Polymerizable liquid crystal material and polymerized liquid crystal film

Abstract

The present invention relates to polymerizable LC materials comprising one or more reactive mesogenic compounds and one or more compounds of formula (I) # imgabs0 wherein each group has one of the meanings given in the claims. The invention further relates to a method for the production thereof, to a polymer film obtainable from the corresponding polymerizable LC material, to a method for the production of such a polymer film, and to the use of such a polymer film and of said polymerizable LC material in optics, electro-optic, in particular in electro-optic devices in the field of augmented reality or virtual reality.

Description

Technical Field

[0001] The present invention relates to a polymerisable liquid crystal (LC) material comprising one or more reactive mesogenic compounds and one or more compounds of formula I,

[0002]

[0003] wherein the respective radicals have one of the meanings given in the claims. The invention furthermore relates to a process for their preparation, to polymer films obtainable from the corresponding polymerizable LC materials, to a process for the preparation of such polymer films, and to the use of such polymer films and of said polymerizable LC materials in electro-optical devices, in particular in the field of augmented reality or virtual reality. Background Art

[0004] Reactive mesogens (RMs), mixtures or formulations containing them, and polymers obtained therefrom can be used to make optical components, such as compensation, retardation or polarizing films, or lenses. These 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.

[0005] For some applications, it is desirable to form a multilayer film, stack or optical component comprising two or more layers that, for example, exhibit different reflection wavelengths.

[0006] For example, multilayer cholesteric polymer films have been described in the prior art, for example US 6,417,902. Furthermore, EP 0 634 674 suggests preparing a multilayer cholesteric liquid crystal polymer film by bonding a pair of chiral nematic liquid crystal polymer films together, applying pressure and heating the polymers above their glass transition temperature to allow the films to adhere.

[0007] Maurer et al., SID 90 Digest, Vol. 21, pp. 110 (1990) describe polarizing color filters obtained by combining several polarizing films with different reflection wavelengths. To prepare 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.

[0008] 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 onto a quarter wave plate.

[0009] However, the methods for preparing multilayer cholesteric films described in the above-mentioned documents have several disadvantages. Therefore, it is usually very difficult and requires high temperatures to achieve uniform alignment in the CLC polymer layer. For example, Maurer et al. mention an alignment temperature of 150° C., while JP01-133003-A and JP08-271731-A mention the need for a temperature far above the glass transition temperature of the CLC polymer. This is particularly disadvantageous when using polymers with high glass transition temperatures (such as acrylates, styrenes or methacrylates) and is particularly unsuitable for large-scale production.

[0010] Furthermore, according to the multilayer production method described, for example, in JP01-133003-A, the polymers must be selected so that different polymer layers exhibit different glass transition temperatures. Therefore, when laminating and aligning, for example, a second layer on top of the 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 in order not to affect the uniform orientation of the first layer, etc. This severely limits the choice of suitable materials and makes the production process more complicated.

[0011] Another aspect is that polymerizable LC materials often need to contain leveling agents, such as surfactants, in order to achieve a good alignment of the resulting polymer. Typically, without the use of surfactants 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 commonly used in such formulations, it may be difficult to achieve a good alignment and coating quality of the second coating of the CLC material required for multilayer applications.

[0012] In this regard, dewetting is defined as the breaking of the thin liquid film on the substrate and the formation of droplets. In the case of multilayer applications, this can lead to an uneven thickness of the second CLC material upon drying. In some cases, the film can be withdrawn from the edges and in the worst case, there is extreme beading of the second coating layer, which leads to zero coverage of the coated area.

[0013] It is therefore an object of the present invention to provide improved polymerisable LC materials or RM mixtures and RM formulations which do not have the disadvantages of the materials known in the prior art. In particular, it is an object to provide RM mixtures and RM formulations which are suitable for the preparation of polymers by in situ UV photopolymerisation and which at the same time exhibit a high birefringence, exhibit good solubility, show an improved broadening potential, have a favourable transition temperature and exhibit a high resistance to yellowing after exposure to UV light. Another object is to provide an improved multilayer stack which does not show the disadvantages of the materials known in the prior art. Other objects of the invention are immediately apparent to the expert from the following description.

[0014] Surprisingly, the inventors of the present invention have found that a polymerisable LC material according to claim 1 meets one or more of the requirements defined above and preferably achieves all objects simultaneously. Summary of the invention

[0015] The present invention relates to polymerisable LC materials comprising one or more reactive mesogenic compounds and one or more compounds of formula I,

[0016]

[0017] in,

[0018] R1 to R6 are each independently a linear, branched or cyclic alkyl radical having 1 to 40, preferably 1 to 25, more preferably 1 to 12 C atoms, which is unsubstituted or mono- or polysubstituted by F, Cl, Br, I or CN, and wherein one or more non-adjacent CH2 groups may each independently of one another be substituted by -C(R x )=C(R x )-、-C≡C-、-N(R x )-, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- substitution.

[0019] Above, R x preferably denotes H, halogen, straight-chain, branched or cyclic alkyl having 1 to 25 C atoms, wherein, in addition, one or more non-adjacent C atoms may be replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, and wherein one or more H atoms may be replaced by fluorine, and

[0020] x and y ≥ 1

[0021] m and n ≥ 1.

[0022] Preferred alkyl groups are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-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., wherein in addition, one or more non-adjacent CH2 groups may each be independently replaced by Alternative.

[0023] Preferred alkenyl groups are, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl and the like.

[0024] Preferred alkynyl groups are, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, octynyl and the like.

[0025] Preferred alkoxy groups are, for example, methoxy, ethoxy, 2-methoxyethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, 2-methylbutoxy, n-pentoxy, n-hexoxy, n-heptoxy, n-octoxy, n-nonoxy, n-decoxy, n-undecyloxy, n-dodecyloxy, etc., wherein in addition, one or more non-adjacent CH2 groups may each independently be Alternative.

[0026] Preferred amino groups include dimethylamino, methylamino, methylphenylamino, and phenylamino.

[0027] Furthermore, the present invention also relates to a corresponding preparation process for preparing a polymerisable LC material, which comprises at least the step of mixing one or more reactive mesogenic compounds and one or more compounds of formula I.

[0028] The present invention also relates to a polymer network or a polymer film obtainable, preferably obtainable, from a polymerisable LC material as described above and below and to a method for the preparation of a polymer film as described above and below.

[0029] The present invention also relates to a method for improving the dewetting behavior of a polymer film obtainable from, preferably from, a polymerizable LC material as described above and below, by adding a block copolymer as described above and below to the polymerizable LC material before polymerization.

[0030] The present invention also relates to an optical component comprising one or more optical films, wherein one optical film is selected from polymer films obtainable from polymerisable LC materials as described above and below.

[0031] The invention also relates to the use of an optical component or a polymer film or a polymerizable LC material 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 different reflection colors, multicolor images, unforgeable documents such as identity cards or credit cards or banknotes.

[0032] The invention also relates to an electro-optical device, such as an LCD or an OLED, comprising one or more optical components or a polymer film or a polymerisable LC material as described above and below.

[0033] The invention also relates to an electro-optical device in the field of augmented or virtual reality, such as a head mounted device comprising one or more optical components, a polymer film of a polymerizable material as described above and below.

[0034] Terms and Definitions

[0035] As used herein, the term "polymer" will be understood to refer to a molecule comprising a backbone of one or more different types of repeating units (the smallest building blocks of a molecule), and includes the well-known terms "oligomer", "copolymer", "homopolymer", etc. In addition, it should be 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. In addition, such residues and other elements, although generally removed during post-polymerization purification, are generally mixed or blended with the polymer so that they are generally retained in the polymer when the polymer is transferred between containers or between solvents or dispersion media.

[0036] The term "(meth)acrylic polymer" as used in the present invention includes polymers obtainable from acrylic monomers, polymers obtainable from methacrylic monomers, and corresponding copolymers obtainable from mixtures of such monomers.

[0037] The term "polymerization" refers to a chemical process of forming a polymer by bonding together a plurality of polymerizable groups or polymer precursors (polymerizable compounds) containing such polymerizable groups.

[0038] The term "film" or "layer" includes rigid or flexible, self-supporting or free-standing films having mechanical stability, as well as coatings or layers on a supporting substrate or between two substrates.

[0039] The term "liquid crystal" or (LC) refers to materials which have a liquid crystal mesophase within some temperature range (thermotropic LC) or within some concentration range in solution (lyotropic LC). They necessarily contain mesogenic compounds.

[0040] The terms "mesogenic compounds" and "liquid crystal compounds" refer to compounds containing one or more rod-shaped (rod or plate / slat-shaped) or disc-shaped (disk-shaped) mesogenic groups. The term "mesogenic group" refers to a group having the ability to induce liquid crystal phase (or mesophase) behavior. Compounds containing mesogenic groups do not necessarily have to exhibit liquid crystal mesophases themselves. They can also exhibit liquid crystal mesophases only in mixtures with other compounds, or when the mesogenic compound or material or a mixture thereof is polymerized. This liquid crystal mesophase includes low molecular weight non-reactive liquid crystal compounds, reactive or polymerizable liquid crystal compounds and liquid crystal polymers.

[0041] The rod-like mesogenic group generally comprises a mesogenic core composed of one or more aromatic or non-aromatic cyclic groups connected to each other directly or via a connecting group, optionally comprising an end group attached to the end of the mesogenic core, and optionally comprising one or more side groups attached to the long side of the mesogenic core, wherein these end groups and side groups are generally selected from, for example, carbon groups (carbyl) or hydrocarbon groups, polar groups (such as halogen, nitro, hydroxyl, etc.) or polymerizable groups.

[0042] The term "reactive mesogen" refers to polymerizable mesogenic or liquid crystal compounds, preferably monomeric compounds. These compounds can be used as pure compounds or as mixtures of reactive mesogens with other compounds acting as photoinitiators, inhibitors, surfactants, stabilizers, chain transfer agents, non-polymerizable compounds, etc.

[0043] Polymerizable compounds having one polymerizable group are also referred to as "monoreactive" compounds, compounds having two polymerizable groups are also referred to as "direactive" compounds, and compounds having more than two polymerizable groups are also referred to as "polyreactive" compounds. Compounds that do not contain polymerizable groups are also referred to as "non-reactive or non-polymerizable" compounds.

[0044] The term "non-mesogenic compound or material" refers to a compound or material that does not contain a mesogenic group as defined above.

[0045] 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.

[0046] Irradiance (E e ) or radiant power is defined as the power of electromagnetic radiation (dθ) per unit area (dA) incident on a surface:

[0047] E e =dθ / dA.

[0048] Radiation exposure or radiation dose (H e ) is the irradiance or radiation power (E) at each time (t) e ):

[0049] H e =E e ·t.

[0050] All temperatures, such as the melting point of the liquid crystal T(C,N) or T(C,S), the transition from the smectic (S) to the nematic (N) phase T(S,N) and the clearing point T(N,I) are given in degrees Celsius. All temperature differences are given in degrees.

[0051] The term "clearing point" refers to the temperature at which the transition between the intermediate phase having the highest temperature range and the isotropic phase occurs.

[0052] 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 such anisotropic molecules, the director is the anisotropy axis.

[0053] The term "alignment" or "orientation" relates to the alignment (orientational ordering) of anisotropic units of a material (e.g., small molecules or fragments of macromolecules) along a consistent direction (called the "alignment direction"). In a liquid crystal material or an alignment layer of 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.

[0054] The term "homogeneous orientation" or "homogeneous alignment" of a liquid crystal or RM material, for example in a layer of the material, means that the long molecular axes (in the case of rod-shaped compounds) or the short molecular axes (in the case of discotic compounds) of the liquid crystal or RM molecules are oriented substantially in the same direction. In other words, the lines of the liquid crystal directors are parallel.

[0055] The terms "homeotropic structure" or "homeotropic orientation" refer to films in which the optical axis is substantially perpendicular to the plane of the film.

[0056] The term "in-plane structure" or "in-plane orientation" refers to a film in which the optical axis is substantially parallel to the plane of the film.

[0057] The term "A-plate" refers to an optical retarder that utilizes a layer of uniaxial birefringent material with its extraordinary axis oriented parallel to the layer plane.

[0058] The term "C-plate" refers to an optical retarder that utilizes a layer of uniaxial birefringent material with its extraordinary axis oriented perpendicular to the plane of the layer.

[0059] In an A / C-plate comprising an optically uniaxial birefringent liquid crystal material having a uniform orientation, the optical axis of the film is given by the direction of the extraordinary axis. An A (or C) plate comprising an optically uniaxial birefringent material having a positive birefringence is also referred to as a "positive A (or C) plate" or "+A (or +C) plate".

[0060] A (or C) plates comprising films of optically uniaxial birefringent materials having negative birefringence, such as discotic anisotropic materials, are also referred to as "negative A (or C) plates" or "-A (or C) plates", depending on the orientation of the discotic material. Films made of cholesteric rod-shaped materials having a reflection band in the UV portion of the spectrum also have the optics of a negative C plate.

[0061] The birefringence Δn is defined as follows

[0062] Δn=n e -n o

[0063] where n e is the extraordinary refractive index and n o is the ordinary refractive index, and the average effective refractive index n av. Given by the following equation:

[0064] n av. =((2n o 2 +n e 2 ) / 3) 1 / 2

[0065] Average effective refractive index n av. and the ordinary refractive index n o This can be measured using an Abbe refractometer. Δn can then be calculated from the above equation.

[0066] Unless the context clearly indicates otherwise, as used herein, plural forms of the terms are to be understood as including the singular form and vice versa.

[0067] Unless explicitly stated otherwise, all physical properties have been measured according to or 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) is measured at a wavelength of 589.3 nm.

[0068] In case of doubt, the definitions as given in C. Tschierske, G. Pelzl and S. Diele, Angew. Chem. 2004, 116, 6340-6368 shall apply.

[0069] Unless otherwise indicated, in the given formulae, the following terms have the following meanings:

[0070] "Carbonyl" means a monovalent or polyvalent organic group containing one or more carbon atoms and containing no other atoms. Or optionally contain one or more other atoms, such as N, O, S, P, Si, Se, As, Te or Ge (e.g., carbonyl, etc.). "Hydrocarbyl" means a carbon group which additionally contains one or more H atoms and optionally one or more heteroatoms, such as N, O, S, P, Si, Se, As, Te or Ge.

[0071] The carbyl or hydrocarbon group may be a saturated or unsaturated group. An unsaturated group is, for example, an aryl, an alkenyl or an alkynyl group. A carbyl or hydrocarbon group having more than 3 C atoms may be straight chain, branched and / or cyclic and may contain spiro-connected or fused rings.

[0072] Preferred carbyl and hydrocarbyl groups are optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy and alkoxycarbonyloxy groups having 1 to 40 C atoms, preferably 1 to 25 C atoms, particularly preferably 1 to 18 C atoms, optionally substituted aryl or aryloxy groups having 6 to 40 C atoms, preferably 6 to 25 C atoms, or optionally substituted alkylaryl, arylalkyl, alkylaryloxy, arylalkyloxy, arylcarbonyl, aryloxycarbonyl, arylcarbonyloxy and aryloxycarbonyloxy groups having 6 to 40 C atoms, preferably 6 to 25 C atoms.

[0073] Other preferred carbon and hydrocarbon groups are C1-C 40 Alkyl, C2-C 40 Alkenyl, C2-C 40 Alkynyl, C3-C 40 Allyl, C4-C 40 Alkyldiene, C4-C 40 Polyene, C6-C 40 Aryl, C6-C 40 Alkyl aryl, C6-C 40 Arylalkyl, C6-C 40 Alkyl aryloxy, C6-C 40 Arylalkyloxy, C2-C 40 Heteroaryl, C4-C 40 Cycloalkyl, C4-C 40 Cycloalkenyl, etc. Particularly preferred are C1-C 22 Alkyl, C2-C 22 Alkenyl, C2-C 22 Alkynyl, C3-C 22 Allyl, C4-C 22 Alkyldiene, C6-C 12 Aryl, C6-C 20 Arylalkyl and C2-C 20 Heteroaryl.

[0074] Other preferred carbon and hydrocarbon radicals are straight-chain, branched or cyclic alkyl radicals having 1 to 40 C atoms, preferably 1 to 25 C atoms, more preferably 1 to 12 C atoms, which are unsubstituted or mono- or polysubstituted by F, Cl, Br, I or CN, and in which one or more non-adjacent CH2 groups can each be replaced independently of one another by -C(R x )=C(R x )-,-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.

[0075] In the above, R x Preferably it is H, halogen, a straight-chain, branched or cyclic alkyl chain having 1 to 25 C atoms, wherein furthermore one or more non-adjacent C atoms may be replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, and wherein one or more H atoms may be replaced by fluorine, optionally substituted aryl or aryloxy having 6 to 40 C atoms or optionally substituted heteroaryl or heteroaryloxy having 2 to 40 C atoms.

[0076] Preferred alkyl groups are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-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., wherein in addition, one or more non-adjacent CH2 groups may each be independently replaced by Alternative.

[0077] Preferred alkenyl groups are, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl and the like.

[0078] Preferred alkynyl groups are, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, octynyl and the like.

[0079] Preferred alkoxy groups are, for example, methoxy, ethoxy, 2-methoxyethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, 2-methylbutoxy, n-pentoxy, n-hexoxy, n-heptoxy, n-octoxy, n-nonoxy, n-decoxy, n-undecyloxy, n-dodecyloxy, etc., wherein in addition, one or more non-adjacent CH2 groups may each independently be Alternative.

[0080] Preferred amino groups include dimethylamino, methylamino, methylphenylamino, and phenylamino.

[0081] Aryl and heteroaryl groups may be monocyclic or polycyclic, i.e. they may have one ring (such as phenyl) or two or more rings, which may also be fused (such as naphthyl) or covalently linked (such as 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.

[0082] Preferred are monocyclic, bicyclic or tricyclic aryl groups with 6 to 25 C atoms and monocyclic, bicyclic or tricyclic heteroaryl groups with 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 and heteroaryl groups, in which in addition 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 one another.

[0083] Preferred aryl groups are, for example, phenyl, biphenyl, terphenyl, [1,1':3',1"]-terphenyl-2'-yl, naphthalene, anthracene, binaphthyl, phenanthrene, pyrene, dihydropyrene, Perylene, tetracene, pentacene, benzopyrene, fluorene, indene, indenofluorene, spirobifluorene, and the like.

[0084] 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, 6-membered rings, 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 fused groups, 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, Benzo-7,8-quinoline, benzisoquinoline, acridine, phenothiazine, phenoxazine, benzopyridazine, benzopyrimidine, quinoxaline, phenazine, naphthyridine, azacarbazole, benzocarboline, phenanthridine, phenanthroline, thieno[2,3b]thiophene, thieno[3,2b]thiophene, dithienothiophene, isobenzothiophene, dibenzothiophene, benzothiadiazolethiophene, or a combination of these groups. The heteroaryl group may also be substituted with an alkyl, alkoxy, sulfanyl, fluorine, fluoroalkyl or other aryl or heteroaryl groups.

[0085] (Non-aromatic) alicyclic groups 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. The heterocyclic ring contains one or more heteroatoms, preferably selected from Si, O, N, S and Se.

[0086] (Non-aromatic) alicyclic groups and heterocyclic groups can be monocyclic, i.e. contain only one ring (e.g. cyclohexane), or polycyclic, i.e. contain multiple rings (e.g. decalin or bicyclooctane). Saturated groups are particularly preferred. In addition, mono-, bi- or tricyclic groups with 3-25 C atoms are preferred, which optionally contain fused rings and which are optionally substituted. Further preferred are 5-, 6-, 7- or 8-membered carbocyclic groups, wherein in addition, one or more C atoms may be substituted by Si and / or one or more CH groups may be substituted by N and / or one or more non-adjacent CH2 groups may be substituted by-O- and / or-S-.

[0087] Preferred alicyclic and heterocyclic groups are, for example, 5-membered groups, such as cyclopentane, tetrahydrofuran, tetrahydrothiophene, pyrrolidine; 6-membered groups, such as cyclohexane, silinane, cyclohexene, tetrahydropyran, tetrahydrothiopyran, 1,3-dioxane, 1,3-dithiane, piperidine; 7-membered groups, such as cycloheptane; and condensed groups, such as tetralin, decalin, indane, 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-methanoindan-2,5-diyl.

[0088] The aromatic, heteroaromatic, (non-aromatic) alicyclic and heterocyclic groups optionally have one or more substituents, which are preferably selected from silyl, sulfonic acid, sulfonyl, formyl, amine, imine, nitrile, mercapto, nitro, halogen, C 1-12 Alkyl, C 6-12 Aryl, C 1-12 Alkoxy, hydroxy or a combination of these groups.

[0089] 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 used to increase the glass transition temperature (Tg) of the polymer, especially bulky groups, such as tert-butyl or optionally substituted aryl groups.

[0090] Preferred substituents (hereinafter also referred to as "L") are, for example, F, Cl, Br, I, -OH, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)N(R x )2, -C(=O)Y x 、-C(=O)R x 、-C(=O)OR x 、-N(R x )2, where R x has the meanings mentioned above, and the above Y xrepresents halogen; optionally substituted silyl; optionally substituted aryl or heteroaryl having 4 to 40, preferably 4 to 20 ring atoms; and straight-chain or branched alkyl, alkenyl, alkynyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 25 C atoms, wherein one or more H atoms may optionally be replaced by F or Cl.

[0091] "Substituted silyl or aryl" preferably refers to substituted silyl or aryl groups with halogen, -CN, R y 、-OR y 、-CO-R y 、-CO-OR y 、-O-CO-R y OR-O-CO-OR y Substitution, where R y represents H, a linear, branched or cyclic alkyl chain having 1 to 12 C atoms.

[0092] In the formulae shown above and below, the substituted phenylene ring

[0093] Preferably

[0094]

[0095] in which L has, identically or differently on each occurrence, one of the meanings given above and below and is preferably 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-, very preferably F, Cl, CN, CH3, C2H5, OCH3, COCH3, OCF3 or P-Sp- and most preferably F, Cl, CH3, OCH3, COCH3 or OCF3.

[0096] "Halogen" means F, Cl, Br or I, preferably F or Cl, more preferably F.

[0097] The "polymerizable group" (P) is preferably selected from groups comprising a C=C double bond or a C≡C triple bond, and groups suitable for ring-opening polymerization, such as, for example, oxetanyl or epoxy groups.

[0098] Preferably, the polymerizable group (P) is selected from CH2=CW 1 -COO-, CH2=CW 1 -CO-,

[0099] CH2=CW2 -

[0100] (O) k3 -, CW 1 =CH-CO-(O) k3 -, CW 1 =CH-CO-NH-, CH2=CW 1 -CO-NH-, CH3-CH=CH-O-, (CH2=CH)2CH-OCO-, (CH2=CH-CH2)2CH-OCO-, (CH2=CH)2CH-O-, (CH2=CH-CH2)2N-, (CH2=CH-CH2)2N-CO-, CH2=CW 1 -CO-NH-, CH2=CH-(COO) k1 -Phe-(O) k2 -, CH2=CH-(CO) k1 -Phe-(O) k2 -, Phe-CH=CH-,

[0101] in

[0102] W 1 represents H, F, Cl, CN, CF3, phenyl or alkyl having 1 to 5 C atoms, in particular H, F, Cl or CH3,

[0103] W 2 represents H or alkyl having 1 to 5 C atoms, in particular H, methyl, ethyl or n-propyl,

[0104] W 3 and W 4 each independently of one another represents H, Cl or an alkyl radical 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, preferred substituents L are F, Cl, CN, NO2, CH3, C2H5, OCH3, OC2H5, COCH3, COC2H5, COOCH3, COOC2H5, CF3, OCF3, OCHF2, OC2F5, and also phenyl, and

[0105] k1, k2 and k3 each independently represent 0 or 1, k3 preferably represents 1, and k4 is an integer of 1 to 10.

[0106] Particularly preferred polymerizable groups P are CH2=CH-COO-, CH2=C(CH3)-COO-, CH2=CF-COO-, CH2=CH-, CH2=CH-O-, (CH2=CH)2CH-OCO-, (CH2=CH)2CH-O-, and Where W 2 represents H or alkyl having 1 to 5 C atoms, in particular H, methyl, ethyl or n-propyl.

[0107] Further preferred polymerizable groups (P) are vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane and epoxy groups, most preferably acrylate or methacrylate, especially acrylate.

[0108] Preferably, all polyreactive polymerizable compounds and subformulae thereof comprise one or more branching groups (polyreactive polymerizable groups) comprising two or more polymerizable groups P instead of one or more groups P-Sp-.

[0109] Suitable groups of this type and polymerizable compounds comprising them are described, for example, in US Pat. No. 7,060,200 B1 or US 2006 / 0172090 A1.

[0110] Particularly preferred are polyreactive polymerizable groups selected from the following formulae

[0111] -X-alkyl-CHP x -CH2-CH2P y I * a

[0112] -X-alkyl-C(CH2P x )(CH2P y )-CH2P z I * b

[0113] -X-alkyl-CHP x CHP y -CH2P z I * c

[0114] -X-alkyl-C(CH2P x )(CH2P y )-C aa H 2aa+1 I * d

[0115] -X-alkyl-CHP x -CH2P y I * e

[0116] -X-alkyl-CHP x P y I * f

[0117] -X-alkyl-CP x P y -C aa H 2aa+1 I * g

[0118] -X-alkyl-C(CH2P v )(CH2P w )-CH2OCH2-C(CH2P x )(CH2Py)CH2P z I * h

[0119] -X-alkyl-CH((CH2) aa P x )((CH2) bb P y ) * i

[0120] -X-alkyl-CHP x CHP y -C aa H 2aa+1 I * k

[0121] in

[0122] Alkyl represents a single bond or a straight-chain or branched alkylene radical having 1 to 12 C atoms, wherein one or more non-adjacent CH2 groups may each be independently replaced by -C(R x )=C(R x )-,-C≡C-,-N(R x )-, -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, and further wherein one or more H atoms may be replaced by F, Cl or CN, wherein R x has one of the meanings mentioned above,

[0123] aa and bb each independently represents 0, 1, 2, 3, 4, 5 or 6,

[0124] X has one of the meanings indicated for X', and

[0125] P v To P z Each independently of the others has one of the meanings indicated above for P.

[0126] 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 wherein in addition, one or more non-adjacent CH2 groups may each be independently substituted by -O-, -S-, -NH-, -NR xx -,-SiR xx R yy -, -CO-, -COO-, -OCO-, -OCO-O-,

[0127] -S-CO-, -CO-S-, -NR xx -CO-O-, -O-CO-NR 0xx -,-NR xx -CO-NR yy -, -CH=CH- or -C≡C- are substituted in such a way that the O and / or S atoms are not directly connected to each other, and wherein R xx and R yy Each independently of one another represents H or alkyl having 1 to 12 C atoms.

[0128] Further preferred spacer groups Sp are selected from the formula Sp'-X', such that the group "P-Sp-" conforms to the formula "P-Sp'-X'-", wherein

[0129] Sp' denotes an alkylene radical having 1 to 20, preferably 1 to 12 C atoms, which is optionally mono- or poly-substituted by F, Cl, Br, I or CN, and in which one or more non-adjacent CH2 groups may each be substituted 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 0xx -,-NR xx -CO-NR yy -, -CH=CH- or -C≡C- are substituted in such a way that the O and / or S atoms are not directly connected to each other,

[0130] X' represents -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR xx -,-NR xx -CO-, -NR xx -CO-NR yy-, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CF2CH2-, -CH2CF2-, -CF2CF2-, -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,

[0131] R xx and R yy each independently of one another represents H or an alkyl group having 1 to 12 C atoms, and

[0132] Y xx and Y yy each independently represents H, F, Cl or CN,

[0133] X' is preferably -O-, -S-CO-, -COO-, -OCO-, -O-COO-, -CO-NR xx -、-NR xx -CO-、-NR xx -CO-NR yy - or single key.

[0134] Typical and preferred spacer groups Sp and / or Sp' are, for example, -(CH2) p1 -,-(CH2CH2O) q1 -CH2CH2-, -CH2CH2-S-CH2CH2-, -CH2CH2-NH-CH2CH2- or -(SiR xx R yy -O) p1 -,

[0135] wherein p1 is an integer from 1 to 12, q1 is an integer from 1 to 3, and R xx and R yy has the meaning given above.

[0136] A particularly preferred group -X'-Sp'- is -(CH2) p1 -,-O-(CH2) p1 -,-OCO-(CH2) p1 -,-OCOO-(CH2) p1 -, wherein p1 is an integer from 1 to 12.

[0137] Particularly preferred radicals Sp and / or Sp′ are, for example, in each case straight-chain methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylenethioethylene, ethylene-N-methyliminoethylene, 1-methylalkylene, vinylene, propenylene and butenylene.

[0138] Often, the term "chiral" is used to describe an object that is non-superimposable on its mirror image.

[0139] An "achiral" (handless) object is one that is identical to its mirror image.

[0140] Unless explicitly described otherwise, the terms "chiral nematic" and "cholesteric" are used synonymously in this application.

[0141] Chiral nematic textures or cholesteric liquid crystals (CLCs) exhibit selective reflection of circularly polarized light, where the direction of rotation of the light vector corresponds to the direction of rotation of the cholesteric helix.

[0142] 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:

[0143] λ=n·p

[0144] CLC media can be prepared, for example, by doping nematic LC media with chiral dopants having a high twisting power. The pitch p of the induced cholesteric helix is ​​then provided by the concentration c of the chiral dopant and the helical twisting power HTP according to the following equation:

[0145] p=(HTP c) -1

[0146] It is also possible to use two or more dopants, 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 reflection wavelength of the CLC medium. 总 ), then the following equation applies approximately:

[0147] HTP total =∑ i c i HTP i

[0148] where c i is the concentration of each individual dopant and HTP i is the helical twisting force of each individual dopant.

[0149] For the present invention,

[0150]

[0151] represents trans-1,4-cyclohexylene, and

[0152]

[0153] It represents 1,4-phenylene.

[0154] For the purposes of the present invention, the group -COO- or -CO2- is represented by The ester group, and the group -OCO-, -O2C- or -OOC- are expressed as Ester group.

[0155] A "polymer network" is one in which all polymer chains are interconnected by numerous cross-linking points to form a single macroscopic entity.

[0156] Polymer networks can occur in the following types:

[0157] - Grafted polymer molecules are branched polymer molecules in which one or more side chains differ in structure or configuration from the main chain.

[0158] -A star polymer molecule is a branched polymer molecule in which a single branch point gives rise to multiple linear chains or arms. If the arms are identical, the star polymer molecule is called regular. If adjacent arms are composed of different repeating subunits, the star polymer molecule is called diversified.

[0159] - Comb polymer molecules consist of a main chain with two or more three-way branching points and linear side chains. If the arms are identical, the comb polymer molecule is called regular.

[0160] - The brush polymer molecules consist of a backbone with linear, unbranched side chains and in which one or more of the branching points have a four-way functionality or greater.

[0161] Throughout the description and claims of this specification, the words "include" and "contain" and variations of the words (such as "comprising" and "comprises") mean "including but not limited to", and are not intended to (and do not) exclude other components. On the other hand, the word "comprising" also encompasses but is not limited to the term "consisting of..."

[0162] Throughout the description and claims of this specification, the wording "obtainable" and "obtained" and variations of the wording mean "including but not limited to", and are not intended to (and do not) exclude other components. On the other hand, the wording "obtainable" also encompasses but is not limited to the term "obtained".

[0163] All concentrations are quoted in percent by weight and relate to the respective mixture as a whole, all temperatures are quoted in degrees Celsius and all temperature differences are quoted in differential degrees.

[0164] Details

[0165] The compound preferably comprises the following variables:

[0166] R1 to R6 each independently represent an alkyl group, linear or branched, optionally containing heteroatoms, preferably C1-C6 alkyl, particularly preferably C1-C4 alkyl, especially C1-C3 alkyl, very preferably C1 or C2,

[0167] R1 and R4 have the same meaning,

[0168] R1 and R4 both represent methyl or ethyl, preferably methyl,

[0169] R2, R3, R5 and R6 have the same meaning,

[0170] R2, R3, R5 and R6 all represent methyl or ethyl, preferably methyl.

[0171] x and y are each and independently an integer from 1 to 25, preferably from 1 to 10, more preferably 1, 2, 3, 4, 5 or 6, even more preferably 1-4, especially 1 or 2,

[0172] and

[0173] n and m are each and independently an integer from 1 to 25, preferably from 1 to 10, more preferably 1, 2, 3, 4, 5 or 6, even more preferably 1-4, especially 1 or 2,

[0174] x and y are the same integer,

[0175] x and y are both 1 or 2, preferably 2,

[0176] m and n are the same integer,

[0177] m and n represent 1 or 2.

[0178] The compounds of formula (I) can be prepared by methods known to those skilled in the art, preferably by methods similar to those described in CN110498734A.

[0179] The compounds can be used alone or in the form of a preparation in a polymerizable liquid crystal material comprising two or more, preferably three or more, compounds of formula I. Such a preparation can be, for example, 800, commercially available from EVONIK, Germany. Typically, such a formulation comprises at least one, preferably two, compounds of formula I selected from the following groups:

[0180]

[0181]

[0182] The compounds of formula (I) can preferably be used as surface active agents, preferably as surfactants, hydrophobizing agents, interface promoters, viscosity reducers, foam stabilizers or emulsifiers.

[0183] Preferably, the concentration of the compound of formula (I) in the polymerisable LC material is from 0.01 to 5 wt.-%, more preferably from 0.05 to 2 wt.-%, even more preferably from 0.1 to 1 wt.-%, based on the entire formulation.

[0184] In a preferred embodiment, the polymerisable LC material comprises one or more reactive mesogens selected from the group consisting of formula RMT,

[0185]

[0186] P is a polymerizable group,

[0187] Sp is a spacer group or a single bond,

[0188] r2 and r3 are independently 0, 1, 2, 3 or 4,

[0189] R 11 is P-Sp-, alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, preferably having 1 to 15 C atoms, which is more preferably optionally fluorinated,

[0190] A and B, in the case of multiple occurrences, independently of one another, denote an aromatic or cycloaliphatic 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-tetrahydronaphthalene-2,6-diyl, indane-2,5-diyl, bicyclooctylene or 1,4-cyclohexylene, in which one or two non-adjacent CH2 groups are optionally replaced by O and / or S, wherein these radicals are unsubstituted or substituted by 1, 2, 3 or 4 radicals L,

[0191] L is P-Sp-, F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)NR x R y , -C(=O)ORx , -C(=O)R x , -NR x R y , -OH, -SF5, or a straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy 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-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy group having 1 to 6 C atoms,

[0192] R x and R y independently of one another represent H or an alkyl radical having 1 to 12 C atoms,

[0193] Z 11 and Z 12 In the case of multiple occurrences, -O-, -S-, -CO-, -COO-, -OCO-, -S-CO-, -CO-S-, -O-COO-, -CO-NR are independently 00 -,-NR 00 -CO-, -NR 00 -CO-NR 000 , -NR 00 -CO-O-, -O-CO-NR 00 -, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH2CH2-, -(CH2) n1 , -CF2CH2-, -CH2CF2-, -CF2CF2-, -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,

[0194] Y 1 and Y 2 independently of each other represents H, F, Cl or CN,

[0195] n is 1, 2, 3 or 4, preferably 1 or 2, most preferably 1,

[0196] m is 0, 1, 2, 3 or 4, preferably 0 or 1, most preferably 0,

[0197] n1 is an integer of 1 to 10, preferably 1, 2, 3 or 4.

[0198] Preferred compounds of formula RMT are those selected from formula RMTa or RMTb,

[0199]

[0200]

[0201] in

[0202] P is a polymerizable group,

[0203] Sp is a spacer group or a single bond,

[0204] 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.

[0205] Preferred compounds of formula RMTa are selected from those of formula RMTa0 to RMTa6

[0206]

[0207] Among them, L, P, Sp, and R 11 As defined in formula RMT, r1 to r3 represent 1, 2, 3, or 4, preferably 1 or 2.

[0208] Preferred compounds of formula RMTa0 to RMTa6 are selected from the following formula

[0209]

[0210]

[0211] Where P 11 represents a group selected from heptadienyl, vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetanyl and epoxy, and very preferably represents an acrylate, methacrylate or oxetanyl, especially an acrylate or methacrylate, in particular an acrylate, 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 denotes alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, preferably having 1 to 15 C atoms, which is more preferably optionally fluorinated and L has on each occurrence one of the meanings given above for the formula RMT.

[0212] Particularly preferred are compounds of formula RMTa2, which are preferably selected from the following formulae:

[0213]

[0214]

[0215]

[0216]

[0217] Where R 11 has one of the meanings given above under the 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.

[0218] Preferred compounds of formula RMTb are those selected from formula RMTb0 to RMTb6

[0219]

[0220] Among them, L, P, Sp and R 11 As defined in formula RMT, r1 to r3 represent 1, 2, 3 or 4, preferably 1 or 2.

[0221] Preferred compounds of formula RMTb0 to RMTb6 are selected from the following formula

[0222]

[0223]

[0224] Where P 11 represents a group selected from heptadienyl, vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetanyl and epoxy, and very preferably represents an acrylate, methacrylate or oxetanyl, especially an acrylate or methacrylate, in particular an acrylate, 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 denotes alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, preferably having 1 to 15 C atoms, which is more preferably optionally fluorinated and L has on each occurrence one of the meanings given above for the formula RMT.

[0225] Particularly preferred are compounds of formula RMTb2, which are preferably selected from the following formulae:

[0226]

[0227]

[0228]

[0229]

[0230] Where R 11 has one of the meanings given above under the formula RMT. Preferably R 11 represents an alkyl group or an alkoxy group.

[0231] Further preferred are compounds of formula RMTb2-A1 selected from compounds of the following formula,

[0232]

[0233]

[0234]

[0235] Where R 11 has one of the meanings given above under the 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.

[0236] 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, in particular the polymerizable LC material comprises a combination of compounds of formula RMTa2-A4 and / or RMTa2-A5 and RMTb2-A3.

[0237] By using one or more compounds of formula RMT in the polymerizable LC material, the birefringence of the polymer film can be advantageously increased. The corresponding reflection bandwidth is related to the birefringence by the following formula:

[0238] Bandwidth = Δn*pitch,

[0239] It can be seen that by increasing the birefringence of cholesteric polymer films, a wider reflection bandwidth can be achieved.By utilizing compounds of formula RMT in polymerizable LC materials, the reflection bandwidth of the corresponding polymer films can be significantly broadened while also not adversely affecting film properties such as wet film crystallization or dewetting.

[0240] The concentration of the compound of formula RMT and its sub-formulae in the polymerisable LC material is preferably from 10% to 99%, more preferably from 20% to 95%, especially from 25% to 90%.

[0241] Compounds of formula RMT are commercially 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.

[0242] In a preferred embodiment, the polymerisable LC material comprises one or more di- or poly-reactive reactive mesogens, which are preferably selected from DRMs of the formula

[0243] P 1 -Sp 1 -MG-Sp 2 -P 2 DRM

[0244] in

[0245] P 1 and P 2 independently of one another represent a polymerizable group,

[0246] Sp 1 and Sp 2 are independently a spacer group or a single bond, and

[0247] MG is a rod-shaped mesogenic group, which is preferably selected from the formula MG

[0248] -(A 1 -Z 1 ) n -A 2 -MG

[0249] in

[0250] A 1 and A 2 represents, in the case of multiple occurrences, independently of one another, an aromatic or cycloaliphatic radical, which optionally contains one or more heteroatoms selected from N, O and S and which is optionally mono- or polysubstituted by L,

[0251] L is P-Sp-, F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)NR x R y 、-C(=O)OR x 、-C(=O)R x 、-NR x R y , -OH, -SF5, optionally substituted silanyl, aryl or heteroaryl (having 1 to 12, preferably 1 to 6 C atoms), and straight-chain 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,

[0252] R x and R y independently of one another represent H or an alkyl radical having 1 to 12 C atoms,

[0253] Z 1 In the case of multiple occurrences, it represents independently of one another -O-, -S-, -CO-, -COO-, -OCO-, -S-CO-, -CO-S-, -O-COO-, -CO-NR x -,-NR x -CO-, -NR x -CO-NR y , -NR x -CO-O-, -O-CO-NR x -, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -(CH2) n1 , -CF2CH2-, -CH2CF2-, -CF2CF2-, -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,

[0254] Y 1 and Y 2 independently of each other represents H, F, Cl or CN,

[0255] n is 1, 2, 3 or 4, preferably 1 or 2, most preferably 2,

[0256] n1 is an integer from 1 to 10, preferably 1, 2, 3 or 4,

[0257] However, there is a proviso that compounds of formula RMT are excluded from compounds of formula DRM.

[0258] Preferred group A 1 and A 2 Including, but not limited to, furan, pyrrole, thiophene, oxazole, thiazole, thiadiazole, imidazole, phenylene, cyclohexylene, bicyclooctylene, cyclohexenylene, pyridine, pyrimidine, pyrazine, azulene, indane, fluorene, naphthalene, tetralin, anthracene, phenanthrene and dithienothiophene, all of which are unsubstituted or substituted with 1, 2, 3 or 4 groups L as described above.

[0259] Particularly preferred groups A 1 and A 2Selected 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, indane-2,5-diyl, bicyclooctylene or 1,4-cyclohexylene, in which one or two non-adjacent CH2 groups are optionally replaced by O and / or S, wherein these groups are unsubstituted or substituted by 1, 2, 3 or 4 groups L as described above.

[0260] Preferred RMs of formula DRM are selected from the group consisting of formula DRMa

[0261]

[0262] in

[0263] P 0 is, in the case of a plurality of occurrences, independently of one another, a polymerizable group, preferably an acryloyl, methacryloyl, oxetanyl, epoxide, vinyl, heptadienyl, vinyloxy, propenyl ether or styryl group,

[0264] Z 0 is -COO-, -OCO-, -CH2CH2-, -CF2O-, -OCF2-, -C≡C-, -CH=CH-, -OCO-CH=CH-, -CH=CH-COO- or a single bond,

[0265] L has, identically or differently on each occurrence, one of the meanings given for L in the formula DRM and is preferably selected independently of one another in the case of multiple occurrences from F, Cl, CN or optionally halogenated alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 5 C atoms,

[0266] r is 0, 1, 2, 3, or 4,

[0267] x and y are independently 0 or the same or different integers from 1 to 12,

[0268] z is 0 or 1, and if the adjacent x or y is 0, then z is 0.

[0269] Very preferred RMs of formula DRM are selected from the following formulae:

[0270]

[0271]

[0272] Where P 0 , L, r, x, y and z are defined as in formula DRMa.

[0273] Particularly preferred are compounds of the formulae DRMa1, DRMa2 and DRMa3, in particular those of the formula DRMa1.

[0274] The concentration of di- or poly-reactive RMs (preferably those of formula DRM and subformulae thereof) in the RM mixture is preferably from 1% to 90%, very preferably from 10% to 80%.

[0275] In another embodiment, the RM mixture comprises one or more mono-reactive RMs. These additional mono-reactive RMs are preferably selected from the formula MRMs:

[0276] P 1 -Sp 1 -MG-R MRM

[0277] Where P 1 、Sp 1 and MG has the meaning given to it in Formula DRM,

[0278] R represents P-Sp-, F, Cl, Br, I, -CN, -NO2, -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, -SF5, optionally substituted silanyl, straight-chain 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,

[0279] X is halogen, preferably F or Cl, and

[0280] R x and R y are independently of one another H or alkyl having 1 to 12 C atoms, with the proviso, however, that compounds of the formula RMT are excluded from compounds of the formula MRM.

[0281] Preferably the compound of formula MRM is selected from the following formula.

[0282]

[0283]

[0284]

[0285] Where P 0 , L, r, x, y and z are as defined in formula DRMa,

[0286] R 0 is alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 or more, preferably 1 to 15, C atoms or represents Y 0 or P-(CH2) y -(O) z -,

[0287] X 0 Is -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR 01 -、-NR 01 -CO-、-NR 01 -CO-NR 01 -, -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,

[0288] Y 0 is F, Cl, CN, NO2, OCH3, OCN, SCN, SF5 or a mono-, oligo- or poly-fluorinated alkyl or alkoxy radical having 1 to 4 C atoms,

[0289] Z 0 is -COO-, -OCO-, -CH2CH2-, -CF2O-, -OCF2-, -CH=CH-, -OCO-CH=CH-, -CH=CH-COO- or a single bond,

[0290] A 0 is, in the case of multiple occurrences, independently of one another, 1,4-phenylene which is unsubstituted or substituted by 1, 2, 3 or 4 radicals L, or trans-1,4-cyclohexylene,

[0291] R 01,02 Independently of each other, H and R 0 or Y 0 ,

[0292] u and v are independently 0, 1, or 2,

[0293] w is 0 or 1,

[0294] The benzene ring and the naphthalene ring may be substituted by one or more identical or different groups L.

[0295] Especially preferred are compounds of the formula MRM1, MRM2, MRM3, MRM4, MRM5, MRM6, MRM7, in particular those having the formula MRM1, MRM4, MRM6 and MRM7.

[0296] The concentration of all mono-reactive RMs (including those with formula RMT) in the polymerisable LC material is preferably from 1% to 80%, very preferably from 5% to 50%.

[0297] In the formula DRM, MRM and preferred subformulae thereof, L is preferably selected from F, Cl, CN, NO2 or a straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy group having 1 to 12 C atoms (wherein the alkyl group is optionally perfluorinated), or P-Sp-.

[0298] Very 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-.

[0299] Preferably, the polymerisable LC material according to the present invention comprises one or more chiral compounds. These chiral compounds may be non-mesogenic compounds or mesogenic compounds. In addition, these chiral compounds, whether mesogenic or non-mesogenic, may be non-reactive, mono-reactive or poly-reactive.

[0300] Preferably, the chiral compounds used have a molecular weight of 20 μm each alone or in combination with one another. -1 or larger, preferably 40 μm -1 or larger, more preferably 60 μm -1 or larger, most preferably within 80 μm -1 or larger up to 260μm -1 The helical twisting forces (IHTP) are in the range of 1.1 to 1.5 % and 1.5 % respectively, in particular those disclosed in WO 98 / 00428. 总 I) absolute value.

[0301] Preferably, the non-polymerizable chiral compound is selected from compounds of formulae CI to C-III,

[0302]

[0303] The latter include the corresponding (S,S) enantiomers,

[0304] wherein E and F are each independently 1,4-phenylene or trans-1,4-cyclohexylene, v is 0 or 1, Z 0 is -COO-, -OCO-, -CH2CH2- or a single bond, and R is an alkyl, alkoxy or alkanoyl group having 1 to 12 C atoms.

[0305] Particularly preferred polymerisable LC materials comprise one or more chiral compounds, which compounds do not necessarily have to exhibit a liquid crystal phase.

[0306] Compounds of formula C-II and their synthesis are described in WO98 / 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.

[0307] Furthermore, commonly used chiral compounds are, for example, the commercially available R / S-5011, CD-1, R / S-811 and CB-15 (from Merck KGaA, Darmstadt, Germany).

[0308] The chiral compounds R / S-5011 and CD-1 mentioned above and the (further) compounds of the formulae CI, C-II and C-III exhibit very high helical twisting powers (HTP) and are therefore particularly useful for the purposes of the present invention.

[0309] The polymerizable LC material preferably comprises 1 to 5, in particular 1 to 3, very preferably 1 or 2 chiral compounds, preferably selected from the above formula C-II, in particular CD-1 and / or formula C-III and / or R-5011 or S-5011, very preferably the chiral compound is R-5011, S-5011 or CD-1.

[0310] Preferably, the polymerisable LC material comprises one or more non-reactive chiral compounds and / or one or more reactive chiral compounds, which compounds are preferably selected from mono-reactive and / or poly-reactive chiral compounds.

[0311] Suitable mesogenically reactive chiral compounds preferably comprise one or more ring elements, which are linked together by a direct bond or via a linking group, and wherein two of these ring elements optionally may be linked to each other directly or via a linking group, which linking group may be the same or different from the mentioned linking group. The ring element is preferably selected from a 4-membered ring, a 5-membered ring, a 6-membered ring or a 7-membered ring, preferably a 5-membered ring or a 6-membered ring.

[0312] Preferred monoreactive chiral compounds are selected from compounds of formula CRMa to CRMc.

[0313]

[0314]

[0315] in

[0316] P 0* represents a polymerizable group P,

[0317] Sp * represents the spacer group Sp,

[0318] A 0 and B 0 is, in the case of multiple occurrences, independently of one another, 1,4-phenylene which is unsubstituted or substituted by 1, 2, 3 or 4 radicals L as defined above, or trans-1,4-cyclohexylene,

[0319] X 1 and X 2 are independently -O-, -COO-, -OCO-, -O-CO-O- or a single bond,

[0320] Z 0* is, in the case of multiple occurrences, independently of one another, -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,

[0321] t is independently 0, 1, 2 or 3,

[0322] a is 0, 1, or 2,

[0323] b is 0 or an integer from 1 to 12,

[0324] z is 0 or 1,

[0325] and the naphthalene ring in the formula CRMa may be additionally substituted by one or more identical or different groups L,

[0326] in

[0327] L is independently of one another F, Cl, CN, haloalkyl having 1 to 5 C atoms, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy.

[0328] The compound of formula CRMa is preferably selected from the compounds of formula CRMa-1.

[0329]

[0330] Where X 2 , A 0 , B 0 , Z 0* , P 0* and b have the meanings given in the formula CRMa or one of the preferred meanings given above and below, and (OCO) represents -O-CO- or a single bond.

[0331] Particularly preferred compounds of formula CRM are selected from the following sub-formula:

[0332]

[0333]

[0334]

[0335] wherein R is -X as defined in formula CRM-a 2 -(CH2) x -P 0* , and the benzene ring and the naphthalene ring are unsubstituted or substituted by 1, 2, 3 or 4 groups L as defined above and below.

[0336] The compound of formula CRMb is preferably selected from the compounds of formulae CRMb-1 to CRMb-3,

[0337]

[0338] Where 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.

[0339] Preferred compounds of formula CRMb-1 are preferably selected from compounds of formula CRMb-1a and CRMb-1b,

[0340]

[0341] Where X 2 , Z 0* , P 0* and b have the meaning given in formula CRMa or one of the preferred meanings given above and below. Preferably, in the compounds of formula CRMb-1a and CRMb-1b, Z 0 represents OCOO, COO, OCO or a single bond. Preferably, in the compounds of formula CRMb-1a and CRMb-1b, X 2represents OCOO, OCO, COO or a single bond. Preferred are compounds of formula CRMb-1b selected from the following compounds,

[0342]

[0343] Where P 0* and b have the meanings given in formula CRMa or one of the preferred meanings given above and below.

[0344] Where P 0* The compound CRMb-1bI in which a represents an acrylate group at each occurrence and b represents 4 at each occurrence is particularly preferred and is commercially available under the trade name LC756 from BASF, Germany.

[0345] The compound of formula CRMc is preferably selected from the compounds of formula CRMc-1,

[0346]

[0347] Where 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.

[0348] Preferred compounds of formula CRMc-1 are preferably selected from compounds of formula CRMc-1a and CRMc-1b,

[0349]

[0350] Where X 2 , Z 0* , P 0* and b have the meaning given in formula CRMa 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. Preferred compounds of formula CRMc-1a are selected from the following compounds,

[0351]

[0352] Where P 0* and b have the meanings given in formula CRMa or one of the preferred meanings given above and below.

[0353] Compound CRMc-1aI (where P 0*Each occurrence of represents an acrylate group and b each occurrence represents 3 or 6, and X 2 represents O or a single bond at each occurrence) is particularly preferred.

[0354] The amount of chiral compound in the liquid-crystalline medium is preferably 1 to 20%, more preferably 1 to 15%, even more preferably 1 to 10%, and most preferably 3 to 7%, based on the weight of the total mixture.

[0355] In a preferred embodiment, the proportion of the polymerizable mesogenic compound as a whole in the polymerizable liquid crystal material according to the present invention is in the range of 30 to 99 wt %, more preferably in the range of 40 to 97 wt %, even more preferably in the range of 50 to 95 wt %.

[0356] Preferably, the proportion of the monoreactive liquid crystal compound, the direactive liquid crystal compound or the polyreactive liquid crystal compound (preferably selected from the compounds of the formula DRM, MRM 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 weight %, more preferably in the range of 40 to 99.9 weight %, even more preferably in the range of 50 to 99.9 weight %.

[0357] In a preferred embodiment, the proportion of the di- or poly-reactive polymerizable mesogenic compound as a whole in the polymerizable liquid crystal material according to the present invention is preferably in the range of 1 to 70 wt %, more preferably in the range of 2 to 60 wt %, even more preferably in the range of 3 to 50 wt %.

[0358] In another preferred embodiment, if present, the proportion of the monoreactive polymerizable mesogenic compound of formula MRM (which does not include the compound of formula RMT) as a whole in the polymerizable liquid crystal material according to the present invention is preferably in the range of 1 to 50 weight %, more preferably in the range of 2 to 45 weight %, even more preferably in the range of 5 to 40 weight %.

[0359] In another preferred embodiment, the proportion of the multi-reactive polymerizable mesogenic compound as a whole in the polymerizable liquid crystal material according to the present invention, if present, is preferably in the range of 1 to 30 wt.-%, more preferably in the range of 2 to 20 wt.-%, even more preferably in the range of 3 to 10 wt.-%.

[0360] In another preferred embodiment the polymerisable LC material does not comprise a polymerisable mesogenic compound having more than two polymerisable groups.

[0361] In another preferred embodiment, the polymerisable LC material comprises one or more monoreactive mesogenic compounds, preferably selected from formula MRM-1, MRM-4, MRM-6 and / or MRM-7, one or more direactive mesogenic compounds, preferably selected from formula DRMa-1.

[0362] If chiral compounds are used, the polymerizable LC materials should also have the property 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 materials is chosen such that their reflection wavelength is in the range within the infrared range of the electromagnetic spectrum, i.e. in the range from 300 nm to 900 nm, more preferably in the range from 350 to 850 nm. In particular, the reflection wavelength of the liquid crystal medium is in the range from 400 nm to 800 nm.

[0363] The polymerisable LC materials according to the invention are prepared in a conventional manner per se, for example by mixing one or more of the above-mentioned polymerisable compounds with one or more of the block copolymers described above and below and one or more chiral compounds (all as described above), and optionally with further liquid-crystalline compounds and / or additives and / or solvents.

[0364] In another preferred embodiment, the polymerisable LC material optionally comprises one or more further additives selected from the group consisting of: additional polymerisation initiators, antioxidants, surfactants, stabilizers, catalysts, sensitizers, inhibitors, chain transfer agents, co-reacted monomers, reactive viscosity reducers, surface active compounds, lubricants, wetting agents, dispersants, hydrophobic agents, adhesives, flow improvers, degassing agents or defoamers, deaerators, diluents, reactive diluents, auxiliaries, colourants, dyes, pigments and nanoparticles.

[0365] In a further preferred embodiment, the polymerisable LC material optionally comprises one or more additives selected from polymerisable non-mesogenic compounds (reactive viscosity reducing agents).The amount of these additives in the polymerisable LC material is preferably 0 to 30%, very preferably 0 to 25%.

[0366] The reactive viscosity reducers used are not only substances which are called reactive viscosity reducers in the actual sense, but also auxiliary compounds already mentioned above, which contain one or more additional reactive units or polymerizable groups P, such as hydroxyl groups, thiol groups or amino groups, through which reactions with polymerizable units of liquid crystal compounds can occur.

[0367] Substances that are generally capable of photopolymerization include, for example, mono-, di- or polyfunctional compounds containing at least one olefinic double bond. Examples are vinyl esters of carboxylic acids, such as vinyl esters of lauric acid, myristic acid, palmitic acid and stearic acid, and vinyl esters of dicarboxylic acids, such as vinyl esters of succinic acid, adipic acid, allyl and vinyl ethers of monofunctional alcohols and methacrylic and acrylates, such as allyl and vinyl ethers and methacrylic and acrylates of lauryl alcohol, myristyl alcohol, palmityl alcohol and stearyl alcohol, and diallyl and divinyl ethers of difunctional alcohols, such as diallyl and divinyl ethers of ethylene glycol and 1,4-butanediol.

[0368] Also suitable are, for example, methacrylates and acrylates of polyfunctional alcohols, in particular those which, in addition to hydroxyl groups, contain no further functional groups or at most ether groups. Examples of such alcohols are difunctional alcohols such as ethylene glycol, propylene glycol and their higher condensation representatives, for example diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, etc., butanediol, pentanediol, hexanediol, neopentyl glycol, alkoxylated phenolic compounds such as ethoxylated and propoxylated bisphenols, cyclohexanedimethanol, trifunctional and polyfunctional alcohols such as glycerol, trimethylolpropane, butanetriol, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol, and the corresponding alkoxylated, in particular ethoxylated and propoxylated alcohols.

[0369] Further suitable reactive viscosity reducing agents are polyester (meth)acrylates, which are (meth)acrylate esters of polyester polyols.

[0370] Examples of suitable polyester polyols are those which can be prepared by esterifying polycarboxylic acids, preferably dicarboxylic acids, with polyols, preferably diols. The starting materials for such hydroxyl-containing polyesters are known to those skilled in the art. Dicarboxylic acids which can be used are succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid and isomers and hydrogenation products thereof, and esterifiable or ester transferable derivatives of the acids, such as 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 glycol, cyclohexanedimethanol and polyglycols of the ethylene glycol and propylene glycol type.

[0371] In addition, suitable reactive viscosity reducing agents are 1,4-divinylbenzene, triallyl cyanurate, acrylic acid esters of tricyclodecenyl alcohol of the formula

[0372]

[0373] Also known as dihydrodicyclopentadienyl acrylate, and allyl esters of acrylic acid, methacrylic acid, and cyanoacrylic acid.

[0374] Among the reactive viscosity reducing agents mentioned by way of example, use is made in particular and in view of the preferred compositions mentioned above, of those comprising photopolymerizable groups.

[0375] This group includes, for example, diols and polyols, such as ethylene glycol, propylene glycol and higher condensed representatives thereof, for example diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol and the like, butanediol, pentanediol, hexanediol, neopentyl glycol, cyclohexanedimethanol, glycerol, trimethylolpropane, butanetriol, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol and the corresponding alkoxylated, in particular ethoxylated and propoxylated, alcohols.

[0376] Furthermore, the group includes, for example, alkoxylated phenolic compounds, such as ethoxylated and propoxylated bisphenols.

[0377] Furthermore, these reactive viscosity reducing agents may be, for example, epoxy or urethane (meth)acrylates.

[0378] Epoxy (meth)acrylates are, for example, those obtainable by reaction of epoxidized olefins or poly- or diglycidyl ethers, such as bisphenol A diglycidyl ether, with (meth)acrylic acid, as is known to the person skilled in the art.

[0379] Urethane (meth)acrylates are, in particular, the reaction products of hydroxyalkyl (meth)acrylates with poly- or diisocyanates, which are likewise known to the person skilled in the art.

[0380] Such epoxy and urethane (meth)acrylates are included as "mixed forms" in the compounds listed above.

[0381] If reactive viscosity reducing agents are used, their amount and properties must be matched to the respective conditions so that on the one hand a satisfactory desired effect, such as the desired color of the composition according to the invention, is achieved, but on the other hand the phase behavior of the liquid crystal composition is not excessively impaired. For example, low-crosslinked (high-crosslinked) liquid crystal compositions can be prepared using corresponding reactive viscosity reducing agents having a relatively low (high) number of reactive units per molecule.

[0382] For example, the group of diluents includes:

[0383] C1-C4-alcohols, for example methanol, ethanol, n-propanol, isopropanol, butanol, isobutanol, sec-butanol, and in particular C5-C12-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, di- and triethylene glycol and di- and tri-propylene glycol, ethers, for example methyl tert-butyl ether, 1,2-ethanediol mono- and di-methyl ether, 1 , 2-ethylene glycol mono- and di-ethyl ether, 3-methoxypropanol, 3-isopropoxypropanol, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), C1-C5-alkyl esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate and amyl acetate, aliphatic and aromatic hydrocarbons such as pentane, hexane, heptane, octane, isooctane, petroleum ether, toluene, xylene, ethylbenzene, tetralin, decalin, dimethylnaphthalene, white solvent naphtha, and Mineral oils, such as gasoline, kerosene, diesel and heating oil, and natural oils, such as olive, soybean, rapeseed, linseed and sunflower oils.

[0384] It is of course also possible to use mixtures of these diluents in the compositions according to the invention.

[0385] These diluents can also be mixed with water as long as there is at least partial miscibility. Examples of suitable diluents here are C1-C4-alcohols, such as methanol, ethanol, n-propanol, isopropanol, butanol, isobutanol and sec-butanol, diols, such as 1,2-ethanediol, 1,2- and 1,3-propylene glycol, 1,2-, 2,3- and 1,4-butanediol, di- and tri-ethylene glycol and di- and tri-propylene glycol, ethers, such as tetrahydrofuran and dioxane, ketones, such as acetone, methyl ethyl ketone and diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), and C1-C4-alkyl esters, such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate.

[0386] 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 polymerisable LC material.

[0387] Defoamers and deaerators (c1)), lubricants and flow aids (c2)), thermal or radiation curing aids (c3)), substrate wetting aids (c4)), wetting and dispersing aids (c5)), hydrophobic agents (c6)), adhesion promoters (c7)) and agents promoting scratch resistance (c8)) cannot be strictly demarcated from one another in terms of their action.

[0388] For example, lubricants and flow aids are often also used as defoamers and / or degassing agents and / or agents that promote scratch resistance. Radiation curing aids can also be used as lubricants and flow aids and / or degassing agents and / or substrate wetting aids. In various cases, some of these aids can also perform the function of adhesion promoters (c8)).

[0389] Corresponding to what has been said above, certain additives can therefore be classified into several groups c1) to c8) described below.

[0390] The defoamers in group c1) include silicon-free and silicon-containing polymers. Silicon-containing polymers are, for example, unmodified or modified polydialkylsiloxanes or branched, comb or block copolymers comprising polydialkylsiloxane and polyether units, the latter being obtainable from ethylene oxide or propylene oxide.

[0391] Degassing agents from group c1) include, for example, organic polymers, such as polyethers and polyacrylates, dialkylpolysiloxanes, in particular dimethylpolysiloxanes, organomodified polysiloxanes, such as arylalkyl-modified polysiloxanes, and fluorosilicones.

[0392] The action of defoamers is essentially based on preventing foam formation or destroying already formed foam. In a medium to be degassed, for example in the composition according to the invention, defoamers essentially act by promoting the merging of subdivided gas or air bubbles to give larger bubbles and thus accelerate the escape of gas (or air). Since defoamers can often also be used as deaerators and vice versa, these additives have been included together in group c1).

[0393] For example, such additives are available from Tego Foamex 800, Foamex805, Foamex 810, Foamex 815, Foamex 825, Foamex 835, Foamex840, Foamex 842, Foamex 1435, Foamex 1488, Foamex 1495, Foamex3062, Foamex 7447, Foamex 8020, Foamex N, Foamex K 3, Antifoam 2-18、 Antifoam 2-18、 Antifoam 2-57、 Antifoam 2-80、 Antifoam 2-82、 Antifoam 2-89、 Antifoam2-92、 Antifoam 14、 Antifoam 28、 Antifoam 81、 Antifoam D90、 Antifoam 93、 Antifoam 200、 Antifoam 201、 Antifoam202、 Antifoam 793、 Antifoam 1488、 Antifoam 3062、 5803、 5852、 5863、 7008、 Antifoam 1-60、 Antifoam 1-62、 Antifoam 1-85、 Antifoam 2-67、 AntifoamWM 20、 Antifoam 50、 Antifoam 105、 Antifoam730、 AntifoamMR 1015、 Antifoam MR 1016、 Antifoam 1435、 Antifoam N、 Antifoam KS 6、 Antifoam KS10、 Antifoam KS 53、 Antifoam KS 95、 Antifoam KS100、 Antifoam KE 600, Antifoam KS 911, Antifoam MR 1000, Antifoam KS1100, Airex 900, Airex 910, Airex 931, Airex 935, Airex 936, Airex 960, Airex970, Airex980 and Airex 985 is commercially available from BYK and Commercially available.

[0394] The auxiliaries in group c1) are optionally used in a proportion of about 0 to 3.0% by weight, preferably about 0 to 2.0% by weight, based on the total weight of the polymerisable LC material.

[0395] In group c2), lubricants and flow aids generally include silicon-free and silicon-containing polymers, such as polyacrylates or 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 (fluoro)alkyl groups, the former being most frequently used.

[0396] The polyether groups in the correspondingly modified polysiloxanes are usually composed of ethylene oxide and / or propylene oxide units. In general, the higher the proportion of these alkylene oxide units in the modified polysiloxanes, the more hydrophilic the resulting product is.

[0397] For example, such additives are available from Tego Glide 100, Glide ZG 400, Glide 406, Glide 410, Glide 411, Glide 415, Glide 420, Glide 435, Glide440, Glide 450, Glide A 115, Glide B 1484 (can also be used as a defoamer and deaerator), Flow ATF, Flow 300, Flow 460, Flow 425 and Flow ZFS 460 is commercially available. Suitable radiation curable lubricants and flow aids, which may also be used to improve scratch resistance, are products Rad 2100, Rad 2200, Rad 2500, Rad 2600 and Rad 2700, also available from TEGO.

[0398] Such additives are also available from BYK as get.

[0399] Such additives are also available from 3M, for example

[0400] Such adjuvants are also available, for example, from Cytonix, such as or

[0401] Such auxiliaries are also commercially available, for example, from Merck KGaA, such as 2300 and 2500.

[0402] The auxiliaries in group c2) are optionally used in an amount of about 0 to 3.0 wt.-%, preferably about 0 to 2.0 wt.-%, based on the total weight of the polymerisable LC material.

[0403] In group c3), radiation curing auxiliaries include, in particular, polysiloxanes with terminal double bonds, for example, components whose terminal double bonds are acrylate groups. Such auxiliaries can be crosslinked by actinic or, for example, electron radiation. These auxiliaries usually combine several properties together. In the uncrosslinked state, they can be used as defoamers, degassing agents, lubricants and flow aids and / or substrate wetting aids, while in the crosslinked state, they particularly improve the scratch resistance of, for example, coatings or films that can be prepared using the composition according to the invention. Precisely the improvement of the gloss properties of, for example, those coatings or films is essentially considered to be the result of the action of these auxiliaries as defoamers, degassing agents and / or lubricants and flow aids (in the uncrosslinked state).

[0404] Examples of suitable radiation curing aids are the products available from TEGO Rad 2100, Rad2200, Rad 2500, Rad 2600 and Rad2700 and products available from BYK

[0405] The heat-curing auxiliaries in group c3) contain, for example, primary OH groups which are capable of reacting, for example, with isocyanate groups of the adhesive.

[0406] Examples of useful thermal curing aids are the products available from BYK and

[0407] The auxiliaries 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 polymerisable LC material.

[0408] The substrate wetting assistants in group c4) are used in particular to improve 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 improvement in the lubrication and flow behavior of such printing inks or coating compositions, which is usually accompanied, has an influence on the appearance of the (for example crosslinked) prints or coatings produced.

[0409] A wide variety of such additives are available, for example, from Tego Wet KL 245, Wet 250, Wet 260 and Wet ZFS 453 and from BYK and Commercially available.

[0410] The auxiliaries in group c4) are optionally used in a proportion of about 0 to 3.0% by weight, preferably about 0 to 1.5% by weight, based on the total weight of the liquid-crystal composition.

[0411] The wetting and dispersing assistants in group c5) serve in particular to prevent flooding and floating and also sedimentation of the pigments and are therefore, if necessary, particularly suitable for use in pigmented compositions.

[0412] These additives stabilize the pigment dispersions substantially by electrostatic repulsion and / or steric hindrance of the pigment particles comprising these additives, wherein in the latter case the interaction of the additives with the surrounding medium (eg binder) plays a major role.

[0413] Since the use of such wetting and dispersing assistants is common practice, for example, in the field of printing ink and coating technology, the selection of suitable assistants of this type generally does not present any difficulties to the person skilled in the art if they are used at all.

[0414] Such wetting and dispersing aids are available, for example, from Tego as Dispers 610, Dispers610S, Dispers 630, Dispers 700, Dispers 705, Dispers710, Dispers 720W, Dispers 725W, Dispers 730W, Dispers735W and Dispers 740W and from BYK

[0415]

[0416] and Commercially available.

[0417] The amount of the auxiliaries in group c5) is used based on the average molecular weight of the auxiliaries. A preliminary experiment is therefore advisable in any case, but this can be easily accomplished by a person skilled in the art.

[0418] The hydrophobic agents in group c6) can be used to impart hydrophobic properties to printed products or coatings produced, for example, using the composition according to the invention. This prevents or at least greatly suppresses swelling due to water absorption and thus, for example, changes in the optical properties of such printed products or coatings. In addition, when the composition is used as a printing ink, for example in offset printing, water absorption can thereby be prevented or at least greatly reduced.

[0419] Such hydrophobic agents are available, for example, from Tego Phobe WF, Phobe 1000, Phobe 1000S, Phobe 1010, Phobe 1030, Phobe 1010, Phobe1010, Phobe 1030, Phobe1040, Phobe 1050, Phobe 1200, Phobe 1300, Phobe 1310 and Phobe 1400 is commercially available.

[0420] The auxiliaries 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 polymerisable LC material.

[0421] The further adhesion promoters from group c7) serve to improve the adhesion of the two interfaces in contact. It is immediately apparent from this that substantially the only part of the effective adhesion promoter is that which is located at one or the other interface or at both interfaces. If, for example, 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 that the substrate must be pretreated with the adhesion promoter (also referred to as priming), i.e., the substrate is given modified chemical and / or physical surface properties.

[0422] If the substrate has been primed with a primer, this means that the interfaces in contact are those of the primer on the one hand and the printing ink or coating composition or lacquer on the other hand. In this case, not only the adhesion properties between substrate and primer, but also the adhesion properties between substrate and printing ink or coating composition or lacquer play a role in the adhesion of the entire multilayer structure on the substrate.

[0423] Adhesion promoters in a broader sense may also be mentioned as substrate wetting assistants already listed under group c4), but these generally do not have the same adhesion-promoting capabilities.

[0424] The diversity of adhesion promoter systems is not surprising in view of the widely varying physical and chemical properties of substrates and of the printing inks, coating compositions and lacquers intended for, for example, printing or coating thereof.

[0425] Adhesion promoters based on silanes are, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N-aminoethyl-3-aminopropyltrimethoxysilane, N-aminoethyl-3-aminopropylmethyldimethoxysilane, N-methyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane and vinyltrimethoxysilane. These and other silanes are available from Hüls, for example under the trade name Commercially available.

[0426] Generally, the corresponding technical information from the manufacturers of such additives should be used or the person skilled in the art can determine this information in a simple manner by corresponding preliminary experiments.

[0427] If, however, these additives are to be added as auxiliaries from group c7) to the polymerisable LC material according to the invention, their proportion optionally corresponds to about 0 to 5.0 wt.-%, based on the total weight of the polymerisable 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. For this case, corresponding technical information is generally available from the manufacturers of such additives or can be determined in a simple manner by a person skilled in the art by corresponding preliminary experiments.

[0428] The auxiliaries in group c8) for improving scratch resistance include, for example, the above-mentioned products available from Tego Rad 2100, Rad 2200, Rad 2500, Rad 2600 and Rad2700.

[0429] The quantitative data given for group c3) also apply to these auxiliaries, ie these additives are optionally 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.

[0430] Examples of other light, heat and / or oxidation stabilizers which may be mentioned are the following substances:

[0431] 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-di(octadecyl)-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenol with linear or branched side chains, such as such as 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(1′-methylundecane-1′-yl)phenol, 2,4-dimethyl-6-(1′-methylheptadecan-1′-yl)phenol, 2,4-dimethyl-6-(1′-methyltridecane-1′-yl)phenol and mixtures of these compounds, alkylthiomethylphenols such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol and 2,6-di(dodecyl)thiomethyl-4-nonylphenol,

[0432] Hydroquinones and alkylated hydroquinones, such as 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydrocrainone, 2,6-diphenyl-4-octadecyloxyphenol, 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,

[0433] Tocopherols, such as alpha-tocopherol, beta-tocopherol, gamma-tocopherol, delta-tocopherol and mixtures of these compounds, and tocopherol derivatives, such as tocopherol acetate, succinate, nicotinate and polyoxyethylene succinate ("tocofersolate"),

[0434] 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,

[0435] Alkylenebisphenols, for example 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- methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tri(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecyl-mercaptobutane, ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene, bis(3-tert-butyl-4-hydroxy-5-methylphenyl) [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-mercaptobutane and 1,1,5,5-tetrakis(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane,

[0436] O-, N- and S-benzyl compounds, such as 3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether, 4-hydroxy-3,5-dimethylbenzylthioglycolate octadecyl, 4-hydroxy-3,5-di-tert-butylbenzylthioglycolate 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 isooctyl-3,5-di-tert-butyl-4-hydroxybenzylthioglycolate,

[0437] 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,

[0438] Triazine compounds, such as 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-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,

[0439] Benzylphosphonates, such as dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and dioctadecyl 5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate,

[0440] Acylaminophenols, such as 4-hydroxylauroylanilide, 4-hydroxystearylanilide and octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate,

[0441] for example propionates and acetates of monohydric or polyhydric alcohols, such as methanol, ethanol, n-octanol, isooctyl alcohol, octadecanol, 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)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]-octane,

[0442] 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,

[0443] Ascorbic acid (vitamin C) and ascorbic acid derivatives, such as ascorbyl palmitate, ascorbyl laurate and ascorbyl stearate, as well as ascorbyl sulfate and ascorbyl phosphate,

[0444] 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-toluenesulfamoyl)diphenylamine, N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyl diphenylamine, 4-isopropoxy diphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octyl-substituted diphenylamines such as p,p′-di-tert-octyl diphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, 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(phenylamino)propane, (o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine, tert-octyl-substituted N-phenyl-1-naphthylamine, mixtures of mono- and di-alkylated tert-butyl / tert-octyl diphenylamines, mixtures of mono- and di-alkylated nonyl diphenylamines, mixtures of mono- and di-alkylated dodecyl diphenylamines, mixtures of mono- and di-alkylated isopropyl / isohexyl diphenylamines mixtures of mono- and di-alkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mixtures of mono- and di-alkylated tert-butyl / tert-octyl phenothiazines, mixtures of mono- and di-alkylated tert-octyl phenothiazines, 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,

[0445] Phosphines, phosphites and phosphonites, such as triphenylphosphine, triphenylphosphite, diphenylalkylphosphites, phenyldialkylphosphites, tris(nonylphenyl)phosphite, trilaurylphosphite, trioctadecylphosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, diisodecylpentaerythritol diphosphite, 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 -tri(tert-butylphenyl))pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4′-diphenylene diphosphite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphocine, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,g]-1,3,2-dioxaphosphocine, bis(2,4-di-tert-butyl-6-methylphenyl)methylphosphite and bis(2,4-di-tert-butyl-6-methylphenyl)ethylphosphite,

[0446] 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-amyl-2′-hydroxyphenyl)benzotriazole, 2-(3,5′-bis-(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole, a mixture of 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]-2′-hydroxyphenyl)-5-chlorobenzotriazole ]-2′-hydroxyphenyl)benzotriazole, 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]; the fully esterified product of 2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazole and polyethylene glycol 300;

[0447] Sulfur-containing peroxide scavengers and sulfur-containing antioxidants, such as esters of 3,3′-thiodipropionic acid, for example the lauryl, stearyl, myristyl and tridecyl esters, mercaptobenzimidazole and the zinc salt of 2-mercaptobenzimidazole, dibutyl zinc dithiocarbamate, dioctadecyl disulfide and pentaerythritol tetrakis(β-dodecylmercapto)propionate,

[0448] 2-Hydroxybenzophenones, such as the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxy and 2′-hydroxy-4,4′-dimethoxy derivatives,

[0449] Esters of unsubstituted and substituted benzoic acid, 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,

[0450] 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)-n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, condensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, condensation product of N,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate, tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate, 1,1′-(1,2-ethyl)-2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine )bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis(1,2,2,6,6-pentamethylpiperidin-4-yl)2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate, 3-n-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, N,N′-bis(2 , 2,6,6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, condensation products of 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 of 2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-pentamethylpiperidin-4-yl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]-decane-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-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidin, a condensation product of N,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensation product of 1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine, a condensation product of 4-butylamino-2,2,6,6-tetramethyl piperidine, 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-oxo-spiro[4.5]-decane, condensation products of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane and epichlorohydrin, condensation products of 4-amino-2,2,6,6-tetramethylpiperidine with tetrakishydroxymethylacetylene diurea and poly(methoxypropyl-3-oxy)-[4(2,2,6,6-tetramethyl)piperidinyl]-siloxane,.

[0451] Oxamides, such as 4,4′-dioctyloxyoxalanilide, 2,2′-diethoxyoxalanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide, 2,2′-di(dodecyloxy)-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxalanilide, N,N′-bis(3-dimethylaminopropyl)oxalamide, 2-ethoxy-5-tert-butyl-2′-ethoxanilide and mixtures thereof with 2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, and mixtures of o- and p-methoxy-disubstituted oxalanilides and mixtures of o- and p-ethoxy-disubstituted oxalanilides, and

[0452] 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-(dodecyloxy / tridecyloxy-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-(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.

[0453] In another preferred embodiment, the polymerisable LC material comprises preferably selected from One or more specific antioxidant additives from the VIZOL series, such as antioxidants available from Ciba, Switzerland. and

[0454] In another preferred embodiment, the polymerisable LC material comprises one or more, more preferably two or more photoinitiators, for example selected from commercially available or (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. Other preferred photoinitiators are selected from oxime ester photoinitiators, for example from the commercially available OXE02 (Ciba AG), NCI 930, N1919T (Adeka), SPI-03 or SPI-04 (Samyang) or TRI-PBG-304 (Changzhou Tronly New Electronic Materials Co. Ltd).

[0455] The concentration of the polymerisation initiator as a whole in the polymerisable LC material is preferably 0.5-10%, very preferably 1-9%, more preferably 3-7%.

[0456] In a preferred embodiment, the polymerisable LC material is dissolved in a suitable solvent, which is preferably selected from organic solvents.

[0457] The solvent is 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 acetoacetate; 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 di- or tri-chloromethane; glycols or their esters such as PGMEA (propylene glycol monomethyl ether acetate), γ-butyrolactone. It is also possible to use binary, ternary or higher mixtures of the above solvents. In particular, for multi-layer application, methyl isobutyl ketone is a solvent preferably used.

[0458] In case the polymerisable LC material comprises one or more solvents, the total concentration of all solids (including RMs) in the solvent is preferably from 10% to 60%, more preferably from 20% to 50%, especially from 30% to 45%.

[0459] Preferably, the polymerisable LC material comprises, in addition to one or more compounds of formula I and the corresponding subformulae

[0460] a) one or more poly- or di-reactive polymerizable mesogenic compounds, preferably selected from compounds of the formula DRM and the corresponding sub-formulae,

[0461] b) optionally one or more polymerizable mesogenic compounds of formula RMT and corresponding subformulae,

[0462] c) optionally one or more chiral mesogenic compounds, preferably selected from the compounds of formulae CRMa to CRMc (more preferably CRMb) and subformulae thereof,

[0463] d) optionally one or more monoreactive mesogens, preferably selected from compounds of formula MRM and corresponding subformulae,

[0464] e) optionally one or more photoinitiators,

[0465] f) optionally one or more antioxidant additives,

[0466] g) optionally one or more adhesion promoters,

[0467] h) optionally one or more other surfactants,

[0468] i) optionally one or more monoreactive, direactive or polyreactive polymerizable non-mesogenic compounds,

[0469] j) optionally one or more dyes showing an absorption maximum at the wavelength used to initiate photopolymerization,

[0470] k) optionally one or more chain transfer agents,

[0471] l) optionally one or more other stabilizers,

[0472] m) optionally one or more lubricants and flow aids, and

[0473] n) optionally one or more diluents,

[0474] o) optionally a non-polymerizable nematic component,

[0475] p) optionally one or more organic solvents.

[0476] More preferably, the polymerisable LC material comprises:

[0477] a) one or more compounds of the formula I or the corresponding preferred subformulae thereof,

[0478] b) optionally one or more, preferably two or more, polymerizable mesogenic compounds of formula RMT and corresponding subformulae, preferably selected from compounds of subformulae RMTa2-A4 and / or RMTa2-A5 and / or RMTb-A3,

[0479] c) one or more, preferably two or more, direactive polymerizable mesogenic compounds, preferably selected from compounds of formula DRMa-1,

[0480] d) optionally one or more, preferably two or more, monoreactive polymerizable mesogenic compounds, preferably selected from compounds of formula MRM-1 and / or MRM-4 and / or MRM-6 and / or MRM-7,

[0481] e) optionally one or more chiral mesogenic compounds of formula CRMb, in particular of formula CRMb-1bI,

[0482] f) optionally one or more antioxidant additives, preferably selected from esters of unsubstituted and substituted benzoic acids, in particular 1076, and if present, preferably 0.01-2 wt. %, very preferably 0.05-1 wt. %,

[0483] g) optionally one or more photoinitiators, preferably a carbazole oxime ester photoinitiator,

[0484] h) optionally one or more organic solvents, preferably methyl isobutyl ketone.

[0485] The present invention further relates to a method for preparing a polymer film by

[0486] - providing a layer of polymerisable LC material as described above and below onto a substrate,

[0487] - polymerizing the polymerizable components of the polymerizable LC material by photopolymerization, and

[0488] - optionally removing the polymerized LC material from the substrate, and / or optionally providing the polymerized LC material onto another substrate.

[0489] The polymerizable LC material may be coated or printed onto the substrate, for example by spin coating, printing or other known techniques, and the solvent evaporated off prior to polymerisation. In most cases it will be appropriate to heat the mixture to facilitate evaporation of the solvent.

[0490] The polymerisable LC material can be applied to the substrate by conventional coating techniques such as spin coating, rod coating or doctor blade coating. The polymerisable LC material can also be applied to the substrate by conventional printing techniques known to the person skilled in the art, such as for example screen printing, offset printing, roll-to-roll printing, letterpress printing, gravure printing, rotogravure printing, flexographic printing, gravure printing, pad printing, heat seal printing, inkjet printing or printing with the aid of a stamp or printing plate.

[0491] Suitable substrate materials and substrates are known to the person skilled in the art and are described in the literature, such as conventional substrates used, for example, 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 naphthalate (PEN), polyvinyl alcohol (PVA), polycarbonate (PC), triacetyl cellulose (TAC), or cycloolefin polymers (COP), or known color filter materials, in particular triacetyl cellulose (TAC), cycloolefin polymers (COP) or known color filter materials.

[0492] The polymerisable LC material preferably shows a uniform alignment throughout the layer.Preferably, the polymerisable LC material shows a uniform planar alignment, a uniform homeotropic alignment, a uniform cholesteric or patterned alignment.

[0493] The Friedel-Creagh-Kmetz rule compares the RM layers (γ RM ) and substrate (γ s ) can be used to predict whether the mixture will adopt a planar or homeotropic alignment:

[0494] If γ RM >γ s , then the reactive mesogenic compound will show a homeotropic alignment if γ RM <γ s , then the reactive mesogen compound will show plane alignment.

[0495] Without being bound by theory, when the surface energy of the substrate is relatively low, the intermolecular forces between reactive mesogens are stronger than the forces across the RM-substrate surface, and therefore, the reactive mesogens align perpendicular to the substrate (homeotropic alignment) to maximize the intermolecular forces.

[0496] Homeotropic 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 homeotropic alignment layer. The polar head of the amphiphilic material is chemically bonded to the substrate, and the hydrocarbon tail is pointed perpendicularly to the substrate. The intermolecular interactions between the amphiphilic material and the RM promote homeotropic alignment. Commonly used amphiphilic surfactants are described above.

[0497] Another method for promoting homeotropic alignment is to apply corona discharge treatment to the plastic substrate, thereby generating alcohol or ketone functional groups on the substrate surface. These polar groups can interact with polar groups present in RMs or surfactants to promote homeotropic alignment.

[0498] When the surface tension of the substrate is greater than that of the RM, the forces across the interface dominate. If the reactive mesogens are aligned parallel to the substrate so that the long axis of the RM can interact with the substrate, the interfacial energy is minimized. Unidirectional planar alignment can be promoted by coating the substrate with a polyimide layer and then rubbing the alignment layer with a velvet cloth.

[0499] Other suitable surface alignment layers are known in the art, such as rubbed polyimides or alignment layers prepared, for example, by photoalignment, as described in US 5,602,661, US 5,389,698 or US 6,717,644.

[0500] In general, an overview of alignment techniques is given by I. Sage in "Thermotropic Liquid Crystals", edited by GWGray, 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 1-63. A further overview of alignment materials and techniques is given by J. Cognard, Mol. Cryst. Liq. Cryst. 78, Supplement 1 (1981), pages 1-77.

[0501] To prepare 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.

[0502] The photopolymerization can be carried out in one step. It is also possible to photopolymerize or crosslink the compounds that did not react in the first step in a second step ("final curing").

[0503] In a preferred method of preparation, a polymerisable LC material is coated on a substrate and then photopolymerised by exposure to actinic radiation as described, for example, in WO 01 / 20394, GB 2,315,072 or WO 98 / 04651.

[0504] Photopolymerization of the LC material is preferably achieved by exposing it to actinic radiation. Actinic radiation refers to 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, in particular with UV light. As a source for actinic radiation, for example a single UV lamp or a group of UV lamps can be used. When using high lamp powers, the curing time can be reduced. Another feasible source for optical radiation is a laser, such as for example a UV laser, an IR laser or a visible laser. Another possible source for optical radiation is an LED lamp.

[0505] The curing time depends inter alia on the reactivity of the polymerisable LC material, the thickness of the coating layer, the type of polymerisation initiator and the power of the UV lamp. The curing time is preferably ≤5 minutes, very preferably ≤3 minutes, most preferably ≤1 minute. For mass production, a short curing time of ≤30 seconds is preferred.

[0506] Suitable UV radiation power is preferably between 5 and 200 mWcm -2 in the range of 50 to 175 mWcm -2 and most preferably in the range of 100 to 150 mWcm -2 within the range.

[0507] Suitable UV doses are preferably in the range of 25 to 7200 mJcm, depending on the UV radiation applied and as a function of time. -2 In the range of 100 to 7200 mJcm -2 and most preferably in the range of 200 to 7200 mJcm -2 within the range.

[0508] The photopolymerization is preferably carried out in an inert gas atmosphere, preferably a heated nitrogen atmosphere, but polymerization in air is also possible.

[0509] The photopolymerization is preferably carried out at a temperature of 1 to 70°C, preferably 5 to 50°C, even more preferably 15 to 30°C.

[0510] The polymerized LC film according to the present invention has good adhesion to plastic substrates, in particular to TAC, COP and color filters. It can therefore be used as an adhesive or base coating for subsequent LC layers that would otherwise not adhere well to the substrate.

[0511] For optical applications of the polymer film, it preferably has a thickness of 0.5 to 10 μm, preferably 0.5 to 5 μm, in particular 0.5 to 3 μm.

[0512] The optical retardation (δ(λ)) of the polymer film as a function of the wavelength (λ) of the incident light beam is given by the following equation (7):

[0513] δ(λ)=(2πΔn·d) / λ (7)

[0514] where (Δn) is the birefringence of the film, (d) is the thickness of the film and λ is the wavelength of the incident beam.

[0515] According to Snellius's law, the birefringence as a function of the direction of the incident beam is defined as

[0516] Δn=sinΘ / sinΨ (8)

[0517] where sinΘ is the angle of incidence or the tilt angle of the optical axis in the film, and sinΨ is the corresponding reflection angle.

[0518] 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 in the film (see Berek compensator). Thus, the skilled person realizes that different optical retardations or different birefringence can be induced by adjusting the orientation of the liquid crystal molecules in the polymer film.

[0519] 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.

[0520] 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.

[0521] 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 are particularly suitable for multilayer applications due to their improved dewetting properties. In this way, stacks of optical films or preferably polymerized LC films can be prepared.

[0522] 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), in decorative images, for the preparation of liquid crystals or effect pigments, and in particular in reflective films with spatially varying reflection colors, for example for decorative multicolor images, information storage or security purposes, such as in non-forgeable documents such as identity cards or credit cards, banknotes, etc.

[0523] The polymerized LC films according to the invention can be used in displays of the transmissive or reflective type. They can be used in conventional OLED displays or LCDs, in particular LCDs.

[0524] The invention has been described in the context of particular reference to preferred embodiments thereof. It should be understood that various changes and modifications can be made therein without departing from the spirit and scope of the invention.

[0525] Many of the compounds or mixtures thereof mentioned above and below are commercially available. All these compounds are known or can be prepared by methods known per se as described in the literature (for example in standard works such as Houben-Weyl, Methoden der Organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart), precisely under reaction conditions known and suitable for the described reactions. Variants known per se and not mentioned here can also be used here.

[0526] It should be understood that the aforementioned embodiments of the present invention may be modified while still falling within the scope of the present invention. Unless otherwise specified, alternative features for the same, equivalent or similar purposes may replace each feature disclosed in this specification. Therefore, unless otherwise specified, each feature disclosed is merely an example of a general concept of an equivalent or similar feature.

[0527] All features disclosed in this specification may be combined in any combination except where at least some of such features and / or steps are mutually exclusive. In particular, preferred features of the present invention are applicable to all aspects of the present invention and may be combined in any combination. Likewise, features described in non-essential combinations may be used separately (not in combination).

[0528] It should be understood that many of the features described above, particularly the features of the preferred embodiments, are inventive in themselves, and not just as part of an embodiment of the present invention. Independent protection for these features may be sought in addition to or in lieu of any invention currently claimed.

[0529] 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. DETAILED DESCRIPTION

[0530] Example 1

[0531] The following mixture was prepared:

[0532] Mixture 1

[0533] Surfactant (see Table 1 below) 1.000%

[0534] Irganox 1076 0.080%

[0535] TR-PBG-304 6.80%

[0536]

[0537] Irganox 1076, LC756 and LC242 are commercially available from BASF, Germany; TR-PBG-304 is commercially available from Changzhou Tronly New Electronic Materials

[0538] Co.Ltd.

[0539] Mixture 2

[0540] Surfactant (see Table 1 below) 1.000%

[0541] Irganox 1076 0.080%

[0542] TR-PBG-304 6.80%

[0543] DK-756 5.00%

[0544]

[0545]

[0546] Irganox 1076, LC756 and LC242 are commercially available from BASF, Germany; TR-PBG-304 is commercially available from Changzhou Tronly New Electronic Materials Co. Ltd; DK-756 is commercially available from Henan Daken Chemical Co. Ltd.

[0547] Mixture 1 and Mixture 2 were doped with surfactants at the above concentrations to prepare comparative formulations and formulations 2 and 9 according to the present invention. The formulation compositions are summarized in Table 1 below.

[0548] Table 1 - Preparation composition

[0549]

[0550] Additives of the Tego series and Dynol series are commercially available from Evonik Tego, Germany. Polyfox PF-656 is commercially available from Omnova Solutions Inc., USA.

[0551] Application Example 1

[0552] Polymer films were produced from Formulations 1 to 7 using the following method:

[0553] Formulations 1-7 were spin coated on polyimide rubbed glass at 3000 rpm for 30 seconds.

[0554] Anneal the film at 60 °C for 60 s

[0555] The film was cured using a DELO 365nm LED lamp (70mW cm -2 , 10s under nitrogen)

[0556] Spin coat a second layer of Formulation 1-7 on top of the first cured layer

[0557] The film was annealed at a given temperature for 60 s.

[0558] The film was cured using a DELO 365nm LED lamp (70mW cm -2 , 10s under nitrogen)

[0559] After initial curing, each multilayer film was visually inspected for RM alignment and visually visible haze and noted in the table below. After the second annealing step, each film was visually inspected for dewetting and recorded in Table 2 below.

[0560] Table 2 – Polymer film detection

[0561]

[0562] O passed / good X failed / bad Δ medium / average

[0563] As can be seen from the table, using Dynol 800 as a surfactant provides an extremely wide annealing temperature range that can be used to achieve RM alignment without causing any dewetting. This surfactant also provides alignment to the upper layer without the need for an additional alignment layer.

[0564] Application Example 2

[0565] Polymer films were produced from Formulations 8 to 14 using the following method:

[0566] Formulations 8-14 were spin coated on polyimide rubbed glass at 3000 rpm for 30 sec. The films were annealed at 60 °C for 60 sec.

[0567] The film was cured using a DELO 365nm LED lamp (70mW cm -2 , 10s under nitrogen)

[0568] Spin coat a second layer of formulation 8-14 on top of the first cured layer

[0569] The film was annealed at a given temperature for 60 s.

[0570] The film was cured using a DELO 365nm LED lamp (70mW cm -2 , 10s under nitrogen)

[0571] After initial curing, each multilayer film was visually inspected for RM alignment and visually visible haze and noted in the table below. After the second annealing step, each film was visually inspected for dewetting and recorded in Table 3 below.

[0572] Table 3 – Polymer film detection

[0573]

[0574]

[0575] O passed / good X failed / bad Δ medium / average

[0576] As can be seen from the table, using Dynol 800 as a surfactant provides an extremely wide annealing temperature range that can be used to achieve RM alignment without causing any dewetting. This surfactant also provides alignment to the upper layer without the need for an additional alignment layer.

Claims

1. A polymerisable LC material comprising one or more reactive mesogenic compounds and one or more compounds of formula I, in, R1 to R6 are each independently a straight-chain, branched or cyclic alkyl radical having 1 to 40 C atoms, which is unsubstituted or mono- or polysubstituted by F, Cl, Br, I or CN, and wherein one or more non-adjacent CH2 groups may each independently of one another be substituted by -C(R x )=C(R x )-、-C≡C-、-N(R x )-, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- substitution. R x represents H, halogen, straight-chain, branched or cyclic alkyl having 1 to 25 C atoms, wherein, in addition, one or more non-adjacent C atoms may be replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, and wherein one or more H atoms may be replaced by fluorine, and x and y are each independently ≥ 1, m and n are each independently ≥1.

2. A polymerisable LC material according to claim 1, wherein the concentration of the compound of formula I is from 0.01 to 5%.

3. A polymerisable LC material according to claim 1 or 2, comprising one or more reactive mesogens selected from the group consisting of formula RMT, in 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, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, preferably having 1 to 15 C atoms and more preferably optionally fluorinated, A and B, in the case of multiple occurrences, independently of one another, denote an aromatic or cycloaliphatic 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-tetrahydronaphthalene-2,6-diyl, indane-2,5-diyl, bicyclooctylene or 1,4-cyclohexylene, in which one or two non-adjacent CH2 groups are optionally replaced by O and / or S, where these radicals are unsubstituted or substituted by 1, 2, 3 or 4 radicals L, L is P-Sp-, F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)NR x R y , -C(=O)OR x , -C(=O)R x , -NR x R y , -OH, -SF5, or a linear or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy 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, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy group having 1 to 6 C atoms, R 00 To R 000 , R x and R y independently of one another represent H or an alkyl radical having 1 to 12 C atoms, Z 11 and Z 12 In the case of multiple occurrences, -O-, -S-, -CO-, -COO-, -OCO-, -S-CO-, -CO-S-, -O-COO-, -CO-NR are independently 00 -,-NR 00 -CO-, -NR 00 -CO-NR 000 , -NR 00 -CO-O-, -O-CO-NR 00 -, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH2CH2-, -(CH2) n1 , -CF2CH2-, -CH2CF2-, -CF2CF2-, -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, Y 1 and Y 2 independently of each other represents 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 of 1 to 10, preferably 1, 2, 3 or 4.

4. Polymerisable LC material according to one or more of claims 1 to 3, wherein the concentration of the compound of formula RMT is from 40% to 99%.

5. A polymerisable LC material according to one or more of claims 1 to 4, comprising one or more compounds selected from the group consisting of DRM of the formula P 1 -Sp 1 -MG-Sp 2 -P 2 DRM in P 1 and P 2 independently of one another represent a polymerizable group, Sp 1 and Sp 2 are independently a spacer group or a single bond, and MG is a rod-shaped mesogenic group, which is preferably selected from the formula MG -(A 1 -Z 1 ) n -A 2 - MG in A 1 and A 2 represents, in the case of multiple occurrences, independently of one another, an aromatic or cycloaliphatic radical, which optionally contains one or more heteroatoms selected from N, O and S and which is optionally mono- or polysubstituted by L, L is P-Sp-, F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)NR x R y 、-C(=O)OR x 、-C(=O)R x 、-NR x R y , -OH, -SF5, optionally substituted silanyl, aryl or heteroaryl having 1 to 12, preferably 1 to 6 C atoms, and straight-chain 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, R x and R y independently of one another represent H or an alkyl radical having 1 to 12 C atoms, Z 1 In the case of multiple occurrences, it represents independently of one another -O-, -S-, -CO-, -COO-, -OCO-, -S-CO-, -CO-S-, -O-COO-, -CO-NR x -,-NR x -CO-, -NR x -CO-NR y , -NR x -CO-O-, -O-CO-NR x -, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -(CH2) n1 , -CF2CH2-, -CH2CF2-, -CF2CF2-, -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 of each other represents 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, However, there is a proviso that compounds of formula RMT are excluded from compounds of formula DRM.

6. Polymerisable LC material according to one or more of claims 1 to 5, wherein the concentration of the di- or poly-reactive mesogen is from 1% to 60%.

7. A polymerisable LC material according to one or more of claims 1 to 6, comprising one or more compounds selected from the group consisting of formula MRM: P 1 -Sp 1 -MG-R MRM in P 1 、Sp 1 and MG has the meaning given to it in Formula DRM, R represents P-Sp-, F, Cl, Br, I, -CN, -NO2, -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, -SF5, optionally substituted silanyl, straight-chain 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 formula RMT are excluded from compounds of formula MRM.

8. A polymerisable LC material according to one or more of claims 1 to 7, optionally comprising one or more reactive chiral compounds selected from compounds of formulae CRMa to CRMc, in P 0* represents a polymerizable group P, A 0 and B 0 is, in the case of multiple occurrences, independently of one another, 1,4-phenylene which is unsubstituted or substituted by 1, 2, 3 or 4 radicals L as defined above, or is trans-1,4-cyclohexylene, X 1 and X 2 are independently -O-, -COO-, -OCO-, -O-CO-O- or a single bond, Z 0* and Z 0 is, in the case of multiple occurrences, independently of one another, -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 naphthalene ring in the formula CRMa may be additionally substituted by one or more identical or different groups L, in L is independently of one another F, Cl, CN, halogenated alkyl having 1 to 5 C atoms, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy.

9. A polymerisable LC material according to claim 8, wherein the concentration amount of the chiral compound in the liquid crystal medium is preferably from 1 to 20%.

10. The polymerizable LC material according to one or more of claims 1 to 9, optionally comprising one or more additives selected from the group consisting of: further surfactants, photoinitiators, stabilizers, catalysts, sensitizers, inhibitors, chain transfer agents, co-reacted monomers, reactive viscosity reducers, surface-active compounds, lubricants, wetting agents, dispersants, hydrophobic agents, binders, flow improvers, degassing agents or defoamers, deaerators, diluents, reactive diluents, auxiliaries, colorants, dyes, pigments and nanoparticles.

11. Method for preparing a polymerisable LC material according to one or more of claims 1 to 10, comprising the following steps: One or more compounds of the formula I as defined in claim 1 are mixed with one or more reactive mesogenic compounds and optionally one or more chiral compounds.

12. A method for preparing a polymer film, the method being achieved by: - providing a layer of polymerisable LC material according to one or more of claims 1 to 10 onto a substrate, - photopolymerizing said polymerizable LC material, and - optionally removing the polymerized LC material from said substrate and / or optionally providing it onto another substrate.

13. Polymer film obtainable from a polymerisable LC material according to one or more of claims 1 to 10 by a process comprising the steps of: - providing a layer of said polymerisable LC material on a substrate, - photopolymerizing the LC material, and - Optionally removing the polymerized LC material from said substrate and / or optionally providing it on another substrate.

14. Use of one or more polymer films according to claim 13 or polymerisable LC materials according to one or more of claims 1 to 10 in an optical component.

15. Optical component comprising one or more polymer films according to claim 13 or polymerisable LC materials according to one or more of claims 1 to 10.

16. Use of the optical component according to claim 15 in an electro-optical device.

17. Use of the electro-optical device according to claim 16, characterized in that: The electro-optical device is selected from devices used in augmented reality applications or virtual reality applications.

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