EP1778667A1 - Compounds and methods for producing anisotropy - Google Patents

Abstract

The invention relates to novel compounds containing at least one multiple bond that is excited by irradiation with polarised light and thus produces an anisotropy in films containing said compounds or amplifies an already existing anisotropy or modifies the orientation thereof. The invention also relates to methods for producing said compounds, to mixtures and polymers containing said compounds, and to the use of the inventive compounds, mixtures, and polymers for producing anisotropic layers, for example for optical components or devices.

Description

 Compounds and methods for producing anisotropy

Subject of the invention

The invention relates to novel compounds containing at least one

Multiple bond, which is excited by irradiation with polarized light and thereby produces anisotropy in these compounds or in mixtures containing these compounds or alters an existing anisotropy. The invention further relates to processes for the preparation of these compounds. The invention further relates to mixtures and polymers containing these

Compounds, as well as the use of the compounds, mixtures and polymers for producing anisotropic layers, for example for optical components or devices.

State of the art

a) Light-induced anisotropy

One possible way to orient polymers or to form polymer films with anisotropic properties is to interact photochromic groups within the polymer with linearly polarized light. The basis of this phenomenon is the transfer of the "order of linearly polarized light" to photochromic groups in polymer films, which are subjected to angle-selective photochemical processes. The most important methods can be subdivided into angle-dependent photoselection / 1 / or photoorientation / 2 / photochromic azobenzene groups. Anisotropy based on photoselection may be the result of angle selective photodegradation or angle selective product formation which alters the original orientation distribution in polymer films or other media. Materials which undergo angle selective product formation [by 2 + 2 cycloaddition] typically contain coumarin, stilbene or cinnamic acid derivatives. Such processes are usually irreversible.

The photo-orientation of azobenzene is based in the first step on an angle-dependent photoprocess - namely a light-induced E / Z-

Isomerization. By repeating the angle selective excitation of the. Isomers in photostationary equilibrium of the photoreaction are effected numerous photo selection cycles and thus a continuous reorientation of the photochromic group perpendicular to the electric field vector of the light. In other words, the photochromic groups in the E field direction are "depleted" and simultaneously "enriched" in the direction perpendicular to E ", with their total number not changing. Such a multi-step orientation process produces a high anisotropy of up to D = 0.5. In addition, react in this process, the photochromic groups at the molecular level thermally back to the initial state, while the orientation direction is maintained in the glassy state of the polymers long-term stability. Thus, the optical properties of films of photochromic polymers are reversibly and continuously changed by photo orientation.

Possible applications include such reversible processes for generating optical anisotropy for optical data storage.

While the effect of angle-dependent photo-selection had been known as the Weigerts effect IM since the late 1920s, the photoregulation of photochromic molecules in photostationary equilibrium in films of amorphous polymers was described for the first time as such by Todorov 1983/3 /.

In recent years, numerous studies on photochemically induced anisotropy by angle-dependent photoselection and photo-orientation and the application of this technology have been published. These work include, for example, the photo alignment of liquid crystals, the production of optical films, and applications of photoinduced anisotropy in optical data storage and for the manufacture of security materials. This applies both to the light-induced orientation within polymer films (induction of anisotropy as bulk property or bulk orientation) and to the light-induced orientation on polymer surfaces (induction of anisotropy as interface property, "command surface"). The following summarizes the main research areas:

a) optical anisotropy by angle-dependent product formation, for example by photocycloaddition of cinnamic acid, stilbene or coumarin derivatives / 3,4 / (angle-dependent photoselection), b) Photo orientation of films of amorphous polymers 151, of optically isotropic and macroscopically oriented films of liquid crystal side group polymers / 6 / and in LB multilayers with azobenzene groups III or

c) the so-called command-surface effect (reversible orientation of liquid crystals on light-induced polymer interfaces with azobenzene units) / 8.9 /,

d) Photo-orientation of liquid crystals (stable light-induced orientation of liquid crystals by anisotropic photocrosslinking of polymeric interfaces) / 10-13 /,

e) light-induced formation of anisotropic networks, which i.a. cause a macroscopically uniform orientation of liquid crystals / 14 /,

f) anisotropic arrangement of dye molecules at light-induced anisotropic polymer interfaces / 15 /,

g) temporary photoreorientation of liquid-crystalline guest-host systems with

Azobenzene and anthraquinone derivatives / 16 /, also known as the Janossy effect.

b) surface photo orientation

The macroscopic orientation of liquid crystals at photoanisotropic interfaces is of technical importance for the production of liquid crystal displays (LCDs). It is of particular interest to orient macroscopically adjacent supramolecular systems, such as liquid crystals, by means of light-induced anisotropic surfaces. (Surface Photoalignment). The light-induced anisotropy of an interface is combined with the self-organization of a non-photochromic material, which is macroscopically uniformly oriented. The light-induced property change of the interface is thus strengthened as it were. In this case, a photochromic monolayer can change the orientation of a liquid crystal film of a few microns thickness. That is, the oriented molecules of the interface are the orientation of several O ⁴ effect adjacent liquid crystal molecules. Such enhancement effects are in analogy to the known AgX photography for the use of photochemical processes of particular interest.

The macroscopic orientation of liquid crystals is based on their tendency to minimize the surface energy by a more or less uniform orientation of the molecular long axes. The orientation direction is determined by the anisotropy of the surface and passed on to the liquid crystal molecules by molecular interaction.

The orienting effect of previously investigated photochromic alignment layers is attributed to mechanisms discussed above, ie, photoorientation of azobenzene or stilbenes / 17 / or angle-selective photocycloaddition of cinnamic acid derivatives / 9,18 /. Furthermore, results are available with (poly) diacetylenes / 19 / and cumarin side-group polymers / 12 /.

The light-induced anisotropy of surfaces in the orientation of liquid crystals in LCDs (liquid crystal displays) and the production of optical components has gained technological importance, in particular for large-area displays (TV, laptop) and for thin displays (ferroelectric liquid crystals) of Meaning is. The macroscopic or pixel-by-pixel orientation of liquid crystals on light-induced anisotropic polymer interfaces has a number of advantages over the classical orientation method, the rubbing of polyimide films, / 13a, b /:

Prevention of impurities and electrostatic effects, adjustable tilt angle, which leads to the improvement of the transmission voltage characteristic, microstructure, different orientations with the same material alone determined by different irradiation conditions, pixels of different orientation, which leads to improvement of the viewing angle and to an excellent gray scale. In addition, polarizers are used for displays, which are also solutions based on the optical anisotropy. Works by Ichimura, Schadt, Resnikov, Chigrinov and Gibbson / Shannon I / 8-11 characterize the current state of the art as to the surface orientation of polymers having different photochromic groups and different types of films (spin-coating films, LB multilayers or chemisorbed ones Silane films) was demonstrated (see also

Review list). At present, we are looking for more energy-efficient, "non-aging", colorless systems, systems with a precisely adjustable tilt angle and appropriate irradiation procedures.

c) bulk photo orientation

In recent years, it has been shown that the anisotropy of continuous photo-oriented films (bulk orientation) of liquid crystal polymers (LCP) upon irradiation in the mesophase, ie above the glass transition temperature (T _g ), leads to an increase in dichroism and birefringence / 20 /. This effect is based on the interaction of light-induced orientation and thermotropic self-organization of the liquid-crystalline polymers.

Thus, the anisotropy obtained by photo-orientation of azobenzene-containing LCP at room temperature in the glass state can be significantly enhanced by subsequent tempering in the mesophase / 21 /. The light-induced anisotropy causes a trend-setting effect in the LCP-FiIm.

Analogous to the azobenzene-containing LCPs, the orientation of liquid-crystalline polymer films can also be characterized by [2 + 2] cycloaddition products of liquid-crystalline

Polymers with z. B. cinnamic acid esters take place / 22 /. In contrast to the reversible bulk photo orientation based on azobenzene as a photochromic group, the crosslinking reaction in the volume of the cinnamic acid ester-containing films leads to insoluble films; the orientation process is therefore irreversible.

The enhancement or development of the anisotropy of LCP, which was previously observable only in the case of azobenzene-containing photo-orientation layers, by means of a downstream thermal ordering process, are of general importance for the efficiency and the use of photochemical processes. Reference should be made to the analogy to the halogen-silver photography process. Through the photochemical orientation process, a nucleus is created, which is light-induced by subsequent self-organization, ie thermal processes, reinforced or developed. This amplification process overcomes the efficiency problem of the induction process even within polymer films. In addition, it has been shown that the liquid-crystalline order leads to a stabilization of the anisotropy.

Alternative systems that show this amplification process are not yet known.

Object of the invention

Although polymeric azobenzene systems can be excellently photochemically oriented, as explained above, they also have serious disadvantages, which severely restricts their commercial use. In particular, the high absorption in the visible spectral range excludes many optical applications.

Other photochromic groups that only absorb in the UV, such as stilbene derivatives, sometimes lead to irreversible intramolecular side reactions or, like cinnamic acid esters, mainly show irreversible bimolecular cycloaddition reactions. In addition, in these photochromic groups, the light-induced anisotropy is usually very low regardless of the irradiation time. Often, the photoproducts show little or no shape anisotropy, so that orientation through them is less efficient.

In addition, in photocrosslinkable LOP, the liquid-crystalline properties of the mesogen are suppressed by the progressive photocrosslinking at higher irradiation doses. Numerous attempts to find a similar efficient photo-orientation system as the Azobenzensystem without the mentioned disadvantages have so far been in vain / 23 /.

The object of this invention was therefore to search for alternative materials with a suitable light-sensitive group which have good reversible orientation properties which are at least comparable or better with azobenzene, and preferably no absorption in the visible wavelength range or exclusive absorption in the UV range (Color neutrality) show. Furthermore, the absorption range should be such that conventional irradiation sources can be used. Another object of this invention was to provide appropriate monomeric and polymeric materials which, in addition to the required photochemical properties, also make good interactions with liquid crystals and allow for an alternative, efficient type of photo-orientation.

This object is achieved according to the invention by the provision of compounds as described below, which contain a multiple bond which is excited upon irradiation with polarized light and thereby causes a preferred orientation of the compound. Surprisingly, it has been found that by suitable choice of the substituents on the multiple bond, this can be excited by irradiation with polarized light and causes an orientation of the compound perpendicular to the E-field vector of the polarized light. The dominant photoreaction is one

Isomerization around the double bond; another photoreaction is not necessary for the orientation of the compound. The light-induced orientation leads to a generation of anisotropy in the compounds according to the invention or in mixtures containing these compounds, or to an enhancement or change in the anisotropy in already anisotropic systems. The compounds of the invention may also themselves contain mesogenic groups or have liquid crystal phases, which additionally favors the generation or enhancement of anisotropy.

In contrast to the photoorientierbaren systems known from the prior art leads in the compounds of the invention, the photonic excitation of the multiple bond, apart from a possible stereoisomerization (for example, formation of diastereomers or enantiomers) to any known structural change or a photochemical reaction to form a reaction product, which would be distinguishable spectroscopically from the educt.

In contrast, for example, to azobenzene compounds of the invention are particularly suitable for the preparation of polymer films for use in optical components or devices such For example, LCDs, as they show no disturbing light absorption in the optical functional area of the component or device.

Since the light-sensitive group does not necessarily have to be photochromic in the compounds according to the invention, these are also referred to below as

"photoactive compounds". Photoactive are generally all compounds that react under the influence of light, regardless of whether it is, for example, photoisomerization, photo rearrangement, cycloaddition, photo orientation or photorotation.

Chiral dissymmetric compounds are inherently known in the art / 24-26 / which contain two sterically bulky groups linked by a C = C double bond ("sterically overcrowded alkenes"). Upon irradiation with polarized or unpolarized light, these compounds exhibit unidirectional rotation and thus can be switched between different stereoisomeric states (e.g., cis / trans isomers or D / L enantiomers) that exhibit different chirality and circular dichroic (CD) spectra. The literature also describes the use of these compounds in optical storage media, as molecular rotors (for the conversion of light energy into mechanical energy) / 24-26 /, and as "switchable" chiral dopants for the purpose of selectively changing the reflection wavelength in chiral nematic or cholesteric, optionally polymerizable , Liquid crystal media / 27 /. However, the use of the compounds to produce anisotropy or compounds having typical side mesogenic groups according to the present invention are not described.

In contrast to the known from the prior art chiral molecular rotors, which are no longer planar and therefore helically chiral due to steric factors (eg, "overcrowded alkenes" or "strained alkenes"), in the compounds of the invention no sterically bulky groups are required. Compounds of the invention containing chiral groups are preferably those with central or axial chirality. In the rotors known from the prior art, the light-induced switching from ice to trans also associated with a spectral change with increase in absorption in the visible range, while in the Compounds of the invention such a spectral change does not occur. Both isomers absorb at the same wavelength and suitable substituent choice exclusively in the UV range. Another advantage of the compounds of the invention is that the substituents on the double bond can be varied and thus also the properties of

Double bond, e.g. their absorption range and their thermal rotation barrier / 28 /.

Description of the invention

The present invention relates to a compound containing at least one multiple bond other than an N = N double bond, which is excited upon irradiation with polarized light and thereby causes preferential orientation of the compound, wherein - the excitation of the multiple bond does not produce a persistent structural change or photochemical reaction with formation a reaction product, except the possible formation of diastereomers or enantiomers (stereoisomerization), and

the orientation in a layer of the compound or a layer of a substance mixture containing the compound produces anisotropy or alters an existing anisotropy.

The invention further relates to processes for the preparation of particularly preferred compounds of the invention.

The invention furthermore relates to mixtures comprising at least one compound according to the invention and at least one further, optionally mesogenic or liquid-crystalline compound, in particular mixtures, in which at least one of the compounds contained therein contains a polymerisable or crosslinkable group or is present in polymerized form.

The invention furthermore relates to (co) polymers comprising at least one compound according to the invention in covalently bonded form, and copolymers comprising at least one compound according to the invention and at least one further, optionally mesogenic or liquid-crystalline compound, in covalently bonded form. The invention furthermore relates to polymer mixtures comprising at least one compound according to the invention or at least one (co) polymer according to the invention, and additionally at least one further isotropic or anisotropic polymer.

The invention further relates to the use of compounds according to the invention, mixtures or (co) polymers for producing anisotropy in an isotropic material or for enhancing the anisotropy in an anisotropic material.

The invention further relates to a method for producing an anisotropic polymer film using compounds, mixtures or (co) polymers according to the invention.

The invention further relates to anisotropic polymer films obtainable by a process according to the invention, in particular anisotropic polymer films containing at least two regions, or a regular pattern of regions having a different degree of anisotropy and / or different orientation.

The invention furthermore relates to the use of compounds according to the invention, mixtures, polymers or anisotropic polymer films in electrooptical or liquid crystal displays (LCD), as optical film, polarizer, compensator, beam splitter, reflective polarizer,

Orientation layer, color filter, holographic element, hot stamping foil, decorative or security element, adhesive film, optical data storage, in nonlinear optics, as a component of electrical semiconductors such as field effect transistors (FET), integrated circuits (IC), thin film transistors (TFT) or radio frequency identification elements (RFID) , in organic light-emitting diodes (OLED), electroluminescent displays or lighting elements, in photovoltaic devices, optical sensors, as photoconductors or for electrophotographic applications. The invention further relates to an orientation layer, a polarizer, compensator or color filter comprising an anisotropic polymer film according to the invention.

Description of the pictures

FIG. 1 shows the photochemically induced dichroism of selected compounds according to the invention in PMMA when irradiated with linearly polarized light of 325 nm and 20 mW / cm ² as a function of the irradiation time.

FIG. 2 shows the angle-dependent extinction at 333 nm of a polymer film according to the invention according to Example P2 before and after irradiation with linearly polarized light of 325 nm and 108 J / cm ² and after heating to 85 ° C. for 3 days.

FIG. 3 shows the UV spectra of the monomer M14 according to the invention and of the copolymer P5 according to the invention.

Figure 4 shows the induction of anisotropy in a film according to the invention according to Example A2 by linearly polarized irradiation with 325 nm and 20 mW / cm ² as a monomer without host matrix (a), as a monomer in PMMA (b), and as a copolymer (c ).

FIG. 5 shows the angle-dependent absorption in a film according to the invention according to Example A3 after linearly polarized irradiation at 325 nm and a dose of 108 J / cm ² and after thermal self-assembly at 85 ^° C.

Figure 6 shows the change in the angle-dependent extinction in a film according to Example A4 under light-induced reorientation with a change in the polarization direction of the light from 90 ° through 45 ° to 0 °.

Figure 7 shows a pixelated anisotropic copolymer film according to Example A5 between crossed polarizers (0790 °) in position 0 ° and 50 °. Figure 8 shows the angle-dependent extinction of a dye in a liquid-crystal mixture after orientation on a polymer film according to the invention according to Example A6.

Preferred embodiments of the invention

The term "layer" as used above and below includes coatings on, for example, a support, substrate or backing, as well as self-supporting films, such as e.g. Polymer films. According to the invention, the layer consists of one or more compounds according to the invention in pure substance, or of a substance mixture or polymer as described below containing one or more compounds according to the invention, with a preferred thickness of 5 nm to 5 μm. The orientation effect observed according to the invention is a volume or surface effect. Exempted are therefore layers consisting of dilute solutions, emulsions,

Dispersions, suspensions, etc. of the compounds or mixtures according to the invention.

With the compounds according to the invention, in particular those in the following forms! I described donor-acceptor compounds, a new class of compounds was found, which causes a light-induced (re) orientation process in photoactive components or polymer films containing them when irradiated with polarized light. This (re) orientation process is similar to that of e.g. Azobenzenen ongoing photo-orientation process. The compounds of the present invention show similar photoorientation properties under linear or circularly polarized radiation as, for example, azobenzene, i. they orient themselves with comparable efficiency perpendicular to the E-field vector, but do not necessarily have an absorption in the visible spectral range, what their use u.a. for display applications.

The (re) orientation process is reversible, irreversible side reactions such as photo-frieze reactions are not necessary for the orientation process. In contrast to the previously known materials, such as azobenzene, the possibly resulting isomers of the compound according to the invention are energetically or spectroscopically identical. The process is cooperative so that orientation of these chromophores also co-orients other molecules such as polymer segments and side groups. The light-induced molecular orientation of these chromophores leads to birefringence, dichroism and, in the case of co-operative

Orientation of additional groups to corresponding anisotropic properties such as anisotropic fluorescence or conductivity. In liquid-crystalline polymers which contain one or more compounds according to the invention, the light-induced order effects an orientation of the overall system. The order is transmitted and amplified in the same direction or developed in the opposite direction. If there is no further irradiation in the UV range, the orientation and the associated anisotropic properties are stable. Thus, the compounds according to the invention prove suitable both for photochemical builing and for interfacial orientation. Due to the reorientation and

Pixelability of the material results in a great variety of local variations of orientation.

The substances according to the invention can be used to prepare anisotropic optical films. Dichroic and birefringent films can be used as optical functional elements, such as polarizers and retarders, or as alignment layers for LCDs. Anisotropically pixelated films can be used in optical data storage. The inclusion of additional anisotropic properties such as fluorescence or conductivity additionally open up a multiplicity of possible applications due to the cooperative orientation of corresponding groups in polymer films.

The compounds according to the invention preferably have one or more electron donor or electron acceptor groups which are linked directly or via a conjugated π system to the multiple bond. Particularly preferred are compounds in which the electron donor and electron acceptor groups are on different sides of the multiple bond. Very particular preference is given to compounds which have one or two electron donor groups and one or two electron acceptor groups which react directly or via a conjugated π system with the

Multiple bond are linked, with the donor and acceptor groups on different pages of the multiple binding. The donor and acceptor groups are preferably π donors or π acceptors. By combining suitable π-donors or π-acceptors, on the one hand, the absorption properties and, on the other hand, the thermal rotation barrier around the double bond system can be set in a wide range. Depending on the application, such undirected thermal isomerizations can be enabled or excluded. Preferred for long-term stable orientations are combinations with a high thermal rotation barrier.

The multiple bond whose excitation causes a molecular movement and associated orientation of the compound according to the invention, preferably perpendicular to the E-vector of the polarized light, is preferably a double bond, in particular a C = B double bond, wherein B represents a Kohlenstoff¬ or a heteroatom , Very particular preference is given to C =C double bonds.

The compounds according to the invention preferably have one or more heteroatoms directly linked to the multiple bond, which may also be part of the electron donor or acceptor group. Particularly preferred heteroatoms are N, O, P and S (wherein P is a phosphorus atom).

Preference is furthermore given to compounds according to the invention which have no measurable absorption of radiation in the visible wavelength range.

Particular preference is given to compounds according to the invention which contain one or more mesogenic groups. The term "mesogenic group" is known to the person skilled in the art and designates, in particular rod-shaped, disc-shaped or board-shaped groups which can bring about liquid-crystalline phase behavior in a compound. Such compounds according to the invention may already have anisotropy or a liquid crystal phase before irradiation, which can be enhanced by the irradiation with polarized light according to the invention. But it is also possible that the mesogenic compounds themselves show no liquid crystal phase before irradiation.

A further preferred embodiment of the invention is directed to compounds of the invention which contain one or more polymerizable or contain crosslinkable groups. These compounds can be irradiated in pure substance or in admixture with other, optionally polymerizable, compounds according to the method according to the invention with polarized light, whereby an orientation takes place. This state can then, if appropriate after prior annealing, be permanently fixed in situ by polymerization or crosslinking.

Particular preference is given to compounds of the formula I according to the invention

DA-MG ¹ - (R ¹ ), I

wherein the individual radicals have the following meaning

DA an electron donor-acceptor system containing at least one multiple bond,

MG ^{1 is} a mesogenic group or a single bond,

R ^{1 is} H, halogen, NO ₂ , SF ₅ , NCS, SiR ⁰ R ⁰⁰ R ⁰⁰⁰ , Pg-Sp, Pg * -Sp- or an organic radical having 1 to 30 C atoms,

Pg is a polymerisable or reactive group,

Pg * a group which can be converted into or replaced by a polymerizable or reactive group Pg,

Sp is a spacer group or a single bond,

R ⁰ , R ⁰⁰ and R ^{000 are} each independently H or aryl or alkyl of 1 to 12 C atoms,

I 0, 1, 2, 3, 4, 5 or 6.

In the compounds of the formula I, the group DA preferably denotes DA ¹ or a group of the formula II

wherein the individual radicals have the following meaning

T, T ¹ and T ^{2 are} each independently, same or different, an electron acceptor group,

QX ¹ and X ^{2 are} each independently, same or different -O-, -S-,

- -NNHH-- ,, - -NN [[IMV G ¹ - (R ¹ ) ιj- or -P- [MG ¹ - (R ¹ ) ¹ ] - (wherein P represents a phosphorus atom),

Y, Y ¹ and Y ^{2 are} each independently, the same or different, a g electron-withdrawing bridging group,

R and R ^{2 are} each independently one of the meanings given for R ¹ in formula I,

Q MG ² a mesogenic group,

k O, 1, 2, 3, 4, 5 or 6,

n1 and n2 are each independently 0, 1, 2 or 3. 5 Examples of suitable and preferred electron-withdrawing electron acceptor groups T, T ¹ and T ² are -CN, -CHO, COR ⁰ , -NO ₂ carboxylic acid derivatives, (COOR ⁰ ), phosphonic acid esters or sulfonic acid esters.

Examples of suitable and preferred electron-withdrawing bridging groups Y, Y ¹ and Y ² are -CO- or -CO-O-.

DA ¹ is preferably selected from the following groups

wherein R has the meaning given in formula II and X has one of the meanings given for X Λ • in formula II.

DA ² is preferably selected from the following groups

(E ₁ Z) (E ₁ Z)

wherein T has the meaning given in formula II and X has one of the meanings given for X ¹ in formula II, and preferably each independently, identically or differently, -S- or -O- and T is CN.

Particularly preferred are compounds wherein DA ^{2 is selected} from the following groups

(E ₁ Z) (E ₁ Z)

In the compounds according to the invention, the mesogenic groups or the groups MG ¹ and MG ^{2 are,} for example, rod-shaped or cylindrical (kalamitic), board-shaped (also eg optically biaxial) or disc-shaped (discotic) groups. Particularly preferred are kalamitic groups.

In the compounds of formula I, MG ¹ preferably represents a group of the following formula

and MG is preferably a group of the following formula

III2

wherein the individual radicals have the following meaning

A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ each independently, the same or different a) trans-1, 4-cyclohexylene, wherein also one or more non-adjacent CH ₂ - groups by -O- and b) 1, 4-phenylene, in which one or two CH groups may be replaced by N, c) a radical from the group 1, 4-bicyclo (2,2,2) - octylene, p-peridine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, indan-2,6- diyl, lnden-2,6-diyl and d) 1, 4-Cyclohexθnylen, e) a radical from the group of O-, S- or N-heterocycles in particular chromandiyl, isochromanediyl, Benzofurandiyl, Dihydrofurandiyl, Benzothiophendiyl, Dihydrobenzothiophendiyl, indolediyl, Dihydroindoldiyl, these groups also one or more times may be substituted by L, and L has one of the meanings given for R ¹ ,

Z \ Z ² , Z ³ , Z ^{4 are} each independently, identically or differently -O-, -S-, -NR ⁰ -, -CO-, -CO-O-, -O-CO-, -O-CO -O-, -CO-NR ⁰ -, -NR ° -CO-, -O-CO-NR ⁰ -, -NR ° -CO-O-, -NR ° -CO-NR ° -, - (CH ₂ ) i-, -CH ₂ O-, -OCH ₂ -, -SCH ₂ -, -CH ₂ S-,

-CF ₂ S-, -SCF ₂ - _, -CF ₂ O-, -OCF ₂ -, -CF ₂ CF ₂ -, -CH ₂ CF ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ O- , -OCF ₂ CH ₂ -, -CH ₂ CH ₂ -, -CH = N-, -N = CH-, -N = N-, -CH = CR ⁰ -, -CY ³ = CY ⁴ -, -CH = CH-, -CF = CF-, -CH = CF-, -CF = CH-, -CH = CH-COO-, -OCO-CH = CH-, -CF = CF-COO-, -O-CO -CF = CF-, -C≡C- or a single bond,

R ⁰ , R ⁰⁰ and R ^{000 are} each independently H or aryl or alkyl of 1 to 12 C atoms,

Y ³ and Y ^{4 are} each independently H, F, Cl or CN,

i 1, 2, 3 or 4,

n, o, p, q, r, s are each independently 0, 1 or 2, where n + o + p> 0 and q + r + s> 0.

In the above-mentioned compound, A ¹ , A ² , A ³ , A ⁴ , A ⁵ and A ^{6 are} preferably selected from the following groups

wherein one or more H atoms may be replaced by L in the phenyl rings.

L is preferably F, Cl, Br, I, CN, NO ₂ or alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 20 C atoms, in which also one or more H atoms may be replaced by F or Cl ,

Particularly preferred groups L are F, Cl, CN, 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 , very particularly preferably F, Cl, CH ₃ , OCH ₃ or COCH ₃ .

MG ¹ and MG ² are preferably selected from the following groups

where the phenyl rings can also be mono- or polysubstituted by L, in particular mono- or disubstituted by F, Cl or CH ₃ .

Particularly preferred mesogenic groups are selected from the following formulas and their mirror images

wherein L has the meaning given above and m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2.

The group in these preferred formulas

preferably or each group independently of one another, the same or different, having the abovementioned meaning.

Particularly preferred are the following compounds

R ² - (Z ⁶ -A ⁶ ) _s - (Z ⁵ -A ⁵ ) _r - (Z ⁴ -AV ₀ r .Sγ (A ¹ -Z ¹⁾ _n - (A ² -Z ² ) ₀ - (A ³ -2 ³ ) _p -R ¹ _{| p}

wherein R, R ¹ , R ² , R ⁰ , A ^{1 "6} , Z ^{1" 6} , n, o, p, q, r, s have the abovementioned meaning, R ^{0 is} preferably alkyl having 1 to 4 carbon atoms and R preferably denotes straight-chain or branched alkyl having 1 to 6 C atoms. The group Z ^{1 "6} (eg Z ⁶ if s = 1 or Z ³ if p = 1) directly adjacent to the donor acceptor group is preferably -CH ₂ - or a single bond.

The groups R ^{(1 "2)} , T ^(1'2) , Y ^{(1" 2)} , X ^{1 "2} , Pg ^ω , DA ^{1" 2} , Sp, MG ^{1 "2} , L, A ^{1" 6} and Z ^{1 "6} are generally chosen so that in the compounds according to the invention O and / or S atoms are not directly linked to one another.

R, R ¹ and R ² in formula I and II are preferably H, halogen, NO ₂ , SF ₅ , NCS, SiR ⁰ R ⁰⁰ R ⁰⁰⁰ , Pg-Sp- or a linear or branched, achiral or chiral, unsubstituted or simple by CN or CF ₃ or mono- or polysubstituted by halogen alkyl radical having 1 to 20 carbon atoms or alkenyl radical having 2 to 20 C atoms, wherein also one or more CH ₂ groups each independently of one another by -O-, -S -, -NR ⁰ -, -CO-, -SiR ⁰ R ⁰⁰ -, -CF ₂ -, -CH = CR ⁰ -, -CY ³ = CY ⁴ - or -C≡C- can be replaced so that O - and / or S atoms are not directly linked to each other, wherein R ^{0 "000} and Y ^{3'4 have} the meaning given above.

If R, R ¹ or R ^{2 is} an alkyl or alkoxy group, this is straight-chain or branched. It is preferably straight-chain, has 3 to 8 C atoms and is, for example, propyl, butyl, pentyl, hexyl, heptyl, octyl, propoxy, butoxy, pentoxy, hexyloxy, heptoxy or octoxy, furthermore nonyl, decyl, undecyl, dodecyl, tridecyl , Tetradecyl, pentadecyl, nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy or tetradecoxy.

CY ³ = CY ⁴ is preferably -CH = CH-, -CH = CF-, -CF = CH-, -CF = CF-, -CH = C (CN) - or -C (CN) = CH-.

Halogen is preferably F, Br or Cl. Heteroatoms are preferably selected from N, O and S.

The reactive or polymerizable group Pg is a group that can undergo a polymerization reaction, where "polymerization" is intended to include all polymer construction reactions known to those skilled in the art, e.g. radical or ionic chain polymerization, polyaddition or polycondensation and metathesis polymerization, or a group which can be grafted onto a polymer backbone in a polymer-analogous reaction, for example by condensation or addition. Particularly preferred are polymerizable groups for

Chain polymerization reactions are suitable, such as free-radical, cationic or anionic polymerization, in particular polymerizable groups containing a C = C olefinic double or triple bond, and polymerizable groups which react under ring opening, such. Oxetanes or epoxides. Also preferred are reactive groups such as epoxides, thiiranes, aziridines, isocyanates, isothiocyanates and cyanates which react with themselves or with complementary nucleophilic groups.

Preferred groups Pg are selected from CH 2 = CW ¹ -COO-,

W ² HC CH -, _j CH ₂ = CW ² - (O) _k1 -, CH ₃ -CH = CH-O-,

(CH ₂ = CH) ₂ CH-OCO-, (CH ₂ = CH) ₂ CH-O-, (CH ₂ = CH-CH ₂ ) ₂ CH-OCO-, (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-, wherein 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} each independently H or alkyl having 1 to 5 C atoms, in particular methyl, ethyl or n-propyl, W ⁴ , W ⁵ and W ^{6 are} each independently each other is Cl, oxaalkyl or Oxacarbonylalkyl having 1 to 5 C-atoms, Phe 1, 4-phenylene and ki and k _{2 are} each independently 0 or 1.

Particularly preferred groups Pg are CH ₂ = CH-COO-, CH ₂ = C (CH 3) -COO-, CH ₂ = CH-, CH ₂ = CH-O-, (CH ₂ = CH) ₂ CH-OCO-, (CH ₂ = CH) ₂ CH-O- and

Very particular preference is given to acrylate and methacrylate groups.

The spacer can be any of the groups known to the person skilled in the art for this purpose. Suitable spacer groups are known in the art and in the

Literature described. Preferred groups Sp are those of the formula Sp'-X, so that Pg-Sp-Pg-Sp'-X-, in which

Sp ^{1 is} linear or branched, achiral or chiral, unsubstituted or substituted by CN or CF ₃ or mono- or polysubstituted by halogen alkylene having 1 to 20 carbon atoms or alkenylene having 2 to 20 carbon atoms, wherein also one or more CH ₂ groups each independently of one another by -O-, -S-, -NR ⁰ -, -CO-, -SiR ⁰ R ⁰⁰ -, -CF ₂ -, -CH = CR ⁰ -, -CY ¹ = CY ² - or -C≡C- can be replaced so that O and / or S atoms are not directly linked to one another,

X is -o, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR ⁰ -, -NR ° -CO-, -OCH ₂ -, -CH ₂ O -, - CH 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 -, -CY ¹ = CY ² -, -C = C-, -CH = CH- COO, -OCO-CH = CH- or a single bond,

mean, and

R ⁰ , R ⁰⁰ , Y ¹ and Y ^{2 have} the abovementioned meaning.

Typical spacer groups Sp ¹ 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 -, -CH ₂ CH ₂ - NH-CH ₂ CH ₂ - or - (SiR ° R ⁰⁰ -O) _p -, wherein p is an integer from 2 to 12, q is an integer from 1 to 3 and R ⁰ and R ^{00 have} the abovementioned meaning have.

Preferred groups Sp ¹ are, for example, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylene thioethylene, ethylene-N-methyl-iminoethylene, 1-methylene-alkylene, ethenylene, Propenylene and butenylene. Further preferred are compounds wherein Sp is a single bond.

In compounds having two or more groups Pg-Sp-, multiply occurring groups Pg and Sp, respectively, may be the same or different.

Another preferred embodiment of the invention is directed to compounds containing one or more groups Pg * -Sp-, where Pg * is a group that can be converted to or replaced by a polymerizable or reactive group, such as a protecting group. Preferably, Pg * has a lower reactivity compared to Pg, in particular with respect to polymerization reactions or polymer-analogous reactions. These compounds can be used, for example, as an intermediate in the synthesis of polymerizable compounds of the invention. They are also useful as precursors of particularly reactive polymerizable compounds which tend to spontaneously polymerize, e.g. should not be stored or transported for long periods of time. This precursor may then be e.g. after storage or transport on site or at the required time, preferably in a simple synthesis step, be converted into a polymerizable compound.

The group Pg * is preferably chosen so that it can be converted in a simple manner and by known methods into a group Pg or replaced by these. Pg * is for example a protected form of the group Pg. Particularly preferred groups Pg * are -OH, cyclic ethers such as THP ethers, or silanes of the formula -O-Si-R ⁰ R ⁰⁰ R ⁰⁰⁰ , wherein R ⁰ , R ⁰⁰ and R ^{000 have} the abovementioned meaning, for example -O-Si (CH ₃ ) ₃ , -O-Si (isopropyl) ₃ , -O-Si (phenyl) ₃ , -O-Si (CH ₃ ) ₂ (phenyl), -O-Si (CH ₃ ) ₂ (tert-butyl), etc., and which can be converted in a simple and known manner, for example, in (meth) acrylate groups.

The compounds of the invention may have a structurally inherent central or axial chirality. In addition or as an alternative to this inherent chirality, the compounds according to the invention may also contain chiral groups, for example groups containing asymmetric C atoms or chiral ones

Carbo- or heterocycles, included. For example, compounds of the Formula I and its preferred sub-formulas one or more chiral groups MG ¹ , MG ² , R ¹ or Sp included. Suitable chiral mesogenic groups MG, chiral terminal groups R ¹ and chiral spacer groups Sp are known from the literature, for example from WO 93/22397, EP 0 261 712, DE 195 04 224, WO 95/22586 and WO 97/00600. Preferably, the inventive

Compounds, however, no additional chiral groups.

Chiral compounds of the invention can be present in an enantiomerically pure form or as a racemate and used. However, a racemate resolution is not absolutely necessary for achieving the effect according to the invention.

Process for the preparation of the compounds according to the invention

Donor-acceptor compounds of the general formula I having mesogenic radicals have hitherto been unknown, as are homopolymers and copolymers containing such compounds. Surprisingly, it has now been found that corresponding compounds can be prepared by novel combinations of known chemical transformations in multi-step synthetic sequences.

Another object of the invention is thus a process for the preparation of compounds of the invention, in particular for the preparation of compounds of formula I, wherein DA (R ² ) κ-MG ² -DA ² - means.

Particularly preferred is a process for the preparation of compounds of formula I, characterized in that

a) an acidic compound of the formula IH

in the presence of a base with CS ₂ or R "-NCS and reacted

b) the resulting dithiolate dianion or the corresponding S ₁ NR "analogue with a compound of formula 112

alkylated, wherein MG ¹ , MG ² , k and I have the meaning given in formulas I and II,

R ³ and R ⁴ each, independently of one another, have one of the meanings given for R ¹ in formula II or signify EG,

R "has one of the meanings given for R ⁰ in formula I,

EG is an end group selected from H, halogen, CN, NO ₂ , CF ₃ , a protected keto, aldehyde, hydroxyl, amino or carboxyl function,

X is a leaving group which is suitable in connection with nucleophilic substitutions on the saturated carbon (SN1 or SN2),

R 'is a radical containing an N-H or C-H-acidic group,

t is 0 or 1, and

n3 and n4 are each independently 0, 1, 2 or 3, where n3 + n4 is 1, 2 or

3,

mean, and optionally the protected end groups R ³ and / or R ⁴ by suitable methods in the end groups R ¹ or R ² as defined in formula I and II.

In the compounds of the formula III, t is preferably 1.

In the compounds of formula II2, MG ^{1 is} preferably not a single bond.

The compounds of the formula III are preferably selected from the following formula (R ⁴ ) _k - (A ⁶ -Z ⁶ ) _s - (A ⁵ -Z ⁵ ) _r (A ⁴ -Z ⁴ ) _q -R 'IM a

The compounds of formula 112 are preferably selected from the following formula

wherein A ^{1 "6} and Z ^{1" 6 have} the meaning given in formulas I and II, k, I, n, o, p, q, r and s are each independently 0, 1 or 2, where q + r + s> 0, and R ³ , R ⁴ , X, n3 and n4 have the meaning given in formula IH and II2.

Particular preference is given to compounds selected from the following formulas

Il2a1

Il2a2

in which A ^1'6 , Z ^1'6 , k, I, n, o, p, q, r, s, R ³ , R ⁴ , X, n ³ and n 4 have the abovementioned meaning and X 1, Br, Cl, Triflate, sulfate, mesylate or tosylate. In the compounds of formula III, the acidic group R ¹ preferably contains at least one Csp ³ -H bond and in α-position to this one, two or three electron-withdrawing groups independently selected from -CO-, CHO, -CN, -NO ₂ , -SO ₂ -, -COO-, CONR ₂ ⁰ , -SO ₃ R ⁰ or phosphonic acid esters. Particularly preferably, R 'is -CO-CH ₂ -R ⁰ , -CO-CH ₂ -CO-R ⁰ ,

-CO-CH ₂ -CHO, -CO-CH ₂ -CN, -CO-CH ₂ -NO ₂ , -CO-CH ₂ -CO-O-, -O-CO-CH ₂ -CO-O-, - 0-CO-CH ₂ -CO-, -O-CO-CH ₂ -NO ₂ , -O-CO-CH ₂ -CN, -O-CO-CH ₂ -CHO, -CH ₂ -CO-R ⁰ , -CH ₂ -CHO, -CH ₂ -CN, -CH ₂ -NO ₂ or -CH ₂ -CO-oR ⁰ wherein R ⁰ has the meaning indicated in formula 1 or (R ⁴⁾ k- (A ⁴ -Z ⁴ ) _q - (A ⁵ -Z ⁵ ) r (A ⁶ -Z ⁶ ) _s -.

X is preferably halogen, in particular Cl, Br or I, or triflate (trifluoromethylsulfonate), tosylate (p-toluenesulfonate) or mesylate (methylsulfonate). In the compounds of the formula IIa 2a, X is preferably Cl, Br, triflate, tosylate or mesylate. In the compounds of the formula IIa2a and H2a3, X is preferably Cl, Br, I, triflate, tosylate or mesylate.

EG is H, halogen (F, Cl, Br, I), CN, NO ₂ , CF ₃ or a protected keto function, a protected aldehyde function, a protected hydroxy function, a protected amino function or a protected carboxyl function. When

Protecting groups are particularly preferred which are stable under neutral and basic conditions, such as cyclic and noncyclic acetals and ketals, tetrahydropyranyl ethers, silyl ethers and silyl esters.

The compounds of the formula III and II2 can be prepared from known precursors by methods known per se in the literature or analogously to these processes. The implementation of the individual process steps of the process according to the invention is described in part in the literature, but not the process according to the invention for the preparation of compounds having a mesogenic radical.

The invention further relates to novel compounds of the formulas III and II2 and their sub-formulas given above and below, in particular compounds of the formula III, IIIa and IIIa1, and also compounds of the formula II2 and IIa wherein n3 is O and n4 is 1 or 2, in particular compounds of the formula II2a1 and Il2a2. Another object of the invention is the use of compounds of formulas III and II2 and their above and below specified sub-formulas for the synthesis of mesogenic or liquid-crystalline compounds.

Synthesis of the compounds of the formula II2

1,2-disubstituted compounds of the formula IIa 2a (S1)

The synthesis of the following non-mesogenic 1, 2-dihalogen compounds has already been described in the literature

in Yegorova et al., Zh. Soot. Fiz.-Khim. O-va; 43; 1911; 1118; and Yegorova et. al. Chem. Zentralbl. 83; I; 1912; 1010, and

in A. Horowitz et al. J. Amer. Chem. Soc. 95; 1973; 6308 to 6313.

As starting compounds for the preparation of the novel, mesogenic 1, 2-disubstituted compounds of the formula II2a1 (S1), preference is given to using compounds of the general formula S2 and reacting these with bromine or chlorine by a known process (Organikum, 21st edition, Wiley-VCH, 2000, p. 299) in an organic solvent.

Preferred for the synthesis is the use of bromine, a reaction temperature interval of -20 to +30 ⁰ C and as a solvent chloroform,

Carbon tetrachloride or acetonitrile. Further compounds of type S1 can be obtained by conversion of functional groups in the RAZAZ framework. For example, CN groups can be converted into protected aldehyde groups via the following reaction sequence.

The compounds of the formula S2 are prepared by known methods as described in the literature (for example in the standard works such as Houben-Weyl, Methods of Organic Chemistry, Georg Thieme Verlag, Stuttgart). Suitable starting materials for the olefins are, for example, corresponding aldehydes or ketones, which via Wittig reactions (optionally followed by

Hydrolysis reactions) can be easily converted into olefins.

1,3-disubstituted compounds of the formula H2a2 (S3)

The synthesis of the following non-mesogenic 1, 3-disubstituted compounds has already been described in the literature

in Sadychow et al., Azerb. Khim. Zh., 2, 1967, 72, 73, Chem. Abstr .; 68; 86860; 1968, and

in US 2,555,912 and Steven M. Viti, Tetrahedron Lett. 23, 44; 1982, 4541-4544. 15

For the synthesis of the 1, 3-disubstituted compounds of the type S3 preferably diols of the structure S5 used and these by reaction with PX ₃ (X = Br, Cl, I) in an organic solvent at temperatures between 25 ⁰ C and 100 ⁰ C. converted to S3. Alternatively, the diols (49 1984 Smith et al .; J. Org. Chem, 431) may be conducted after Mukaiyama at 0-10 ⁰ C with triphenylphosphine / Br2 or triphenylphosphine / imidazole / are converted I _2, wherein, as solvent acetonitrile Toluene or mixtures of these are preferred.

⁾ _p - ^(A2 - ^Z2) ₀ - <3 ^> - <r

S3 E3r

For S5, preference is given to the reaction with PBr _β , since higher yields result. Diols of type S5 can be obtained from corresponding precursors, for example by the following very efficient reaction sequence. By acylation of monoethyl malonate dianion, which in the reaction of 2 equiv. BuIi with monoethyl malonate is obtained in good yields, with an acid chloride with mesogenic residue is obtained after appropriate acidic workup the corresponding α-ketoester. Reduction by sodium borohydride in a mixed solvent system gives the diol (Soai et al., Synthesis, 7, 1984, 605-607). This multi-step process provides high yields for both aromatic and purely aliphatic compounds and is generally applicable.

1. 2 equiv. BuLi -78 ⁰ C -> O ⁰ C

NaBH ₄₁ THF, MeOH, reflux OH v 2 -, 2,

(R ^o ) _r (A ^o -Z °) _p - (A'-ZV <OH

1,3-disubstituted compounds of the formula II2a3 (S4)

1, 3-Dihalogenverbindungen the structure S4 are already known (WO 98/32721 A1) and can be obtained from diols of type S6 by reaction with PBr ₃ or by reaction with triphenylphosphine / Br2.

S4

Diolθ of the type S6 are partially commercially available or can be prepared according to published literature specifications, e.g. according to the method of Tschierske (Tschierske et al., Mol. Cryst. Liq. Cryst. 191, 1990, 295, and EP 0 400 861 A1).

Analogous to the structures S1, S2 and S4, compounds can be prepared which carry a para-substituted aromatic instead of the cyclohexyl ring (see structures S1, S2, S4).

Synthesis of Acidic Compounds of Formula III

Typical acidic components are ketones, aliphatic aldehydes, 1,3-diketones, α-cyano ketones, α-cyanoesters, malonic esters and similar compounds typically used for Knoevennagel, Aldol or Michael reactions. Typical base solvent combinations are KOH in water or alcohol, bulky alcoholates or phenolates in THF or Et ₂ O, LDA in THF, ether or HMPTA, NaH or KH in DMF, DMSO or toluene and other combinations. Examples of such combinations in the synthesis of non-mesogenic compounds can be found in the review articles by Dieter (RK Dieter et al., Tetrahedron 42, 12, 1986, 3029-3096) and Junjappa (H.Junjappa et al., Tetrahedron 46, Vol. 16, 1990, 5423-5506).

Preference is given to the use of cyanoacetic acid esters with mesogenic alcohol radicals as C-H-acidic component III. Of these, particular preference is given to cyanoacetic acid esters of the formula IIa1a (S7) with mesogenic radicals which have not generally been described hitherto.

In particular, compounds with a protective group, which allow further functionalization after coupling (see synthesis scheme below), are valuable θ intermediates for the synthesis of polymeric donor-acceptor alkenes, which are also the subject of the invention.

The synthesis of the following non-mesogenic C-H-acidic compounds has already been described in the literature

in Newman et al., J. Amer. Chem. Soc., 68, 1946, 2112-2114.

For example, compounds of type S7 are made by DCC-, ^. Coupling of cyanoacetic acid with corresponding alcohols, by conventional esterification or by reaction of freshly prepared cyanoacetic acid chloride or cyanoacetic anhydride with the alcohols in pyridine or triethylamine (Organikum, 21st edition, 2001, 474, 480). The required alcohols can be readily recovered from corresponding ketones by ₂ "reduction with sodium borohydride in isopropanol or lithium aluminum hydride in THF. (Organikum, 21st Edition, 2001, 568-572). Here, the corresponding carbonyl compounds can be used, which are also used to construct the structures S2.

" _P. Instead of the particularly preferred cyanoacetic acid cyclohexanol esters of the type S7, cyanoacetic acid esters of phenols, benzyl alcohols or cyclohexylmethanols with mesogenic radicals can also be prepared. These are synthesized from corresponding phenol / alcohol precursors analogously to the methods described above.

30

Reaction of acidic compounds of the formula III with mesogenic radicals in

Presence of a base with CS? or R-NCS (step a) and the following alkylation with compounds of the formula H2 to form the donor-acceptor alkenes according to the invention (step b)

35

In coupling step a) of the process according to the invention are acidic

Compounds of the formula III with mesogenic radicals with CS ₂ or R "-NCS in Presence of a base in DMF converted to Dithiolatdianionen or their S, N analogs. At this step, the photoactive group is built up. The products formed are either first isolated as salts or alkylated in situ with the above-described 1, 2 or 1, 3-disubstituted compounds of formula II2 (step b). When CS _{2 is} used, ketene dithioacetals are thus obtained. The following examples are intended to illustrate this reaction without limiting it.

In the reaction with alkyl isothiocyanates instead of the CS ₂ , the corresponding S ₁ NR ketene acetals are formed.

The general procedure in the implementation of these known in principle reactions is described in several documents of the prior art, which are essentially in the nature of the base used and the Distinguish solvents. A comprehensive review can be found in the review articles by Dieter (RK Dieter et al., Tetrahedron 42, 12, 1986, 3029-3096) and Junjappa (Junjappa H. et al., Tetrahedron 46, 16, 1990, 5423-5506).

The following process variants are preferred for the synthesis of donor-acceptor alkenes according to the invention

• to a suspension containing the compound III, a solvent and a base, the CS ₂ or R "-NCS is added between 0 ⁰ C and 25 ° C, the compound II2, optionally after 0.5 to 3 hours of stirring added and then stirred at 25 to 70 ⁰ C for about 1 to 12 hours.

• About 1 equivalent of compound 111, about 3 equivalents of base, about 1.5 equivalents of CS ₂ or about 1.2 equivalents of R "-NCS and about 1

Equivalent of compound II2 used,

Alkali metal carbonates, alkali metal hydrides or alkyl alcoholates, preferably alkali metal carbonates, in particular potassium carbonate, are used as the base,

The solvent used is preferably a dipolar aprotic solvent such as, for example, DMF or DMSO,

• the CS ₂ or R "-NCS is added at approx. ⁰ ° C.

Particularly preferred for the synthesis of donor-acceptor alkenes according to the invention is a process variant in which to a suspension of the CH-acidic component IM (1 equiv.) And an alkali metal carbonate (preferably potassium carbonate) (3 equiv.) In DMF at 0 ⁰ C. CS ₂ (1.5 equiv.) or R-NCS (1.2 equiv.) is added. After about 1 hour of stirring, the alkylating agent II2 is added and stirred for about 3-6 hours at 35-60 ⁰ C bath temperature.

This preferred method is based on a synthesis of Mellor (J.M.

Mellor et al., Tetrahedron, 53, 50, 1997, 17151-17162), differs therefrom in that the alkylation is not carried out at RT, shorter reaction times are needed and other amounts of solvent are used. Reaction at RT by the method of Mellor provides no product, complete absence of solvent provides only with solid alkylating agents very little or no product. In contrast, the modified process according to the invention, especially in the case of poorly soluble products, surprisingly yields excellent yields (> 90%). Despite the basic conditions, hydrolysis of the ester does not occur even at higher temperatures. In addition, this method was here for the first time on the synthesis of S ₁ NR

Ketenacetalen applied.

Synthesis of donor-acceptor monomers with polymerizable side chains

Another object of the invention is the introduction of polymerizable

Side chains (Pg-Sp) in the inventive donor-acceptor compounds, in particular by using appropriately suitable intermediates with protective groups.

In order to polymerize the compounds of the invention, the introduction of a polymerizable side chain is necessary. For this purpose, preferably the protecting groups are needed, the donor-acceptor unit are stable on the one hand under the synthesis conditions of the formation (pH 12, DIvIF, the presence of strong nucleophiles and of alkylating agents at -6O ⁰ C) be removed selectively, on the other hand by means of appropriate reagents may.

Surprisingly, a synthetic sequence was found which allows efficient access with consistently good yields.

The synthesis is described in the following scheme with reference to a concrete example.

A further, detailed description of the synthesis can be found in the examples.

The crucial intermediate is the use of the functionalized cyanoacetic acid ester with a protected carbonyl group. 5-ring ketals (1,3-dioxolanes) are particularly preferred since they show very good stability under the coupling conditions, but on the other hand can be cleaved selectively with palladium (II) chloride in aqueous acetone without the donor-acceptor unit attack.

The following esters can be used analogously to the above example:

Instead of the compounds shown, it is also possible to use corresponding derivatives, for example with 1,3-dioxane protective groups or compounds derived therefrom. Also explicitly included are derivatives in which one or more H atoms on the phenyl rings are replaced by F, Cl, CF 3 or CN. Phenol esters with two ortho-fluoro groups, however, give only poor yields.

Synthesis of polymers or copolymers

It has furthermore been found that (co) polymers obtainable from at least one compound according to the invention having at least one polymerizable group, in particular from compounds of the formula I, wherein at least one of the radicals R ¹ and R ^{2 is} Pg-Sp-, and optionally at least one further polymerizable mesogenic compound (so-called "reactive mesogens"), also show the orientation effect according to the invention.

Another object of the invention are thus (co) polymers containing one or more compounds of the invention in covalently bonded form.

Another object of the invention are copolymers containing at least one compound of the invention and at least one further, optionally mesogenic or liquid crystalline compound in covalently bonded form.

Particularly preferred are copolymers obtainable from at least one compound of the formula I in which at least one of the radicals R ¹ and R ^{2 is} Pg-Sp- bθdeutet, and at least one polymerizable mesogenic compound (comonomer).

The polymerizable mesogenic compounds (comonomers) are preferably selected from formula IV

Pg-Sp-MG-R IV

wherein Pg, Sp and R have the meaning given in formula I, and MG means a mesogenic group. Preferably, MG is selected from formula 1111 as well as the preferred sub-formulas given above.

The (co) polymers are preferably prepared from polymerizable mixtures, for example by bulk or solution polymerization.

Another object of the invention is therefore a mixture containing at least one compound of the invention and at least one further, optionally mesogenic or liquid crystalline compound, wherein at least one of the compounds contained therein contains a polymerizable or crosslinkable group or is present in polymerized form.

The polymerizable mixture according to the invention may be an isotropic, anisotropic or liquid-crystalline mixture. Liquid-crystalline mixtures are preferably those having a nematic or smectic phase, for example a smectic A phase, more preferably nematic LC mixtures.

The polymerizable mixture preferably comprises at least one compound having a polymerizable group (monoreactive compound) and at least one compound having two or more polymerizable groups (di- or multireactive compound).

The above and below polymerizable compounds are preferably monomers. Polymerizable mono-, di- or multi-reactive mesogenic compounds suitable as comonomers are known to the person skilled in the art or can be prepared by methods known per se which are described in standard works of organic chemistry, such as Houben-Weyl, Methods of Organic Chemistry, Thieme-Verlag , Stuttgart.

Typical examples of polymerizable mesogenic compounds useful as comonomers are disclosed, 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 these documents are intended to be exemplary only, without limiting the scope of the invention.

Examples of particularly suitable and preferred chiral and achiral polymerizable mono- and di-reactive mesogenic compounds (reactive mesogens) are shown in the following list, which is intended to illustrate the invention without limiting it

(COO) _U CH ₂ CH (CH ₃ ) C ₂ H ₅ (R 12)

P (CHJ _x O

In the above formulas R1-R23, P represents a polymerisable group, preferably acrylic, methacrylic, vinyl, vinyloxy, propenyl ether, epoxy, oxetane or styryl, x and y each independently an integer from 1 to 12, A and D each independently 1,4-phenylene which may also be monosubstituted, disubstituted, trisubstituted or trisubstituted by L ¹ , or 1,4-cyclohexylene, u and v are each, independently of one another, 0 or 1, Z ^{0 are} each, independently of one another, -O-, -S-, -COO-, -OCO-, -O-COO-, NR ° -CO-NR ° -, -O-CO-NR ⁰ -, NR ° -COO-, -CH ₂ CH ₂ -, - CH = CH-, -C≡C- or a single bond, R ⁰ H, aryl or alkyl having 1 to 12 C atoms, R ^x H or a polar or nonpolar terminal group, Ter a terpene such as menthyl, Chol a cholesteryl group , m is 0, 1, 2, 3 or 4, L ¹ and L ^{2 are} each independently H, F, Cl, CN or optionally halogenated alkyl, alkoxy, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl or alkoxycarbonyloxy having 1 to 7 carbon atoms. The phenyl rings in the formulas shown above are optionally substituted by L ¹ one, two, three or four times. In the spacer groups (CH ₂ ) _X and (CH ₂ ) _y also one or more non-adjacent CH ₂ groups can be replaced by -O-, -CO-, -CO-O-, -O-CO-O-, -NR ° -CO-NR ° -, -O-CO-NR ⁰ -, -NR ° -CO-O -, - CH = CH- or -C≡C- be replaced, and one or more H atoms by F, Cl or CN replaced.

The term "polar group" in this context means a group selected from F, Cl, CN, NO ₂ , OH, OCH ₃ , OCN, SCN, optionally fluorinated alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl or alkoxycarbonyloxy having up to 4 C atoms or mono -, oligo- or polyfluorinated alkyl or alkoxy having 1 to 4 carbon atoms. The term "nonpolar group" in this context means optionally halogenated alkyl, alkoxy, alkylcarbonyl,

Aikylcarbonyloxy, alkoxycarbonyl or alkoxycarbonyloxy having 1 or more, preferably 1 to 12 C atoms, which does not fall under the above definition "polar group".

Preference is given to polymerizable mixtures containing 1-90% by weight, in particular from 5 to 80% by weight, of compounds of the invention, in particular those of the formula I.

Another preferred polymerizable mixture contains a) 5-80%, preferably 15-75% of one or more mono- or direaktiv

Compounds of the formula I, b) 20-95%, preferably 30-85%, of one or more other mono- or direactive mesogenic compounds.

The other monoreactive mesogenic compounds are preferably selected from the formulas R1, R2, R3, R4, R5 and R6.

The further reactive mesogenic compounds are preferably selected from formula R19.

In a further preferred embodiment, the polymerizable

Mixture, preferably up to 40% by weight, particularly preferably up to 20% by weight, of one or more non-mesogenic compounds having two or more polymerizable groups (crosslinkers), for example alkyldiacrylates or alkyldimethacrylates having 1 to 20 C atoms, or higher functional crosslinkers such as trimethylpropane trimethacrylate or pentaerythritol tetraacrylate.

The mixtures of the invention may also contain one or more chiral compounds or chiral dopants and chirally liquid crystalline phases, such as a cholesteric phase having. The chiral compounds may be polymerizable and / or mesogenic or liquid crystalline. Suitable chiral polymerizable mesogenic compounds are, for example, those of the formulas R12-R17 and R20-R23 shown above. Suitable chiral dopants are for example selected from the commercially available compounds cholesteryl nonanoate (CN), CB15, R / S-811, R / S-1011, R / S-2011, R / S-3011 or R / S-4011 (Merck KGaA , Darmstadt). Particularly suitable are dopants with high twisting power, for example chiral sugar derivatives, in particular derivatives of dianhydrohexitols such as isosorbitol, isomannitol or iditol, particularly preferably isosorbitol derivatives as disclosed, for example, in WO 98/00428. Also preferred are hydrobenzoine derivatives as described, for example, in GB 2,328,207, chiral binaphthyls as described, for example, in WO 02/94805, chiral binaphthols as described, for example, in WO 02/34739, chiral TADDOLs as described, for example, in WO 02/06265, and chiral compounds with a fluorinated one Bridge group and a terminal or central chiral group as described for example in WO 02/06196 and WO 02/06195. In a further preferred embodiment, the polymerizable mixture contains one or more chain transfer agents, for example thiol compounds such as dodecanethiol or trimethylpropane tri (3-mercaptopropionate), in particular liquid-crystalline thiol compounds. By adding such reagents, for example, the free chain length of

Polymers, or the chain length between two crosslinking points can be reduced.

In a further preferred embodiment, the polymerisable mixture contains one or more polymeric or polymerisable binders or dispersing aids, as described, for example, in WO 96/02597.

The polymerizable mixture may also contain other components or adjuvants such as, for example, catalysts, sensitizers, stabilizers, chain transfer agents, inhibitors, comonomers, surfactants, plasticizers, wetting agents, dispersing aids, leveling agents, viscosity reducers, hydrophobizing agents, adhesives, flow agents, defoaming agents, deaerating agents or degassing agents , Thinners, reactive diluents, dyes, colorants or pigments.

The preparation of the polymers according to the invention is preferably carried out in the form of thin films. For this, the polymerizable material is first placed on a substrate, in the alternative, e.g. by known coating or printing processes, from which the polymer film can then optionally be removed again later.

Suitable coating methods are, for example, rolling, spraying, knurling, spin coating (spin coating) or dipping; suitable printing methods are, for example, flexographic printing, offset printing, gravure printing, high-pressure or inkjet printing.

Suitable substrates are, for example, films or films made of plastic, paper, cardboard, leather, cellulose, textiles, glass, ceramics or metal. Suitable plastics are, for example, polyesters such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), polyvinyl alcohol (PVA), polycarbonate (PC), di- or triacetylcellulose (DAC, TAC), in particular PET or TAC and polyimides and polyamides which are used in LC Displays are used. The polymerizable material may also be applied as a solution or suspension in an organic solvent and the solvent subsequently removed, for example by heating. Suitable solvents are, for example, toluene, xylene, MEK, acetone, cyclohexanone, isopropyl alcohol,

Methyl, ethyl, propyl or butyl acetate, PGMEA (propylene glycol monomethyl ether acetate) or mixtures thereof.

In a further preferred embodiment, the polymerisable mixture contains one or more additives, for example surface-active

Substances that have a planar orientation anisotropic or liquid crystalline

Induce or enhance molecules on the substrate. Suitable substances are known to the person skilled in the art and are described, for example, in J. Cognard, Mol. Cryst. Liq.

Cryst. 78, Supplement 1, 1-77 (1981). Particular preference is given to nonionic compounds, for example nonionic fluorinated hydrocarbons, such as the commercially available Fluorad FC-171® (3M) or Zonyl FSN®

(DuPont).

The polymerization or crosslinking is preferably carried out in situ, for example by thermal polymerization or by treatment with actinic radiation such as UV light, IR light or visible light, X-rays, gamma rays or high-energy particles such as ions or electrons. Particularly preferred is photopolymerization, in particular polymerization with UV light. As a radiation source, for example, a single UV lamp or a series of UV lamps can be used. Other possible radiation sources are, for example, lasers, such as UV lasers, IR lasers or lasers in the visible wavelength range.

The polymerization is preferably carried out in the presence of an initiator which absorbs the actinic radiation. In UV photopolymerization, for example, a photoinitiator is used which decomposes on UV irradiation, releasing free radicals or ions which initiate a polymerization reaction. UV photoinitiators are particularly preferred. Such photoinitiators are known to the person skilled in the art and are commercially available, for example Irgacure® 907, Irgacure® 651, Irgacure® 184, Darocure® 1173 or Darocure® 4205 (Ciba AG) or UVI 6974 (Union Carbide). Particularly preferred for the preparation of polymers according to the invention is the thermally or photochemically induced radical polymerization.

Compounds according to the invention having corresponding groups Pg can also be linked or grafted onto these by polymer-analogous reaction with an existing polymer main chain. For example, vinyl-terminated compounds can be added to the Si-H functions of a polyhydrogen siloxane. Compounds with e.g. terminal isocyanate or carboxylic acid groups, for example, with the OH

Functions of a poly (hydroxyalkyl) acrylate or methacrylate or the NH functions of a polyimide by addition or condensation.

Thus, it is also possible to apply compounds of the invention to already existing polymer films or coatings (e.g., polyimides) and covalently link with the polymer, e.g. by polymer-analogous reaction as described above. In the polymer film thus modified, the desired anisotropy or orientation can then be produced or specifically changed by irradiation with linearly polarized light according to the method according to the invention as described above and below.

Blends of polymers of the invention

Furthermore, it has been found that blends obtained from a donor acceptor monomer or homopolymer or copolymer of the present invention as described above and one or more other isotropic polymers as a host material also exhibit the orientation effect of the present invention demonstrate. The strength of the orientation depends on the host material.

Another object of the invention is thus a polymer mixture containing at least one compound of the invention or at least one inventive (co) polymer, and additionally at least one further, isotropic or anisotropic polymer. As the host material, various polymer materials are usable, for example, isotropic or anisotropic polymers such as PMMA, polystyrene, polyimide or the like.

The host materials should be compatible with the system of the present invention and provide sufficient solubility.

The proportion of the host material in the polymer blend is preferably from 1% to 50%.

Properties and use

With the substances according to the invention, a class of compounds has been found which shows all the outstanding properties of azobenzene with respect to the light-induced generation of anisotropy, the reversibility of the molecular photoreaction and the orientation, without having their disadvantages such as absorption of visible light.

In addition, for the first time, a class of compounds was found whose orientation upon irradiation with polarized light is not associated with the classical photochromism known from the prior art.

For films of the compounds of the present invention, a photoinduced induction of anisotropy by irradiation with polarized UV light at room temperature has been demonstrated without a significant change in the absorption properties. Upon excitation, the compounds according to the invention undergo a photoisomerization around the double bond with subsequent rotational diffusion of the molecules, although, in contrast to azobenzene, no spectroscopically distinguishable photoproduct can be detected for reasons of structure.

Such light induced rotational or pendulum motions, when using polarized light and the associated repeated photoselection, result in a preferred orientation, preferably perpendicular to the E-vector of the polarized light. This converts light into molecular dynamics. Non-directional thermal isomerization can be prevented by using high rotation barrier compounds. Depending on the structure, a parallel orientation is observed in individual cases.

The excitation of the multiple bond in the compounds according to the invention is carried out by irradiation with linearly or circularly polarized light, preferably with linearly polarized light. Particular preference is given to compounds having a multiple bond which exhibit absorption and thereby excitation outside the visible wavelength range, for example in the UV or IR range, in particular in the UV range. Particular preference is given to compounds which have an absorption band in the UV wavelength range from 300 nm to 350 nm, ie are excited by UV radiation in this wavelength range. For excitation, in principle, all known radiation sources can be used, such as UV lamps or lasers. An irradiation dose between 10 J / cm ² and 300 J / cm ² is preferred.

In the case of compounds according to the invention which, in contrast to the known azobenzene system for example, have no absorption in the visible spectral range, absorption and color effects are eliminated. Such compounds are therefore particularly suitable for applications in optics. They are suitable for example for the orientation of liquid crystals and the production of anisotropic optical films for displays such. In addition, the favorable absorption properties of the compounds cause the photoactive group to be exposed to visible light before re-light-induced polarization and phase shift elements ("retarders")

Changes such as in a display under glass and a transparent electrode layer of e.g. ITO (English, "indium tin oxide"), is fully protected.

When used in optical data storage and the production of pixelated films, the UV excitation of compounds of the invention allows a higher resolution than excitation in the visible range.

If the compounds according to the invention are applied to a substrate in the form of coatings or films, for example, anisotropic properties are induced in these films upon interaction with polarized light. Thus, films containing compounds of the invention, Dichroitic and birefringent or anisotropically fluorescent with the involvement of fluorescent groups. When suitable groups are incorporated, other physical properties may also become anisotropic upon orientation of the films, such as conductivity, extensibility, and magnetism.

Surprisingly, it has been found that the efficiency of the orientation, apart from the length or substitution of the compound under investigation, depends on the angle subtended by the compound of the invention. As can be seen from Figure 1, for example, the compounds of the invention M11, M14 and M16 according to formula I with asymmetric substitution on Dischwefelring (ni ≠ n ₂ )

a stronger orientation effect (expressed in Figure 1 by the dichroism) than the inventive compounds M4, M5 and M10 with symmetrical substitution (ni = nz).

Furthermore, the compounds MIO and M5, which has a more angular structure than M4 due to a lack of methylene group in the bridge group between DA ² and MG ² , for example, by a factor of 2 (M5) and 3 (M 10) stronger orientation effect than M5. (For definition and measurement of dichroism, see Example A1-A8).

Compounds of the formula I and their preferred sub-formulas in which DA is a group of the formula II and DA ^{2 is} the following structural element

where n1 ≠ n2, are therefore particularly preferred.

Anisotropic films can be obtained by irradiating the compounds of the invention in different starting films, such as, for example, in US Pat

Filming the pure compounds of the invention, Polymer films in which the compounds according to the invention are covalently bonded,

Polymer films or film-forming monomers wherein the compounds of the invention are incorporated as a guest (i.e., non-covalently bonded).

If the photoactive group is part of liquid-crystalline polymers, the room-temperature induced light-induced ansiotrophy can be enhanced by self-assembly of the polymers by annealing. This leads to complete orientation of the polymer films. This results in films with very high values of optical anisotropy as well as with values of birefringence Δn to 0.4 or more, and dichroic films with dichroic values D of up to 0.8 or more. Particularly preferred are films having a birefringence Δn of 0.03 to 0.5 and dichroic films having a dichroism D of 0.5 to 1.

Both the photochemical and the thermal orientation are in each case cooperative with the other groups in the polymer film. Thus, anisotropy transfer to groups with different physical properties (conductivity, fluorescence) is possible.

Figure 2 shows, for example, the angle-dependent extinction as a measure of orientation in a polymer film of the invention according to Example P2 after irradiation with linearly polarized light and annealing. Therein, the orientation of the anisotropic molecules is perpendicular to the E-field vector of the polarized light.

Surprisingly, it has been found that the primary induced orientation direction can be overwritten or modified by renewed irradiation with a changed polarization plane. Thus, for example, the orientation may be in defined, small portions ("pixels") of the film and varied in different directions.

By choosing suitable irradiation conditions, pixels of different birefringence can additionally be obtained. Due to the repeated photo orientation with variation of the angle of incidence of the light, defined tilt angles can also be set. Due to the possibility of pixel-wise reorientation in connection with the directional dependence of the orientation at different irradiation doses and homeotropic alignment (ie perpendicular to the film plane) after different reorientation steps are films of the invention

Compounds in a high variety of variations pixelable and tilt angle variable adjustable.

It is also possible to irradiate different regions of the films with polarized light of different intensity and / or for different duration, for example by using a photomask. Thereby, films having different regions or a regular pattern of regions or pixels having a different degree of anisotropy and / or different orientation can be easily and inexpensively produced.

The generated or altered orientation in the irradiated films is then permanently fixed, for example by crosslinking, formation of hydrogen bonds or polymerization. Preferably, after irradiation, the films are preferably annealed within the liquid crystalline phase of the material for between 10 minutes and 1 day to assist in the orientation process.

Another object of the invention is thus a process for the preparation of an anisotropic polymer film using compounds of the invention, mixtures, (co) polymers or polymer blends.

Another object of the invention are anisotropic polymer films obtainable by a method according to the invention.

Particularly preferred is a process for producing an anisotropic polymer film, characterized by the following steps

A) applying a layer comprising one or more compounds, mixtures or (co) polymers according to the invention to a substrate, at least one of the compounds contained in the layer having a polymerizable group or being present in polymerized form, B) irradiating the layer with polarized light of a wavelength which causes excitation of the multiple bond in the compound according to the invention,

C) optionally annealing the layer, D) if appropriate, polymerization or crosslinking of the layer,

E) optionally removing the polymer film from the substrate.

Particularly preferred is a method wherein the layer contains one or more compounds which are in polymerized form prior to irradiation and are crosslinked after or simultaneously with the irradiation or annealing.

Particular preference is also given to processes, hereinafter referred to as "drop-in processes", as are commonly used in the production of LCDs, but differing from these only in that the classical orienting process of the polyimide layer (rubbing) by a photo orientation is replaced using the compounds of the invention. For this purpose, for example, the substance according to the invention is applied to the not yet rubbed Poiyimidschicht and then oriented by polarized irradiation.

Further preferred is a process wherein the layer contains one or more compounds which are present in unpolymerized form prior to irradiation and polymerized or crosslinked after or simultaneously with the irradiation or annealing.

Also preferred is a method wherein different areas of the layer of polarized radiation of different duration and / or intensity are exposed, for example by using a photomask. Another object of the invention are anisotropic polymer films prepared by this process, which contain at least two regions or a regular pattern of regions which have a different degree of anisotropy and / or different orientation.

The compounds, mixtures, polymers and anisotropic polymer films according to the invention are particularly suitable for use in electro-optical or liquid-crystal displays (LCD), as optical film, polarizer, compensator, Beam splitter, reflective polarizer, orientation layer, color filter, holographic element, hot stamping foil, decorative or security element, adhesive film, optical data storage, in non-linear optics, as a component of electrical semiconductors such as field effect transistors (FET), integrated circuits (IC), thin film transistors (TFT) or radio frequency

Identification elements (RFID), in organic light-emitting diodes (OLED), electroluminescent displays or lighting elements, in photovoltaic devices, optical sensors, as photoconductors or for electrophotographic applications.

Particularly preferred is an orientation layer, a polarizer, compensator or color filter containing an anisotropic polymer film according to the invention.

The following examples are intended to illustrate the invention without limiting it. Above and below, percentages are by weight unless otherwise stated. Temperatures are given in degrees Celsius. Mp means melting point, bp = clearing point. Furthermore, K = crystalline state, S = smectic phase, N = nematic phase, Ch = cholesteric phase and I = isotropic phase. The information between these symbols represents the transition temperatures.

Example 1 -5: Compounds of the formula IIa 2a (SD

Example 1: all-trans-4 '- (1'-dibromoethvD-bicyclohexyl-φ-carbonitrile

To a solution of 100 g of 4'-vinyl-bicyclohexyl-4-carbonitrile in 500 ml of chloroform at 0-5 ⁰ C, a solution of 23.6 ml of bromine in 300 ml of chloroform is slowly added dropwise. The reaction mixture is warmed to RT and stirred overnight at RT. For workup, the reaction mixture is concentrated by rotary evaporation (200 g

Crude product) and recrystallized from n-heptane / toluene / chloroform. This gives 149 g (yield 85%) of almost colorless solid (98.5% HPLC). Analog are produced:

Example alcohol dibromide yield

This oil

Example 5: 2-l ^' 4' - (1, 2-Dibromo-ethoxy-bicyclohexyl-4-ylH1, 31dioxolane

Step 1: DiBAH reduction

66.3 ml of DIBAH solution are added dropwise at ⁰ ° C. to a solution of 31.6 g of educt in 400 ml of toluene. After TLC control, the reaction is complete after 2 hours. For work-up, it is poured onto ice / HCl and stirred for 2 hours. It sucks everything on a large suction filter, washed with toluene, separates the organic phase and extracted the aqueous phase several times. The combined organic phases are dried and the solvent removed. Purification by chromatography over 1 liter of silica gel Pentane: DCM (1: 1) as eluent gives 23.3 g of a colorless solid (yield 73%).

Step 2: Dioxolan Noyori

To a solution of 15 g of aldehyde and 9.76 g of bissilyl ether in 400 ml of methylene chloride are injected in a heated flask at -78 ⁰ C 0.07 ml of TMSOTF. The mixture is stirred at this temperature for 12 hours, before adding 20 ml of conc. NaHCO ₃ solution quenches. The organic phase is separated and the aqueous phase extracted several times with methylene chloride. The combined organic phases are washed with water, dried over sodium sulfate, concentrated by rotary evaporation and the residue is purified by column chromatography on silica gel (toluene as eluent). This gives 15.4 g of a solid having an HPLC content of 90% (yield 84%).

Example 6-7: Compounds of the formula II2a2 (S3)

Example 6: 4 '- (1, 3-Dibromo-propyl-4-pentyl-bicyclohexane

Step 1-Oxo-3- (4'-pentyl-bicyclohexyl-4-yl) -propionic acid ethyl ester To a solution of 27.8 g of monoethyl malonate and 50 mg of 2,2'-bipyridine in 500 ml of THF at -78 ° C 257th ml of BuLi (15%) is slowly added dropwise and then warmed to -5 ° C. If the color remains at -5 ° C is cooled again to -65 ° C and the carboxylic acid chloride was added dropwise at this temperature. After 20 minutes the solution is allowed to warm slowly to -10 ^0C. It is then quenched by the addition of ether and ammonium chloride solution. It is diluted with toluene and neutralized with HCl and the org. Phase separated. The aqueous phase is nachextraiert several times. The united org. Phases are dried, concentrated by rotary evaporation and fritted over 500 g of silica gel (eluent: toluene). This gives 37.5 g (yield 81%) of white solid (HPLC 88.2%).

Step 2 4 '1- (4'-Pentyl-bicyclohexyl-4-yl) -propane-1,3-diol

In a 1-liter three-necked flask with reflux condenser (dropper), dropping funnel and septum to a solution of 36 g of the product from step 1 in 225 ml of THF 10.6 g of sodium borohydride (fine granules, lightly mined) entered. The reaction mixture is heated to 73 ° C. and 90 ml of methanol are added dropwise over 1 hour, during which vigorous evolution of H ₂ occurs.

The mixture is stirred for 1 hour at 75 ° C, cooled and stirred at RT overnight. It is mixed with ethyl acetate, quenched with ammonium chloride solution and neutralized with acetic acid (possibly H ₂ evolution). The org. Phase is separated and the aqueous phase repeatedly extracted with EA. The combined organic phases are washed well with water, dried, concentrated by rotary evaporation and the residue is recrystallised from heptane / toluene (allowed to crystallize over WE at -18 ° C.). From the mother liquor after concentration concentrated further product. After aspiration, a total of 26 g (yield 93%) of colorless solid. (HPLC 100%).

Step 3 4 '- (1,3-Dibromo-propyl-4-pentyl-bicyclohexane

In a 250 ml flask with reflux condenser and gas discharge in the hood

Dissolve 17.5 g of diol in 35 ml of carbon tetrachloride and add 4.2 ml of PBr ₃ (slightly exothermic). It is heated to 70 ⁰ C for 4 hours, with low

Quantities of HBr are released. It is poured onto cold water / MTBE, the organic phase is separated, the aqueous phase is extracted several times with MTBE and the combined org. Phases with water and sat. NaCl solution. It is dried over sodium sulfate, the solvent is removed on a rotary evaporator and the residue is purified by column chromatography on silica gel (eluent: heptane). This gives 16.8 g of an oil (43% yield) which, according to HPLC and NMR, contains 68% of the desired product.

By analogous sequences can be prepared:

Example 7: 1- (1,3-Dibromo-propyl) -4- (4-propyl-cyclohexyl) -benzene

Under N ₂ , 59.6 g of triphenylphosphine and 27.6 g of the diol are suspended in 500 ml of CH ₃ CN, cooled to about 10 ⁰ C and added dropwise at 0-8 ° C 11, 0 ml of bromine. It is stirred overnight. For workup, heptane, water and a little methanol, shake vigorously and separates the upper org. Phase off. The lower phase is extracted several times with heptane. The united org. Phases are dried and evaporated. The residual crude product is chromatographed on a silica gel-filled frit (eluent heptane). (Black-brown color on silica gel, product partly decomposes on silica gel). The appropriate fractions are rotated. 17.1 g of a tan oil are obtained.

Example 8-10: Compounds of the formula U2a3 (S4)

Example 8: 4 '- (1, 3-Dibromo-propyl-4-pentyl-bicyclohexane

Example 9: 4 '- (1, 3-Diiodo-propyl-4-pentyl-bicyclohexane

In a suspension of 262 g of triphenylphosphine, 65.1 g of imidazole and 95 g of the diol in a mixture of 500 ml of acetonitrile and 700 ml of toluene at 10 ⁰ C (ice bath) 242.9 g of iodine are added in portions, so that the temperature is not rises above 33 ° C. After 12 hours of stirring at RT, the reaction (MTBE: toluene 60:40) is complete. Then it is mixed with 800 ml of water and 800 ml of pentane, shaken well (3 phases) and the top, org. Phase separated. The aqueous phase is extracted several times with pentane, the org. Phases united and concentrated. Purification by filtration over 900 ml of silica gel (heptane as eluent) gives, after removal of the solvent, 197 g of a colorless, photosensitive solid (yield 99%).

Example 10: 4 '- (1, 3-Dibromo-propyl-4-pentyl-bicyclohexane

is prepared analogously from the corresponding diol.

Example 11-20: C-H-acidic compounds of the formula IIa1a (S7)

Example 11: All-trans-cyanoacetic acid ^ '- propyl-bicyclohex-1-yl-ester

Step 1: All-trans-4'-propyl-bicyclohexyl-4-ol 55 g of 4'-propyl-bicyclohexyl-4-one are introduced in portions into a solution of 3 g of sodium borohydride in 250 ml of isopropanol and 200 ml of THF. The The reaction mixture is stirred overnight, quenched with 2N HCl and neutralized. The solvent is largely evaporated, the residue taken up in toluene, the toluene phase washed several times with water, dried and evaporated to dryness. The residue is recrystallized from heptane / toluene. This gives 40.4 g of colorless solid (92% trans, HPLC), further recrystallization gives pure all-trans-4'-propyl-bicyclohexyl-4-ol.

Step 2: all-trans-cyanoacetic acid ^ '- propyl-bicyclohex-1-yl-ester

To a solution of 44.9 g of dicyclohexylcarbodiimide, 17.8 g of cyanoacetic acid (98%) and 800 mg of 4-aminopyridine in 500 ml of dichloromethane, a solution of 47.4 g of all-trans-4 'slowly at about 5 ⁰ C slowly. Propyl-bicyclohexyl-4-ol was added dropwise in 150 ml of dichloromethane. After a short time, urea starts to precipitate. The reaction mixture is stirred overnight and treated with 2.5 g of oxalic acid. After 1 hour of stirring is filtered off, the solid washed with dichloromethane, the filtrate evaporated and the residue taken up in a little toluene and filtered through about 400 g of silica gel (eluent toluene). The product fractions are collected and evaporated. This gives 58 g of colorless solid (HPLC 100%).

Example 12: all-trans-C -an acetic acid ^ '- heptyl-bicyclohex ^ -yl ester

is prepared analogously to the above scheme.

Example 13: 4- (1,4-dioxa-spirof4.51dec-8-yl) -cyclohexyl all-trans-cyanoacetic acid

is prepared analogously to the above scheme.

Example 14: all-trans-cyanacetic acid - ^ - O ^. Δ-trifluoro-phenyl-bicyclohexyl-yl ester

is prepared analogously to the above scheme.

Analogously to Example 8, step 2 are prepared by DCC coupling:

Example alcohol ester yield

Example 21 -44: Donor Acceptor Unit Compounds

Example 21: All-trans-covano-f5- (4-propylcyclohexyl) -f1, 31dithian-2-ylidene-1-acetic acid ethyl ester

1 1, 4 g of ethyl cyanoacetate, 9.06 ml of CS ₂ and 41, 4 g of potassium carbonate are dissolved in DMF

(100ml) and stirred for 1 hour at ⁰ ° C. under N ₂ (-> yellow suspension). Subsequently, a solution of 39.1 g of 1- [2- (1, 3-dibromopropyl)] - 4-propyl-cyclohexane in 50 ml of DMF is slowly added dropwise at RT without cooling. The reaction mixture warms slightly, the yellow solid partially goes into solution. The mixture is stirred for 4 hours at 6O ⁰ C. The warm solution is poured into 300 ml of ice-water, whereby a yellowish solid precipitates. This is filtered off and recrystallized from about 1800 ml of ethanol. 31.5 g of yellowish needles are obtained (yield 89%).

Analog are produced:

Example ester alkylating product yield unge¬

35 13 55-63%

commercially available (Lancaster Synthesis, UK) Example 41: All-trans-cano-β-methyl-δ-α-propyl-cclorie-xyl-HI, 31-thiazine-2-ylid6n-acetic acid 4'-pentyl-bicyclohexyl-4-yl-methyl ester

To a suspension of 8.7 g of the above ester and 10.4 g

Potassium carbonate in 40 ml of DMF are added at 0 ⁰ C 2.2 g of methyl isothiocyanate and stirred for 30 minutes at RT under N ₂ (-> yellow suspension). Subsequently, a solution of 9.8 g of 1- [2- (1, 3-dibromopropyl)] - 4-propylcyclohexane in 5 ml of DMF is slowly added dropwise at RT without cooling. The

The reaction mixture heats up slightly, and the yellow solid partially dissolves. The mixture is allowed to stir at 60 ^° C. for 4 hours. The warm solution is poured into 800 ml of ice-water, whereby a yellowish solid precipitates. This is filtered off, washed thoroughly with water and finally recrystallized from toluene. This gives 12.6 g of white solid (yield 88%). 0

Analog are produced:

Eg Ester Alkylation Product Yield

5 ^a iso-propyl isothiocyanate was used instead of methyl isothiocyanate.

Example 45-47: Compounds with polymerizable side chain

Example 45: All-trans succinic acid 4 '- {2-cvano-2- [4- (4'-cyano-bicyclohexyl-4- acryloyloxyVethylester

Step 1: Removal of the protecting group

A solution of 50 g of compound 35 and 1, 1 g of bis (acetonitrile) dichloropalladium in 500 ml of acetone and 700 ml of methyl chloride is stirred for 2 hours at 35 ⁰ C and then for 14 hours at room temperature. For workup will the reaction mixture is concentrated by rotary evaporation and chromatographed on silica gel (eluent DCM / EA 10%). 33.4 g of a pale yellow powder are obtained.

Step 2: Chemoselective reduction of the carbonyl group To a solution of 30 g of the deprotected compound from step 1, 17.2 g

Cerium (III) chloride heptahydrate in 100 ml of methyl chloride and 100 ml of ethanol at -20 ⁰ C as long as a solution of 1, 0 g of sodium borohydride in 150 ml of ethanol is slowly added dropwise until the conversion after TLC control (DCM / EA 1: 1 ) is complete (about 80 ml). The reaction mixture is concentrated by rotary evaporation and purified by chromatography on silica gel (eluent: DCM / EA 19: 1 → 9: 1). 15.1 g of a white powder are obtained (HPLC> 97%).

Step 3: DCC coupling

To a solution of 4.8 g of the alcohol from step 2, 2.4 g of succinic mono- [2- (2-methyl-acryloyloxy) ethyl] ester and 55 mg of DMAP in 50 ml of dichloromethane at 5 ⁰ C under nitrogen, a solution of 2.06 g of N ₁ N-dicyclohexylcarbodiimide in 25 ml of dichloromethane was added dropwise. After stirring for 14 hours, the product is filtered off with suction, washed with DCM and the concentrated filtrate is purified by chromatography on silica gel (eluent DCM / EA 19: 1). 6.5 g of a colorless solid are obtained.

Example 46: Acrylic acid 6- (4- {2-rcvano- (4'-propyl-bicyclohexyl-4-yloxycarbonyl) -methylene-1-ri, 31dithian-5-yl) -phenyl) -hexyl ester

Step 1: Removal of the protecting group

4.0 g of the protected alcohol are suspended in 77 ml of acetone and 0.7 ml of water, and 0.43 g of bis (acetonitrile) dichloropalladium (II) are added. Thereafter, it is heated to 75 ^° C. (reflux) for 3 hours, the reaction progress being monitored at regular intervals by means of TLC. When complete conversion is achieved, the cooled reaction solution is passed through Celite filtered off with suction and washed with acetone. The concentrated residue is purified by chromatography on silica gel (CH ₂ Ci ₂ -> CH ₂ Cl ₂ : EE 4: 1) and receives 3.1 g of the free alcohol as a pale yellowish powder.

Step 2: Esterification

To a solution of 1.0 g of the above alcohol in 30 ml of dichloromethane, 4 mg of 4-dimethylaminopyridine and 0.175 ml of aryl chloride are added under N ₂ . At ⁰ ° C., 0.212 g of triethylamine in 10 ml of dichloromethane were then added dropwise so that the temperature did not rise above 5 ^° C. It is stirred for 15 hours at RT. The reaction mixture is concentrated by rotary evaporation and the residue is purified by column chromatography on silica gel (eluent: dichloromethane). This gives 0.585 g of the ester (yield 46%) as a colorless powder.

Example 47: Methacrylic acid 6- (4- {2-cyano- (4'-propyl-bicyclohexyl-4-yloxycarbonyl) methylene-1, 31-dithian-5-yl) -phenyl) -hexyl ester

esterification

The esterification is carried out analogously to the above example (yield 78%).

Example P1-P10: Copolymerization

Apart from the donor-acceptor compounds according to the invention, the following reactive mesogens are used as comonomers:

Example P4: Copolymerization of RM23 with compound 45

314.8 mg of RM-2 (0.8 mmol) are mixed with 615.2 mg (0.8 mmol) of succinic acid 4'- {2-cyano-2- [4- (4'-cyano-bicyclohexyl-4-) yl) - [1, 3] dithiolan-2-ylidene] -acetoxy} -bicyclohexyl-4-yl-ester 2- (2-methyl-acryloyloxy) -ethyl ester (Example 45) in 15 ml of anhydrous dimethylformamide and dissolved with 1 , 5 mol%

Azoisobutyronitrile, dissolved in 2 ml of DMF, added and heated with nitrogen purge with stirring at 70 ° C for 24 hours. Thereafter, the formed co-polymer is precipitated by dropwise addition of the reaction solution in ten times the amount of methanol and dried. The resulting 810 mg are purified by repeated dissolution in dichloromethane and precipitation in methanol. There remain 510 mg of co-polymer which is characterized by gel permeation chromatography in tetrahydrofuran.

The following polymers are prepared analogously:

Example Reactive Donor Ratio M _w ¹⁾ Polydisomer Acceptor Persistency ¹⁾ Monomer

P1 RM-2 46 1: 1 4.955 1, 24 P2 RM-2 47 (M10) 1: 1 21, 457 2.23 P3 RM-2 45 (M14) 3: 7 62.697 2.27 P4 RM-2 45 (M14) 1: 1 37.694 2, 18

P5 RM-2 45 (M14) 7: 3 24.576 1, 71

P6 RM-2 45 (M14) 8.5: 1, 5 32.047 1, 65

P7 RM-2 - 1: 0 32,377 1, 57

P8 RM-3 45 (M14) 7: 3 35.016

P9 RM-1 45 (M14) 3: 7 55.140

P10 - 45 (M14) 0: 1

D to GPC (using PMMA for calibration)

Example A1 -A8: Preparation and measurement of the properties of anisotropic polymer films

A) Production of the films

The preparation of isotropic films is carried out by spinning (2000 rpm, 700 rpm / s, 30 s (spin-coater Karl Suess RC10)) from a solution consisting of matrix polymer and the photoactive compound or a photoactive copolymer. The following concentrations and solvents are used for the spin coating solutions:

Share Share Share Auxiliary

Film monomer copolymer in polymer in solvent in solution solution solution

Blend 0.02M

Monomer / (1, 2-1, 7 0 11, 5 wt% toluene

PMMA% by weight)

blend

Unknown _. ,. , Monomer / 0 4.2% by weight of (i, 8 wt% r γ- ^But y ^rolacton AL3046 ¹⁾

Copolymer 0 2.7% by weight of chloroform

* at 20 g polyimide to 1 l solvent

¹⁾ Commercially available polyimide (JSR Co. Ltd., Japan)

For complete removal of the solvent, the layers are one day at room temperature stored (copolymer; PMMA monomer blend) or about 2 minutes at 85 ⁰ C annealed (copolymer-polyimide blend). The irradiation is carried out with linearly polarized (LP) light at 325 nm time-dependent with a dose of 1.2 - 258 J / cm ² on a HeCd laser (Kimmon Electronics) or alternatively at 365 nm with a dose of 46 J / cm ² on a mercury vapor lamp with interference filter and Glan Thomson prism. Copolymer films are annealed at 85 ° C for up to three days after irradiation for complete alignment.

B) Characterization of anisotropic films

All films are characterized by absorption spectroscopy. Angle-dependent UV / Vis spectra are performed with a diode array spectrometer (Polytec X-dap-04 V 2.3) in conjunction with a Glan Thomson prism. Spectra are recorded by a 5 ° stepper motor control of the polarizer from 0-180 °. As a measure of the order of the chromophores, the dichroism D is calculated from the extinction parallel E _p and perpendicular E ₃ to the plane of the incident light according to formula (1). In order to avoid a negative sign of the dichroism in an orientation parallel to the E-FeId vector of the light, the values E _max and E _171J0 are used in parallel or vertically in the denominator for E _p or E ₃ , depending on the magnitude of the extinction.

Examples of the photo properties

Example A1: Spectral properties of the substance class

Unless stated otherwise, the photoactive donor-acceptor group of the examples listed above and below absorbs only in the UV range below 350 nm, ie the photoisomerization is carried out by means of UV light. It is not possible to differentiate spectrally between the two isomers of the substance class, so that the excitation of "both isomers" occurs at the same wavelength The absorption of the copolymer is characterized by a further band of the mesogen below 300 nm, thus allowing the photoactive group and mesogenic group Excite at different wavelengths and detect well spectroscopically The UV spectra of compound M14 and the polymer P5 are shown as an example in Figure 3. The spectra of the other prepared monomers and polymers are similar. Example A2: Preparation of anisotropic films

Linearly polarized irradiation induces anisotropy perpendicular to the irradiated light plane over time. The extent of the photochemically induced order of the compounds according to the invention is comparable to that of azobenzene chromophores. The order depends, among other things, on the host matrix and the radiation dose. For example, Figure 4 shows the induction of anisotropy by linearly polarized irradiation of a film of monomer M14 at 325 nm and 20 mW / cm ² without host matrix (a), in PMMA (b) and as copolymer film P5 (c).

Example A3: Preparation of anisotropic polymer films by linearly polarized irradiation and thermal self-assembly ("BuIk Alignment")

A linearly polarized irradiated film (dose 10 - 258 J / cm ² ) of the liquid crystalline copolymer P5 can be thermally organized by heating at 85 ° C to a value of D = 0.5. Figure 5 shows the angle-dependent extinction and dichroism (D) in a film of copolymer P5 according to the invention after linearly polarized irradiation with 325 nm and a dose of 108 J / cm ² and after thermal self-assembly at 85 ⁰ C for one day.

Example A4: Reorientation of the photoactive group

A (as described in Example A3) photochemically oriented film of the copolymer P5 according to the invention is irradiated with rotation of the plane of the linearly polarized light again with 108 mJ / cm ² . Here, a reorientation of the film takes place perpendicular to the E-FeId vector. The original order decreases with a double reorientation by 45 ° from D = 0.27, over 0.22 to 0.14. The decrease in anisotropy is associated with a decrease in the absorption of the film. Figure 6 shows the change in the angle-dependent extinction in a P5 film under light-induced reorientation with a change in the polarization direction of the light from 90 ° through 45 ° to 0 °. Example A5: Pixelization

The reorientation effect of these photoactive compounds is useful for making anisotropic pixels. Thus, from a film of copolymer P5 after 2-stage irradiation process with 1) linearly polarized irradiation in a

Direction and 2) linearly polarized radiation with mask in another direction, a pixel-by-pixel orientation of the entire film. After pixel-wise irradiation of the copolymer film, the order in the individual pixels is then thermally amplified. Figure 7 shows a thus prepared pixelated anisotropic film of the copolymer P5 between crossed polarizers (0790 °) in position 0 ° and 50 °.

Example A6: Surface alignment with a blend of copolymer and polyimide

A film prepared by spin coating a solution of 48 mg P5 in 1 ml polyimide (AL3046) is irradiated with linearly polarized light. As in other polymer matrices, anisotropy in the film is produced perpendicular to the polarization plane of the incident light. This varies after LP irradiation at 325 nm with a dose of 108 J / cm ² between D = 0.10-0.18. A similar behavior is found in films consisting of the inventive monomer compound M14 and AL3046.

Such prepared films act as an orientation layer for liquid crystals. Thus, for example, a commercial liquid crystal mixture ZLI1132 / K15 (Merck KGaA, Darmstadt, Germany), which contains for spectroscopic detection 0.3% by weight of a stilbene dye of the following formula,

are orientated by the above-described linearly polarized light-irradiated film of the photosensitive copolymer-polyimide blend P5 / AL3046. Figure 8 shows the angle-dependent extinction of the dye in the oriented liquid-crystal mixture (dichroism of the dye of D = 0.6 in the liquid-crystal mixture). Similarly, a P5 topcoat made by a drop-in process acts on polyimide (ZLI 2650), which has also been photochemically and thermally oriented, based on the same liquid crystal mixture. A physical attachment of P5 to polyimide was achieved by thermal means with sufficient stability for testing purposes.

Examples A7: Overview of light-induced dichroism of selected monomer compounds

The compounds M1 -M17 are prepared as described for example 21 -40 or in analogy thereto. The following table shows the absorption band A _ma χ (nm) and the dichroism D after irradiation with linearly polarized light (325 nm, irradiation dose 108 J / cm ² )

Example structural formula Amax D

/ nm (LP 325nm 108J / cm ² )

Example A8: Overview of light-induced and thermally amplified dichroism of selected copolymer compounds The following table shows the dichroism D of selected copolymers of the invention after irradiation with linearly polarized light (325 nm, 108 J / cm ² ) or after subsequent annealing at 78-125 ° C.

Example Reactive Photoactive Ratio D D

Mesogen group photochemically thermal

(LP 325nm (78 ° C - 108 J / cm ² ) 125 ° C)

P2 RM-2 M10 1: 1 0.13 0.55

P3 RM-2 M14 3: 7 0.11 0.11

P4 RM-2 M14 1: 1 0.14 0.15

P5 RM-2 M14 7: 3 0.27 0.48

P6 RM-2 M14 8.5: 1, 5 0.30 0.40

P8 RM-3 M14 7: 3 0.17 0

Literature:

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(4) J. Michl, "Photochromism by Orientation" in H. Dürr, H. Bouas-Laurent (Eds.) Photochromism, Molecules and Systems, Elsevier, Amsterdam, 1990. (5) L. Läsker, Th. Fischer, J Stumpe, S. Kostromin, S. Ivanov, V. Shibaev, R. Ruhmann, Mol. Cryst. Liq. Cryst., 246, 347, 1994.

(6) M. Eich, J.H. Wendorff, B. Reck, H. Ringsdorf, Makromol. Chem., Rapid. Commun. 8, 59, 1987,

(7) M.I. Bamik, V.M. Kozenkov, N.M. Shytykov, S.P. Palto, S.Yudin, J.Mol. Electronics 5, 53, 1988.

(8) K. Ichimura, Y. Suzuki, T. Seki, A. Hosoki, K. Aoki, Langmuir, 4, 1214, 1988.

(9) W. Gibbsons, P.J. Shannon, S. Sun, B.J. Swetlin, Nature, 351, 49, 1991.

(10) M. Schadt, H. Seiberle, A. Schuster, St. M. Kelly, Jpn. Appl. Phys. 34, 764 and 3240, 1995.

(11) V.P. Vorlusev, H.-S. Kitzerov, V.G. Chigrinov, Jpn.J. Appl. Phys. 34, 3240, 1995.

(12) G.P. Bryan-Brown, I.C. Sage, Liquid crystals, 20, 825, 1996.

(13) M. Schadt, Phys. P. 52, 695, 1996. (13a) EP-A-0 525 477

(13b) EP-A-0 611 981

(14) S.C. Jain, S. Kitzerow, Appl. Phys. Lett. 64, 2946, 1994.

(15) K. Ichimura, M. Momose, K. Kudo, H. Akiyama, N. Ishizuki, Langmuir, 11, 2341, 1995. (16) I. Janossy, A. D. Lloyd, B.S. Wherrett, Mol. Cryst. Liq. Cryst., 179, 1, 1990.

(17) S.P. Palto, J. Malthete, C. Germain, G. Durand, Mol. Cryst. Liq. Cryst. 282, 451, 1996.

(18) M. Schonhoff, M. Mertesdorf, M. Delsche, J. Phys. Chem. 100, 7558, 1996.

(19) I. Janossy, Phys. Rev. E. 49 (N4), 2957, 1994. (20) J. Stumpe, L. Lasker, Th. Fischer, S. Kostromin, J. Photochem. Photobiol., A: Chem, 80, 453, 1994.

(21) T. Fischer, L. Läsker, S. Czapla, J Rübner, J. Stumpe, Mol. Cryst. LJQ. Cryst., 297-298, [489] / 213, 1997. (22) R. Date, A.H. Fawcett, J. Haferkorn, J. Stumpe, Macromolecules, 31,

4935-49, 1998.

(23) K. Nakatani, Y. Atassi, J.A. Delaire, R. Guglielmetti, Nonlinear Optics, 8, 33, 1994.

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(25) N. Koumura, E.M. Geertsema, A. Meetsma, B.L. Feringa, JACS, 2000, 122, 12005-12006.

(26) US 5,327,750.

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Reviews

(I) C.B. McArdle, The application of side chain liquid crystal polymers to optical data storage, in C.B. McArdle (Ed.) Side chain liquid crystalline polymers, Blackie, 1989.

(II) S. Xie, A. Natansohn, P. Rochon, Chem. Mater., 5, 403, 1993. (HI) VP Shibaev, SG Kostromin, SA Ivanov, Comb-hatched Polymers with Mesogenic Side Groups as Electro and Photooptical Active Media "in VP Shibaev, Polymers as Electrooptical and Photooptical Active Media, Springer-Verlag, 1996. (IV) LM Blinov, J. of Nonlinear Optical Physics and Materials, 5, 165, 1996. (V) Th. Fuhrmann, J. Wendorff, Optical Storage "in Polymer Liquid Crystals

Vol. 4, Ed. W. Brostow, A. Collyer, Chapman and Hall, 1997. (VI) K. Ichimura, T. Seki, Y. Kawanishi, Y. Suzuki, M. Sauragi, T. Tamaki "Photocontrols of Liquid Crystal Alignment by Command Surfaces" M. Irie (Ed.) Photo-reactive Materials for Ultrahigh Density Optical Memories, Elsevier, 1994. (VII) K. Ichimura, "Photoregulation of liquid crystal alignment by photochromic molecules and polymeric thin films" in V. Shibaev Polymers as Electrooptical and Photooptical Active; Media, Springer, 1996.

(VIII) V. Shibaev, A. Bobrovsky, N. Boiko, "Photoactive Liquid Crystalline Polymer Systems with Light Controllable and Optical Properties" in Progress in Polymer Science 28, 729-836, 2003, Elsevier.

(IX) V. Shibaev, A. Bobrovsky, N. Boiko, "Optically Controlled Multifunctional Liquid Crystalline Polymer", Polymer Science Se. C 42, 103-128, 2000.

(X) T. Ikeda, A. Kanazawa, Photochemical Modulation of Alignment in Liquid Crystals, Bull. Chem. Soc. Jpn., 73, 1715-1733, 2000.

Claims

claims

1. A compound containing at least one of a N = N double bond different multiple bond, which is excited upon irradiation with polarized light and thereby a preferred orientation of

Connection causes, where

- the excitation of the multiple bond causes no permanent structural change or photochemical reaction with formation of a Reaktionsprόduktes, except for the possible formation of diastereomers or enantiomers (stereoisomerization), and

- The orientation in a layer of the compound or in a layer of a mixture containing the compound produces anisotropy or alters an existing anisotropy.

2. A compound according to claim 1, characterized in that it comprises at least one electron donor or Elektronenakzeptorgruppe which is linked directly or via a conjugated π system with the multiple bond.

3. A compound according to claim 2, characterized in that it comprises at least one each electron donor and Elektronenakzeptorgruppe on different sides of the multiple bond, which are linked directly or via a conjugated π system with the multiple bond.

4. A compound according to claim 2 or 3, characterized in that the donor and acceptor groups are π donors or π acceptors.

5. A compound according to any one of the preceding claims, characterized in that the multiple bond is a C = B double bond, wherein B represents a carbon or a heteroatom.

6. A compound according to at least one of the preceding claims, characterized in that it contains at least one linked directly to the multiple bond heteroatom, which may also be part of a Elektronendonor- or -akzeptorgruppe.

A compound according to claim 6, characterized in that the heteroatom is N, O, P or S (wherein P is a phosphorus atom).

8. A compound according to at least one of the preceding claims, characterized in that it does not appreciable absorption of

Having radiation in the visible wavelength range.

9. A compound according to at least one of the preceding claims, characterized in that it contains one or more mesogenic groups.

10. A compound according to at least one of the preceding claims, characterized in that it contains one or more polymerizable or crosslinkable groups.

11. A compound according to at least one of the preceding claims, selected from the following formula

DA-MG ¹ - (R ¹ ) ι I

wherein the individual radicals have the following meaning

DA an electron donor-acceptor system containing at least one

Multiple bond,

MG ^{1 is} a mesogenic group or a single bond,

R ^{1 is} H, halogen, NO ₂ , SF ₅ , NCS, SiR ⁰ R ⁰⁰ R ⁰⁰⁰ , Pg-Sp, Pg * -Sp- or an organic radical having 1 to 30 C atoms,

Pg is a polymerisable or reactive group,

Pg ^* a group which can be converted into or replaced by a polymerizable or reactive group Pg,

Sp is a spacer group or a single bond,. R ⁰ , R ⁰⁰ and R ^{000 are} each independently H or aryl or alkyl of 1 to 12 C atoms,

I 0, 1, 2, 3, 4, 5 or 6.

12. A compound according to claim 11, wherein DA DA represents ¹ or a group of the following formula

(R ² ) _k -MG ² -DA ² -) |

wherein the individual radicals have the following meaning

1 2

T, T, T are each independently, identically or differently, an electron acceptor group,

X ¹ , X ^{2 are} each, independently of one another, identical or different -O-, -S-, -NH-, -N [MG ¹ - (R ¹ ) ι] - or -P- [MG ¹ - (R ¹ ) ι ] -, (where P is an

Phosphorus atom),

Y, Y ¹ , Y ^{2 are} each, independently of one another, identical or different, an electron-withdrawing bridging group, R, R ^{2 are} each independently one of the meanings given for R ¹ in formula I,

MG ² a mesogenic group,

k 0, 1, 2, 3, 4, 5 or 6,

n1 and n2 are each independently 0, 1, 2 or 3.

A compound according to claim 12, wherein DA ^{1 is selected} from the following groups

wherein R has the meaning given in formula II and X has one of the meanings given for X ¹ in formula II.

14. A compound according to claim 12 or 13, wherein DA ^{2 is selected} from the following

Groups is selected

wherein T has the meaning given in formula II and X has one of the meanings given for X ¹ in formula II.

15. Compounds according to claim 13 or 14, wherein each X is independently, same or different, -S- or -O- and T is CN.

A compound according to claim 14, wherein DA is selected from the following groups

17. A compound according to any one of claims 11 to 16, wherein R, R ¹ and R ^{2 are} each independently H, halogen, NO ₂ , SF ₅ , NCS, SiR ⁰ R ⁰⁰ R ⁰⁰⁰ , Pg-Sp- or a linear or branched, achiral or chiral, unsubstituted or substituted by CN or CF ₃ or mono- or polysubstituted by halogen alkyl radical having 1 to 20 carbon atoms or alkenyl radical having 2 to 20 carbon atoms, wherein also one or more CH ₂ groups each independently of one another by -O-, -S-, -NR ⁰ -, -CO-, -SiR ⁰ R ⁰⁰ -, -CF ₂ -, -CH = CR ⁰ -, -CY ³ = CY ⁴ - or -CsC- may be replaced so that O atoms are not directly linked together, wherein R ⁰ , R ⁰⁰ and R ^{000 have} the meaning given in formula I and Y ³ and Y ^{4 are} each independently H, F, Cl or CN ,

18. A compound according to any one of claims 11 to 17, wherein Pg has one of the following meanings CH ₂ = CW ¹ -COO-,

W ² HC CH ₂ = CW - (O) _k1 -, CH ₃ -CH = CH-O-

, (CH ₂ = CH) ₂ CH-OCO-, (CH ₂ = CH) ₂ CH-O-, (CH ₂ = CH-CH ₂ ) ₂ CH-OCO-, (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) _ki-Phe- (O) k2-, Phe-CH = CH-, HOOC-, OCN-, -SCN, -NCS, - NGO, -OH, -SH, -NH ₂ , COX ¹ and W ⁴ W ⁵ W ⁶ Si-, wherein W ¹ H, Cl ₁ CN, phenyl or alkyl having 1 to 5 C atoms, W ² and W ³ each independently of one another H or Aikyl having 1 to 5 C-atoms, W ⁴ , W ⁵ and W ^{6 are} each independently of one another Cl, oxaalkyl or oxacarbonylalkyl with

1 to 5 carbon atoms, Phe 1, 4-phenylene, X ¹ halogen, OH, H, -O-alkyl having 1 to 12 carbon atoms or O-aryl having 1 to 12 carbon atoms, and ki and k ₂ each independently represent O or 1.

19. A compound according to any one of claims 11 to 18, wherein MG ^{1 is} a group of the following formula

- (A ¹ -ZV (A ² -Z ² ) o- (A ³ -Z ³ ) _p -1111

and MG ^{2 is} a group of the following formula

- (A ⁶ -Z ⁶ ) _s - (A ⁵ -Z ⁵ ) r (A ⁴ -Z ⁴ ) _q -1111

in which the individual radicals have the following meaning

A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ each independently, the same or different a) trans-1, 4-cyclohexylene, wherein also one or more non-adjacent

CH ₂ groups are replaced by -O- and / or -S-, may be replaced, b) 1, 4-phenylene, in which one or two CH groups may be replaced by N, c) a radical from the group 1, 4- Bicyclo (2,2,2) octylene, piperidine-1, 4-diyl,

Naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1, 2,3,4-

Tetrahydronaphthalene-2,6-diyl, indan-2,6-diyl, indene-2,6-diyl,

d) 1,4-cyclohexenylene, e) a radical from the group of the O, S or N heterocycles, in particular chromanediyl, isochromanediyl, benzofurandiyl,

Dihydrofurandiyl, benzothiophenediyl, dihydrobenzothiophendiyl,

Indolediyl, dihydroindolediyl, these groups may also be monosubstituted or polysubstituted by L, and L has one of the meanings given for R ¹ ,

Z \ Z ² , Z ³ , Z ^{4 are} each independently, identically or differently -O-, -S-, -NR ⁰ -, -CO-, -CO-O-, -O-CO-, -O-CO -O-, -CO-NR ⁰ -, -NR ° -CO-, -O-

CO-NR ⁰ , -NR ° -CO-O-, -NR ° -CO-NR ° -, - (CH ₂ ) r -CH ₂ O-, -OCH ₂ -, -SCH ₂ -, -CH ₂ S, -CF ₂ S-, -SCF ₂ -, -CF ₂ O-, -OCF ₂ -, -CF ₂ CF ₂ -, -CH ₂ CF ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF. ₂ O, -OCF ₂ CH ₂ -, -CH ₂ CH ₂ -, -CH = N-, -N = CH-, -N = N-, -CH = CR ⁰ -, -CY ³ = CY ⁴ - , -CH = CH-, -CF = CF-, -CH = CF-, -CF = CH-, -CH = CH-COO-, -OCO-CH = CH-, -CF = CF-COO-, - 0-CO-CF = CF-, -C≡C- or one

Single bond,

R ⁰ , R ⁰⁰ and R ^{000 are} each independently H or aryl or alkyl of 1 to 12 C atoms,

Y ³ and Y ^{4 are} each independently H, F, Cl or CN,

i 1, 2, 3 or 4,

n, o, p, q, r, s are each independently 0, 1 or 2, where n + o + p> 0 and q + r + s> 0.

A compound according to claim 19, wherein A ¹ , A ² , A ³ , A ⁴ , A ⁵ and A ^{6 are} each independently selected from the following groups

wherein in the phenyl rings and one or more H atoms may be replaced by R ¹ .

A compound according to claim 20, wherein MG ¹ and MG ² are selected from the following groups

where the phenyl rings can also be monosubstituted or polysubstituted by R ¹ .

22. A compound according to any one of claims 11 to 21, selected from the following formulas

wherein R, R ¹ , R ² , R ⁰ , A ^{1 "6} , Z ^{1" 6} , n, o, p, q, r, s have the meaning given in claims 11 to 21, R ^{0 is} preferably alkyl with 1 to 4 C atoms and R preferably denotes straight-chain or branched Aikyl having 1 to 6 C atoms

23. Mixture comprising at least one compound according to at least one of the preceding claims and at least one further, optionally mesogenic or liquid-crystalline, compound. vJVj

24. Mixture according to claim 23, characterized in that at least one of the compounds contained therein contains a polymerizable or crosslinkable group, is present in polymerized form or contains a group which is suitable for entering into a chemical or physical connection with a suitable substrate surface.

25. (co) polymer comprising at least one compound according to at least one of the preceding claims in covalently bonded form.

26. A copolymer comprising at least one compound according to at least one of the preceding claims and at least one further, optionally mesogenic or liquid-crystalline compound, in covalently bonded form.

27. A polymer mixture, characterized in that it contains at least one compound or at least one (co) polymer according to at least one of the preceding claims, and additionally contains at least one further, isotropic or anisotropic, polymer.

28. Use of compounds, mixtures or (co) polymers according to at least one of the preceding claims for the production of

Anisotropy in an isotropic material or to enhance anisotropy in an anisotropic material.

29. A process for producing an anisotropic polymer film, characterized by the following steps

A) applying a layer containing one or more compounds, mixtures or (co) polymers according to at least one of the preceding claims to a substrate, wherein at least one of the compounds contained in the layer has a polymerizable or other group according to claim 24 linkable group or in polymerized Shape is present,

B) irradiation of the layer with polarized light of a wavelength which causes excitation of the multiple bond in the compound according to claim 1 to 22, C) optionally annealing the layer,

D) optionally polymerization or crosslinking of the layer,

E) optionally removing the polymer film from the substrate.

30. The method according to claim 29, characterized in that the layer contains one or more compounds which before irradiation in polymerized form and be crosslinked after or simultaneously with the irradiation or annealing.

31. The method according to claim 29, characterized in that the layer contains one or more compounds which are present before irradiation in unpolymerized form and polymerized after or simultaneously with the irradiation or annealing or crosslinked.

32. The method according to at least one of claims 29 to 31, characterized in that different areas of the layer polarized

Radiation of different duration and / or intensity are exposed, for example by using a photomask.

An anisotropic polymer film obtainable by a process according to any one of claims 29 to 32.

An anisotropic polymer film containing at least two regions, or a regular pattern of regions having a different degree of anisotropy and / or different orientation, obtainable by a process according to claim 32.

35. Use of an anisotropic polymer film according to one of the preceding claims in electro-optical or liquid crystal displays (LCD), as optical film, polarizer, compensator, beam splitter, reflective polarizer, orientation layer, color filter, holographic

Element, hot stamping foil, decorative or security element, adhesive film, optical data storage, in non-linear optics, as a component of electrical semiconductors such as field effect transistors (FET), integrated circuits (IC), thin film transistors (TFT) or radio frequency identification elements (RFID), in organic

Light-emitting diodes (OLED), electroluminescent displays or lighting elements, in photovoltaic devices, optical sensors, as photoconductors or for electrophotographic applications.

36. Orientation layer, polarizer, compensator or color filter containing an anisotropic polymer film according to one of claims 33 and 34.