Polymerizable liquid crystal material and polymerized liquid crystal film

Abstract

A polymerizable liquid crystal material and a polymerized liquid crystal film are provided. The present invention relates to a polymerizable LC material comprising one or more reactive mesogenic compounds and one or more compounds of formula I. [C7] TIFF2025531827000070.tif49166 (wherein the individual groups have one of the meanings as given in the claims). The present invention further relates to a preparation method thereof, a polymer film obtainable from the corresponding polymerizable LC material, a method for preparing such a polymer film, and the use of such a polymer film and said polymerizable LC material in the fields of optics, electro-optics, in particular augmented reality or virtual reality.

Description

[Technical Field]

[0001] The present invention relates to a polymerizable LC material comprising one or more reactive mesogenic compounds and one or more compounds of formula I.

[0002] [ka]

[0003] wherein the individual radicals have one of the meanings as given in the claims. Furthermore, the invention relates to the preparation methods, to polymer films obtainable from the corresponding polymerizable LC materials, to methods for the preparation of such polymer films, and to the use of such polymer films and said polymerizable LC materials in the fields of optics, electro-optics, in particular augmented reality or virtual reality. [Background technology]

[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, the RMs or RM mixtures are polymerized through an in situ polymerization process.

[0005] In some applications, it is desirable to form multilayer film stacks or optical components that include, for example, two or more layers that exhibit different reflected wavelengths.

[0006] For example, multilayer cholesteric polymer films have been described in the prior art, such as U.S. Patent No. 6,417,902. Furthermore, European Patent No. 0 634 674 suggests preparing a multilayer cholesteric liquid crystal polymer film by laminating a pair of chiral nematic liquid crystal polymer films together, applying pressure, and heating the polymer above its glass transition temperature to bond the films.

[0007] Maurer et al., SID 90 Digest, Vol. 21, p. 110 (1990) (Non-Patent Document 1) describes polarizing color filters obtained by combining multiple polarizing films with different reflection wavelengths. To prepare each film, a layer of CLC side-chain polysiloxane containing chiral and achiral side-chain groups is placed between two glass plates and oriented by shearing at high temperature.

[0008] Japanese Patent Laid-Open Publication No. 01-133003 (Patent Document 3) (Sumitomo Chemical Co., Ltd.) and Japanese Patent Laid-Open Publication No. 08-271731 (Patent Document 4) (Nitto Denko) disclose polarizing plates obtained by laminating one or more CLC polymer layers on a quarter-wave plate.

[0009] However, the methods for producing multilayer cholesteric films as described in the above documents have several drawbacks. Therefore, achieving uniform orientation in CLC polymer layers is often very difficult and requires high temperatures. For example, Maurer et al. mention an orientation temperature of 150°C, while JP-A-01-133003 (Patent Document 3) and JP-A-08-271731 (Patent Document 4) state that temperatures significantly higher than the glass temperature of the CLC polymer are required. This is particularly disadvantageous when using polymers with high glass temperatures, such as acrylates, styrenes, or methacrylates, making them highly unsuitable for mass production.

[0010] Furthermore, according to the multilayer preparation method described in, for example, JP-A-01-133003 (Patent Document 3), polymers must be selected so that different polymer layers exhibit different glass temperatures. Therefore, for example, when a second layer is laminated on a first layer and oriented, the orientation temperature (and therefore the glass temperature) of the second layer must be lower than that of the first layer so as not to affect the uniform orientation of the first layer. This significantly limits the selection of suitable materials and makes the manufacturing process more complicated.

[0011] Another aspect is that polymerizable LC materials typically require the inclusion of leveling agents, such as surfactants, to achieve good alignment of the resulting polymer. Without the use of surfactants in the formulation, increased haze, poor helix orientation in the CLC polymer, and uneven thickness across the film can be observed. Meanwhile, the leveling agents typically used in such formulations can make it difficult to achieve good alignment and coating integrity in the second coating of CLC materials required for multilayer applications.

[0012] In this context, dewetting is defined as the breaking up of a thin liquid film on the substrate, forming droplets. This can lead to uneven thickness of the second CLC material when drying in multi-layer applications. In some cases, the film can recede from the edges, and in the worst case, the second coated layer can bend excessively, resulting in zero coated area. [Prior art documents] [Patent documents]

[0013] [Patent Document 1] U.S. Patent No. 6,417,902 [Patent Document 2] European Patent No. 0 634 674 [Patent Document 3] Japanese Patent Application Publication No. 01-133003 [Patent Document 4] Japanese Patent Application Publication No. 08-271731 [Non-patent literature]

[0014] [Non-Patent Document 1] Maurer et al., SID 90 Digest, Vol. 21, p. 110 (1990) DISCLOSURE OF THE INVENTION [Problem to be solved by the invention]

[0015] It is therefore an object of the present invention to provide improved polymerizable LC materials or RM mixtures and formulations that do not have the disadvantages of materials known from the prior art. In particular, it is an object to provide RM mixtures and formulations that are suitable for preparing polymers by in situ UV photopolymerization and that simultaneously exhibit high birefringence, good solubility, improved potential broadband properties, favorable transition temperatures, and high resistance to yellowing after exposure to UV light. Another object is to provide improved multilayer stacks that do not exhibit the disadvantages of materials known from the prior art. Other objects of the present invention will be readily apparent to those skilled in the art from the following description.

[0016] Surprisingly, the inventors of the present invention have found that a polymerizable LC material according to claim 1 fulfils one or more of the requirements defined above, and preferably reaches all objectives simultaneously. [Means for solving the problem]

[0017] <Summary of the Invention> The present invention relates to a polymerizable LC material comprising one or more reactive mesogenic compounds, one or more compounds of formula I.

[0018] [ka]

[0019] During the ceremony, R1 to R6 are each independently a linear, branched or cyclic alkyl group having 1 to 40 C atoms, preferably 1 to 25 C atoms, more preferably 1 to 12 C atoms, and are unsubstituted or mono- or polysubstituted with F, Cl, Br, I or CN, provided that one or more non-adjacent CH2 groups are each independently -C(R x )=C(R x )-, -C≡C-, -N(R x )-, -O-, -S-, -CO-, -CO-O-, -O-CO-, or O-CO-O-.

[0020] R above x preferably represents H, halogen, or a linear, branched, or cyclic alkyl chain having 1 to 25 C atoms, in which one or more non-adjacent C atoms may be substituted by -O-, -S-, -CO-, -CO-O-, -O-CO-, or -O-CO-O-, and one or more H atoms may be substituted by fluorine; x and y are each independently 1 or greater; m and n each independently represent 1 or more.

[0021] Preferred alkyl groups are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, n-hexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, dodecanyl, trifluoromethyl, perfluoro-n-butyl, 2,2,2-trifluoroethyl, perfluorooctyl, perfluorohexyl, etc., with the proviso that in addition one or more non-adjacent CH groups are each, independently of one another, [ka] may be replaced by

[0022] Preferred alkenyl groups are, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, and the like.

[0023] Preferred alkynyl groups are, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, octynyl, and the like.

[0024] Preferred alkoxy groups are, for example, methoxy, ethoxy, 2-methoxyethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, 2-methylbutoxy, n-pentoxy, n-hexoxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy, etc., with the proviso that in addition one or more non-adjacent CH groups are each, independently of one another, [ka] may be replaced by

[0025] Preferred amino groups are, for example, dimethylamino, methylamino, methylphenylamino, phenylamino, and the like.

[0026] Furthermore, the present invention also relates to a corresponding method for preparing a polymerizable LC material, which method comprises at least the step of mixing one or more reactive mesogenic compounds with one or more compounds of formula I.

[0027] The present invention further relates to a polymer network or a polymer film obtainable or preferably obtained from a polymerizable LC material as described above and below, and to a method for producing a polymer film as described above and below.

[0028] The present invention further relates to a method for improving the dewetting behavior of a polymer film obtainable or preferably obtained 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.

[0029] The present invention further relates to an optical component comprising one or more optical films, one of which is selected from polymer films obtainable from polymerizable LC materials as described above and below.

[0030] The present invention further 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 whose reflected color spatially varies, multicolor images, unforgeable documents such as IDs or credit cards or banknotes.

[0031] The invention further relates to an electro-optical device such as an LCD or OLED comprising one or more optical components or polymer films or polymerizable LC materials as described above and below.

[0032] The invention further relates to electro-optical devices in the field of augmented reality, such as head-mounted devices, comprising one or more optical components as described above and below, a polymer film of polymerizable material. DETAILED DESCRIPTION OF THE INVENTION

[0033] <Terms and definitions>

[0034] As used herein, the term "polymer" will be understood to mean a molecule that includes a backbone of one or more different types of repeating units (the smallest building blocks of a molecule), and includes well-known terms such as "oligomer," "copolymer," "homopolymer," and the like. Furthermore, the term polymer will be understood to include, in addition to the polymer itself, residues from initiators, catalysts, and other elements incident to the synthesis of such a polymer, where such residues are understood not to be covalently incorporated therein. Furthermore, such residues and other elements are usually removed in post-polymerization purification processes, but are typically mixed or entrained with the polymer, and they generally remain with the polymer when transferred between containers or solvents or dispersion media.

[0035] As used herein, the term "(meth)acrylic polymer" includes polymers obtained from acrylic monomers, polymers obtained from methacrylic monomers, and the corresponding copolymers obtained from mixtures of such monomers.

[0036] The term "polymerization" refers to a chemical process for forming a polymer by linking together multiple polymerizable groups or polymer precursors (polymerizable compounds) containing such polymerizable groups.

[0037] The terms "film" and "layer" include rigid or flexible, self-supporting or free-standing films with mechanical stability, as well as coatings or layers on a supporting substrate or between two substrates.

[0038] The terms "liquid crystal" or "LC" refer to materials that have a liquid crystalline mesophase within a certain temperature range (thermotropic LC) or a certain concentration range in solution (lyotropic LC). They necessarily contain mesogenic compounds.

[0039] The terms "mesogenic compound" and "liquid crystal compound" refer to compounds containing one or more calamitic (rod- ​​or board / lath-shaped) or discotic (disk-shaped) mesogenic groups. The term "mesogenic group" refers to a group capable of inducing liquid crystal phase (or mesophase) behavior. A compound containing a mesogenic group does not necessarily exhibit liquid crystal mesophases by itself; it may exhibit liquid crystal mesophases only in mixtures with other compounds, or when the mesogenic compound or material, or mixtures thereof, are polymerized. This includes small molecule non-reactive liquid crystal compounds, reactive or polymerizable liquid crystal compounds, and liquid crystal polymers.

[0040] Calamitic mesogenic groups typically comprise a mesogenic core consisting of one or more aromatic or non-aromatic cyclic groups bonded to each other directly or via linking groups, optionally comprising terminal groups attached to the ends of the mesogenic core, and optionally comprising one or more side groups attached to the long chain of the mesogenic core, where these terminal and side groups are typically selected from, for example, carbyl groups, hydrocarbyl groups, polar groups such as halogen groups, nitro groups, hydroxy groups, etc., or polymerizable groups.

[0041] The term "reactive mesogen" refers to polymerizable mesogenic or liquid crystal compounds, preferably monomeric compounds, which can be used as pure compounds or as mixtures of reactive mesogens with other compounds that function as photoinitiators, inhibitors, surfactants, stabilizers, chain transfer agents, non-polymerizable compounds, etc.

[0042] Polymerizable compounds with one polymerizable group are also called "monoreactive" compounds, compounds with two polymerizable groups are called "direactive" compounds, compounds with three or more polymerizable groups are called "multireactive" compounds, and compounds with no polymerizable groups are also called "nonreactive or nonpolymerizable" compounds.

[0043] The term "non-mesogenic compound or material" means a compound or material that does not contain a mesogenic group as defined above.

[0044] Visible light is electromagnetic radiation having wavelengths ranging from about 400 nm to about 740 nm. Ultraviolet (UV) light is electromagnetic radiation having wavelengths ranging from about 200 nm to about 450 nm.

[0045] Irradiance (E e ) or radiation power is defined as the electromagnetic power (dθ) per unit area (dA) incident on a surface: E e = dθ / dA.

[0046] Radiation exposure or radiation dose (H e ) is the irradiance or radiation output (E e ) is defined as: H e =E e ·t.

[0047] All temperatures are expressed in degrees Celsius, e.g., the melting point of a liquid crystal, T(C,N) or T(C,S), the transition from the smectic (S) phase to the nematic (N) phase, T(S,N), and its clearing point, T(N,I). All temperature differences are expressed in degrees Celsius.

[0048] The term "clearing point" means the temperature at which the transition between the mesophase and the isotropic phase occurs over the maximum temperature range.

[0049] The term "director" is known in the art and refers to the preferred orientation direction of the long molecular axis (in the case of calamitic compounds) or the short molecular axis (in the case of discotic compounds) of liquid crystal or RM molecules. When such anisotropic molecules are uniaxially aligned, the director is the axis of anisotropy.

[0050] The term "alignment" or "orientation" refers to the alignment (orientational order) of anisotropic units of a material, such as small molecule and macromolecular fragments, in a common direction called the "orientation direction." In an alignment layer of a liquid crystal or RM material, the orientation direction corresponds to the direction of the anisotropy axis of the material, so that the liquid crystal director coincides with the orientation direction.

[0051] The terms "uniform orientation" or "uniform alignment" of liquid crystal or RM materials, for example in a material layer, means that the long molecular axes (in the case of calamitic compounds) or short molecular axes (in the case of discotic compounds) of the liquid crystal or RM molecules are aligned in substantially the same direction; in other words, the liquid crystal director lines are parallel.

[0052] The terms "homeotropic structure" or "homeotropic orientation" refer to a film in which the optic axis is substantially perpendicular to the film plane.

[0053] The terms "planar structure" or "planar orientation" refer to a film in which the optical axis is substantially parallel to the film plane.

[0054] The term "A-plate" refers to an optical retarder that utilizes a layer of uniaxially birefringent material with its extraordinary axis oriented parallel to the plane of the layer.

[0055] The term "C-plate" refers to an optical retarder that utilizes a layer of uniaxially birefringent material with its extraordinary axis oriented perpendicular to the plane of the layer.

[0056] In an A / C plate containing optically uniaxially birefringent liquid crystal material with uniform orientation, the optic axis of the film is given by the direction of the extraordinary axis. An A (or C) plate containing optically uniaxially birefringent material with positive birefringence is also called a "positive A (or C) plate" or "+A (or +C) plate".

[0057] A (or C) plates comprising films of optically uniaxially birefringent materials with negative birefringence, such as discotic anisotropic materials, are also called "negative A (or C) plates" or "-A (or C) plates", depending on the orientation of the discotic material. Films made of cholesteric calamitic materials with reflection bands in the UV part of the spectrum also have the optics of a negative C plate.

[0058] The birefringence Δn is defined as: Δn=n e -n o , where ne is the extraordinary refractive index, no is the ordinary refractive index, and the effective average refractive index n av. is given by: n av. =((2n o 2 +n e 2 ) / 3) 1 / 2 .

[0059] Average refractive index n av. and the ordinary refractive index n o can be measured using an Abbe refractometer. Δn can be calculated from the above formula.

[0060] Unless the context clearly indicates otherwise, as used herein, plural forms of the terms herein are to be construed as including the singular and vice versa.

[0061] All physical properties are determined according to "Merck Liquid Crystals, Physical Properties of Liquid Crystals", November 1997, Merck, Germany, and are given at a temperature of 20°C unless expressly stated otherwise. The optical anisotropy (Δn) is determined at a wavelength of 589.3 nm.

[0062] In case of doubt, the definition given in C. Tschierske, G. Pelzl and S. Diele, Angew. Chem. 2004, 116, 6340-6368 shall be followed.

[0063] In a given general formula, unless otherwise stated, the following terms have the following meanings:

[0064] A "carbyl group" refers to a monovalent or polyvalent organic group having at least one carbon atom, which group either contains no additional atoms (e.g., -C≡C-) or optionally contains one or more additional atoms such as N, O, S, P, Si, Se, As, Te, or Ge (e.g., carbonyl, etc.). A "hydrocarbyl group" refers to a carbyl group which further contains one or more H atoms and optionally one or more heteroatoms such as N, O, S, P, Si, Se, As, Te, or Ge.

[0065] The carbyl or hydrocarbyl group may be saturated or unsaturated. Unsaturated groups may be, for example, aryl, alkenyl, or alkynyl groups. Carbyl or hydrocarbyl groups having more than three carbon atoms may be linear, branched, and / or cyclic, and may contain spiro-linked or fused rings.

[0066] Preferred carbyl and hydrocarbyl groups are optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy and alkoxycarbonyloxy having 1 to 40, preferably 1 to 25, particularly preferably 1 to 18 carbon atoms; optionally substituted aryl or aryloxy having 6 to 40, preferably 6 to 25 carbon atoms; or optionally substituted alkylaryl, arylalkyl, alkylaryloxy, arylalkyloxy, arylcarbonyl, aryloxycarbonyl, arylcarbonyloxy and aryloxycarbonyloxy having 6 to 40, preferably 6 to 25 carbon atoms. Further preferred carbyl and hydrocarbyl groups are C1 to C6 40 Alkyl, C2-C 40 Alkenyl, C2-C 40 Alkynyl, C3-C 40 Allyl, C4~C 40 Alkyldienyl, C4-C 40 Polyenyl, C6-C 40 Aryl, C6-C 40 Alkylaryl, C6-C40 Aryl alkyl, C6-C 40 Alkylaryloxy, C6-C 40 Arylalkyloxy, C2-C 40 Heteroaryl, C4-C 40 Cycloalkyl, C4-C 40 Cycloalkenyl, etc. In particular, C1-C 22 Alkyl, C2-C 22 Alkenyl, C2-C 22 Alkynyl, C3-C 22 Allyl, C4~C 22 Alkyldienyl, C6-C 12 Aryl, C6-C 20 Aryl alkyl, and C2-C 20 Heteroaryl is preferred.

[0067] Further preferred carbyl and hydrocarbyl groups are linear, branched or cyclic alkyl groups having 1 to 40, preferably 1 to 25, carbon atoms, more preferably 1 to 12 carbon atoms, which are unsubstituted or mono- or polysubstituted by F, Cl, Br, I or CN, and in which one or more non-adjacent CH groups are each, independently of one another, -C(R x )=C(R x )-, -C≡C-, -N(R x )-, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-.

[0068] In the above, R x preferably represents H, halogen, or a linear, branched, or cyclic alkyl chain having 1 to 25 carbon atoms, wherein, further, one or more non-adjacent carbon atoms may be replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, or -O-CO-O-, and one or more H atoms may be replaced by fluorine, an optionally substituted aryl or aryloxy group having 6 to 40 carbon atoms, or an optionally substituted heteroaryl or heteroaryloxy group having 2 to 40 carbon atoms.

[0069] Preferred alkyl groups are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, n-hexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, dodecanyl, trifluoromethyl, perfluoro-n-butyl, 2,2,2-trifluoroethyl, perfluorooctyl, perfluorohexyl, etc., with the proviso that in addition one or more non-adjacent CH groups are each, independently of one another, [ka] may be replaced by

[0070] Preferred alkenyl groups are, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, and the like.

[0071] Preferred alkynyl groups are, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, octynyl, and the like.

[0072] Preferred alkoxy groups are, for example, methoxy, ethoxy, 2-methoxyethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, 2-methylbutoxy, n-pentoxy, n-hexoxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy, etc., with the proviso that in addition one or more non-adjacent CH groups are each, independently of one another, [ka] may be replaced by

[0073] Preferred amino groups are, for example, dimethylamino, methylamino, methylphenylamino, phenylamino, and the like.

[0074] Aryl and heteroaryl groups can be monocyclic or polycyclic, i.e., they can have one ring (e.g., phenyl) or two or more rings, which can be fused (e.g., naphthyl) or covalently linked (e.g., biphenyl), or can contain a combination of fused and linked rings. Heteroaryl groups contain one or more heteroatoms preferably selected from O, N, S, and Se.

[0075] In particular, monocyclic, bicyclic, or tricyclic aryl groups having 6 to 25 carbon atoms and monocyclic, bicyclic, or tricyclic heteroaryl groups having 2 to 25 carbon atoms are preferred, which optionally contain fused rings and are optionally substituted. Furthermore, 5-, 6-, or 7-membered aryl and heteroaryl groups are preferred, in which one or more CH groups may be replaced by N, S, or O such that the O and / or S atoms are not directly bonded to each other.

[0076] Preferred aryl groups are, for example, phenyl, biphenyl, terphenyl, [1,1':3',1"]terphenyl-2'-yl, naphthyl, anthracene, binaphthyl, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, tetracene, pentacene, benzopyrene, fluorene, indene, indenofluorene, spirobifluorene, and the like.

[0077] Preferred heteroaryl groups are, for example, five-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, phenanthrimidazole, pyridoimidazole, pyrazineimidazole, quinoxalineimidazole, benzoxazole, naphth Heteroaryl groups include oxazole, anthroxazole, phenanthroxazole, 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, benzothiadiazothiophene, or combinations of these groups. Heteroaryl groups may be substituted with alkyl, alkoxy, thioalkyl, fluorine, fluoroalkyl, or further aryl or heteroaryl groups.

[0078] (Non-aromatic) alicyclic and heterocyclic groups include both saturated rings, i.e., those containing only single bonds, and partially unsaturated rings, i.e., those which may contain multiple bonds. Heterocyclic rings preferably contain one or more heteroatoms selected from Si, O, N, S and Se.

[0079] (Non-aromatic) alicyclic and heterocyclic groups may be monocyclic, i.e., containing only one ring (e.g., cyclohexane), or polycyclic, i.e., containing multiple rings (e.g., decahydronaphthalene or bicyclooctane). Saturated groups are particularly preferred. Furthermore, monocyclic, bicyclic, or tricyclic groups having 3 to 25 carbon atoms are preferred, which groups optionally contain fused rings and are optionally substituted. Furthermore, 5-, 6-, 7-, or 8-membered carbocyclic groups are preferred, in which, further, one or more carbon atoms may be replaced by Si, and / or one or more CH groups may be replaced by N, and / or one or more non-adjacent CH groups may be replaced by -O- and / or -S-.

[0080] Preferred alicyclic and heterocyclic groups are, for example, 5-membered ring groups such as cyclopentane, tetrahydrofuran, tetrahydrothiofuran, pyrrolidine, 6-membered ring groups such as cyclohexane, silynan, cyclohexene, tetrahydropyran, tetrahydrothiopyran, 1,3-dioxane, 1,3-dithiane, piperidine, 7-membered ring groups such as cycloheptane, and fused groups such as tetrahydronaphthalene, decahydronaphthalene, 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.

[0081] The aryl, heteroaryl, (non-aromatic) alicyclic and heterocyclic groups optionally carry one or more substituents, which groups are preferably silyl, sulfo, sulfonyl, formyl, amine, imine, nitrile, mercapto, nitro, halogen, C1-C 12 Alkyl, C6-C 12 Aryl, C1-C 12 It is selected from the group comprising alkoxy, hydroxyl, or a combination of these groups.

[0082] Preferred substituents are, for example, solubility-promoting groups such as alkyl or alkoxy, electron-withdrawing groups such as fluorine, nitro or nitrile, or substituents for increasing the glass transition temperature (Tg) of the polymer, especially bulky groups such as t-butyl or optionally substituted aryl groups.

[0083] 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 above meaning, and Y x represents 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 carbon atoms, wherein one or more H atoms may optionally be replaced by F or Cl.

[0084] "Substituted silyl or aryl" preferably includes halogen, -CN, R y , -OR y , -CO-R y , -CO-OR y , -O-CO-R y or -O-CO-OR y (In the formula, R y means substituted with H, a straight, branched or cyclic alkyl chain having 1 to 12 carbon atoms.

[0085] In the formulas shown above and below, the substituted phenylene ring [ka] In the formula, L, identically or differently in each occurrence, has one of the meanings given above and below and is preferably F, Cl, CN, NO, CH, C, H, C(CH), CH(CH), CHCH(CH)C, H, OCH, OC, H, COCH, COC, H, COOCH, COOC, H, CF, OCF, OCHF, OC, F or P-Sp-, very preferably F, Cl, CN, CH, C, H, OCH, COCH, OCF or P-Sp-, most preferably F, Cl, CH, OCH, COCH or OCF.

[0086] "Halogen" represents F, Cl, Br or I, preferably F or Cl, more preferably F.

[0087] The "polymerizable group" (P) is preferably selected from groups containing a C=C double bond or a C≡C triple bond and groups suitable for polymerization with ring opening, such as oxetane or epoxide groups.

[0088] Preferably, the polymerizable group (P) is CH2=CW 1 -COO-, CH2=CW 1 -CO-, [ka] CH2=CW 2 -(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-, During the ceremony, W 1 represents H, F, Cl, CN, CF3, phenyl or alkyl having 1 to 5 carbon atoms, in particular H, F, Cl or CH3, W 2 represents H or alkyl having 1 to 5 carbon atoms, in particular H, methyl, ethyl or n-propyl, W 3 and W 4 each, independently of one another, denotes H, Cl or alkyl having 1 to 5 carbon atoms, Phe denotes 1,4-phenylene, which is optionally substituted by one or more groups L as defined above, but which are 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, also phenyl, k1, k2 and k3 each independently represent 0 or 1, k3 preferably represents 1, and k4 is an integer of 1-10.

[0089] Particularly preferred 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-, [ka] where W 2 represents H or alkyl having 1 to 5 carbon atoms, in particular H, methyl, ethyl or n-propyl.

[0090] Further preferred groups (P) are vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane and epoxide, most preferably acrylate or methacrylate, especially acrylate.

[0091] Preferably, all multireactive polymerizable compounds and subformulas thereof contain one or more groups PS Instead of p-, it contains one or more branched groups containing two or more polymerizable groups P (multireactive polymerizable groups).

[0092] Suitable groups of this type, and polymerizable compounds containing them, are described, for example, in US Pat. No. 7,060,200 or US Patent Application Publication No. 2006 / 0172090.

[0093] In particular, the following formula: [ka] Preferred are multi-reactive polymerizable groups selected from During the ceremony, alkyl represents a single bond or a straight or branched alkylene having 1 to 12 carbon atoms, wherein one or more non-adjacent CH groups are each, independently of one another, -C(R x )=C(R x )-, -C≡C-, -N(R x )-, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, wherein, further, one or more H atoms may be replaced by F, Cl or CN, wherein R x has one of the meanings given above, aa and bb each independently represent 0, 1, 2, 3, 4, 5 or 6; X has one of the meanings given for X', and P v ~P z each, independently of one another, has one of the meanings given above for P.

[0094] Preferred spacer groups Sp are selected from alkylenes having 1 to 20, preferably 1 to 12, C atoms, which may be mono- or polysubstituted with F, Cl, Br, I or CN, provided that in addition one or more non-adjacent CH groups are present, such that O and / or S atoms are not directly linked to each other, e.g., -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 may be replaced independently by -, -CH=CH-, or -C≡C-, and with the proviso that R xx and R yy each independently represent H or alkyl having 1 to 12 C atoms.

[0095] Further preferred spacer groups Sp are selected from the formula Sp'-X', such that the group "P-Sp-" corresponds to the formula "P-Sp'-X'-", wherein: Sp' represents alkylene having 1 to 20, preferably 1 to 12, carbon atoms, optionally mono- or polysubstituted by F, Cl, Br, I or CN, wherein, in addition, one or more non-adjacent CH groups are each independently -O-, -S-, -NH-, -NR-, so that O and / or S atoms are not directly bonded to each other. 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 may be replaced by -, -CH=CH- or -C≡C-; X' is -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR xx -, -NR xx -CO-, -NRxx -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 represents -, -C≡C-, -CH=CH-COO-, -OCO-CH=CH- or a single bond; R xx and R yy each independently represent H or alkyl having 1 to 12 carbon atoms, and Y xx and Y yy each independently represent H, F, Cl or CN.

[0096] X' is preferably -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, or -CO-NR xx -, -NR xx -CO-, -NR xx -CO-NR yy - or a single bond.

[0097] 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 -, where p1 is an integer from 1 to 12, q1 is an integer from 1 to 3, and R xx and R yy has the above meaning.

[0098] Particularly preferred groups -X'-Sp'- are -(CH2) p1 -, -O-(CH2) p1 -, -OCO-(CH2) p1 -, -OCOO-(CH2)p1 -, where p1 is an integer from 1 to 12.

[0099] Particularly preferred groups Sp and / or Sp′ are, for example, linear methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylenethioethylene, ethylene-N-methyliminoethylene, 1-methylalkylene, ethenylene, propenylene and butenylene, respectively.

[0100] The term "chiral" is generally used to describe an object that is not superimposable on its mirror image.

[0101] "Achiral" objects are objects that are identical to their mirror images.

[0102] Unless otherwise specified, the terms "chiral nematic" and "cholesteric" are used interchangeably herein.

[0103] Chiral nematic textures or cholesteric liquid crystals (CLCs) exhibit selective reflection of circularly polarized light, with the direction of rotation of the light vector corresponding to the direction of rotation of the cholesteric helix.

[0104] The reflected 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 formula:

[0105]

number

[0106] CLC media can be prepared, for example, by doping a nematic LC medium with a chiral dopant having a high twisting power, and the pitch p of the induced cholesteric helix is ​​given by the concentration c of the chiral dopant and the helical twisting power HTP according to the following equation:

[0107]

number

[0108] 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 achieve a low temperature dependence of the helical pitch and reflection wavelength of the CLC medium. total ), the following equation holds approximately:

[0109]

number

[0110] c in the formula i are the concentrations of the individual dopants, and HTP i are the helical twisting powers of the respective individual dopants.

[0111] In the case of the present invention, [ka] represents trans-1,4-cyclohexylene, [ka] represents 1,4-phenylene.

[0112] In the present invention, the group -COO- or -CO2- has the formula [ka] and the groups -OCO-, -OC- or -OOC- represent an ester group of the formula [ka] represents an ester group of the formula:

[0113] A "polymer network" is a network in which all polymer chains are interconnected by numerous cross-links to form a single macroscopic entity.

[0114] Polymer networks occur in the following types:

[0115] · Graft polymer molecules are branched polymer molecules in which one or more side chains differ structurally or configurationally from the main chain.

[0116] A star polymer molecule is a branched polymer molecule in which multiple chains or arms arise from a single branch point. If the arms are identical, the star polymer molecule is said to be regular. If adjacent arms are composed of different repeating subunits, the star polymer molecule is said to be diverse.

[0117] Comb polymer molecules consist of a main chain with two or more three-way branch points and linear side chains. Comb polymer molecules are said to be regular if the main chains are identical.

[0118] Brush polymer molecules consist of a main chain and linear, unbranched side chains, with one or more branching points carrying functional groups in four or more directions.

[0119] Throughout the description and claims of this specification, the terms "comprise" and "containing" and variations thereof, such as "comprising" and "comprises," mean "including, but not limited to," and are not intended to exclude (or exclude) other elements. On the other hand, the term "comprise" also encompasses, but is not limited to, the term "consisting of."

[0120] Throughout the description and claims of this specification, the terms "obtainable" and "obtained" and variations thereof mean "including, but not limited to," and are not intended to exclude (or exclude) other elements. Meanwhile, the term "obtainable" also encompasses, but is not limited to, the term "obtained."

[0121] All concentrations are given as weight percent, all temperatures are given in degrees Celsius (°C), and all temperature differences are given in degrees Celsius for each total mixture.

[0122] <Detailed explanation> The compounds preferably contain the following substituents: R 1 ~R 6 are each independently a linear or branched alkyl which may contain heteroatoms, preferably a C1-C6 alkyl, particularly preferably a C1-C4 alkyl, in particular a C1-C3 alkyl, very particularly preferably a C1 or C2 alkyl, R 1 and R 4 have the same meaning, R 1 and R 4 are both methyl or ethyl, preferably methyl; R 2 , R 3 , R 5 and R 6 have the same meaning, R 2 , R 3 , R 5 and R 6 are all methyl or ethyl, preferably methyl; x and y are each independently an integer of 1 to 25, preferably 1 to 10, more preferably 1, 2, 3, 4, 5 or 6, even more preferably 1 to 4, and particularly 1 or 2; n and m each independently represent an integer of 1 to 25, preferably 1 to 10, more preferably 1, 2, 3, 4, 5, or 6, even more preferably 1 to 4, particularly 1 or 2; x and y are the same integer, x and y are both 1 or 2, preferably 2; m and n are the same integer, m and n are both 1 or 2.

[0123] 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 Chinese Patent Publication No. 110498734.

[0124] These compounds can be used in polymerizable liquid crystal materials either alone or as blends containing two or more, preferably three or more, compounds of formula I. Such blends are commercially available, for example, as DYNOL® 800 from EVONIK GmbH, Germany. Typically, such blends contain at least one, preferably two, compounds of formula I selected from the following group of compounds:

[0125] [ka]

[0126] The compounds of formula (I) can be used preferably as surfactants, preferably as surfactants, hydrophobizing agents, surface enhancers, viscosity reducers, foam stabilizers or emulsifiers.

[0127] The concentration of the compound of formula (I) in the polymerizable liquid crystal material is preferably 0.01 to 5% by weight, more preferably 0.05 to 2% by weight, and even more preferably 0.1 to 1% by weight, based on the total amount blended.

[0128] In a preferred embodiment the polymerisable LC material comprises one or more reactive mesogens selected of formula RMT.

[0129] [ka]

[0130] P is a polymerizable group, Sp is a spacer group or a single bond; r2 and r3 are each independently 0, 1, 2, 3, or 4; R 11 is P-Sp-, preferably alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 15 C atoms, more preferably said group being optionally fluorinated, A and B, in the case of several occurrences, independently of one another, represent an aromatic or alicyclic group, which may contain one or more heteroatoms selected from N, O and S and which may be 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, indan-2,5-diyl, bicyclooctylene or 1,4-cyclohexylene, with the proviso that one or two non-adjacent CH groups may be replaced by O and / or S, and with the proviso that these groups are unsubstituted or substituted by 1, 2, 3 or 4 groups 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 1 to 12 linear or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, with the proviso that one or more H atoms may be replaced by F or Cl, preferably F, -CN or 1 to 6 C-atom linear or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, R x and R y each independently represent H or alkyl having 1 to 12 C atoms, Z 11 and Z 12 When occurring multiple times, they are each independently represented by -O-, -S-, -CO-, -COO-, -OCO-, -S-CO-, -CO-S-, -O-COO-, and -CO-NR 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 represents -, -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 each independently 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.

[0131] Preferred compounds of formula RMT are those selected from formula RMTa or RMTb.

[0132] [ka]

[0133] During the ceremony, P is a polymerizable group, Sp is a spacer group or a single bond; r1, r2, r3 are each independently 0, 1, 2, 3 or 4, preferably 0, 1 or 2; L, R 11 , Z 12 , ring B and m have one of the meanings as given above in formula RMT.

[0134] Preferred compounds of formula RMTa are those selected from formulae RMTa1 to RMTa6.

[0135] [ka]

[0136] In the formula, L, P, Sp and R 11 is as defined in the formula RMT, and r1 to r3 represent 1, 2, 3 or 4, preferably 1 or 2.

[0137] Preferred compounds of formula RMTa1 to RMTa6 are selected from the following formulae:

[0138] [ka]

[0139] [ka]

[0140] In the formula, P 11 represents a group selected from the group consisting of heptadiene, vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane and epoxide groups, very preferably an acrylate, methacrylate or oxetane group, in particular an acrylate or methacrylate group, especially an acrylate group; x is an integer from 0 to 12, preferably from 1 to 8, more preferably 3, 4, 5 or 6, in particular x is 3 or 6, especially 6; R 11 represents alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, which preferably has 1 to 15 C atoms and more preferably may be fluorinated, and L has in each occurrence one of the meanings as given above in formula RMT.

[0141] Particularly preferred are compounds of formula RMTa2, which are preferably selected from the following formulae:

[0142] [ka]

[0143] [ka]

[0144] [ka]

[0145] In the formula, R 11 has one of the meanings as given above in the formula RMT, preferably R 11 represents alkyl or alkoxy, more preferably methoxy, ethoxy, propoxy, methyl, ethyl, propyl, butyl, pentyl, isopropyl or isobutyl, especially methoxy.

[0146] Preferred compounds of formula RMTb are those selected from formulae RMTb0 to RMTb6.

[0147] [ka]

[0148] In the formula, L, P, Sp and R 11 is as defined in the formula RMT, and r1 to r3 represent 1, 2, 3 or 4, preferably 1 or 2.

[0149] Preferred compounds of formulae RMTb0 to RMTb6 are selected from the following formulae:

[0150] [ka]

[0151] [ka]

[0152] In the formula, P 11 represents a group selected from the group consisting of heptadiene, vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane and epoxide groups, very preferably an acrylate, methacrylate or oxetane group, in particular an acrylate or methacrylate group, especially an acrylate group; x is an integer from 0 to 12, preferably from 1 to 8, more preferably 3, 4, 5 or 6, in particular x is 3 or 6, especially 6; R 11 represents alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, which preferably has 1 to 15 C atoms and more preferably may be fluorinated, and L has in each occurrence one of the meanings as given above in formula RMT.

[0153] Particularly preferred are compounds of formula RMTb2, which are preferably selected from the following formulae:

[0154] [ka]

[0155] [ka]

[0156] [ka]

[0157] R in the formula 11 has one of the meanings as given above in the formula RMT, preferably R 11 represents alkyl or alkoxy.

[0158] Further preferred are compounds of formula RMTb2-A1 selected from compounds of the following formulae:

[0159] [ka]

[0160] [ka]

[0161] [ka]

[0162] In the formula, R 11 has one of the meanings as given above in the formula RMT, preferably R 11 represents alkyl or alkoxy, more preferably methoxy, ethoxy, propoxy, methyl, ethyl, propyl, butyl, pentyl, isopropyl or isobutyl, especially methoxy.

[0163] Preferably the polymerisable LC material comprises one or more, preferably two or more compounds selected from formulae RMTa2-A3 to RMTa2-A6 or RMTb2-A3, in particular the polymerisable LC material comprises one or more compounds of formula RMTb2-A3, in particular the polymerisable LC material comprises a combination of RMTa2-A4 and / or RMTa2-A5 with compounds of formula RMTb2-A3.

[0164] The use of one or more compounds of formula RMT in the polymerizable LC material can beneficially increase the birefringence of the polymer film. The corresponding reflection bandwidth is related to the birefringence by the following equation:

[0165]

number

[0166] It can be seen that a wider reflection band can be achieved by increasing the birefringence of the cholesteric polymer film. By utilizing compounds of formula RMT in polymerizable LC materials, it is possible to significantly broaden the reflection bandwidth of the corresponding polymer film without adversely affecting film properties such as wet film crystallization or dewetting.

[0167] The concentration of compounds of formula RMT and its sub-formulae in the polymerisable LC material is preferably 10% to 99%, more preferably 20 to 95%, especially 25 to 90%.

[0168] Compounds of formula RMT are either commercially available from Merck, Darmstadt, or can be synthesized according to the procedures given in, for example, U.S. Pat. No. 6,514,578 or U.S. Patent Application Publication No. 15 / 575,415.

[0169] In a preferred embodiment the polymerisable LC material comprises one or more di- or multi-reactive mesogens, preferably selected from formula DRM.

[0170] [ka]

[0171] During the ceremony, P 1 and P 2 each independently represents a polymerizable group, Sp 1 and Sp 2 are each independently a spacer group or a single bond, MG is a rod-shaped mesogenic group, which is preferably selected from the formula MG [ka] During the ceremony, A 1 and A 2 when present in plurality, independently represent an aromatic or alicyclic group, 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 silyl, aryl or heteroaryl having 1 to 12, preferably 1 to 6, C atoms, and linear or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12, preferably 1 to 6, C atoms, in which one or more H atoms are optionally replaced by F or Cl, R x and R y represent, independently of one another, H or alkyl having 1 to 12 C atoms, Z 1When there are a plurality of groups independently, they are each represented by -O-, -S-, -CO-, -COO-, -OCO-, -S-CO-, -CO-S-, -O-COO-, or -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 represents -, -C≡C-, -CH═CH-COO-, -OCO-CH═CH- or a single bond, preferably -COO-, -OCO- or a single bond; Y 1 and Y 2 represent, independently of one another, H, F, Cl or CN, n is 1, 2, 3 or 4, preferably 1 or 2, most preferably 2; n1 is an integer of 1 to 10, preferably 1, 2, 3, or 4; provided that compounds of formula RMT are excluded from compounds of formula DRM.

[0172] Preferred Group A 1 and A 2 include, but are not limited to, furan, pyrrole, thiophene, oxazole, thiazole, thiadiazole, imidazole, phenylene, cyclohexylene, bicyclooctylene, cyclohexenylene, pyridine, pyrimidine, pyrazine, azulene, indane, fluorene, naphthalene, tetrahydronaphthalene, anthracene, phenanthrene, and dithienothiophene, all of which are unsubstituted or substituted with 1, 2, 3, or 4 groups L as defined above.

[0173] Preferred Group A1 and A 2 is selected from 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, thiophene-2,5-diyl, naphthalene-2,6-diyl, 1,2,3,4-tetrahydro-naphthalene-2,6-diyl, indan-2,5-diyl, bicyclooctylene or 1,4-cyclohexylene, in which one or two non-adjacent CH groups are optionally replaced by O and / or S, and in which these groups are unsubstituted or substituted by 1, 2, 3 or 4 groups L as defined above.

[0174] Preferred RMs of the formula DRM are selected from the formula RDMa:

[0175] [ka]

[0176] During the ceremony, P 0 are, independently of one another when they occur in plurality, a polymerizable group, preferably an acrylic, methacrylic, oxetane, epoxy, vinyl, heptadiene, vinyloxy, propenyl ether or styrene group, Z 0 is -COO-, -OCO-, -CH2CH2-, -CF2O-, -OCF2-, -C≡C-, -CH=CH-, -OCO-CH=CH-, -CH=CH-COO- or a single bond, L, identically or differently, in each occurrence has one of the meanings given for L in formula DRM and, in several occurrences, is selected independently from F, Cl, CN or optionally halogenated alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 5 C atoms, r is 0, 1, 2, 3 or 4; x and y are each independently 0 or the same or different integers of 1 to 12, z is 0 or 1, except that it is 0 if the adjacent x or y is 0.

[0177] Highly preferred RMs of formula DRM are selected from the following formulae:

[0178] [ka]

[0179] [ka]

[0180] In the formula, P 0 , L, r, x, y and z are as defined in the formula DRMa.

[0181] Compounds of formula DRMa1, DRMa2 and DRMa3, especially those of formula DRMa1, are particularly preferred.

[0182] The concentration of the bi- or multi-reactive RMs, preferably of formula DRM and its sub-formulas, in the RM mixture is preferably 1% to 90%, very preferably 10 to 80%.

[0183] In another preferred embodiment, the RM mixture comprises one or more monoreactive RMs. These additional monoreactive RMs are preferably selected from the formula MRM.

[0184] [ka]

[0185] In the formula, P 1 , Sp 1 and MG has the meaning given in formula DRM, R is 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 silyl, linear or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12, preferably 1 to 6, C atoms, with the proviso that one or more H atoms may be replaced by F or Cl, X is a halogen, preferably F or Cl; R x and R y are each independently H or alkyl having 1 to 12 C atoms, However, it is provided that compounds of the formula RMT are excluded from compounds of the formula MRM.

[0186] Preferably the compound of formula MRM is selected from the following formulae:

[0187] [ka]

[0188] [ka]

[0189] [ka]

[0190] In the formula, P 0 , L, r, x, y and z are as defined in formula DRMa; R 0 is an alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 or more, preferably 1 to 15, carbon atoms, or Y 0 or P-(CH2) y -(O) z - represents X 0 -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, Y 0 is F, Cl, CN, NO2, OCH3, OCN, SCN, SF5, or a mono-, oligo- or polyfluorinated alkyl or alkoxy having 1 to 4 carbon atoms; Z 0 is -COO-, -OCO-, -CH2CH2-, -CF2O-, -OCF2-, -CH=CH-, -OCO-CH=CH-, -CH=CH-COO- or a single bond, A 0 are, if present in plural, independently 1,4-phenylene or trans-1,4-cyclohexylene which are unsubstituted or substituted by 1, 2, 3 or 4 groups L, R 01、02 are H, R, respectively, independently of each other. 0 or Y 0 and u and v are each independently 0, 1 or 2; w is 0 or 1, However, the benzene ring and the naphthalene ring may be additionally substituted with one or more groups L, which may be the same or different.

[0191] Compounds of formula MRM1, MRM2, MRM3, MRM4, MRM5, MRM6, MRM7, especially those of formula MRM1, MRM4, MRM6 and MRM7 are particularly preferred.

[0192] The concentration of all monoreactive RMs, including those of formula RMT, in the polymerizable LC material is preferably 1-80%, very preferably 5-50%.

[0193] In the formulae DRM, MRM and their preferred sub-formulae, L is preferably selected from F, Cl, CN, NO2 or linear or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, where the alkyl group may be perfluorinated, or P-Sp-.

[0194] 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-.

[0195] Preferably, the polymerizable LC material according to the present invention comprises one or more chiral compounds. These chiral compounds may be non-mesogenic or mesogenic. In addition, these chiral compounds, whether mesogenic or non-mesogenic, may be non-reactive, monoreactive or polyreactive.

[0196] Preferably, the chiral compounds utilized are 20 μm each alone or in combination with each other. -1 More than 40 μm, preferably -1 More than 60 μm, preferably -1 Within the above range, most preferably 80 μm -1 More than ~260μm -1 The absolute value of the helical twisting force (|HTP total |), in particular as disclosed in WO 98 / 00428.

[0197] Preferably, the non-polymerizable chiral compound is selected from the group of compounds of formulae CI to C-III:

[0198] [ka]

[0199] The latter includes each (S,S) enantiomer.

[0200] In the formula, E and F are each independently 1,4-phenylene or trans-1,4-cyclohexylene, v is 0 or 1, and Z 0 is -COO-, -OCO-, -CH2CH2- or a single bond, and R is alkyl, alkoxy or alkanoyl having 1 to 12 C atoms.

[0201] Particularly preferred are polymerisable LC materials comprising one or more chiral compounds which do not necessarily exhibit a liquid crystalline phase.

[0202] The compounds of formula C-II and their synthesis are described in WO 98 / 00428. Compound CD-1 shown in Table D below is particularly preferred. The compounds of formula C-III and their synthesis are described in British Patent No. 2,328,207.

[0203] Further typically used chiral compounds are, for example, commercially available R / S-5011, CD-1, R / S-811 and CB-15 (Merck, Darmstadt, Germany).

[0204] The chiral compounds R / S-5011 and CD-1 described above, as well as the (other) compounds of formulae CI, C-II and C-III, exhibit very high helical twisting power (HTP) and are therefore particularly useful for the purposes of the present invention.

[0205] 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.

[0206] Preferably the polymerisable LC material comprises one or more non-reactive chiral compounds and / or one or more reactive chiral compounds preferably selected from mono- and / or poly-reactive chiral compounds.

[0207] Suitable mesogenically reactive chiral compounds preferably comprise one or more ring structural elements linked together via a direct bond or a linking group, two of which may be linked to each other either directly or via a linking group which may be the same as or different from the aforementioned linking groups. The ring structural elements are preferably selected from the group of 4-, 5-, 6- or 7-membered rings, preferably 5- or 6-membered rings.

[0208] Preferred monoreactive chiral compounds are selected from compounds of formulae CRMa to CRMc.

[0209] [ka]

[0210] During the ceremony, P 0* represents a polymerizable group P, Sp * represents a spacer group Sp, A 0 and B 0 are, independently in the case of multiple occurrences, 1,4-phenylene which is unsubstituted or substituted by 1, 2, 3 or 4 groups L as defined above, or trans-1,4-cyclohexylene, X 1 and X 2are each independently -O-, -COO-, -OCO-, -O-CO-O- or a single bond, Z 0* when occurring multiple times, are each independently -COO-, -OCO-, -O-CO-O-, -OCH2-, -CHO-, -CF2O-, -OCF2-, -CH2CH2-, -(CH2)4-, -CF2CH2-, -CH2CF2-, -CF2CF2-, -C≡C-, -CH=CH-, -CH=CH-COO-, -OCO-CH=CH- or a single bond; t's are each 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, with the proviso that the naphthalene ring in formula CRMa may additionally be substituted with one or more identical or different groups L; Here, L's are each independently F, Cl, CN, a halogenated alkyl having 1 to 5 C atoms, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy.

[0211] The compound of formula CRMa is preferably selected from the group of compounds of formula CRMa-1.

[0212] [ka]

[0213] In the formula, X 2 , A 0 , B 0 , Z 0* , P 0* and b has the meaning given in formula CRMa or one of the preferred meanings given above and below, and (OCO) represents -O-CO- or a single bond.

[0214] Particularly preferred compounds of formula CRM are selected from the group consisting of the following subformulae:

[0215] [ka]

[0216] [ka]

[0217] where R is -X as defined in formula CRM-a. 2 -(CH2) x -P 0* wherein the benzene and naphthalene rings are unsubstituted or substituted with one, two, three or four groups L as defined above and below.

[0218] The compound of formula CRMb is preferably selected from the group of compounds of formula CRMb-1 to CRMb-3.

[0219] [ka]

[0220] In the formula, X 2 , A 0 , B 0 , Z 0* , P 0* and b has the meaning given in formula CRMa or one of the preferred meanings given above and below.

[0221] Preferred compounds of formula CRMb-1 are preferably selected from the group of compounds of formula CRMb-1a and CRMb-1b:

[0222] [ka]

[0223] In the formula, 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 2 represents OCOO, OCO, COO or a single bond. Preferred are compounds of formula CRMb-1b selected from the following compounds:

[0224] [ka]

[0225] In the formula, P 0* and b has the meaning given in formula CRMa or one of the preferred meanings given above and below.

[0226] P 0* Particularly preferred is the compound CRMb-1bI, in which x represents an acrylate group at each occurrence and b represents 4 at each occurrence, and is commercially available from BASF GmbH, Germany under the trade name LC756.

[0227] The compound of formula CRMc is preferably selected from the group of compounds of formula CRMc-1:

[0228] [ka]

[0229] In the formula, X 2 , A 0 , B 0 , Z 0* , P 0* and b has the meaning given in formula CRMa or one of the preferred meanings given above and below.

[0230] Preferred compounds of formula CRMc-1 are preferably selected from the group of compounds of formula CRMc-1a and CRMc-1b:

[0231] [ka]

[0232] In the formula, X 2 , Z 0* , P 0* and b have the meanings 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 OCOO, OCO, COO or a single bond.

[0233] Preferred are compounds of formula CRMc-1a selected from the following compounds:

[0234] [ka]

[0235] In the formula, P 0* and b has the meaning given in formula CRMa or one of the preferred meanings given above and below.

[0236] P 0* represents an acrylate group in each occurrence; b represents 3 or 6 in each occurrence; X 2 Particularly preferred are compounds CRMc-1aI, in which each occurrence represents O or a single bond.

[0237] The amount of the chiral compound in the liquid crystal medium is preferably 1 to 20%, more preferably 1 to 15%, even more preferably 1 to 10%, and most preferably 3 to 7% by weight of the total mixture.

[0238] In a preferred embodiment, the proportion of the polymerizable mesogenic compound in the entire polymerizable liquid crystal material according to the present invention is in the range of 30 to 99% by weight, more preferably in the range of 40 to 97% by weight, and even more preferably in the range of 50 to 95% by weight.

[0239] Preferably, the proportion of said mono-, di- or multi-reactive liquid crystal compounds, preferably selected from compounds of formula DRM, MRM as given above and below, in the total polymerizable liquid crystal material according to the present invention is preferably in the range of 30-99.9 wt.%, more preferably in the range of 40-99.9 wt.%, even more preferably in the range of 50-99.9 wt.%.

[0240] In a preferred embodiment, the proportion of the direactive or multireactive polymerizable mesogenic compound in the entire polymerizable liquid crystal material according to the present invention is preferably in the range of 1 to 70% by weight, more preferably in the range of 2 to 60% by weight, and even more preferably in the range of 3 to 50% by weight.

[0241] In another preferred embodiment, the proportion of monoreactive polymerizable mesogenic compounds of formula MRM excluding compounds of formula RMT in the whole polymerizable liquid crystal material according to the present invention, if any, is preferably in the range of 1 to 50 wt %, more preferably in the range of 2 to 45 wt %, even more preferably in the range of 5 to 40 wt %.

[0242] In another preferred embodiment, the proportion of the multireactive polymerizable mesogenic compound in the entire polymerizable liquid crystal material according to the present invention, if present, is preferably in the range of 1 to 30% by weight, more preferably in the range of 2 to 20% by weight, and even more preferably in the range of 3 to 10% by weight.

[0243] In another preferred embodiment the polymerisable LC material does not comprise polymerisable mesogenic compounds with more than two polymerisable groups.

[0244] In a further preferred embodiment the polymerisable LC material comprises one or more monoreactive mesogenic compounds preferably selected from formulae MRM-1, MRM-4, MRM-6 and / or MRM-7 and one or more direactive mesogenic compounds preferably selected from formula DRMa-1.

[0245] When using chiral dopants, the polymerizable LC material should additionally be such that different reflection wavelengths, especially in the VIS light region, can be easily and targetedly changed. Preferably, the cholesteric pitch of the polymerizable LC material is selected so that their reflection wavelengths are in the infrared range of the electromagnetic spectrum, i.e., in the range of 300 nm to 900 nm, more preferably in the range of 350 to 850 nm. In particular, the reflection wavelength of the liquid crystal medium is in the range of 400 nm to 800 nm.

[0246] The polymerizable LC material according to the present invention is prepared in a manner conventional per se, e.g. by mixing one or more of the above-mentioned polymerizable compounds with one or more block copolymers as described above and below, one or more chiral compounds, both as defined above, and optionally further liquid crystalline compounds and / or additives and / or solvents.

[0247] In a further preferred embodiment the polymerizable LC material optionally further comprises one or more additives selected from the group consisting of further polymerization initiators, antioxidants, surfactants, stabilizers, catalysts, sensitizers, inhibitors, chain transfer agents, co-reactant monomers, reactive thinners, surface-active compounds, lubricants, wetting agents, dispersants, hydrophobizing agents, adhesives, flow improvers, degassing or anti-foaming agents, defoamers, diluents, reactive diluents, adjuvants, colorants, dyes, pigments and nanoparticles.

[0248] In another preferred embodiment, the polymerizable LC material optionally comprises one or more additives selected from polymerizable non-mesogenic compounds (reactive thinners). The amount of these additives in the polymerizable LC material is preferably 0-30%, very preferably 0-25%.

[0249] The reactive thinners used are not only substances that are called reactive thinners in the actual sense, but also auxiliary compounds as already mentioned above that contain one or more complementary reactive units or polymerizable groups P, such as hydroxyl groups, thiol groups or amino groups, through which reaction with the polymerizable units of the liquid-crystalline compound can occur.

[0250] Photopolymerizable substances typically include mono-, di-, and polyfunctional compounds containing at least one olefinic double bond, such as vinyl esters of carboxylic acids, such as lauric acid, myristic acid, palmitic acid, and stearic acid, and vinyl esters of dicarboxylic acids, such as succinic acid, adipic acid, allyl, and vinyl ethers, as well as methacrylic and acrylic esters of monofunctional alcohols, such as lauryl, myristyl, palmitic, and stearyl alcohol, and difunctional alcohols, such as diallyl and divinyl ethers of ethylene glycol and 1,4-butanediol.

[0251] Also suitable are, for example, methacrylic and acrylic esters of polyfunctional alcohols, especially those that do not contain any further functional groups other than hydroxyl groups or contain at most ether groups.Examples of such alcohols are difunctional alcohols, such as ethylene glycol, propylene glycol and their more highly condensed representatives, such as 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, especially ethoxylated and propoxylated alcohols.

[0252] Other suitable reactive thinners are polyester(meth)acrylates, which are (meth)acrylic acid esters of polyesterols.

[0253] Examples of suitable polyesterols are those that can be prepared by esterifying polycarboxylic acids, preferably dicarboxylic acids, with polyols, preferably diols. Starting materials for such hydroxyl-containing polyesters are known to those skilled in the art. Dicarboxylic acids that can be used include succinic acid, glutaric acid, adipic acid, sebacic acid, o-phthalic acid, and their isomers and hydrogenated products, as well as esterifiable and transesterifiable derivatives of the aforementioned acids, such as anhydrides and dialkyl esters. Suitable polyols are the above-mentioned alcohols, 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.

[0254] Suitable reactive thinners are further compounds of the formula: 1,4-divinylbenzene, triallyl cyanurate, dihydrodicyclopentadienyl acrylate, also known as: [ka] and the acrylic acid esters of tricyclodecenyl alcohol, and the allyl esters of acrylic acid, methacrylic acid, and cyanoacrylic acid.

[0255] Of the reactive thinners given as examples, those having photopolymerizable groups are used in particular and in view of the preferred compositions mentioned above.

[0256] This group includes, for example, dihydric and polyhydric alcohols such as ethylene glycol, propylene glycol and their more highly condensed representatives, such as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, etc., butanediol, pentanediol, hexanediol, neopentyl glycol, cyclohexanedimethanol, glycerol, trimethylolpropane, butanetriol, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol and the corresponding alkoxylated, especially ethoxylated and propoxylated, alcohols.

[0257] The group also includes, for example, alkoxylated phenolic compounds such as ethoxylated and propoxylated bisphenols.

[0258] These reactive thinners may further be, for example, epoxides or urethane (meth)acrylates.

[0259] Epoxide (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 known to those skilled in the art.

[0260] Urethane (meth)acrylates are in particular products of the reaction of hydroxyalkyl (meth)acrylates with poly- or diisocyanates, which are likewise known to the person skilled in the art.

[0261] Such epoxides and urethane (meth)acrylates are included among the compounds listed above as "mixed forms."

[0262] When reactive thinners are used, their amount and properties must be adapted to the respective conditions so that, on the one hand, a satisfactory desired effect, for example, the desired color of the composition according to the present invention, is obtained, and, on the other hand, the phase behavior of the liquid crystal composition is not excessively impaired. For example, a low-crosslinking (high-crosslinking) liquid crystal composition can be prepared using a corresponding reactive thinner having a relatively small (large) number of reactive units per molecule.

[0263] Examples of groups of diluents include: C1-C4 alcohols, such as methanol, ethanol, n-propanol, isopropanol, butanol, isobutanol, sec-butanol, 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; glycols, such as 1,2-ethylene glycol, 1,2- and 1,3-propylene glycol, 1,2-, 2,3- and 1,4-butylene glycol, di- and triethylene glycol, and di- and tripropylene glycol; ethers, such as methyl tert-butyl ether, 1,2-ethylene glycol mono- and dimethyl ether, 1,2-ethylene glycol mono- and diethyl ether, 3-methoxy- Mention may be made of cyclopropanol, 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 spirit, Shellsol® and Solvesso® mineral oils such as gasoline, kerosene, diesel and heating oil, and also natural oils such as olive oil, soybean oil, rapeseed oil, linseed oil and sunflower oil.

[0264] Of course, it is also possible to use mixtures of these diluents in the compositions according to the invention.

[0265] These diluents can also be mixed with water, as long as they are at least partially miscible. Examples of suitable diluents herein are C1-C4 alcohols such as methanol, ethanol, n-propanol, isopropanol, butanol, isobutanol and sec-butanol, glycols such as 1,2-ethylene glycol, 1,2- and 1,3-propylene glycol, 1,2-, 2,3- and 1,4-butylene glycol, di- and triethylene glycol, and di- and tripropylene 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, ethyl, propyl and butyl acetate.

[0266] The diluent is optionally used in an amount of about 0 to 10.0% by weight, preferably about 0 to 5.0% by weight, based on the total weight of the polymerizable LC material.

[0267] Antifoaming and defoaming agents (c1)), lubricants and flow aids (c2)), heat-curing or radiation-curing aids (c3)), substrate-wetting aids (c4)), wetting and dispersing aids (c5)), hydrophobizing agents (c6)), adhesion promoters (c7)) and aids for promoting scratch resistance (c8)) cannot be strictly distinguished from one another in their action.

[0268] For example, lubricants and flow aids often act as anti-foaming and / or defoaming agents and / or as aids to improve scratch resistance. Radiation curing aids may also act as lubricants and flow aids and / or defoaming agents and / or as substrate wetting aids. In some cases, some of these aids may also function as adhesion promoters (c8)).

[0269] Corresponding to the above, certain additives can therefore be classified into a number of groups c1) to c8) below.

[0270] Antifoaming agents of group c1) include silicon-free and silicon-containing polymers, such as unmodified or modified polydialkylsiloxanes or branched copolymers, comb or block copolymers containing polydialkylsiloxane and polyether units, the latter being derived from ethylene oxide or propylene oxide.

[0271] Degassing agents of group c1) include, for example, organic polymers such as polyethers and polyacrylates, dialkylpolysiloxanes, in particular dimethylpolysiloxanes, organically modified polysiloxanes, such as arylalkyl-modified polysiloxanes, and fluorosilicones.

[0272] The action of antifoaming agents is essentially based on preventing the formation of foam or destroying already formed foam. Antifoaming agents essentially act by promoting the aggregation of finely divided gases or bubbles to produce larger bubbles in the medium to be defoamed, such as the compositions according to the invention, and thus promoting the escape of gas (air). Antifoaming agents can often also be used as defoamers, and vice versa, and these additives are collectively included in group c1).

[0273] Such auxiliaries include, for example, TEGO® Foamex 800, TEGO® Foamex 805, TEGO® Foamex 810, TEGO® Foamex 815, TEGO® Foamex 825, TEGO® Foamex 835, TEGO® Foamex 840, TEGO® Foamex 842, TEGO® Foamex 1435, TEGO® Foamex 1488, TEGO® Foamex 1495, TEGO® Foamex 1496, TEGO® Foamex 1497, TEGO® Foamex 1498, TEGO® Foamex 1499, TEGO® Foamex 1500, TEGO® Foamex 1501, TEGO® Foamex 1502, TEGO® Foamex 1503, TEGO® Foamex 1504, TEGO® Foamex 1505, TEGO® Foamex 1506, TEGO® Foamex 1507, TEGO® Foamex 1508, TEGO® Foamex 1509, TEGO® Foamex 1510, TEGO® Foamex 1511, TEGO® Foamex 1512, TEGO® Foamex 1513, TEGO® Foamex 1514, TEGO® Foamex 1515, TEGO® Foamex 1516, TEGO® Foamex 1517, TEGO® Foamex 1518, TEGO® Foamex 1519, TEGO® Foamex 1520, TEGO® Foamex 1521, TEGO® Foamex 1522, TEGO® Foamex 1523, TE amex3062, TEGO® Foamex7447, TEGO® Foamex8020, Tego® FoamexN, TEGO® FoamexK3, TEGO® Antifoam2-18, TEGO® Antifoam2-18, TEGO® Antifoam2-57, TEGO® Antifoam2-80, TEGO® Antifoam2-82, TEGO® Antifoam2-89, TEGO® Antifoam2-92 , TEGO® Antifoam 14, TEGO® Antifoam 28, TEGO® Antifoam 81, TEGO® Antifoam D90, TEGO® Antifoam 93, TEGO® Antifoam 200, TEGO® Antifoam 201, TEGO® Antifoam 202, TEGO® Antifoam 793, TEGO® Antifoam 1488, TEGO® Antifoam 3062, TEGO PRE N® 5803, TEGOPREN® 5852, TEGOPREN® 5863, TEGOPREN® 7008, TEGO® Antifoam 1-60, TEGO® Antifoam 1-62, TEGO® Antifoam 1-85, TEGO® Antifoam 2-67, TEGO® Antifoam WM20, TEGO® Antifoam 50, TEGO® Antifoam 105, TEGO® Antifoam 730,TEGO® Antifoam MR1015, TEGO® Antifoam MR1016, TEGO® Antifoam 1435, TEGO® Antifoam N, TEGO® Antifoam KS6, TEGO® Antifoam KS10, TEGO® Antifoam KS53, TEGO® Antifoam KS95, TEGO® Antifoam KS100, TEGO® Antifoam KE6 00, TEGO® Antifoam KS911, TEGO® Antifoam MR1000, TEGO® Antifoam KS1100, Tego® Airex 900, Tego® Airex 910, Tego® Airex 931, Tego® Airex 935, Tego® Airex 936, Tego® Airex 960, Tego® Airex 970, Tego® Airex 980 and and Tego® Airex 985 from Tego, and are available as BYK®-011, BYK®-019, BYK®-020, BYK®-021, BYK®-022, BYK®-023, BYK®-024, BYK®-025, BYK®-027, BYK®-031, BYK®-032, BYK®-033, BYK®-034, BYK®-035, BYK®-036, BYK®-037, BYK®-038, BYK®-039, BYK®-040, BYK®-041, BYK®-042, BYK®-043, BYK®-044, BYK®-045, BYK®-046, BYK®-047, BYK®-048, BYK®-049, BYK®-050, BYK®-051, BYK®-052, BYK®-053, BYK®-054, BYK®-055, BYK®-056, BYK®-057, BYK®-058, BYK®-059, BYK®-060, BYK®-061, BYK®-062, BYK®-063, BYK®-064, BYK®-065, BYK®-066, BYK®-067, BYK®-068, BYK®-069, BYK®-069, BYK®-069, BYK®-068, BYK®-069, BYK®-069, BYK®-070, BYK®-07 5, BYK®-036, BYK®-037, BYK®-045, BYK®-051, BYK®-052, BYK®-053, BYK®-055, BYK®-057, BYK®-065, BYK®-066, BYK®-070, BYK®-080, BYK®-088, BYK®-141, and BYK®-A530.

[0274] The auxiliaries of 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 RM formulation.

[0275] In group c2), lubricants and flow aids generally include not only silicon-free polymers, but also silicon-containing polymers, such as polyacrylates or modifiers, low molecular weight polydialkylsiloxanes. The modification consists in some of the alkyl groups being replaced by a wide variety of organic groups. These organic groups are, for example, polyethers, polyesters, or even long-chain (fluorinated) alkyl groups, the former being most frequently used.

[0276] The polyether groups in the corresponding modified polysiloxanes are usually composed of ethylene oxide and / or propylene oxide units. Generally, the higher the proportion of these alkylene oxide units in the modified polysiloxane, the more hydrophilic the resulting product.

[0277] Such auxiliaries are commercially available from Tego, for example, as TEGO® Glide 100, TEGO® Glide ZG400, TEGO® Glide 406, TEGO® Glide 410, TEGO® Glide 411, TEGO® Glide 415, TEGO® Glide 420, TEGO® Glide 435, TEGO® Glide 440, TEGO® Glide 450, TEGO® Glide A115, TEGO® Glide B1484 (which may also be used as an antifoam and defoamer), TEGO® Flow ATF, TEGO® Flow 300, TEGO® Flow 460, TEGO® Flow 425, and TEGO® Flow ZFS460. Suitable radiation curable lubricants and flow aids that may also be used to improve scratch resistance are the TEGO® Rad2100, TEGO® Rad2200, TEGO® Rad2500, TEGO® Rad2600 and TEGO® Rad2700 products, also available from TEGO.

[0278] Such auxiliaries are also available from BYK as, for example, BYK®-300, BYK®-306, BYK®-307, BYK®-310, BYK®-320, BYK®-333, BYK®-341, Byk® 354, Byk® 361, Byk® 361N, BYK® 388.

[0279] For example, such an auxiliary is also available from 3M as FC4430®.

[0280] For example, such agents are also available from Cytonix as FluorN® 561 or FluorN® 562.

[0281] For example, such agents are also available from Merck as Tivida® FL2300 and Tivida® FL2500.

[0282] The auxiliary agents of group c2) 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 RM formulation.

[0283] In group c3), radiation curing coagents include, in particular, polysiloxanes having terminal double bonds, such as acrylate group components. Such coagents can be crosslinked by actinic radiation or, for example, electron beams. These coagents generally combine many properties. In the uncrosslinked state, they can act as antifoaming agents, defoaming agents, lubricants, and flow aids and / or substrate wetting aids, while in the crosslinked state, they improve, in particular, the scratch resistance of coatings or films produced using the compositions according to the invention. For example, the improvement in the gloss properties of these coatings or films is essentially attributed to the action of these coagents as antifoaming agents, defoaming agents, and / or lubricants, and flow aids (in the uncrosslinked state).

[0284] Examples of suitable radiation curing coagents are the products TEGO® Rad2100, TEGO® Rad2200, TEGO® Rad2500, TEGO® Rad2600 and TEGO® Rad2700 available from TEGO and the product BYK®-371 available from BYK.

[0285] The thermosetting coagents of group c3) contain, for example, primary OH groups which are capable of reacting with, for example, isocyanate groups of the binder.

[0286] Examples of thermal curing coagents that can be used are the products BYK®-370, BYK®-373 and BYK®-375 available from BYK.

[0287] The auxiliaries of group c3) are optionally used in a proportion of about 0 to 5.0 wt. %, preferably about 0 to 3.0 wt. %, based on the total weight of the polymerizable LC material.

[0288] The substrate wetting aids of group c4) serve in particular to increase the wetting of the substrate to be printed or coated, for example with a printing ink or coating composition, such as a composition according to the invention. The improved lubrication and flow behavior of such printing inks or coating compositions is often accompanied by an effect on the appearance of the finished (e.g. crosslinked) print or coating.

[0289] A wide variety of such auxiliaries are commercially available, for example, from Tego as TEGO® WetKL245, TEGO® Wet250, TEGO® Wet260 and TEGO® WetZF453, and from BYK as BYK®-306, BYK®-307, BYK®-310, BYK®-333, BYK®-344, BYK®-345, BYK®-346 and BYK®-348.

[0290] The auxiliary agents of 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.

[0291] The wetting and dispersing auxiliaries of group c5) serve in particular to prevent the pigment from becoming waterlogged, floating or settling and are therefore particularly suitable for the pigment composition according to the invention, if required.

[0292] These adjuvants essentially stabilize the pigment dispersions by electrostatic repulsion and / or steric hindrance of the pigment particles containing these additives, although in the latter case the interaction of the adjuvant with the surrounding medium (e.g. the binder) plays a major role.

[0293] The use of such wetting and dispersing auxiliaries is common practice, for example, in the art of printing inks and paints, so that the use of suitable auxiliaries of this type generally presents no problems for the skilled person.

[0294] Such wetting and dispersing aids are available, for example, from Tego as TEGO® Dispers 610, TEGO® Dispers 610S, TEGO® Dispers 630, TEGO® Dispers 700, TEGO® Dispers 705, TEGO® Dispers 710, TEGO® Dispers 720W, TEGO® Dispers 725W, TEGO® Dispers 730W, TEGO® Dispers 735W, and TEGO® Dispers 740W. Disperbyk® Dispers 740W and is sold by BYK under the trade names Disperbyk®, Disperbyk®-107, Disperbyk®-108, Disperbyk®-110, Disperbyk®-111, Disperbyk®-115, Disperbyk®-130, Disperbyk®-160, Disperbyk®-161, Disperbyk®-162, Disperbyk®-163, Disperbyk®-164, Disperbyk®-165, Disperbyk®-166, Disperbyk®-167, Disperbyk®-168, Disperbyk®-169, Disperbyk®-170, Disperbyk®-171, Disperbyk®-172, Disperbyk®-173, Disperbyk®-174, Disperbyk®-175, Disperbyk®-176, Disperbyk®-177, Disperbyk®-178, Disperbyk®-179, Disperbyk®-180, Disperbyk®-181, Disperbyk®-182, Disperbyk®-183, Disperbyk®-184, Disperbyk®-185, Disperbyk®-186, Disperbyk®-187, Disperbyk®-188, Disperbyk®-189, Disperbyk®-190, Disperbyk®-200, Disperbyk®-201, Disperbyk®-202, Disperbyk®-203, Disperbyk®-204, Disperbyk®-205, Disperbyk®-206, Disperbyk®-207, Disperbyk®-208, Disperbyk®-209, Disperbyk®-210, Disper )-163, Disperbyk®-164, Disperbyk®-165, Disperbyk®-166, Disperbyk®-167, Disperbyk®-170, Disperbyk®-174, Disperbyk®-180, Disperbyk®-181, Disperbyk®-182, Disperbyk®-183, Disperbyk®-184, Disperbyk®-185, D isperbyk®-190, Anti-Terra®-U, Anti-Terra®-U80, Anti-Terra®-P, Anti-Terra®-203, Anti-Terra®-204, Anti-Terra®-206, BYK®-151, BYK®-154, BYK®-155, BYK®-P104S, BYK®-P105, Lactimon®, Lactimon®-WS,and Bykumen®.

[0295] The amount of auxiliary used in group c5) is based on the average molecular weight of the auxiliary. Therefore, preliminary experiments are advisable in each case, but this can be easily carried out by a person skilled in the art.

[0296] The hydrophobizing agents of group c6) can be used, for example, to impart water repellency to prints or coatings produced using the compositions according to the invention. This prevents or at least significantly reduces swelling due to water absorption and thus, for example, changes in the optical properties of such prints or coatings. Also, when the compositions are used, for example, as printing inks for offset printing, water absorption can be prevented or at least significantly reduced.

[0297] Such hydrophobizing agents are commercially available, for example, from Tego as Tego® PhobeWF, Tego® Phobe1000, Tego® Phobe1000S, Tego® Phobe1010, Tego® Phobe1030, Tego® Phobe1010, Tego® Phobe1010, Tego® Phobe1030, Tego® Phobe1040, Tego® Phobe1050, Tego® Phobe1200, Tego® Phobe1300, Tego® Phobe1310, and Tego® Phobe1400.

[0298] The auxiliaries of group c6) are optionally used in a proportion of about 0 to 5.0 wt. %, preferably about 0 to 3.0 wt. %, based on the total weight of the polymerizable LC material.

[0299] Further adhesion promoters from group c7) serve to improve the adhesion of two interfaces in contact. From this it follows immediately that the only effective part of the adhesion promoter is that which is located at either one or both interfaces. For example, if it is desired to apply a liquid or pasty printing ink, coating composition or paint to a solid substrate, this generally means that either the adhesion promoter must be added directly to the latter or the substrate must be pretreated with the adhesion promoter (also known as priming), i.e., the substrate is endowed with modified chemical and / or physical surface properties.

[0300] If the substrate has been previously primed with a primer, this means that the contacting interfaces are those of the primer on the one hand and the printing ink or coating composition or paint on the other hand, and in this case not only the adhesion between the substrate and the primer but also the adhesion between the substrate and the printing ink or coating composition or paint contributes to the adhesion of the entire multilayer structure on the substrate.

[0301] Adhesion promoters which may be described in a broader sense are also the substrate wetting aids already mentioned in group c4), but these generally do not have the same adhesion-promoting capabilities.

[0302] The variety of adhesion promoter systems is not surprising in view of the wide variety of substrates and the physical and chemical properties of, for example, the printing inks, coating compositions and paints intended for printing or coating them.

[0303] Examples of silane-based adhesion promoters include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N-aminoethyl-3-aminopropyltrimethoxysilane, N-aminoethyl-3-aminopropylmethyldimethoxysilane, N-methyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, and vinyltrimethoxysilane. These and other silanes are commercially available, for example, from Huels under the trade name DYNASILAN®.

[0304] Corresponding technical information from the manufacturers of such additives should generally be used, or a person skilled in the art can obtain this information in a simple manner through corresponding preliminary experiments.

[0305] However, if these additives are added to the polymerizable LC material according to the invention as auxiliaries from group c7), their proportion optionally corresponds to about 0 to 5.0 wt. %, based on the total weight of the polymerizable LC material. These concentration data are merely a guideline, since the amount and type of additive in each case depends on the nature of the substrate and the nature of the printing / coating composition. Corresponding technical information is usually available in this case from the manufacturer of such additives or can be determined by the skilled person in a simple manner through corresponding preliminary experiments.

[0306] Examples of additives for improving scratch resistance of group c8) include the above-mentioned products TEGO® Rad2100, TEGO® Rad2200, TEGO® Rad2500, TEGO® Rad2600 and TEGO® Rad2700 available from Tego.

[0307] For these auxiliaries, the quantitative data given for group c3) are equally suitable, i.e. 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.

[0308] Examples that may be mentioned of light, heat and / or oxidation stabilizers are: Alkylated monophenols, such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, linear or branched nonylphenols having a side chain of the formula (I), such as 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(1'-methylundec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methylheptadec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyltridec-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-didodecylthiomethyl-4-nonylphenol;

[0309] Hydroquinone and alkylated hydroquinones, such as 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-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,

[0310] Tocopherols, such as α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures of these compounds, and tocopherol derivatives, such as tocopheryl acetate, succinate, nicotinate and polyoxyethylene succinate ("tocopherolate");

[0311] hydroxylated diphenyl thioethers, 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-dis-sec-amylphenol) and 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide,

[0312] Alkylidenebisphenols, 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-ethylidenebis(4,6- di-tert-butylphenol), 2,2'-ethylidenebis(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-tris(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 [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,

[0313] O-, N- and S-benzyl compounds, such as 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl 4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, tridecyl 4-hydroxy-3,5-di-tert-butylbenzyl mercaptoacetate, 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-hydroxybenzyl mercaptoacetate,

[0314] Aromatic hydroxybenzyl compounds, such as 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 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;

[0315] triazine compounds, for example, 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, 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,

[0316] 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,

[0317] acylaminophenols, such as 4-hydroxylauroylanilide, 4-hydroxystearoylanilide, and octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate;

[0318] Propionic and acetic acid esters, for example, of mono- or polyhydric alcohols, such as, for example, methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]-octane;

[0319] 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,

[0320] Ascorbic acid (vitamin C) and ascorbic acid derivatives, such as ascorbyl palmitate, laurate, and stearate, and ascorbyl sulfate and phosphate;

[0321] 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-(2-naphthyl)-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-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octyl-substituted diphenylamines such as p,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoyl Aminophenol, 4-octadecanoylaminophenol, bis[4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 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, mixture of mono- and di-alkylated tert-butyl / tert-octyldiphenylamines, mixture of mono- and di-alkylated nonyldiphenylamines, mixture of mono- and di-alkylated dodecyldiphenylamines, mixture of mono- and di-alkylated isopropyl / isohexyldiphenylamines, mixture 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-octylphenothiazines, mixtures of mono- and di-alkylated tert-octylphenothiazines, N-allylphenothiazine, 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,

[0322] Phosphines, phosphites and phosphonites, for example, 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, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6- methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl))pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphocin, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,g]-1,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite, and bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite,

[0323] 2-(2'-hydroxyphenyl)benzotriazoles, for example, 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'-ditert-amyl-2'-hydroxyphenyl)benzotriazole, 2-(3,5'-bis-(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5' 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-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3'-t tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-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]; 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole complete esterification product with polyethylene glycol 300,

[0324] Sulfur-containing peroxide scavengers and sulfur-containing antioxidants, such as esters of 3,3'-thiodipropionic acid, such as the lauryl, stearyl, myristyl, and tridecyl esters, mercaptobenzimidazole, and 2-mercaptobenzimidazole, dibutyl zinc dithiocarbamate, dioctadecyl disulfide, and the zinc salt of pentaerythritol tetrakis(β-dodecylmercapto)propionate;

[0325] 2-hydroxybenzophenones, for example 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyclooxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy, 2'-hydroxy-4,4'-dimethoxy derivatives,

[0326] Esters of unsubstituted and substituted benzoic acid, for example 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,

[0327] Acrylates, for example, 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-hydroxybenzyl malonate, condensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine with succinic acid, N,N'-bis(2,2,6,6-tetramethylpiperidine- 4-yl)hexamethylenediamine and condensation products of 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-ethylene)bis(3,3,5,5-tetramethylpiperidin-4-yl) Methylpiperazinone), 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, condensation products of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidin-4-yl)-1,3 ,5-triazine and 1,2-bis(3-aminopropylamino)ethane condensation products, 2-chloro-4,6-di(4-n-butylamino-1,2,2,6,6-pentamethylpiperidin-4-yl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane condensation products, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]-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-tetramethylpiperidine, condensation products of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, 1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5 -Condensation products of triazine, 4-butylamino-2,2,6,6-tetramethylpiperidine, N-(2,2,6,6-tetramethylpiperidin-4-yl)-n-dodecylsuccinimide, N-(1,2,2,6,6-pentamethylpiperidin-4-yl)-n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]-decane, 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4.5] Condensation products of decane and epichlorohydrin, condensation products of 4-amino-2,2,6,6-tetramethylpiperidine with tetramethylolacetylenediurea and poly(methoxypropyl-3-oxy)-[4(2,2,6,6-tetramethyl)piperidinyl]-siloxane,.

[0328] Oxalamides, such as 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, 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 ortho-, para-methoxy-disubstituted oxanilides, and mixtures of ortho- and para-ethoxy-disubstituted oxanilides, and

[0329] 2-(2-hydroxyphenyl)-1,3,5-triazines, 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-propyloxyphenyl)-6-(2,4-dimethylphenyl)- 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-butyloxypropoxy)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-(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.

[0330] In another preferred embodiment, the polymerizable LC material comprises one or more specific antioxidants, preferably selected from the Irganox® series, e.g. the antioxidants Irganox® 1076 and Irganox® 1010 commercially available from Ciba, Switzerland.

[0331] In another preferred embodiment the polymerizable LC material comprises one or more, more preferably one or two, photoinitiators, for example selected from the commercially available Irgacure® or Darocure® (Ciba) 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. Further preferred photoinitiators are selected from commercially available oxime ester photoinitiators such as OXE02 (Ciba), NCI930, N1919T (Adeka), SPI-03 or SPI-04 (Samyang) or TRI-PBG-304 (Changzhou Tronly New Electronic Materials Co., Ltd).

[0332] The overall concentration of the polymerization initiator(s) in the polymerizable LC material is preferably 0.5-10%, very preferably 1-9%, more preferably 3-7%.

[0333] In a preferred embodiment the polymerisable LC material is dissolved in a suitable solvent, preferably selected from organic solvents.

[0334] 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, ethyl, or butyl acetate or methyl acetoacetate; alcohols such as methanol, ethanol, or isopropyl alcohol; aromatic solvents such as toluene or xylene; alicyclic hydrocarbons such as cyclopentane or cyclohexane; halogenated hydrocarbons such as dichloromethane or trichloromethane; glycols or their esters, such as PGMEA (propyl glycol monomethyl ether acetate), γ-butyrolactone. It is also possible to use binary, ternary, or higher mixtures of the above solvents. Methyl isobutyl ketone is a preferred solvent, particularly for multilayer applications.

[0335] When the polymerizable LC material comprises one or more solvents, the total concentration of all solids including RM in the solvent(s) is preferably 10-60%, more preferably 20-50%, especially 30-45%.

[0336] Preferably the polymerisable LC material contains, in addition to one or more compounds of formula I and corresponding sub-formulas, a) one or more poly- or di-reactive polymerizable mesogenic compounds, preferably selected from the formula DRM and corresponding sub-formulas, b) optionally one or more polymerizable mesogenic compounds of formula RMT and corresponding sub-formulas, c) any one or more chiral mesogenic compounds preferably selected from compounds of formulae CRMa to CRMc, more preferably formula CRMb and sub-formulae thereof, d) optionally one or more monoreactive mesogens, preferably selected from compounds of formula MRM and corresponding sub-formulas, e) optionally one or more photoinitiators; f) optionally one or more antioxidant additives; g) optionally one or more adhesion promoters; h) optionally further comprising one or more surfactants; i) optionally one or more mono-, di- or multi-reactive polymerizable non-mesogenic compounds, j) optionally, one or more dyes that exhibit an absorption maximum at the wavelength used to initiate photopolymerization; k) optionally one or more chain transfer agents; l) optionally one or more further stabilizers; m) optionally one or more lubricants and flow aids, and n) optionally one or more diluents; o) optionally a non-polymeric nematic component; p) optionally one or more organic solvents Includes.

[0337] More preferably the polymerizable LC material is a) one or more compounds of formula I or the corresponding preferred sub-formulas thereof, b) optionally one or more, preferably two or more polymerizable mesogenic compounds selected from the compounds of the formula RMT and corresponding sub-formulas, preferably of the sub-formulas RMTa2-A4 and / or RMTa2-A5 and / or RMTb-A3, c) one or more, preferably two or more, bireactive polymerizable mesogenic compounds, preferably selected from compounds of formula DRMa-1, 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, e) optionally one or more chiral mesogenic compounds of formula CRMb, in particular of formula CRMb-1bI, f) optionally one or more antioxidants, preferably chosen from esters of unsubstituted and substituted benzoic acid, in particular Irganox® 1076, if present, preferably in an amount of 0.01 to 2% by weight, very preferably 0.05 to 1% by weight, g) optionally one or more photoinitiators, preferably carbazole oxime ester photoinitiators; h) optionally one or more organic solvents, preferably methyl isobutyl ketone Includes.

[0338] The present invention further comprises: providing a layer of a polymerizable LC material as described above and below on a substrate, Polymerizing the polymerizable component of the polymerizable LC material by photopolymerization, and Optionally removing the polymerized LC material from the substrate and / or optionally providing it on another substrate. The present invention relates to a method for preparing a polymer film.

[0339] The polymerizable LC material is then applied or printed onto a substrate by known techniques, such as spin coating or printing, and the solvent is evaporated before polymerization. It is often suitable to heat the coated solution to accelerate solvent evaporation.

[0340] The polymerizable LC material can be applied to the substrate by conventional coating techniques such as spin coating, bar coating or blade coating, or by conventional printing techniques known to the expert, such as screen printing, offset printing, reel-to-reel printing, letterpress printing, gravure printing, rotogravure printing, flexography, intaglio printing, pad printing, heat seal printing, inkjet printing, stamp or printing plate printing, etc.

[0341] Suitable substrate materials and substrates are known to experts and described in the literature, such as conventional substrates used in the optical film industry, such as glass or plastic. Preferred substrates particularly suitable for polymerization are polyesters such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), polyvinyl alcohol (PVA), polycarbonate (PC), triacetylcellulose (TAC), or cycloolefin polymers (COP), or commonly known color filter materials, in particular triacetylcellulose (TAC), cycloolefin polymers (COP), or commonly known color filter materials.

[0342] The polymerizable LC material preferably exhibits uniform alignment throughout the layer. Preferably, the polymerizable LC material exhibits uniform planar, uniform homeotropic, uniform cholesteric or patterned alignment.

[0343] The Friedel-Creagh-Kmetz law states that the RM layer (γ RM ) and the substrate (γ s ) can be used to predict whether a mixture will adopt a planar or homeotropic orientation.

[0344] gamma RM >γ s In the case of γ, the reactive mesogenic compound exhibits homeotropic alignment, RM <γ s In this case, the reactive mesogenic compound exhibits homogeneous alignment.

[0345] Without being bound by theory, when the surface energy of the substrate is relatively low, the intermolecular forces between the reactive mesogens are stronger than the forces across the RM-substrate interface, and as a result, the reactive mesogens align perpendicular to the substrate (homeotropic alignment) to maximize the intermolecular forces.

[0346] Homeotropic alignment can also be achieved 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 heads of the amphiphile are chemically bonded to the substrate, and the hydrocarbon tails point perpendicular to the substrate. Intermolecular interactions between the amphiphile and the RM promote homeotropic alignment. Commonly used amphiphilic surfactants are listed above.

[0347] Another method used to promote homeotropic alignment is to subject plastic substrates to corona discharge treatment, which generates functional groups on the surface, such as alcohols and ketones. These polar groups can interact with polar groups present in RMs or surfactants to promote homeotropic alignment.

[0348] 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, the interfacial energy is minimized and the long axis of the RM can interact with the substrate. One method to promote parallel alignment is to coat the substrate with a polyimide layer and rub it with a velvet cloth.

[0349] Other suitable planar alignment layers are known in the art, such as alignment layers prepared by rubbing polyimide or photoalignment, as described, for example, in U.S. Pat. No. 5,602,661, U.S. Pat. No. 5,389,698 or U.S. Pat. No. 6,717,644.

[0350] A general review of alignment techniques is given, for example, in I. Sage, "Thermotropic Liquid Crystals," edited by GW Gray, John Wiley & Sons, 1987, pp. 75-77, and T. Uchida and H. Seki, "Liquid Crystals - Applications and Uses Vol. 3," edited by B. Bahadur, World Scientific Publishing, Singapore, 1992, pp. 1-63. A review of alignment materials and techniques is given in J. Cognard, Mol. Cryst. Liq. Cryst., Vol. 78, Supplement 1 (1981), pp. 1-77.

[0351] To produce a polymer film according to the present invention, the polymerizable compounds in the polymerizable LC material are polymerized or crosslinked (if one compound contains two or more polymerizable groups) in situ by photopolymerization.

[0352] Photopolymerization can be carried out in one step, or compounds that did not react in the first step can be photopolymerized or crosslinked in a second step ("final cure").

[0353] In a preferred preparation method, the polymerizable LC material is coated onto a substrate and then photopolymerized, e.g. by exposure to light irradiation, as described, e.g., in WO 01 / 20394, GB 2,315,072 or WO 98 / 04651.

[0354] Photopolymerization of the LC material is preferably achieved by exposure to actinic radiation. By actinic radiation is meant irradiation with light, such as ultraviolet, infrared, or visible light, irradiation with X-rays or gamma rays, or irradiation with high-energy particles, such as ions or electrons. Preferably, polymerization is carried out by photoirradiation, particularly irradiation with UV light. For example, a single UV lamp or a set of UV lamps can be used as a light source for actinic radiation. Using high lamp power can shorten the curing time. Another possible light source for photoirradiation is a laser, such as a UV laser, an IR laser, or a visible laser. Another possible photoirradiation source is an LED lamp.

[0355] The curing time depends, inter alia, on the reactivity of the polymerizable LC material, the thickness of the coating layer, the type of polymerization initiator, and the power of the UV lamp. The curing time is preferably 5 minutes or less, very preferably 3 minutes or less, and most preferably 1 minute or less. For mass production, short curing times of 30 seconds or less are preferred.

[0356] The preferred UV radiation power is 5 to 200 mW cm -2 in the range of 50 to 175 mWcm -2 in the range of 100-150 mWcm -2 is within the range.

[0357] A suitable UV dose as a function of time relative to the applied UV radiation is preferably between 25 and 7200 mJ cm -2 in the range of 100 to 7200 mJcm -2 in the range of 200 to 7200 mJcm -2 is within the range.

[0358] The photopolymerization is preferably carried out in an inert gas atmosphere, preferably in a heated nitrogen atmosphere, but polymerization in air is also possible.

[0359] The photopolymerization is carried out at a temperature of preferably 1 to 70°C, more preferably 5 to 50°C, and even more preferably 15 to 30°C.

[0360] The polymerized LC films according to the present invention have good adhesion to plastic substrates, especially TAC, COP, and color filters, and can therefore be used as adhesives or base coatings for subsequent LC layers that would otherwise not adhere well to the substrate.

[0361] For optical applications of the polymer film, it preferably has a thickness of 0.5 to 10 μm, very preferably 0.5 to 5 μm, in particular 0.5 to 3 μm.

[0362] The optical retardation (δ(λ)) of a polymer film as a function of the wavelength of incident light is given by the following equation (7): δ(λ)=(2πΔn d) / λ (7) where (Δn) is the birefringence of the film, (d) is the thickness of the film, and λ is the wavelength of the incident beam.

[0363] According to Snellius' law, the birefringence as a function of the incident beam direction is defined as: Δn=sinΘ / sinΨ (8) where sinΘ is the angle of incidence to the film or the tilt angle of the optical axis, and sinΨ is is the corresponding reflection angle.

[0364] Based on these laws, birefringence, and therefore optical retardation, depends on the film thickness and the tilt angle of the optical axis within the film (see Berek compensator). Therefore, those skilled in the art recognize that by adjusting the orientation of liquid crystal molecules in a polymer film, different optical retardation or different birefringence can be induced.

[0365] 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.

[0366] The optical retardation as a function of thickness of the polymer films according to the present invention is less than 200 nm, preferably less than 180 nm, even more preferably less than 150 nm.

[0367] The polymer film of the present invention can also be used as an alignment film or a substrate for other liquid crystal or RM materials. The inventors have found that polymer films obtained from the above-mentioned and below-mentioned polymerizable LC materials are particularly useful for multilayer applications due to their excellent dewetting properties. In this way, optical films, preferably laminates of polymerized LC films, can be prepared.

[0368] In summary, the polymerized LC films and polymerizable LC materials according to the present invention are useful in optical elements such as polarizers, compensators, alignment layers, circular polarizers or color filters for liquid crystal displays or projection systems, decorative images, preparation of liquid crystals or effect pigments, and in particular in reflective films with spatially varying reflected color, e.g. multicolor images for decoration, information storage or security applications, e.g. for ID or unmanufactured documents such as credit cards, banknotes etc.

[0369] The polymerized LC films according to the present invention can be used in transmissive or reflective displays. They can be used in conventional OLED displays or LCDs, especially LCDs.

[0370] The present invention is described above and below with particular reference to preferred embodiments, it being understood that various changes and modifications can be made therein without departing from the spirit and scope of the invention.

[0371] Many of the compounds mentioned above and below or their mixtures are commercially available.All of these compounds are known or can be prepared by methods known per se, as described in the literature (for example, standard works such as Houben-Weyl, Methoden der Organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart), precisely under known and suitable reaction conditions for the reactions.Also, modifications known per se, but not mentioned here, can be used.

[0372] It will be understood that modifications can be made to the above-described embodiments of the invention that fall within the scope of the invention. Alternative features serving the same, equivalent, or similar purpose may be substituted for each feature disclosed herein, unless expressly stated otherwise. Thus, unless expressly stated otherwise, each feature disclosed is only an example of a generic series of equivalent or similar features.

[0373] All features disclosed herein may be combined in any combination, except combinations in which at least some of such features and / or steps are mutually exclusive. In particular, preferred features of the invention are applicable to all aspects of the invention and may be used in any combination. Similarly, features described in non-essential combinations may be used separately (not in combination).

[0374] It will be appreciated that many of the features described above, particularly those of the preferred embodiments, are inventive in their own right and not just as part of embodiments of the present invention, and that independent protection may be sought for these features in addition to or in place of the presently claimed invention.

[0375] The present invention will now be described in more detail with reference to the following examples, which are illustrative and not intended to limit the scope of the present invention. [Example]

[0376] <Example 1> The following mixture is prepared:

[0377] [Table 1]

[0378] Irganox 1076, LC756 and LC242 are commercially available from BASF, Germany, and TR-PBG-304 is commercially available from Changzhou Tronly New Electronic Materials Co., Ltd.

[0379] [Table 2]

[0380] 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.; and DK-756 is commercially available from Henan Daken Chemical Co., Ltd.

[0381] To Mix 1 and Mix 2, surfactants are added in the concentrations described above to make the comparative formulations and inventive formulations 2 and 9. The formulation compositions are summarized in Table 1 below.

[0382]

[0383] [Table 3]

[0384] The Tego and Dynol series additives are commercially available from Evonik Tego GmbH, Germany. Polyfox PF-656 is commercially available from Omnova Solutions Inc., USA.

[0385] <Usage example 1> Polymer films were prepared from Formulations 1-7 using the following method. Formulations 1-7 are spin coated onto polyimide-rubbed glass at 3000 rpm for 30 seconds. Anneal the film at 60°C for 60 seconds. · Film is used with DELO 365nm LED lamp (70mWcm -2 , under nitrogen atmosphere for 10 seconds). A second layer of formulations 1-7 is spin coated onto the cured first layer. Anneal the film at the desired temperature for 60 seconds. · Film is used with DELO 365nm LED lamp (70mWcm -2 , under nitrogen atmosphere for 10 seconds).

[0386] After the initial curing, each multilayer film was visually inspected for RM orientation and visual haze, and the results are recorded in the table below. After the second annealing step, each film was visually inspected for dewetting, and the results are recorded in Table 2 below.

[0387]

[0388] [Table 4]

[0389] As can be seen, using Dynol 800 as a surfactant allows for RM alignment without dewetting over a very wide annealing temperature range, and this surfactant also provides alignment for the top layer without the need for an additional alignment layer.

[0390] <Usage example 2> Polymer films were prepared from formulations 8-14 using the following method. Formulations 8-14 were spin coated onto polyimide-rubbed glass at 3000 rpm for 30 seconds. Anneal the film at 60°C for 60 seconds. · Film is used with DELO 365nm LED lamp (70mWcm -2 , under nitrogen atmosphere for 10 seconds). A second layer of formulation 8-14 is spin coated onto the cured first layer. Anneal the film at the desired temperature for 60 seconds. · Film is used with DELO 365nm LED lamp (70mWcm -2 , under nitrogen atmosphere for 10 seconds).

[0391] After the initial cure, each multilayer film was visually inspected for RM orientation and visual haze, and the results are recorded in the table below. After the second annealing step, each film was visually inspected for dewetting, and the results are recorded in Table 3 below.

[0392]

[0393] [Table 5]

[0394] As can be seen, using Dynol 800 as a surfactant allows for RM alignment without dewetting over a very wide annealing temperature range, and this surfactant also provides alignment for the top layer without the need for an additional alignment layer.

Claims

1. A polymerizable LC material comprising one or more reactive mesogenic compounds and one or more compounds of formula I. 【Chemistry 1】 (In the formula, R １ ~R ６ Each of these is an independent linear, branched, or cyclic alkyl group having 1 to 40 carbon atoms, and is either unsubstituted or monosubstituted or polysubstituted with F, Cl, Br, I, or CN, provided that it contains one or more non-adjacent CH groups. ２ The groups are independent of each other, and the O atoms and / or S atoms do not directly bond to each other, -C(R) ｘ ) = C(R ｘ )-, -C≡C-, -N(R ｘ ) -, -O-, -S-, -CO-, -CO-O-, -O-CO-, O-CO-O- may also be substituted, R ｘ This represents a linear, branched, or cyclic alkyl chain having H, a halogen, and 1 to 25 C atoms, and furthermore, one or more non-adjacent C atoms may be substituted with -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, and one or more H atoms may be substituted with fluorine. x and y are each independently greater than or equal to 1. (m and n are each independently greater than or equal to 1.)

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

3. The polymerizable LC material according to claim 1, comprising one or more reactive mesogens selected from formula RMT. 【Chemistry 2】 (In the formula, P is a polymerizable group, Sp is a spacer group or a single bond. r2 and r3 are each independently 0, 1, 2, 3, or 4. R １１ This is an alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy group having P-Sp-, 1 to 15 C atoms, and the group may be fluorinated. When a plurality of A and B occur, each of A and B independently represents an aromatic or alicyclic group (said group may contain one or more heteroatoms selected from N, O and S, and may be mono- or poly-substituted with L), with the proviso that one or two non-adjacent CH ２ groups may be replaced by O and / or S, with the proviso that these groups are unsubstituted or substituted with one, two, three or four groups L, L is P-Sp-, F, Cl, Br, I, -CN, -NO ２ , -NCO, -NCS, -OCN, -SCN, -C(=O)NR ｘ R ｙ , -C (=O) OR ｘ , -C(=O)R ｘ , -NR ｘ R ｙ -OH, -SF ５ Alternatively, a linear or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, wherein one or more H atoms may be replaced with F or Cl. R ００ ~R ０００ , R ｘ and R ｙ Each of these represents an alkyl group having either H or 1 to 12 C atoms independently of each other. Z １１ and Z １２ If multiple occurrences occur, they are treated independently as -O-, -S-, -CO-, -COO-, -OCO-, -S-CO-, -CO-S-, -O-COO-, -CO-NR ００ -, -NR ００ -CO-, -NR ００ -CO-NR ０００ -, -NR ００ -CO-O-, -O-CO-NR ００ -, -OCH ２ -ien-CH ２ O-, -SCH ２ -ien-CH ２ S-, -CF ２ O-, -OCF ２ -, -CF ２ S-, -SCF ２ -ien-CH ２ CH ２ -, - (CH ２ ) ｎ１ -, -CF ２ CH ２ -ien-CH ２ CF ２ -, -CF ２ CF ２ -, -CH=N-, -N=CH-, -N=N-, -CH=CR ００ -, -CY １ =CY ２ -, -C≡C-, -CH=CH-COO-, -OCO-CH=CH-, or single bond are represented. Y １ and Y ２ Each of these independently represents H, F, Cl, or CN. n is 1, 2, 3 or 4, m is 0, 1, 2, 3 or 4, n1 is an integer between 1 and 10.

4. The polymerizable LC material according to claim 3, wherein the concentration of the compound of formula RMT is 40% to 99%.

5. The polymerizable LC material according to claim 1, comprising one or more compounds selected from formula DRM. 【Transformation 3】 (In the formula, P １ and P ２ These represent polymerizable groups independently of each other, Sp １ and Sp ２ These are spacer groups or single bonds, independently of each other. MG is a rod-shaped mesogenic group, However, this is subject to the condition that compounds of formula RMT are excluded from compounds of formula DRM. 【Chemistry 4】 (In the formula, P is a polymerizable group, Sp is a spacer group or a single bond. r2 and r3 are each independently 0, 1, 2, 3, or 4. R11 is a P-Sp- alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy group having 1 to 15 carbon atoms, and the group may be fluorinated. If A and B appear in multiple locations, they are independently aromatic or alicyclic groups (these groups may contain one or more heteroatoms selected from N, O, and S, and may be monosubstituted or polysubstituted with L), provided that one or two non-adjacent CH2 groups are replaced with O and / or S, provided that these groups are unsubstituted or substituted with one, two, three, or four L groups. L is P-Sp-, F, Cl, Br, I, -CN, -NO₂, -NCO, -NCS, -OCN, -SCN, -C(=O)NRxRy, -C(=O)ORx, -C(=O)Rx, -NRxRy, -OH, -SF₅, or a linear or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, wherein one or more H atoms may be replaced with F or Cl. R 00 to R 000, R x, and R y each independently represent an alkyl group having H or 1 to 12 C atoms. If Z11 and Z12 appear multiple times, they are independent of each other: -O-, -S-, -CO-, -COO-, -OCO-, -S-CO-, -CO-S-, -O-COO-, -CO-NR 00-, -NR 00-CO-, -NR 00-CO-NR 000-, -NR 00-CO-O-, -O-CO-NR 00-, -OCH 2-, -CH 2 O-, -SCH 2-, -CH 2 S-, -CF 2 O-, -OCF 2-, -CF 2 S-, -SCF 2-, -CH 2 CH 2-, -(CH 2) n1-, -CF 2 CH 2-, -CH 2 CF 2-, -CF 2 CF 2 -, -CH=N-, -N=CH-, -N=N-, -CH=CR 00 -, -CY 1 =CY 2 -, -C≡C-, -CH=CH-COO-, -OCO-CH=CH- or represents a single bond, Y1 and Y2 each independently represent H, F, Cl, or CN. n is 1, 2, 3 or 4, m is 0, 1, 2, 3 or 4, n1 is an integer between 1 and 10.

6. The polymerizable LC material according to claim 1, wherein the concentration of the direactive or polyreactive reactive mesogen is 1% to 60%.

7. The polymerizable LC material according to claim 1, comprising one or more compounds selected from formula MRM. 【Transformation 5】 (In the formula, P1 represents a polymerizable group, Sp 1 is a spacer group or a single bond. MG is a rod-shaped mesogenic group, R is P-Sp-, F, Cl, Br, I, -CN, -NO ２ , -NCO, -NCS, -OCN, -SCN, -C(=O)NR ｘ R ｙ , -C(=O)X, -C(=O)OR ｘ , -C(=O)R ｙ , -NR ｘ R ｙ -OH, -SF ５ , represents a substituted silyl, linear or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, wherein one or more H atoms may be replaced with F or Cl. X is a halogen, R ｘ and R ｙ Each of these is an alkyl group having H or 1 to 12 C atoms independently of each other. However, this is subject to the condition that compounds of formula RMT are excluded from compounds of formula MRM. 【Transformation 6】 (In the formula, P is a polymerizable group, Sp is a spacer group or a single bond. r2 and r3 are each independently 0, 1, 2, 3, or 4. R11 is a P-Sp- alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy group having 1 to 15 carbon atoms, and the group may be fluorinated. If A and B appear in multiple locations, they are independently aromatic or alicyclic groups (these groups may contain one or more heteroatoms selected from N, O, and S, and may be monosubstituted or polysubstituted with L), provided that one or two non-adjacent CH2 groups are replaced with O and / or S, provided that these groups are unsubstituted or substituted with one, two, three, or four L groups. L is P-Sp-, F, Cl, Br, I, -CN, -NO₂, -NCO, -NCS, -OCN, -SCN, -C(=O)NRxRy, -C(=O)ORx, -C(=O)Rx, -NRxRy, -OH, -SF₅, or a linear or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, wherein one or more H atoms may be replaced with F or Cl. R 00 to R 000, R x, and R y each independently represent an alkyl group having H or 1 to 12 C atoms. If Z11 and Z12 appear multiple times, they are independent of each other: -O-, -S-, -CO-, -COO-, -OCO-, -S-CO-, -CO-S-, -O-COO-, -CO-NR 00-, -NR 00-CO-, -NR 00-CO-NR 000-, -NR 00-CO-O-, -O-CO-NR 00-, -OCH 2-, -CH 2 O-, -SCH 2-, -CH 2 S-, -CF 2 O-, -OCF 2-, -CF 2 S-, -SCF 2-, -CH 2 CH 2-, -(CH 2) n1-, -CF 2 CH 2-, -CH 2 CF 2-, -CF 2 CF 2 -, -CH=N-, -N=CH-, -N=N-, -CH=CR 00 -, -CY 1 =CY 2 -, -C≡C-, -CH=CH-COO-, -OCO-CH=CH- or represents a single bond, Y1 and Y2 each independently represent H, F, Cl, or CN. n is 1, 2, 3 or 4, m is 0, 1, 2, 3 or 4, n1 is an integer between 1 and 10.

8. The polymerizable LC material according to claim 1, comprising one or more reactive chiral compounds selected from compounds of formula CRMa to CRMc. 【Transformation 7】 (In the formula, P ０＊ This represents a polymerizable group, A ０ and B ０ If multiple instances occur, they are 1,4-phenylene or trans-1,4-cyclohexylene, either unsubstituted or substituted with one, two, three, or four L groups independently of each other. X １ and X ２ These are, independently of each other, -O-, -COO-, -OCO-, -O-CO-O-, or single bonds, Z ０＊ and Z ０ When multiple occurrences occur, they are treated independently as -COO-, -OCO-, -O-CO-O-, and -OCH. ２ -ien-CH ２ O-, -CF ２ O-, -OCF ２ -ien-CH ２ CH ２ -, - (CH ２ ) ４ -, -CF ２ CH ２ -ien-CH ２ CF ２ -, -CF ２ CF ２ -, -C≡C-, -CH=CH-, -CH=CH-COO-, -OCO-CH=CH- or single bond, t is 0, 1, 2, or 3, each independently of the others. a is 0, 1, or 2. b is an integer from 0 to 12. z is either 0 or 1, However, the naphthalene ring in formula CRMa may be substituted with one or more identical or different groups L. However, L is each independently of F, Cl, CN, an alkyl halide, an alkoxy, an alkylcarbonyl, an alkoxycarbonyl, an alkylcarbonyloxy, or an alkoxycarbonyloxy having 1 to 5 carbon atoms.

9. The polymerizable LC material according to claim 8, wherein the concentration of the chiral compound in the liquid crystal medium is 1 to 20%.

10. A polymerizable LC material according to claim 1, comprising one or more additives selected from the group consisting of further surfactants, photoinitiators, stabilizers, catalysts, sensitizers, inhibitors, chain transfer agents, co-reaction monomers, reactive thinners, surface-active compounds, lubricants, wetting agents, dispersants, hydrophobic agents, adhesives, flow modifiers, degassing or defoaming agents, defoaming agents, diluents, reactive diluents, auxiliary agents, colorants, dyes, pigments, and nanoparticles.

11. A method for preparing a polymerizable LC material according to any one of claims 1 to 10, A method comprising the step of mixing one or more compounds of formula I as defined in claim 1 with one or more reactive mesogenic compounds and optionally one or more chiral compounds.

12. A method for preparing a polymer film, - A layer of polymerizable LC material according to any one of claims 1 to 10 is provided on a substrate, - Photopolymerize polymerizable LC material, and A method in which the polymerized LC material may be optionally removed from the substrate and / or optionally provided on another substrate.

13. A polymer film which is a polymer of the polymerizable LC material according to any one of claims 1 to 10.

14. Use in an optical component of a polymer film which is a polymer of one or more polymerizable LC materials according to any one of claims 1 to 10, or of a polymerizable LC material according to any one of claims 1 to 10.

15. A polymer film which is a polymer of one or more polymerizable LC materials according to any one of claims 1 to 10, or an optical component comprising a polymerizable LC material according to any one of claims 1 to 10.

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

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

Images