C₄H₉ H F H F

408 n-C₅Hn H F H F

410 n-C₇Hι₅ H F H F

411 n-C₈H₁₇ H F H F

412 n-CgHig H F H F

413 n-CιoH₂ι H F H F

414 CH₂=CH H F H F

415 CH =CH-CH₂ H F H F

416 CH₃-CH=CH H F H F

417 CH₃ F F F F

418 C₂H₅ F F F F

419 n-C₃H₇ F F F F

420 n-C H₉ F F F F

421 n-C₅Hn F F F F

423 π-C₇H₁₅ F F F F

424 n-C₈H₁₇ F F F F

426 n-CιoH₂ι F F F F

427 CH₂=CH F F F F

428 CH₂ ⁼CH-CH₂ F F F F

429 CH₃-CH=CH F F F F Examples 430 to 481

Analogously to example 1 the following compounds are prepared:

No. R 11 12 13 14

Phases (T/°C)

430 CH₃ H H H H

431 C₂H_δ H H H H

432 n-C₃H₇ H H H H

433 n-C₄H₉ H H H H

434 n-C₅Hn H H H H

436 n-C₇H₁₅ H H H H

437 n-C₈H₁₇ H H H H

439 n-CιoH₂ι H H H H

440 CH₂=CH H H H H

441 CH =CH-CH₂ H H H H

442 CH₃-CH=CH H H H H

443 CH₃ H H F F

444 C₂H_δ H H F F

445 n-C₃H₇ H H F F

446 n-C₄H₉ H H F F

447 n-C₅Hn H H F F

449 n-C₇H₁₅ H H F F

450 n-C₈H₁₇ H H F F

452 n-CιoH₂ι H H F F No. R L¹¹ L¹² _L13 L¹⁴ Phases (T/°C)

453 CH₂=CH H H F F

454 CH₂=CH-CH₂ H H F F

455 CH₃-CH= CH H H F F

456 CH₃ H F H F

457 C₂Hs H F H F

458 n-C₃H₇ H F H F

459 π-C₄H₉ H F H F

460 n-C₅Hn H F H F

462 n-C₇H₁₅ H F H F

463 n-C₈H₁₇ H F H F

465 n-CιoH₂ι H F H F

466 CH₂=CH H F H F

467 CH₂=CH-CH₂ H F H F

468 CH₃-CH= CH H F H F

469 CH₃ F F F F

470 C₂H_δ F F F F

471 n-C₃H₇ F F F F

472 n-C₄H₉ F F F F

473 n-C₅Hn F F F F

475 n-C₇H₁₅ F F F F

476 n-C₈H₁₇ F F F F

478 n-CιoH₂ι F F F F

479 CH₂=CH F F F F

480 CH₂=CH-CH₂ F F F F

481 CH₃-CH= CH F F F F Examples 482 to 658

Analogously to example 1 the following compounds are prepared:

No. R 11 »12 11 12 13 14

Phases (T/°C)

482 CH₃ n-C₃H₇ H H H H

483 C₂H_δ n-C₃H₇ H H H H

484 n-C₃H₇ n-C₃H₇ H H H H

485 n-C₄H₉ n-C₃H₇ H H H H

486 n-C₅Hn n-C₃H₇ H H H H

487 n-C₈Hι₃ n-C₃H₇ H H H H

488 n-C₇Hιs n-C₃H₇ H H H H

489 n-C₈Hι₇ n-C₃H₇ H H H H

490 CH₂=CH n-C₃H₇ H H H H

491 CH₂=CH-CH₂ n-C₃H₇ H H H H

492 CH₃ n-C₃H₇ F H H H

493 C₂H_δ n-C₃H₇ F H H H

494 n-C₃H₇ n-C₃H₇ F H H H

495 n-C₄H₉ n-C₃H₇ F H H H

496 n-C₅Hn n-C₃H₇ F H H H

498 n-C₇H₁₅ n-C₃H₇ F H H H

499 n-C₈Hι₇ n-C₃H₇ F H H H

500 CH₂=CH n-C₃H₇ F H H H

501 CH₂=CH-CH₂ n-C₃H₇ F H H H

502 CH₃ n-C₃H₇ H H F H

503 C₂H_δ n-C₃H₇ H H F H

504 n-C₃H₇ n-C₃H₇ H H F H No. R¹¹ R¹² L¹¹ L¹² _L13 _L14 Phases (T/°C)

505 n-C₄H₉ n-C₃H₇ H H F H

506 n-C₅Hn n-C₃H₇ H H F H

508 n-C₇H₁₅ n-C₃H₇ H H F H

510 CH₂=CH n-C₃H₇ H H F H

511 CH₂=CH-CH₂ n-C₃H₇ H H F H

512 CH₃ n-C₃H₇ F H F H

513 C₂H_δ n-C₃H₇ F H F H

514 n-C₃H₇ n-C₃H₇ F H F H

515 n-C₄H₉ n-C₃H₇ F H F H

516 n-C₅Hn n-C₃H₇ F H F H

518 n-C₇H₉ n-C₃H₇ F H F H

520 CH₂=CH n-C₃H₇ F H F H

521 CH₂=CH-CH₂ n-C₃H₇ F H F H

522 CH₃ n-C₃H₇ F F H H

523 C₂H_δ n-C₃H₇ F F H H

524 n-C₃H₇ n-C₃H₇ F F H H

525 n-C₄H₉ n-C₃H₇ F F H H

526 n-C₅Hn n-C₃H₇ F F H H

528 n-C₇H₁₅ n-C₃H₇ F F H H

529 n-C₈H₁₇ n-C₃H₇ F F H H

530 CH₂=CH n-C₃H₇ F F H H

531 CH₂=CH-CH₂ n-C₃H₇ F F H H

532 CH₃ n-C₃H₇ F F F H

533 C₂H_δ n-C₃H₇ F F F H

534 n-C₃H₇ n-C₃H₇ F F F H

535 n-C₄H₉ n-C₃H₇ F F F H

536 n-C₅Hn n-C₃H₇ F F F H

538 n-C₇H₁₅ n-C₃H₇ F F F H

539 π-C₈H₁₇ n-C₃H₇ F F F H No. R 11 R 12 _Ln _L12 _L13 _L p_{hases (T}/oQ

540 CH₂=CH n-C₃H₇ F F F H

541 CH₂=CH-CH₂ n-C₃H₇ F F F H

542 CH₃ n-C₃H₇ H H F F

543 C₂H₅ n-C₃H₇ H H F F

544 n-C₃H₇ n-C₃H₇ H H F F

545 n-C₄H₉ n-C₃H₇ H H F F

546 n-C₅Hn n-C₃H₇ H H F F

547 -CβH-₁₃ n-C₃H₇ H H F F

548 n-C₇H₁₅ n-C₃H₇ H H F F

549 n-C₈H₁₇ n-C₃H₇ H H F F

550 CH₂=CH n-C₃H₇ H H F F

551 CH₂=CH-CH₂ n-C₃H₇ H H F F

552 CH₃ n-C₃H₇ F H F F

553 C₂H_δ n-C₃H₇ F H F F

554 n-C₃H₇ n-C₃H₇ F H F F

555 n-C₄H₉ n-C₃H₇ F H F F

556 n-C₅Hn n-C₃H₇ F H F F

558 n-C₇H₁₅ n-C₃H F H F F

559 n-C₈H₁₇ n-C₃H₇ F H F F

560 CH₂=CH n-C₃H₇ F H F F

561 CH₂=CH-CH₂ n-C₃H₇ F H F F

562 CH₃ n-C₃H₇ F F F F

563 C₂H₅ n-C₃H₇ F F F F

564 n-C₃H₇ n-C₃H₇ F F F F

565 n-C₄H₉ n-C₃H₇ F F F F

566 n-C₅Hn n-C₃H₇ F F F F

567 n-C_δHι₃ n-C₃H₇ F F F F

568 n-C₇H₉ n-C₃H₇ F F F F

569 n-C₈H₁₇ n-C₃H₇ F F F F

570 CH₂=CH n-C₃H₇ F F F F

571 CH₂=CH-CH₂ n-C₃H₇ F F F F

572 CH₃ n-C₅Hn H H H H

573 C₂H₅ n-C₅Hn H H H H

6 n-C₃H₇ n-C₅Hn H H H H C 85°C No. R 11 R 12 11 12 13 14 Phases (T/°C)

574 n-C₄H₉ n-C₅Hn H H H H

575 n-C₅Hn n-C₅Hn H H H H

577 n-C₇H₁₅ n-C₅Hn H H H H

578 n-C₈Hι₇ n-C₅Hn H H H H

579 CH₂=CH n-C₅Hn H H H H

580 CH₂=CH-CH₂ n-C₅Hn H H H H

581 CH₃ n-C₅Hn F H H H

582 C₂Hs π-C₅Hn F H H H

583 n-C₃H₇ n-C₅Hn F H H H

584 n-C₄H₉ n-C₅Hn F H H H

585 n-C₅Hn n-C₅Hn F H H H

587 n-C₇H₁₅ n-C₅Hn F H H H

588 n-C₈H₁₇ n-C₅Hn F H H H

589 CH₂=CH n-C₅Hn F H H H

590 CH₂=CH-CH₂ n-C₅Hn F H H H

591 CH₃ n-C₅Hn H H F H

592 C₂H₅ n-C₅Hn H H F H

593 n-C₃H₇ n-C₅Hn H H F H

594 n-C₄H₉ n-C₅Hn H H F H

595 n-C₅Hn n-C₅Hn H H F H

597 n-C₇H₁₅ n-C₅Hn H H F H

598 n-C₈Hι₇ n-C₅Hn H H F H

599 CH₂=CH n-C₅Hn H H F H

600 CH₂ ⁼CH-CH₂ n-C₅Hn H H F H

601 CH₃ n-C₅Hn F H F H

602 C₂H₅ n-C₅Hn F H F H

603 n-C₃H₇ π-C₅Hn F H F H

604 n-C₄H₉ n-C₅Hn F H F H

605 n-C₅Hn n-C₅Hn F H F H

608 π-C₈H₁₇ n-C₅Hn F H F H No. R 11 R 12 11 12 13 14

Phases (T/°C)

609 CH₂=CH π-C₅Hn F H F H

610 CH₂=CH-CH₂ n-C₅Hn F H F H

611 CH₃ n-C₅Hn F F H H

612 C₂H_δ π-C₅Hn F F H H

613 n-C₃H₇ n-C₅Hn F F H H

614 n-C₄H₉ n-C₅Hn F F H H

615 n-C₅Hn π-C₅Hn F F H H

616 n-C_δHis n-C₅Hn F F H H

618 n-C₈H₁₇ π-C₅Hn F F H H

619 CH₂=CH n-C₅Hn F F H H

620 CH₂=CH-CH₂ n-C₅Hn F F H H

621 CH₃ π-C₅Hn F F F H

622 C₂H_δ π-C₅Hn F F F H

623 n-C₃H₇ n-C₅Hn F F F H

624 n-C₄H₉ n-C₅Hn F F F H

625 n-C₅Hn n-C₅Hn F F F H

627 n-C₇H₁₅ n-C₅Hn F F F H

628 n-C₈H₁₇ n-C₅Hn F F F H

629 CH₂=CH n-C₅Hn F F F H

630 CH₂=CH-CH₂ n-C₅Hn F F F H

631 CH₃ n-C₅Hn H H F F

632 C₂H₅ n-C₅Hn H H F F

633 n-C₃H₇ n-C₅Hn H H F F

634 n-C₄H₉ n-C₅Hn H H F F

635 n-C₅Hn n-CsHn H H F F

637 n-C₇H₁₅ n-C₅Hn H H F F

638 n-C₈H₁₇ n-C₅Hn H H F F

639 CH₂=CH n-C₅Hn H H F F

640 CH₂=CH-CH₂ n-C₅Hn H H F F

641 CH₃ n-C₅Hn F H F F

642 C₂Hs n-C₅Hn F H F F

643 n-C₃H₇ n-C₅Hn F H F F 12

No. ,11 R 11 12 13 14

Phases (T/°C)

644 n-C₄H₉ n-C₅Hn F H F F

645 /7-C5H11 n-C₅Hn F H F F

648 n-C₈H₁₇ n-C₅Hn F H F F

649 CH₂=CH n-C₅Hn F H F F

650 CH₂=CH-CH₂ π-CsHu F H F F

651 CH₃ n-CsHn F F F F

652 C₂H_δ n-C₅Hn F F F F

653 n-C₃H₇ n-C₅Hn F F F F

654 n-C₄H₉ n-C₅Hn F F F F

655 n-C₅Hn n-C₅Hn F F F F

657 n-C₇H₁₅ n-C₅Hn F F F F

656 n-C₈H₁₇ /1-C5H11 F F F F

657 CH₂=CH n-C₅Hn F F F F

658 CH₂=CH-CH₂ n-C₅Hn F F F F

Examples 659 to 836

Analogously to example 1 the following compounds are prepared:

No. R 11 ,12 11 12 13 14

Phases (T/°C)

659 CH₃ n-C₃H₇ H H H H

660 C₂H₅ n-C₃H₇ H H H H

661 n-C₃H₇ n-C₃H₇ H H H H

662 n-C₄H₉ n-C₃H₇ H H H H No. R¹¹ R¹² L¹¹ L¹² _L13 L¹⁴ Phases (T/°C)

663 n-C₅Hn n-C₃H₇ H H H H

665 n-C₇H₁₅ n-C₃H₇ H H H H

666 π-C₈H₁₇ n-C₃H₇ H H H H

667 CH₂=CH n-C₃H₇ H H H H

668 CH₂=CH-CH₂ n-C₃H₇ H H H H

669 CH₃ n-C₃H₇ F H H H

670 C₂H_δ n-C₃H₇ F H H H

671 n-C₃H₇ n-C₃H₇ F H H H

672 n-C₄H₉ n-C₃H₇ F H H H

673 n-C₅Hn n-C₃H₇ F H H H

674 n-C_&H^₃ n-C₃H₇ F H H H

675 n-C₇H₁₅ n-C₃H₇ F H H H

676 n-C₈H₁₇ n-C₃H₇ F H H H

677 CH₂=CH n-C₃H₇ F H H H

678 CH₂=CH-CH₂ n-C₃H₇ F H H H

679 CH₃ n-C₃H₇ H H F H

680 C₂H_δ n-C₃H₇ H H F H

681 n-C₃H₇ n-C₃H₇ H H F H

682 n-C₄H_g n-C₃H₇ H H F H

683 n-C₅Hn n-C₃H₇ H H F H

685 n-C₇H₁₅ π-C₃H₇ H H F H

686 n-C₈Hι₇ n-C₃H₇ H H F H

687 CH₂=CH n-C₃H₇ H H F H

688 CH₂=CH-CH₂ n-C₃H₇ H H F H

689 CH₃ n-C₃H₇ F H F H

690 C₂H₅ n-C₃H₇ F H F H

691 n-C₃H₇ n-C₃H₇ F H F H

692 n-C₄H₉ n-C₃H₇ F H F H

693 n-C₅Hn n-C₃H₇ F H F H

695 n-C₇H₉ n-C₃H₇ F H F H

696 n-C₈H₁₇ n-CsH₇ F H F H

697 CH₂=CH n-C₃H F H F H 11 12 13

No. ,11 R 12 14 Phases (T/°C)

698 CH₂=CH-CH₂ n-C₃H₇ F H F H

699 CH₃ n-C₃H₇ F F H H

700 C₂Hs n-C₃H₇ F F H H

701 n-C₃H₇ n-C₃H₇ F F H H

702 n-C₄H₉ n-C₃H₇ F F H H

703 n-C_δHn n-C₃H₇ F F H H

704 n-C₈Hι₃ n-C₃H₇ F F H H

705 n-C₇H₁₅ n-C₃H₇ F F H H

706 n-C₈H₁₇ n-C₃H₇ F F H H

707 CH₂=CH n-C₃H₇ F F H H

708 CH₂=CH-CH₂ n-C₃H₇ F F H H

709 CH₃ n-C₃H₇ F F F H

710 C₂H_δ n-C₃H₇ F F F H

711 n-C₃H₇ n-C₃H₇ F F F H

712 n-C₄H₉ n-C₃H₇ F F F H

713 n-C₅Hn n-C₃H₇ F F F H

714 -C₈Hι₃ n-C₃H₇ F F F H

715 n-C₇H₁₅ n-C₃H₇ F F F H

716 n-C₈H₁₇ n-C₃H₇ F F F H

717 CH₂=CH n-C₃H₇ F F F H

718 CH₂=CH-CH₂ n-C₃H₇ F F F H

719 CH₃ n-C₃H₇ H H F F

720 C₂H_δ n-C₃H₇ H H F F

721 n-C₃H₇ n-C₃H₇ H H F F

722 n-C₄H₉ n-C₃H₇ H H F F

723 n-C₅Hn n-C₃H₇ H H F F

725 n-C₇H₁₅ n-C₃H₇ H H F F

726 n-C₈H₁₇ n-C₃H₇ H H F F

727 CH₂=CH n-C₃H₇ H H F F

728 CH₂=CH-CH₂ n-C₃H₇ H H F F

729 CH₃ n-C₃H₇ F H F F

731 n-C₃H₇ n-C₃H₇ F H F F

732 n-C₄H₉ n-C₃H₇ F H F F No. R¹¹ R¹ L¹¹ L¹* L^1J L¹⁴ Phases (T/°C)

733 n-C₅Hn n-C₃H₇ F H F F

735 n-C₇H₁₅ n-C₃H₇ F H F F

736 n-C₈H₁₇ n-C₃H₇ F H F F

737 CH₂=CH n-C₃H₇ F H F F

738 CH₂=CH-CH₂ n-C₃H₇ F H F F

739 CH₃ n-C₃H₇ F F F F

740 C₂Hs n-C₃H₇ F F F F

741 n-C₃H₇ n-C₃H₇ F F F F

742 n-C₄H₉ n-C₃H₇ F F F F

743 n-CsHn n-C₃H₇ F F F F

745 n-C₇H₉ n-C₃H₇ F F F F

746 n-C₈H₁₇ n-C₃H₇ F F F F

747 CH₂=CH n-C₃H₇ F F F F

748 CH₂=CH-CH₂ n-C₃H₇ F F F F

749 CH₃ t7-C₅Hn H H H H

750 C₂H_δ n-C₅Hn H H H H

751 n-C₃H₇ n-C₅Hn H H H H C 85°C 1

752 n-C H₉ n-C₅Hn H H H H

753 n-C₅Hn . n-C₅Hn H H H H

755 π-C₇Hι₅ n-C₅Hn H H H H

756 n-C₈H₁₇ n-C₅Hn H H H H

757 CH₂=CH n-C₅Hn H H H H

756 CH₂=CH-CH₂ n-C₅Hn H H H H

757 CH₃ n-C₅Hn F H H H

759 n-C₃H₇ n-C₅Hn F H H H

760 n-C₄H₉ n-C₅Hn F H H H

761 n-C₅Hn n-C₅Hn F H H H

763 n-C₇H₁₅ n-C₅Hn F H H H

764 n-C₈H₁₇ n-C₅Hn F H H H

765 CH₂=CH π-C₅Hn F H H H No. R 11 ,12 11 12 13 14

Phases (T/°C)

766 CH₂=CH-CH₂ n-C₅Hn F H H H

767 CH₃ π-C₅Hn H H F H

769 n-C₃H₇ n-CsHn H H F H

770 n-C₄H_g π-CsHu H H F H

771 n-C₅Hn π-C₅Hn H H F H

774 n-C₈H₁₇ π-C₅Hn H H F H

775 CH₂=CH π-C₅Hn H H F H

776 CH₂ ⁼CH-CH₂ n-C₅Hn H H F H

777 CH₃ n-C₅Hn F H F H

778 C₂H₅ n-CsHn F H F H

779 n-C₃H₇ n-C₅Hn F H F H

780 n-C₄H₉ n-C₅Hn F H F H

781 n-C₅Hn n-CsHn F H F H

784 n-C₈H₁₇ n-C₅Hn F H F H

785 CH₂=CH n-CsHn F H F H

786 CH2=CH-CH2 n-C₅Hn F H F H

787 CH₃ n-C₅Hn F F H H

788 C₂H₅ n-CsHn F F H H

789 n-C₃H₇ n-C₅Hn F F H H

790 n-C₄H₉ n-C₅Hn F F H H

791 n-C₅Hn n-C₅Hn F F H H

793 π-C₇H₁₅ n-CsHn F F H H

794 n-C₈H₁₇ n-CsHn F F H H

795 CH₂=CH n-CsHn F F H H

796 CH₂=CH-CH₂ π-CsHu F F H H

797 CH₃ -CsHn F F F H

798 C₂Hs n-C₅Hn F F F H

799 n-C₃H₇ n-C₅Hn F F F H

800 n-C₄H₉ n-C₅Hn F F F H CO CO r en en o en o en

844 n-C₈H_i7 n-C₃H₇

845 CH₂=CH n-C₃H₇

846 CH₂ ⁼CH-CH₂ n-C₃H₇

No. R R' Phases (T/°C)

857 CH₃ n-C₅Hn

858 C₂H_δ n-CsHn

859 n-C₃H₇ n-C₅Hn

860 n-C₄H₉ n-C₅Hn

861 n-C₅Hn n-CsHn

863 n-C₇Hι₅ n-C₅Hn

864 n-C₈H₁₇ n-C₅Hn

865 CH₂=CH n-C₅Hn

866 CH₂=CH-CH₂ n-C₅Hn

867 CH₃ CH₃

868 C₂Hs C₂Hs

870 n-C₇H₁₅ n-C₇H₁₅

871 n-C₈H₁₇ n-C₈H₁₇

872 CH₂=CH CH₂=CH

873 CH₂=CH-CH₂ CH₂=CH-CH

Examples 874 to 909

Analogously to example 1 the following compounds are prepared:

No. R R' Phases (T/°C)

874 CH₃ n-C₃H₇

875 C₂H₅ n-C₃H₇

876 n-C₃H₇ n-C₃H₇

877 n-C₄H₉ n-C₃H₇ No. R Phases (T/°C)

878 n-C₅Hn n-C₃H₇

880 n-C₇H₁₅ n-C₃H₇

881 n-C₈H₁₇ n-C₃H₇

882 CH₂=CH n-C₃H₇

883 CH₂=CH-CH₂ π-C₃H₇

884 CH₃ n-C₄H₉

885 C₂Hs n-C₄H₉

886 n-C₃H₇ n-C₄H₉

887 n-C₄H₉ n-C₄H₉

888 n-C₅Hn n-C₄H₉

889 n-C_δHι₃ n-C₄H₉

890 n-C₇H₁₅ n-C₄H₉

891 n-C₈Hι₇ n-C H₉

892 CH₂=CH n-C₄H₉

893 CH₂=CH-CH₂ n-C₄H₉

894 CH₃ n-C₅Hn

895 C₂Hs n-C₅Hn

896 n-C₃H₇ n-C₅Hn

897 n-C₄H₉ n-C₅Hn

898 n-C₅Hn n-C₅Hn

899 n-C₈Hι₃ n-C₅Hn

900 n-C₇H₁₅ n-C₅Hn

901 n-C₈Hι₇ n-C₅Hn

902 CH₂=CH n-C₅Hn

903 CH₂=CH-CH₂ n-C₅Hn

904 CH₃ CH₃

905 C₂Hs C₂H_δ

907 n-C₇H₁₅ n-C₇Hιs

908 n-C₈Hι₇ n-C₈H₁₇

909 CH₂=CH CH₂=CH

910 CH₂=CH-CH₂ CH₂=CH Examples 911 to 947

Analogously to example 1 the following compounds are prepared:

No. R' Phases (T/°C)

91 1 CH₃ n-C₃H₇

912 C₂Hs n-C₃H₇

913 n-C₃H₇ n-C₃H₇

914 n-C₄H₉ n-C₃H₇

916 n-C₈Hι₃ n-C₃H₇

917 n-C₇H₁₅ n-C₃H₇

918 n-C₈H₁₇ n-C₃H₇.

919 CH₂=CH n-C₃H₇

920 CH₂=CH-CH₂ n-C₃H₇

921 CH₃ n-C₄H₉

922 C₂H_δ n-C₄H₉

923 n-C₃H₇ n-C₄H₉

924 n-C₄H₉ n-C₄H₉

925 n-C₅Hn n-C₄H₉

927 n-C₇Hι₅ n-C₄H₉

928 n-C₈H₁₇ n-C₄H₉

929 CH₂=CH n-C₄H₉

930 CH₂=CH-CH₂ n-C₄H₉

931 CH₃ n-C₅Hn

933 n-C₃H₇ n-C₅Hn No. R R' Phases (T/°C)

934 n-C₄H₉ n-CsHn

935 n-C₅Hn n-CsHn

937 n-C₇H₁₅ n-CsHn

938 π-C₈Hι₇ n-C₅Hn

939 CH₂=CH n-C₅Hn

940 CH₂=CH-CH₂ n-C₅Hn

941 CH₃ CH₃

944 n-C₇Hι₅ π-C₇H₁₅

945 n-C₈Hι₇ n-C₈H₁₇

946 CH₂=CH CH₂=CH

947 CH₂=CH-CH₂ CH₂=CH-CH

Example 948

Analoguosly to example 1 the compound

is prepared according to the following scheme starting from the compound of example 7.

The compound has a glass transition temperature at -37°C.

Examples 949 to 977

Analoguosly to example 1 the following compounds are prepared

Example No. Formula

- 1.91.

Z6£P00/ς00ZdΑ/13d OtSzH/SOOz OΛV

T_g = -60 °C

Comparative Use-example 1

5% of the chiral agent R-5011 are solved in the achiral liquid crystal mixture H-0 with the composition and properties given in table 1 below.

Table 1 : Composition and Properties of Host Mixture H-0

Compound Concentration Physical Properties

Abbreviation / mass-%

GZU-3A-N 15.0 T(N, I) 56.5 °C

GZU-4A-N 15.0

GZU-40-N 15.0 Δn (20°C, 589 nm) = 0.164

UZU-3A-N 8.0

CUZU-2-N 9.0

CUZU-3-N 9.0

CUZU-4-N 9.0

HP-3N.F 6.0

HP-4N.F 6.0

HP-5N.F 8.0

Σ 100.0

The resulting mixture CM-0 is filled into an electro optical test cell with interdigital electrodes on one substrate side. The electrode width is 10 μm, the distance between adjacent electrodes is 10 μm and the cell gap is also 10 μm. This test cell is evaluated electro-optically between crossed polarisers.

At low temperatures, the filled cell showed the typical texture of a chiral nematic mixture, with an optical transmission between crossed polarisers without applied voltage. On heating, at a temperature of 36°C the mixture was optically isotropic, being dark between the crossed polarisers. This indicated the transition from the chiral nematic phase to the blue phase at 36°C. This temperature is called T-i or Ttrans ■

Up to a temperature of 43°C the cell shows a clear electro optical effect under applied voltage, for example at 38°C, applying a voltage of 46 V leads to a maximum of the optical transition. This temperature is called T₂ and the respective voltage is called V_max or V ₀o. At a temperature of 43°C the voltage needed for a visible electro-optical effect starts to increase strongly, indicating the transition from the blue phase to the isotropic phase at this temperature.

The temperature range (ΔT(BP)), where the mixture can be used electro- optically in the blue phase is identified as ranging from 36°C to 43°C, i.e. as being 7° wide (= T₂ - T = 43°C - 36°C). The results are listed in table 2 below. Further the response times for switching on (τ_on) and for switching off (τ_0ft) are been determined. The response times decrease with increasing temperature above Ti and the temperature at which both response times have fallen below 5 ms each is called T₃. This is the case in this comparative use example at a temperature of 43°C or slightly above. Thus, the range of usable flat behaviour i.e. the usable flat range (ΔT(FR)), which is defined as ΔT(FR) = T₂ - T₃, in case T₂ > T₃ and ΔT(FR) = 0, in case T₂ < T₃, is 0° in this comparative use example.

Comparative Use-example 2

In this comparative use-example 10 % of the compound of the formula

disclosed in EP 03 018 708.2 and used in EP 03 018 707.4 (both still unpublished) are solved together with 5% of the chiral agent R-5011 in the achiral liquid crystal mixture H-0 used in the comparative use-example 1 described just above. The composition of this mixture (CM-1 ) and its properties are given in the table below (table 2).

Table 2: Results

Remarks: Refs. Compound used in EP 03 018 707.4 (see above),

*. upper limit not easy to detect,

# lower limit not easy to detect, n.d.: not determined.

Use-example 1

In this use-example alternatively 10 % of the respective compound of examples 1 to 6 are solved each together with 5% of the chiral agent R-5011 in the achiral liquid crystal mixture H-0 used in the comparative use-example 1 described above. The resultant mixtures H-1-1 , H-2-1 H-3-1 , H-4-1 ,H-5-1 and H-6-1 have the composition and properties shown in tables 2 to 5. In additional experiments 5 % of the compounds of examples 1 to 6, are solved each together with 5% of the chiral agent R- 501 1 in the achiral liquid crystal mixture H-0 leading to mixtures H-1 -2,

H-2-2, H-3-2, H-4-3, H-5-2 and H-6-2, respectively, which are also included with their properties in tables 2 to 5. Last not least the compound of example 4 has been used in a concentration of 7%, respectively of 3%, together wit 5% of R-5011 in the host mixture H-0 leading to mixtures H-4- 2 and H-4-4, respectively, as shown in table 4.

The resulting mixtures H-1-1 to H-6-2 are filled into respective electro optical test cell like that used in the comparative use-example 1 and investigated as described there. The results are listed in tables 2 to 5.

At low temperatures, the cell filled with H-1 showed the typical texture of a chiral nematic mixture, with an optical transmission between crossed polarisers without applied voltage. On heating, at a temperature between -10.0°C and -5.0°C the mixture was optically isotropic, being dark between the crossed polarisers. This indicated the transition from the chiral nematic phase to the blue phase latest at -5.0°C, which is used as the respective reference temperature here. Up to a temperature of 13.0°C, the cell showed a clear electro optical effect under applied voltage.

The temperature range (ΔT(BP)), where the mixture can be used electro- optically in the blue phase was identified as ranging from -5.0°C to 13°C, i.e. as being 18.0° wide (= T₂ - Ti = 13.0°C - -5.0°C). This is significantly larger than the respective range of 7.0°, being found in the chiral reference mixture CM-0 with only 5% of R-5011 added to mixture H-0 and at the same time the phase range of the blue phase is shifted significantly closer to ambient temperature, which facilitates practical handling. And, at the same time, the operation voltage is reduced.

Further, again the response times for switching on (τ_on) and for switching off (τ_0ff) have been determined. The response times decrease with increasing temperature above Ti and the temperature at which both response times have fallen below 5 ms each (T₃) is above 13°C here, however. Thus, ΔT(FR) is ΔT(FR) = 0°(= T₂ - T₃, = 13°C - 13°C) in this use example, just as in comparative use examples 1-0 and 1-1. However the width of the blue phase is 18° wide here, which is more than twice the width of comparative use-example 1-0 and still 64% wider than that of the comparative use-example 1-1. For use examples 1-2a to 1 -6b comparable results are obtained, as e.g. included in tables 2 and 3.

Table 3: Results

Remarks: Refs. Compound used in EP 03 018 707.4 (see above),

*. upper limit not easy to detect,

# lower limit not easy to detect, n.d. not determined.

Table 4: Results

Remarks: Refs. Compound used in EP 03 018 707.4 (see above), upper limit not easy to detect, lower limit not easy to detect, n.d.: not determined. Use-example 2

In this use-example 10 % of the compound of example 1 have been solved together with 5 % of the chiral agent R-5011 in the achiral liquid crystal mixture A-0 with the composition given in the following table.

Table 6: Composition of Host Mixture A-0

Compound Concentration

Abbreviation / mass-%

AUUQU-3-N 11.76

CUZU-3-N 10.59

CUZU-4-N 10.59

HP-3N.F 9.41

AUUQU-3-OT 11.77

AUUQU-3-F 10.59

AUUQU-3-T 9.41

AUUQP-3-T 5.88

PUZU-2-F 10.59

PUZU-5-F 9.41

Σ 100.00

The results are shown in table 7 below.

Table 7: Results

Remarks: Refs. Compound used in EP 03 018 707.4 (see above),

*. upper limit not easy to detect,

# lower limit not easy to detect, n.d.: not determined.

Use-example 3

In this use-example various amounts 5 % of each the compound of example 1 and of the chiral agent R-5011 have been solved together in the achiral liquid crystal mixture B-0 with the composition given in following table.

Table 8: Composition of Host Mixture B-0

Compound Concentration

Abbreviation / mass-%

AUUQU-3-N 12.0

AUZU-3-N 12.0

AUZU-5-N 12.0

GZU-2-F 9.0

UZU-2-F 9.0

AUUQU-3-OT 12.0

AUUQU-3-F 8.0

AUUQU-3-T 8.0

PUZU-2-F 6.0

PUZU-5-F 12.0

Σ 100.0

The results are included for comparison in table 6 above.

Use-example 4

In this use-example various amounts each of the compound of example 1 and of the chiral agent R-5011 have been solved together in the achiral liquid crystal mixture C-0 with the composition given in following table. Table 9: Composition of Host Mixture C-0

Compound Concentration

Abbreviation / mass-%

AUUQU-3-N 12.0

AUZU-3-N 12.0

AUZU-5-N 12.0

GZU-2-F 9.0

UZU-2-F 9.0

AUUQU-3-OT 12.0

AUUQU-3-F 8.0

AUUQU-3-T 8.0

PUZU-2-F 6.0

PUZU-5-F 12.0

Σ 100.0

The results of the final mixtures C-1 to C-6 are shown in tables 10 and 11 below.

Table 10: Results

Remarks: Refs. Compound used in EP 03 018 707.4 (see above), upper limit not easy to detect, # lower limit not easy to detect, n.d. not determined.

Use-example 5

In this use-example 5 % of the compound of example 1 have been solved together with 9 % of the pentyl homolog of the chiral agent R-5011 in the achiral liquid crystal mixture C-0 used in use-example 4 above

The results of the final mixture C-7 are shown in table 11 below. Table 11 : Results

Remarks: Refs. Compound used in EP 03 018 707.4 (see above),

*. upper limit not easy to detect,

# lower limit not easy to detect, n.d.: not determined.

Use-example 6

In this use-example 5% of the compound of example 1 and 9% of the chiral agent R-5011 have been solved together in the achiral liquid crystal mixture D-0 with the composition and properties given in following table. Table 12: Composition of Host Mixture D-0

Compound Concentration

Abbreviation / mass-%

AUUQGU-3-F 9.0

AUUQU-2-N 8.0

AUUQU-3-N 9.0

AUUQU-3-OT 10.0

AUUQU-3-T 10.0

AUUQU-3-F 9.0

CUZU-2-N 7.0

CUZU-3-N . 7.0

HP-3N.F 8.0

PUZU-2-F 5.0

PUZU-5-F 9.0

UZU-5-F 9.0

Σ 100.0

The results of the final mixture D-1 are shown in table 11 above.

Use-example 7

In this use-example a nematic liquid crystal mixture (called E) has been prepared, which contains 10 % of the compound of example 3, and evaluated for its physical properties, as given in the following table. Table 13: Composition and Properties of Mixture E

Compound Concentration Physical Properties

Abbreviation / mass-%

Cpd. Ex. 3 10.0 T(N, I) 58.6 °C

PCH-5F.F 9.0

PCH-6F.F 7.2 Δn (20°C, 589 nm) = 0.085

PCH-7F.F 5.4

CCP-20CF3 7.2 Δε(20°C) 5.2

CCP-30CF3 10.8

CCP-40CF3 6.3

CCP-50CF3 9.9

ECCP-30CF3 4.5

ECCP-50CF3 4.5

BCH-3F.F 10.8

BCH-5F.F 9.0

CBC-33F 1.8

CBC-53F 1.8

CBC-55F 1.8

Σ 100.0

Claims

Claims

Mesogenic compound, characterized in that it comprises at least one mesogenic group and at least one discotic-like group.

Compound according to claim 1 , characterized in that the discotic-like group is preferably a phenyl ring, which is bearing for alkoxy groups or modified alkoxy groups in positions 1 , 2, 4 and 5 and at least one mesogenic group in one of the remaining positions 3 and 6, respectively.

Compound according to claim 2, characterized in that the phenyl ring, which is bearing the four alkoxy groups or modified alkoxy groups, is bearing two mesogenic groups.

Compound according to claim 2, characterized in that it the phenyl ring which is bearing the four alkoxy groups or modified alkoxy groups, is bearing a fifth alkoxy group or modified alkoxy group and a mesogenic group.

Compound according to at least one of claims 1 to 3, characterized in that it is bearing two discotic-like groups.

Compound according to at least one of claims 1 to 5, characterized in that it is a compound of formula I

wherein

R¹¹ to R¹⁶ are, independently of each other, H, F, Cl, CN, NCS,

SF₅ , SO₂CF₃ or alkyl, which is straight chain, branched, cyclic or contains a cyclic moiety, preferably has 1 to 20 C-atoms, is unsubstituted, mono- or poly-substituted by F, Cl, or CN, and in which one or more non-adjacent CH₂ groups are optionally replaced, in each case

5 independently from one another, by -0-, -S-, -NH-, -

NR⁰¹-, -SiR⁰¹R⁰²-, -CO-, -COO-, -OCO-, -OCO-0-, -S- CO-, -CO-S-, -CY¹=CY²-, -C≡C- or an aromatic biradical, which optionally may be substituted, preferably by halogen or alkyl and in which one or more

1 o CH groups may be replaced by N atoms, in such a manner that O and/or S atoms are not linked directly to one another, and in which one or more non-adjacent CH groups, when present, may optionally be replaced by N, or, alternatively, one or more of R¹¹ to R¹⁶ are Sa-SG-

15 PG and/or at least one of R¹¹ and R¹² may be

and A , are, indpendently of each

and/or

occurring more than once, also these are in each occurrence independently of each other, an aromatic and/or alicyclic ring, or a group comprising two or more fused aromatic or alicyclic rings,

35 wherein these rings optionally contain one or more hetero atoms selected from N, O and/or S, and are optionally monosubstituted or polysubstituted by R,

R has one of the meanings given for R¹¹,

SG is a spacer group,

PG is a polamerisable group or a reactive group,

Z¹¹ and Z ² are, independently of each other, and in case Z¹¹ and/or Z ² are occurring more than once, also these are in each occurrence independently of each other, -CO-O-, -0-CO-, -S-CO-, -CO-S-, -CO-NR⁰¹-, -NR⁰¹-CO-, -OCH₂-, -CH₂0-, -SCH₂-, -CH₂S-, -CF₂0-, -OCF₂-, -CF₂S-, -SCF₂-, -CH₂CH₂-,

-CF₂CH₂-, -CH₂CF₂-, -CF₂CF₂-, -CH=N-, -N=CH-, -N=N-, -CH=CR⁰¹-, -CR⁰¹=CH-, -CY⁰¹=CY⁰²-, -C≡C-, -(CH₂) ₄-, -CH=CH-CO-0-, -0-CO-CH=CH- or a single bond,

Y⁰¹ and Y⁰² are, independently of each other, F, Cl or CN, and alternatively one of them may be H,

R⁰¹ and R⁰² are, independently of each other, H or alkyl with 1 to 12 C-atoms,

n and m are, independently of each other 1 , 2, 3 or 4 , while

n + m is 1 , 2, 3, 4, 5 or 6.

7. Compound according to at least one of claims 1 to 6, characterized in that it at least one of Z¹¹ and Z¹² is -CF₂-0- or -0-CF₂-.

8. Compound according to at least one of claims 1 to 7, characterized in that it comprises two mesogenic groups

, which are identical to each other.

9. Compound according to at least one of claims 1 to 8, characterized in that R¹³ to R¹⁴ are identical to each other.

10. Medium, characterized in that it comprises a compound according to at least one of claims 1 to 9.

11. Medium according to claim 10, characterized in that it is a mesogenic medium.

12. Medium according to at least one of claims 10 and 11 , characterized in that it is a light modulation medium.

13. Medium according to at least one of claims 10 to 13, characterized in that it has a blue phase.

14. Light modulation element, characterized in that it comprises a medium according to at least one of claims 10 to 13.

15. Use of a compound according to at least one of claims 1 to 9 in a mesogenic medium.

16. Use of a medium according to at least one of claims 10 to 13 in a light modulation element.

17. Electro-optical display, characterized in that it comprises a medium according to at least one of claims 10 to 13.