KR20030082920A - Polymerisable compounds comprising a cinnamic acid group and an acetylene group - Google Patents

Abstract

The present invention provides a novel polymerizable mesogenic or liquid crystalline compound comprising cinnamic acid and an acetylene group, a polymerizable mesogenic or liquid crystalline mixture and an anisotropic polymer prepared thereof, and optical and electro-optical devices, adhesives, anisotropic mechanical properties. Synthetic resins, cosmetics, diagnostics, liquid crystal pigments, decorative and safety applications, nonlinear optics, optical information storage, electronic devices such as organic field effect transistors (FETs or OFETs), in electroluminescent devices, or chiral dopants And to the use of the novel compounds as well as the mixtures and polymers prepared thereof.

Description

Polymerizable compound comprising cinnamic acid group and acetylene group {POLYMERISABLE COMPOUNDS COMPRISING A CINNAMIC ACID GROUP AND AN ACETYLENE GROUP}

The present invention provides novel polymerizable mesogenic or liquid crystalline compounds comprising cinnamic acid and acetylene groups, polymerizable mesogenic or liquid crystalline mixtures and prepared anisotropic polymers thereof, and optical and electro-optical devices, adhesives, anisotropic mechanical properties. As synthetic resins, cosmetics, diagnostics, liquid crystal pigments, decorative and safety applications, nonlinear optics, optical information storage, electronic devices such as organic field effect transistors (FETs or OFETs), in electroluminescent devices, or as chiral dopants It relates to the use of the novel compounds and the mixtures and polymers prepared thereof.

Polymerizable mesogenic or liquid crystalline compounds, also known as reactive mesogenic compounds, have been described in the prior art for various purposes. For example, it can be used to prepare linear or crosslinked liquid crystal side chain polymers. It is also aligned with its liquid crystal phase and then polymerized in situ to produce a linear or crosslinked liquid crystal polymer film having a high uniform orientation. This film can be used as an optical element such as a polarizer or a compensator in flat panel displays, as described, for example, in EP 0 397 263, WO 98/00475, WO 98/04651 or WO 98/12584.

The polymerizable mesogenic compounds also selectively reflect visible light, for example as described in EP 0 606 940 or WO 97/35219, with narrowband or broadband reflecting polarizers or color filters. Polymerized cholesteric liquid crystal films, suitable for the same optical film, or for use in coatings, or for the production of liquid crystal pigments, for example as described in WO 97/30136, have been proposed. Use in other important fields is a safety indication as described, for example, in US 5,678,863 or a hot stamping foil as described, for example, in GB 2,357,061.

In addition to their use as optical films in displays, polymerizable mesogenic compounds have been proposed for use in switchable layers, which are active in liquid crystal displays.

For example, PDLC (polymers) as described in WO 93/22397, comprising a low molecular weight liquid crystal (LC) medium and a phase-separated polymerized liquid crystal material, switched between a transparent and scattering state Dispersed liquid crystal) displays, or displays such as polymer gel or polymer network displays in scattering form as described in US Pat. No. 5,538,768, US Pat. No. 5,543,075 or EP 0 451 905.

In addition, for example, a low molecular weight LC medium is switched between two non-scattering states, further comprising polymerized liquid crystal material to create a multidomain structure to improve contrast at a wide viewing angle, or Displays such as conventional displays of the TN or STN, ECB, VA or IPS schemes are known which stabilize different switching states to reduce drive voltage and switching time. Such displays are described, for example, in US 5,189,540, US 6,177,972, EP 0 903 392 and in Hasebe et al., Jpn. J. Apple. Phys. 1994, 33, 6245.

Generally, mixtures of two or more polymerizable mesogenic compounds are used in these applications because they have a lower melting point and a broader liquid crystalline phase than a single compound. It is preferred to have an available polymerizable mixture, preferably a nematic or chiral nematic phase, which exhibits a liquid crystalline phase at room temperature so that alignment and polymerization can be carried out at low temperatures. For this purpose, it is advantageous if a single polymerizable compound exhibits a wide range of liquid crystalline phases in advance.

For use in switchable layers of liquid crystal displays, typically mixed with low molecular weight LC media, polymerizable mesogenic compounds need to have properties similar to those of LC media (such as liquid crystal phase range and birefringence). many. When used in switchable displays that are not in scattered form, and where the polymerized material is not phase separated from the low molecular weight LC medium by microscope, the polymerizable compound should preferably exhibit good miscibility with the LC medium.

However, the polymerizable mesogenic compounds described in the prior art often have a negative effect on the liquid crystal phase action of the LC mixture, show low solubility in low molecular weight LC media and have an adversely low value of birefringence.

Polymerizable mesogenic tolan or phenylacetylene have been reported in the prior art to exhibit high birefringence values, for example JP-A-05-339189, JP-A-07-017910, EP-A-0659 865, JP- A-08-231958, JP-A-11-147853, GB-A-2 351 734, JP-A-2000-281628, JP-A-2000-281629 and US-A-2002 / 0006479. However, these compounds often do not have sufficiently high birefringence, or when used in LC mixtures, often have a negative effect on the properties of the mixture or do not exhibit sufficient stability to UV light.

Thus, polymerizable mesogenic compounds which do not have the above drawbacks, in particular have high birefringence and can be used for the preparation of oriented liquid crystal polymer films or as compounds in the active layer of switchable LC devices in mixtures with low molecular weight LC media. Compound is required.

In addition, in view of the wide range of applications for polymerizable mesogenic compounds, it is desirable for professionals to have another compound of this type available that is easy to synthesize and meets the various needs above.

It is an object of the present invention to provide a polymerizable mesogenic compound having the above advantageous properties, thereby extending the range of polymerizable mesogenic compounds available to the expert. Other objects of the present invention will immediately become apparent to those skilled in the art from the following detailed description.

It has been found that this object can be achieved by providing a polymerizable compound according to the present invention.

One object of the present invention is to provide a polymerizable compound of formula 1:

(Wherein

P is a polymerizable group,

Sp is a spacer group or a single bond,

X is -O-, -S-, -CO-, -COO-, -OCO-, , -OCO-O, -S-CO- , -CO-S, -CO-NR 0 -, -NR 0 -CO-, -OCH 2 -, -CH 2 O-, -SCH 2 -, -CH 2 S-, -CH = CH-COO-, -OOC-CH = CH-, CH ₂ CH ₂ or a single bond,

Z ¹ and Z ² are each _{independently, -COO-, -OCO-, -CH 2 CH} 2 -, -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 = CH-, -CH = CH-, -CF = CH-, -CH = CF-, -CF = CF-, -CH = CH-COO-, -OCO-CH = CH-, -C≡C- or single Is a combination,

A ¹ and A ² are each independently an aliphatic or aromatic carbocyclic or heterocyclic group having 16 or less carbon atoms, which may consist of a conjugated ring and which may be unsubstituted or mono- or polysubstituted with L. ,

m1 and m2 are each independently 0, 1, 2 or 3, with m1 + m2 <5,

R may be H, F, Cl, Br, I, CN, SCN, SF ₅ , unsubstituted, mono-, or polysubstituted by F, Cl, Br, I or CN, and also one or more non-contiguous CH ₂ groups are independently of each other at each occurrence: -O-, -S-, -NH-, -NR ^0- , -SiR ⁰ R ^00- , -CO-, -COO-, -OCO-, -OCO-O O and / or S atoms are each other by-, -S-CO-, -CO-S-, -SO ₂ , -SO-O-, -O-SO-, -CH = CH- or -C≡C- Straight or branched chain alkyl having 25 or less carbon atoms, which may be replaced in a manner not directly connected, or P-Sp-X,

R ⁰ and R ⁰⁰ are, independently from each other, H or alkyl having 1 to 4 carbon atoms,

L is F, Cl, Br, I, CN, NO ₂ or alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl or alkylcarbonyl having 1 to 7 carbon atoms, in which one or more H atoms may be substituted by F or Cl Oxy,

r is 0, 1, 2, 3 or 4)

to be.

Another object of the present invention is a polymerizable liquid crystal mixture comprising at least one compound of the formula (1).

Another object of the present invention is an anisotropic polymer or polymer film prepared from at least one compound of formula (1) or from a polymerizable liquid crystal mixture comprising at least one compound of formula (1).

Still another object of the present invention is an optical film, polarizer, compensator, beam splitter, reflector, alignment layer, color filter, holographic component, hot stamping foil, colored image, decorative or safety marking Electronic devices such as liquid crystal pigments, adhesives, synthetic resins having anisotropic mechanical properties, cosmetics, diagnostics, nonlinear optics, optical information storage, as chiral dopants, for example as field effect transistors (FETs) as components of integrated circuits. In organic light emitting diode (OLED) applications such as flat panel display applications or as thin film transistors for Radio Frequency Identification (RFID) tags, or electroluminescent displays or for example liquid crystal displays. Electrodes in a battery, for photovoltaic or sensor devices, in the component of the semiconductor for the backlight of the For electrophotographic applications such as, or electrophotographic recording, as a photoconductor as quality, the use of the polymerizable compound, the polymerizable mixture and the produced polymer thereof of the formula (I).

Another object of the present invention is a liquid crystal display comprising a mixture or polymer comprising at least one compound of formula 1 or at least one compound of formula 1 in an active layer.

Definition of Terms

The term 'membrane' as used herein refers to self-supporting, ie, free-standing film, also on a support substrate, which exhibits more or less obvious mechanical stability and flexibility. Or a coating or layer between two substrates.

The term 'mesogenic compound' as used above and below refers to a rod-shaped, lath-shaped or disk-shaped mesogenic group, ie, mesophase action. A compound with a group capable of This compound does not necessarily have to exhibit mesophase action alone. This compound may also exhibit mesophase action only in admixture with other compounds or when the mesogenic compound or mixture comprising it is polymerized. Rod and las mesogenic groups are particularly preferred.

For simplicity, the term 'liquid crystal material' is used hereinafter for both liquid crystal material and mesogenic material, and the term 'mesogen' is used for the mesogenic group of the material.

Detailed description of the invention

The compounds of formula 1 are particularly suitable for use in liquid crystalline polymerizable compositions which induce high birefringence. They do not have to exhibit mesophase action, but they must exhibit mesophase action in mixtures with other compounds. However, particular preference is given to compounds of the formula (1) having a wide range of meso phases. In addition, the compounds of formula 1 tend to inhibit crystallization of the mixture and to exhibit improved UV stability.

Especially,

m1 + m2 = 1 or 2,

m1 = m2 = 0,

m1 = m2 = 1,

A ¹ and A ² are aromatic groups, preferably m 1 or m 2 is 1,

m is 1 and A 1 is a phenylene group in which one or more CH groups are replaced by N,

Z ¹ and Z ² are selected from -COO-, -OCO- and -C≡C-,

r is 0,

r is 1 or 2,

r is 1 or 2 and L is F.

R has one of the meanings of P-Sp-X-,

-Sp-X- is different from a single bond,

Sp is the number of carbons, optionally mono- or polysubstituted by F and at least one non-contiguous CH ₂ can be replaced by -O-, -CH = CH- or -C≡C- independently of each other in each case; Alkylene having 1 to 12,

-X is -O-, -COO-, -OCO-, -OCOO- or a single bond,

Preferred are compounds of formula 1, wherein Sp and X are single bonds.

In Formula 1, L is preferably F, Cl, CN, OH, NO ₂ , CH ₃ , C ₂ H ₅ , OCH ₃ , OC ₂ H ₅ , COCH ₃ , COC ₂ H ₅ , COOCH ₃ , COOC ₂ H ₅ , CF ₃ , OCF ₃ , OCHF ₂ or OC ₂ F ₅ , in particular F, Cl, CN, CH ₃ , C ₂ H ₅ , OCH ₃ , COCH ₃ or OCF ₃ , most preferably F, Cl, CH ₃ , OCH ₃ or COCH ₃ .

In Formula 1, A ¹ and A ² are preferably aromatic, in which the ring may comprise at least one hetero atom, in particular a hetero atom selected from N, O and S, and may also be mono- or polysubstituted by L. Or a cycloaliphatic 5- or 6-ring, or a group comprising two or three conjugated aromatic or cycloaliphatic 5- or 6-rings.

In Formula 1, preferred A ¹ and A ² groups are, for example, furan, pyrrole, thiophene, oxazole, thiazole, thiadiazole, imidazole, phenylene, pyridine, pyrimidine, pyrazine, indane, naphthalene, tetra Hydronaphthalene, anthracene and phenanthrene.

Especially preferably, A ¹ and A ² are furan-2,5-diyl, thiophen-2,5-diyl, wherein one or two non-adjacent CH ₂ groups can also be replaced by O and / or S. , Pyrrole-2,5-diyl, 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, 1,2,3,4-tetra Hydronaphthalene-2,6-diyl, indan-2,5-diyl, also 1,4-cyclohexylene, all such groups may be unsubstituted or mono- or polysubstituted by L as defined above.

Preferably, in the formula ¹ (Z 1 -A 1) _m1 and (A ² -Z ²⁾ _m2 group, m1 = m2 a monocyclic group containing only the A ¹ and A ^2. Very ^{preferably, - (A 1 -Z 1)} m1 - and _{^{- (Z 2 -A 2) m2}} - groups are, independently, it represents a single or with two of the 5- or 6-membered ring with each other. _{^{- (A 1 -Z 1) m1}} - and _{^{- (Z 2 -A 2) m2}} - groups are the same or different from each other. Particular preference is given to compounds in which-(A ¹ -Z ¹ ) _m1 -and-(Z ² -A ² ) _m2 -are different.

Preferred chemical formulas for the groups-(A ¹ -Z ¹ ) _m1 -and-(Z ² -A ² ) _m2 -are listed below. For simplicity, Phe in this group is 1,4-phenylene, Phe L is a 1,4-phenylene group substituted by 1 to 4 L groups as defined above, Pyd is pyridine-2,5-diyl Pyr is pyrimidine-2,5-diyl. Preferred _{^{- (A 1 -Z 1) m1}} - and _{^{- (Z 2 -A 2) m2}} - to a list of the groups is a radical tolran compound of Formula 2a to 2p is connected groups of formula (1) through Z, also its enantiomers Contains:

-Phe-Z-

-Pyd-Z-

-Pyr-Z-

-PheL-Z-

-Phe-Z-Phe-Z-

-Phe-Z-Pyd-Z-

-Pyd-Z-Phe-Z-

-Phe-Z-Pyr-Z-

-Pyr-Z-Phe-Z-

-PheL-Z-Phe-Z-

-PheL-Z-Pyd-Z-

-PheL-Z-Pyr-Z-

-Pyr-Z-Pyd-Z-

-Pyd-Z-Pyd-Z-

-Pyr-Z-Pyr-Z-

-PheL-Z-PheL-Z-.

In this preferred group, Z has the meaning of Z ¹ as given in formula (1). Preferably, Z is -COO-, -OCO-, -CH ₂ CH _2- , -C≡C- or a single bond.

Very ^{preferably, - (A 1 -Z 1)} m1 - and _{^{- (Z 2 -A 2) m2}} - is of formula below, that is, independently of each other, via the radicals Z tolran connection group of the formula:

(Wherein Z and L have the meanings given above and r is 0, 1, 2, 3 or 4, preferably 0, 1 or 2)

And mirror images thereof.

Attached to the acetylene in the formula ^{1 - (A 1 -Z 1)} m1 -, Z is preferably a single bond in the formula 2aa preferred to 2ff for groups.

In this preferred formula Very preferably, L each independently has one of the meanings given above, , or , Also Indicates.

Particular preference is given to the formulas 2aa, 2cc, 2ff, 2gg and 2hh, especially the formulas 2aa, 2dd and 2ff.

one or more r is 1 Particular preference is given to compounds of the formula (1) comprising a group.

two or more with r equal to 1 One or more groups and / or r is 2 More preferred are compounds of formula (1) comprising a group.

In formula (1), R is preferably an alkyl, alkoxy, sulfanylalkyl, thiocarboxyl, alkylsulfonyl or alkenyl radical.

When R in the formula (1) is an alkyl or alkoxy radical, ie when the terminal CH ₂ group is replaced by —O—, it may be straight or branched. It is preferably straight-chain and has 2, 3, 4, 5, 6, 7 or 8 carbon atoms and thus for example ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, ethoxy, propoxy, butoxy , Pentoxy, hexoxy, heptoxy, or octoxy, also methyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, nonoxy, decocky, undecoxy, dodecoxy, Tridecoxy or tetradecoxy is preferred.

Oxaalkyl, ie oxaalkyl in which one CH ₂ group is replaced by -O-, is, for example, straight chain 2-oxapropyl (= methoxymethyl), 2-(= ethoxymethyl) or 3-oxabutyl (= 2-methoxyethyl), 2-, 3-, or 4-oxapentyl, 2-, 3-, 4- or 5-oxhexyl, 2-, 3-, 4-, 5-, or 6- Oxaheptyl, 2-, 3-, 4-, 5-, 6- or 7-oxactyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanonyl or 2-, Preference is given to 3-, 4-, 5-, 6-, 7-, 8- or 9-oxadecyl.

When R in Formula 1 is an alkylsulfanyl radical, that is, when the CH ₂ group linked to an adjacent group is alkyl replaced by -S-, it may be straight or branched. It is preferably straight-chain and has 1, 2, 3, 4, 5, 6, 7 or 8 carbon atoms and thus, for example, methylsulfanyl, ethylsulfanyl, propylsulfanyl, butylsulfanyl, pentylsulfanyl , Hexylsulfanyl, heptylsulfanyl, octylsulfanyl, nonylsulfanyl, decylsulfanyl, undecylsulfanyl or dodecylsulfanyl is preferred.

When R is a thiocarboxyl or alkylsulfanylcarbonyl group, ie when the CH ₂ group linked to a neighboring group is an alkyl group replaced by -CO-S- or -S-CO-, it may be straight or branched. . It is preferably straight-chain and has 2, 3, 4, 5, 6, 7 or 8 carbon atoms and thus, for example, thioacetyl, thiopropionyl, thiobutyryl, thiopentanoyl, thiohexanoyl, thiohepta Preferred are noyl, thiooctanoyl, methylsulfanylcarbonyl, ethylsulfanylcarbonyl, propylsulfanylcarbonyl, butylsulfanylcarbonyl, pentylsulfanylcarbonyl, hexylsulfanylcarbonyl or heptylsulfanylcarbonyl .

When R is an alkylsulfonyl group, that is, when the CH ₂ group adjacent to an adjacent group is an alkyl group replaced by a sulfonyl group or —SO ₂ —, it may be straight or branched. It is preferably straight-chain and has 1, 2, 3, 4, 5, 6, 7 or 8 carbon atoms and, for example, methylsulfone, ethylsulfone, propylsulfone, butylsulfone, pentylsulfone, hexylsulfone, heptyl Sulfone or octyl sulfone, also nonyl sulfone, decyl sulfone, undecyl sulfone or dodecyl sulfone is preferred.

If R is an alkyl group wherein at least one CH ₂ group is replaced by —CH═CH—, it may be straight or branched. It is preferably straight-chain and has 2 to 10 carbon 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, deck-1-, 2-, 3-, 4-, 5-, 7-, 8- or deck-9-enyl.

Particularly preferred alkenyl groups are C ₂ -C ₇ -1E-alkenyl, C ₄ -C ₇ -3E-alkenyl, C ₅ -C ₇ -4-alkenyl, C ₆ -C ₇ -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 include 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. In general, groups having 5 or less carbon atoms are preferred.

When R is an alkyl group in which one CH ₂ group is replaced by -O- and one is replaced by -CO-, it is preferred that these radicals are present next to each other. Thus, these radicals together form a carbonyloxy group -CO-O- or an oxycarbonyl group -O-CO-. Preferably this R group is straight and has 2 to 6 carbon atoms.

Thus, it is acetyloxy, propionyloxy, butyryloxy, pentanoyloxy, hexanoyloxy, acetyloxymethyl, propionyloxymethyl, butyryloxymethyl, pentanoyloxymethyl, 2-acetyloxyethyl, 2-propy Onyloxyethyl, 2-butyryloxyethyl, 3-acetyloxypropyl, 3-propionyloxypropyl, 4-acetyloxybutyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, Pentoxycarbonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, butoxycarbonylmethyl, 2- (methoxycarbonyl) ethyl, 2- (ethoxycarbonyl) ethyl, 2 -(Propoxycarbonyl) ethyl, 3- (methoxycarbonyl) propyl, 3- (ethoxycarbonyl) propyl, 4- (methoxycarbonyl) -butyl are preferred.

If R is an alkyl group wherein at least two CH ₂ groups are replaced by -O- and / or -COO-, it can be straight or branched. It is preferably straight chain and has 3 to 12 carbon atoms. Thus it is 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- (methoxy Carbonyl) -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- (in Preference is given to oxycarbonyl) -propyl, 4,4-bis- (ethoxycarbonyl) -butyl, 5,5-bis- (ethoxycarbonyl) -hexyl.

When R is an alkyl or alkenyl group mono-substituted by CN or CF ₃ , it is preferably straight chain. Substitution with CN or CF ₃ is possible at any desired position.

When R is an alkyl or alkenyl group which is at least monosubstituted by halogen, it is preferably straight chain. Halogen is preferably F or Cl and, in the case of multiple substitutions, preferably F. The resulting groups also include perfluorinated groups. In the case of monosubstitution, the F or Cl substituent may be present at any desired position, but is preferably at the ω-position. Examples of particularly preferred straight chain groups having terminal F substituents 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 in Formula 1 may be a polar or nonpolar group. For polar groups, it is selected from CN, SF ₅ , halogen, OCH ₃ , SCN, COR ⁵ , COOR ⁵ or mono- oligo- or polyfluorinated alkyl or alkoxy having 1 to 4 carbon atoms. R ⁵ is optionally fluorinated alkyl having 1 to 4 carbon atoms, preferably 1 to 3 carbon 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 having up to 15 carbon atoms or alkoxy having 2 to 15 carbon atoms.

R in Formula 1 may be an achiral or chiral group. In the case of a chiral group, this is preferably of the formula 3:

(Wherein

Q ¹ is an alkylene or alkylene-oxy group having 1 to 9 carbon atoms or a single bond,

Q ² may be unsubstituted or mono- or polysubstituted by F, Cl, Br or CN, and also in such a way that one or more non-adjacent CH ₂ groups are independently of each other in each case, so that the oxygen atoms are not directly connected to each other , -C≡C-, -O-, -S-, -NH-, N (CH ₃ )-, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO- or An alkyl or alkoxy group having 1 to 10 carbon atoms, which may be replaced by -CO-S-,

Q ³ is an alkyl or alkoxy group as defined for F, Cl, Br, CN or Q ² but different from Q ² )

Is selected from.

When Q ¹ in the formula (3) is an alkylene-oxy group, the O atom is preferably adjacent to a chiral C atom.

Preferred chiral groups of formula 3 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-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-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- to Methoxypropyl-2-oxy, 1-propoxypropyl-2-oxy, 1-butoxypropyl-2-oxy, 2-fluorooctyloxy, 2-fluorodecyloxy, 1,1,1-trifluoro in -2-octyloxy, 1,1,1-trifluoro-2-octyl, 2-fluoromethyloctyloxy. 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 is very preferred.

In addition, compounds of formula (1) comprising the achiral branching group R may often be important, for example, due to a decrease in the tendency to crystallize. Generally, this type of branching group does not include one or more chain branches. Preferred achiral branching groups are isopropyl, isobutyl (= methylpropyl), isopentyl (= 3-methylbutyl), isopropoxy, 2-methylpropoxy and 3-methylbutoxy.

The polymerizable or reactive group P is preferably H ¹ , H, Cl, CN, phenyl or alkyl having 1 to 5 carbon atoms, in particular H, Cl or CH ₃ , and W ² and W ³ are independently of each other H or carbon atoms Alkyl having 1 to 5, in particular methyl, ethyl or n-propyl, W ⁴ , W ⁵ and W ⁶ are independently of each other Cl, oxaalkyl or oxacarbonylalkyl having 1 to 5 carbon atoms, Phe is 1, CH ₂ = CW ¹ -COO-, wherein 4-phenylene and k ₁ and k ₂ are each independently 0 or 1 , , CH ₂ = CW ^2- (O) _k1- , -CH ₃ -CH = CH-O-, (CH ₂ = CH ₂ ) CH-OCO-, (CH ₂ = CH-CH ₂ ) CH-OCO-, (CH ₂ = CH ₂ ) ₂ CH-O-, (CH ₂ = CH-CH ₂ ) ₂ N-, HO-CW ² W ^3- , HS-CW ² W ^3- , HW ² N-, HO-CW _{^{2 W 3 -NH-, CH 2 =}} CW 1 -CO-NH-, CH 2 = CH- (COO) k1 -Phe- (O) k2 -, Phe-CH = CH-, HOOC-, OCN-, and W ⁴ W ⁵ W ⁶ Si-.

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

As for the spacer group Sp, all groups known to those skilled in the art for this purpose can be used. The spacer group Sp preferably further comprises at least one non-contiguous CH ₂ group being -O-, -S-, -NH-, -N (CH ₃ )-, -CO-, -O-CO-, -S-CO -, -O-COO-, -CO-S-, -CO-O-, -CH (halogen)-, -C (halogen) ₂ , -CH (CN)-, -CH = CH- or -C≡ C-, a straight or branched chain alkylene group having 1 to 20 carbon atoms, in particular 1 to 12 carbon atoms, which may be replaced by siloxane groups.

Typical spacer groups include, for example,-(CH ₂ ) _p -,-(CH ₂ , wherein p is an integer from 2 to 12, r is an integer from 1 to 3 and R ⁰ and R ⁰⁰ have the meanings given in formula (1). CH ₂ O) _r- , -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- .

Preferred spacer groups are, for example, 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.

More preferred are compounds having one or two P-Sp-X groups, wherein Sp and / or X are a single bond.

In the case of compounds having two P-Sp-X groups, each of the two polymerizable groups P, two spacer groups Sp, and two bonding groups X may be the same or different.

In another preferred embodiment of the invention, the chiral compound of formula 1 is a chiral group of formula 4:

(Wherein

Q ¹ and Q ³ have the meaning given in formula (3),

Q ⁴ is an alkylene or alkylene-oxy group or a single bond having 1 to 10 carbon atoms, different from Q ¹ )

At least one spacer group Sp.

Particularly preferred compounds of formula 1 are compounds of formula

(Wherein P, Sp, X, R, L and r have the meanings given above).

Particularly preferred are compounds of the above formula, wherein R is P-Sp-X, and compounds of the above formula, wherein R is H or alkyl having 1 to 8 carbon atoms.

Compounds of formula (I) are known per se and according to, or similar to, methods described in standard workbooks of organic chemistry such as, for example, Hauben-Weyl, Methoden der organischen Chemie, Tieme-Verlag, Stuttgart It can be synthesized by the method. Several specific manufacturing methods can be obtained from the examples.

Compounds of formula (1) are, for example, IPS (planar switched) or VA, such as TN or STN displays, active matrix displays, VANs (vertically aligned nematic) or VAC (vertically aligned cholesteric) (Vertically aligned) display, ECB (electrically controlled birefringence), DAP (aligned phase deformation), CSH (color super homeotropic) or ASM (axis symmetric microcell) display, phase-change Can be used in guest-host, flexoelectric, ferroelectric displays, bistable nematic and cholesteric displays such as polymer stabilized cholesteric structures (PSCT), or PDLC, polymer gel or polymer network displays have.

In particular, the polymerizable compounds of formula (1) and mixtures comprising them are intended for the purpose of helping to improve alignment, mesophase stability and / or electro-optic properties, in particular for achieving faster reaction times and / or lower threshold voltages. It is useful for liquid crystal displays comprising polymers or polymer network components for the purpose or for creating multidomain structures to achieve improved contrast at a wide viewing angle. Such displays are, for example, TN, STN, ECB, VA, IPS, multidomain or hybrid displays, which are described, for example, in US 5,189,540, US 6,177,972, EP 0 903 392, and in Hasebe et al., Jpn. J. Appl. Phys. 1994, 33, 6245).

In addition, compounds of Formula 1 are described, for example, as described in H. Guillard and P. Sixou, Liq. Cryst. (2001) 28 (6), 933, the entire disclosure of which is incorporated herein by reference. The same active broadband polymer stabilized liquid crystal displays are suitable as polymerizable components. This display comprises an active cholesteric layer with a broadened reflected wavelength band that can switch between planar reflection, scattering and homeotropic transparent states.

Compounds of formula 1 are also suitable as polymer components in polymer stabilized displays, such as bistable PSCT (polymer stabilized cholesteric structure) displays, or in PDLC or polymer gel displays in scattering form. Anisotropic polymer gels and displays comprising them are for example disclosed in DE 195 04 224, GB 2 279 659, WO 93/22937, US 5,538,768, US 5,543,075 and EP 0 451 905.

Accordingly, another object of the present invention is a liquid crystal mixture, in particular a nematic liquid crystal mixture, comprising at least one compound of the formula (1).

Another object of the present invention is a liquid crystal display comprising a liquid crystal medium containing at least one compound of the formula (1).

For the above applications, the liquid crystal mixture preferably contains a nematic host mixture comprising at least one compound of the formula (1), and at least one nematic or nematogenic compound.

Preferably the liquid crystal mixture consists of 2 to 25, preferably 3 to 15 compounds, at least one of which is a compound of formula (1). Other compounds forming the nematic host mixture are preferably nematic or nematogenic substances, for example axoxybenzene, benzylidene-aniline, biphenyl, terphenyl, phenyl or cyclohexyl benzoate of known kind, Phenyl or cyclohexyl ester of cyclohexanecarboxylic acid, phenyl or cyclohexyl ester of cyclohexylbenzoic acid, phenyl or cyclohexyl ester of cyclohexylcyclohexanecarboxylic acid, of benzoic acid, cyclohexanecarboxylic acid and cyclohexylcyclo Cyclohexylphenyl ester of hexanecarboxylic acid, phenylcyclohexane, cyclohexylbiphenyl, phenylcyclohexylcyclohexane, cyclohexylcyclohexane, cyclohexylcyclohexene, cyclohexylcyclohexylcyclohexene, 1,4-bis-cyclohexyl Benzene, 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, benzyl phenyl ether, tolan, substituted cinnamic acid and another kind of nematic or nematogenic material. In addition, the 1,4-phenylene group in this compound may be mono- or difluorinated in a side chain.

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

The most important compounds possible as components of such liquid crystal mixtures are represented by the formula:

R'-L'-G'-E-R "

(Wherein

L 'and E, which may be the same or different, are independently of each other at each occurrence a Phe unsubstituted or fluorine-substituted 1,4-phenylene and Cyc is trans-1,4-cyclohexylene or 1, 4-cyclohexenylene, Pyr is pyrimidine-2,5-diyl or pyridine-2,5-diyl, Dio is 1,3-dioxane-2,5-diyl, and B is 2- (trans -Phe-, -Cyc-,-which is -1,4-cyclohexyl) ethyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl or 1,3-dioxane-2,5-diyl Divalent radicals and mirror images thereof from the groups formed by Phe-Phe-, -Phe-Cyc-, -Cyc-Cyc-, -Pyr-, -Dio-, -B-Phe- and -B-Cyc-)

It may be characterized by.

G 'in this compound is represented by the following divalent groups -CH = CH-, -N (O) N-, -CH = CY-, -CH = N, wherein Y is halogen, preferably chlorine, or -CN. (O)-, -C≡C-, -CH ₂ -CH _2- , -CO-O-, -CH ₂ -O-, -CO-S-, -CH ₂ -S-, -CH = N- , -COO-Phe-COO- or a single bond.

R 'and R "in each case independently of each other, alkyl, alkenyl, alkoxy, alkenyloxy, alkanoyloxy, alkoxycarbonyl or alkoxycarbonyloxy having 1 to 18 carbon atoms, preferably 3 to 12 carbon atoms Or optionally one of R 'and R "is F, CF ₃ , OCF ₃ , Cl, NCS or CN.

R 'and R "in most of these compounds, independently of each other in each case, are alkyl having different chain lengths, in which the sum of the carbon numbers of the nematic medium is generally from 2 to 9, preferably from 2 to 7, Alkenyl or alkoxy.

Many of these compounds or mixtures thereof are commercially available. All of these compounds are known or exactly known and under reaction conditions suitable for the reaction, for example, Hauben-Weyl, Methoden der Organischen Chemie [Methods of Organic Chemistry], Georg-Thime-Verlag, Stuttgart It may be prepared by a method known per se as described in a standard workbook such as. While known per se, variations not mentioned herein can be used in the present application.

Compounds of formula (1) and polymerizable liquid crystal mixtures comprising the same are more useful for the production of anisotropic polymer films or coatings.

For the preparation of anisotropic polymer gels or polymer films, the liquid crystal mixture should comprise at least one polymerizable compound, which can be a compound of formula 1 or an additional polymerizable mesogenic or liquid crystalline compound.

Examples of suitable polymerizable mesogenic compounds that can be used as comonomers with compounds of formula 1 in the polymerizable liquid crystal mixtures are described, for example, in WO 93/22397; EP 0,261,712; DE 195,04,224; WO 95/22586 and WO 97/00600. However, the compounds disclosed in this document should be considered as examples that do not limit the scope of the invention.

Preferably the polymerizable liquid crystal mixture comprises at least one polymerizable mesogenic compound having one polymerizable functional group and at least one polymerizable mesogenic compound having two or more polymerizable functional groups.

Examples of particularly useful chiral and achiral polymerizable mesogenic compounds, which are illustrative only and not intended to limit the present invention, are described in the following list:

Wherein P has the meaning of Formula 1 and one of the preferred meanings above, x and y are the same or different integers from 1 to 12, and A and D are 1,4-phenylene or 1,4-cyclo Hexylene, v is 0 or 1, Y is a polar group, R ⁰ is a nonpolar alkyl or alkoxy group, Ter is a terpenoid radical such as, for example, menthyl, Chol is a cholesteryl group, L ¹ and L ² are each independently H, F, Cl, OH, CN, NO ₂ or optionally alkyl, alkoxy, alkylcarbonyl or alkoxycarbonyl having 1 to 7 carbon atoms).

In this regard, the term 'polar group' refers to F, Cl, CN, NO ₂ , OH, OCH ₃ , OCN, SCN, optionally fluorinated carbonyl or carboxyl groups having 4 or less carbon atoms or having 1 to 4 carbon atoms. A group selected from mono-, oligo- or polyfluorinated alkyl or alkoxy groups. The term 'non-polar group' means an alkyl group having 1 or more carbon atoms, preferably 1 to 12 or an alkoxy group having 2 or more carbon atoms, preferably 2 to 12 carbon atoms.

The polymerizable liquid crystal mixture according to the present invention may also comprise one or more non-reactive chiral dopants, additionally or optionally chiral polymerizable mesogenic compounds. Commonly used chiral dopants are, for example, commercially available R or S 811, R or S 1011, R or S 2011 or CB 15 (Merck KGaA, manufactured by Darmstadt, Germany).

A chiral dopant with high helix twisting force (HTP), in particular a dopant comprising a sorbitol group as described in WO 98/00428, a dopant comprising a hydrobenzoin group as described in GB 2,328,207, as described in WO 02/94805 Chiral binaphthyl derivatives such as, chiral binaphthol acetal derivatives as described in WO 02/34739, chiral TADDOL derivatives as described in WO 02/06265, and at least one fluorine as described in WO 02/06196 and WO 02/06195. Very preferred are chiral compounds with ized bond groups and terminal or central chiral groups.

To produce an anisotropic polymer film, a polymerizable liquid crystal is preferably coated on a substrate and aligned and polymerized in situ, for example by exposure to heat or actinic radiation to fix the orientation of the liquid crystal molecules. Alignment and curing are carried out on the liquid crystalline phase of the mixture.

The substrate is, for example, a glass or quartz sheet or a plastic film or sheet, and may or may not be removed after polymerization. Suitable plastic substrates are, for example, polyethylene terephthalate (PET) of polyvinyl alcohol (PVA), polycarbonate (PC) or triacetyl cellulose (TAC). The polymerizable chiral LC material may also be dissolved or dispersed in an organic solvent which is evaporated before or during the polymerization.

For example, the liquid crystal material can be aligned by treating the substrate on which the material is coated, shearing the material during or after coating, applying a magnetic or electric field to the coated material, or adding a surface-active compound to the liquid crystal material. have. Alignment techniques are described, for example, in I. Sage in "Thermotropic Liquid Crystals", edited by IGW Gray, John Wiley & Sons, 1987, pages 75-77, and T. Uchida and H. Seki in "Liquid Crystals-Applications. and Uses Vol. 3 ", edited by B. Bahadur, World Scientific Publishing, Singapore 1992, pages 1-63. Alignment materials and techniques are reviewed in J. Cognard, Mol. Cryst. Liq. Cryst. 78, Supplement 1 (1981), pages 1-77.

Exposure to heat or actinic radiation results in polymerization. Actinic radiation refers to irradiation with light such as UV light, IR light or visible light, irradiation with X-rays or gamma ray, or irradiation with high energy particles such as ions or electrons. Preferably, the polymerization is carried out by UV radiation at non-absorbing wavelengths. As a source of actinic radiation, for example, a single UV lamp or a set of UV lamps can be used. If high lamp power is used, the curing time can be reduced. Another possible source of actinic radiation is a laser such as a UV laser, IR laser or visible laser.

The polymerization is carried out in the presence of an initiator that absorbs at the wavelength of actinic radiation. For example, when polymerizing through UV light, photoinitiators that decompose under UV radiation can be used to produce free radicals or ions that initiate the polymerization reaction. When curing the polymerizable mesogen having acrylate or methacrylate groups, a radical photoinitiator is preferably used, and when curing the polymerizable mesogen vinyl and epoxide groups, cationic photoinitiators are preferably used. It is also possible to use polymerization initiators which produce free radicals or ions which decompose when heated to start the polymerization. As photoinitiators for radical polymerization, for example, commercially available Irgacure 651, Irgacure 184, Darocure 1173 or Darocure 4205 (all manufactured by Ciba Geigy AG) can be used, whereas in the case of cationic photopolymerization commercially available. Possible UVI 6974 (Union Carbide) can be used.

Polymerizable materials also include, for example, catalysts, sensitizers, stabilizers, inhibitors, antioxidants, chain-transfer agents, co-reacting monomers, surface-active compounds, lubricants, wetting agents, dispersants, hydrophobic agents And one or more other suitable ingredients such as adhesives, flow improvers, antifoams, degassers, diluents, reactive diluents, adjuvants, colorants, dyes or pigments.

Compounds of formula (1) comprising chiral groups are suitable as chiral dopants.

In addition, the compounds of formula (1) are, for example, thin film transistors for flat panel display applications or for Radio Frequency Identification (RFID) tags in electronic devices such as field effect transistors (FETs) as components of integrated circuits, Or organic light emitting diode (OLED) applications such as electroluminescent displays or components of semiconductors for backlighting, for example liquid crystal displays, electrophotographic applications such as photovoltaic or sensor devices, photoconductors, or electrophotographic recording devices. Suitable as comonomers for liquid crystal materials having semiconductor or charge carrier properties, which can be used in the field.

For example, a semiconductor comprising a polymerizable liquid crystal compound is disclosed in WO 00/79617, JP-A-2000-347432, JP-A-11-209761, Sirringhaus et al., Appl. Phys. Lett., 77 (3) (2000) 406-408 and in Grell et al., J. Korean Phys. Soc . 2000, 36 (6), 331. Electroluminescent devices using liquid crystal materials are described, for example, in WO 95/17018 and WO 95/04306. Organic photoconductors with liquid crystal properties are described, for example, in EP 0 563 768 and EP 0 527 376.

Without further effort, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. Accordingly, the following examples are to be construed as illustrative only, and in no way limit the rest of the disclosure.

Example

In the above and the following examples, unless otherwise indicated, all temperatures are given in uncorrected degrees Celsius and all parts and percentages are percent by weight. The following abbreviations are used to describe the liquid crystalline phase action of the compounds: K = liquid crystalline; N = nematic; S = smectic; Ch = cholesteric; I = anisotropy. Numbers between the symbols indicate the phase transition temperature in ° C. Mp. Is the melting point, Δn is the optical anisotropy measured at 20 ° C. and 589 nm, and Δε is the dielectric anisotropy at 20 ° C. and 1 kHz.

Example 1

The compound of formula 7 is prepared according to the following scheme:

.

In a similar manner to prepare a compound of formula 8:

K 92 S _A 175 N 190 I

Δn = 0.3156.

According to the invention, it is possible to obtain compounds which have high birefringence and which can be used for the preparation of oriented liquid crystal polymer films or which can be used as compounds in the active layer of switchable LC devices in mixtures with low molecular weight LC media.

Claims (10)

Polymerizable Compounds of Formula 1: [Formula 1] (Wherein P is a polymerizable group, Sp is a spacer group or a single bond, X is -O-, -S-, -CO-, -COO-, -OCO-, , -OCO-O, -S-CO- , -CO-S, -CO-NR 0, -NR 0 -CO-, -OCH 2 -, -CH 2 O-, -SCH 2 -, -CH 2 S -, -CH = CH-COO-, -OOC-CH = CH-, CH ₂ CH ₂ or a single bond, Z ¹ and Z ² are each _{independently, -COO-, -OCO-, -CH 2 CH} 2 -, -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 = CH-, -CH = CH-, -CF = CH-, -CH = CF-, -CF = CF-, -CH = CH-COO-, -OCO-CH = CH-, -C≡C- or single Is a combination, A ¹ and A ² are each independently an aliphatic or aromatic carbocyclic or heterocyclic group having 16 or less carbon atoms, which may consist of a conjugated ring and which may be unsubstituted or mono- or polysubstituted with L. , m1 and m2 are each independently 0, 1, 2 or 3, with m1 + m2 <5, R may be H, F, Cl, Br, I, CN, SCN, SF ₅ , unsubstituted, mono-, or polysubstituted by F, Cl, Br, I or CN, one or more non-contiguous CH ₂ groups are independently of each other at each occurrence: -O-, -S-, -NH-, -NR ^0- , -SiR ⁰ R ^00- , -CO-, -COO-, -OCO-, -OCO-O O and / or S atoms are each other by-, -S-CO-, -CO-S-, -SO ₂ , -SO-O-, -O-SO-, -CH = CH- or -C≡C- Straight or branched chain alkyl having 25 or less carbon atoms, which may be replaced in a manner not directly connected, or P-Sp-X, R ^O and R ^OO are independently of each other H or alkyl having 1 to 4 carbon atoms, L is F, Cl, Br, I, CN, NO ₂ or alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl or alkylcarbonyl having 1 to 7 carbon atoms, in which one or more H atoms may be substituted by F or Cl Oxy, r is 0, 1, 2, 3 or 4). The method of claim 1, A polymerizable compound wherein R has one of the meanings of P-Sp-X in formula (1). The method according to claim 1 or 2, A polymerizable compound, characterized in that m1 + m2 = 1 or 2. The method according to any one of claims 1 to 3, Furan-2,5-diyl, thiophene-2,5-diyl, pyrrole-2, wherein A ¹ and A ² may additionally be replaced by O and / or S with one or two non-contiguous CH ₂ groups , 5-diyl, 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2 , 6-diyl, indan-2,5-diyl, and also 1,4-cyclohexylene, wherein all such groups can be unsubstituted or mono- or polysubstituted by L as defined in formula (1) A polymerizable compound which consists of. The method according to any one of claims 1 to 4, -(A ¹ -Z ¹ ) _m1 -and-(Z ² -A ² ) _m2 -independently of each other, combine with the tolan group of formula 1 via the radical Z: [Formula 2aa] [Formula 2bb] [Formula 2cc] [Formula 2dd] [Formula 2ee] [Formula 2ff] [Formula 2gg] [Formula 2hh] (Wherein L and r have the meaning of formula 1 and Z has one of the meanings of Z ¹ in formula 1) And a mirror image thereof. The compound of any one of claims 1 to 5, wherein [Formula 1a] [Formula 1b] [Formula 1c] [Formula 1d] [Formula 1e] [Formula 1f] [Formula 1g] (Wherein P, Sp, X, R, L and r have the meanings given above) A polymerizable compound, characterized in that is selected from. A polymerizable liquid crystal mixture comprising at least one compound according to any one of claims 1 to 6. Anisotropic polymer or polymer film obtained from the polymerizable liquid crystal mixture according to claim 7. Optical films, polarizers, compensators, beam splitters, reflecting films, alignment layers, color filters, holographic components, hot stamping foils, colored images, decorative or safety markings, liquid crystal pigments, adhesives, synthetic resins with anisotropic mechanical properties, cosmetics, In electronics, such as field effect transistors (FETs) as chiral dopants, for example as components of integrated circuits in diagnostics, nonlinear optics, optical information storage, in flat panel display applications or in frequency recognition system (RFID) tags Electrode materials in batteries, for photovoltaic or sensor devices, as thin film transistors, or in components of semiconductors for organic light emitting diode (OLED) applications such as electroluminescent displays or for backlights, such as for example liquid crystal displays. Electrophotographic application, such as, as a photoconductor, or electrophotographic recording Use of the polymerizable liquid crystal material according to any one of claims 1 to 6, the mixture according to claim 7 or the polymer or polymer membrane according to claim 8 for the field. A liquid crystal display comprising at least one compound according to any one of claims 1 to 6, a mixture according to claim 7, or a polymer or polymer film according to claim 8 in an active layer.