JP4744809B2 - Chiral compound - Google Patents

Description

  The present invention relates to chiral compounds, liquid crystal media, liquid crystal devices, anisotropic polymers, optics, electro-optics, decoration, security, cosmetics, diagnostics, electricity, electrons, charge transfer, semiconductors, optical recording, electroluminescence, It relates to their use in photoconductors, electrophotography and laser irradiation applications. The invention further relates to liquid crystal media, polymers, optical components, displays and decorative or security markings comprising said chiral compound.

による液晶ホスト混合物におけるキラルなドーパントの濃度ｃに反比例する。比例定数は、キラルなドーパントのらせんねじれ力（ＨＴＰ）である。 Chiral compounds can be used as dopants to induce or enhance helical twisting, for example in liquid crystal mixtures used in liquid crystal displays. The molecular helix pitch p in the first approximation, which is sufficient for most practical applications, is given by equation (1):

Is inversely proportional to the concentration c of the chiral dopant in the liquid crystal host mixture. The proportionality constant is the helical twisting power (HTP) of the chiral dopant.

  For many applications it is desirable to have an LC mixture with a twisted phase. Among these are, for example, phase change displays, guest-hosts, including displays having temperature compensated properties, eg, by appropriate selection of cholesteric compounds of the present invention, for example alone or in combination with other chiral dopants. Displays, passive and active matrix TN and STN displays, such as AMD-TN, ferroelectric and cholesteric displays, such as SSCT (surface stabilized cholesteric texture), PSCT (polymer stabilized cholesteric texture) display or "blue phase" display There is. For these applications, it is advantageous to have available chiral dopants with high HTP to reduce the amount of dopant needed to induce the desired pitch.

  For some applications, it is desirable to have an LC mixture that exhibits a strong helical twist and thus a short pitch length. For example, in a liquid crystal mixture used in selectively reflective cholesteric displays such as SSCT or PSCT, the pitch must be selected such that the maximum wavelength reflected by the cholesteric helix is in the visible range. Another possible application is a polymer film with a chiral liquid crystal phase for optical elements such as cholesteric broadband polarizers or retardation films.

As is apparent from equation (1), a short pitch can be achieved by using a large amount of dopant or using a dopant having a high HTP.
Chiral compounds are disclosed in, for example, Patent Document 1, Patent Document 2, and Patent Document 3.

However, prior art chiral dopants often exhibit low values of HTP, thus requiring large amounts of dopant. This is a disadvantage because chiral dopants can only be used as pure enantiomers and are therefore expensive and difficult to synthesize.
Furthermore, when using large amounts of prior art chiral dopants, these often adversely affect the properties of the liquid crystal host mixture, such as clearing point, dielectric anisotropy Δε, viscosity, drive voltage or switching time.

  Another disadvantage of the prior art chiral compounds is that they often exhibit low solubility in liquid crystal host mixtures, which results in undesired crystallization at low temperatures. To overcome this drawback, typically two or more different chiral dopants must be added to the host mixture. This leads to high costs and requires additional effort for temperature compensation of the mixture, as different dopants must be selected to compensate for these temperature coefficients of twist with each other.

  Therefore, it is easy to synthesize and can be used in small amounts, for example using a constant reflection wavelength, showing improved temperature stability of the cholesteric pitch, and without affecting the properties of the liquid crystal host mixture, There is a significant need for chiral compounds with high HTP that exhibit good solubility in the mixture.

International Publication No. 95/16007 Pamphlet International Publication No. 98/00428 Pamphlet British Patent No. 2 328 207 A

The present invention aims to provide chiral compounds having these properties, but without the disadvantages of the prior art chiral dopants discussed above.
Another object of the present invention is to expand the pool of chiral compounds that can be used as dopants that are useful to professionals.
It has been found that these objectives can be achieved by providing the chiral compounds described below.

式中、
Ｋ^１−４は、互いに独立して、アネレートされた(anellated)ベンゼン、シクロヘキサンまたはシクロヘキセンであり、ここで、１つまたは２つ以上のＣＨ基は、随意に、Ｎにより置換されており、１つまたは２つ以上のＣＨ_２基は、随意に、Ｏおよび／またはＳにより、Ｏおよび／またはＳ原子が互いに直接結合しないように置換されており、 SUMMARY OF THE INVENTION The present invention provides a compound of formula I

Where
K ^1-4 is, independently of each other, anellated benzene, cyclohexane or cyclohexene, wherein one or more CH groups are optionally substituted by N, One or more CH ₂ groups are optionally substituted by O and / or S so that the O and / or S atoms are not directly bonded to each other;

U ^1-4 independently of one another is CH ₂ , O, S, CO, NH or CF ₂ ;
V ^1-4 is independent of each other, provided that O, S and NH have ^one of the meanings of U ^{1 under} the condition that they are not directly adjacent to each other, or represent a single bond,
Z is C, Si, Ge, Sn or Ti;
X ^1-12 are each independently R, P-Sp, or -W ¹ -A ^1- (W ² -A ² ) _m -R;

R, at each occurrence, independently has _{H, F, Cl, Br,} I, CN, NO 2, OH, NCS, SF 5, 1-40 C atoms, which is unsubstituted , F, Cl, Br, I or CN is a linear or branched alkyl mono- or polysubstituted, wherein one or more CH ₂ groups are optionally In some cases, independently of one another, —O—, —S—, —NH—, —NR ⁰ —, —SiR ⁰ R ⁰⁰ —, —CO—, —COO—, —OCO—, —OCO—O—, -S-CO-, -CO-S-, -SO _2- , -CG ¹ = CG ² -or -C≡C- is substituted so that two O or two S atoms are not directly bonded to each other Or indicates P-Sp-
R ⁰ and R ⁰⁰ , independently of one another, are H or alkyl having 1 to 12 C atoms;
G ¹ and G ² are independently of each other H, F, Cl or CN;
P is a polymerizable or reactive group,
Sp is a spacer group or a single bond,

A ¹ and A ^2, in each occurrence, is independently substituted or unsubstituted aromatic ring or alicyclic ring, or two or three or more Kaoru aromatic rings and / or alicyclic ring is fused, a radicals, where these rings may optionally contain one or more hetero atoms selected from N, O and S,
W ¹ and W ² , in each occurrence, independently represent —O—, —S—, —CO—, —COO—, —OCO—, —S—CO—, —CO—S—, —O. _{^{-COO -, - CO-NR 0}} -, - NR 0 -CO -, - OCH 2 -, - CH 2 O -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 - _{, -CF 2 S -, - SCF} 2 -, - CH 2 CH 2 -, - CF 2 CH 2 -, - CH 2 CF 2 -, - CF 2 CF 2 -, - CH = N -, - N = CH -, - N = N -, - CH = CH -, - CH = CR 0 -, - CR 0 = CR 00 -, - CG 1 = CG 2 -, - C≡C -, - CH = CH-COO- , -OCO-CH = CH- or a single bond,
m is independently 0, 1, 2 or 3 in each occurrence,

The invention further comprises an optical, in particular for doping liquid crystal mixtures, comprising one or more chiral compounds of the formula I and optionally one or more additional chiral compounds. Active material or chiral dopant material.
The invention further relates to a liquid crystal mixture comprising at least one compound of the formula I or comprising a chiral dopant material as described above.
The invention further relates to a polymerizable liquid crystal material comprising at least one compound of formula I or comprising a chiral dopant material as described above.

The invention further comprises at least one compound of formula I and at least one polymerizable mesogenic compound, which can be said compound of formula I and / or an additional compound. And a polymerizable liquid crystal mixture.
The present invention further relates to a linear compound obtained by polymerizing a polymerizable compound represented by formula I or a polymerizable liquid crystal mixture containing one or more compounds represented by formula I. Or relates to a crosslinked polymer.

The present invention further comprises polymerizing a polymerizable compound represented by Formula I or a polymerizable liquid crystal mixture comprising one or more compounds represented by Formula I in an aligned state. It relates to an anisotropic polymer having a twisted structure, preferably an anisotropic polymer film obtained from a layer of said polymerizable material.
The invention further relates to the use of the compounds of the formula I as chiral dopants in liquid crystal materials or as optical, electrooptical, electrical, semiconductive or electronic components or devices.

  The invention further relates to an electro-optical display, liquid crystal display, optical film, polarizing plate, compensator, beam splitter of a compound of formula I, a liquid crystal mixture, a polymer or a polymer film described herein. , Reflective film, alignment layer, color filter, holographic element, high temperature stamping foil, colored pattern, eg decoration or security marking for consumer goods or securities, LC pigments, adhesives, anisotropic mechanical properties As a chiral dopant in synthetic resins, cosmetics, diagnostics, nonlinear optics, optical information storage, as an electronic device as an element of an integrated circuit, such as a field effect transistor (FET), as a thin film transistor in flat panel display applications, or as a radio wave system Recognition (RFID Batteries in tags or in semiconductive elements for organic light emitting diode (OLED) applications, electroluminescent displays or LCD backlights, for photovoltaic or sensor devices, in laser irradiation applications and devices The present invention relates to the use as an electrode or an electrolyte material in US Pat.

  The invention further relates to a liquid crystal device comprising a compound of formula I as described herein, a liquid crystal mixture, a polymer or a polymer film.

Definition of terms The terms “liquid crystal or mesogenic material” or “liquid crystal or mesogenic compound” refer to one or more rod-type, lath-type or disc-type mesogenic groups, ie the ability to induce LC phase behavior. It means a material or compound containing a group having. Compounds or materials that contain mesogenic groups need not necessarily exhibit LC phases themselves. It is also possible that they exhibit LC phase behavior only in mixtures with other compounds or when polymerizing mesogenic compounds or materials or mixtures thereof.

The terms “polymerizable” and “reactive” refer to compounds or groups that can participate in polymerization reactions, such as radical or ionic chain polymerization, polyaddition or polycondensation, and polymer main reactions in, for example, polymerization-like reactions. Contains reactive compounds or reactive groups that can be grafted to the chain by condensation or addition.
The term “film” includes a self-supporting, or stand-alone film that exhibits some significant mechanical stability and flexibility, as well as a coating or layer on a support substrate or between two substrates.

The term “director” means the preferred orientation direction of the mesogens in the liquid crystal material, the long axis of the molecule in the case of calamitic compounds or the short axis of the molecules in the case of discotic compounds.
The term “planar structure” or “planar orientation” means a layer of optically anisotropic material whose optic axis is approximately parallel to the plane of the layer.

  The term “helically twisted structure” means that the mesogens are oriented with their primary molecular axes in the preferred direction within the molecular sublayer, and the aforementioned preferred orientation directions in the various sublayers are By means of a film comprising one or more layers of liquid crystal material, twisted around at an angle φ. The term “helically twisted structure having a planar orientation” is a film having the aforementioned spirally twisted structure, wherein the helical axis is substantially perpendicular to the film plane, ie with respect to the film normal. It means the film which is substantially parallel.

  The present invention relates to both enantiomeric forms of the chiral compounds of the formula I. Either the R and S forms of the enantiomers of the compounds of formula I can be used as optically active materials or chiral dopants to induce, for example, helical twists in liquid crystal materials.

Chiral compounds of the formula I have several advantages.
These show high HTP with low temperature dependence,
-These show high solubility in the liquid crystal mixture,
-These can exhibit a liquid crystalline phase,
They exhibit high thermal and chemical stability,

When using these as chiral dopants in a liquid crystal mixture, high twists (= low pitch) can be obtained with higher amounts of dopants due to their high solubility,
When a large amount of dopant is required, the adverse effect on the liquid crystal phase of the host mixture is small due to the wide liquid crystal phase of the dopant of the present invention.
-Due to its high HTP, a smaller amount of the dopant of the invention is necessary to achieve a high pitch, so that the adverse effect on the liquid crystal properties of the mixture is small,

Both the R and S enantiomers of the chiral compounds of formula I are easy to produce with a high degree of enantiomeric purity,
These are commercially available and can be easily synthesized from inexpensive chiral starting materials,
These can be easily modified for specific applications,
The usefulness of both helices is a significant advantage for use in security applications, for example, to allow the production of chiral films or coatings that reflect a single rotationally circularly polarized light.

  The chiral compounds of the formula I can be mesogenic or even liquid crystalline. That is, they can elicit or enhance mesophase behavior, for example in a mixture with other compounds, or even themselves exhibit one or more mesophases. It is also possible for the compounds of the present invention to exhibit mesophase behavior only when (co) polymerized, in a mixture with other compounds or in the case of polymerizable compounds. The mesogenic chiral compounds of the invention are particularly preferred.

The compounds of formula I are for use in mixtures for LCD applications, in particular for applications using LC mixtures in nematic or isotropic phases where high birefringence, high polarity and high dielectric anisotropy are required. Especially suitable.
Furthermore, the compounds of the formula I can be used as reflective mesogens, for use as optical films in LCDs, in particular as optical retardation or compensation films, alignment layers, color filters or polarizing plates. A polymer or polymer film can be produced.

  Another field for using polymerizable compounds of formula I is as semiconductors or charge transfer materials. These materials can be used in electronic devices such as field effect transistors (FETs) as elements of integrated circuits, as thin film transistors in flat panel display applications, or for radio frequency identification (RFID) tags, or organic light emitting diodes (OLEDs). It can be used for photovoltaic or sensor devices in semi-conductive elements, electroluminescent displays or LCD backlights for applications.

  The compounds of formula I can also be copolymerized via the group P with other polymerizable mesogenic monomers and other compounds of formula I to induce or enhance LC phase behavior. It is also possible to do.

  The LCD of the present invention is, for example, a conventional LCD, in particular a DAP (orientation phase deformation) or VA (vertical alignment) mode, for example an ECB (electrically controlled birefringence), CSH (color super homeotropic) LCD VA or VAC (vertical alignment cholesteric) display, MVA (multi-domain vertical alignment) or PVA (patterned vertical alignment) display, bend mode display or hybrid type display, eg OCB (optically compensated) Bending cell or optically compensated birefringence, R-OCB (reflective OCB), HAN (hybrid alignment nematic) or pi-cell (π cell) display, TN (twisted nematic), HTN (highly twisted) Nematic) or STN ( Super twisted nematic) display, AMD-TN (active matrix driven TN) display, IPS (in-plane switching) mode display, also known as “super TFT” display, or for example DE 102 172 73 and WO 02 / A display using liquid crystals in the isotropic state, also referred to in 93244 A1, hereinafter referred to briefly as “isotropic mode display”, and also phase change, guest-host, ferroelectric, flexoelectric or cholesteric A display, for example a display based on SSCT (surface stabilized cholesteric structure), PSCT (polymer stabilized cholesteric structure) or “blue phase”.

  Particularly preferred are TN, STN, AMD-TN, cholesteric, ferroelectric and isotropic mode displays.

−Ｋ^１、Ｋ^２、Ｋ^３およびＫ^４がアネレートされたシクロヘキサンである、式Ｉ２で表される化合物。

Formula I specifically includes the following compounds:
-K ^{1, K} 2, ^{K 3} and ^{K 4} is benzene, the compound of formula I1.

-K ^{1, K} 2, ^{K 3} and ^{K 4} is cyclohexane which is Anereto, compounds of the formula I2.

で表される化合物。
−Ｋ^１およびＫ^２がベンゼンであり、Ｋ^３およびＫ^４がアネレートされたシクロヘキサンもしくはシクロヘキセンであるか、またはＫ^３およびＫ^４がベンゼンであり、Ｋ^１およびＫ^２がアネレートされたシクロヘキセンもしくはシクロヘキサジエンである化合物。 A compound wherein K ¹ , K ² , K ³ and K ⁴ are annelated cyclohexene, for example

A compound represented by
-K ¹ and K ² are benzene and K ³ and K ⁴ are annelated cyclohexane or cyclohexene, or K ³ and K ⁴ are benzene and K ¹ and K ² are annelated cyclohexene or cyclo A compound that is hexadiene.

One or more of —K ^1-4 is benzene, annelated cyclohexane or cyclohexene as shown in formulas I1-I4, but one or more CH groups are further substituted by N A compound wherein one or more CH ₂ groups are substituted by O and / or S so that the O and / or S atoms are not directly bonded to one another, for example

で表される化合物。

A compound represented by

  Particularly preferred are compounds of the formulas I1 to I8, most preferred are compounds of the formulas I1, I2, I7 and I8.

More preferred is
The compound is optically active,
The compound has an enantiomeric purity of at least 90%,
-Z is Si or ^Ti, if each of the ^{U 1 -V 1, U 2 -V} 2, U 3 -V 3 and ^U 4 -V ⁴ is ^O, at least one of K 1 ~K ⁴ One is different from unsubstituted phenylene and / or at least one of X ^{1 to} X ¹² is different from H,
-Z is ^C, and when each of ^{U 1 -V 1, U 2 -V} 2, U 3 -V 3 and ^U 4 -V ⁴ is O, is O-CH ₂ or _C 2 _{H 4} is At least one of K ¹ -K ⁴ is different from unsubstituted phenylene and / or at least one of X ¹ -X ¹² is different from H;

-V ¹ and ^{V 2} is a single bond, ^{V 3} and ^{V 4} is not a single bond,
-V ¹ and ^{V 2} is not a single bond, ^{V 3} and ^{V 4} represents a single bond,
-V ^{1, V} 2, ^{V 3} and ^{V 4} represents a single bond,
-V ^{1, V} 2, ^{V 3} and ^{V 4} is not a single bond,
-U ^1-4 is selected from CH ₂ , O and CO,
-V ^1-4 is selected from _CH 2, O and CO as well as a single bond,

-U ¹ = U ² = U ³ = U ⁴
-U ¹ = U ² ≠ U ³ = U ⁴
−V ¹ = V ² = V ³ = V ⁴
−V ¹ = V ² ≠ V ³ = V ⁴ ,
-Z is a carbon atom,
−K ¹ = K ² = K ³ = K ⁴

-W ¹ is a single bond,
At least one of -X ^1-12 is different from H;
-X ¹ , X ² , X ⁴ , X ⁷ , X ⁸ and X ¹⁰ are different from H and X ³ , X ⁵ , X ⁶ , X ⁹ , X ¹¹ and X ¹² are H.
-X ¹ , X ² , X ⁷ and X ⁸ are different from H and X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁹ , X ¹⁰ , X ¹¹ and X ¹² are H.
One or more of -X ^1-12 represents R different from H;

—R or X ^1-12 has F, Cl, Br, I, CN, OH, NO ₂ , NCS, SF ₅ or 1 to 40 C atoms and is unsubstituted or F, Cl , Br, I or CN, wherein one or more CH ₂ groups are optionally independently of one another in each case —O—, —S—. , —NH—, —NR ⁰ —, —SiR ⁰ R ⁰⁰ —, —CO—, —COO—, —OCO—, —OCO—O—, —S—CO—, —CO—S—, —SO ₂ Selected from linear or branched alkyl, wherein the oxygen atoms are substituted so that they are not directly bonded to each other by-, -CG ¹ = CG ² -or -C≡C-

—R or X ^1-12 is F, Cl, CN, NO ₂ , linear or branched alkyl having 1 to 20 C atoms, alkenyl, alkynyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyl Selected from oxy, thioether, alkylsulfonyl, alkylsulfanyl, alkylsulfanylcarbonyl, aminoalkyl or aminodialkyl, wherein one or more H atoms are optionally substituted by F or Cl Very preferably selected from F, Cl, CN and alkyl or alkoxy having 1 to 12 C atoms,

At least one, preferably one or two of -X ^1-12 represents or contains a polymerizable group;
At least one, preferably one or two groups R is P-Sp-
At least one, preferably 2, 4 or 6 of -X ^1-12 is -W ¹ -A ^1- (W ² -A ² ) _m -R;
--A ^1- (W ² -A ² ) _m -comprises one, two or three five- or six-membered rings,
--A ^1- (W ² -A ² ) _m -is bicyclohexyl, biphenyl, phenylcyclohexyl, cyclohexylphenyl or biphenylcyclohexyl, wherein the phenyl ring is optionally one or two F atoms. Is replaced with

-W ¹ and ^W 2 are, -COO -, - OCO -, - CH 2 -CH 2 - and is selected from a single bond,
At least one of —W ¹ and W ² is —CF ₂ O—, —OCF ₂ —, —CF ₂ CF ₂ — or —CF═CF—, and the other is —COO—, —OCO—, — CH ₂ —CH ₂ — or a single bond,
At least one of -W ¹ and W ² is -C≡C-;
-M is 0 or 1;
A compound represented by Formula I.

A ¹ and A ^2, independently of one another, an aromatic ring or alicyclic ring, preferably 5,6 or 7 membered ring, or two or three or more, preferably two or three Kaoru aromatic Rings and / or alicyclic rings are fused groups, wherein these rings optionally contain one or more heteroatoms selected from N, O and S, optionally Monosubstituted or polysubstituted by L, where L has one of the meanings of R.

Preferred groups A ¹ and A ² are, for example, furan, pyrrole, thiophene, oxazole, thiazole, thiadiazole, imidazole, phenylene, cyclohexylene, cyclohexenylene, pyran, di or tetrahydropyran, dioxane, dithiane, pyridine, pyrimidine, pyrazine. , Azulene, indane, naphthalene, tetra- or decahydronaphthalene, anthracene and phenanthrene.

Most preferably, A ¹ and A ² are further 1,4-phenylene in which one or more CH groups can be substituted by N, furthermore one or two non-adjacent CH 1,4-cyclohexylene, 1,3-dioxolane-4,5-diyl, 1,4-cyclohexenylene, 1,4-bicyclo- ( ₂ groups can be substituted by O and / or S 2,2,2) -octylene, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6- It is selected from diyl and all these groups can be unsubstituted or mono- or polysubstituted with L.

Particularly preferred groups A ¹ and A ² are 1,4-phenylene, trans-1,4-cyclohexylene, 2,6-dioxane-, optionally substituted by L at the 2, 3, 5 and / or 6 position. 1,4-diyl, 3,5-dioxane-1,4-diyl, tetrahydropyran-2,5-diyl and tetrahydropyran-3,6-diyl.

L is preferably, F, Cl, Br, I , CN, OH, NO 2, NCS, SF 5 or straight-chain or branched alkyl having 1 to 8 C atoms, alkenyl, alkynyl, alkoxy, Alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, thioether, alkylsulfonyl, alkylsulfanyl, alkylsulfanylcarbonyl, aminoalkyl or aminodialkyl, wherein one or more H atoms are optionally F or Cl Is replaced by

L is very preferably F, Cl, CN, OH, NO ₂ , CH ₃ , C ₂ H ₅ , OCH ₃ , OC ₂ H ₅ , OC ₃ H ₇ , COCH ₃ , COC ₂ H ₅ , COOCH ₃ , COOC ₂ H ₅ , SO ₂ CF ₃ , CF ₃ , OCF ₃ , OCHF ₂ or OC ₂ F ₅ , especially F, Cl, CN, CH ₃ , C ₂ H ₅ , OCH ₃ , COCH ₃ or OCF ₃ , most preferred Is F, Cl, CH ₃ , OCH ₃ or COCH ₃ .

Preferably, the group -A ^1- (W ² -A ² ) _m- contains only the monocyclic groups A ¹ and A ² . Most preferably, the group -A ^1- (W ² -A ² ) _m -is a group having one or two 5- or 6-membered rings.

Particularly preferred groups -A ^1- (W ² -A ² ) _m -R are shown in Table 1 below.
Table 1

式中、Ｒは、式Ｉの意味の１つを有し、Ｙ^１−１３は、互いに独立して、前に示したＬの意味の１つを有し、Ｗ、Ｗ^１およびＷ^２は、互いに独立して、式ＩにおけるＷ^１の意味の１つを有する。

In which R has one of the meanings of formula I, Y ^1-13 independently of one another has one of the meanings of L given previously, W, W ¹ and W ² are , Independently of one another, has ^one of the meanings of W ¹ in formula I.

  R in these groups is preferably linear alkyl or alkoxy having 1 to 12, preferably 1 to 8 C atoms or alkenyl having 2 to 12, preferably 2 to 7 C atoms. Or P-Sp.

Y ^1-13 in these groups is preferably H, F, Cl, linear or branched alkyl having 1 to 8, preferably 1 to 4 C atoms, alkenyl, alkynyl, alkoxy, Denotes alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, sulfanylalkyl or sulfonylalkyl, wherein one or more H atoms are optionally substituted by F or Cl, in particular CF ₃ , OCF ₃ , SO ₂ CF ₃ or SCF ₃ .

W, W ¹ and W ² in these groups are preferably a single bond, CH═CH, C≡C, OCF ₂ , CF ₂ O, CH ₂ CH ₂ , CF ₂ CH ₂ , CH ₂ CF ₂ , CF _{2 represents} CF ₂ , COO, OOC, CH ₂ O or OCH ₂ .

Particularly preferred are the following compounds:

式中、Ｕ^１−４、Ｖ^１−４、Ｘ^１−１２およびＺは、式Ｉの意味または本明細書中に示す好ましい意味の１つを有する。

In which U ^1-4 , V ^1-4 , X ^1-12 and Z have the meaning of formula I or one of the preferred meanings given herein.

Particularly preferred are compounds of the formulas Ia to If, wherein X ¹ , X ² , X ³ , X ⁷ , X ⁸ and X ¹⁰ are selected from the groups shown in Table 1.
Further preferred are compounds of the formulas Ia to If, wherein Z is a C atom.

は、好ましくは、

から選択される。 In formulas Ia and Ib

Is preferably

Selected from.

は、好ましくは、

から選択される。 In formulas Ic and Id

Is preferably

Selected from.

は、好ましくは、

から選択される。 In formulas Ie and If

Is preferably

Selected from.

Where one of R, L or X ^1-12 is an alkyl or alkoxy group, ie where the terminal CH ₂ group is substituted by —O—, this is linear or branched Can be. This is preferably straight-chain and has 2, 3, 4, 5, 6, 7 or 8 carbon atoms and is therefore preferably, for example, ethyl, propyl, butyl, pentyl, hexyl, Heptyl, octyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy or octoxy, and methyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, nonoxy, deoxy, undecoxy, dodecoxy, tridecoxy or tetradecoxy.

Oxaalkyl, ie one in which one CH ₂ group is substituted by —O— is preferably, for example, linear 2-oxapropyl (= methoxymethyl), 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.

When one of R, L or X ^1-12 is an alkyl group in which one or more CH ₂ groups are substituted by —CH═CH—, this is a straight-chain or branched Can be. It is preferably straight-chain and has 2 to 10 C atoms and is therefore 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.

Particularly preferred alkenyl _groups, C _{2 ~C} 7 -1E- _alkenyl, C _{4 ~C} 7 -3E- _alkenyl, C _{5 ~C} 7 -4- _alkenyl, C _{6 ~C} 7 -5- alkenyl and _C 7 -6 - alkenyl, in particular _C 2 _{-C 7-1E-alkenyl,} C ₄ -C 7 -3E-alkenyl and _C 5 _-C 7-4-alkenyl. Examples of particularly preferred alkenyl groups are vinyl, 1E-propenyl, 1E-butenyl, 1E-pentenyl, 1E-hexenyl, 1E-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.

When one of R, L or X ^1-12 is an alkyl group, wherein one CH ₂ group is substituted by —O— and one is substituted by —CO— The groups are preferably adjacent. Accordingly, these groups together form a carbonyloxy group —CO—O— or an oxycarbonyl group —O—CO—. Preferably, this group is straight-chain and has 2 to 6 C atoms.

  Therefore, this is preferably acetyloxy, propionyloxy, butyryloxy, pentanoyloxy, hexanoyloxy, acetyloxymethyl, propionyloxymethyl, butyryloxymethyl, pentanoyloxymethyl, 2-acetyloxyethyl, 2- Propionyloxyethyl, 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- Propoxycarbonyl) ethyl, 3- (methoxycarbonyl) propyl, 3- (ethoxycarbonyl) propyl, 4- (methoxycarbonyl) - butyl.

Where one of R, L or X ^1-12 is an alkyl group, where two or more CH ₂ groups are substituted by —O— and / or —COO— Can be linear or branched. This is preferably straight-chain and has 3 to 12 C atoms. This is therefore 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- (me Xoxycarbonyl) -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.

When one of R, L or X ^1-12 is an alkyl or alkenyl group that is monosubstituted by CN or CF ₃ , it is preferably linear. Substitution with CN or CF ₃ can be at any desired position.

If one of R, L or X ^1-12 is an alkyl or alkenyl group that is at least monosubstituted by halogen, it is preferably linear. Halogen is preferably F or Cl, and is preferably F in the case of polysubstitution. The resulting group also contains a perfluorinated group. In the case of monosubstitution, the F or Cl substituent can be at any desired position, but is preferably at the ω position. Examples of particularly preferred linear groups with a terminal F substituent are fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl and 7-fluoroheptyl. . However, other positions of F are not excluded.
Halogen is preferably F or Cl.

R, L or X ^1-12 can be a polar or nonpolar group. In the case of a polar group, which, CN, SF _{5, ^{halogen, OCH 3, SCN, COR 1}} , COOR 1 or mono having 1 to 4 C atoms, alkyl or alkoxy groups are oligo- or polyfluorinated Is selected from. R ¹ is optionally fluorinated alkyl having 1 to 4, preferably 1 to 3 C atoms. Particularly preferred polar groups are F, Cl, CN, OCH ₃ , COCH ₃ , COC ₂ H ₅ , COOCH ₃ , COOC ₂ H ₅ , CF ₃ , CHF ₂ , CH ₂ F, OCF ₃ , OCHF ₂ , OCH ₂ F , C ₂ F ₅ and OC ₂ F ₅ , in particular F, Cl, CN, CF ₃ , OCHF ₂ and OCF ₃ . In the case of nonpolar groups, this is preferably alkyl with up to 15 C atoms or alkoxy with 2 to 15 C atoms.

式中、
Ｑ^１は、１〜９個のＣ原子を有するアルキレンもしくはアルキレンオキシ基または単結合であり、
Ｑ^２は、非置換であるか、Ｆ、Ｃｌ、ＢｒまたはＣＮにより単置換または多置換されていることができる、１〜１０個のＣ原子を有するアルキルまたはアルコキシ基であり、また、１つまたは２つ以上の隣接していないＣＨ_２基が、各々の場合において、互いに独立して、−Ｃ≡Ｃ−、−Ｏ−、−Ｓ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯ−Ｏ−、−Ｓ−ＣＯ−または−ＣＯ−Ｓ−により、酸素原子が互いに直接結合しないように置換されていることも可能であり、
Ｑ^３は、Ｆ、Ｃｌ、Ｂｒ、ＣＮまたは、Ｑ^２について定義したがＱ^２とは異なる、アルキルもしくはアルコキシ基である、
から選択される。 R, L or X ^1-12 can be an achiral or a chiral group. When it is a chiral group, it is preferably of formula III:

Where
Q ¹ is an alkylene or alkyleneoxy group having 1 to 9 C atoms or a single bond,
Q ² is an alkyl or alkoxy group having 1 to 10 C atoms that can be unsubstituted, mono- or polysubstituted by F, Cl, Br, or CN, and Or two or more non-adjacent CH ₂ groups, in each case, independently of one another, —C≡C—, —O—, —S—, —NH—, —N (CH ₃ ) —, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO- or -CO-S- may be substituted so that oxygen atoms are not directly bonded to each other,
Q ³ are, F, Cl, Br, CN or has been defined for ^{Q 2} is different from the ^{Q 2,} an alkyl or alkoxy group,
Selected from.

When Q ^{1 in} formula III is an alkyleneoxy group, the O atom is preferably adjacent to the chiral C atom.
Preferred chiral groups of formula III are 2-alkyl, 2-alkoxy, 2-methylalkyl, 2-methylalkoxy, 2-fluoroalkyl, 2-fluoroalkoxy, 2- (2-ethyne) -alkyl, 2- (2-ethyne) -alkoxy, 1,1,1-trifluoro-2-alkyl and 1,1,1-trifluoro-2-alkoxy.

  Particularly preferred chiral groups are, for example, 2-butyl (= 1-methylpropyl), 2-methylbutyl, 2-methylpentyl, 3-methylpentyl, 2-ethylhexyl, 2-propylpentyl, especially 2-methylbutyl, 2-methyl 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-methylbuty Ryloxy, 3-methylvaleroyloxy, 4-methylhexanoyloxy, 2 Chloropropionyloxy, 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-fluoro Decyloxy, 1,1,1-trifluoro-2-octyloxy, 1,1,1-trifluoro-2-octyl, 2-fluoromethyloctyloxy. Highly preferred are 2-hexyl, 2-octyl, 2-octyloxy, 1,1,1-trifluoro-2-hexyl, 1,1,1-trifluoro-2-octyl and 1,1,1- Trifluoro-2-octyloxy.

Furthermore, compounds containing an achiral branched group R, L or X ^1-12 may sometimes be important, for example, due to a reduced tendency to crystallization. This type of branched group generally does not contain more than one chain branch. Preferred achiral branched groups are isopropyl, isobutyl (= methylpropyl), isopentyl (= 3-methylbutyl), isopropoxy, 2-methylpropoxy and 3-methylbutoxy.

から選択されており、Ｗ^１は、Ｈ、Ｃｌ、ＣＮ、フェニルまたは１〜５個のＣ原子を有するアルキル、特にＨ、ＣｌまたはＣＨ_３であり、Ｗ^２およびＷ^３は、互いに独立して、Ｈまたは１〜５個のＣ原子を有するアルキル、特にメチル、エチルまたはｎ−プロピルであり、Ｗ^４、Ｗ^５およびＷ^６は、互いに独立して、Ｃｌ、１〜５個のＣ原子を有するオキサアルキルまたはオキサカルボニルアルキルであり、Ｐｈｅは、１，４−フェニレンであり、ｋ_１およびｋ_２は、互いに独立して０または１である。 The polymerizable or reactive group P is preferably

W ¹ is H, Cl, CN, phenyl or alkyl having 1 to 5 C atoms, in particular H, Cl or CH ₃ , W ² and W ³ are independently of each other , H or alkyl having 1 to 5 C atoms, in particular methyl, ethyl or n-propyl, W ⁴ , W ⁵ and W ⁶ are independently of each other Cl, 1 to 5 C atoms Having oxaalkyl or oxacarbonylalkyl, Phe is 1,4-phenylene, and k ₁ and k ₂ are each independently 0 or 1.

  Particularly preferably P is a vinyl group, acrylate group, methacrylate group, oxetane group or epoxy group, particularly preferably an acrylate or methacrylate group.

For the spacer group Sp, all groups known for this purpose to those skilled in the art can be used. The spacer group Sp is preferably represented by the formula Sp′-X, such that P-Sp— is P-Sp′-X—, where
Sp ′ is an alkylene having up to 20 C atoms, which can be unsubstituted or mono- or polysubstituted by F, Cl, Br, I or CN, one or more Each non-adjacent CH ₂ group is independently from each other in each case —O—, —S—, —NH—, —NR ⁰ —, —SiR ⁰ R ⁰⁰ —, —CO—, —COO—. , -OCO-, -OCO-O-, -S-CO-, -CO-S-, -CH = CH- or -C≡C-, so that O and / or S atoms are not directly bonded to each other Is also possible,
X is —O—, —S—, —CO—, —COO—, —OCO—, —O—COO—, —CO—NR ⁰ —, —NR ⁰ —CO—, —OCH ₂ —, —CH ₂ O—, —SCH ₂ —, —CH ₂ S—, —CF ₂ O—, —OCF ₂ —, —CF ₂ S—, —SCF ₂ —, —CF ₂ CH ₂ —, —CH ₂ CF ₂ — , -CF ₂ CF _2- , -CH = N-, -N = CH-, -N = N-, -CH = CR ^0- , -CG ¹ = CG ^2- , -C≡C-, -CH = CH—COO—, —OCO—CH═CH— or a single bond,
R ⁰ , R ⁰⁰ , G ¹ and G ² have one of the meanings shown in formula I.

X is preferably —O—, —S—, —OCH ₂ —, —CH ₂ O—, —SCH ₂ —, —CH ₂ S—, —CF ₂ O—, —OCF ₂ —, —CF _{2. S -, - SCF 2 -,} - CH 2 CH 2 -, - CF 2 CH 2 -, - CH 2 CF 2 -, - CF 2 CF 2 -, - CH = N -, - N = CH -, - N = N-, -CH = CR ^0- , -C G ¹ = C G ^2- , -C≡C- or a single bond, in particular -O-, -S-, -C≡C-, -C G ¹ = C G ² — or a single bond, very preferably a group capable of forming a conjugated system, for example —C≡C— or —C G ¹ = C G ² — or a single bond.

Exemplary groups Sp ′ are, for example, — (CH ₂ ) _p —, — (CH ₂ CH ₂ O) _q —CH ₂ CH ₂ —, —CH ₂ CH ₂ —S—CH ₂ CH ₂ — or —CH. ₂ CH ₂ —NH—CH ₂ CH ₂ — or — (SiR ⁰ R ⁰⁰ —O) _p —, p is an integer of 2 to 12, q is an integer of 1 to 3, and R ⁰ And R ⁰⁰ have the meanings indicated above.

  Preferred groups Sp ′ are, for example, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylene-thioethylene, ethylene-N-methylimino. Ethylene, 1-methylalkylene, ethenylene, propenylene and butenylene.

  Further preferred are compounds having one or two groups P-Sp-, where Sp is a single bond. In the case of compounds having two groups P-Sp, each of the two polymerizable groups P and the two spacer groups Sp can be the same or different.

式中、
Ｑ^１およびＱ^３は、式ＩＩＩにおいて示した意味を有し、
Ｑ^４は、Ｑ^１とは異なる、１〜１０個のＣ原子を有するアルキレンもしくはアルキレン−オキシ基または単結合であり、
Ｑ^１は、重合可能な基Ｐに結合している、
で表されるキラルな基である。 In another preferred embodiment, the group Sp ′ has the formula IV:

Where
Q ¹ and Q ³ have the meanings indicated in formula III
Q ⁴ is different from Q ¹ and is an alkylene or alkylene-oxy group having 1 to 10 C atoms or a single bond,
Q ¹ is bound to a polymerizable group P,
Is a chiral group represented by

  Another preferred embodiment relates to chiral compounds of formula I comprising a photoisomerizable group, such as a group having a C═C, C═N or N═N double bond. These compounds change their shape, for example by EZ or cis-trans isomerization by irradiation with UV light.

Particular preference is given to one or more groups —W ¹ — in which W ¹ or W ² is a photoisomerizable group, in particular —CH═CH—COO— or —OCO—CH═CH—. It is a photoisomerizable compound represented by Formula I, including A ^1- (W ² -A ² ) _m —R. Very particular preference is given to one or more groups —W ¹ —A ¹ — (W ² —), wherein W ¹ is —OCO—CH═CH— and A ¹ is optionally substituted phenylene. A ² ) A photoisomerizable compound of the formula I containing _m- R.

  The compounds of the formula I are known and can be synthesized by methods analogous to or analogous to those described in the literature. In particular, they can be prepared by or analogously to the reaction scheme shown below. Other methods for preparing the compounds of the invention can be taken from the examples.

Starting materials shown below, for example (1) to (5), are, for example, a) DS Lingenfelter, RC Helgeson, DJ Cram, J. Org. Chem. 1981, 46, 393-406; b) P. Wipf, JK Jung, J. Org. Chem. 2000, 65, 6319-6337; c) PJ Cox, W. Wang, V. Snieckus, Tet. Letters 1992, 33, 2253-2256; d) L. Pu, Chem. Rev. 1998, 98, 2405-2494; e) Y. Tian, QC Yang, TCW Mak, Tetrahedron 2002, 58, 3951-3961; f) HF Chow, MK Ng, Tet. Asymmetry 1996, 7, 2251-2262 and g) It can be synthesized using the procedure described in M. Hatsuda, H. Hiramatsu, M. Seki, J. Org. Chem. 2001, 66, 4437-4439.

  The synthesis of compounds of formula I from starting materials is performed as shown, for example, in a) D. Yang, M.-K. Wong, J. Am. Chem. Soc. 1998, as shown in Schemes 1-3 below. 120) 5943-5952; b) J. Jamrozik, S. Schab, K. Nagraba, Monatsh. Fuer Chemie 1994, 125, 451-456; c) I. Shibuya, Y. Gama, M. Shimizu, Heterocycles 1998, 48 D) A. Gaucher, Y. Zuliani, J.-P. Mazaleyrat, Tet. Asymm. 2001, 12, 2571-2580 and e) D. Xiao, Z. Zhang, X. Zhang, Org. It can be achieved by the procedure described in Lett. 1999, 1, 1679-1681 or in a similar manner.

Scheme 1

Scheme 2

Scheme 3

  A compound of formula I can be used to display a helically twisted molecular structure of a liquid crystal matrix, such as an active or passive matrix type TN display, STN, phase change, guest-host, ferroelectric or cholesteric display, such as It can be used in liquid crystal mixtures for displays based on SSCT (surface stabilized cholesteric texture), PSCT (polymer stabilized cholesteric texture) or “blue phase”.

Accordingly, another object of the invention is a liquid crystal mixture, in particular a chiral smectic or cholesteric liquid crystal mixture, comprising at least one chiral compound of the formula I.
Another object of the invention is a liquid crystal display comprising a liquid crystal medium comprising at least one chiral compound of the formula I.

  Chiral compounds of the formula I are characterized by high values of HTP. This allows the production of liquid crystal mixtures having a high helix twist, i.e. a low pitch, by using only small amounts of chiral compounds of the formula I. This is a significant advantage since adding large amounts of chiral dopants to the liquid crystal mixture is often observed to adversely affect this liquid crystal phase behavior and electro-optical properties such as dielectric anisotropy, viscosity or clearing point. It is. Thus, by using the chiral compound of formula I in a liquid crystal mixture or display, this property only changes to a lesser extent compared to prior art dopants, for example lower in display A threshold voltage and a faster switching time are provided.

The chiral compounds of the formula I are further characterized by a high solubility in the liquid crystal host mixture. Undesirable spontaneous crystallization at low temperatures is reduced and the operating temperature range of the mixture can be expanded. Thus, the use of a second dopant that is often added to avoid crystallization can be avoided.
Accordingly, a particularly preferred embodiment of the present invention relates to a liquid crystal mixture comprising only one chiral compound, a compound of formula I, and a display comprising such a mixture.

The chiral compounds of formula I also show a low temperature dependence of HTP when added to a liquid crystal host mixture. They are therefore useful as chiral dopants for liquid crystal mixtures and displays with low temperature dependence of the pitch.
The liquid-crystal mixtures according to the invention preferably contain from 0.1 to 30% by weight, in particular from 1 to 25% by weight and very particularly preferably from 2 to 15% by weight, of chiral compounds of the formula I. This preferably comprises one, two or three chiral compounds of the formula I.

  The compounds of the formula I are particularly suitable for use in cholesteric liquid crystal mixtures for cholesteric displays, in particular SSCT or PSCT displays. Cholesteric displays are described, for example, in WO 92/19695, WO 93/23496, US 5,453,863 or US 5,493,430, the entire disclosures of these documents are incorporated by reference into this application.

  When chiral compounds of formula I are used as dopants in cholesteric liquid crystal media for SSCT or PSCT displays, they exhibit good solubility in nematic host mixtures and have a helical pitch and reflection wavelength. It has been found to induce high helical twists with low temperature dependence. Cholesteric mixtures having a high brightness of the reflected color and a low temperature dependence can also be achieved by using only one chiral dopant according to formula I, preferably in small amounts. This requires a large amount of dopant, and two or more dopants (eg, a dopant having a positive temperature dependency and a dopant having a negative temperature dependency) having a temperature dependence opposite to the helical twist. It is a significant advantage over the prior art, which is often necessary to achieve good temperature compensation of the reflected wavelength.

Accordingly, a particularly preferred embodiment of the present invention is preferably 15% or less, in particular 10% or less, very particularly preferably 5% or less of one chiral dopant which is a compound of formula I. For cholesteric liquid crystal media for use in SSCT and PSCT displays.
For the applications described above, the liquid crystal mixture preferably comprises a chiral component comprising at least one chiral compound of formula I, and one or more nematic or nematogenic compounds. Contains nematic ingredients.

  Preferably, the liquid crystal mixture consists of 2 to 25 compounds, preferably 3 to 15 compounds, at least one of which is a chiral compound represented by formula I. Other compounds forming the nematic component are preferably nematic or nematogenic substances such as azoxybenzene, benzylidene-aniline, biphenyl, terphenyl, phenyl benzoate or cyclohexyl benzoate, phenyl or cyclohexyl esters of cyclohexanecarboxylic acid, Phenyl or cyclohexyl ester of cyclohexylbenzoic acid, phenyl or cyclohexyl ester of cyclohexylcyclohexanecarboxylic acid, cyclohexylphenylester of benzoic acid, cyclohexanecarboxylic acid and cyclohexylcyclohexanecarboxylic acid, phenylcyclohexane, cyclohexylbiphenyl, phenylcyclohexylcyclohexane, cyclohexylcyclohexane, cyclohexylcyclohexyl , Cyclohexylcyclohexylcyclohexene, 1,4-biscyclohexylbenzene, 4,4'-bis-cyclohexylbiphenyl, phenyl or cyclohexylpyrimidine, phenyl or cyclohexylpyridine, phenyl or cyclohexylpyridazine, phenyl or cyclohexyldioxane, phenyl or cyclohexyl-1, 3-dithiane, 1,2-diphenyl-ethane, 1,2-dicyclohexylethane, 1-phenyl-2-cyclohexylethane, 1-cyclohexyl-2- (4-phenylcyclohexyl) ethane, 1-cyclohexyl-2-biphenyl- Ethane, 1-phenyl-2-cyclohexylphenylethane, optionally halogenated stilbene, benzylphenyl ether, tolan, substituted Selected from known groups of nematic or nematogenic substances Lee cinnamic acid and other groups are low molecular weight liquid crystal compounds. The 1,4-phenylene group in these compounds may also be mono- or difluorinated laterally.

  The liquid crystal mixture of this preferred embodiment is based on this type of achiral compound.

The most important compounds possible as components of these liquid crystal mixtures are those of the formula R′-L′-G′-ER ”
Wherein L ′ and E, which may be the same or different, in each case, independently of one another, represent -Phe-, -Cyc-, -Phe-Phe-, -Phe-Cyc-, -Cyc -Cyc-, -Pyr-, -Dio-, -B-Phe- and -B-Cyc- and divalent groups from the group formed by their mirror images, where Phe is unsubstituted or Fluorine-substituted 1,4-phenylene, Cyc is trans-1,4-cyclohexylene or 1,4-cyclohexenylene, and Pyr is pyrimidine-2,5-diyl or pyridine-2,5-diyl Dio is 1,3-dioxane-2,5-diyl and B is 2- (trans-1,4-cyclohexyl) ethyl, pyrimidine-2,5-diyl, pyridine- 2,5-diyl or 1,3-dioxane-2,5-diyl,
Can be characterized.

G ′ in these compounds represents the following divalent groups: —CH═CH—, —N (O) N—, —CH═CY—, —CH═N (O) —, —C≡C—, — _{CH 2 -CH 2 -, - COO} -, - CH 2 -O -, - CO-S -, - CH 2 -S -, - CH = N -, - from COO-Phe-COO- or a single bond Selected, Y is halogen, preferably chlorine, or -CN.

R ′ and R ″ in each case, independently of one another, are alkyl, alkenyl, alkoxy, alkenyloxy, alkanoyloxy, alkoxycarbonyl or alkoxycarbonyl having 1 to 18, preferably 3 to 12 C atoms. Alternatively, one of R ′ and R ″ is F, CF ₃ , OCF ₃ , Cl, NCS or CN.

  In most of these compounds, R ′ and R ″, in each case, independently of one another, are alkyl, alkenyl or alkoxy having various chain lengths, where the C atom in the nematic medium The total is generally 2-9, preferably 2-7.

  Many of these compounds or mixtures thereof are commercially available. All of these compounds are known or described in the literature (eg standard academic books such as Houben-Weyl, Methoden der Organischen Chemie, Georg-Thieme-Verlag, Stuttgart) As is known precisely, it can be prepared by methods known per se under reaction conditions suitable for the reactions described above. Variations known per se but not mentioned here can also be used here.

  Preferred uses of the compounds of the formula I show polymerizable liquid crystal mixtures, anisotropic polymer gels and anisotropic polymer films, in particular a helically twisted molecular structure with a uniform planar orientation, ie , The production of a polymer film whose helical axis is oriented perpendicular to the plane of the film, for example an oriented cholesteric film.

Anisotropic polymer gels and displays containing them are disclosed, for example, in DE 195 04 224 and GB 2 279 659.
Oriented cholesteric polymer films can be used, for example, as broadband reflective polarizers, color filters, security markings, or for the production of liquid crystal pigments.

  Broadband cholesteric reflective polarizers are described, for example, in EP 0 606 940, WO 97/35219 or EP 0 982 605. Color filters are described, for example, in EP 0 720 041 or EP 0 685 749 and R. Maurer et al., SID 1990 Digest, 110-113. Liquid crystal pigments are described, for example, in EP 0 601 483, WO 97/27251, WO 97/27252, WO 97/30136 or WO 99/11719.

For the production of anisotropic polymer gels or oriented polymer films, the liquid crystal mixture must contain at least one polymerizable compound, preferably a polymerizable mesogenic compound.
Accordingly, another object of the present invention is a polymerizable liquid crystal mixture comprising at least two compounds, of which at least one is a chiral compound of formula I, of which at least one is Is a polymerizable compound. The polymerizable compound can be at least one compound of formula I described above or an additional compound.

Preferably, the polymerizable liquid crystal mixture comprises at least one polymerizable mesogenic compound having one polymerizable functional group and at least one polymerization having two or more polymerizable functional groups. Contains possible mesogenic compounds.
The polymerizable mesogenic monoreactive, direactive and polyreactive compounds used for the present invention are known per se, for example standard academic books on organic chemistry, such as Houben-Weyl, Methoden der organischen Chemie. , Thieme-Verlag, Stuttgart.

  Examples of suitable polymerizable mesogenic compounds that can be used as monomers or comonomers with the compounds of the invention in polymerizable LC mixtures are, for example, WO 93/22397, EP 0 261 712, DE 195 04 224, WO 95/22586, WO 97/00600 and GB 2 351 734. However, the compounds disclosed in these documents should be regarded as merely examples which should not limit the scope of the present invention.

  Examples of particularly useful chiral and achiral polymerizable mesogenic compounds (reactive mesogens) are given in the following list, which should be construed as merely illustrative and the present It is not intended to limit the invention, but instead is intended to illustrate the invention:

In the above formula, P is a polymerizable group, preferably an acrylic, methacrylic, vinyl, vinyloxy, propenyl ether, epoxy, oxetane or styryl group, and x and y are the same or different integers from 1 to 12. A is 1,4-phenylene, or 1,4-cyclohexylene, optionally mono-, di- or tri-substituted by L ¹ , and u and v are independently of each other 0 or 1 and Z ⁰ is —COO—, —OCO—, —CH ₂ CH ₂ —, —CH═CH—, —C≡C— or a single bond, and R ⁰ is a polar group or a nonpolar group. in it, Ter is a terpenoid radical, for example menthyl, Chol is a cholesteryl group, L, ^{L 1} and ^{L 2} are independently of each other, H, F, Cl, CN or 1-7 Having a C atoms, optionally alkyl which is halogenated, alkoxy, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl or alkoxycarbonyloxy group, r is 0, 1, 2, 3 or 4. The phenyl ring in the above formula is optionally substituted by 1, 2, 3 or 4 groups L.

In this connection, the term “polar group” means F, Cl, CN, NO ₂ , OH, OCH ₃ , OCN, SCN, optionally fluorinated alkylcarbonyl, alkoxycarbonyl, having up to 4 C atoms, It means an alkylcarbonyloxy or alkoxycarbonyloxy group or a group selected from mono, oligo or polyfluorinated alkyl or alkoxy groups having 1 to 4 C atoms. The term “nonpolar group” is optionally encompassed by alkyl, alkoxy, alkyl, having one or more, preferably 1 to 12, C atoms, not encompassed by the definition of “polar group” above. Means a carbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy group;

Polymerizable liquid crystal mixtures for the production of anisotropic polymer films or polymer gels are preferably 0.1 to 35% by weight, in particular 0.5 to 15% by weight and very particularly preferably 0.5 to 5% by weight. % Of one or more polymerizable chiral compounds of the formula I.
Polymerizable liquid crystal mixtures containing 1 to 3 chiral compounds of the formula I are preferred.

Further preferred are polymerizable liquid crystal mixtures comprising at least one chiral compound of the formula I having at least one polymerizable group P.
To produce an anisotropic polymer film, a polymerizable LC mixture is preferably applied onto a substrate, oriented and polymerized in situ, for example by exposure to heat or actinic radiation, Fix LC molecule orientation. Orientation and curing are performed in the LC phase of the mixture. This technique is well known in the industry and is generally described, for example, in DJ Broer, et al., Angew. Makromol. Chem. 183, (1990), 45-66.

  The orientation of the LC material is applied to the applied material, for example by treatment of the substrate to which the material is applied, by shearing of the material during or after application, or by adding a surface active compound to the LC material Can be achieved. An overview of orientation techniques is given, for example, by I. Sage in “Thermotropic Liquid Crystals”, edited by GW Gray, John Wiley & Sons, 1987, pages 75-77, and by T. Uchida and H. Seki, “Liquid Crystal— Applications and Uses, Volume 3 ”, edited by B. Bahadur, World Scientific Publishing, Singapore 1992, pages 1-63. An overview of alignment materials and techniques is given in J. Cognard, Mol. Cryst. Liq. Cryst. 78, Supplement 1 (1981), pages 1-77.

  Polymerization occurs upon exposure to heat or actinic radiation. Actinic radiation means irradiation with light, for example UV light, IR light or visible light, irradiation with X-rays or gamma rays or irradiation with high energy particles, for example ions or electrons. Preferably the polymerization is carried out by UV irradiation at a non-absorbing wavelength. As a source of actinic radiation, for example, a single UV lamp or a set of UV lamps can be used. When using high lamp power, the curing time can be reduced. Other possible sources of actinic radiation are lasers, such as UV lasers, IR lasers or visible lasers.

  The polymerization is preferably carried out in the presence of an initiator that exhibits absorption at the wavelength of actinic radiation. For example, when polymerizing with UV light, a photoinitiator can be used that decomposes under UV irradiation to produce free radicals or ions that initiate the polymerization reaction. When curing polymerizable mesogens with acrylate or methacrylate groups, preferably using radical photoinitiators, and when curing polymerizable mesogens with vinyl, epoxide and oxetane groups, preferably cationic light Use an initiator. It is also possible to use a polymerization initiator that decomposes when heated to produce free radicals or ions that initiate polymerization. As photoinitiators for radical polymerization, for example, commercially available Irgacure 651, Irgacure 184, Darocure 1173 or Darocure 4205 (all from Ciba Geigy AG) can be used, whereas the cation In the case of neutral photopolymerization, commercially available UVI 6974 (Union Carbide) can be used.

  Preferably, the polymerization is carried out under an atmosphere of inert gas, preferably under a nitrogen atmosphere.

  As the substrate, for example, a glass or quartz sheet and a plastic film or sheet can be used. It is also possible to place the second substrate on top of the coated mixture before, during and / or after polymerization. The substrate can be removed or not removed after polymerization. In the case of curing with actinic radiation, when using two substrates, at least one substrate must be transparent to the actinic radiation used for the polymerization. Isotropic or birefringent substrates can be used. In the case where the substrate is not removed from the polymerized film after polymerization, an isotropic substrate is preferably used. Preferably, the at least one substrate is a plastic substrate, for example a film of polyester, such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), polyvinyl alcohol (PVA), polycarbonate (PC) or triacetyl cellulose (TAC), Particularly preferred is a PET film or a TAC film. As the birefringent substrate, for example, a plastic film extending in a uniaxial direction can be used. For example, PET film is commercially available from ICI Corp. under the trade name Melinex.

The polymerizable mixture is preferably coated as a thin layer on or between substrates and oriented in its chiral intermediate phase, for example a cholesteric or chiral smectic phase, to give a planar orientation, ie where The axis of the molecular helix extends across the layers. Planar orientation can be achieved, for example, by shearing the mixture, for example with a doctor blade. It is also possible to provide an alignment layer, for example a rubbed polyimide or sputtered SiO _x layer, on top of at least one of the substrates. Alternatively, the second substrate is placed on top of the coated material. In this case, the shear caused by placing the two substrates together is sufficient to produce good orientation. It is also possible to apply an electric or magnetic field to the coated mixture.

  In some cases, providing a second substrate is advantageous not only to assist in the orientation of the polymerizable mixture, but also to eliminate oxygen that can inhibit polymerization. Alternatively, curing can be carried out under an inert gas atmosphere. However, curing in air is also possible with a suitable photoinitiator and high lamp power. When using cationic photoinitiators, oxygen exclusion is not necessary in most cases, but water must be excluded.

  The polymerizable liquid-crystal mixtures according to the invention for the production of anisotropic polymer films are preferably 0.1 to 35% by weight, in particular 0.5 to 15% by weight and very particularly preferably 0.5 to 5% by weight. % Of one or more polymerizable chiral compounds of the formula I. Polymerizable liquid crystal mixtures containing 1 to 3 chiral compounds of the formula I are preferred.

  The polymerizable material may further comprise one or more other suitable components such as catalysts, sensitizers, stabilizers, inhibitors, chain transfer agents, co-reacting monomers, surfactant compounds, lubricants, wetting Agents, dispersants, hydrophobing agents, adhesives, flow improvers, defoamers, deaerators, diluents, reactive diluents, adjuvants, colorants, dyes or pigments can be included.

  Preferably, the polymerizable mixture of the present invention comprises a stabilizer that is used, for example, to prevent undesired spontaneous polymerization during storage of the composition. As stabilizers, in principle all compounds known to the person skilled in the art for this purpose can be used. Many of these compounds are commercially available. Typical examples for stabilizers are 4-ethoxyphenol or butylated hydroxytoluene (BHT).

  Also, non-mesogenic compounds with two or more polymerizable functional groups, preferably in an amount up to 20% by weight, in order to increase the cross-linking of the polymer, are polyfunctional mesogenic polymerizable It is also possible to add to the polymerisable mixture instead of or in addition to this compound. Typical examples for bifunctional non-mesogenic monomers are alkyl diacrylates or alkyl dimethacrylates having alkyl groups with 1 to 20 C atoms. Typical examples for non-mesogenic monomers having more than two polymerizable groups are trimethylpropane trimethacrylate or pentaerythritol tetraacrylate.

Polymerization of the composition of the present invention comprising a compound having only one polymerizable functional group yielded a linear polymer, while crosslinked in the presence of a compound having more than one polymerizable functional group. A polymer is obtained.
For the production of anisotropic polymer gels, the liquid crystal mixture can be polymerized in situ as described above, but in this case the orientation of the polymerizable mixture is not always necessary.

  The chiral dopant material or optically active material of the present invention can also include one or more additional chiral dopants in addition to the chiral compound of Formula I. Typically used chiral dopants are, for example, commercially available R or S811, R or S1011, R or S2011, R or S3011, R or S4011, or CB15 (from Merck KGaA, Darmstadt, Germany). . Highly preferred are chiral dopants with high helical twisting power (HTP), in particular dopants containing sorbitol groups as described in WO 98/00428, dopants containing hydrobenzoin groups as described in GB 2,328,207, WO 02 Chiral binaphthyl derivatives as described in WO / 94805, chiral binaphthol acetal derivatives as described in WO 02/34739, chiral TADDOL derivatives as described in WO 02/06265 and WO 02/06196 and WO 02/06195 A chiral dopant having at least one fluorinated linking group and a terminal or central chiral group.

  The above-mentioned liquid crystal mixture or polymerizable liquid crystal mixture is a dopant material containing one or more optically active compounds represented by formula I or one or more compounds represented by formula I And can include one or more additional dopants selected, for example, from those listed above.

  Chiral compounds of the formula I and liquid crystal mixtures, liquid crystal polymers or liquid crystal pigments containing them can also be used for coloring cosmetic products for use in cosmetics and pharmaceutical compositions, for example as described in EP 815 826. Or as a UV filter for the protection of human skin or hair, in particular in protection against UV-A and UV-B radiation, as described, for example, in DE 196 29 761 or EP 1 038 941 Is preferable. The dopants of the present invention have a high HTP, so only a small amount is necessary to obtain a short pitch, reflect in the UV range and obtain a material suitable as a UV filter.

  A liquid crystal mixture, liquid crystal polymer or liquid crystal pigment comprising a chiral compound of formula I and reflecting in particular UV light with a wavelength of 200 to 400 nm is another object of the invention. Other objects include chiral compounds of the formula I as cosmetic compositions, in particular UV filters, in particular 200-440 nm, in particular 280-400 nm, 200-230 nm (UV-C) and 280-330 nm ( Cosmetic or pharmaceutical composition for the protection of human skin or hair, comprising a liquid crystal mixture, a liquid crystal polymer or a liquid crystal pigment that reflects UV light of a wavelength in the range of UV-B).

The chiral compounds of the formula I are particularly suitable for the production of cholesteric liquid crystal films or layers having a planar orientation, i.e. a helically twisted structure whose helical axis is approximately perpendicular to the film plane. Such a layer or film exhibits a selective reflection of circularly polarized visible light caused by the interaction of incident light with the helically twisted structure of the cholesteric material. The reflection center wavelength λ is given by equation (2)
λ = n · p (2)
Depends on the pitch p and the average refractive index n of the cholesteric material.

The bandwidth Δλ of the reflected wavelength band is given by equation (3)
Δλ = Δn · p (3)
Depending on the pitch and birefringence Δn of the cholesteric material.

The reflection wavelength λ of a cholesteric layer having a planar orientation is given by equation (4)
λ (α) = λ (0) cos [arcsin ((sinα) / n)] (4)
In the formula, λ (0) is a reflection wavelength in normal observation, and λ (α) is a reflection wavelength at a viewing angle α.
Thus, in the first approximation, it depends on the viewing angle (see Eberle et al., Liq. Cryst. 1989, 5 (3), 907-916). Therefore, the reflected color at a larger viewing angle varies in the direction of a shorter wavelength. This phenomenon is also known to professionals as a “colour flop” and is used in decorative or security applications.

  Therefore, the present invention further provides a chiral anisotropic polymer film obtained by polymerizing the compound represented by formula I or the polymerizable LC mixture described herein in this oriented state. In particular, it relates to cholesteric films.

  It is also possible to produce cholesteric reflective films that can easily change optical properties, such as pitch or reflection wavelength, viewing angle or temperature dependence, reflection bandwidth or handedness of reflected light. Is possible. For example, a reflective film having a pattern of at least two regions having different orientations and / or different optical properties can be produced by using various cholesteric materials and / or light masking techniques. Preferably, such a film exhibits a pattern (color flop) of at least two regions differing in at least one characteristic selected from the helical pitch, the reflection wavelength, the rotation direction of the reflected light, and the viewing angle dependency of the reflected light. . Such a film is another object of the present invention.

  For example, a cholesteric reflective film having a horizontal pattern that includes regions of different reflective wavelengths λ or a broadband reflective film having a broad bandwidth Δλ in the reflected wavelength band can be produced. The production of such films is described, for example, in WO 00/34808 and P. van de Witte et al., J. Mater. Chem. 9 (1999) 2087-2094, see this disclosure in its entirety. Are incorporated into this application.

  Such a film can also be produced, for example, by using the liquid crystal mixture of the present invention comprising a chiral compound having a photoisomerizable group. The chiral photoisomerizable compound can be a compound of formula I as described above or an additional compound. As mentioned above, photoisomerizable compounds change their shape, for example by EZ or cis-trans isomerization, for example by irradiation with UV light, thus the molecular shape and thus the physical molecular properties. For example, the helical twisting force is completely changed. For example, if photoisomerization reduces the HTP of the compound, this in turn increases the pitch and thus the reflection wavelength of the liquid crystal mixture.

  Light irradiation can be achieved using, for example, irradiation with UV light or other high energy source, such as a laser. By using a light masking technique, it is possible to change the chirality only in selected areas of the material, which is then fixed, for example by polymerization. In this way, a pattern in the shape of the optical mask is obtained, where different regions of the layer exhibit different reflection wavelengths. Since the change in HTP of a chiral photoisomerizable compound is usually dependent on the intensity of light irradiation, a change in twist in the liquid crystal mixture can also be used, eg using a gray filter instead of or in addition to a photomask Thus, it can be controlled by a local change in irradiation intensity.

  In addition, liquid crystal mixtures containing chiral isomerizable and chiral non-isomerizable compounds with different concentrations and / or HTP and / or rotational direction can be used to determine the pitch and / or rotational direction of the reflected light. It is also possible to produce films that can be easily changed. Changes in the direction of twist in such a film or this selected part can be achieved by appropriate selection of the amount of the two chiral compounds and HTP. For example, liquid crystal mixtures include chiral isomerizable and chiral nonisomerizable compounds, one of which is levorotatory and the other is dextrorotatory. The isomerizable compound has a higher HTP and / or is present in an excess amount compared to the non-isomerizable compound, so the net twist direction of the liquid crystal mixture is the twist of the isomerizable compound. Corresponds to the direction. Irradiation reduces the HTP of the isomerizable compound, while chiral compounds that cannot be isomerized do not change this HTP. As a result, the net twist direction of the chiral liquid crystal mixture is reversed.

  Also, a change in twist in the direction perpendicular to the plane of the cholesteric film or layer is achieved by adding a dye, for example a UV dye, to a liquid crystal mixture having an absorption maximum at the wavelength at which the isomerizable compound exhibits photoisomerization. It is also possible to do. The dye forms a gradient in the intensity of light irradiation through the thickness of the layer, so that the isomerization and thus the change in twist is faster at the top of the layer than at the bottom. In this way, a pitch gradient is formed, resulting in an expansion of the reflected wavelength band. This method is particularly useful for the production of broadband reflective polarizers.

  The LC film of the present invention is an optical element such as a polarizing plate, a compensator, a circular polarizing plate or a color filter in a liquid crystal display or projection system, as a decorative pattern, for the production of liquid crystals or effect pigments, in nonlinear optics, For reflective recordings with spatially varying reflective colors, for decorative recording or information storage, decoration, information storage or security use, eg identification, certification or identification of product labels or articles or ID cards, banknotes, Useful for patterned or multicolored films or pictures for security marking to prevent counterfeiting of credit card tickets or other securities.

  The LC film of the present invention can be used in a transmissive or reflective display. These can be used in conventional LCDs, in particular DAP (orientation phase deformation) or VA (vertical alignment) modes, such as ECB (electrically controlled birefringence), CSH (color hyperhomeotropic) LCDs, VAN or VAC ( In vertical alignment nematic or cholesteric) display, MVA (multi-domain vertical alignment) or PVA (patterned vertical alignment) display, bend mode display or hybrid type display, eg OCB (optically compensated bending) In cell or optically compensated birefringence, R-OCB (reflective OCB), HAN (hybrid alignment nematic) or pi-cell (π-cell) displays, TN (twisted nematic), HTN (highly twisted) Nemati Or STN (super twisted nematic) mode display, AMD-TN (active matrix driven TN) display, or IPS (in-plane switching) mode display, also known as "super TFT" display Can be used.

  In the examples above and below, unless otherwise indicated, all temperatures are given in degrees Celsius without correction, and all parts and percentages are by weight.

The value of the helical twisting force HTP of the chiral compound in the liquid crystal host is denoted by μm ⁻¹ according to the equation HTP = (p * c) ⁻¹ , where p is the pitch of the molecular helix denoted by μm, c is the weight concentration of the chiral compound in the host, expressed as a relative value (thus, for example, a concentration of 1% by weight corresponds to a value of c of 0.01). Unless otherwise stated, HTP values were determined in the commercially available liquid crystal host mixture MLC-6260 (Merck KGaA, Darmstadt, Germany) at a concentration of 0.5% and a temperature of 20 ° C.

The following abbreviations are used to illustrate the liquid crystalline phase behavior of compounds: G = glassy, C = crystalline; N = nematic; S = smectic; N ^* , Ch = chiral nematic or cholesteric; I = isotropic. The number between these symbols indicates the phase transition temperature in degrees Celsius.

Example 1
Compound (1) is produced as follows.

To a solution of carbon disulfide (0.4 mL, 7 mmol), R-(+)-1,1′-bi-2-naphthol (5 g, 17 mmol) and triethylamine (7 mL, 51 mmol) in acetonitrile (35 mL), Silver trifluoroacetate (7.7 g, 35 mmol) was added in portions over 3 minutes with stirring on an ice-water bath. The reaction mixture was stirred continuously at room temperature for 5 hours. After evaporation of the solvent under reduced pressure, ethyl acetate was added to the residue and silver sulfide was removed by filtration. The resulting organic solution was passed through a silica gel column to give a colorless solid (3 g, 30%).

Similarly, the following compounds were obtained.

Claims (24)

Formula I

Where
K ¹ -K ⁴ , independently of one another, are annelated benzene, cyclohexane or cyclohexene, wherein one or more CH groups may be substituted by N, one or two One or more CH ₂ groups may be substituted by O and / or S so that the O and / or S atoms are not directly bonded to each other,
U ^{1 to} U ⁴ are independently of each other CH ₂ , O, S, CO, NH or CF ₂ ;
V ^{1 to} V ⁴ are independently of each other CH ₂ , O, S, CO, NH or CF ₂ (where O, S and NH are not directly adjacent to each other) or a single bond Show
Z is C;
X ^{1 to} X ¹² are each independently R, P-Sp or —W ¹ -A ^1- (W ² -A ² ) _m -R;
R, at each occurrence, independently has _{H, F, Cl, Br,} I, CN, NO 2, OH, NCS, SF 5, 1-40 C atoms, which is unsubstituted , F, Cl, Br, I or CN is a straight-chain or branched alkyl mono- or polysubstituted, wherein one or more CH ₂ groups are in each case Independently of each other, —O—, —S—, —NH—, —NR ⁰ —, —SiR ⁰ R ⁰⁰ —, —CO—, —COO—, —OCO—, —OCO—O—, —S— CO—, —CO—S—, —SO ₂ —, —CG ¹ ═CG ² — or —C≡C— is substituted so that two O or two S atoms are not directly bonded to each other. Or indicate P-Sp-
R ⁰ and R ⁰⁰ , independently of one another, are H or alkyl having 1 to 12 C atoms;
G ¹ and G ² are independently of each other H, F, Cl or CN;
P is

W ¹ ′ is H, Cl, CN, phenyl or alkyl having 1 to 5 C atoms, and W ² ′ and W ³ ′ are each independently H or 1 to Alkyl having 5 C atoms, W ⁴ ′, W ⁵ ′ and W ⁶ ′, independently of one another, are Cl, oxaalkyl or oxacarbonylalkyl having 1 to 5 C atoms, Phe Is 1,4-phenylene, k ₁ and k ₂ are independently 0 or 1,
Sp is a single bond or represented by Sp′-X,
Sp ′ is an alkylene having up to 20 C atoms that is unsubstituted or may be mono- or polysubstituted by F, Cl, Br, I or CN, and is one or more Non-adjacent CH ₂ groups are, in each case, independently of one another, —O—, —S—, —NH—, —NR ⁰ —, —SiR ⁰ R ⁰⁰ —, —CO—, —COO—, —OCO—, —OCO—O—, —S—CO—, —CO—S—, —CH═CH— or —C≡C— is substituted so that the O and / or S atoms are not directly bonded to each other. You may,
X is —O—, —S—, —CO—, —COO—, —OCO—, —O—COO—, —CO—NR ⁰ —, —NR ⁰ —CO—, —OCH ₂ —, —CH ₂ O—, —SCH ₂ —, —CH ₂ S—, —CF ₂ O—, —OCF ₂ —, —CF ₂ S—, —SCF ₂ —, —CF ₂ CH ₂ —, —CH ₂ CF ₂ — , -CF ₂ CF _2- , -CH = N-, -N = CH-, -N = N-, -CH = CR ^0- , -CG ¹ = CG ^2- , -C≡C-, -CH = CH—COO—, —OCO—CH═CH— or a single bond,
A ¹ and A ² are each independently, in each occurrence, a substituted or unsubstituted aromatic ring or alicyclic ring, or two or more aromatic rings and / or alicyclic rings are fused. Wherein these rings may contain one or more heteroatoms selected from N, O and S;
W ¹ and W ² , in each occurrence, independently represent —O—, —S—, —CO—, —COO—, —OCO—, —S—CO—, —CO—S—, —O. _{^{-COO -, - CO-NR 0}} -, - NR 0 -CO -, - OCH 2 -, - CH 2 O -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 - _{, -CF 2 S -, - SCF} 2 -, - CH 2 CH 2 -, - CF 2 CH 2 -, - CH 2 CF 2 -, - CF 2 CF 2 -, - CH = N -, - N = CH -, - N = N -, - CH = CH -, - CH = CR 0 -, - CR 0 = CR 00 -, - CG 1 = CG 2 -, - C≡C -, - CH = CH-COO- , -OCO-CH = CH- or a single bond,
m is independently 0, 1, 2 or 3 in each occurrence,
A chiral compound used as a dopant in a liquid crystal medium.
(Provided that di- (β-dinaphthol) -orthocarbonate, and

Is excluded. ) Formula I '

Where
K ¹ -K ⁴ , independently of one another, are annelated benzene, cyclohexane or cyclohexene, wherein one or more CH groups may be substituted by N, one or two One or more CH ₂ groups may be substituted by O and / or S so that the O and / or S atoms are not directly bonded to each other,
U ^{1 to} U ⁴ are independently of each other CH ₂ , O, S, CO, NH or CF ₂ ;
V ^{1 to} V ⁴ are independently of each other O, S, CO, NH or CF ₂ (where O, S and NH are not directly adjacent to each other) or represent a single bond,
Z is C;
X ^{1 to} X ¹² are each independently R, P-Sp or —W ¹ -A ^1- (W ² -A ² ) _m -R;
R, at each occurrence, independently has _{H, F, Cl, Br,} I, CN, NO 2, OH, NCS, SF 5, 1-40 C atoms, which is unsubstituted , F, Cl, Br, I or CN is a straight-chain or branched alkyl mono- or polysubstituted, wherein one or more CH ₂ groups are in each case Independently of each other, —O—, —S—, —NH—, —NR ⁰ —, —SiR ⁰ R ⁰⁰ —, —CO—, —COO—, —OCO—, —OCO—O—, —S— CO—, —CO—S—, —SO ₂ —, —CG ¹ ═CG ² — or —C≡C— is substituted so that two O or two S atoms are not directly bonded to each other. Or indicate P-Sp-
R ⁰ and R ⁰⁰ , independently of one another, are H or alkyl having 1 to 12 C atoms;
G ¹ and G ² are independently of each other H, F, Cl or CN;
P is

W ¹ ′ is H, Cl, CN, phenyl or alkyl having 1 to 5 C atoms, and W ² ′ and W ³ ′ are each independently H or 1 to Alkyl having 5 C atoms, W ⁴ ′, W ⁵ ′ and W ⁶ ′, independently of one another, are Cl, oxaalkyl or oxacarbonylalkyl having 1 to 5 C atoms, Phe Is 1,4-phenylene, k ₁ and k ₂ are independently 0 or 1,
Sp is a single bond or represented by Sp′-X,
Sp ′ is an alkylene having up to 20 C atoms that is unsubstituted or may be mono- or polysubstituted by F, Cl, Br, I or CN, and is one or more Non-adjacent CH ₂ groups are, in each case, independently of one another, —O—, —S—, —NH—, —NR ⁰ —, —SiR ⁰ R ⁰⁰ —, —CO—, —COO—, —OCO—, —OCO—O—, —S—CO—, —CO—S—, —CH═CH— or —C≡C— is substituted so that the O and / or S atoms are not directly bonded to each other. You may,
X is —O—, —S—, —CO—, —COO—, —OCO—, —O—COO—, —CO—NR ⁰ —, —NR ⁰ —CO—, —OCH ₂ —, —CH ₂ O—, —SCH ₂ —, —CH ₂ S—, —CF ₂ O—, —OCF ₂ —, —CF ₂ S—, —SCF ₂ —, —CF ₂ CH ₂ —, —CH ₂ CF ₂ — , -CF ₂ CF _2- , -CH = N-, -N = CH-, -N = N-, -CH = CR ^0- , -CG ¹ = CG ^2- , -C≡C-, -CH = CH—COO—, —OCO—CH═CH— or a single bond,
A ¹ and A ² are each independently, in each occurrence, a substituted or unsubstituted aromatic ring or alicyclic ring, or two or more aromatic rings and / or alicyclic rings are fused. Wherein these rings may contain one or more heteroatoms selected from N, O and S;
W ¹ and W ² , in each occurrence, independently represent —O—, —S—, —CO—, —COO—, —OCO—, —S—CO—, —CO—S—, —O. _{^{-COO -, - CO-NR 0}} -, - NR 0 -CO -, - OCH 2 -, - CH 2 O -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 - _{, -CF 2 S -, - SCF} 2 -, - CH 2 CH 2 -, - CF 2 CH 2 -, - CH 2 CF 2 -, - CF 2 CF 2 -, - CH = N -, - N = CH -, - N = N -, - CH = CH -, - CH = CR 0 -, - CR 0 = CR 00 -, - CG 1 = CG 2 -, - C≡C -, - CH = CH-COO- , -OCO-CH = CH- or a single bond,
m is independently 0, 1, 2 or 3 in each occurrence;
However,
At least one of X ^{1 to} X ¹² is different from H,
And / or K ¹ -K ⁴ are, independently of one another, annelated cyclohexane or cyclohexene, wherein one or more CH groups may be substituted by N, Two or more CH ₂ groups may be substituted by O and / or S so that the O and / or S atoms are not directly bonded to each other,
A chiral compound represented by The chiral compound according to claim 1, wherein at least one of X ^{1 to} X ¹² is different from H. 4. K ¹ -K ⁴ , independently of one another, are annelated cyclohexane or cyclohexene, wherein one or more CH groups may be substituted by N, one or more 4. The CH ₂ group according to claim 1, wherein O and / or S may be substituted so that the O and / or S atoms are not directly bonded to one another. Compound. The two groups V ¹ and V ² , or two groups V ³ and V ⁴ , or all of V ^{1 to} V ⁴ are all single bonds, according to claim 1. The described chiral compound. The chiral compound according to claim 5, wherein all of V ^{1 to} V ⁴ are single bonds. The chiral compound according to any one of claims 1 to 4, characterized in that all V ¹ , V ² , V ³ and V ⁴ are not single bonds. The following formula

Wherein U ^{1 to} U ⁴ , V ^{1 to} V ⁴ , X ^{1 to} X ¹² and Z have one of the meanings in formula I of claim 1,
The chiral compound according to claim 1, wherein the chiral compound is selected from the group consisting of: The chiral compound according to claim 1, wherein at least one of R and X ^{1 to} X ¹² is a group represented by P-Sp—. R and X ^{1 to} X ¹² are, independently of one another, F, Cl, CN, NO ₂ , linear or branched alkyl having 1 to 20 C atoms, alkenyl, alkynyl, alkoxy, alkylcarbonyl, Selected from alkoxycarbonyl, alkylcarbonyloxy, thioether, alkylsulfonyl, alkylsulfanyl, alkylsulfanylcarbonyl, aminoalkyl or aminodialkyl, wherein one or more H atoms are replaced by F or Cl A chiral compound according to any one of claims 1 to 9, characterized in that 11. The chiral group according to claim 1, wherein at least one of X ^{1 to} X ¹² is —W ¹ -A ^1- (W ² -A ² ) _m —R. Compound. A ¹ and A ² are further 1,4-phenylene, in which one or more CH groups can be substituted by N, furthermore one or two non-adjacent CH ₂ groups are O And / or 1,4-cyclohexylene, 1,3-dioxolane-4,5-diyl, 1,4-cyclohexenylene, 1,4-bicyclo- (2,2, 2) selected from -octylene, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl And all these groups can be unsubstituted, mono- or polysubstituted with L, wherein L is 1 of the meaning of R in formula I of claim 1. Have one Wherein the chiral compound according to any one of claims 1 to 11.   An optically active material comprising one or more chiral compounds of formula I of claim 1 or formula I 'of claim 2 according to any one of claims 1-11. Or a chiral dopant material.   14. An optically active material or chiral dopant material according to claim 13, comprising one or more additional chiral compounds. At least one comprises a chiral compound, liquid crystal mixture as claimed in any one of claims 1 to 12. At least one containing chiral compounds, polymerisable liquid crystal material according to any one of claims 1 to 12. Claim 1 is represented by at least one formula I or formula of claim 2 I of claim 1 'according to any one of 12 and our compounds, formula I or formula according to claim 2 of claim 1 A polymerizable liquid crystal mixture comprising at least one polymerizable mesogenic compound, which can be said compound represented by I ′ or an additional compound. Obtained by polymerizing a compound according to any one of claims 1 to 12 linear or crosslinked polymers. An anisotropic polymer film having a twisted structure obtained by polymerizing a layer of the compound according to any one of claims 1 to 12 in an oriented state. 13. Use of a compound according to any one of claims 1 to 12 as a chiral dopant or an optical, electrooptical, electrical, semiconducting or electronic element or device in a liquid crystal material. Of a compound according to any one of claims 1 to 12 electro-optical displays, liquid crystal displays, optical films, polarizers, compensators, beam splitters, reflective films, alignment layers, color filters, holographic elements , High temperature stamping foil, colored pattern, decoration or security marking for consumer goods or securities, LC pigments, adhesives, synthetic resins with anisotropic mechanical properties, cosmetics, diagnostics, nonlinear optics, optical information storage As chiral dopants, electronic devices as elements of integrated circuits, electronic devices in field effect transistors (FETs), as thin film transistors in flat panel display applications, or for radio frequency identification (RFID) tags, or organic light emitting diodes (OLED) Applications, D In semiconductive elements for electroluminescent displays or LCD backlights, for photovoltaic or sensor devices, in laser irradiation applications and devices, as electrodes or electrolyte materials in batteries, as photoconductors, electrophotography Use or use for electrophotographic recording. In any one of claims 1 to 12 comprising a compound according liquid crystal display. An optical film, retardation or compensation film, alignment layer, color filter, polarizing plate, liquid crystal pigment, decorative pattern, spatially characterized by comprising the compound according to any one of claims 1 to 12. Reflective film with changing reflective color, decoration, patterned or multicolor film or picture for information storage or security use, identification, proof or appraisal of goods or ID card, banknote, credit card ticket or others Product labels or security markings to prevent counterfeiting of securities. Characterized in that it comprises a compound according to any one of claim 1 to 12 a semiconductor or charge transport material, an electronic device, a field effect transistor (FET), elements of the integrated circuit, thin film transistors, Radio Frequency Identification ( RFID) tags, semiconductive elements of organic light emitting diodes (OLEDs), electroluminescent displays or display backlights, photovoltaic or sensor devices.