TW202415750A - Polymerizable liquid crystal material and polymerized liquid crystal film - Google Patents

Abstract

The invention relates to a polymerizable LC material comprising one or more reactive mesogenic compounds and one or more compounds of formula I,

Description

Polymerizable liquid crystal material and polymerized liquid crystal film

The invention relates to a polymerisable LC material comprising one or more reactive mesogen compounds and one or more compounds of formula I, (R ¹ -CHF-CF ₂ -Y-) _m Spacer (X) _n I wherein R ¹ = fluorinated linear or branched alkyl, optionally containing heteroatoms, Spacer = single bond or divalent organic group, X = hydrophilic group, Y = S, SO or SO ₂ , m is ≥ 1 and n is ≥ 1, wherein the individual groups have one of the meanings given in the claims. Furthermore, the invention also relates to a method for preparing the same, a polymer film obtainable from the corresponding polymerisable LC material, a method for preparing the polymer film, and the use of the polymer film and the polymerisable LC material in optics, electro-optics, decoration or security devices.

Reactive mesogens (RMs), mixtures or formulations thereof and polymers obtained therefrom can be used to prepare optical components such as compensating, retardant or polarizing films or prisms. Such optical components can be used in optical or electro-optical devices (such as LC) displays. Typically, RMs or RM mixtures are polymerized by an in-situ polymerization process.

For some applications, it is desirable to form a multi-layer film stack or optical component that includes two or more layers that, for example, exhibit different reflection wavelengths.

For example, multilayer cholesteric polymer films have been described in the prior art, for example in US 6,417,902. In addition, EP 0 634 674 suggests preparing a multilayer cholesteric liquid crystal polymer film by bringing together a pair of chiral nematic liquid crystal polymer films, applying pressure and heating the polymers above their glass transition temperature to allow the films to adhere.

Maurer et al., SID 90 Digest, Vol. 21, p. 110 (1990) describe the production of polarizing filters by combining several polarizing films with different reflection wavelengths. For the preparation of each film, a layer of CLC-side-chain polysiloxane containing chiral and non-chiral side groups is placed between two glass plates and oriented by shearing at high temperature.

JP 01-133003-A (Sumitomo Chem. Ind.) and JP 08-271731-A (Nitto Denko) disclose polarizing plates obtained by laminating one or more CLC polymer layers on a quarter-wave plate.

However, the method for preparing a multilayer cholesteric membrane as described in the above documents has several disadvantages. Therefore, it is usually extremely difficult and requires high temperatures to achieve a uniform alignment of the CLC polymer layer. For example, Maurer et al. mention an alignment temperature of 150° C., whereas JP 01-133003-A and JP 08-271731-A mention the need for a temperature higher than the glass transition temperature of the CLC polymer. This is particularly disadvantageous when using polymers with a high glass transition temperature, such as acrylates, styrenes or methacrylates, and in particular is highly unsuitable for mass production.

Furthermore, according to the method of multi-layer preparation as described, for example, in JP 01-133003-A, the polymers must be selected so that the different polymer layers exhibit different glass transition temperatures. Thus, when, for example, a second layer is laminated and aligned on top of a first layer, the alignment temperature (and therefore the glass transition temperature) of the second layer must be lower than the glass transition temperature of the first layer, so that uniform orientation of the first layer is not achieved, etc. This severely limits the choice of suitable materials and makes the production process more complicated.

Another aspect is that polymerizable LC materials often need to include a leveling agent, such as a surfactant, to achieve a good alignment of the resulting polymer. Typically, without the use of a surfactant in the formulation, increased haze, poor alignment of the helices in the CLC polymer, and uneven thickness across the film can be observed. On the other hand, due to the leveling agents normally used in such formulations, it can be difficult to achieve a good alignment and coating quality with a second coating of CLC materials required for multi-layer applications.

In this context, wetting resistance is defined as the breaking up of the liquid film on the substrate and the formation of droplets. In the case of multi-layer applications, this can lead to a non-uniform thickness of the second CLC material when drying. In some cases, the film can retract from the edges and in the worst case, there is extreme curling of the second coating layer, which leads to zero coverage of the coated area.

It is therefore an object of the present invention to provide improved polymerizable LC materials or RM mixtures and RM formulations which do not have the disadvantages of the materials known from the prior art. In particular, an object is to provide RM mixtures and RM formulations which are suitable for the preparation of polymers by in situ UV photopolymerization and which at the same time exhibit a high birefractive index, exhibit good solubility, show an increased broadening potential, have a favorable transition temperature, and show a high anti-yellowing resistance after exposure to UV light. Another object is to provide improved multilayer stacks which do not show the disadvantages of the materials known from the prior art. Other objects of the present invention will be apparent to the expert from the following description.

Surprisingly, the inventors of the present invention have found that a polymerizable LC material according to claim 1 satisfies one or more of the requirements defined above and preferably achieves all objectives simultaneously.

The present invention relates to polymerizable LC materials comprising one or more reactive mesogen compounds and one or more compounds of formula I (R ¹ —CHF—CF ₂ —Y—) _m Spacer (X) _n I wherein R ¹ = fluorinated linear or branched alkyl, optionally containing heteroatoms, Spacer = single bond or divalent organic group, X = hydrophilic group, Y = S, SO or SO ₂ , m is ≥ 1 and n is ≥ 1.

Furthermore, the present invention also relates to a corresponding process for producing a polymerisable LC material, comprising at least the step of mixing one or more reactive mesogen compounds with one or more compounds of formula I.

The invention further relates to polymer networks or polymer films obtainable, preferably obtainable, from a polymerizable LC material as described above and below and to methods for producing polymer films as described above and below.

The invention further relates to a method for improving the anti-wetting behavior of a polymer film obtainable, preferably obtainable, from a polymerizable LC material as described above and below by adding a block copolymer as described above and below to a polymerizable LC material before polymerization.

The invention further relates to an optical component comprising one or more optical films, one of which is selected from polymer films obtainable from polymerizable LC materials as described above and below.

The invention further relates to the use of optical components or polymer films or polymerizable LC materials as described above and below in optical, electro-optical, information storage, decorative and security applications, such as liquid crystal displays, projection systems, polarizers, compensators, alignment layers, circular polarizers, color filters, decorative images, liquid crystal pigments, reflective films with spatially varying reflected colors, multi-color images, unforgeable documents (such as identity cards or credit cards or banknotes).

The invention further relates to an electro-optical device, such as an LCD or an OLED, comprising one or more optical components or polymer films or polymerizable LC materials as described above and below.

The invention further relates to an electro-optical device in the field of augmented reality or virtual reality, such as a head-mounted device, which comprises one or more optical components as described above and below, a polymer film of a polymerizable material.

Terms and Definitions As used herein, the term "polymer" is understood to mean a molecule comprising a backbone of one or more different types of repeating units (the smallest building block of a molecule) and includes the commonly known terms "oligomer,""copolymer,""homopolymer," and the like. Furthermore, it is understood that the term polymer includes, in addition to the polymer itself, residues from initiators, catalysts, and other elements accompanying the synthesis of such polymers, wherein such residues are understood not to be covalently incorporated therein. Furthermore, such residues and other elements, while normally removed during post-polymerization purification processes, are typically mixed or co-mingled with the polymer so that they are generally retained in the polymer when it is transferred between containers or between solvents or dispersion media.

As used in the present invention, the term "(meth)acrylic polymer" includes polymers obtained from acrylic monomers, polymers obtainable from methacrylic monomers and corresponding copolymers obtainable from mixtures of these monomers.

The term "polymerization" refers to the chemical process of forming a polymer by bonding together a plurality of polymerizable groups or polymer precursors (polymerizable compounds) containing such polymerizable groups.

The terms "film" and "layer" include mechanically stable rigid or flexible self-supporting or freestanding films, as well as coatings or layers on a supporting substrate or between two substrates.

The term "liquid crystal" or "LC" refers to a material that has a liquid crystal phase in a certain temperature range (thermotropic LC) or is a solution in a certain concentration range (lyotropic LC). It must contain a mesogen compound.

The terms "mesogenic compound" and "liquid crystal compound" mean a compound containing one or more rod-shaped (rod-shaped or plate-shaped/lath-shaped) or discotic/disk-shaped mesogenic groups. The term "mesogenic group" means a group having the ability to induce liquid crystal phase (or mesophase) behavior. A compound containing a mesogenic group does not necessarily have to exhibit a liquid crystal mesophase by itself. It is also possible that it exhibits a liquid crystal mesophase only in a mixture with other compounds or when the mesogenic compound or material or a mixture thereof is polymerized. This includes low molecular weight non-reactive liquid crystal compounds, reactive or polymerizable liquid crystal compounds and liquid crystal polymers.

The rod-shaped liquid crystal protogroup generally comprises a liquid crystal protocore composed of one or more aromatic or non-aromatic cyclic groups connected to each other directly or via a linking group, optionally comprising an end group connected to the end of the liquid crystal protocore, and optionally comprising one or more side groups connected to the long side of the liquid crystal protocore, wherein these end groups and side groups are generally selected from (for example) carbon groups or alkyl groups, polar groups (such as halogen, nitro group, hydroxyl group, etc.) or polymerizable groups.

The term "reactive mesogen" means a polymerizable mesogen or liquid crystal compound, preferably a monomeric compound. Such compounds can be used as pure compounds or as a mixture of reactive mesogens and other compounds that function as photoinitiators, inhibitors, surfactants, stabilizers, chain transfer agents, non-polymerizable compounds, etc.

A polymerizable compound having one polymerizable group is also referred to as a "monoreactive" compound, a compound having two polymerizable groups is referred to as a "direactive" compound, and a compound having more than two polymerizable groups is referred to as a "polyreactive" compound. A compound having no polymerizable groups is also referred to as a "non-reactive or non-polymerizable" compound.

The term "non-mesogenic compound or material" refers to a compound or material that does not contain a mesogenic group as defined above.

Visible light is electromagnetic radiation having a wavelength in the range of about 400 nm to about 740 nm. Ultraviolet (UV) light is electromagnetic radiation having a wavelength in the range of about 200 nm to about 450 nm.

Irradiance (E _e ) or radiant power is defined as the power of electromagnetic radiation occurring on a surface (dθ) per unit area (dA): E _e = dθ/dA.

Radiation exposure or radiation dose (H _e ) is irradiance or radiation power (E _e )/time (t): _He = E _e ∙ t.

All temperatures, such as, for example, the melting point T(C,N) or T(C,S) of the liquid crystal, the phase transition from smectic (S) to nematic (N) T(S,N) and the clearing point T(N,I) are quoted in degrees Celsius. All temperature differences are quoted in differential degrees.

The term "clearing point" refers to the temperature at which the transition between the intermediate phase and the maximum temperature range occurs.

The term "director" is known in the prior art and refers to the preferred orientation direction of the long molecular axis (in the case of rod-shaped compounds) or the short molecular axis (in the case of discotic compounds) of the liquid crystal or RM molecules. In the case of uniaxial ordering of these anisotropic molecules, the director is the axis of anisotropy.

The term "alignment" or "direction" refers to the alignment (directional ordering) of anisotropic units of a material (such as small molecules or fragments of macromolecules) in a common direction called the "alignment direction". In the alignment layer of a liquid crystal or RM material, the liquid crystal director is aligned with the alignment direction so that the alignment direction corresponds to the direction of the anisotropic axis of the material.

The term liquid crystal or RM material, e.g., "uniformly oriented" or "uniformly aligned" in a layer of material means that the long molecular axes (in the case of rod-shaped compounds) or short molecular axes (in the case of discotic compounds) of the liquid crystal or RM molecules are oriented in substantially the same direction. In other words, the lines of the liquid crystal directors are parallel.

The terms "vertical structure" or "vertical orientation" refer to films in which the optical axis is substantially perpendicular to the plane of the film.

The terms "planar structure" or "planar orientation" refer to films in which the optical axis is substantially parallel to the plane of the film.

The term "A-plate" refers to an optical retarder utilizing a layer of uniaxial birefringent material in which the extraordinary axis of the material is oriented parallel to the plane of the layer.

The term "C-plate" refers to an optical block utilizing a layer of uniaxial birefringent material in which the extraordinary axis of the material is oriented perpendicular to the plane of the layer.

In an A/C plate comprising an optical uniaxial birefringent liquid crystal material having a uniform orientation, the optical axis of the film is provided by the direction of an extraordinary axis. An A (or C) plate comprising an optical uniaxial birefringent material having a positive birefringent index is also referred to as a "positive A (or C) plate" or "+ A (or + C) plate".

A (or C) plates comprising films of optically uniaxial birefringent materials (such as discotic anisotropic materials) having negative birefringence are also referred to as "negative A (or C) plates" or "-A (or C) plates", depending on the orientation of the discotic material. Films prepared from cholesteric rod-shaped materials having a reflection band in the UV portion of the spectrum also have the optics of negative C plates.

The birefringent index Δn is defined as Δn = _{ne -no} where ne _is the extraordinary refractive index and _no is the ordinary refractive index, and the average effective refractive index n _av. is given by the following equation: n _av. = ((2n _o ² + _ne ² )/3) ^½ The average effective refractive index n _av. and the ordinary refractive index _no can be measured using an Abbe refractometer. Δn can then be calculated from the above equation.

As used herein, plural forms of the terms herein are to be construed as including the singular form and vice versa, unless the context clearly indicates otherwise.

Unless explicitly stated otherwise, all physical properties have been measured according to "Merck Liquid Crystals, Physical Properties of Liquid Crystals", Status, November 1997, Merck KGaA, Germany and are given for a temperature of 20°C. The optical anisotropy (Δn) was measured at a wavelength of 589.3 nm.

In case of doubt, the definitions provided by C. Tschierske, G. Pelzl and S. Diele, Angew. Chem. 2004, 116, 6340-6368 should apply.

Unless expressly specified otherwise in a given general formula, the following terms have the following meanings:

"Carbonyl" means a monovalent or polyvalent organic group containing one or more carbon atoms, which does not contain additional atoms (such as, for example, -C≡C-) or optionally contains one or more additional atoms, such as, for example, N, O, S, P, Si, Se, As, Te or Ge (e.g., carbonyl, etc.). "Alkyl" means a carbon group, which additionally contains one or more H atoms and optionally one or more impurity atoms, such as, for example, N, O, S, P, Si, Se, As, Te or Ge.

The carbonyl or alkyl group may be a saturated or unsaturated group. Unsaturated groups are, for example, aryl, alkenyl or alkynyl. Carbonyl or alkyl groups with more than 3 C atoms may be straight chain, branched chain and/or cyclic and may contain spiro-connected or condensed rings.

Preferred carbonyl and alkyl groups are optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy and alkoxycarbonyloxy groups having 1 to 40, preferably 1 to 25, particularly preferably 1 to 18 C atoms, optionally substituted aryl or aryloxy groups having 6 to 40, preferably 6 to 25 C atoms, or optionally substituted alkylaryl, aralkyl, alkylaryloxy, arylalkoxy, arylcarbonyl, aryloxycarbonyl, arylcarbonyloxy and aryloxycarbonyloxy groups having 6 to 40, preferably 6 to 25 C atoms. In addition, preferred carbon groups and carbon groups are _C1 - _C40 alkyl groups, _C2 - _C40 alkenyl groups, _C2 - _C40 alkynyl groups, _C3 - _C40 allyl groups, _C4 - _C40 alkadienyl groups, _C4 - _C40 polyenyl groups, _C6 - _C40 aryl groups, _C6 - _C40 alkylaryl groups, _C6 - _C40 aralkyl groups, _{C6-C40 alkylaryloxy groups, C6 -C40 arylalkoxy groups} , _C2 - _C40 heteroaryl groups, _C4 -C40 cycloalkyl groups, _C4 - _C40 cycloalkenyl groups _, and the like. Particularly preferred are C ₁ -C ₂₂ alkyl, C ₂ -C ₂₂ alkenyl, C ₂ -C ₂₂ alkynyl, C 3 -C ₂₂ allyl, C ₄ -C ₂₂ alkyldienyl, C _{6 -C 12} aryl, C ₆ -C ₂₀ aralkyl and C ₂ -C ₂₀ heteroaryl.

In addition, preferred carbonyl and alkyl groups are straight chain, branched chain or cyclic alkyl groups having 1 to 40, preferably 1 to 25 C atoms, more preferably 1 to 12 C atoms, which are unsubstituted or mono- or poly-substituted with F, Cl, Br, I or CN, and wherein one or more non-adjacent _CH2 groups can be independently replaced by -C( ^Rx )=C( ^Rx )-, -C≡C-, -N( ^Rx )-, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- in such a way that the O and/or S atoms are not directly connected to each other.

In the above, ^Rx preferably represents H, a halogen, a straight chain, a branched chain or a cyclic alkyl chain having 1 to 25 C atoms, and one or more non-adjacent C atoms thereof may be replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, and one or more H atoms thereof may be replaced by fluorine, an aryl or aryloxy group having 6 to 40 C atoms which may be substituted as the case may be, or a heteroaryl or heteroaryloxy group having 2 to 40 C atoms which may be substituted as the case may be.

Preferred alkyl groups are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, n-hexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, dodecyl, trifluoromethyl, perfluoro-n-butyl, 2,2,2-trifluoroethyl, perfluorooctyl, perfluorohexyl, etc. In addition, one or more non-adjacent CH ₂ groups may be independently substituted by Replace.

Preferred alkenyl groups include ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl and the like.

Preferred alkynyl groups include, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, octynyl and the like.

Preferred alkoxy groups include, for example, methoxy, ethoxy, 2-methoxyethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, 2-methoxybutoxy, n-pentoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy, etc. In addition, one or more non-adjacent _CH2 groups may be independently substituted by Replace.

Preferred amino groups include, for example, dimethylamino, methylamino, methylanilino, and anilino.

Aryl and heteroaryl groups may be monocyclic or polycyclic, i.e., they may have one ring (such as, for example, phenyl) or two or more rings, which may also be fused (such as, for example, naphthyl) or covalently linked (such as, for example, biphenyl), or contain a combination of fused and linked rings. Heteroaryl groups contain one or more heteroatoms, preferably selected from O, N, S and Se.

Preferred are monocyclic, bicyclic or tricyclic aryl groups having 6 to 25 C atoms and monocyclic, bicyclic or tricyclic heteroaryl groups having 2 to 25 C atoms, which optionally contain fused rings and which are optionally substituted. In addition, preferred are 5-, 6- or 7-membered aryl groups and heteroaryl groups, in which one or more CH groups may be replaced by N, S or O in such a way that O atoms and/or S atoms are not directly connected to each other.

Preferred aryl groups are, for example, phenyl, biphenyl, terphenyl, [1,1':3',1'']terphenyl-2'-yl, naphthyl, anthracene, binaphthyl, phenanthrene, pyrene, dihydropyrene, , perylene, tetracene, pentacene, benzoperylene, fluorene, indene, indenofluorene, spirobifluorene, etc.

Preferred heteroaryl groups are, for example, 5-membered rings such as pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, furan, thiophene, selenophene, oxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4 -thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole; a 6-membered ring such as pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine; or a condensed group such as indole, isoindole, indolizine, Indazole, benzimidazole, benzotriazole, purine, naphthimidazole, phenanthimidazole, pyridimidazole, pyrazimidazole, quinoxalineimidazole, benzoxazole, naphthimidazole, anthraxazole, phenanthimidazole, isoxazole, benzothiazole, benzofuran, isobenzofuran, dibenzofuran, quinoline, isoquinoline, pteridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzene thieno[2,3b]thiophene, thieno[3,2b]thiophene, dithienothiophene, isobenzothiophene, dibenzothiophene, benzothiazolylthiophene or a combination of these groups. The heteroaryl group may also be substituted by an alkyl, alkoxy, sulfanyl, fluorine, fluorine alkyl or another aryl or heteroaryl group.

(Non-aromatic) alicyclic and heterocyclic groups include both saturated rings, i.e. those containing only single bonds, and partially unsaturated rings, i.e. those which may also contain multiple bonds. Heterocyclic rings contain one or more heteroatoms, preferably selected from Si, O, N, S and Se.

(Non-aromatic) alicyclic and heterocyclic groups may be monocyclic, i.e. contain only one ring (such as, for example, cyclohexane), or polycyclic, i.e. contain a plurality of rings (such as, for example, decahydronaphthalene or bicyclooctane). Saturated groups are particularly preferred. Furthermore, monocyclic, bicyclic or tricyclic groups having 3 to 25 C atoms, which may contain fused rings and which may be substituted, are preferred. Furthermore, 5-, 6-, 7- or 8-membered carbocyclic groups are preferred, in which, moreover, one or more C atoms may be replaced by Si and/or one or more CH groups may be replaced by N and/or one or more non-adjacent _CH2 groups may be replaced by -O- and/or -S-.

Preferred alicyclic and heterocyclic groups are, for example 5-membered groups such as cyclopentane, tetrahydrofuran, tetrahydrothiophene, pyrrolidine; 6-membered groups such as cyclohexane, silacyclohexane, cyclohexene, tetrahydropyran, tetrahydrothiopyran, 1,3-dioxane, 1,3-dithiane, piperidine; 7-membered groups such as cycloheptane; and condensed groups such as tetrahydronaphthalene, decahydronaphthalene, dihydroindene, bicyclo[1.1.1]pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl, spiro[3.3]heptane-2,6-diyl, octahydro-4,7-hydroxymethyldihydroindene-2,5-diyl.

The aryl, heteroaryl, (non-aromatic) alicyclic and heterocyclic groups may optionally have one or more substituents, preferably selected from the group consisting of silyl, sulfo, sulfonyl, formyl, amine, imine, nitrile, hydroxyl, nitro, halogen, C _1-12 alkyl, C _6-12 aryl, C _1-12 alkoxy, hydroxyl or a combination of these groups.

Preferred substituents are, for example, solubility-promoting groups such as alkyl or alkoxy groups; electron-withdrawing groups such as fluorine, nitro or nitrile; or substituents which increase the glass transition temperature (Tg) of the polymer, in particular bulky groups such as, for example, tert-butyl or optionally substituted aryl groups.

Preferred substituents also referred to as "L" hereinafter are, for example, F, Cl, Br, I, -OH, -CN, _-NO2 , -NCO, -NCS, -OCN, -SCN, -C(=O)N( ^Rx ) ₂ , -C(=O) ^Yx , -C(=O) ^Rx , -C(=O) ^ORx , -N( ^Rx ) ₂ , wherein ^Rx has the meanings mentioned above, and Y ^x represents a halogen, an optionally substituted silyl, an optionally substituted aryl or heteroaryl having 4 to 40, preferably 4 to 20 ring atoms, and a straight or branched chain alkyl, alkenyl, alkynyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy group having 1 to 25 C atoms, wherein one or more H atoms may be optionally replaced by F or Cl.

"Substituted silyl or aryl" preferably means substituted with halogen, -CN, R ^y , -OR ^y , -CO-R ^y , -CO-OR ^y , -O-CO-R ^y or -O-CO-OR ^y , wherein R ^y represents H, a straight chain, branched chain or cyclic alkyl chain having 1 to 12 C atoms.

In the formulae shown above and below, the substituted phenylene ring Preferably in which L has, on each occurrence, identically or differently, one of the meanings given above or below, and is preferably F, Cl, CN, NO ₂ , CH ₃ , C ₂ H ₅ , C(CH ₃ ) ₃ , CH(CH ₃ ) ₂ , CH ₂ CH(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 , OC ₂ F ₅ or P-Sp-, very preferably F, Cl, CN, CH ₃ , C ₂ H ₅ , OCH ₃ , COCH ₃ , OCF ₃ or P-Sp-, most preferably F, Cl, CH ₃ , OCH ₃ , COCH ₃ or OCF ₃ .

"Halogen" means F, Cl, Br or I, preferably F or Cl, most preferably F.

The "polymerizable group" (P) is preferably selected from groups containing a C=C double bond or a C≡C triple bond and groups suitable for ring-opening polymerization, such as, for example, cyclohexane or epoxide groups.

Preferably, the polymerizable group (P) is selected from the group consisting of: CH ₂ ═CW ¹ -COO—, CH ₂ ═CW ¹ -CO—, , , , , CH ₂ =CW ² -(O) _k3 -, CW ¹ =CH-CO-(O) _k3 -, CW ¹ =CH-CO-NH-, CH ₂ =CW ¹ -CO-NH-, CH ₃ -CH=CH-O-, (CH ₂ =CH) ₂ CH-OCO-, (CH ₂ =CH-CH ₂ ) ₂ CH-OCO-, (CH ₂ =CH) ₂ CH-O-, (CH ₂ =CH-CH ₂ ) ₂ N-, (CH ₂ =CH-CH ₂ ) ₂ N-CO-, CH ₂ =CW ¹ -CO-NH-, CH ₂ =CH-(COO) _k1 -Phe-(O) _k2 -, CH ₂ =CH-(CO) _k1 -Phe-(O) _k2 -, Phe-CH=CH-, wherein W ¹ represents H, F, Cl, CN, CF ₃ , phenyl or alkyl having 1 to 5 C atoms, in particular H, F, Cl or CH ₃ , W ² represents H or alkyl having 1 to 5 C atoms, in particular H, methyl, ethyl or n-propyl, W ³ and W ⁴ each independently represent H, Cl or alkyl having 1 to 5 C atoms, Phe represents 1,4-phenylene, which is optionally substituted by one or more radicals L as defined above but different from P-Sp-, preferably the substituent L is 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 , OC ₂ F ₅ , in addition to phenyl, and k ₁ , k ₂ and k _{k 3} each independently represents 0 or 1, k ₃ preferably represents 1, and k ₄ represents an integer from 1 to 10.

Particularly preferred polymerizable groups P are CH ₂ =CH-COO-, CH ₂ =C(CH ₃ )-COO-, CH ₂ =CF-COO-, CH ₂ =CH-, CH ₂ =CH-O-, (CH ₂ =CH) ₂ CH-OCO-, (CH ₂ =CH) ₂ CH-O-, and , wherein W ² represents H or an alkyl group having 1 to 5 C atoms, in particular H, methyl, ethyl or n-propyl.

Further preferred polymerizable groups (P) are vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, cyclohexane and epoxide, most preferably acrylate or methacrylate, in particular acrylate.

Preferably, all polyreactive polymerizable compounds and their subformulae contain one or more branching chain groups containing two or more polymerizable groups P (polyreactive polymerizable groups) instead of one or more groups P-Sp-.

Suitable groups of this type and polymerizable compounds containing them are described in (for example) US 7,060,200 B1 or US 2006/0172090 A1.

Particularly preferred are multi-reactive polymerizable groups selected from the following formulae: wherein alkyl represents a single bond or a straight or branched chain alkyl group having 1 to 12 C atoms, wherein one or more non-adjacent _CH2 groups may each independently be replaced by -C( ^Rx )=C( ^Rx )-, -C≡C-, -N( ^Rx )-, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, and in addition, wherein one or more H atoms may be replaced by F, Cl or CN, wherein ^Rx has one of the above-mentioned meanings, _aa and _bb each independently represent 0, 1, 2, 3, 4, 5 or 6, X has one of the meanings specified for X', and ^Pv to ^Pz each independently have one of the meanings specified above for P.

Preferred spacer groups Sp are selected from alkylene groups having 1 to 20, preferably 1 to 12 C atoms, which are optionally mono- or polysubstituted by F, Cl, Br, I or CN and in which one or more non-adjacent CH ₂ groups can each be replaced independently of one another by -O-, -S-, -NH-, -NR ^xx -, -SiR ^xx R ^yy -, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO-, -CO-S-, -NR xx -CO-O-, -O-CO-NR ^xx -, -NR ^xx -CO ^- NR ^yy -, -CH=CH- or -C≡C- in such a way that the O and/or S atoms are not directly connected to one another, and in which R ^xx and R ^yy each independently of one another represent H or an alkyl group having 1 to 12 C atoms.

In addition, preferred spacer groups Sp are selected from the formula Sp'-X', so that the group "P-Sp-" conforms to the formula "P-Sp'-X'-", wherein Sp' represents an alkylene group having 1 to 20, preferably 1 to 12 C atoms, which is optionally mono- or polysubstituted by F, Cl, Br, I or CN and in addition, one or more non-adjacent _CH2 groups can each be independently replaced by -O-, -S-, -NH-, ^-NRxx- , -SiRxxRyy-, -CO-, -COO-, -OCO-, -OCO ^- O-, -S ^- CO-, -CO-S-, -NRxx-CO-O-, -O-CO- ^NRxx- , -NRxx-CO- ^NRyy- , -CH=CH- or -C≡C- in such a way that ^the O ^and /or S atoms are not directly connected to each other, X' represents -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR ^xx -, -NR xx -CO-, -NR ^xx -CO ^- NR ^yy -, -OCH ₂ -, -CH 2 O-, -SCH 2 -, -CH ₂ S-, -CF ₂ O-, -OCF ₂ -, -CF ₂ S-, -SCF _{2 -, -CF 2 CH 2 -, -CH 2 CF 2 -, -CF 2 CF 2 - , -CH = N- ,} -N=CH-, -N=N-, -CH=CR ^xx -, -CY ^xx =CY ^xx -, -C≡C-, -CH=CH-COO-, -OCO-CH=CH- or a single bond, R ^xx and R ^yy each independently represent H or an alkyl group having 1 to 12 C atoms, and Y ^xx and Y ^yy each independently represents H, F, Cl or CN. X' is preferably -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR ^xx -, -NR ^xx -CO-, -NR ^xx -CO-NR ^yy - or a single bond.

Typical and preferred spacer groups Sp and/or Sp' are _, for example, -( _CH2 ) _p1- , -( _CH2CH2O ) _q1 - ^CH2CH2- _{, -CH2CH2 -} S-CH2CH2-, _-CH2CH2 -NH _{- CH2CH2-} , or -( _{SiRxxRyy -} ^O ) _p1- , wherein _p1 is an integer from 1 to 12, q1 is an integer _from 1 to 3, and ^Rxx and ^Ryy have the meanings mentioned above.

Particularly preferred groups -X'-Sp'- are -(CH ₂ ) _p1 -, -O-(CH ₂ ) _p1 -, -OCO-(CH ₂ ) _p1 -, -OCOO-(CH ₂ ) _p1 -, wherein p1 is an integer from 1 to 12.

Particularly preferred radicals Sp and/or Sp' in each case of a linear chain are, for example, methylene, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, octadecyl, ethyloxyethyl, methyleneoxybutyl, ethylthioethyl, ethyl-N-methyliminoethyl, 1-methylalkyl, vinyl, propenyl and butenyl.

The term "opposition" is generally used to describe objects whose mirror images are not superimposable.

Achiral/non-chiral objects are objects that are identical to their mirror images.

Unless expressly specified otherwise, the terms "chiral nematic" and "choleric" are used synonymously in this application.

Chiral nematic textures or cholesteric liquid crystals (CLC) exhibit selective reflection of circularly polarized light, where the direction of rotation of the photocarrier corresponds to the direction of rotation of the cholesteric helix.

The reflection wavelength λ is given by the pitch p of the cholesteric helix and the average birefringence n of the cholesteric liquid crystal according to the following equation: λ = ^n.p

CLC media can be prepared, for example, by doping a nematic LC medium with a chiral dopant having a high twist power. The pitch p of the induced cholesteric helix is then given by the concentration c and the helix twist power HTP of the chiral dopant according to the following equation: p = (HTP c) ^-1

Two or more dopants may also be used, for example, to compensate for the temperature dependence of the HTP of the individual dopants and thus achieve a low temperature dependence of the helical pitch and the reflected wavelength of the CLC medium. The following equation then holds for the total HTP ( _HTPtotal ): _HTPtotal = ∑ _i c _i HTP _i where c _i is the concentration of each individual dopant and HTP _i is the helical twisting power of each individual dopant.

According to the present invention, represents trans-1,4-cyclohexylene, and It represents 1,4-phenylene.

For the present invention, the group -COO- or -CO ₂ - is represented by Ester group, and the group -OCO-, -O ₂ C- or -OOC- The ester group.

A "polymer network" is a network in which all polymer chains are interconnected by many cross-links to form a single macroscopic entity.

Polymer networks can occur in the following types: -Graft polymer molecules are branched polymer molecules in which one or more side chains are structurally or conformationally different from the main chain. -Star polymer molecules are branched polymer molecules in which a single branch point gives rise to multiple straight chains or arms. If the arms are identical, the star polymer molecule is called regular. If adjacent arms contain different repeating subunits, the star polymer molecule is called diversified. -Comb polymer molecules consist of a main chain with two or more three-way branch points and linear side chains. If the arms are identical, the comb polymer molecule is called regular. -Brush polymer molecules consist of a main chain with linear unbranched side chains and in which one or more of the branch points has a four-way functionality or greater.

Throughout the description and patent application of this specification, the words "comprise" and "contain" and variations of the words, for example, "comprising/comprises" means "including but not limited to", and is not intended to (and does not) exclude other components. On the other hand, the word "comprising" also includes the term "consisting of", but is not limited to the term.

Throughout the description and patent application of this specification, the words "obtainable" and "obtained" and variations of the words mean "including but not limited to", and are not intended to (and do not) exclude other components. On the other hand, the word "obtainable" also includes the term "obtained", but is not limited to the term.

The concentrations used are quoted in % by weight and relative to the respective mixture as a whole, all temperatures are quoted in degrees Celsius and all temperature differences are quoted in degrees differential.

The compounds of formula I preferably do not contain a -OO- bond. The novel compounds preferably contain the following variables: ^R1 = straight or branched chain, optionally containing heteroatoms, perfluoroalkyl, preferably perfluoroC1-C6-alkyl, particularly preferably perfluoroC1-C4-alkyl, specifically perfluoroC1-C3-alkyl, spacer = saturated or unsaturated branched or unbranched hydrocarbon unit optionally containing heteroatoms, wherein the -OO- bond is absent, X = anionic, cationic, nonionic or amphoteric group, Y = S, SO or _SO2 , preferably S, m = 1, 2, 3, 4, 5 or 6, preferably 2 to 4, specifically 2 to 3, and n = 1, 2, 3 or 4, preferably 1 or 2.

Particularly preferred compounds of formula (I) are those wherein all variables have the preferred meanings.

The fluorinated group ^R1 is preferably selected from the group consisting of: _CF3- ( _CF2 ) _0-3- , _CF3- ( _CF2 ) _0-3 -O-, CF3-(CF2)0-3-O-(CF2) _1-3- , CF3-( _CF2 ) _0-3 -O-(CF2)1-3-O-, _CF3- ( _CF2 ) _0-3 -O-( _{CF2 ) 1-3 - O-} , CF3-( _CF2 ) _0-3 -O-( _CF2 )1-3-O-, CF3-(CF2) _0-3 - _O- ( _CF2 ) _{1-3 -} O-CF2-, CF3-(CF2)0-3-O-( _CF2 -O) _1-8- and _CF3- ( _CF2 ) _0-3 -O-( _CF2 -O) _1-8 - _CF2- .

The fluorinated group R ¹ is particularly preferably a CF ₃ —(CF ₂ ) _1-2 —O— group, specifically a CF ₃ —CF ₂ —CF ₂ —O group.

Preferred anionic groups X may be selected from COO ^- , ‑SO ₃ ^- , -OSO ₃ ^- , -PO ₃ ^2- , ‑OPO ₃ ^2- , ‑OP(O)(O ^- )O- , -(OCH ₂ CH ₂ ) _s -O-(CH ₂ ) _t -COO ^- , ‑(OCH ₂ CH ₂ ) _s ‑O-(CH ₂ ) _t -SO ₃ ^- , -(OCH ₂ CH ₂ ) _s ‑O‑(CH ₂ ) _t ‑OSO ₃ ^‑ , ‑(OCH ₂ CH ₂ ) _s ‑O‑(CH ₂ ) _t ‑PO ₃ ^2- , ‑(OCH ₂ CH ₂ ) _s ‑O‑(CH ₂ ) _t ‑OPO ₃ ^2- or from Formulas A to C, Wherein s represents an integer in the range of 1 to 1000, t represents an integer selected from 1, 2, 3 or 4 and w represents an integer selected from 1, 2 or 3.

Preferred anionic groups herein specifically include -COO ^- , -SO ₃ ^- , -OSO ₃ ^- , -PO ₃ ^2- , -OPO ₃ ^2- , -OP(O)(O ^- )O- , subformula A and -(OCH ₂ CH ₂ ) _s -O-(CH ₂ ) _t -COO ^- , -(OCH ₂ CH ₂ ) _s -O-(CH ₂ ) _t -SO ₃ ^- and -(OCH ₂ CH ₂ ) _s -O-(CH ₂ ) _t -OSO ₃ ^- , wherein each of these groups itself may be preferred. X may also represent the corresponding acid.

In this context, particularly preferred anionic groups include -SO ₃ ^- , -OSO ₃ ^- , -COO ^- , -PO ₃ ^2- , -OP(O)(O ^- )O- or OPO ₃ ^2- . In particular, the sulfonate group -SO ₃ ^- is preferred.

Preferred counterions for the anionic group X are monovalent cations, in particular H ⁺ , alkali metal cations or NR ₄ ⁺ , where R = H or optionally C1-C6-alkyl substituted with OH and all Rs may be the same or different. Particularly preferred are H ⁺ , Na ⁺ , K ⁺ , Li ⁺ and NH ₄ ⁺ and HO-(CH ₂ ) ₂ -NH ₃ ⁺ , and particularly preferred is Na ⁺ .

Preferred cationic groups X can be selected from ‑NR ¹ R ² R ^{3 +} Z ^‑ , ‑PR ¹ R ² R ^{3 +} Z ^‑ , wherein R in any desired position represents H or C _1-4 -alkyl, Z ^- represents Cl ^- , Br ^- , I ^- , CH ₃ SO ₃ ^- , CF ₃ SO ₃ ^- , CH ₃ PhSO ₃ ^- , PhSO ₃ ^- , R ¹ , R ² and R ³ each independently represent H, C _1-30 -alkyl, Ar or -CH ₂ Ar and Ar represents an unsubstituted or mono- or polysubstituted aromatic ring or condensed ring system having 6 to 18 C atoms, and in addition, one or two CH groups may be replaced by N.

Preferred cationic groups herein specifically include ‑NR ¹ R ² R ^{3 +} Z ^‑ and Each of these groups itself may be preferred.

Preferred non-ionic groups X can be selected from: linear or branched alkyl groups in which one or more non-adjacent C atoms have been replaced by O, S and/or N, ‑OH, ‑SH, ‑O‑(glycoside) _o' , ‑S‑(glycoside) _o' , ‑OCH ₂ ‑CHOH‑CH ₂ ‑OH, ‑O CH ₂ Ar(‑NCO) _p' , ‑OAr(‑NCO) _p' , amine oxides, u represents an integer in the range of 1 to 6, preferably 1 to 4, o' represents an integer in the range of 1 to 10, p' represents 1 or 2, Ar represents an unsubstituted, monosubstituted or polysubstituted aromatic ring or condensed ring system having 6 to 18 C atoms, in which one or two CH groups may be replaced by C=O, and glycoside represents an etherified carbohydrate, preferably a monoglycoside, a diglycoside, a triglycoside or an oligoglycoside.

Preferred non-ionic groups X herein include in particular linear or branched alkyl groups in which one or more non-adjacent C atoms have been replaced by O, S and/or N, -OH and -O- (glycosidic) _o' .

If X = alkyl, wherein one or more non-adjacent C atoms have been replaced by O, S and/or N, it is preferably equal to R ⁴ -(BA) _m'' -, wherein R ⁴ = H or C1-4-alkyl, in particular H or CH ₃ , A = linear or branched alkyl, preferably having 1 to 10 carbon atoms, in particular having 1 to 4 carbon atoms, B = O or S, preferably O, and m'' = an integer in the range preferably 1 to 100, particularly preferably 1 to 30.

The nonionic group X is particularly preferably a group R ⁴ -(O-CH ₂ CHR ⁵ ) _m'' -, wherein m'' = 1 to 100, preferably 1 to 30, particularly an integer in the range of 1 to 25, and R ⁴ and R ⁵ = H or C1-4-alkyl, particularly H or CH ₃ . R ⁴ -(BA) _m'' - is particularly preferably a polyethylene glycol or polypropylene glycol unit.

The non-ionic group X is particularly preferably a group -CH(OH)-CH ₂ -NH-sach, where sach = various sugars and a group -Y-(CH ₂ -CH ₂ -O) _v -R ⁴ , where Y = S, O or NH, preferably O, R ⁴ = H or alkyl, preferably H or CH ₃ , and v = 1 to 100, preferably 1 to 30, particularly also 1 to 25.

Preferred amphiphilic groups X can be selected from functional groups of acetyldiamine, N-alkylamino acids, N-alkylaminosulfonic acids, betaine, sulfobetaine or corresponding derivatives, in particular selected from (wherein M represents H or an alkaline metal ion, preferably Li ⁺ , Na ⁺ or K ⁺ ): -NH-CH ₂ -COOM; -NH-CH ₂ -CH ₂ -COOM -[(C(=O)-NH-(CH ₂ ) _(1-8) ] _{(0 or 1)} -N ⁺ R ¹ R ² -CH ₂ -COO ^- , wherein R ¹ and R ² each independently represent a C1-8-alkyl group, preferably a methyl group or an ethyl group -C(=O)-NH-(CH ₂ ) _1-3 -N ⁺ R ¹ R ² -CH ₂ -CH(OH)-CH ₂ -(O) _{(0 or 1)} -(S or P)O ₃ ^- , wherein R ¹ and R ² each independently represent a C1-8-alkyl group, preferably a methyl group or an ethyl group

Particularly preferred compounds according to the present invention are those containing, as the hydrophilic group X, one of a preferred anionic group, a preferred non-ionic group or a preferred zwitterionic group.

Particularly preferred are compounds containing the groups -SO ₃ ^- , -OSO ₃ ^- , -COO ^- , -PO ₃ ^2- , -OP(O)(O ^- )O- or OPO ₃ ^2- , polyethylene glycol or polypropylene glycol, -CH(OH)-CH ₂ -NH-sach, -Y-(CH ₂ -CH ₂ -O) _v -R ⁴ , betaine or sulfobetaine. Preferred counterions herein are H ⁺ , Na ⁺ , K ⁺ and NH ₄ ⁺ , particularly Na ⁺ . Particularly preferred are: -SO ₃ ^- , -COO ^- , -OP(O)(O ^- )O- or -OPO ₃ ^2- , polyethylene glycol or polypropylene glycol, sulfobetaine, the group -CH(OH)-CH ₂ -NH-sach and the group -Y-(CH ₂ -CH ₂ -O) _v -R ⁴ . Herein, sach = various sugars and Y = S, O or NH, preferably O, R ⁴ = H or alkyl, preferably H or CH ₃ , and v = 1 to 100, preferably 1 to 30, particularly also 1 to 25. Compounds in which X = -SO ₃ ^- may also be particularly advantageous.

The hydrocarbon unit of the spacer of the compound of formula (I) can be an aliphatic or aromatic unit, optionally with heteroatoms. The spacer is preferably a saturated branched or unbranched hydrocarbon unit, preferably a saturated branched or unbranched alkylene unit, wherein one or more non-adjacent C atoms can be replaced by O or N, preferably O, or connected to O. Preferably, for example, C1-C6-alkylene, in particular, C1-C4-alkylene.

In a variation of the present invention, the preferred heteroatom-containing hydrocarbon units used are polyethylene glycol or polypropylene glycol units.

Preferred are compounds of formulae (II) to (V), wherein R ¹ and R ² are independently a fluorinated linear or branched alkyl group optionally containing heteroatoms, o = 0 to 100, preferably 1 to 30 and 5 to 30, in particular 3, 5, 6, 10, 12, 15, 18, 20 or 24, and X ¹ and X ² are independently a hydrophilic group, in particular an anionic, cationic, non-ionic or amphoteric group, preferably X is also equal to H, preferably one of the groups of formulae (IIa), (IIb), (IIc) and (V):

In preferred variations of the compounds of formulae (II) to (V), ^X1 and ^X2 are independently anionic or nonionic groups, in particular preferred groups for X, and ^R1 and ^R2 are independently _CF3- ( _CF2 ) _1-2 -O-groups. ^R1 and ^R2 and ^X1 and ^X2 are preferably the same.

Particularly preferred are compounds containing the groups -SO ₃ ^- , -OSO ₃ ^- , -COO ^- , -PO ₃ ^2- , -OP(O)(O ^- )O- or -OPO ₃ ^2- , polyethylene glycol or polypropylene glycol, -CH(OH)-CH ₂ -NH-sach, -Y-(CH ₂ -CH ₂ -O) _v -R ⁴ , betaine or sulfobetaine as X ¹ and/or X ^2. Preferred counterions herein are H ⁺ , Na ⁺ , K ⁺ and NH ₄ ⁺ , particularly Na ⁺ . Particularly preferred are: -SO ₃ ^- , -COO ^- , -OP(O)(O ^- )O- or -OPO ₃ ^2- , polyethylene glycol or polypropylene glycol, sulfobetaine, the group -CH(OH)-CH ₂ -NH-sach and the group -Y-(CH ₂ -CH ₂ -O) _v -R ⁴ . Herein, sach = various sugars and Y = S, O or NH, preferably O, R ⁴ = H or alkyl, preferably H or CH ₃ , and v = 1 to 100, preferably 1 to 30, in particular also 1 to 25. Compounds in which X = -SO ₃ ^- may also be particularly advantageous. Compounds of formula (IIa) and (III) to (V), especially those having preferred variables, are particularly preferred.

In another variant of the invention, the fluorinated compound is preferably based on an ester of maleic acid and acicular acid. These compounds are represented by formulae (VI) and (VII), wherein L ¹ , L ² and L ³ are independently a saturated or unsaturated branched or unbranched hydrocarbon unit optionally containing heteroatoms, wherein the -OO- bond is absent, in particular a straight or branched C1-C6-alkyl group, particularly preferably a C1-C4-alkyl group, X is a hydrophilic group and R ¹ , R ² and R ³ are independently a fluorinated straight or branched alkyl group optionally containing heteroatoms:

In preferred variations of the compounds of formula (VI) and (VII), L ¹ , L ² and L ³ are independently linear or branched C ₁ -C ₆ -alkyl, particularly preferably C ₁ -C ₄ -alkyl, X is an anionic or non-ionic group and R ¹ , R ² and R ³ are independently CF ₃ -(CF ₂ ) _1-2 -O-group. Preferably, L ¹ , L ² and L ³ are identical and R ¹ , R ² and R ³ are identical.

Compounds of the formulae (I) to (VII) in which one or more of the variables have preferred meanings are particularly advantageous. Compounds of the formulae (I) to (VII) in which all of the variables have preferred meanings, in particular particularly preferred meanings, are particularly advantageous.

Particularly preferred are compounds of the formulae (VIII) to (XVIII), in which the variables have the meanings given for formulae (I) to (VII), in particular the preferred meanings, and PEG represents polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether or polypropylene glycol alkyl ether and ^Ra , ^Rb and ^Rc = H or _C1-4 -alkyl, in particular H or _CH3 . The alkyl ether is preferably a _C1 - _C4 -alkyl ether, in particular a _C1 - _C2 -alkyl ether, especially a methyl ether:

Particularly preferred are compounds of the formulae (VIII) to (XVIII) in which the fluorinated groups ^R1 and ^R2 or ^R1 , ^R2 and ^R3 are independently selected from the group consisting of _CF3- ( _CF2 ) _0-3- , _CF3- ( _CF2 ) _0-3 -O-, CF3-(CF2) _0-3 -O-(CF2) _1-3- , CF3-( _CF2 ) _0-3 -O-( _CF2 ) _1-3 -O- _, CF3-( _CF2 ) _{0-3 -} O-(CF2) _{1-3 -} O-, CF3-( _CF2 ) _0-3 -O-( _CF2 ) _1-3 -O-CF2-, _CF3- ( _CF2 ) _0-3- O-( _CF2 -O) _1-8- and _CF3- ( _CF2 ) _0-3 -O-( _CF2 -O) _1-8 - _CF2- .

The fluorinated groups ^R1 and ^R2 or ^R1 , ^R2 and ^R3 are preferably independently _CF3- ( _CF2 ) _1-2 -O groups, in particular _CF3 - _CF2 - _CF2 -O groups. In particular, ^R1 and ^R2 are the same and ^R1 , ^R2 and ^R3 are the same. o is preferably equal to 1 to 30, in particular 3, 5, 6, 10, 12, 15, 18, 20 or 24, in particular 3, 10 or 18. The compounds of formulae (VIII) to (XIV) and (XV), (XVI), (XVII) and (XVIII), in particular those having preferred variables are particularly preferred.

Specifically, the following compounds of formula (XIX) to (XXIV) (wherein o = 0, 10 or 18 and R = methyl or ethyl) are particularly preferred:

Compounds of formula (XIXa) and (XX) to (XXIX), especially those having preferred variables, are particularly preferred.

The fluorinated surfactants of formula (I) to (XXIX) have lower stability than conventional fluorinated surfactants and can therefore be more easily degraded by physical/chemical processes, and are preferably less persistent. In addition, they are distinguished by a very effective reduction in the surface tension energy of aqueous solutions. Likewise, they have a low CMC and foaming behavior.

In particular, the fluorosurfactants of formula (I) to (XXIX) are readily biodegradable and are beneficial with regard to their ecotoxicological profile.

Furthermore, the introduction of thioether bridges enables widening of the molecular structure. As is known, thioethers can be converted into thiooxides using methods known to those skilled in the art from the literature, which allow additional "trimming" of the polarity of the molecule relative to its hydrophilicity.

Furthermore, the thiol precipitates used for the preparation of fluorosurfactants show a significantly higher reactivity compared to the corresponding alcohols due to their increased nucleophilicity. This advantage can be exploited by the esterification of monofunctional or polyfunctional alcohols which additionally contain one or more thiol groups, with the selective formation of thioethers at the thiol groups, without the need to protect the free OH groups of the monofunctional or polyfunctional alcohols. These free OH groups can then react in a further step. This allows a great simplification of the synthesis of fluorosurfactants with fewer reaction steps and increased yields compared to the synthesis of the corresponding compounds prepared from alcohols without thiol groups.

The compounds of formula (I) to (XXIX) can be prepared by methods known to those skilled in the art.

The compounds of formula (I) to (XXIX) are preferably used as surfactants, preferably as surfactants, hydrophobic agents, interface promoters, viscosity reducers, foam stabilizers or emulsifiers.

Preferably, the concentration of the compound of formula (I) to (XXIX) in the polymerizable LC material is 0.01 to 5 wt.-%, more preferably 0.01 to 1 wt.-%, based on the entire formulation.

In a preferred embodiment, the polymerizable LC material comprises one or more reactive mesogens selected from the formula RMT, P is a polymerizable group, Sp is a spacer group or a single bond, r2 and r3 are independently 0, 1, 2, 3 or 4, ^R11 is P-Sp-, preferably an alkyl group having 1 to 15 C atoms, an alkoxy group, a sulfanyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkoxycarbonyloxy group, which is more preferably fluorinated as the case may be. A and B, in the case of multiple occurrences, independently of one another represent an aromatic or alicyclic radical, which optionally contains one or more heteroatoms selected from N, O and S and is optionally mono- or polysubstituted by L, preferably 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, thiophene-2,5-diyl, naphthalene-2,6-diyl, 1,2,3,4-tetrahydro-naphthalene-2,6-diyl, dihydroindene-2,5-diyl, bicyclooctylene or 1,4-cyclohexylene, wherein one or two non-adjacent _CH2 radicals are optionally replaced by O and/or S, wherein these radicals are unsubstituted or substituted by 1, 2, 3 or 4 radicals L, L is P-Sp-, F, Cl, Br, I, -CN, -NO ₂ , -NCO, -NCS, -OCN, -SCN, -C(=O)NR ^x R ^y , -C(=O)OR ^x , -C(=O)R ^x , -NR ^x R ^y , -OH, -SF ₅ , or a linear or branched alkyl group, alkoxy group, alkylcarbonyl group, alkoxycarbonyl group, alkylcarbonyloxy group or alkoxycarbonyloxy group having 1 to 12 C atoms, wherein one or more H atoms are optionally replaced by F or Cl, preferably F, -CN or a linear or branched alkyl group, alkoxy group, alkylcarbonyl group, alkoxycarbonyl group, alkylcarbonyloxy group or alkoxycarbonyloxy group having 1 to 6 C atoms, R ^x and R ^y are independently H or an alkyl group having 1 to 12 C atoms, Z ¹¹ and Z ¹² In the case of multiple occurrences, it represents -O-, -S-, -CO-, -COO-, -OCO-, -S-CO-, -CO-S-, -O-COO-, -CO-NR ^{00 -, -NR 00} -CO-, -NR ⁰⁰ -CO-NR ⁰⁰⁰ , -NR ⁰⁰ -CO-O-, -O-CO-NR ⁰⁰ -, -OCH ₂ -, -CH 2 O-, -SCH 2 _{-, -CH 2 S-, -CF 2} ^O- _, -OCF ₂ -, -CF ₂ S-, -SCF ₂ -, -CH ₂ CH ₂ - _, -(CH ₂ ) _n1 , -CF ₂ CH _{2 -} , -CH ₂ CF ₂ -, -CF ₂ CF ₂ -, -CH=N-, -N=CH-, -N=N-, -CH=CR ⁰⁰ -, -CY ¹ =CY ² -, -C≡C-, -CH=CH-COO-, -OCO-CH=CH- or a single bond, preferably -COO-, -OCO-, -C≡C- or a single bond, R ⁰⁰ and R ⁰⁰⁰ independently represent an alkyl group, an alkoxy group, a sulfanyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkoxycarbonyloxy group having 1 or more, preferably 1 to 15 C atoms, or represent Y ⁰ or P-(CH ₂ ) _y -(O) _z -, Y ⁰ is F, Cl, CN, NO ₂ , OCH ₃ , OCN, SCN, SF ₅ or a low-fluorinated or polyfluorinated alkyl or alkoxy group having 1 to 4 C atoms, y is 0 or an integer from 1 to 12, z is 0 or 1, wherein if the adjacent y is 0, then z is 0, Y ¹ and Y ² independently represent H, F, Cl or CN, n is 1, 2, 3 or 4, preferably 1 or 2, most preferably 1, m is 0, 1, 2, 3 or 4, preferably 0 or 1, most preferably 0, n1 is an integer from 1 to 10, preferably 1, 2, 3 or 4.

Preferred compounds of formula RMT are those selected from formula RMTa or RMTb, wherein P is a polymerizable group, Sp is a spacer group or a single bond, r1, r2, r3 are independently 0, 1, 2, 3 or 4, preferably 0, 1 or 2 and L, R ¹¹ , Z ¹² , Ring B and m have one of the meanings given above under formula RMT.

Preferred RMTa compounds are those selected from the group consisting of RMTa1 to RMTa6 wherein L, P, Sp and R ¹¹ are as defined in formula RMT, and r1 to r3 represent 1, 2, 3 or 4, preferably 1 or 2.

Preferred compounds of formula RMTa1 to RMTa6 are selected from the following formulas: wherein P ¹¹ represents a group selected from the group consisting of heptadiene, vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, cyclohexane and epoxy, and very preferably represents an acrylate, methacrylate or cyclohexane group, especially an acrylate or methacrylate group, in particular an acrylate group, and x is an integer from 0 to 12, preferably from 1 to 8, more preferably 3, 4, 5 or 6, in particular x represents 3 or 6, in particular 6 and R ¹¹ represents an alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy group, preferably having 1 to 15 C atoms, which is more preferably optionally fluorinated and L has one of the meanings given above under the formula RMT for each occurrence.

Particularly preferred are compounds of formula RMTa2, which are preferably selected from the following formulas: wherein R ¹¹ has one of the meanings given above under formula RMT, preferably R ¹¹ represents alkyl or alkoxy, more preferably methoxy, ethoxy, propoxy, methyl, ethyl, propyl, butyl, pentyl, isopropyl or isobutyl, in particular methoxy.

Preferred compounds of formula RMTb are those selected from formula RMTb0 to RMTb6 wherein L, P, Sp and R ¹¹ are as defined in formula RMT, and r1 to r3 represent 1, 2, 3 or 4, preferably 1 or 2.

Preferred compounds of formula RMTb0 to RMTb6 are selected from the following formulas: wherein P ¹¹ represents a group selected from the group consisting of heptadiene, vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, cyclohexane and epoxy, and very preferably represents an acrylate, methacrylate or cyclohexane group, especially an acrylate or methacrylate group, in particular an acrylate group, and x is an integer from 0 to 12, preferably from 1 to 8, more preferably 3, 4, 5 or 6, in particular x represents 3 or 6, in particular 6 and R ¹¹ represents an alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy group, preferably having 1 to 15 C atoms, which is more preferably optionally fluorinated and L has one of the meanings given above under formula RMT for each occurrence.

Particularly preferred are compounds of formula RMTb2, which are preferably selected from the following formulas: wherein R ¹¹ has one of the meanings given above under formula RMT, preferably R ¹¹ represents alkyl or alkoxy.

Also preferred is a compound of formula RMTb2-A1, which is selected from the following compounds: wherein R ¹¹ has one of the meanings given above under formula RMT, preferably R ¹¹ represents alkyl or alkoxy, more preferably methoxy, ethoxy, propoxy, methyl, ethyl, propyl, butyl, pentyl, isopropyl or isobutyl, in particular methoxy.

Preferably, the polymerizable LC material comprises one or more, preferably two or more, compounds selected from formula RMTa2-A3 to RMTa2-A6 or RMTb2-A3, in particular the polymerizable LC material comprises one or more compounds of formula RMTb2-A3, specifically the polymerizable LC material comprises a combination of compounds of formula RMTa2-A4 and/or RMTa2-A5 and RMTb2-A3.

By utilizing one or more compounds of the formula RMT in a polymerizable LC material, the birefringence of the polymer film can be beneficially increased. The corresponding reflection bandwidth is related to the birefringence by the following formula: Bandwidth = Δn * pitch, It can be seen that by increasing the birefringence of the cholesteric polymer film, a wider bandwidth of emission can be achieved. By utilizing compounds of the formula RMT in a polymerizable LC material, the reflection bandwidth of the corresponding polymer film can be significantly widened, while also not negatively affecting film properties such as wet film crystallization or resistance to wetting.

The concentration of the compound of formula RMT and its subformulae in the polymerisable LC material is preferably from 10% to 99%, more preferably from 20 to 95%, especially from 25 to 90%.

Compounds of formula RMT are available from Merck KGaA, Darmstadt or can be synthesized according to the procedures given, for example, in US 6,514,578 or US 15/575,415.

In a preferred embodiment, the polymerizable LC material comprises one or more di- or poly-reactive mesogens, preferably selected from the group consisting of DRMs wherein ^P1 and ^P2 are independently polymerizable groups, ^Sp1 and ^Sp2 are independently spacer groups or single bonds, and MG is a rod-shaped liquid crystal group, which is preferably selected from the formula MG wherein ^A1 and ^A2, when they appear multiple times, independently represent an aromatic or alicyclic group, which optionally contains one or more heteroatoms selected from N, O and S, and optionally is mono- or poly-substituted by L, and L is P-Sp-, F, Cl, Br, I, -CN, _-NO2 , -NCO, -NCS, -OCN, -SCN, -C(=O)NRxRy ^{, -C} (=O) ^ORx , -C(=O) ^Rx , ^-NRxRy , ^-OH , _-SF5 , an optionally substituted silyl, an aryl or heteroaryl group having 1 to 12, preferably 1 to 6 C atoms, and a straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy group having 1 to 12, preferably 1 to 6 C atoms, wherein one or more H atoms are optionally replaced by F or Cl, ^Rx and ^Ry are each independently H or an alkyl group having 1 to 12 C atoms, ^Z1 , in the case of multiple occurrences, is each independently -O-, -S-, -CO-, -COO-, -OCO-, -S-CO-, -CO-S-, -O-COO-, -CO- ^NRx- , -NRx-CO-, -NRx-CO ^{- NRy} , -NRx ^- CO- ^O- , -O-CO- ^NRx- , _-OCH2- , -CH ₂ O-, -SCH ₂ -, -CH 2 S-, -CF ₂ O-, -OCF ₂ -, -CF ₂ S-, -SCF ₂ - _, -(CH ₂ ) _n1 , -CF ₂ CH _{2 -} , -CH 2 CF ₂ -, -CF ₂ CF ₂ -, -CH=N-, -N=CH-, -N=N-, -CH=CR ^x -, -CY ¹ =CY ² -, -C≡C-, -CH=CH-COO-, -OCO-CH=CH- or a single bond, preferably -COO-, -OCO- or a single bond, Y ¹ and Y ² independently represent H, F, Cl or CN, n is 1, 2, 3 or 4, preferably 1 or 2, most preferably 2, n1 is an integer from 1 to 10, preferably 1, 2, 3 or 4, However, there is a proviso that compounds of formula RMT are not included in the equation of compounds of formula DRM.

Preferred groups ^A1 and ^A2 include, but are not limited to, furan, pyrrole, thiophene, oxazole, thiazole, thiadiazole, imidazole, phenylene, cyclohexylene, bicyclooctylene, cyclohexenylene, pyridine, pyrimidine, pyrazine, azulene, dihydroindene, fluorene, naphthalene, tetrahydronaphthalene, anthracene, phenanthrene and dithienothiophene, all of which are unsubstituted or substituted with 1, 2, 3 or 4 groups L as defined above.

Particularly preferred radicals ^A1 and ^A2 are selected from 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, thiophene-2,5-diyl, naphthalene-2,6-diyl, 1,2,3,4-tetrahydro-naphthalene-2,6-diyl, dihydroindene-2,5-diyl, bicyclooctylene or 1,4-cyclohexylene, wherein one or two non-adjacent _CH2 radicals are optionally replaced by O and/or S, wherein these radicals are unsubstituted or substituted by 1, 2, 3 or 4 radicals L as defined above.

The best RM for DRM is DRMMa wherein ^P0 , in the case of multiple occurrences, is independently a polymerizable group, preferably an acrylate group, a methacrylate group, an oxadiene group, an epoxide group, an epoxide group, a vinyl group, a heptadiene group, a vinyloxy group, an ether group or a styrene group, ^Z0 is -COO-, -OCO-, -CH2CH2-, -CF2O- _{, -OCF2- ,} -C≡C-, -CH=CH-, -OCO-CH=CH-, -CH=CH-COO- or a single bond, _L , in each occurrence, has, identically or differently, one of the meanings given for L in formula DRM and, in the case of multiple occurrences, is preferably independently selected from F, Cl, CN or an optionally halogenated alkyl group having 1 to 5 C atoms, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkoxycarbonyloxy group, r is 0, 1, 2, 3 or 4, x and y are independently 0 or the same or different integers from 1 to 12, z is 0 or 1, wherein if the adjacent x or y is 0, then z is 0.

The best RM for DRM is selected from the following: wherein P ⁰ , L, r, x, y and z are as defined in formula DRMa.

Particularly preferred are compounds of the formulae DRMa1, DRMa2 and DRMa3, in particular those of the formula DRMa1.

The concentration of di- or poly-reactive RM, preferably DRM and its sub-formulae, in the RM mixture is preferably 1% to 90%, very preferably 10 to 80%.

In another preferred embodiment, the RM mixture comprises one or more single reactive RMs. These additional single reactive RMs are preferably selected from the MRM of the formula: wherein P ¹ , Sp ¹ and MG have the meanings given in formula DRM, R represents P-Sp-, F, Cl, Br, I, -CN, -NO ₂ , -NCO, -NCS, -OCN, -SCN, -C(=O)NR ^x R ^y , -C(=O)X, -C(=O)OR ^x , -C(=O)R ^y , -NR ^x R ^y , -OH, -SF ₅ , optionally substituted silyl, linear or branched alkyl having 1 to 12, preferably 1 to 6 C atoms, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, wherein one or more H atoms are optionally replaced by F or Cl, X is a halogen, preferably F or Cl, and R ^x and R ^y are independently H or alkyl having 1 to 12 C atoms, with the proviso that compounds of the formula RMT are not included in compounds of the formula MRM.

Preferably, the MRM compound is selected from the following formula. wherein ^P0 , L, r, x, y and z are as defined in formula DRMa, ^R0 is an alkyl group, an alkoxy group, a sulfanyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkoxycarbonyloxy group having 1 or more, preferably 1 to 15 C atoms, or represents ^Y0 or P-( _CH2 ) _y- (O) _z- , ^X0 is -O-, -S-, -CO-, -COO-, -OCO- _, -O-COO-, -CO- ^NR01- , ^-NR01 _- CO-, ^-NR01 _- CO- ^NR01- , -OCH2-, _{-CH2O- , -SCH2- ,} -CH2S- _, -CF2O- _{, -OCF2- ,} -CF2S-, -SCF2- _, -CF2CH2- _, -CH2CF2-, _-CF2CF2 -, -CH=N-, -N=CH-, -N=N-, -CH=CR ⁰¹ -, -CF=CF-, -C≡C-, -CH=CH-COO-, -OCO-CH=CH- or a single bond, Y ⁰ is F, Cl, CN, NO ₂ , OCH ₃ , OCN, SCN, SF ₅ or a monofluorinated, subfluorinated or polyfluorinated alkyl or alkoxy group having 1 to 4 C atoms, Z ⁰ is -COO-, -OCO-, -CH ₂ CH ₂ -, -CF ₂ O-, -OCF ₂ -, -CH=CH-, -OCO-CH=CH-, -CH=CH-COO- or a single bond, A ⁰ , in the case of multiple occurrences, is independently 1,4-phenylene which is unsubstituted or substituted by 1, 2, 3 or 4 groups L, or trans-1,4-cyclohexylene, R ^O1, O2 are independently H, R ⁰ or Y ⁰ , u and v are independently 0, 1 or 2, w is 0 or 1, and the benzene ring and the naphthyl ring may be further substituted by one or more identical or different groups L.

Particularly preferred are compounds of the formulae MRM1, MRM2, MRM3, MRM4, MRM5, MRM6, MRM7, in particular those of the formulae MRM1, MRM4, MRM6 and MRM7.

The concentration of all monoreactive RMs (including those of formula RMT) in the polymerisable LC material is preferably 1 to 80%, very preferably 5 to 50%.

In the formula DRM, MRM and preferred subformulae thereof, L is preferably selected from F, Cl, CN, _NO2 or a linear or branched alkyl group, alkoxy group, alkylcarbonyl group, alkoxycarbonyl group, alkylcarbonyloxy group or alkoxycarbonyloxy group having 1 to 12 C atoms, wherein the alkyl groups are optionally perfluorinated, or P-Sp-.

Most preferably _, L is selected from F, Cl, CN, _NO2 , _CH3 , _C2H5 , C( _CH3 ) ₃ , CH( _{CH3 ) 2} , _CH2CH ( _{CH3 ) C2H5 , OCH3} , _OC2H5 , _COCH3 , _{COC2H5 ,} COOCH3, _COOC2H5 , _CF3 , _OCF3 , _{OCHF2 , OC2F5} or P-Sp-, in particular F, Cl, CN, _CH3 , _C2H5 , C( _CH3 ) ₃ , CH( _CH3 ) ₂ , OCH3, _{COCH3 or OCF3} , most preferably F, _Cl , _CH3 , C( _CH3 ) ₃ , _OCH3 or _COCH3 , or P _- Sp-.

Preferably, the polymerizable LC material according to the present invention comprises one or more chiral compounds. These chiral compounds may be non-mesogen compounds or mesogen compounds. Furthermore, these chiral compounds (regardless of whether they are mesogen or non-mesogen) may be non-reactive, monoreactive or polyreactive.

Preferably, the chiral compounds used individually or in combination have an absolute value of their helical twisting power (I HTPtotal I ) in the range of 20 µm ^-1 or more, preferably 40 µm ^-1 or more, more preferably 60 µm ^-1 or more, most preferably 80 µm ^-1 or more to 260 _µm ^-1 , in particular, disclosed in WO 98/00428.

Preferably, the non-polymerizable chiral compound is selected from the group consisting of compounds of formula CI to C-III, The latter includes each (S,S) enantiomer, wherein E and F are each independently 1,4-phenylene or trans-1,4-cyclohexylene, v is 0 or 1, ^Z0 is -COO-, _-OCO- , _-CH2CH2- or a single bond, and R is alkyl, alkoxy or alkanoyl having 1 to 12 C atoms.

A particularly preferred polymerisable LC material comprising one or more chiral compounds does not necessarily have to exhibit a liquid crystal phase.

Compounds of formula C-II and their synthesis are described in WO 98/00428. Particularly preferred is compound CD-1, as shown in Table D below. Compounds of formula C-III and their synthesis are described in GB 2 328 207.

In addition, commonly used chiral compounds are, for example, commercially available R/S-5011, CD-1, R/S-811 and CB-15 (from Merck KGaA, Darmstadt, Germany).

The above-mentioned chiral compounds R/S-5011 and CD-1 and (other) compounds of formula C-I, C-II and C-III exhibit very high helical twisting power (HTP) and are therefore particularly useful for the purposes of the present invention.

The polymerizable LC material preferably comprises 1 to 5, particularly 1 to 3, most preferably 1 or 2 chiral compounds, preferably selected from the above formula C-II, particularly CD-1, and/or formula C-III and/or R-5011 or S-5011, most preferably, the chiral compound is R-5011, S-5011 or CD-1.

Preferably, the polymerisable LC material comprises one or more non-reactive chiral compounds and/or one or more reactive chiral compounds, which reactive chiral compounds are preferably selected from monoreactive and/or polyreactive chiral compounds.

Suitable mesogen-reactive chiral compounds preferably comprise one or more ring elements linked together by direct bonds or via linkers, wherein two of these ring elements may be linked to each other directly or via linkers which may be the same or different from the mentioned linkers, as the case may be. The ring elements are preferably selected from the group of four-, five-, six- or seven-membered, preferably five- or six-membered rings.

The preferred monoreactive chiral compound is selected from the compounds of formula CRMa to CRMc, wherein P0 ^* represents a polymerizable group P Sp* represents a spacer Sp ^A0 and ^B0 , when they appear multiple times, are independently 1,4-phenylene, which is unsubstituted or substituted with 1, 2, 3 or 4 groups L as defined above, or trans-1,4-cyclohexylene, ^X1 and ^X2 are independently -O-, -COO-, -OCO-, -O-CO-O- or a single bond, Z0 ^* and ^Z0 , when they appear multiple times, are independently -COO-, _-OCO- , _-O -CO-O- _, -OCH2- _{, -CH2O- , -CF2O- ,} -OCF2-, -CH2CH2-, -( _CH2 ) _4- , -CF2CH2- _{, -CH2CF2- , -CF2CF2} -, -C≡C-, -CH=CH-, -CH=CH-COO-, -OCO-CH=CH- or a single bond, t is independently 0, 1, 2 or 3, a is 0, 1 or 2, b is 0 or an integer from 1 to 12, z is 0 or 1, and the naphthyl rings in the formula CRMa may be further substituted by one or more identical or different groups L, wherein L is independently F, Cl, CN, a halogenated alkyl group having 1 to 5 C atoms, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkoxycarbonyloxy group.

The compound of formula CRMa is preferably selected from the group of compounds of formula CRMa-1. wherein X ² , A ⁰ , B ⁰ , Z ^0* , P ^0* and b have the meanings given in formula CRMa or one of the preferred meanings given above and below, and (OCO) represents -O-CO- or a single bond.

Particularly preferred CRM compounds are selected from the group consisting of the following subformulae: wherein R is ^-X2- ( _CH2 ) _x - ^P0* as defined in formula CRM-a, and the benzene rings and naphthyl rings are unsubstituted or substituted with 1, 2, 3 or 4 groups L as defined above and below.

The compound of formula CRMb is preferably selected from the group consisting of compounds of formula CRMb-1 to CRMb-3, wherein X ² , A ⁰ , B ⁰ , Z ^0* , P ^0* and b have the meanings given in formula CRMa or one of the preferred meanings given above and below.

The preferred compound of formula CRMb-1 is preferably selected from the group consisting of compounds of formula CRMb-1a and CRMb-1b. wherein X ² , Z ^0* , P ^0* and b have the meanings given in formula CRM a or one of the preferred meanings given above and below. Preferably, in the compounds of formula CRM b-1a and CRM b-1b, Z ⁰ represents OCOO, COO, OCO or a single bond. Preferably, in the compounds of formula CRM b-1a and CRM b-1b, X ² represents OCOO, OCO, COO or a single bond. Preferably, the compound of formula CRM b-1b is selected from the following compounds, wherein P ^0* and b have the meanings given in formula CRMa or one of the preferred meanings given above and below.

The compound CRMb-1bI (in which P ^0* represents an acrylate group at each occurrence and b represents 4 at each occurrence) is particularly preferred and is available from BASF, Germany under the trade name LC756.

The compound of formula CRMc is preferably selected from the group of compounds of formula CRMc-1, wherein X ² , A ⁰ , B ⁰ , Z ^0* , P ^0* and b have the meanings given in formula CRMa or one of the preferred meanings given above and below.

The preferred compound of formula CRMc-1 is preferably selected from the group consisting of compounds of formula CRMc-1a and CRMc-1b. wherein X ² , Z ^0* , P ^0* and b have the meanings given in formula CRM a or one of the preferred meanings given above and below. Preferably, in the compounds of formula CRMc-1a and CRMc-1b, Z ⁰ represents OCOO, COO, OCO or a single bond. Preferably, in the compounds of formula CRMc-1a and CRMc-1b, X ² represents O, OCOO, OCO, COO or a single bond. Preferably, the compound of formula CRMc-1a is selected from the following compounds, wherein P ^0* and b have the meanings given in formula CRMa or one of the preferred meanings given above and below.

The compound CRMc-1aI in which P ^0* represents an acrylate group at each occurrence and b represents 3 or 6 at each occurrence, and X ² represents O or a single bond at each occurrence is particularly preferred.

The amount of the chiral compound in the liquid crystal medium is preferably 1 to 20%, more preferably 1 to 15%, even more preferably 1 to 10%, and most preferably 3 to 7% by weight of the total mixture.

In a preferred embodiment, the proportion of the polymerizable mesogen compound in the polymerizable liquid crystal material according to the present invention as a whole is in the range of 30 to 99 wt %, more preferably in the range of 40 to 97 wt % and even more preferably in the range of 50 to 95 wt %.

Preferably, the proportion of the monoreactive, direactive or polyreactive liquid crystal compound preferably selected from the formula DRM, MRM compounds given above and below in the polymerizable liquid crystal material according to the present invention as a whole is preferably in the range of 30 to 99.9 wt %, more preferably in the range of 40 to 99.9 wt % and even more preferably in the range of 50 to 99.9 wt %.

In a preferred embodiment, the proportion of the di-reactive or multi-reactive polymerizable liquid crystal primordial compound in the polymerizable liquid crystal material according to the present invention as a whole is preferably in the range of 1 to 70 wt %, more preferably in the range of 2 to 60 wt % and even more preferably in the range of 3 to 50 wt %.

In another preferred embodiment, if present, the proportion of the single-reactive polymerizable liquid crystal primordial compound of formula MRM excluding the compound of formula RMT in the polymerizable liquid crystal material according to the present invention as a whole is preferably in the range of 1 to 50 weight %, more preferably in the range of 2 to 45 weight % and even more preferably in the range of 5 to 40 weight %.

In another preferred embodiment, if present, the proportion of the multi-reactive polymerizable liquid crystal prima compound in the polymerizable liquid crystal material according to the present invention as a whole is preferably in the range of 1 to 30 wt %, more preferably in the range of 2 to 20 wt % and even more preferably in the range of 3 to 10 wt %.

In another preferred embodiment, the polymerizable LC material does not contain a polymerizable mesogen compound having more than two polymerizable groups.

In another preferred embodiment, the polymerizable LC material comprises one or more monoreactive mesogen compounds preferably selected from formula MRM-1, MRM-4, MRM-6 and/or MRM-7, and one or more direactive mesogen compounds preferably selected from formula DRMa-1.

If chiral compounds are used, the polymerizable LC material should furthermore have properties such that different reflection wavelengths, in particular in the VIS light region, can be achieved by simple and targeted variation. Preferably, the cholesteric pitch of the polymerizable LC material is chosen such that its reflection wavelength is in the range of the infrared range of the electromagnetic spectrum, i.e. in the range of 300 nm to 900 nm, more preferably in the range of 350 to 850 nm. In particular, the reflection wavelength of the liquid crystal medium is in the range of 400 nm to 800 nm.

The polymerizable LC materials according to the invention are prepared in a manner known per se, for example by mixing one or more of the above-mentioned polymerizable compounds with one or more block copolymers as described above and below, and one or more chiral compounds (all as defined above) and optionally with further liquid-crystalline compounds and/or additives and/or solvents.

In another preferred embodiment, the polymerizable LC material optionally comprises one or more additional additives selected from the group consisting of: additional polymerization initiators, antioxidants, surfactants, stabilizers, catalysts, sensitizers, inhibitors, chain transfer agents, co-reactive monomers, reactive viscosifiers, surface-active compounds, lubricants, wetting agents, dispersants, hydrophobic agents, tackifiers, flow improvers, degassing or defoaming agents, deaerators, diluents, reactive diluents, auxiliary agents, colorants, dyes, pigments and nanoparticles.

In another preferred embodiment, the polymerizable LC material optionally comprises one or more additives selected from polymerizable non-mesogenic compounds (reactive viscosity reducing agents). The amount of these additives in the polymerizable LC material is preferably 0 to 30%, and most preferably 0 to 25%.

The reactive detackifier used is not only a substance called a reactive detackifier in the practical sense, but also an auxiliary compound mentioned above, which contains one or more complementary reactive units or polymerizable groups P, for example, hydroxyl groups, thiol groups or amine groups, through which the polymerizable units of the liquid crystal compound can react.

Typical photopolymerizable substances include, for example, monofunctional, difunctional, and polyfunctional compounds containing at least one olefinic double bond. Examples are vinyl esters of carboxylic acids (e.g., lauric acid, myristic acid, palmitic acid, and stearic acid), and vinyl esters of dicarboxylic acids (e.g., succinic acid, adipic acid), allyl and vinyl ethers and methacrylates and acrylates of monofunctional alcohols (e.g., lauryl alcohol, myristic alcohol, palmitic acid, and stearyl alcohol), and diallyl and divinyl ethers of difunctional alcohols (e.g., ethylene glycol and 1,4-butanediol).

Also suitable are, for example, methacrylates and acrylates of polyfunctional alcohols, in particular those which, apart from hydroxyl groups, contain no further functional groups or contain at most ether groups. Examples of such alcohols are difunctional alcohols such as ethylene glycol, propylene glycol and their more highly condensed representatives (e.g. diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, etc.), butanediol, pentanediol, hexanediol, neopentyl glycol, alkoxylated phenolic compounds (e.g. ethoxylated and propoxylated bisphenols), cyclohexanedimethanol, trifunctional and polyfunctional alcohols (e.g. glycerol, trihydroxymethylpropane, butanetriol, trihydroxymethylethane, pentaerythritol, ditrihydroxymethylpropane, dipentaerythritol, sorbitol, mannitol) and the corresponding alkoxylated (in particular ethoxylated and propoxylated) alcohols.

Other suitable reactive detackifiers are polyester (meth)acrylates, which are (meth)acrylate esters of polyester polyols.

Examples of suitable polyester polyols are those which can be prepared by esterification of polycarboxylic acids, preferably dicarboxylic acids, with polyols, preferably diols. The starting materials for these hydroxyl-containing polyesters are known to those skilled in the art. Dicarboxylic acids which may be employed are succinic acid, glutamic acid, adipic acid, sebacic acid, phthalic acid and isomers and hydrogenation products thereof, and esterified and transesterified derivatives of these acids (e.g., anhydrides and dialkyl esters). Suitable polyols are the alcohols mentioned above, preferably ethylene glycol, 1,2- and 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl alcohol, cyclohexanedimethanol and polyglycols of the ethylene glycol and propylene glycol type.

In addition, suitable reactive viscosity reducers are 1,4-divinylbenzene, triallyl cyanurate, and acrylate of tricyclic decanol of the following formula: , also known under the name dihydrodicyclopentadiene acrylate, and the allyl esters of acrylic acid, methacrylic acid and cyanoacrylate.

Among the reactive viscosity reducing agents mentioned by way of example, those containing a photopolymerizable group are particularly mentioned in view of the use of the preferred composition mentioned above.

This group includes, for example, diols and polyols, such as ethylene glycol, propylene glycol and their more highly condensed representatives (e.g., diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, etc.), butanediol, pentanediol, hexanediol, neopentyl glycol, cyclohexanedimethanol, glycerol, trihydroxymethylpropane, butanetriol, trihydroxymethylethane, pentaerythritol, ditrihydroxymethylpropane, dipentaerythritol, sorbitol, mannitol and the corresponding alkoxylated (in particular ethoxylated and propoxylated) alcohols.

Furthermore, this group also includes, for example, alkoxylated phenolic compounds, such as, for example, ethoxylated and propoxylated bisphenols.

In addition, such reactive detackifiers may be, for example, epoxide (meth)acrylates or urethane (meth)acrylates.

Epoxide (meth)acrylates are those obtainable, for example, by reaction of alkylene oxides or polyglycidyl ethers or diglycidyl ethers (such as bisphenol A diglycidyl ether) with (meth)acrylic acid in a manner known to those skilled in the art.

In particular, urethane (meth)acrylates are the products of the reaction of hydroxyalkyl (meth)acrylates with polyisocyanates or diisocyanates, as is known to those skilled in the art.

Included in the compounds listed above as "mixed forms" are these epoxide (meth)acrylates and urethane (meth)acrylates.

If reactive detackifiers are used, their amount and nature must be matched to the respective conditions in such a way that on the one hand the desired effect is achieved, for example the desired color of the composition according to the invention, but on the other hand the phase behavior of the liquid crystal composition is not excessively influenced. Low-crosslinked (high-crosslinked) liquid crystal compositions can, for example, be prepared using corresponding reactive detackifiers having a relatively low (high) number of reactive units per molecule.

The group of diluents includes, for example: C ₁ -C ₄ -alcohols, for example, methanol, ethanol, n-propanol, isopropanol, butanol, isobutanol, sec-butanol and in particular, C ₅ -C ₁₂ -alcohols, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, n-undecanol and n-dodecanol, and isomers thereof, diols, for example 1,2-ethanediol, 1,2- and 1,3-propylene glycol, 1,2-, 2,3- and 1,4-butanediol, diethylene glycol, triethylene glycol and dipropylene glycol and tripropylene glycol, ethers, for example methyl tert-butyl ether, 1,2-ethanediol monomethyl ether and dimethyl ether, 1,2-ethanediol monoethyl ether and diethyl ether, 3-methoxypropanol, 3-isopropoxypropanol, tetrahydrofuran and dioxane, ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone and diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), C ₁ -C ₅ -alkyl esters, for example, methyl acetate, ethyl acetate, propyl acetate, butyl acetate and amyl acetate, aliphatic and aromatic hydrocarbons, for example, pentane, hexane, heptane, octane, isooctane, petroleum ether, toluene, xylene, ethylbenzene, tetrahydronaphthalene, decahydronaphthalene, dimethylnaphthalene, white spirits, Shellsol® and Solvesso® mineral oils, for example, gasoline, kerosene, diesel and heating oil, and natural oils, for example, olive oil, soybean oil, rapeseed oil, linseed oil and sunflower oil.

Of course, mixtures of these diluents may also be used in the compositions according to the invention.

These diluents can also be mixed with water as long as there is at least partial miscibility. Examples of suitable diluents here are C ₁ -C ₄ -alcohols, for example methanol, ethanol, n-propanol, isopropanol, butanol, isobutanol and sec-butanol, diols, for example 1,2-ethanediol, 1,2- and 1,3-propylene glycol, 1,2-, 2,3- and 1,4-butanediol, diethylene glycol and triethylene glycol and dipropylene glycol and tripropylene glycol, ethers, for example tetrahydrofuran and dioxane, ketones, for example acetone, methyl ethyl ketone and diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), and C ₁ -C ₄ -alkyl esters, for example methyl acetate, ethyl acetate, propyl acetate and butyl acetate.

The diluent is optionally used in a proportion of about 0 to 10.0 wt %, preferably about 0 to 5.0 wt %, based on the total weight of the polymerizable LC material.

Defoamers and degassing agents (c1)), lubricants and flow aids (c2)), heat curing or radiation curing aids (c3)), substrate wetting aids (c4)), wetting and dispersing aids (c5)), hydrophobic agents (c6)), adhesion promoters (c7)) and agents that promote scratch resistance (c8)) cannot be strictly limited in their functions.

For example, lubricants and flow aids usually also act as defoamers and/or deaerators and/or agents for improving scratch resistance. Radiation curing aids can also act as lubricants and flow aids and/or deaerators and/or substrate wetting aids. In individual cases, some of these aids can also fulfill the function of adhesion promoters (c8).

Corresponding to the above, therefore, a certain additive can be classified into the following groups c1) to c8).

The defoamers in group c1) include silicone-free and silicone-containing polymers. Silicon-containing polymers are, for example, unmodified or modified polydialkylsiloxanes or branched chain copolymers, comb-shaped or block copolymers comprising polydialkylsiloxanes and polyether units, the latter being obtainable from ethylene oxide or propylene oxide.

The degassing agents in group c1) include, for example, organic polymers such as polyethers and polyacrylates, dialkylpolysiloxanes (particularly dimethylpolysiloxane), organically modified polysiloxanes (for example, aralkyl-modified polysiloxanes) and fluoropolysiloxanes.

The action of defoamers is essentially based on preventing foam formation or destroying already formed foam. Defoamers essentially work by promoting the condensation of finely divided gases or bubbles to obtain larger bubbles in the medium to be degassed (e.g., the composition according to the invention), and thus accelerate the escape of the gas (air). Therefore, defoamers can also frequently be used as deaerators and vice versa, these additives being included together under group c1).

Suitable auxiliaries are available, for example, from Tego, such as TEGO® Foamex 800, TEGO® Foamex 805, TEGO® Foamex 810, TEGO® Foamex 815, TEGO® Foamex 825, TEGO® Foamex 835, TEGO® Foamex 840, TEGO® Foamex 842, TEGO® Foamex 1435, TEGO® Foamex 1488, TEGO® Foamex 1495, TEGO® Foamex 3062, TEGO® Foamex 7447, TEGO® Foamex 8020, Tego® Foamex N, TEGO® Foamex K 3. TEGO® Defoamer 2-18, TEGO® Defoamer 2-18, TEGO® Defoamer 2-57, TEGO® Defoamer 2-80, TEGO® Defoamer 2-82, TEGO® Defoamer 2-89, TEGO® Defoamer 2-92, TEGO® Defoamer 14, TEGO® Defoamer 28, TEGO® Defoamer 81, TEGO® Defoamer D 90, TEGO® Defoamer 93, TEGO® Defoamer 200, TEGO® Defoamer 201, TEGO® Defoamer 202, TEGO® Defoamer 793, TEGO® Defoamer 1488, TEGO® Defoamer 3062, TEGOPREN® 5803, TEGOPREN® 5852, TEGOPREN® 5863, TEGOPREN® 7008, TEGO® Defoamer 1-60, TEGO® Defoamer 1-62, TEGO® Defoamer 1-85, TEGO® Defoamer 2-67, TEGO® Defoamer WM 20, TEGO® Defoamer 50, TEGO® Defoamer 105, TEGO® Defoamer 730, TEGO® Defoamer MR 1015, TEGO® Defoamer MR 1016, TEGO® Defoamer 1435, TEGO® Defoamer N, TEGO® Defoamer KS 6, TEGO® Defoamer KS 10, TEGO® Defoamer KS 53, TEGO® Defoamer KS 95, TEGO® Defoamer KS 100, TEGO® Defoamer KE 600, TEGO® Defoamer KS 911, TEGO® Defoamer MR 1000, TEGO® Defoamer KS 1100, Tego® Airex 900, Tego® Airex 910, Tego® Airex 931, Tego® Airex 935, Tego® Airex 936, Tego® Airex 960, Tego® Airex 970, Tego® Airex 980 and Tego® Airex 985 and purchased from BYK, such as BYK®-011, BYK®-019, BYK®-020, BYK®-021, BYK®-022, BYK®-023, BYK®-024, BYK®-025, BYK®-027, BYK®-031, BYK®-032, BYK®-033, BYK®-034, BYK®-0 BYK®-35, BYK®-036, BYK®-037, BYK®-045, BYK®-051, BYK®-052, BYK®-053, BYK®-055, BYK®-057, BYK®-065, BYK®-066, BYK®-070, BYK®-080, BYK®-088, BYK®-141 and BYK®-A 530.

The auxiliary agents in group c1) are optionally used in a proportion of about 0 to 3.0 wt. %, preferably about 0 to 2.0 wt. %, based on the total weight of the polymerizable LC material.

In group c2), lubricants and flow aids generally include not only silicone-free polymers but also silicone-containing polymers, for example, polyacrylates or, as modifiers, low molecular weight polydialkylsiloxanes. The modification consists in that some of the alkyl groups have been replaced by a wide variety of organic groups. These organic groups are, for example, polyethers, polyesters or even long-chain (fluorinated) alkyl groups, the former being most frequently used.

The polyether groups in the correspondingly modified polysiloxanes are usually built up from ethylene oxide and/or propylene oxide units. In general, the higher the proportion of these ethylene oxide units in the modified polysiloxane, the higher the hydrophilicity of the resulting product.

Such additives are available, for example, from Tego as TEGO® Glide 100, TEGO® Glide ZG 400, TEGO® Glide 406, TEGO® Glide 410, TEGO® Glide 411, TEGO® Glide 415, TEGO® Glide 420, TEGO® Glide 435, TEGO® Glide 440, TEGO® Glide 450, TEGO® Glide A 115, TEGO® Glide B 1484 (which can also be used as a defoamer and deaerator), TEGO® Flow ATF, TEGO® Flow 300, TEGO® Flow 460, TEGO® Flow 425 and TEGO® Flow ZFS 460. Suitable radiation-curable lubricants and flow aids which can also be used to improve scratch resistance are the products TEGO® Rad 2100, TEGO® Rad 2200, TEGO® Rad 2500, TEGO® Rad 2600 and TEGO® Rad 2700, which are likewise available from TEGO.

Such additives are also available, for example, from BYK, such as BYK®-300, BYK®-306, BYK®-307, BYK®-310, BYK®-320, BYK®-333, BYK®-341, Byk® 354, Byk® 361, Byk® 361N, BYK® 388.

Such additives are also available, for example, from 3M as FC4430®.

Such adjuvants are also available, for example, from Cytonix, such as FluorN® 561 or FluorN® 562.

Such auxiliaries are also available, for example, from Merck KGaA as Tivida® FL 2300 and Tivida® FL 2500.

The auxiliary agents in group c2) are optionally employed in a proportion of about 0 to 3.0 wt. %, preferably about 0 to 2.0 wt. %, based on the total weight of the polymerizable LC material.

In group c3), radiation curing aids include, in particular, polysiloxanes with terminal double bonds, which are, for example, components of acrylate groups. These aids can be crosslinked actinically or, for example, by electron radiation. These aids generally combine a number of properties. In the non-crosslinked state, they can act as defoamers, degassing agents, lubricants and flow aids and/or substrate wetting aids, while in the crosslinked state, they in particular increase, for example, the scratch resistance of the coating or film that can be produced using the composition according to the invention. The improvement of, for example, the gloss properties of the coatings or films is essentially considered to be the result of the action of additives such as defoamers, deaerators and/or lubricants and flow aids (in the non-crosslinked state).

Examples of suitable radiation curing aids are the products TEGO® Rad 2100, TEGO® Rad 2200, TEGO® Rad 2500, TEGO® Rad 2600 and TEGO® Rad 2700 from TEGO and the product BYK®-371 from BYK.

The heat-curing auxiliaries in group c3) contain, for example, primary OH groups which are capable of reacting with, for example, isocyanate groups of the binder.

Examples of heat curing aids that can be used are the products BYK®-370, BYK®-373 and BYK®-375 from BYK.

The auxiliary agents in group c3) are optionally used in a proportion of about 0 to 5.0 wt. %, preferably about 0 to 3.0 wt. %, based on the total weight of the polymerizable LC material.

In particular, the substrate wetting additives in group c4) serve to increase the wettability of substrates to be printed or coated, for example, with printing inks or coating compositions, for example, the compositions according to the invention. The substantially concomitant improvement in the lubrication and flow behavior of these printing inks or coating compositions has an effect on the appearance of the finished (for example, crosslinked) print or coating.

A wide variety of such additives is available, for example, from Tego, such as TEGO® Wet KL 245, TEGO® Wet 250, TEGO® Wet 260 and TEGO® Wet ZFS 453 and from BYK, such as BYK®-306, BYK®-307, BYK®-310, BYK®-333, BYK®-344, BYK®-345, BYK®-346 and Byk®-348.

The auxiliary agents in group c4) are optionally used in a proportion of about 0 to 3.0 wt %, preferably about 0 to 1.5 wt %, based on the total weight of the liquid crystal composition.

In particular, the wetting and dispersing aids in group c5) are used to prevent flooding and floating and settling of the pigments and are therefore, if necessary, particularly suitable for use in pigmented compositions.

These additives stabilize the pigment dispersion essentially by electrostatic repulsion and/or steric hindrance of these additives with the pigment particles, wherein in the latter case the interaction of the additives with the surrounding medium (e.g. binder) plays an important role.

Since the use of such wetting and dispersing additives is common practice, for example, in the field of printing ink and paint technology, the selection of suitable additives of this type, if used, generally does not present any difficulties to the person skilled in the art.

Such wetting and dispersing aids are available from Tego, for example, TEGO® Dispers 610, TEGO® Dispers 610 S, TEGO® Dispers 630, TEGO® Dispers 700, TEGO® Dispers 705, TEGO® Dispers 710, TEGO® Dispers 720 W, TEGO® Dispers 725 W, TEGO® Dispers 730 W, TEGO® Dispers 735 W and TEGO® Dispers 740 W and purchased from BYK, such as Disperbyk®, Disperbyk®-107, Disperbyk®-108, Disperbyk®-110, Disperbyk®-111, Disperbyk®-115, Disperbyk®-130, Disperbyk®-160, Disperbyk®-161, Disperbyk®-162, Disperbyk®-163, Disperbyk®-164, Disperbyk®- -154, BYK®-155, BYK®-P 104 S, BYK®-P 105, Lactimon®, Lactimon®-WS and Bykumen®.

The amount of the auxiliary in group c5) is based on the average molecular weight of the auxiliary. In any case, therefore, preliminary experiments are advisable, but this can be easily carried out by those skilled in the art.

The hydrophobic agents in group c6) can be used to provide water-repellent properties to, for example, prints or coatings produced using the compositions according to the invention. This prevents or at least greatly inhibits swelling due to absorption and thus, for example, changes in the optical properties of these prints or coatings. In addition, when using the composition, for example, as a printing ink for offset printing, water absorption can thereby be prevented or at least greatly reduced.

Such hydrophobes are available from, for example, Tego, such as Tego® Phobe WF, Tego® Phobe 1000, Tego® Phobe 1000 S, Tego® Phobe 1010, Tego® Phobe 1030, Tego® Phobe 1010, Tego® Phobe 1010, Tego® Phobe 1030, Tego® Phobe 1040, Tego® Phobe 1050, Tego® Phobe 1200, Tego® Phobe 1300, Tego® Phobe 1310, and Tego® Phobe 1400.

The auxiliary agents in group c6) are optionally used in a proportion of about 0 to 5.0 wt. %, preferably about 0 to 3.0 wt. %, based on the total weight of the polymerizable LC material.

The further adhesion promoter from group c7) is used to improve the adhesion of the two interfaces in contact. It can be seen from this that only a part of the effective adhesion promoter is located at one interface or the other interface or at both interfaces. For example, if it is desired to apply a liquid or pasty printing ink, a coating composition or a paint to a solid substrate, this generally means that the adhesion promoter must be added directly to the latter or the substrate must be pretreated with the adhesion promoter (also called primer), that is, the substrate is provided with modified chemical and/or physical surface properties.

If the substrate has been previously primed, this means that the contact interfaces are those of the primer on the one hand and of the printing ink or coating composition or paint on the other hand. In this case, not only the adhesion properties between substrate and primer, but also between substrate and printing ink or coating composition or paint play a role in the adhesion of the overall multi-layer structure of the substrate.

Adhesion promoters in a broader sense may also be mentioned as substrate wetting agents already listed under group c4), but these generally do not have the same adhesion promoting capabilities.

The diversity of adhesion promoter systems is not surprising in view of the widely varying physical and chemical properties of substrates and, for example, the printing inks, coating compositions and paints upon which they are desired to be printed or coated.

Silane-based adhesion promoters are, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N-aminoethyl-3-aminopropyltrimethoxysilane, N-aminoethyl-3-aminopropylmethyldimethoxysilane, N-methyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-butylpropyltrimethoxysilane, 3-chloropropyltrimethoxysilane and vinyltrimethoxysilane. These and other silanes are available, for example, from Hüls under the trade name DYNASILAN®.

Generally, the corresponding technical information from the manufacturers of these additives should be used, or those familiar with this technology can obtain this information in a simple way through corresponding preliminary experiments.

If, however, these additives are added as auxiliaries from group c7) to the polymerizable LC material according to the invention, their proportions correspond, as the case may be, to about 0 to 5.0% by weight, based on the total weight of the polymerizable LC material. These concentration data serve only as a guide, since the amount and identity of the additive is determined in each individual case by the properties of the substrate and the printing/coating composition. Corresponding technical information is generally available for this case from the manufacturers of these additives or can be determined in a simple manner by corresponding preliminary experiments by those skilled in the art.

The additives in group c8) for improving the scratch resistance include, for example, the above-mentioned products TEGO® Rad 2100, TEGO® Rad 2200, TEGO® Rad 2500, TEGO® Rad 2600 and TEGO® Rad 2700, which are available from Tego.

For these auxiliary agents, the quantitative data given for group c3) also apply, that is, these additives are used in a proportion of about 0 to 5.0% by weight, preferably about 0 to 3.0% by weight, based on the total weight of the liquid crystal composition.

Examples of further light, heat and/or oxidation stabilizers which may be mentioned are the following: Alkylated monophenols such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenol with straight or branched side chains (e.g., 2,6-dinonyl-4-methylphenol), 2,4-dimethyl-6-(1′-methylundec-1′-yl)phenol, 2,4-dimethyl-6-(1′-methylheptadeca-1′-yl)phenol, 2,4-dimethyl-6-(1′-methyltrideca-1′-yl)phenol and mixtures of these compounds, alkylthiomethylphenols (e.g., 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol and 2,6-dimethoxy-4-nonylphenol), Hydroquinones and alkylated hydroquinones, such as 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecylphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate and bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate, Tocopherols, such as α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures of these compounds, and tocopherol derivatives, such as tocopherol acetate, succinate, nicotinate and polyoxyethylene succinate ("tocofersolate"), Hydroxylated diphenyl sulfides, such as 2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol), 4,4′-thiobis(6-tert-butyl-3-methylphenol), 4,4′-thiobis(6-tert-butyl-2-methylphenol), 4,4′-thiobis(3,6-di-sec-amylphenol) and 4,4′-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide, Alkylene bisphenols, such as 2,2′-methylenebis(6-tert-butyl-4-methylphenol), 2,2′-methylenebis(6-tert-butyl-4-ethylphenol), 2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol], 2,2′-methylenebis(4-methyl-6-cyclohexylphenol), 2,2′-methylenebis(6-nonyl-4-methylphenol), 2,2′-methylenebis(4,6-di-tert-butylphenol), 2,2-ethylenebis( 4,6-di-tert-butylphenol), 2,2′-ethylenebis(6-tert-butyl-4-isobutylphenol), 2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol], 2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4′-methylenebis(2,6-di-tert-butylphenol), 4,4′-methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenol phenyl) butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecyl-butylbutane, ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene, bis[ 2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecyl-butylbutane and 1,1,5,5-tetrakis(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane, O-, N- and S-benzyl compounds, such as 3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether, 4-hydroxy-3,5-dimethylbenzyl octadecyl acetate, 4-hydroxy-3,5-di-tert-butylbenzyl acetate tridecyl, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide and 3,5-di-tert-butyl-4-hydroxybenzyl acetate isooctyl, Aromatic hydroxybenzyl compounds, such as 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethyl-benzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethyl-benzene and 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol, Triazine compounds, such as 2,4-bis(octylphenyl)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylphenyl-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylphenyl-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate and 1,3,5-tris(2-hydroxyethyl) isocyanurate, Benzyl phosphates, such as 2,5-di-tert-butyl-4-hydroxybenzyl dimethyl phosphate, 3,5-di-tert-butyl-4-hydroxybenzyl diethyl phosphate, 3,5-di-tert-butyl-4-hydroxybenzyl dioctadecyl phosphate and 5-tert-butyl-4-hydroxy-3-methylbenzyl dioctadecyl phosphate. Aminophenols, such as 4-hydroxylaurylaniline, 4-hydroxystearylaniline and N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate octyl ester, For example, propionates and acetates of monohydric or polyhydric alcohols such as methanol, ethanol, n-octanol, iso-octanol, octadecyl alcohol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propylene glycol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trihydroxymethylpropane and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]-octane, Propionamides based on amine derivatives, such as N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine and N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, Ascorbic acid (vitamin C) and ascorbic acid derivatives, such as ascorbic acid palmitate, laurate and stearate, and ascorbic acid sulfates and phosphates, Antioxidants based on amine compounds, such as N,N'-diisopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis(1-methylheptyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl- p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4-(p-toluidinesulfonyl)diphenylamine, N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octyl-substituted diphenylamines (e.g., p,p'-di-tert-octyldiphenylamine), 4-n-butylaminophenol, 4-butylaminophenol, 4-nonylaminophenol, 4-dodecylaminophenol, 4-octadecylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminophenol Methylphenol, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(anilino)propane, (o-tolyl)biguanidine, bis[4-(1',3'-dimethylbutyl)phenyl]amine, tert-octyl-substituted N-phenyl-1-naphthylamine, mixture of mono- and di-alkylated tert-butyl/tert-octyl diphenylamine, mixture of mono- and di-alkylated nonyl diphenylamine, mixture of mono- and di-alkylated dodecyl diphenylamine, mixture of mono- and di-alkylated isopropyl/isohexyl diphenylamine mixture of mono- and di-alkylated tert-butyldiphenylamine, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mixture of mono- and di-alkylated tert-butyl/tert-octyl phenothiazine, mixture of mono- and di-alkylated tert-octyl phenothiazine, N-allyl phenothiazine, N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene, N,N-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine, bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one and 2,2,6,6-tetramethylpiperidin-4-ol, Phosphine, phosphinate and phosphonate, such as triphenylphosphine, triphenylphosphinate, diphenylalkylphosphinate, phenyldialkylphosphinate, tris(nonylphenyl)phosphinate, trilaurylphosphinate, trioctadecylphosphinate, distearylpentaerythritol diphosphinate, tris(2,4-di-tert-butylphenyl)phosphinate, diisodecylpentaerythritol diphosphinate, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, diisodecylpentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, Bis(2,4,6-tris(tert-butylphenyl))pentaerythritol diphosphonite, tristearyl sorbitol triphosphonite, tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenyl diphosphonate, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphinocyclooctane, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,g]-1,3,2-dioxaphosphinocyclooctane, bis(2,4-di-tert-butyl-6-methylphenyl)methylphosphonite and bis(2,4-di-tert-butyl-6-methylphenyl)ethylphosphite, 2-(2′-Hydroxyphenyl)benzotriazole, such as 2-(2′-hydroxy-5′-methylphenyl)benzotriazole, 2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl) -5-chlorobenzotriazole, 2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole, 2-(3′,5′-di-tert-pentyl-2′-hydroxyphenyl)benzotriazole, 2-(3,5′-bis-(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3′-tert-butyl-5′-[ 2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]- A mixture of 2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole and 2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol]; a complete esterification product of 2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazole and polyethylene glycol 300; Sulfur-containing peroxide scavengers and sulfur-containing antioxidants, such as esters of 3,3′-thiodipropionic acid (e.g., lauryl, stearyl, myristyl and tridecyl), zinc salts of butylbenzimidazole and 2-butylbenzimidazole, dibutylzinc dithiocarbamate, dioctadecyl disulfide and pentaerythritol tetra(β-dodecylbutyl)propionate, 2-Hydroxybenzophenones, such as 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxy and 2′-hydroxy-4,4′-dimethoxy derivatives, Unsubstituted and substituted benzoic acid esters, such as 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate and 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, Acrylates, such as ethyl α-cyano-β,β-diphenylacrylate, isooctyl α-cyano-β,β-diphenylacrylate, methyl α-methoxycarbonylcinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, butyl α-cyano-β-methyl-p-methoxycinnamate and methyl α-methoxycarbonyl-p-methoxycinnamate, Sterically hindered amines, such as bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis(2,2,6,6-tetramethylpiperidin-4-yl) succinate, bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis(1,2,2,6,6-pentamethylpiperidin-4-yl) malonate-n-butyl-3,5-di-tert-butyl-4- Benzyl hydroxylate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid condensate, N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine condensate, tris(2,2,6,6-tetramethylpiperidin-4-yl)nitrilotriacetate, tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)-1,2,3,4- Butane tetracarboxylate, 1,1'-(1,2-ethylidene)bis(3,3,5,5-tetramethylpiperidinone), 4-benzoyl-2,2,6,6-tetramethylpiperidin, 4-stearyloxy-2,2,6,6-tetramethylpiperidin, bis(1,2,2,6,6-pentamethylpiperidin-4-yl)malonate-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate, 3-octyl-7,7,9,9-tetramethyl-1,3,8 -triazaspiro[4.5]decane-2,4-dione, bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate, condensation product of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-morpholinyl-2,6-dichloro-1,3,5-triazine, 2-chloro-4,6-bis(4-n-butylamino-2, 2,6,6-tetramethylpiperidin-4-yl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane condensation products, 2-chloro-4,6-di(4-n-butylamino-1,2,2,6,6-pentamethylpiperidin-4-yl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane condensation products, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]dec-2 ,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidine-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethylpiperidin-4-yl)pyrrolidine-2,5-dione, a mixture of 4-hexadecyl- and 4-stearyloxy-2,2,6,6-tetramethylpiperidin, N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-cyclohexylamino-2, 6-dichloro-1,3,5-triazine condensation products, 1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine, 4-butylamino-2,2,6,6-tetramethylpiperidine condensation products, N-(2,2,6,6-tetramethylpiperidin-4-yl)-n-dodecylsuccinimide, N-(1,2,2,6,6-pentamethylpiperidin-4-yl)-n-dodecylsuccinimide, 2-undecyl-7,7,9,9- Tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane, 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane and epichlorohydrin condensation product, 4-amino-2,2,6,6-tetramethylpiperidine and tetrahydroxymethylacetylene diurea and poly(methoxypropyl-3-oxy)-[4(2,2,6,6-tetramethyl)piperidinyl]-siloxane condensation product, Oxalamides, such as 4,4'-dioctyloxyoxalyldiphenylamine, 2,2'-diethoxyoxalyldiphenylamine, 2,2'-dioctyloxy-5,5'-di-tert-butyloxalyldiphenylamine, 2,2'-di-dodecyl-5,5'-di-tert-butyloxalyldiphenylamine, 2-ethoxy-2'-ethyloxalyldiphenylamine, N,N'-bis(3-dimethylaminopropyl)oxalyldiphenylamine, 2-ethoxy-5-tert-butyl-2'-ethyloxalyldiphenylamine and mixtures thereof with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxalyldiphenylamine, mixtures of oxalyldiphenylamine disubstituted by o-methoxy and p-methoxy groups, and mixtures of oxalyldiphenylamine disubstituted by o-ethoxy and p-ethoxy groups, and 2-(2-Hydroxyphenyl)-1,3,5-triazine, such as 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylphenyl) -1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butoxypropoxy)phenyl]-4, 6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[4-(dodecyl/tridecyl-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine and 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine.

In another preferred embodiment, the polymerizable LC material comprises one or more specific antioxidant additives, preferably selected from the Irganox® series, such as the commercially available antioxidants Irganox® 1076 and Irganox® 1010 from Ciba, Switzerland.

In another preferred embodiment, the polymerizable LC material comprises one or more, more preferably two or more photoinitiators, for example, selected from the commercially available Irgacure® or Darocure® (Ciba AG) series, in particular Irgacure 127, Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 817, Irgacure 907, Irgacure 1300, Irgacure, Irgacure 2022, Irgacure 2100, Irgacure 2959 or Darcure TPO. In addition, the preferred photoinitiator is selected from oxime ester photoinitiators, such as commercially available OXE02 (Ciba AG), NCI 930, N1919T (Adeka), SPI-03 or SPI-04 (Samyang).

The concentration of the polymerization initiator(s) as a whole in the polymerizable LC material is preferably 0.5 to 10%, very preferably 0.8 to 8%, more preferably 1 to 7%.

In a preferred embodiment, the polymerizable LC material is dissolved in a suitable solvent, which is preferably selected from organic solvents.

The solvents are preferably selected from ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone or cyclohexanone; acetates such as methyl acetate, ethyl acetate or butyl acetate or methyl acetylacetate; alcohols such as methanol, ethanol or isopropanol; aromatic solvents such as toluene or xylene; alicyclic hydrocarbons such as cyclopentane or cyclohexane; halogenated hydrocarbons such as dichloromethane or trichloromethane; glycols or their esters such as PGMEA (propylene glycol monomethyl ether acetate), γ-butyrolactone. Binary, ternary or higher mixtures of the above solvents may also be used. In particular, methyl isobutyl ketone is a preferred solvent for multi-layer applications.

If the polymerisable LC material contains one or more solvents, the total concentration of all solids (including RM) in the solvent(s) is preferably 10 to 60%, more preferably 20 to 50%, in particular 30 to 45%.

Preferably, in addition to one or more block copolymers, the polymerizable LC material comprises, a) one or more polymerizable liquid crystal compounds of formula I and corresponding sub-formulas, b) one or more multi-reactive or di-reactive polymerizable liquid crystal compounds, preferably selected from formula DRM and corresponding sub-formula compounds, c) one or more chiral liquid crystal compounds, preferably selected from formulas CRMa to CRMc, more preferably CRMb and sub-formula compounds thereof, d) one or more monoreactive liquid crystals, preferably selected from formula MRM and corresponding sub-formula compounds, e) one or more photoinitiators, f) one or more antioxidant additives, g) one or more adhesion promoters, h) one or more surfactants, if applicable, i) one or more monoreactive, direactive or polyreactive polymerizable non-mesogenic compounds, if applicable, j) one or more dyes, if applicable, which exhibit an absorption maximum at the wavelength used to initiate photopolymerization, k) one or more chain transfer agents, if applicable, l) one or more additional stabilizers, if applicable, m) one or more lubricants and flow aids, if applicable, and n) one or more diluents, if applicable, o) a non-polymerizable nematic component, if applicable, p) one or more organic solvents, if applicable.

More preferably, the polymerizable LC material comprises, a) one or more compounds of formula I or its corresponding preferred subformula, b) one or more, preferably two or more polymerizable liquid crystal compounds of formula RMT and corresponding subformulas, preferably selected from compounds of subformulas RMTa2-A4 and/or RMTa2-A5 and/or RMTb-A3, c) one or more, preferably two or more di-reactive polymerizable liquid crystal compounds, preferably selected from compounds of formula DRMa-1, d) one or more, preferably two or more mono-reactive polymerizable liquid crystal compounds, preferably selected from compounds of formula MRM-1 and/or MRM-4 and/or MRM-6 and/or MRM-7, e) one or more chiral mesogen compounds of formula CRMb, in particular formula CRMb-1bI, f) one or more antioxidant additives, preferably selected from unsubstituted and substituted benzoic acid esters, in particular Irganox® 1076, and if present, preferably in an amount of 0.01 to 2 wt%, most preferably 0.05 to 1 wt%, g) one or more photoinitiators, preferably carbazole oxime ester photoinitiators, h) one or more organic solvents, preferably methyl isobutyl ketone, as appropriate.

The invention further relates to a method for preparing a polymer film by: - providing a layer of a polymerizable LC material as described above and below on a substrate, - polymerizing the polymerizable components of the polymerizable LC material by photopolymerization, and - removing the polymerized LC material from the substrate as appropriate and/or providing it on another substrate as appropriate.

The polymerisable LC material may be coated or printed on a substrate, for example by spin coating, printing or other known techniques, and the solvent evaporated before polymerisation. In most cases it is appropriate to heat the mixture to promote evaporation of the solvent.

The polymerizable LC material can be applied to the substrate by known coating techniques, such as spin coating, rod coating or doctor blade coating. It can also be applied to the substrate by known printing techniques known to the expert, such as, for example, screen printing, offset printing, web printing, letter printing, gravure printing, rotogravure printing, flexographic printing, intaglio printing, pad printing, heat seal printing, inkjet printing or printing with the aid of a stamp or printing plate.

Suitable substrate materials and substrates are known to the expert and described in the literature, such as, for example, known substrates used in the optical film industry, such as glass or plastics. Particularly suitable and preferred substrates for polymerization are polyesters, such as polyethylene terephthalate (PET) or polyethylene naphthoate (PEN), polyvinyl alcohol (PVA), polycarbonate (PC), triacetyl cellulose (TAC) or cycloolefin polymers (COP), or generally known color filter materials, in particular triacetyl cellulose (TAC), cycloolefin polymers (COP) or generally known color filter materials.

The polymerisable LC material preferably exhibits a uniform alignment throughout the entire layer. Preferably, the polymerisable LC material exhibits a uniform planar, uniform homeotropic, uniform cholesteric or patterned alignment.

The Friedel-Creagh-Kmetz rule can be used to predict whether the mixture will adopt a planar or homeotropic alignment by comparing the surface energies of the RM layer (γ _RM ) and the substrate (γ _s ): if γ _RM > γ _s , the reactive mesogen compound will exhibit homeotropic alignment, if γ _RM < γ _s , the reactive mesogen compound will exhibit a uniform alignment.

Without being bound by theory, when the surface energy of the substrate is relatively low, the intermolecular forces between the reactive mesogens are stronger than the forces across the RM-substrate interface and therefore, the reactive mesogens are aligned perpendicular to the substrate (vertical alignment) to maximize the intermolecular forces.

Vertical alignment can also be achieved by using amphiphilic materials; they can be added directly to the polymerizable LC material, or the substrate can be treated with these materials in the form of a vertical alignment layer. The polar head of the amphiphilic material is chemically bonded to the substrate, and the carbon tail points vertically to the substrate. Intermolecular interactions between the amphiphilic material and the RM promote vertical alignment. Commonly used amphiphilic surfactants are described above.

Another method for promoting vertical alignment is to apply a corona discharge treatment to the plastic substrate to obtain alcohol or ketone functional groups on the substrate surface. These polar groups can interact with the polar groups present in the RM or surfactant to promote vertical alignment.

When the surface tension of the substrate is greater than the surface tension of the RM, the forces across the interface dominate. If the reactive mesogen is aligned parallel to the substrate, the interface energy is minimized so that the long axis of the RM can interact with the substrate. One method that can promote planar alignment is by coating the substrate with a polyimide layer and then rubbing the alignment layer with a velvet cloth.

Other suitable planar alignment layers are known in the art, such as, for example, rubbed polyimide layers or alignment layers prepared by photoalignment, as described in US 5,602,661, US 5,389,698 or US 6,717,644.

In general, reviews of alignment techniques are provided, for example, by I. Sage in "Thermotropic Liquid Crystals", edited by G. W. Gray, John Wiley & Sons, 1987, pages 75-77; and by T. Uchida and H. Seki in "Liquid Crystals - Applications and Uses Vol. 3", edited by B. Bahadur, World Scientific Publishing, Singapore 1992, pages 1 to 63. A further review of alignment materials and techniques is provided by J. Cognard, Mol. Cryst. Liq. Cryst. 78, Supplement 1 (1981), pages 1 to 77.

For producing the polymer film according to the invention, the polymerisable compounds in the polymerisable LC material are polymerised or crosslinked (if one compound contains two or more polymerisable groups) by in situ photopolymerisation.

Photopolymerization can be carried out in one step. It is also possible to photopolymerize or crosslink the unreacted compounds in the first step in a second step ("final curing").

In a preferred preparation method, a polymerisable LC material is coated onto a substrate and subsequently photopolymerised, for example by exposure to actinic radiation, as described, for example, in WO 01/20394, GB 2,315,072 or WO 98/04651.

Photopolymerization of the LC material is preferably achieved by exposing it to actinic radiation. Actinic radiation means irradiation with light, such as UV light, IR light or visible light, irradiation with X-rays or gamma rays, or irradiation with high-energy particles, such as ions or electrons. Preferably, the polymerization is carried out by irradiation with light, in particular with UV light. As source of actinic radiation, for example a single UV lamp or a group of UV lamps can be used. When high lamp powers are used, the curing time can be reduced. Another possible source of light radiation is lasers, such as for example UV lasers, IR lasers or visible lasers. Another possible source of light radiation is LED lamps.

The curing time depends inter alia on the reactivity of the polymerizable LC material, the thickness of the coating layer, the type of polymerization initiator and the power of the UV lamp. The curing time is preferably ≤ 5 minutes, very preferably ≤ 3 minutes, and most preferably ≤ 1 minute. For mass production, a short curing time of ≤ 30 seconds is preferred.

The suitable UV radiation power is preferably in the range of 5 to 200 mWcm ^-2 , more preferably in the range of 50 to 175 mWcm ^-2 and most preferably in the range of 100 to 150 mWcm ^-2 .

In combination with the applied UV radiation and as a function of time, the suitable UV dose is preferably in the range of 25 to 7200 mJcm ^-2 , more preferably in the range of 100 to 7200 mJcm ^-2 and most preferably in the range of 200 to 7200 mJcm ^-2 .

Photopolymerization is preferably carried out in an inert gas atmosphere, preferably in a heated nitrogen atmosphere, but polymerization in air is also possible.

The photopolymerization is preferably carried out at a temperature of 1 to 70°C, more preferably 5 to 50°C, even more preferably 15 to 30°C.

The polymerized LC film according to the present invention has good adhesion to plastic substrates, in particular to TAC, COP and color filters. Therefore, it can be used as an adhesive or base coating for subsequent LC layers that originally have poor adhesion to the substrate.

For optical applications of the polymer film, it preferably has a thickness of 0.5 to 10 μm, very preferably 0.5 to 5 μm, in particular 0.5 to 3 μm.

The optical retardation (δ(λ)) of a polymer film as a function of the wavelength (λ) of the incident beam is given by the following equation (7): δ(λ) = (2πΔn∙d)/λ                                                     (7) where (Δn) is the birefringence of the film, (d) is the thickness of the film and λ is the wavelength of the incident beam.

According to Snellius's law, the birefringence as a function of the direction of the incident beam is defined as Δn = sinΘ / sinΨ                                                   (8) where sinΘ is the angle of incidence or tilt of the optical axis of the film and sinΨ is the corresponding reflection angle.

Based on these laws, the birefringence and therefore the optical retardation depends on the thickness of the film and the tilt angle of the optical axis of the film (compare Berek's compensator). Therefore, the skilled expert realizes that different optical retardation or different birefringence can be induced by adjusting the orientation of the liquid crystal molecules in the polymer film.

The birefringence (Δn) of the polymer film according to the present invention is preferably in the range of 0.01 to 0.4, more preferably in the range of 0.01 to 0.3 and even more preferably in the range of 0.01 to 0.25.

The optical retardation as a function of the thickness of the polymer film according to the invention is less than 200 nm, preferably less than 180 nm and even more preferably less than 150 nm.

The polymer films of the invention can also be used as alignment films or substrates for other liquid crystal or RM materials. The inventors have found that polymer films obtainable from polymerizable LC materials as described above and below can be used in particular for multilayer applications due to their improved anti-wetting properties. In this way, stacks of optical films or preferably polymerized LC films can be prepared.

In summary, the polymerized LC films and polymerizable LC materials according to the invention can be used in optical elements, such as polarizers, compensators, alignment layers, circular polarizers or color filters in liquid crystal displays or projection systems, for preparing decorative images of liquid crystals or effect pigments, and especially reflective films with spatially varying reflected colors, for example, as multicolor images for decoration, information storage or security purposes, such as unforgeable documents (such as identity cards or credit cards), banknotes, etc.

The polymeric LC film according to the invention can be used in transmissive or reflective displays. It can be used in known OLED displays or LCDs, in particular LCDs.

The present invention is described above and below with particular reference to preferred embodiments. It should be appreciated that various changes and modifications may be made therein without departing from the spirit and scope of the present invention.

Many of the compounds mentioned above and below or their mixtures are commercially available. All these compounds are known or can be prepared by methods known per se to be practiced under reaction conditions known and suitable for the reactions, as described in the literature (e.g., standard works such as Houben-Weyl, Methoden der Organischen Chemie [Organic Chemistry Methods], Georg-Thieme-Verlag, Stuttgart). Variants known per se but not mentioned here can also be used here.

It should be understood that variations of the above-described embodiments of the present invention may be made while still falling within the scope of the present invention. Unless otherwise specified, alternative features serving the same, equivalent, or similar purpose may replace each feature disclosed in this specification. Therefore, unless otherwise specified, each feature disclosed is merely an example of a general series of equivalent or similar features.

All features disclosed in this specification can be combined in any combination, except combinations in which at least some of these features and/or steps are mutually exclusive. In particular, the preferred features of the present invention are applicable to all aspects of the present invention and can be used in any combination. Similarly, features described in non-essential combinations can be used alone (not in combination).

It should be understood that many of the features described above (particularly the preferred embodiments) are inventive in their own right and are not merely part of the embodiments of the present invention. Independent protection may be sought for these features in addition to or in lieu of any invention currently claimed.

The present invention will now be described in more detail with reference to the following working examples, which are merely illustrative and do not limit the scope of the present invention.

Examples Example 1 The following mixture was prepared: Mixture 1 Surfactant (see Table 1 below) 1.000% Irganox 1076 0.080% TR-PBG-304 6.80% 19.00% 30.000% 43.12% Mixture 2 Surfactant (see Table 1 below) 0.50% Irganox 1076 0.08% TR-PBG-304 6.80 19.50% 30.00% 43.12% Mixture 3 Surfactant (see Table 1 below) 0.25% Irganox 1076 0.08% TR-PBG-304 6.80% 19.75% 30.00% 43.12%

Irganox 1076, LC756, and LC242 were purchased from BASF, Germany, and SPI-3 was purchased from Samyang Corporation, Korea.

Mixtures 1, 2 and 3 were each doped with the surfactant at the concentrations specified above to create comparative formulations 1 to 27 and formulations 28 to 30 according to the present invention. The formulation compositions are summarized in Table 1 below. Table 1 - Formulation Compositions Comparison formulations: Surfactants Mixture 1 Mixture 2 Mixture 3 BYK361N Preparation 1 Preparation 2 Preparation 3 BYK 310 Preparation 4 Preparation 5 Preparation 6 FluorN 562 Preparation 7 Preparation 8 Preparation 9 FluorN 561 Preparation 10 Preparation 11 Preparation 12 Tego Airex 980 Preparation 13 Preparation 14 Preparation 15 Dynol 980 Preparation 16 Preparation 17 Preparation 18 Tego Flow 300 Preparation 19 Preparation 20 Preparation 21 Tego Flow 425 Preparation 22 Preparation 23 Preparation 24 BYK 388 Preparation 25 Preparation 26 Preparation 27 The formulation according to the present invention: XXV Preparation 28 Preparation 29 Preparation 30

Tego Airex 980, Tego Airex 920, Tego Airex 931, Tego Airex 962, Tego Glide 435, Tego Wet 260, Tego Wet 500, Tego Wet 510, Tego Twin 4000 were purchased from Evonik Tego, Germany. Polyfox PF-3320, Polyfox PF-7002, Polyfox PF-656 were purchased from Omnova Solutions Inc., USA.

Use Example 1 Polymer films were produced from Formulations 1 to 30 using the following method: § Spin coat Formulations 1 to 30 on polyimide rubbed glass at 3000 rpm for 30 seconds § Anneal the film at 60°C for 60 seconds § Cure the film in a Light Hammer 6 Fusion conveyor belt UV lamp (250 mJ cm ^-2 ) under N ₂

The RM alignment and visible haze of each film were visually inspected after the initial cure and are recorded in the table below. The moisture resistance of each film was visually inspected after the second annealing step and is recorded in Table 2 below. Table 2 - Polymer Film Inspection Preparation Surfactant concentration [% w/w] Alignment in the first coating Alignment in the second coating No moisture resistance in the second coat Preparation 1 1.00% O Δ O Preparation 2 0.50% O X O Preparation 3 0.25% O X O Preparation 4 1.00% O Δ O Preparation 5 0.50% O Δ Δ Preparation 6 0.25% O Δ Δ Preparation 7 1.00% O X O Preparation 8 0.50% O X O Preparation 9 0.25% O X O Preparation 10 1.00% O X O Preparation 11 0.50% O X O Preparation 12 0.25% O Δ O Preparation 13 1.00% O X Δ Preparation 14 0.50% O X Δ Preparation 15 0.25% O Δ O Preparation 16 1.00% O O Δ Preparation 17 0.50% O O Δ Preparation 18 0.25% O O Δ Preparation 19 1.00% Δ Δ X Preparation 20 0.50% Δ Δ Δ Preparation 21 0.25% Δ Δ X Preparation 22 1.00% O O X Preparation 23 0.50% O O X Preparation 24 0.25% O O Δ Preparation 25 1.00% O O Δ Preparation 26 0.50% O O X Preparation 27 0.25% O O X Preparation 28 1.00% O O O Preparation 29 0.50% O O O Preparation 30 0.25% O O O O Pass / Good X Fail / Poor Δ Moderate / Average

As can be seen from Table 2, the use of fluorosurfactant XXVa as surfactant according to the present invention ( in bold herein ) provides a very wide concentration range that can be used to achieve good RM alignment compared to the comparative example ( in italics herein ). Compared to the comparative example, this surfactant choice also has a wide concentration range where it does not cause anti-wetting of subsequent coating layers and also provides alignment to the upper layers, so no additional alignment layers are needed between RM layers.

Claims (16)

A polymerizable LC material comprising one or more reactive mesogen compounds and one or more compounds of formula I (R ¹ —CHF—CF ₂ —Y—) _m Spacer (X) _n I wherein R ¹ = fluorinated linear or branched alkyl, optionally containing heteroatoms, Spacer = single bond or divalent organic group, X = hydrophilic group, Y = S, SO or SO ₂ , m is ≥ 1 and n is ≥ 1. The polymerizable LC material of claim 1, wherein the concentration of the compound of formula I is from 0.01% to 1%. The polymerizable LC material of claim 1, comprising one or more reactive mesogens selected from the formula RMT, wherein P is a polymerizable group, Sp is a spacer group or a single bond, r2 and r3 are independently 0, 1, 2, 3 or 4, R ¹¹ is P-Sp-, alkyl, alkoxy, sulfanyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, preferably having 1 to 15 C atoms, more preferably fluorinated as appropriate, A and B In the case of multiple occurrences, independently of one another, represent an aromatic or alicyclic radical, which optionally contains one or more heteroatoms selected from N, O and S and which is optionally mono- or polysubstituted by L, preferably 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, thiophene-2,5-diyl, naphthalene-2,6-diyl, 1,2,3,4-tetrahydro-naphthalene-2,6-diyl, dihydroindene-2,5-diyl, bicyclooctylene or 1,4-cyclohexylene, wherein one or two non-adjacent _CH2 radicals are optionally replaced by O and/or S, wherein these radicals are unsubstituted or substituted by 1, 2, 3 or 4 radicals L, L being P-Sp-, F, Cl, Br, I, -CN, -NO ₂ , -NCO, -NCS, -OCN, -SCN, -C(=O)NR ^x R ^y , -C(=O)OR ^x , -C(=O)R ^x , -NR ^x R ^y , -OH, -SF ₅ , or a straight or branched chain alkyl group, alkoxy group, alkylcarbonyl group, alkoxycarbonyl group, alkylcarbonyloxy group or alkoxycarbonyloxy group having 1 to 12 C atoms, wherein one or more H atoms are optionally replaced by F or Cl, preferably F, -CN or a straight or branched chain alkyl group, alkoxy group, alkylcarbonyl group, alkoxycarbonyl group, alkylcarbonyloxy group or alkoxycarbonyloxy group having 1 to 6 C atoms, R ^x and R ^y independently represent H or an alkyl group having 1 to 12 C atoms, Z ¹¹ and Z ¹² In the case of multiple occurrences, it represents -O-, -S-, -CO-, -COO-, -OCO-, -S-CO-, -CO-S-, -O-COO-, -CO-NR ^{00 -, -NR 00} -CO-, -NR ⁰⁰ -CO-NR ⁰⁰⁰ , -NR ⁰⁰ -CO-O-, -O-CO-NR ⁰⁰ -, -OCH ₂ -, -CH 2 O-, -SCH 2 _{-, -CH 2 S-, -CF 2} ^O- _, -OCF ₂ -, -CF ₂ S-, -SCF ₂ -, -CH ₂ CH ₂ - _, -(CH ₂ ) _n1 , -CF ₂ CH _{2 -} , -CH ₂ CF ₂ -, -CF ₂ CF ₂ -, -CH=N-, -N=CH-, -N=N-, -CH=CR ⁰⁰ -, -CY ¹ =CY ² -, -C≡C-, -CH=CH-COO-, -OCO-CH=CH- or a single bond, preferably -COO-, -OCO-, -C≡C- or a single bond, R ⁰⁰ and R ⁰⁰⁰ independently represent an alkyl group, an alkoxy group, a sulfanyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkoxycarbonyloxy group having 1 or more, preferably 1 to 15 C atoms, or represent Y ⁰ or P-(CH ₂ ) _y -(O) _z -, Y ⁰ is F, Cl, CN, NO ₂ , OCH ₃ , OCN, SCN, SF ₅ or a mono-low-fluorinated or polyfluorinated alkyl or alkoxy group having 1 to 4 C atoms, y is 0 or an integer from 1 to 12, z is 0 or 1, wherein if the adjacent y is 0, then z is 0, Y ¹ and Y ² independently represent H, F, Cl or CN, n is 1, 2, 3 or 4, preferably 1 or 2, most preferably 1, m is 0, 1, 2, 3 or 4, preferably 0 or 1, most preferably 0, n1 is an integer from 1 to 10, preferably 1, 2, 3 or 4. A polymerizable LC material as claimed in claim 3, wherein the concentration of the RMT compound is 40% to 99%. A polymerisable LC material as claimed in any one of claims 1 to 4, comprising one or more compounds selected from the group consisting of a DRM of the formula wherein ^P1 and ^P2 are independently polymerizable groups, ^Sp1 and ^Sp2 are independently spacer groups or single bonds, and MG is a rod-shaped liquid crystal group, which is preferably selected from the formula MG wherein ^A1 and ^A2, when they appear multiple times, independently represent an aromatic or alicyclic group, which optionally contains one or more heteroatoms selected from N, O and S, and optionally is mono- or poly-substituted by L, and L is P-Sp-, F, Cl, Br, I, -CN, _-NO2 , -NCO, -NCS, -OCN, -SCN, -C(=O)NRxRy ^{, -C} (=O) ^ORx , -C(=O) ^Rx , ^-NRxRy , ^-OH , _-SF5 , an optionally substituted silyl group; an aryl or heteroaryl group having 1 to 12, preferably 1 to 6 C atoms; and a straight-chain or branched alkyl group, alkoxy group, alkylcarbonyl group, alkoxycarbonyl group, alkylcarbonyloxy group or alkoxycarbonyloxy group having 1 to 12, preferably 1 to 6 C atoms, wherein one or more H atoms are optionally replaced by F or Cl, ^Rx and ^Ry are each independently H or an alkyl group having 1 to 12 C atoms, ^Z1 , in the case of multiple occurrences, is each independently -O-, -S-, -CO-, -COO-, -OCO-, -S-CO-, -CO-S-, -O-COO-, -CO- ^NRx- , -NRx-CO-, -NRx- ^CO - ^NRy , -NRx ^- CO- ^O- , -O-CO- ^NRx- , _-OCH2- , -CH ₂ O-, -SCH ₂ -, -CH 2 S-, -CF ₂ O-, -OCF ₂ -, -CF ₂ S-, -SCF ₂ -, -(CH ₂ ) _n1 , -CF ₂ CH _{2 -} , -CH 2 CF ₂ -, -CF ₂ CF ₂ -, -CH=N-, -N=CH-, ^-N =N-, -CH=CR ^x -, -CY ¹ =CY ₂ -, -C≡C-, -CH=CH-COO-, -OCO-CH=CH- or a single bond, Y ¹ and Y ² independently represent H, F, Cl or CN, n is 1, 2, 3 or 4, n1 is an integer from 1 to 10, preferably 1, 2, 3 or 4, provided, however, that compounds of the formula RMT are not included in the compounds of the formula DRM. A polymerizable LC material as claimed in any one of claims 1 to 4, wherein the concentration of the di-reactive or multi-reactive mesogen is from 1% to 60%. A polymerisable LC material as claimed in any one of claims 1 to 4, comprising one or more compounds selected from the group consisting of formula MRM, wherein P ¹ , Sp ¹ and MG have the meanings given in formula DRM, R represents P-Sp-, F, Cl, Br, I, -CN, -NO ₂ , -NCO, -NCS, -OCN, -SCN, -C(=O)NR ^x R ^y , -C(=O)X, -C(=O)OR ^x , -C(=O)R ^y , -NR ^x R ^y , -OH, -SF ₅ , optionally substituted silyl; linear or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12, preferably 1 to 6 C atoms, wherein one or more H atoms are optionally replaced by F or Cl, X is halogen, preferably F or Cl, and R ^x and R ^y are independently H or alkyl having 1 to 12 C atoms, However, there is a proviso that compounds of the formula RMT are not included in compounds of the formula MRM. A polymerisable LC material as claimed in any one of claims 1 to 4, optionally comprising one or more reactive chiral compounds selected from compounds of formulae CRMa to CRMc, wherein P0 ^* represents a polymerizable group P Sp* represents a spacer Sp ^A0 and ^B0 , when they appear multiple times, are independently 1,4-phenylene, which is unsubstituted or substituted with 1, 2, 3 or 4 groups L as defined above, or is trans-1,4-cyclohexylene, ^X1 and ^X2 are independently -O-, -COO-, -OCO-, -O-CO-O- or a single bond, Z0 ^* and ^Z0 , when they appear multiple times, are independently -COO-, -OCO- _, -O-CO-O- _, -OCH2- _{, -CH2O- , -CF2O- ,} -OCF2-, -CH2CH2-, -( _{CH2 ) 4-} , -CF2CH2- _{, -CH2CF2- , -CF2CF2} -, -C≡C-, -CH=CH-, -CH=CH-COO-, -OCO-CH=CH- or a single bond, t is independently 0, 1, 2 or 3, a is 0, 1 or 2, b is 0 or an integer from 1 to 12, z is 0 or 1, and the naphthyl rings in the formula CRMa may be further substituted by one or more identical or different groups L, wherein L is independently F, Cl, CN, a halogenated alkyl group having 1 to 5 C atoms, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkoxycarbonyloxy group. The polymerizable LC material of claim 8, wherein the concentration of the chiral compound in the liquid crystal medium is preferably 1 to 20%. A polymerizable LC material as claimed in any one of claims 1 to 4, which optionally comprises one or more additives selected from the group consisting of: additional surfactants, photoinitiators, stabilizers, catalysts, sensitizers, inhibitors, chain transfer agents, co-reactive monomers, reactive detackifiers, surface-active compounds, lubricants, wetting agents, dispersants, hydrophobic agents, tackifiers, flow improvers, degassing or defoaming agents, deaerators, diluents, reactive diluents, additives, colorants, dyes, pigments and nanoparticles. A method for preparing a polymerizable LC material as claimed in any one of claims 1 to 10, comprising the step of mixing one or more compounds of formula I as defined in claim 1 with one or more reactive mesogen compounds and, optionally, one or more chiral compounds. A method of preparing a polymer film by providing a layer of a polymerizable LC material as claimed in any one of claims 1 to 10 on a substrate, photopolymerizing the polymerizable LC material, and removing the polymerized LC material from the substrate as appropriate and/or providing it on another substrate as appropriate. A polymer film obtainable from a polymerizable LC material according to any one of claims 1 to 10 by a process comprising the following steps: providing a layer of the polymerizable LC material on a substrate, photopolymerizing the LC material, and removing the polymerized LC material from the substrate as appropriate and/or providing it on another substrate as appropriate. A use of one or more polymer films as claimed in claim 13 or a polymerizable LC material as claimed in any one of claims 1 to 10 in an optical component. An optical component comprising one or more polymer films as claimed in claim 13 or a polymerizable LC material as claimed in any one of claims 1 to 10. A use of an optical component as claimed in claim 15 in an electro-optical device.