Process of preparing a polymer film from a homeotropically aligned reactive mesogen mixture

Abstract

The invention relates to process of preparing a polymer film from a homeotropically aligned reactive mesogen mixture (RMM) (as a subcategory of liquid crystal material) on a substrate, a PFAS-free RMM used in such a process, enabling the reduction of perfluorocarbons, a polymer film obtained by such a process, and its use as optical element in optical or electrooptical components or devices.

Description

[0001] Process of Preparing a Polymer Film from a Homeotropically Aligned Reactive Mesogen Mixture

[0002] Technical Field of the Invention

[0003] The invention relates to process of preparing a polymer film from a homeotropically aligned reactive mesogen mixture (RMM) (as a subcategory of liquid crystal material) on a substrate, a PFAS-free RMM used in such a process, enabling the reduction of perfluorocarbons, a polymer film obtained by such a process, and its use as optical element in optical or electrooptical components or devices.

[0004] Background and Prior Art

[0005] Polymer films comprising polymerized acrylate RMs with homeotropic orientation (also known as +C films) are challenging to align on industry standard substrates, which are typically plastic substrates like TAC (triacetyl cellulose) or COP (cycloolefinic polymer), due to the requirement for specific, thermodynamically unfavourable molecular interaction. Typically, the acrylate endgroups of RMs will only align homeotropically on a sufficiently polar substrate such as raw glass. Plastic substrates, such as TAC or COP, on the other hand are usually too apolar, meaning that these substrates must first be pre-treated either with alignment layers or surface modifying corona plasma treatment.

[0006] A secondary effect of this molecular orientation is that adhesion between the cured RM film and substrates is typically poor. This problem is typically resolved using coated primer layers or the addition of adhesion promoters such as for Tego Addid 900 (an amino-functional alkoxysilane). However, such additional coatings for primers mean higher costs and longer and more complicated film production processes, and moreover can also can negatively impact solubility of the RM mixture.

[0007] In prior art it is also suggested using in LC or RM materials additives like wetting-, flow- and leveling agents, for example based on non-ionic fluorosurfactants, which can also promote homeotropic alignment However, following the ban on polyfluoroalkyl substances (PFAS) for environmental reasons many such fluorosurfactants must be replaced in the near future, creating a further need for alternative solutions.

[0008] Therefore, there is a need for improved methods of homeotropically aligning RM materials for the preparation of +C films, and for improved RM materials suitable for these methods, which do not exhibit the drawbacks of prior art methods and materials, do not require the use of environmentally critical fluorocarbon compounds, enable the preparation of polymer films with uniform homeotropic alignment and strong adhesion to the substrate, in a simple, time- and cost-effective way and in reproducible quality and large quantity, and are compatible for mass production.

[0009] One aim of the present invention is to provide improved methods of homeotropically aligning RM materials, improved RM materials for use therein, and improved +C polymer films with good alignment and strong adhesion made by these methods and materials. Other aims of the present invention are immediately evident to the person skilled in the art from the following detailed description.

[0010] Surprisingly, the inventors of the present invention have found that one or more of these aims can be achived by providing a process and RMM as disclosed and claimed hereinafter.

[0011] Summary of the Invention

[0012] The invention relates to a process of preparing a polymer film comprising a homeotropically aligned, polymerized reactive mesogen mixture (RMM) on a substrate, said process comprising the following steps:

[0013] - providing a layer of the RMM, or a formulation comprising the RMM and further comprising one or more solvents, onto the substrate,

[0014] - optionally removing any solvents, if present,

[0015] - optionally annealing the layer of the RM mixture, preferably at a temperature where it exhibits a nematic phase,

[0016] - irradiating the RM layer with actinic radiation, preferably with UV radiation, causing polymerization of the polymerizable components and formation of a polymer film,

[0017] - optionally removing the polymer film from the substrate, characterized in that the RMM comprises one or more, preferably two or more, mono-, di- or multireactive mesogens, and further comprises from 1 to 15%, preferably from 2 to 10%, of one or more additives selected from methacrylic and acrylic esters of polyfunctional alcohols, wherein said additives do only contain terminal groups selected from acrylic, methacrylic and hydroxy groups, and wherein preferably the RMM does not contain a compound with at least one CF3 or CF2 group (PFAS), and very preferably the RMM does not contain a compound with a polyfluorinated alkyl or aryl group or a perfluorocarbon group. More preferably the RMM does not contain a compound with a fluorinated aliphatic C atom, most preferably the RMM does not contain a compound with a fluorinated C atom.

[0018] The invention further relates to an RMM as described above and below, which does not contain a PFAS, and very preferably does not contain a compound with a polyfluorinated C atom.

[0019] The invention further relates to a polymer film obtained from a process as described above and below.

[0020] The invention further relates to an optical, electrooptical or electronic device or a component thereof comprising a polymer film as described above and below.

[0021] Said components include, without limitation, optical retardation films, polarizers, optical compensators, diffraction or surface gratings such as Bragg polarization gratings (Bragg PG), polarization volume gratings (PVG), Pancharatnam Berry gratings (PBG) or Pancharatnam Berry lenses (PBL), furthermore nonmechanical beam steering elements, optical waveguides, optical couplers or combiners, polarization beam splitters, partial mirrors, reflective films, alignment layers, colour filters, antistatic protection sheets, electromagnetic interference protection sheets, lenses for light guides, focusing and optical effects, polarization controlled lenses, and IR reflection films; for example for use in LC displays (LCDs), organic light emitting diodes (OLEDs), autostereoscopic 3D displays, see-through near-eye displays, augmented real ity( AR) or virtual reality (VR) systems, switchable windows, spatial light modulators, optical data storage, remote optical sensing, holography, spectroscopy, optical telecommunications, polarimetry or front / back-lighting.

[0022] Said devices include, without limitation, electro optical displays, especially LCDs, OLEDs, non-linear optic (NLO) devices, autostereoscopic 3D displays, see-through near-eye displays, AR / VR systems, goggles for AR / VR applications, switchable windows, spatial light modulators, optical data storage devices, optical sensors, holographic devices, spectrometers, optical telecommunication systems, polarimeters or front- / backlights.

[0023] Terms and Definitions Throughout the description and claims of this specification, the words “comprise” and “contain” and variations of the words, for example “comprising” and “comprises”, mean “including but not limited to”, and are not intended to (and do not) exclude other components.

[0024] Unless the context clearly indicates otherwise, as used herein plural forms of the terms herein are to be construed as including the singular form and vice versa.

[0025] The term “per- and / or polyfluoroalkyl substance (PFAS)” as used herein (following the definition by the OECD) means a substance or compound that contains at least one fully fluorinated methyl or methylene C atom (without any H / CI / Br / l atom attached to it), i.e. , a compound with at least one CF3 or CF2 group.

[0026] The expression “polyfluorinated alkyl or aryl group” as used herein means an alkyl or aryl group which is substituted by two or more F atoms (wherein the F atoms may be attached either to the same or different C atoms), thus including perfluorocarbon groups.

[0027] The term “+C film” as used herein means a film or layer of uniaxially birefringent LC or RM material with positive birefringence and with its extraordinary axis being oriented perpendicular to the plane of the layer.

[0028] The term "film" as used herein includes rigid or flexible, self-supporting or freestanding films with mechanical stability, as well as coatings or layers on a supporting substrate or between two substrates.

[0029] As used herein, the terms "reactive mesogen" and "RM" will be understood to mean a compound containing a mesogenic or liquid crystalline skeleton, and one or more functional groups attached thereto, optionally via spacer groups, which are suitable for polymerization and are also referred to as "polymerizable group" or "P".

[0030] In contrast thereto, the one or more additives selected from methacrylic and acrylic esters of polyfunctional alcohols contained in the RMM as described above and below are not RMs in the sense of the present invention.

[0031] Unless stated otherwise, the term "polymerizable compound" as used herein will be understood to mean a polymerizable monomeric compound. Polymerizable compounds or RMs with one polymerizable group are also referred to as "monoreactive" compounds, polymerizable compounds or RMs with two polymerizable groups as "direactive" compounds, and polymerizable compounds or RMs with more than two polymerizable groups as "multireactive" compounds. Compounds without a polymerizable group are also referred to as "non-reactive" compounds.

[0032] The terms "liquid crystal", "mesogen" and "mesogenic compound" as used herein mean a compound that under suitable conditions of temperature, pressure and concentration can exist as a mesophase or in particular as a LC phase.

[0033] The term “clearing point” means the temperature at which the transition between the mesophase with the highest temperature range and the isotropic phase occurs.

[0034] The term "mesogenic group" as used herein is known to the person skilled in the art and described in the literature, and means a group which, due to the anisotropy of its attracting and repelling interactions, essentially contributes to causing a liquid-crystal (LC) phase in low-molecular-weight or polymeric substances. Compounds containing mesogenic groups (mesogenic compounds) do not necessarily have to have an LC phase themselves. It is also possible for mesogenic compounds to exhibit LC phase behaviour only after mixing with other compounds and / or after polymerization. Typical mesogenic groups are, for example, rigid rod- or disc-shaped units. An overview of the terms and definitions used in connection with mesogenic or LC compounds is given in Pure Appl. Chem. 2001, 73(5), 888 and C. Tschierske, G. Pelzl, S. Diele, Angew. Chem. 2004, 116, 6340-6368.

[0035] The term "spacer group", hereinafter also referred to as "Sp", as used herein is known to the person skilled in the art and is described in the literature, see, for example, Pure Appl. Chem. 2001, 73(5), 888 and C. Tschierske, G. Pelzl, S. Diele, Angew. Chem. 2004, 116, 6340-6368. As used herein, the terms "spacer group" or "spacer" mean a flexible group, for example an alkylene group, which connects the mesogenic group and the polymerizable group(s) in a polymerizable mesogenic compound.

[0036] As used herein, the term "RM mixture" means a mixture comprising one or more, preferably two or more, more preferably two to ten, very preferably two to six RMs.

[0037] As used herein, the term "RM formulation" means at least one RM or RM mixture, and one or more other materials added to the at least one RM or RM mixture to provide, or to modify, specific properties of the RM formulation and / or of the at least one RM therein. It will be understood that an RM formulation is also a vehicle for carrying the RM to a substrate to enable the forming of layers or structures thereon. Exemplary materials include, but are not limited to, solvents, polymerization initiators, surfactants and adhesion promoters, etc. as described in more detail below.

[0038] Unless stated otherwise, the percentage of a compound in an RM mixture as given above and below means % by weight of the total RM mixture, excluding solvents or additives as described above and below that are used in the RM formulation.

[0039] Unless stated otherwise, the percentage of a compound in an RM formulation as given above and below means % by weight of all solids in the RM formulation, including liquid additives as described below but excluding solvents.

[0040] As used herein, the term "polymer" will be understood to mean a molecule that encompasses a backbone of one or more distinct types of repeating units (the smallest constitutional unit of the molecule) and is inclusive of the commonly known terms “oligomer”, “copolymer”, “homopolymer” and the like. Further, it will be understood that the term polymer is inclusive of, in addition to the polymer itself, residues from initiators, catalysts, and other elements attendant to the synthesis of such a polymer, where such residues are understood as not being covalently incorporated thereto. Further, such residues and other elements, while normally removed during post polymerization purification processes, are typically mixed or co-mingled with the polymer such that they generally remain with the polymer when it is transferred between vessels or between solvents or dispersion media.

[0041] The term “polymerization” means the chemical process to form a polymer by bonding together multiple polymerizable groups or polymer precursors (polymerizable compounds) containing such polymerizable groups.

[0042] The birefringence An is defined as follows

[0043] An = ne-n0wherein neis the extraordinary refractive index and n0is the ordinary refractive index, and the effective average refractive index nav. is given by the following equation: nav. = ((2n02+ ne2) / 3)1 / 2 The average refractive index nav. and the ordinary refractive index n0can be measured using an Abbe refractometer. An can then be calculated from the above equations.

[0044] On the molecular level, the birefringence of a liquid crystal depends on the anisotropy of the polarizability (Aa=a11-aj-). "Polarisability" means the ease with which the electron distribution in the atom or molecule can be distorted. The polarizability increases with greater number of electrons and a more diffuse electron cloud. The polarizability can be calculated using a method described in e.g. Jap. J. Appl. Phys. 42, (2003) p. 3463.

[0045] The "optical retardation" at a given wavelength R( ) (in nm) of a layer of liquid crystalline or birefringent material is defined as the product of birefringence at that wavelength An(X) and layer thickness d (in nm) according to the following equation:

[0046] R(A) = An(X) ■ d

[0047] The optical retardation R represents the difference in the optical path lengths in nanometres travelled by S-polarised and P-polarised light whilst passing through the birefringent material. "On-axis" retardation means the retardation at normal incidence to the sample surface.

[0048] The retardation (R( )) of a material can be measured using a spectroscopic ellipsometer, for example the M2000 spectroscopic ellipsometer manufactured by J. A. Woollam Co. This instrument can measure the optical retardance in nanometres of a birefringent sample e.g., Quartz over a range of wavelengths typically, 370nm to 2000nm. From this data it is possible to calculate the dispersion (R(450) / R(550) or An(450) / An(550)) of a material.

[0049] A method for carrying out these measurements was presented at the National Physics Laboratory (London, UK) by N. Singh in October 2006 and entitled “Spectroscopic Ellipsometry, Parti -Theory and Fundamentals, Part 2 - Practical Examples and Part 3 - measurements”. In accordance with the measurement procedures described Retardation Measurement (RetMeas) Manual (2002) and Guide to WVASE (2002) (Woollam Variable Angle Spectroscopic Ellipsometer) published by J. A. Woollam Co. Inc (Lincoln, NE, USA). Unless stated otherwise, this method is used to determine the retardation of the materials, films and devices described in this invention. The term "director" is known in prior art and means the preferred orientation direction of the long molecular axes (in case of calamitic compounds) or short molecular axes (in case of discotic compounds) of the liquid-crystalline or RM molecules. In case of uniaxial ordering of such anisotropic molecules, the director is the axis of anisotropy.

[0050] The term “alignment” or “orientation” relates to alignment (orientational ordering) of anisotropic units of material such as small molecules or fragments of big molecules in a common direction named “alignment direction”. In an aligned layer of liquidcrystalline or RM material the liquid-crystalline director coincides with the alignment direction so that the alignment direction corresponds to the direction of the anisotropy axis of the material.

[0051] The terms "uniform orientation" or "uniform alignment" of an liquid-crystalline or RM material, for example in a layer of the material, mean that the long molecular axes (in case of calamitic compounds) or the short molecular axes (in case of discotic compounds) of the liquid-crystalline or RM molecules are oriented substantially in the same direction. In other words, the lines of liquid-crystalline director are parallel.

[0052] The terms "homeotropic structure I alignment I orientation" refer to a film wherein the optical axis is substantially perpendicular to the film plane.

[0053] All temperatures, such as, for example, the melting point T(C,N) or T(C,S), the transition from the smectic (S) to the nematic (N) phase T(S,N) and the clearing point T(N,I) of the liquid crystals, are quoted in degrees Celsius. All temperature differences are quoted in differential degrees.

[0054] In case of doubt the definitions as given in C. Tschierske, G. Pelzl and S. Diele, Angew. Chem. 2004, 116, 6340-6368 shall apply.

[0055] If in the formulae shown above and below a group R, including any variations thereof such as R1, R°, R00, R0*, R11, R*, R**, Rc, R3, R4etc., or L denotes an alkyl radical and / or an alkoxy radical, this may be straight-chain or branched. It is preferably straight-chain, has 2, 3, 4, 5, 6 or 7 C atoms and accordingly preferably denotes ethyl, propyl, butyl, pentyl, hexyl, heptyl, ethoxy, propoxy, butoxy, pentoxy, hexyloxy or heptyloxy, furthermore methyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy or tetradecyloxy. If in the formulae shown above and below a group R including any variations thereof such as R1, R°, R°°, R*°, R11, R22, Rc, R3, R4etc., or L denotes an alkyl radical and / or an alkoxy radical, this may be straight-chain or branched. It is preferably straightchain, has 2, 3, 4, 5, 6 or 7 C atoms and accordingly preferably denotes ethyl, propyl, butyl, pentyl, hexyl, heptyl, ethoxy, propoxy, butoxy, pentoxy, hexyloxy or heptyloxy, furthermore methyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy or tetradecyloxy.

[0056] If in the formulae shown above and below a group R including any variations thereof such as R1, R°, R°°, R°*, R11, R22, Rc, R3, R4etc., or L denotes an alkyl radical wherein one or more CH2 groups are replaced by S, this may be straight-chain or branched. It is preferably straight-chain, has 1 , 2, 3, 4, 5, 6 or 7 C atoms and accordingly preferably denotes thiomethyl, thioethyl, thiopropyl, thiobutyl, thiopentyl, thiohexyl or thioheptyl.

[0057] Oxaalkyl preferably denotes straight-chain 2-oxapropyl (= methoxymethyl), 2-oxabutyl (= ethoxymethyl) or 3-oxabutyl (= 2-methoxyethyl), 2-, 3- or 4-oxapentyl, 2-, 3-, 4- or 5-oxahexyl, 2-, 3-, 4-, 5- or 6-oxaheptyl, 2-, 3-, 4-, 5-, 6- or 7-oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanonyl, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-oxadecyl.

[0058] If in the formulae shown above and below a group R including any variations thereof such as R1, R°, R00, R*°, R11, R22, Rc, R3, R4etc., or L denotes an alkoxy or oxaalkyl group it may also contain one or more additional oxygen atoms, provided that oxygen atoms are not linked directly to one another.

[0059] In another preferred embodiment, one or more of R including any variations thereof such as R1, R°, R°°, R*°, R11, R22, Rc, R3, R4etc., or L are selected from the group consisting of

[0060] H, Ci-12-alkyl or C2-i2-alkenyl, and very preferably are selected from the group consisting of

[0061] -OCH2OCH3, -O(CH2)2OCH3, -O(CH2)3OCH3, -O(CH2)4OCH3, -O(CH2)2F, -O(CH2)3F and -O(CH2)4F.

[0062] If in the formulae shown above and below a group R including any variations thereof such as R1, R°, R00, R*°, R11, R22, Rc, R3, R4etc., or L denotes an alkyl radical in which one CH2 group has been replaced by -CH=CH-, this may be straight-chain or branched. It is preferably straight-chain and has 2 to 10 C atoms. Accordingly, it denotes, in particular, vinyl, prop-1- or -2-enyl, but-1-, -2- or -3-enyl, pent-1-, -2-, -3- or -4-enyl, hex-1-, -2-, -3-, -4- or -5-enyl, hept-1-, -2-, -3-, -4-, -5- or -6- enyl, oct-1-, -2-, -3-, -4-, -5-, -6- or -7-enyl, non-1-, -2-, -3-, -4-, -5-, -6-, -7- or -8-enyl, dec-1-, -2-, -3-, -4-, -5-, -6-, -7-, -8- or -9-enyl.

[0063] If in the formulae shown above and below a group R including any variations thereof such as R1, R°, R°°, R*°, R11, R22, Rc, R3, R4etc., or L denotes an alkyl or alkenyl radical which is at least monosubstituted by halogen, this radical is preferably straightchain, and halogen is preferably F or Cl. In the case of polysubstitution, halogen is preferably F. The resultant radicals also include perfluorinated radicals. In the case of monosubstitution, the fluorine or chlorine substituent may be in any desired position, but is preferably in the o-position.

[0064] Above and below, denotes a trans-1 ,4-cyclohexylene ring, and denotes a 1 ,4-phenylene ring. Halogen is preferably F or Cl, very preferably F.

[0065] The group -CR°=CR00- is preferably -CH=CH-.

[0066] -OC-, -CO-, -C(=O)- and -C(O)- denote a carbonyl group, i.e.

[0067] Preferred substituents L, are, for example, F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)N(RX)2, -C(=O)Y1, -C(=O)RX, -N(RX)2, straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy each having 1 to 25 C atoms, in which one or more H atoms may optionally be replaced by F or Cl, optionally substituted silyl having 1 to 20 Si atoms, or optionally substituted aryl having 6 to 25, preferably 6 to 15, C atoms, wherein Rxdenotes H, F, Cl, CN, or straight chain, branched or cyclic alkyl having 1 to 25 C atoms, wherein one or more non-adjacent CH2-groups are optionally replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- in such a manner that O- and / or S-atoms are not directly connected with each other, and wherein one of the H atoms is each optionally replaced by F, Cl, P- or P-Sp-, and Y1denotes halogen.

[0068] Particularly preferred substituents L are, for example, F, Cl, CN, NO2, CH3, C2H5, OCH3, SCH3, OC2H5, SC2H5, COCH3, COC2H5, COOCH3, COOC2H5, CF3, OCF3, OCHF2, OC2F5, furthermore phenyl. in which L has one of the meanings indicated above.

[0069] Throughout the application, the term “aryl and heteroaryl groups” encompass groups, which can be monocyclic or polycyclic, i.e. they can have one ring (such as, for example, phenyl) or two or more rings, which may also be fused (such as, for example, naphthyl) or covalently linked (such as, for example, biphenyl), or contain a combination of fused and linked rings. Heteroaryl groups contain one or more heteroatoms, preferably selected from O, N, S and Se. Particular preference is given to mono-, bi- or tricyclic aryl groups having 6 to 25 C atoms and mono-, bi- or tricyclic heteroaryl groups having 2 to 25 C atoms, which optionally contain fused rings, and which are optionally substituted. Preference is furthermore given to 5 , 6 or 7- membered aryl and heteroaryl groups, in which, in addition, one or more CH groups may be replaced by N, S or O in such a way that O atoms and / or S atoms are not linked directly to one another. 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, more preferably 1 ,4- phenylene, 4,4’-biphenylene, 1 , 4-tephenylene.

[0070] Preferred heteroaryl groups are, for example, 5 membered rings, such as pyrrole, pyrazole, imidazole, 1 ,2,3-triazole, 1 ,2,4-triazole, tetrazole, furan, thiophene, selenophene, oxazole, isoxazole, 1 ,2 thiazole, 1 ,3-thiazole, 1 ,2,3-oxadiazole, 1 ,2,4 oxadiazole, 1 ,2,5-oxadiazole, 1 ,3,4-oxadiazole, 1 ,2,3-thiadiazole, 1 ,2,4-thiadiazole, 1 ,2,5-thiadiazole, 1 ,3,4-thiadiazole, 6 membered rings, such as pyridine, pyridazine, pyrimidine, pyrazine, 1 ,3,5-triazine, 1 ,2,4-triazine, 1 ,2,3-triazine, 1 ,2,4,5-tetrazine, 1 ,2,3,4-tetrazine, 1 ,2,3,5-tetrazine, or condensed groups, such as indole, iso-indole, indolizine, indazole, benzimidazole, benzotriazole, purine, naphthimidazole, phenanthrimidazole, pyridimidazole, pyrazinimidazole, quinoxalinimidazole, benzoxazole, naphthoxazole, anthroxazole, phen-anthroxazole, isoxazole, benzothiazole, benzofuran, isobenzofuran, dibenzofuran, quinoline, isoquinoline, pteridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, benzoisoquinoline, 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. The heteroaryl groups may also be substituted by alkyl, alkoxy, thioalkyl, fluorine, fluoroalkyl or further aryl or heteroaryl groups.

[0071] In a group the single bond shown between the two ring atoms can be attached to any free position of the benzene ring.

[0072] -OC-, -CO-, -C(=O)- and -C(O)- denote a carbonyl group, i.e.

[0073] The polymerizable group P, including any variations thereof such as P°, P1, P2, P*°, is a group which is suitable for a polymerization reaction, such as, for example, free- radical or ionic chain polymerization, polyaddition or polycondensation, or for a polymer-analogous reaction, for example addition or condensation onto a main polymer chain. Particular preference is given to groups for chain polymerization, in particular those containing a C=C double bond or -C=C- triple bond, and groups which are suitable for polymerization with ring opening, such as, for example, oxetane or epoxide groups.

[0074] Preferred groups P, including any variations thereof such as P°, P1, P2, P*°, are selected from the group consisting of

[0075] (COO)ki-Phe-(O)k2-, CH2=CH-(CO)ki-Phe-(O)k2-, Phe-CH=CH-, HOOC-, OCN- and WW ^Si-, in which W1denotes H, F, Cl, CN, CF3, phenyl or alkyl having 1 to 5 C atoms, in particular H, F, Cl or CH3, W2and W3each, independently of one another, denote H or alkyl having 1 to 5 C atoms, in particular H, methyl, ethyl or n-propyl, W4, W5and W3each, independently of one another, denote Cl, oxaalkyl or oxacarbonylalkyl having 1 to 5 C atoms, W7and W8each, independently of one another, denote H, Cl or alkyl having 1 to 5 C atoms, Phe denotes 1 ,4-phenylene, which is optionally substituted by one or more radicals L as defined above which are other than P-Sp-, ki , k2and k3each, independently of one another, denote 0 or 1 , k3preferably denotes 1 , and k4 denotes an integer from 1 to 10.

[0076] Very preferred groups P, including any variations thereof such as P°, P1, P2, P*°, are selected from the group consisting of CH2=CH-(COO)ki-Phe-(O)k2-, CH2=CH-(CO)ki-Phe-(O)k2-, Phe-CH=CH- and WWSi- , in which W1denotes H, F, Cl, CN, CF3, phenyl or alkyl having 1 to 5 C atoms, in particular H, F, Cl or CH3, W2and W3each, independently of one another, denote H or alkyl having 1 to 5 C atoms, in particular H, methyl, ethyl or n-propyl, W4, V^ and W5each, independently of one another, denote Cl, oxaalkyl or oxacarbonylalkyl having 1 to 5 C atoms, W7and W8each, independently of one another, denote H, Cl or alkyl having 1 to 5 C atoms, Phe denotes 1 ,4-phenylene, ki, k2and k3each, independently of one another, denote 0 or 1 , k3preferably denotes 1 , and k4 denotes an integer from 1 to 10.

[0077] Very particularly preferred groups P, including any variations thereof such as P°, P1, P2, P*°, are selected from the group consisting of CH2=CW1-CO-O-, in particular H-O-,

[0078] Further preferred polymerizable groups P, including any variations thereof such as P°, P1, P2, P*°, are selected from the group consisting of vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane and epoxide, most preferably from acrylate and methacrylate.

[0079] In another preferred embodiment of the invention, in a polymerizable compound or RM as disclosed above and below, including but not limited to compounds of formula DRM, MRM, CRM1-CRM3 and their subformulae, all polymerizable groups have the same meaning, and preferably denote acrylate or methacrylate, very preferably acrylate.

[0080] The spacer group, including any variations thereof such as Sp°, Sp1, Sp2, Sp*°, when being different from a single bond, is preferably of the formula Sp"-X", so that the respective radical P-Sp- etc. conforms to the formula P-Sp"-X"-, wherein

[0081] Sp" denotes linear or branched alkylene having 1 to 20, preferably 1 to 12, C atoms, which is optionally mono- or polysubstituted by F, Cl, Br, I or CN and in which, in addition, one or more non-adjacent CH2groups may each be replaced, independently of one another, by -O-, -S-, -NH-, -N(R°)-, -Si(R°R00)-, -CO-, -CO- O-, -O-CO-, -O-CO-O-, -S-CO-, -CO-S-, -N(R°°)-CO-O-, -O-CO-N(R°)-, -N(R°)- CO-N(R00)-, -CH=CH- or -C=C- in such a way that O and / or S atoms are not linked directly to one another,

[0082] X" denotes -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CO-N(R°)-, -N(R°)-CO-, - N(R°)-CO-N(R00)-, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, - SCF2-, -CF2CH2-, -CH2CF2-, -CF2CF2-, -CH=N-, -N=CH-, -N=N-, -CH=CR0-, - CY2=CY3-, -OC-, -CH=CH-CO-O-, -O-CO-CH=CH- or a single bond,

[0083] R° and R°° each, independently of one another, denote H or alkyl having 1 to 20 C atoms, and

[0084] Y2and Y3each, independently of one another, denote H, F, Cl or CN.

[0085] X" is preferably -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR0-, -NR°-CO-, -NR°- CO-NR00- or a single bond.

[0086] Typical spacer groups Sp, including any variations thereof such as Sp°, Sp1, Sp2, Sp*°, and -Sp"-X"- are, for example, -(CH2)PI-, -(CH2)PI-O-, -(CH2)PI-O-CO-, -(CH2)PI-CO-O-, - (CH2)PI-O-CO-O-, -(CH2CH2O)qi-CH2CH2-, -CH2CH2-S-CH2CH2-, -CH2CH2-NH-CH2CH2- or -(SiR°R00-O)pi-, in which p1 is an integer from 1 to 12, q1 is an integer from 1 to 3, and R° and R°° have the meanings indicated above.

[0087] Particularly preferred groups Sp, including any variations thereof such as Sp°, Sp1, Sp2, Sp*°, and -Sp"-X"- are -(CH2)PI-, -(CH2)PI-O-, -(CH2)PI-O-CO-, -(CH2)PI-CO-O-, -(CH2)PI-O- CO-O-, in which p1 and q1 have the meanings indicated above.

[0088] Particularly preferred groups Sp" are, in each case straight-chain, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylenethioethylene, ethylene-N-methyliminoethylene, 1 -methylalkylene, ethenylene, propenylene and butenylene.

[0089] In another preferred embodiment of the invention, the polymerizable compounds as disclosed above and below, including compounds of formula I and its subformulae, contain a spacer group Sp, including any variations thereof such as Sp°, Sp1, Sp2, Sp*°, that is substituted by one or more polymerizable groups P, so that the group Sp- P etc. corresponds to Sp(P)s, with s being >2 (branched polymerizable groups). Preferred polymerizable compounds according to this preferred embodiment are those wherein s is 2, i.e., compounds which contain a group Sp(P)2. Very preferred polymerizable compounds according to this preferred embodiment contain a group selected from the following formulae:

[0090] -X-alkyl-CHPP S1

[0091] -X-alkyl-CH((CH2)aaP)((CH2)bbP) S2

[0092] -X-N((CH2)aaP)((CH2)bbP) S3

[0093] -X-alkyl-CHP-CH2-CH2P S4

[0094] -X-alkyl-C(CH2P)(CH2P)-CaaH2aa+iS5

[0095] -X-alkyl-CHP-CH2P S6

[0096] -X-alkyl-CPP-CaaH2aa+iS7

[0097] -X-alkyl-CHPCHP-CaaH2aa+iS8 in which P is as defined in formula I, alkyl denotes a single bond or straight-chain or branched alkylene having 1 to 12 C atoms which is unsubstituted or mono- or polysubstituted by F, Cl or CN and in which one or more non-adjacent CH2groups may each, independently of one another, be replaced by -C(R°)=C(R0)-, -C=C-, -N(R0)-, -O-, -S-, -CO-, -CO-O-, -O- CO-, -O-CO-O- in such a way that O and / or S atoms are not linked directly to one another, where R° has the meaning indicated above, aa and bb each, independently of one another, denote 0, 1 , 2, 3, 4, 5 or 6,

[0098] X has one of the meanings indicated for X", and is preferably O, CO, SO2, O-CO-, CO-O or a single bond.

[0099] Preferred groups Sp(P)2are selected from formulae S1 , S2 and S3.

[0100] Very preferred groups Sp(P)2are selected from the following subformulae: -CHPP S1a

[0101] -O-CHPP S1b

[0102] -CH2-CHPP S1c

[0103] -OCH2-CHPP S1d

[0104] -CH(CH2-P)(CH2-P) S2a

[0105] -OCH(CH2-P)(CH2-P) S2b

[0106] -CH2-CH(CH2-P)(CH2-P) S2C

[0107] -OCH2-CH(CH2-P)(CH2-P) S2d

[0108] -CO-NH((CH2)2P)((CH2)2P) S3a

[0109] Detailed Description of the Invention

[0110] The multiacrylate additives as used in the process and materials of the present invention have been disclosed in prior art, among others, for example for use as reactive thinners or to improve crosslinking in RM mixtures, or as polymeric binder in alignment layers or precursors thereof. However, they have so far not been proposed for use as alignment agents to create or improve homeotropic alignment of RM mixtures on plastic substrates without the need of an additional alignment layer.

[0111] The process of the present invention, the RMMs used therein and the polymer firns prepared therefrom provide one or more of the following advantages over prior art:

[0112] - the multiacrylate additives promote homeotropic alignment of RM mixtures on various plastic substrates, especially on non-polar substrates such as untreated TAG, removing the need for additional pre-treatment steps or alignment layers,

[0113] - the promotion of homeotropic alignment by the multiacrylate additives allows for more flexibility in RM and additive selection, enabling material combinations which would otherwise not have been possible, - the multiacrylate additives improve adhesion of the polymerized RM film to the substrate, especially to polar substrates such as corona treated COP or TAC,

[0114] - increasing the amount of the multiacrylate additive in the RM mixture or formulation is correlated with improved film adhesion, so that the RM mixture or formulation can be tailored to match customer requirements as well as cost limitations,

[0115] - improved alignment quality of the bulk RM formulations also allows the use of a wider range of surfactants, and ultimately even enables the replacement of the environmentally critical PFAS materials or other fluorinated compounds, enabling the reduction of perfluorocarbons and providing a more environmental friendly material.

[0116] In a preferred embodiment, the RM mixture comprises one or more additives selected from multiacrylates of pentaerythritol or di pentaerythritol which contain at least four, preferably four, five or six, very preferably five or six, acrylate or methacrylate groups. Very preferably said one or more additives selected from pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, di pentaerythritol hexaacrylate or mixtures thereof, most preferably di pentaerythritol pentaacrylate, dipentaerythritol hexaacrylate or mixtures thereof.

[0117] The concentration of the additives selected from methacrylic and acrylic esters of polyfunctional alcohols, and preferably from multiacrylates of pentaerythritol or dipentaerythritol as described above and below, in the RM mixture is from 1 to 15%, preferably from 2 to 10%, very preferably from 2 to 6%.

[0118] In a preferred embodiment, the RM mixture does not contain a PFAS, and very preferably does not contain a compound with a polyfluorinated alkyl or aryl group.

[0119] In another preferred embodiment, the RM mixture does not contain a compound with a mono- or polyfluorinated aliphatic group. In another preferred embodiment, the RM mixture does not contain a compound with a mono- or polyfluorinated aryl or heteroaryl group.

[0120] The RM mixture preferably exhibits a nematic phase or a smectic LC phase and a nematic LC phase, very preferably a nematic LC phase at room temperature. In a preferred embodiment, the RM mixture comprises one or more RMs having only one polymerizable functional group (monoreactive RMs) and / or one or more RMs having two or more polymerizable functional groups (di- or multireactive RMs).

[0121] The di- or multireactive RMs are preferably selected of formula DRM

[0122] P1-Sp1-MGD-Sp2-P2DRM wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings

[0123] P1, P2a polymerizable group,

[0124] Sp1, Sp2a spacer group or a single bond, and

[0125] MGDa rod-shaped mesogenic group, preferably selected of formula MGD

[0126] -(A1-Z1)n-A2- MGD

[0127] A1, A2an aromatic or alicyclic group, which optionally contains one or more heteroatoms selected from N, O and S, and is optionally mono- or polysubstituted by LD,

[0128] LDP-Sp-, F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)NRxRy,

[0129] -C(=O)ORX, -C(=O)RX, -NRxRy, -SFs, optionally substituted silyl, aryl or heteroaryl with 1 to 12, preferably 1 to 6 C atoms, and straight chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 12, preferably 1 to 6 C atoms, wherein one of the H atoms is optionally replaced by F or Cl,

[0130] Rx, RyH or alkyl with 1 to 12 C-atoms,

[0131] Z1 single bond, preferably -COO-, -OCO- or a single bond, Y1and Y2H, F, Cl or CN, n 1 , 2, 3 or 4, preferably 1 or 2, most preferably 2, n1 an integer from 1 to 10, preferably 1 , 2, 3 or 4.

[0132] In formula DRM preferably A1and A2are selected from furan, pyrrol, 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 by 1 , 2, 3 or 4 groups L as defined above.

[0133] More preferably A1and A2are selected from 1 ,4-phenylene, pyridine-2, 5-diyl, pyrimidine-2,5-diyl, thiophene-2, 5-diyl, naphthalene-2,6-diyl, naphthalene-1 ,4-diyl, 1 ,2,3,4-tetrahydro-naphthalene-2,6-diyl, indane-2, 5-diyl, bicyclooctylene or 1 ,4- cyclohexylene wherein one or two non-adjacent CH2 groups are optionally replaced by O and / or S, wherein these groups are unsubstituted or substituted by 1 , 2, 3 or 4 groups L as defined above.

[0134] Very preferably A1and A2are selected from 1 ,4-phenylene, naphthalene-2,6-diyl and naphthalene-1 ,4-diyl, wherein one or two non-adjacent CH2 groups are optionally replaced by O and / or S, wherein these groups are unsubstituted or substituted by 1 , 2, 3 or 4 groups LDas defined above.

[0135] In formula DRM preferably P1and P2denote an acrylate, methacrylate, oxetane, epoxy, vinyl, heptadiene, vinyloxy, propenyl ether or styrene group, very preferably an acrylate or methacrylate group.

[0136] In formula DRM preferably Sp1and Sp2are selected from -(CH2)PI-, -(CH2)PI-O-, - (CH2)PI-O-CO-, -(CH2)PI-CO-O- and -(CH2)PI-O-CO-O- in which p1 is an integer from 1 to 12, preferably from 1 to 6.

[0137] Preferably the RMs of formula DRM do not contain a OH group.

[0138] Preferred RMs of formula DRM are selected from the following subformulae: wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings

[0139] P° a polymerizable group, preferably an acrylate, methacrylate, oxetane, epoxy, vinyl, heptadiene, vinyloxy, propenyl ether or styrene group, very preferably an acrylate or methacrylate group,

[0140] Z° -COO-, -OCO-, -CH2CH2-, -CF2O-, -OCF2-, -C=C-, -CH=CH-,-OCO- CH=CH-, -CH=CH-COO-, or a single bond,

[0141] L has one of the meanings given for LDin formula DRM, and is preferably selected from F, Cl, CN or optionally halogenated alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 5 C atoms, r 0, 1 , 2, 3 or 4, s 0, 1 , 2 or 3, t 0, 1 or 2, x, y 0 or an integer from 1 to 12, preferably from 3 to 6, z 0 or 1 , with z being 0 if the adjacent x or y is 0. Especially preferred RMs of formula DRMa are selected from the following subformulae: wherein P°, L, r, x, y and z are as defined in formula DRMa.

[0142] Further preferred are RMs selected from formulae DRMf, DRMg, DRMh, DRMi, DRMk and DRMm.

[0143] Especially preferred are RMs of formula DRMal, DRMa2 and DRMa3, in particular those of formula DRMal . The monoreactive RMs are preferably selected from formula MRM:

[0144] P1-Sp1-MGM-R22MRM wherein the individual radical, independently of each other and on each occurrence identically or differently, have the following meanings

[0145] P1a polymerizable group,

[0146] Sp1a spacer group or a single bond,

[0147] MGMa rod-shaped mesogenic group, preferably selected of formula MGM

[0148] -(A1-Z1)n-A2- MGM

[0149] A1, A2an aromatic or alicyclic group, which optionally contains one or more heteroatoms selected from N, O and S, and is optionally mono- or polysubstituted by LM,

[0150] LMF, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)NRxRy, -

[0151] C(=O)ORX, -C(=O)RX, -NRxRy, -SFs, optionally substituted silyl, aryl or heteroaryl with 1 to 12, preferably 1 to 6 C atoms, and straight chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 12, preferably 1 to 6 C atoms, wherein one of the H atoms is optionally replaced by F or Cl,

[0152] R22F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)NRxRy, -

[0153] C(=O)X, -C(=O)ORX, -C(=O)Ry, -NRxRy, -SFs, optionally substituted silyl, straight chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 12, preferably 1 to 6 C atoms, wherein one of the H atoms is optionally replaced by F or Cl,

[0154] X halogen, preferably F or Cl,

[0155] Rx, RyH or alkyl with 1 to 12 C-atoms,

[0156] Z1-O-, -S-, -CO-, -COO-, -OCO-, -S-CO-, -CO-S-, -O-COO-, -CO-NR00-, -

[0157] NR00-CO-, -NR00-CO-NR000, -NR00-CO-O-, -O-CO-NR00-, -OCH2-, - CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH2CH2-, - (CH2)ni, -CF2CH2-, -CH2CF2-, -CF2CF2-, -CH=N-, -N=CH-, -N=N-, - CH=CR00-, -CY1=CY2-, -OC-, -CH=CH-COO-, -OCO-CH=CH- or a single bond, preferably -COO-, -OCO- or a single bond,

[0158] Y1, Y2H, F, Cl or CN, n 1 , 2, 3 or 4, preferably 1 or 2, most preferably 2, n1 an integer from 1 to 10, preferably 1 , 2, 3 or 4.

[0159] In formula MRM preferably A1and A2are selected from furan, pyrrol, 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 by 1 , 2, 3 or 4 groups L as defined above.

[0160] More preferably A1and A2are selected from 1 ,4-phenylene, pyridine-2, 5-diyl, pyrimidine-2,5-diyl, thiophene-2, 5-diyl, naphthalene-2,6-diyl, naphthalene-1 ,4-diyl, 1 ,2,3,4-tetrahydro-naphthalene-2,6-diyl, indane-2, 5-diyl, bicyclooctylene or 1 ,4- cyclohexylene wherein one or two non-adjacent CH2groups are optionally replaced by O and / or S, wherein these groups are unsubstituted or substituted by 1 , 2, 3 or 4 groups L as defined above.

[0161] Very preferably A1and A2are selected from 1 ,4-phenylene, naphthalene-2,6-diyl and naphthalene-1 ,4-diyl, wherein one or two non-adjacent CH2groups are optionally replaced by O and / or S, wherein these groups are unsubstituted or substituted by 1 , 2, 3 or 4 groups LDas defined above.

[0162] In formula MRM preferably P1denotes an acrylate, methacrylate, oxetane, epoxy, vinyl, heptadiene, vinyloxy, propenyl ether or styrene group, very preferably an acrylate or methacrylate group.

[0163] In formula MRM preferably Sp1is selected from -(CH2)PI-, -(CH2)PI-O-, -(CH2)PI-O-CO-, -(CH2)PI-CO-O- and -(CH2)PI-O-CO-O- in which p1 is an integer from 1 to 12, preferably from 1 to 6. Preferably the RMs of formula MRM do not contain a OH group.

[0164] Preferred RMs of formula MRM are selected from the following subformulae: wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings P° a polymerizable group, preferably an acrylate, methacrylate, oxetane, epoxy, vinyl, heptadiene, vinyloxy, propenyl ether or styrene group, very preferably an acrylate or methacrylate group,

[0165] R° alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 or more, preferably 1 to 15 C atoms, or Y°,

[0166] Y° F, Cl, CN, NO2, OCH3, OCN, SCN, SF5, or mono- oligo- or polyfluorinated alkyl or alkoxy with 1 to 4 C atoms, preferably CN or OCH3,

[0167] A01 ,4-phenylene that is unsubstituted or substituted with 1 , 2, 3 or 4 groups

[0168] L, or trans-1,4-cyclohexylene,

[0169] Z° -COO-, -OCO-, -CH2CH2-, -CF2O-, -OCF2-, -C=C-, -CH=CH-,-OCO- CH=CH-, -CH=CH-COO-, or a single bond,

[0170] L has one of the meanings given for LMin formula MRM and is preferably selected from F, Cl, CN or optionally halogenated alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 5 C atoms, r 0, 1 , 2, 3 or 4, s 0, 1 , 2 or 3, t 0, 1 or 2, u, v 0, 1 or 2, w 0 or 1 , preferably 1 , x 0 or an integer from 1 to 12, preferably from 3 to 6, z 0 or 1 , with z being 0 if the adjacent x or y is 0, and wherein the benzene and naphthalene rings can additionally be substituted with one or more identical or different groups LM. Especially preferred are RMs of formula MRM1 , MRM4, MRM5, MRM6, MRM7, MRM8, MRM9, MRM10, MRM11 , MRM28, MRM29, MRM30, MRM31 , MRM32, MRM33 and MRM34, in particular those of formula MRM1 , MRM4, MRM7 and MRM8, furthermore those of formulae MRM9, MRM10, MRM28, MRM29, MRM30, MRM31 , MRM32, MRM33 and MRM34. Most preferred are RMs of formula MRM1 and MRM7.

[0171] In formulae DRM, MRM and their preferred subformulae, L is preferably selected from F, Cl, CN, NO2 or straight chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 12 C atoms, wherein the alkyl groups are optionally perfluorinated, or in formula DRM and its subformulae also P-Sp-.

[0172] 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 in formula DRM and its subformulae also P-Sp-.

[0173] The total concentration of the mono-, di- or multireactive RMs, preferably those of formula DRM and / or MRM and their subformulae, in the RM mixture is preferably from 60 to 99%, more preferably from 85 to 99%, very preferably from 90 to 98%.

[0174] The concentration of the di- or multireactive RMs, preferably those of formula DRM and its subformulae, in the RM mixture is preferably from 30 to 80%, very preferably from 35 to 75%.

[0175] The concentration of the monoreactive RMs, preferably those of formula MRM, in the RM mixture is preferably from 30 to 80%, very preferably from 35 to 70%.

[0176] In another preferred embodiment the RM mixture according to the present invention does not contain any chiral compounds.

[0177] In another preferred embodiment the RM mixture according to the present invention does not contain any RMs with an OH group.

[0178] Another object of the invention is an RM formulation comprising an RM mixture as described above and below, and further comprising one or more solvents and / or additives. The proportion of the RM mixture comprising, preferably consisting of, compounds selected from formulae DRM, MRM and their subformulae in the RM formulation is preferably from 85 to 100%, more preferably from 85 to 99%, very preferably from 90 to 99% of total solids and liquid additives, i.e., excluding the solvents.

[0179] In a preferred embodiment the RM mixure or RM formulation additionally comprises one or more additives selected from the group consisting of polymerisation initiators, surfactants, stabilisers, catalysts, sensitizers, inhibitors, chain-transfer agents, co-reacting monomers, reactive thinners, surface-active compounds, lubricating agents, wetting agents, dispersing agents, hydrophobing agents, adhesive agents, flow improvers, degassing or defoaming agents, deaerators, diluents, reactive diluents, auxiliaries, colourants, dyes, pigments and nanoparticles.

[0180] In another preferred embodiment the RM mixure or RM formulation comprises one or more specific antioxidant additives, preferably selected from the Irganox® series, e.g. the commercially available antioxidants lrganox®1076 and lrganox®1010, from Ciba, Switzerland.

[0181] In another preferred embodiment, the RM mixture or RM formulation comprises a combination of one or more, more preferably of two or more photoinitiators, for example, selected from the commercially available Irgacure® or Darocure® (Ciba AG) series, in particular, Irgacure 127, Irgacure 184, Irgacure 369, Irgacure 651 , Irgacure 817, Irgacure 907, Irgacure 1300, Irgacure, Irgacure 2022, Irgacure 2100, Irgacure 2959, or Darcure TPO, further selected from the commercially available OXE02 (Ciba AG), NCI 930, N1919T (Adeka), SPI-03 or SPI-04 (Samyang), TR-PBG 304 or TR- PGB 345 (Tronly).

[0182] The concentration of the polymerisation initiator(s) as a whole in the RM mixure or RM formulation is preferably from 0.1 to 6%, very preferably from 0.3 to 5%, more preferably from 0.7 to 4%.

[0183] In another preferred embodiment the RM mixure or RM formulation optionally comprises one or more additives selected from polymerisable non-mesogenic compounds (reactive thinners). The amount of these additives in the RM mixture or RM formulation is preferably from 0 to 30 %, very preferably from 0 to 25 %. The reactive thinners used are not only substances which are referred to in the actual sense as reactive thinners, but also auxiliary compounds already mentioned above which contain one or more complementary reactive units, for example hydroxyl, thiol-, or amino groups, via which a reaction with the polymerisable units of the liquidcrystalline compounds can take place.

[0184] The substances which are usually capable of photopolymerisation include, for example, mono-, bi- and polyfunctional compounds containing at least one olefinic double bond. Examples thereof are vinyl esters of carboxylic acids, for example of lauric, myristic, palmitic and stearic acid, and of dicarboxylic acids, for example of succinic acid, adipic acid, allyl and vinyl ethers and methacrylic and acrylic esters of monofunctional alcohols, for example of lauryl, myristyl, palmityl and stearyl alcohol, and diallyl and divinyl ethers of bifunctional alcohols, for example ethylene glycol and 1 ,4-butanediol.

[0185] Also suitable are, for example, methacrylic and acrylic esters of polyfunctional alcohols, in particular those which contain no further functional groups, or at most ether groups, besides the hydroxyl groups. Examples of such alcohols are bifunctional alcohols, such as ethylene glycol, propylene glycol and their more highly condensed representatives, for example diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol etc., butanediol, pentanediol, hexanediol, neopentyl glycol, alkoxylated phenolic compounds, such as ethoxylated and propoxylated bisphenols, cyclohexanedimethanol, trifunctional and polyfunctional alcohols, such as glycerol, trimethylolpropane, butanetriol, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol, and the corresponding alkoxylated, in particular ethoxylated and propoxylated alcohols.

[0186] Other suitable reactive thinners are polyester (meth)acrylates, which are the (meth)acrylic ester of polyesterols.

[0187] Examples of suitable polyesterols are those which can be prepared by esterification of polycarboxylic acids, preferably dicarboxylic acids, using polyols, preferably diols. The starting materials for such hydroxyl-containing polyesters are known to the person skilled in the art. Dicarboxylic acids which can be employed are succinic, glutaric acid, adipic acid, sebacic acid, o-phthalic acid and isomers and hydrogenation products thereof, and esterifiable and transesterifiable derivatives of said acids, for example anhydrides and dialkyl esters. Suitable polyols are the abovementioned alcohols, preferably ethyleneglycol, 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.

[0188] Suitable reactive thinners are furthermore 1,4-divinylbenzene, triallyl cyanurate, acrylic esters of tricyclodecenyl alcohol of the following formula also known under the name dihydrodicyclopentadienyl acrylate, and the allyl esters of acrylic acid, methacrylic acid and cyanoacrylic acid.

[0189] Of the reactive thinners which are mentioned by way of example, those containing photopolymerisable groups are used in particular and in view of the abovementioned preferred compositions.

[0190] This group includes, for example, dihydric and polyhydric alcohols, for example ethylene glycol, propylene glycol and more highly condensed representatives thereof, for example 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, in particular ethoxylated and propoxylated alcohols.

[0191] The group furthermore also includes, for example, alkoxylated phenolic compounds, for example ethoxylated and propoxylated bisphenols.

[0192] These reactive thinners may furthermore be, for example, epoxide or urethane (meth)acrylates.

[0193] Epoxide (meth)acrylates are, for example, those as obtainable by the reaction, known to the person skilled in the art, of epoxidized olefins or poly- or diglycidyl ether, such as bisphenol A diglycidyl ether, with (meth)acrylic acid. Urethane (meth)acrylates are, in particular, the products of a reaction, likewise known to the person skilled in the art, of hydroxylalkyl (meth)acrylates with poly- or diisocyanates.

[0194] Such epoxide and urethane (meth)acrylates are included amongst the compounds listed above as “mixed forms”.

[0195] If reactive thinners are used, their amount and properties must be matched to the respective conditions in such a way that, on the one hand, a satisfactory desired effect, for example the desired colour of the composition according to the invention, is achieved, but, on the other hand, the phase behaviour of the liquid-crystalline composition is not excessively impaired. The low-crosslinking (high-crosslinking) liquid-crystalline compositions can be prepared, for example, using corresponding reactive thinners which have a relatively low (high) number of reactive units per molecule.

[0196] The group of diluents include, for example:

[0197] C1-C4-alcohols, for example methanol, ethanol, n-propanol, isopropanol, butanol, isobutanol, sec-butanol and, in particular, the C5-C12-alcohols n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, n-undecanol and n-dodecanol, and isomers thereof, glycols, for example 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, for example methyl tert-butyl ether, 1 ,2-ethylene glycol mono- and dimethyl ether, 1 ,2-ethylene glycol mono- and -diethylether, 3- methoxypropanol, 3-isopropoxypropanol, tetrahydrofuran and dioxane, ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone and diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), C1-C5-alkyl esters, for example methyl acetate, ethyl acetate, propyl acetate, butyl acetate and amyl acetate, aliphatic and aromatic hydrocarbons, for example pentane, hexane, heptane, octane, isooctane, petroleum ether, toluene, xylene, ethylbenzene, tetralin, decalin, dimethylnaphthalene, white spirit, Shellsol® and Solvesso® mineral oils, for example gasoline, kerosine, diesel oil and heating oil, but also natural oils, for example olive oil, soya oil, rapeseed oil, linseed oil and sunflower oil.

[0198] It is of course also possible to use mixtures of these diluents in the compositions according to the invention. So long as there is at least partial miscibility, these diluents can also be mixed with water. Examples of suitable diluents here are C1-C4-alcohols, for example methanol, ethanol, n-propanol, isopropanol, butanol, isobutanol and sec-butanol, glycols, for example 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, for example tetrahydrofuran and dioxane, ketones, for example acetone, methyl ethyl ketone and diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), and C1-C4-alkyl esters, for example methyl, ethyl, propyl and butyl acetate.

[0199] The diluents are optionally employed in a proportion of from about 0 to 10.0% by weight, preferably from about 0 to 5.0% by weight, based on the total weight of the RM formulation.

[0200] In another preferred embodiment the RM mixture or RM formulation comprises one or more additives selected from the group consisting of antifoams and deaerators (c1 )), lubricants and flow auxiliaries (c2)), thermally curing or radiation-curing auxiliaries (c3)), substrate wetting auxiliaries (c4)), wetting and dispersion auxiliaries (c5)), hydrophobicizing agents (c6)), adhesion promoters (c7)) and auxiliaries for promoting scratch resistance (c8)), wherein the additives of groups cannot always strictly be delimited from one another in their action.

[0201] Preferably, the RM mixture and RM formulation do not contain any additive, including but not limited to those selected from groups (c1) to (c8) as described above and below, which is a PFAS, preferably which contains a polyfluorinated alkyl or aryl group.

[0202] For example, lubricants and flow auxiliaries often also act as antifoams and / or deaerators and / or as auxiliaries for improving scratch resistance. Radiation-curing auxiliaries can also act as lubricants and flow auxiliaries and / or deaerators and / or as substrate wetting auxiliaries. In individual cases, some of these auxiliaries can also fulfil the function of an adhesion promoter (c8)).

[0203] Corresponding to the above-said, a certain additive can therefore be classified in a number of the groups c1) to c8) described below.

[0204] The antifoams in group c1) include silicon-free and silicon-containing polymers. The silicon-containing polymers are, for example, unmodified or modified polydialkylsiloxanes or branched copolymers, comb or block copolymers comprising polydialkylsiloxane and polyether units, the latter being obtainable from ethylene oxide or propylene oxide.

[0205] The deaerators in group c1) include, for example, organic polymers, for example polyethers and polyacrylates, dialkylpolysiloxanes, in particular dimethylpolysiloxanes, organically modified polysiloxanes, for example arylalkyl-modified polysiloxanes, and fluorosilicones.

[0206] The action of the antifoams is essentially based on preventing foam formation or destroying foam that has already formed. Antifoams essentially work by promoting coalescence of finely divided gas or air bubbles to give larger bubbles in the medium to be deaerated, for example the compositions according to the invention, and thus accelerate escape of the gas (of the air). Since antifoams can frequently also be employed as deaerators and vice versa, these additives have been included together under group c1).

[0207] Such auxiliaries are, for example, commercially available from Tego as TEGO® Foamex 800, TEGO® Foamex 805, TEGO® Foamex 810, TEGO® Foamex 815, TEGO® Foamex 825, TEGO® Foamex 835, TEGO® Foamex 840, TEGO® Foamex 842, TEGO® Foamex 1435, TEGO® Foamex 1488, TEGO® Foamex 1495, TEGO® Foamex 3062, TEGO® Foamex 7447, TEGO® Foamex 8020, Tego® Foamex N, TEGO® Foamex K 3, TEGO® Antifoam 2-18, TEGO® Antifoam 2-18, TEGO® Antifoam 2-57, TEGO® Antifoam 2-80, TEGO® Antifoam 2-82, TEGO® Antifoam 2-89, TEGO® Antifoam 2-92, TEGO® Antifoam 14, TEGO® Antifoam 28, TEGO® Antifoam 81 , TEGO® Antifoam D 90, TEGO® Antifoam 93, TEGO® Antifoam 200, TEGO® Antifoam 201 , TEGO® Antifoam 202, TEGO® Antifoam 793, TEGO® Antifoam 1488, TEGO® Antifoam 3062, TEGOPREN® 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 WM 20, TEGO® Antifoam 50, TEGO® Antifoam 105, TEGO® Antifoam 730, TEGO® Antifoam MR 1015, TEGO® Antifoam MR 1016, TEGO® Antifoam 1435, TEGO® Antifoam N, TEGO® Antifoam KS 6, TEGO® Antifoam KS 10, TEGO® Antifoam KS 53, TEGO® Antifoam KS 95, TEGO® Antifoam KS 100, TEGO® Antifoam KE 600, TEGO® Antifoam KS 911 , TEGO® Antifoam MR 1000, TEGO® Antifoam KS 1100, Tego® Ai rex 900, Tego® Airex 910, Tego® Airex 931 , Tego® Airex 935, Tego® Airex 936, Tego® Airex 960, Tego® Airex 970, Tego® Airex 980, and Tego® Airex 985, and from BYK 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, BYKO-036, BYKO-037, BYKO-045, BYK®-051 , BYK®-052, BYK®-053, BYK®-055, BYK®-057, BYK®-065, BYK®-066, BYK®-070, BYK®-080, BYK®-088, BYK®-141 and BYK®-A 530.

[0208] The auxiliaries in group c1) are optionally employed in a proportion of from about 0 to 3.0% by weight, preferably from about 0 to 2.0% by weight, based on the total weight of the RM mixture or RM formulation.

[0209] In group c2), the lubricants and flow auxiliaries typically include silicon-free, but also silicon-containing polymers, for example polyacrylates or modifiers, low-molecular- weight polydialkylsiloxanes. The modification consists in some of the alkyl groups having been replaced by a wide variety of organic radicals. These organic radicals are, for example, polyethers, polyesters or even long-chain alkyl radicals, the former being used the most frequently.

[0210] The polyether radicals in the correspondingly modified polysiloxanes are usually built up from ethylene oxide and / or propylene oxide units. Generally, the higher the proportion of these alkylene oxide units in the modified polysiloxane, the more hydrophilic is the resultant product.

[0211] Such auxiliaries are, for example, commercially available from Tego as TEGO® Glide 100, TEGO® Glide ZG 400, TEGO® Glide 406, TEGO® Glide 410, TEGO® Glide 411 , TEGO® Glide 415, TEGO® Glide 420, TEGO® Glide 435, TEGO® Glide 440, TEGO® Glide 450, TEGO® Glide A 115, TEGO® Glide B 1484 (can also be used as antifoam and deaerator), TEGO® Flow ATF, TEGO® Flow 300, TEGO® Flow 460, TEGO® Flow 425 and TEGO® Flow ZFS 460. Suitable radiation-curable lubricants and flow auxiliaries, which can also be used to improve the scratch resistance, are the products TEGO® Rad 2100, TEGO® Rad 2200, TEGO® Rad 2500, TEGO® Rad 2600 and TEGO® Rad 2700, which are likewise obtainable from TEGO.

[0212] Such-auxiliaries are available, for example, from BYK as BYK®-300 BYK®-306, BYK®-307, BYK®-310, BYK®-320, BYK®-333, BYK®-341, Byk® 354, Byk®361, Byk®361 N, BYK®388.

[0213] The auxiliaries in group c2) are optionally employed in a proportion of from about 0 to 3.0% by weight, preferably from about 0 to 2.0% by weight, based on the total weight of the RM mixture or RM formulation. In group c3), the radiation-curing auxiliaries include, in particular, polysiloxanes having terminal double bonds which are, for example, a constituent of an acrylate group. Such auxiliaries can be crosslinked by actinic or, for example, electron radiation. These auxiliaries generally combine a number of properties together. In the uncrosslinked state, they can act as antifoams, deaerators, lubricants and flow auxiliaries and / or substrate wetting auxiliaries, while, in the crosslinked state, they increase, in particular, the scratch resistance, for example of coatings or films which can be produced using the compositions according to the invention. The improvement in the gloss properties, for example of precisely those coatings or films, is regarded essentially as a consequence of the action of these auxiliaries as antifoams, deaerators and / or lubricants and flow auxiliaries (in the uncrosslinked state).

[0214] Examples of suitable radiation-curing auxiliaries are the products TEGO® Rad 2100, TEGO® Rad 2200, TEGO® Rad 2300, TEGO® Rad 2500, TEGO® Rad 2600 and TEGO® Rad 2700 available from TEGO and the product BYK®-371 available from BYK.

[0215] Thermally curing auxiliaries in group c3) contain, for example, primary OH groups which are able to react with isocyanate groups, for example of the binder.

[0216] Examples of thermally curing auxiliaries which can be used are the products BYK®- 370, BYK®-373 and BYK®-375 available from BYK.

[0217] The auxiliaries in group c3) are optionally employed in a proportion of from about 0 to 5.0% by weight, preferably from about 0 to 3.0% by weight, based on the total weight of the RM mixture or RM formulation.

[0218] The substrate wetting auxiliaries in group c4) serve, in particular, to increase the wettability of the substrate to be printed or coated, for example, by printing inks or coating compositions, for example compositions according to the invention. The generally attendant improvement in the lubricant and flow behaviour of such printing inks or coating compositions has an effect on the appearance of the finished (for example crosslinked) print or coating.

[0219] A wide variety of such auxiliaries are commercially available, for example from Tego as TEGO® Wet KL 245, TEGO® Wet 250, TEGO® Wet 260, TEGO® Wet ZFS 453 and TEGO® Wet 505 and from BYK as BYK®-306, BYK®-307, BYK®-310, BYK®- 333, BYK®-344, BYK®-345, BYK®-346, Byk®-348 and BYK®-3550. The auxiliaries in group c4) are optionally employed in a proportion of from about 0 to 3.0% by weight, preferably from about 0 to 1.5% by weight, based on the total weight of the liquid-crystalline composition.

[0220] The wetting and dispersion auxiliaries in group c5) serve, in particular, to prevent the flooding and floating and the sedimentation of pigments and are therefore, if necessary, suitable in particular in pigmented compositions according to the invention.

[0221] These auxiliaries stabilize pigment dispersions essentially through electrostatic repulsion and / or steric hindrance of the pigment particles containing these additives, where, in the latter case, the interaction of the auxiliary with the ambient medium (for example binder) plays a major role.

[0222] Since the use of such wetting and dispersion auxiliaries is common practice, for example in the technical area of printing inks and paints, the selection of a suitable auxiliary of this type generally does not present the person skilled in the art with any difficulties, if they are used.

[0223] Such wetting and dispersion auxiliaries are commercially available, for example from Tego, as TEGO® Dispers 610, TEGO® Dispers 610 S, TEGO® Dispers 630, TEGO® Dispers 700, TEGO® Dispers 705, TEGO® Dispers 710, TEGO® Dispers 720 W, TEGO® Dispers 725 W, TEGO® Dispers 730 W, TEGO® Dispers 735 W and TEGO® Dispers 740 W and from BYK as Disperbyk®, Disperbyk®-107, Disperbyk®-108, Disperbyk®-110, Disperbyk®-111 , Disperbyk®-115, Disperbyk®-130, Disperbyk®- 160, Disperbyk®-161 , Disperbyk®-162, Disperbyk®-163, Disperbyk®-164, Disperbyk®-165, Disperbyk®-166, Disperbyk®- 167, Disperbyk®-170, Disperbyk®- 174, Disperbyk®-180, Disperbyk®-181, Disperbyk®- 182, Disperbyk®-183, Disperbyk®-184, Disperbyk®-185, Disperbyk®-190, Anti-Terra®-U, Anti-Terra®-U 80, Anti-Terra®-P, Anti-Terra®-203, Anti-Terra®-204, Anti-Terra®-206, BYK®-151 , BYK®- 154, BYK®-155, BYK®-P 104 S, BYK®-P 105, Lactimon®, Lactimon®-WS and Bykumen®.

[0224] The amount of the auxiliaries in group c5) used on the mean molecular weight of the auxiliary. In any case, a preliminary experiment is therefore advisable, but this can be accomplished simply by the person skilled in the art. Another preferred group of auxiliaries, which can be allocated to group c2), c4) or c5), includes wetting-, flow- and leveling agents, in particular based on non-ionic fluorosurfactants, which are commercially available from Synthomer under the Polyfox™ series, for example Polyfox™PF-656.

[0225] In a preferred embodiment, however, the RM mixture and RM formulation do not contain a fluorosurfactant.

[0226] The hydrophobicizing agents in group c6) can be used to give water-repellent properties to prints or coatings produced, for example, using compositions according to the invention. This prevents or at least greatly suppresses swelling due to water absorption and thus a change in, for example, the optical properties of such prints or coatings. In addition, when the composition is used, for example, as a printing ink in offset printing, water absorption can thereby be prevented or at least greatly reduced.

[0227] Such hydrophobicizing agents are commercially available, for example, from Tego as Tego® Phobe WF, Tego® Phobe 1000, Tego® Phobe 1000 S, Tego® Phobe 1010, Tego® Phobe 1030, Tego® Phobe 1010, Tego® Phobe 1010, Tego® Phobe 1030, Tego® Phobe 1040, Tego® Phobe 1050, Tego® Phobe 1200, Tego® Phobe 1300, Tego® Phobe 1310 and Tego® Phobe 1400.

[0228] The auxiliaries in group c6) are optionally employed in a proportion of from about 0 to 5.0% by weight, preferably from about 0 to 3.0% by weight, based on the total weight of the RM mixture or RM formulation.

[0229] Adhesion promoters from group c7) serve to improve the adhesion of two interfaces in contact. It is directly evident from this that essentially the only fraction of the adhesion promoter that is effective is that located at one or the other or at both interfaces. If, for example, it is desired to apply liquid or pasty printing inks, coating compositions or paints to a solid substrate, this generally means that the adhesion promoter must be added directly to the latter or the substrate must be pre-treated with the adhesion promoters (also known as priming), i.e. this substrate is given modified chemical and / or physical surface properties.

[0230] If the substrate has previously been primed with a primer, this means that the interfaces in contact are that of the primer on the one hand and of the printing ink or coating composition or paint on the other hand. In this case, not only the adhesion properties between the substrate and the primer, but also between the substrate and the printing ink or coating composition or paint play a part in adhesion of the overall multilayer structure on the substrate.

[0231] Adhesion promoters in the broader sense which may be mentioned are also the substrate wetting auxiliaries already listed under group c4), but these generally do not have the same adhesion promotion capacity.

[0232] In view of the widely varying physical and chemical natures of substrates and of printing inks, coating compositions and paints intended, for example, for their printing or coating, the multiplicity of adhesion promoter systems is not surprising.

[0233] Adhesion promoters based on silanes are, for example, 3- aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- aminopropylmethyldiethoxysilane, N-aminoethyl-3-aminopropyltrimethoxysilane, N- aminoethyl-3-aminopropylmethyldimethoxysilane, N-methyl-3- aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3- methacryloyloxypropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3- mercaptopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane and vinyltrimethoxysilane. These and other silanes are commercially available from Huis, for example under the tradename DYNASILAN®.

[0234] Corresponding technical information from the manufacturers of such additives should generally be used or the person skilled in the art can obtain this information in a simple manner through corresponding preliminary experiments.

[0235] However, if these additives are to be added as auxiliaries from group c7) to the RM mixtures or RM formulations according to the invention, their proportion optionally corresponds to from about 0 to 5.0% by weight, based on the total weight of the RM mixture or RM formulation. These concentration data serve merely as guidance, since the amount and identity of the additive are determined in each individual case by the nature of the substrate and of the printing / coating composition. Corresponding technical information is usually available from the manufacturers of such additives for this case or can be determined in a simple manner by the person skilled in the art through corresponding preliminary experiments.

[0236] The auxiliaries for improving the scratch resistance in group c8) include, for example, the abovementioned products TEGO® Rad 2100, TEGO® Rad 2200, TEGO® Rad 2500, TEGO® Rad 2600 and TEGO® Rad 2700, which are available from Tego. For these auxiliaries, the amount data given for group c3) are likewise suitable, i.e. these additives are optionally employed in a proportion of from about 0 to 5.0% by weight, preferably from about 0 to 3.0% by weight, based on the total weight of the liquid-crystalline composition.

[0237] Examples which may be mentioned of light, heat and / or oxidation stabilizers are the following: alkylated monophenols, such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6- dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di- tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(a-methylcyclohexyl)- 4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di- tert-butyl-4-methoxymethylphenol, nonylphenols which have a linear or branched side chain, for example 2,6-dinonyl-4-methylphenol, 2, 4-dimethyl-6-(1 '-methylundec- T- 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,

[0238] Hydroquinones and alkylated hydroquinones, such as 2,6-di-tert-butyl-4- methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydrocrainone, 2,6- diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4- hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate and bis(3,5-di-tert-butyl-4-hydroxyphenyl)adipate,

[0239] Tocopherols, such as a-tocopherol, p-tocopherol, y-tocopherol, b-tocopherol and mixtures of these compounds, and tocopherol derivatives, such as tocopheryl acetate, succinate, nicotinate and polyoxyethylenesuccinate (“tocofersolate”), 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-di-sec-amylphenol) and 4,4'-bis(2,6-dimethyl-4- hydroxyphenyl)disulfide,

[0240] Alkylidenebisphenols, such as 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'- methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(a- 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-(a-methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-(a,a- 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-

[0241] 2-methylphenyl)pentane,

[0242] O-, N- and S-benzyl compounds, such as 3,5,3',5'-tetra-tert-butyl-4,4'- dihydroxydi benzyl ether, octadecyl 4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl 4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, 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-hydroxybenzylmercaptoacetate, aromatic hydroxybenzyl compounds, such as 1 ,3,5-tris(3,5-di-tert-butyl-4- hydroxybenzyl)-2,4,6-trimethyl-benzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)- 2,3,5,6-tetramethyl-benzene and 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol,

[0243] Triazine compounds, such as 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4- hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4- hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4- hydroxyphenoxy)-1 , 3, 5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1 ,2,3- triazine, 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1 , 3, 5-tris(4-tert-butyl-

[0244] 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,

[0245] 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,

[0246] Acylaminophenols, such as 4-hydroxylauroylanilide, 4-hydroxystearoylanilide and octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate,

[0247] Propionic and acetic esters, for example of monohydric or polyhydric alcohols, such as 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,

[0248] 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,

[0249] Ascorbic acid (Vitamin C) and ascorbic acid derivatives, such as ascorbyl palmitate, laurate and stearate, and ascorbyl sulfate and phosphate,

[0250] Antioxidants based on amine compounds, such as N,N'-diisopropyl-p- phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N, N'-bis(1 ,4- dimethylpentyl)-p-phenylenediamine, N,N'-bis(1-ethyl-3-methylpentyl)-p- phenylenediamine, N,N'-bis(1-methylheptyl)-p-phenylenediamine, N,N'-dicyclohexyl-p- phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p- phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1 ,3-dimethylbutyl)- N'-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine, N- cyclohexyl-N'-phenyl-p-phenylenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N,N'- dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1 -naphthylamine, N-(4-tert-octyl phenyl)- 1- naphthylamine, N-phenyl-2-naphthylamine, octyl-substituted diphenylamine, such as p,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4- nonanoylaminophenol, 4-dodecanoylaminophenol, 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, a mixture of mono- and dialkylated tert-butyl / tert-octyldiphenylamine, a mixture of mono- and dialkylated nonyldiphenylamine, a mixture of mono- and dialkylated dodecyldiphenylamine, a mixture of mono- and dialkylated isopropyl / isohexyldiphenylamine, a mixture of mono- and dialkylated tert-butyldiphenylamine, 2,3-dihydro-3,3-dimethyl-4H-1,4- benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert-butyl / tert- octylphenothiazine, a mixture of mono- and dialkylated tert-octylphenothiazine, 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,

[0251] Phosphines, Phosphites and phosphonites, such as triphenylphosnine triphenylphosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, diisodecyloxy pentaerythritol 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'-biphenylenediphosphonite, 6- isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocine, 6-fluoro- 2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocine, bis(2,4-di-tert- butyl-6-methylphenyl)methyl phosphite and bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite,

[0252] 2-(2'-Hydroxyphenyl)benzotriazoles, such as 2-(2'-hydroxy-5'- methylphenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'- tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-(1 ,1,3,3- tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5- chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chlorobenzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-4'- octyloxyphenyl)benzotriazole, 2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole, 2- (3,5'-bis-(a,a-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, a mixture of 2-(3'-tert- butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert- butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxy phenyl)-5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert- butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2- (2-ethylhexyloxy)carbonylethyl]-2'-hydroxy phenyl)benzotriazole, 2-(3'-dodecyl-2'- hydroxy-5'-methylphenyl)benzotriazole and 2-(3'-tert-butyl-2'-hydroxy-5'-(2- isooctyloxycarbonylethyl)phenyl benzotriazole, 2,2'-methylenebis[4-(1 ,1,3,3- tetramethylbutyl)-6-benzotriazol-2-ylphenol]; the product of complete esterification of 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300; sulfur-containing peroxide scavengers and sulfur-containing antioxidants, such as esters of 3,3'-thiodipropionic acid, for example the lauryl, stearyl, myristyl and tridecyl esters, mercaptobenzimidazole and the zinc salt of 2-mercaptobenzimidazole, dibutylzinc dithiocarbamates, dioctadecyl disulfide and pentaerythritol tetrakis(P- dodecylmercapto)propionate,

[0253] 2-hydroxybenzophenones, such as the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decycloxy, 4-dodecyloxy, 4-benzyloxy, 4, 2 ',4 '-tri hydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives,

[0254] Esters of unsubstituted and substituted benzoic acids, such as 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert- butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4- hydroxybenzoate, hexadecyl-3, 5-di-tert-butyl-4-hydroxybenzoate, octadecyl-3, 5-di-tert- butyl-4-hydroxybenzoate and 2-methyl-4,6-di-tert-butylphenyl-3,5-di-tert-butyl-4- hydroxybenzoate,

[0255] Acrylates, such as ethyl a-cyano-p,p-diphenylacrylate, isooctyl a-cyano-p,p- diphenylacrylate, methyl a-methoxycarbonylcinnamate, methyl a-cyano-p-methyl-p- methoxycinnamate, butyl-a-cyano-p-methyl-p-methoxycinnamate and methyl-a- methoxycarbonyl-p-methoxycinnamate, sterically hindered amines, such as bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate, bis(2,2,6,6-tetramethylpiperidin-4- yl)succinate, bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate, bis(1-octyloxy-2, 2,6,6- tetramethylpiperidin-4-yl)sebacate, bis(1,2,2,6,6-pentamethylpiperidin-4-yl)-n-butyl-3,5- di-tert-butyl-4-hydroxybenzylmalonate, the condensation product of 1-(2-hydroxyethyl)- 2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the condensation product of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-tert- octylamino-2,6-dichloro-1 ,3,5-triazine, tris(2,2,6,6-tetramethylpiperidin-4- yl)nitrilotriacetate, tetrakis(2, 2,6, 6-tetramethylpiperidin-4-yl)1 , 2,3,4- butanetetracarboxylate, 1,1'-(1,2-ethylene)bis(3,3,5,5-tetramethylpiperazinone), 4- benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis(1, 2,2,6, 6-pentamethylpiperidin-4-yl)2-n-butyl-2-(2-hydroxy-3,5-di-tert- butylbenzyl)malonate, 3-n-octyl-7,7,9,9-tetramethyl-1 ,3,8-triazaspiro[4.5]decane-2,4- dione, bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate, bis(1-octyloxy-2, 2,6,6- tetramethylpiperidin-4-yl)succinate, the condensation product of N, N'-bis(2, 2,6,6- tetramethylpiperidin-4-yl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1 ,3,5- triazine, the condensation product of 2-chloro-4,6-bis(4-n-butylamino-2, 2,6,6- tetramethylpiperidin-4-yl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, the condensation product of 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, 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, the condensation product of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4- cyclohexylamino-2,6-dichloro-1,3,5-triazine, the condensation product of 1 ,2-bis(3- aminopropylamino)ethane and 2,4,6-trichloro-1 ,3,5-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-oxo-spiro[4.5]-decane, the condensation product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4.5]decane and epichlorohydrin, the condensation products of 4-amino-2,2,6,6-tetramethylpiperidine with tetramethylolacetylenediureas and poly(methoxypropyl-3-oxy)-[4(2, 2,6,6- tetramethyl)piperidinyl]-siloxane,

[0256] 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 its mixture 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

[0257] 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)-1 ,3,5-triazine, 2-(2-hydroxy-4- octyloxyphenyl)-4,6-bis(4-methylphenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4- dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4- tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine, 2-[2-hydroxy-4-(2- hydroxy-3-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-triazi ne, 2-[2-hydroxy-4-(2-hydroxy-3- dodecyloxypropoxy)phenyl]-4,6-bis-(2,4-dimethylphenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4- hexyloxyphenyl)-4,6-diphenyl-1 ,3,5-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6- diphenyl-1 ,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]- 1 ,3,5-triazine and 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1 ,3,5-triazine.

[0258] In a preferred embodiment the RM mixture or RM formulation is dissolved in a suitable solvent, which are preferably selected from organic solvents.

[0259] The solvents are preferably selected from ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, cyclopentanone or cyclohexanone; carbonates such as dimethyl carbonate; 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 2-methyl tetra hydrofuran, cyclopentane or cyclohexane; halogenated hydrocarbons such as di- or trichloromethane; glycols or their esters such as PGMEA (propyl glycol monomethyl ether acetate), y-butyrolactone. It is also possible to use binary, ternary or higher mixtures of the above solvents. Very preferred are methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, dimethyl carbonate, 2-methyl tetra hydrofuran or mixtures thereof, in particular mixtures comprising cyclopentanone. For multilayer applications, methyl iso butyl ketone or mixtures thereof are the preferred utilized solvents.

[0260] In case the RM formulation contains one or more solvents, the total concentration of all solids, including the RMs, in the solvent(s) is preferably from 5 to 60%, more preferably from 10 to 50%, in particular from 10 to 35%.

[0261] In another preferred embodiment, the RM mixture or RM formulation does not contain a silicon compound.

[0262] In another preferred embodiment, the RM mixture or RM formulation does not contain a surface-active compound, and preferably does not contain any of the above- mentioned reactive thinners or additives of groups c1) to c8). In another preferred embodiment, the RM mixture consists of 85 to 99%, preferably 90 to 98%, of one or more, preferably two or more, mono-, di- or multireactive mesogens, preferably selected from formulae DRMal, MRM1 and MRM7, 1 to 15%, preferably 2 to 10%, of one or more additives selected from methacrylic and acrylic esters of polyfunctional alcohols as defined above, optionally a photoinitiator and optionally an antioxidant additive. An RM formulation according to this preferred embedment consists of such an RM mixture and one or more organic solvents.

[0263] Preferably, the RM mixture or RM formulation comprises one or more components selected from the group consisting of components a) to n) or any combination thereof, provided that at least component a) and one or both of components b) and c) are present: a) one or more additives selected from methacrylic and acrylic esters of polyfunctional alcohols or the preferred embodiments thereof as described above and below, and b) one or more multi - or direactive polymerisable mesogenic compounds, preferably selected from compounds of formula DRM and corresponding subformulae, and / or c) one or more monoreactive polymerisable mesogenic compounds, preferably selected from compounds of formula MRM and corresponding subformulae, and / or d) one or more photoinitiators, and / or e) one or more antioxidative additives, and / or f) optionally one or more adhesion promotors, and / or g) optionally one or more surfactants, and / or h) optionally one or more mono-, di- or multireactive polymerisable non-mesogenic compounds, and / or i) optionally one or more dyes showing an absorption maximum at the wavelength used to initiate photo polymerisation, and / or j) optionally one or more chain transfer agents, and / or k) optionally one or more (UV) stabilizers, and / or l) optionally one or more lubricants and flow auxiliaries, and / or m) optionally one or more diluents, and / or n) optionally a non-polymerisable nematic component, and / or o) one or more organic solvents.

[0264] Preferably the additives of groups e) to n) are selected from PFAS-free compounds.

[0265] Very preferably the RM mixture consists of components a) and d), components b) and / or c), and optionally component e). Very preferably the RM formulation consists of components a), d) and o), components b) and / or c), and optionally component e).

[0266] More preferably, the RM mixture or RM formulation comprises one or more components selected from the group consisting of components 1) to 6) or any combination thereof, provided that at least component 1) and one or both of components 2) and 3) are present:

[0267] 1) one or more additives selected from methacrylic and acrylic esters of polyfunctional alcohols or the preferred embodiments thereof as described above and below, and

[0268] 2) one or more, preferably two or more, direactive polymerisable mesogenic compounds, preferably selected from the compounds of formula DRM or its subformulae, more preferably from subformulae DRMa to DRMm, very preferably from subformula DRMa-1 , and / or

[0269] 3) one or more, preferably two or more, monoreactive polymerisable mesogenic compounds, preferably selected from formula MRM, more preferably from subformulae MRM1 to MRM34, very preferably from subformulae MRM-1, MRM- 4, MRM-7 and MRM-8, and / or

[0270] 4) optionally one or more antioxidative additives, and / or

[0271] 5) optionally one or more photoinitiators, and / or

[0272] 6) optionally one or more organic solvents.

[0273] Very preferably the RM mixture consists of components 1) and 5), components 2) and / or 3), and optionally component 4). Very preferably the RM formulation consists of components 1), 5) and 6), components 2) and / or 3), and optionally component 4).

[0274] The RM mixture and RM formulation can be prepared in a manner conventional per se, for example by mixing one or more of the above-mentioned preferred additives with one or more RMs as defined above, and optionally with further additives.

[0275] The invention further relates to a process of preparing a polymer film by polymerizing an RM mixture according to the present invention, preferably wherein the polymerizable compounds are aligned into uniform orientation, and preferably at a temperature where the polymerizable compounds or the RM mixture exhibit a liquid crystal phase, preferably a nematic phase. A preferred embodiment of the invention relates to a process of preparing a polymer film comprising, preferably consisting of, the steps of

[0276] - providing a layer of an RM mixture or RM formulation as described above and below onto a substrate, preferably a plastic substrate, which has optionally been subjected to surface treatment, preferably corona plasma treatment, before the RM mixture or formulation is provided thereon, and which preferably does not carry an alignment layer,

[0277] - optionally removing any solvents, if present,

[0278] - optionally annealing the layer of the RM mixture (i.e., without solvent), preferably at a temperature where it is in the nematic phase,

[0279] - irradiating the RM layer with actinic radiation, preferably with UV radiation, causing polymerization of the polymerizable components and formation of a polymer film,

[0280] - optionally removing the polymer film from the substrate.

[0281] The invention further relates to a polymer film obtainable by a process as described above and below.

[0282] Preferably in the processes according to the present invention all irradiation or UV exposure steps are carried out at room temperature, and the layer of the polymerizable LC medium is not subjected to heat treatment during or between the irradiation or UV exposure steps.

[0283] This RM mixture or RM formulation can be coated or printed onto the substrate, for example by spin-coating, printing, or other known techniques, and the solvent is evaporated off before polymerization. In most cases, it is suitable to heat the mixture in order to facilitate the evaporation of the solvent.

[0284] The RM mixture or RM formulation can be applied onto a substrate by conventional coating techniques like spin coating, bar coating or blade coating. It can also be applied to the substrate by conventional printing techniques which are known to the expert, like for example screen printing, offset printing, reel-to-reel printing, letter press printing, gravure printing, rotogravure printing, flexographic printing, intaglio printing, pad printing, heat-seal printing, ink-jet printing or printing by means of a stamp or printing plate.

[0285] The substrate can be a plastic film or a glass substrate which is preferably a raw glass substrate (i.e., untreated and without an alignment layer), very preferably a plastic substrate. Suitable and preferred plastic substrates are known to the expert and described in the literature, as for example conventional substrates used in the optical films industry. Especially suitable and preferred substrates are polyesters such as polyethyleneterephthalate (PET) or polyethylenenaphthalate (PEN), polyvinylalcohol (PVA), polycarbonate (PC), triacetylcellulose (TAC), cyclo-olefin polymers (COP) or commonly known color filter materials.

[0286] In a preferred embodiment of the present invention, the plastic substrate is subjected to corona plasma treatment before the RMM is provided thereon.

[0287] Preferably the substrate is selected from TAC, COP or PET, which are optionally subjected to surface treatment, preferably corona plasma treatment, or raw glass, very preferably from TAC, COP or PET, which are optionally subjected to surface treatment, preferably corona plasma treatment.

[0288] Very preferably the substrate is selected from untreated or corona plasma treated TAC, and corona plasma treated COP.

[0289] In a preferred embodiment, the process according to the invention contains a process step where the RM mixture or RM formulation is allowed to rest for a period of time in order to evenly redistribute the polymerizable LC medium on the substrate (herein referred to as “annealing”).

[0290] In a preferred embodiment, after providing the RM mixture or RM formulation onto the substrate, the layer stack is annealed for a time between 10 seconds and 1 hour, preferably between 20 seconds and 10 minutes and most preferably between 30 seconds and 2 minutes. The annealing is preferably performed at room temperature.

[0291] The RM mixture preferably consists of compounds that aling spontaneously when being deposited as a mixture onto the substrate. Therefore, preferably the RM mixture is not subjected to heat treatment to align the mesogenic or liquid-crystalline compounds before the UV exposure.

[0292] If necessary, the layer stack can be cooled down to room temperature after annealing at an elevated temperature. The cooling can be performed actively with the help of cooling aids or passively just by letting the layer stack rest for a given time.

[0293] Photopolymerization of the RM mixture is preferably achieved by exposing it to actinic radiation. Actinic radiation means irradiation with light, like UV light, IR light or visible light, irradiation with X-rays or gamma rays, or irradiation with high-energy particles, such as ions or electrons. Preferably, polymerization is carried out by photo irradiation, in particular with UV light. As a source for actinic radiation, for example a single UV lamp or a set of UV lamps can be used. When using a high lamp power the curing time can be reduced. Another possible source for photo radiation is a laser, like e.g. a UV laser, an IR laser, or a visible laser.

[0294] The curing time for the photopolymerization is dependent, inter alia, on the reactivity of the polymerizable LC medium, the thickness of the coated layer, the type of polymerization initiator and the power of the UV lamp. The curing time is preferably < 5 minutes, very preferably < 3 minutes, most preferably < 1 minute. For mass production, short curing times of < 30 seconds are preferred.

[0295] A suitable UV radiation power for the photopolymerization is preferably in the range from 100 to 1000 mWcm-2, more preferably in the range from 200 to 800 mWcm’2and most preferably in the range from 250 to 600 mWcm’2.

[0296] In connection with the applied UV radiation and as a function of time, a suitable UV dose is preferably in the range from 25 to 16500 mJcnr2, more preferably in the range from 50 to 7200 mJcnr2, very preferably in the range from 100 to 3500 mJcnr2and most preferably in the range from 200 to 2000 mJcnr2.

[0297] Photopolymerization is preferably performed under an inert gas atmosphere, preferably in a nitrogen atmosphere. Further preferably photopolymerization is performed at room temperature.

[0298] The preferred thickness of a polymerized LC film according to the present invention is determined by the optical properties desired from the film or the final product.

[0299] For optical applications of the polymer film, it preferably has a thickness of from 0.1 to 10 pm, very preferably from 0.1 to 2 pm, in particular from 0.1 to 1 pm.

[0300] The optical retardation (5(X)) of a polymer film as a function of the wavelength of the incident beam ( ) is given by the following equation (7):

[0301] 5(X) = (27tAn-d) / X (7) wherein (An) is the birefringence of the film, (d) is the thickness of the film and is the wavelength of the incident beam.

[0302] The birefringence and accordingly optical retardation depends on the thickness of a film and the tilt angle of optical axis in the film (cf. Berek’s compensator). Therefore, the skilled expert is aware that different optical retardations or different birefringence can be induced by adjusting the orientation of the liquid-crystalline molecules in the polymer film.

[0303] The birefringence (An) of the polymer film according to the present invention is preferably in the range from 0.08 to 0.25, more preferably from 0.09 to 0.20, very preferably from 0.10 to 0.15.

[0304] After photopolymerization, the resulting polymer film can be removed from the substrate and combined with other substrates or optical films by a laminating process known by the skilled person. Suitable substrates and optical films are given above and include especially polarisers, in particular linear polarisers, photoalignment layers, or diffraction gratings, for example PB gratings.

[0305] The polymer film according to the present invention has good adhesion to plastic substrates, in particular to TAG, COP, and colour filters. Accordingly, it can be used as adhesive or base coating for subsequent polymerized RM layers or LC layers which otherwise would not well adhere to the substrates.

[0306] The polymer film of the present invention can also be used as alignment film or substrate for other liquid-crystalline or RM materials. The inventors have found that the polymer film obtainable from a RM formulation as described above and below, is in particular useful for multilayer applications due to its improved dewetting characteristics. In this way, stacks of optical films or preferably polymerized LC films can be prepared.

[0307] The invention further relates to an optical, electrooptical or electronic device or a component comprising an RM mixture or a polymer film as described above and below.

[0308] In summary, the polymer film and RM mixture according to the present invention are useful in optical elements like polarisers, compensators, alignment layer, circular polarisers or colour filters in liquid crystal displays or projection systems, decorative images, for the preparation of liquid crystal or effect pigments, and especially in reflective films with spatially varying reflection colours, e.g. as multicolour image for decorative, information storage or security uses, such as non-forgeable documents like identity or credit cards, banknotes etc..

[0309] The polymer film according to the present invention can be used in displays of the transmissive or reflective type. It can be used in conventional OLED displays or LCDs, in particular LCDs.

[0310] The present invention is described above and below with particular reference to the preferred embodiments. It should be understood that various changes and modifications might be made therein without departing from the spirit and scope of the invention.

[0311] Many of the compounds or mixtures thereof mentioned above and below are commercially available. All of these compounds are either known or can be prepared by methods which are known per se, as described in the literature (for example in the standard works such as Houben-Weyl, Methoden der Organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart), to be precise under reaction conditions which are known and suitable for said reactions. Use may also be made here of variants which are known per se, but are not mentioned here.

[0312] It will be appreciated that variations to the foregoing embodiments of the invention can be made while still falling within the scope of the invention. Alternative features serving the same, equivalent, or similar purpose may replace each feature disclosed in this specification, unless stated otherwise. Thus, unless stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features.

[0313] All of the features disclosed in this specification may be combined in any combination, except combinations where at least some of such features and / or steps are mutually exclusive. In particular, the preferred features of the invention are applicable to all aspects of the invention and may be used in any combination. Likewise, features described in non-essential combinations may be used separately (not in combination).

[0314] It will be appreciated that many of the features described above, particularly of the preferred embodiments, are inventive in their own right and not just as part of an embodiment of the present invention. Independent protection may be sought for these features in addition to or alternative to any invention presently claimed. Unless explicitly noted otherwise, all temperature values indicated in the present application, such as, for example, for the melting point T(K,N), the transition from the smectic (S) to the nematic (N) phase T(S,N) and the clearing point T(N,I), are quoted in degrees Celsius (°C). Furthermore, K denotes the crystalline state, N denotes the nematic phase, and I denotes the isotropic phase. The data between these symbols represent the transition temperatures.

[0315] Unless explicitly noted otherwise, all physical properties have been and are determined according to "Merck Liquid Crystals, Physical Properties of Liquid Crystals", Status Nov. 1997, Merck KGaA, Germany and are given for a temperature of 20 °C, unless explicitly stated otherwise.

[0316] Above and below, percentages are per cent by weight unless stated otherwise. All temperatures are given in degrees Celsius.

[0317] Above and below, m.p. denotes the melting point, TNI and cl.p. denote the nematic- isotropic phase transition temperature (or clearing point), Tgdenotes glass transition temperature. Furthermore, C denotes the crystalline state, N denotes the nematic phase, SA, SB etc. denotes the smectic A phase, smectic B phase etc., Sx denotes an unidentified smectic phase, X denotes an unidentified mesophase and I denotes the isotropic phase. The values between these symbols represent the transition temperature in °C. Unless stated otherwise, the onset temperature is given for TNI. An denotes the optical anisotropy or birefringence (An = ne- n0, where n0denotes the refractive index perpendicular to the longitudinal molecular axes and nedenotes the refractive index parallel thereto) at 589 nm and room temperature. The optical and electro optical data are measured at 20°C, unless expressly stated otherwise.

[0318] "Clearing point" and "clearing temperature" mean the temperature of the transition from an LC phase into the isotropic phase. “MEK” means methyl ethyl ketone, “MIBK” means methyl isobutyl ketone. “DMC” means dimethyl carbonate, “2-MTHF” means 2- methyl tetra hydrofuran. “RT” means room temperature. “Rth” means the out of plane retardation (nm).

[0319] Unless stated otherwise, the percentages of individual solid compounds in an RM mixture as described above and below refer to the total amount of solids in the mixture, i.e., without any solvents. Unless stated otherwise, all optical, electro optical properties and physical parameters like birefringence, permittivity, electrical conductivity, electrical resistivity and sheet resistance, refer to a temperature of 20°C.

[0320] The invention will now be described in more detail by reference to the following working examples, which are illustrative only and do not limit the scope of the invention.

[0321] Example 1

[0322] The following RM mixture is prepared:

[0323] M1 Cone.

[0324] SPI-03 2.50%

[0325] BYKO-3550 0.50%

[0326] MRM1a 5.00%

[0327] Dipentaerythritol Penta- / hexaacrylate (CAS: 60506-81-2)

[0328] SPI-03 is a photoinitiator, being commercially available (Samyang). BYK®-3550 is a PFAS- free wetting agent, being commercially available (BYK). Irganox®1076 is an antioxidant stabilizer, being commercially available (Ciba AG).

[0329] The RM mixture M1 contains the additive dipentaerythritol penta- / hexaacrylate without any terminal methyl groups according to the present invention.

[0330] The following RM mixture is prepared:

[0331] M2 Cone.

[0332] SPI-03 2.50% BYKO-3550 0.50% lrganox®1076 0.08% MRM7a 27.58% DRMala 22.98% DRMalb 22.98%

[0333] Pentaerythritol Tetraacrylate (CAS: 4986-89-4)

[0334] The RM mixture M2 contains the additive pentaerythritol tetraacrylate without any terminal methyl groups according to the present invention.

[0335] The following RM mixture is prepared:

[0336] The RM mixture C1 contains the additive di(trimethylolpropane) tetraacrylate with two terminal methyl groups.

[0337] Comparison Example 2

[0338] The following RM mixture is prepared: Tri methylol propane triacrylate (CAS: 15625-89-5)

[0339] The RM mixture C2 contains the additive trimethylolpropane triacrylate with a terminal methyl group.

[0340] The following RM mixture is prepared:

[0341] C3 Cone.

[0342] SPI-03 2.50%

[0343] PolyfoxTMPF-656 1 .00% lrganox®1076 0.08%

[0344] MRM7a 33.75%

[0345] DRMala 21.70%

[0346] DRMal b 21.70%

[0347] MRM1a 19.27%

[0348] Polyfox™PF-656 is a fluorosurfactant, being commercially available (Synthomer).

[0349] The RM mixture C3 does not contain a multiacrylate additive.

[0350] Comparison Example 4

[0351] The following RM mixture is prepared:

[0352] C3 Cone.

[0353] SPI-03 2.50%

[0354] BYKO-3550 0.75% lrganox®1076 0.08%

[0355] MRM7a 33.84%

[0356] DRMala 21.76%

[0357] DRMal b 21.76%

[0358] MRM1a 19.32%

[0359] The RM mixture C4 does not contain a multiacrylate additive. Formulations are prepared from the above RM mixtures by dissolving each mixture at a concentration of 20% in a solvent system as shown in Table 1 below.

[0360] Table 1 - RM Formulations

[0361] Use Example A: Polymer Films

[0362] Polymer films are prepared from the RM formulations on different treated or untreated plastic substrates by the following process:

[0363] The RM formulation is heated and stirred until the RM mixture is completely dissolved. The formulation is then coated onto a substrate with a Bar Coat MB#4. The substrate is a Fuji 60 .m zTAC substrate for mixtures F11 , F21 , CF11 , CF21 , CF31 , CF41 or a Zeon COP substrate for mixtures F12, F22, CF12, CF22, CF32. The substrate with the coated RM formulation is heated on a hot stage at 50°C for 60s to evaporate the solvent and anneal the RM layer.

[0364] Pre-treatment of the substrates is carried out by exposure to Corona Plasma (15x, 6A). The substrate with the coated RM layer is then purged in a nitrogen environment for 1 minute and cooled to RT. Following that, the RM layer is then exposed to UV light (high pressure mercury lamp LH6 fusion, 250 mJ / cm2) to polymerize the RM layer and form a polymer film.

[0365] The out of plane retardation Rth of the polymer films is determined by ellipsometry (JA Woollam, -60 to 40° every 20°, 400-1 OOOnm). The alignment quality of the polymer films is determined by optical microscopy (POM Microscope, Dark State, 4X Objective, 200ms Exposure). The wetting of the substrates is determined by eye observation.

[0366] The adhesion of the polymer films is determined by an adhesion tape test (Nichiban 405 Tape, 2x per substrate, 0B = worst, 5B = best).

[0367] The retardation, alignment, wetting and adhesion of the polymer films prepared on the corona treated and untreated zTAC substrates are summarized in Table 2 (O = good, A = medium, X = bad).

[0368] Table 2 - Polymer Films prepared on zTAC Substrate

[0369] 1)Values given for two measurements

[0370] In case of polymer films prepared on the untreated zTAC substrate, the polymer films P11 and P21 prepared from formulations which contain a multiacrylate additive according to the present invention show good homeotropic alignment and high retardation. Compared thereto, the polymer films CP11 , CP21 , CP31 and CP41 prepared from the comparison formulations, which do either contain a different multiacrylate additive or do not contain a multiacrylate additive, show bad alignment and no retardation. In case of polymer films prepared on the corona treated zTAC substrate, the polymer films P11 and P21 prepared from formulations according to the present invention show good homeotropic alignment and strong adhesion. Compared thereto, the polymer films CP11 and CP21 prepared from the comparison formulations show worse adhesion, and the polymer film CP31 shows both bad alignment and bad adhesion.

[0371] Typically, good homeotropic alignment of polymer films made from acrylate RMs on untreated COP is difficult to achieve. Therefore, retardation, alignment, wetting and adhesion were determined for polymer films prepared on corona treated COP substrates. The results are summarized in Table 3 (O = good, A = medium, X = bad).

[0372] Table 3 - Polymer Films prepared on corona treated COP Substrate

[0373] 2)Values given for two measurements

[0374] All polymer films show good homeotropic alignment, however, the polymer films P12, P22, P13 and P14 prepared from formulations according to the present invention show much stronger adhesion than the polymer films CP12, CP22 and CP32 prepared from the comparison formulations.

[0375] Example 3

[0376] The following RM mixture is prepared:

[0377] M3 Cone.

[0378] SPI-03 2.50%

[0379] PolyfoxTMPF-656 1 .00% lrganox®1076 0.08%

[0380] MRM7a 32.00%

[0381] DRMala 20.58% DRMal b 20.58%

[0382] MRM1a 18.27%

[0383] Dipentaerythritol Penta- / hexaacrylate 5.00%

[0384] The RM mixture M3 contains the additive dipentaerythritol penta- / hexaacrylate without any terminal methyl groups according to the present invention.

[0385] Example 4

[0386] The following RM mixture is prepared:

[0387] M4 Cone.

[0388] SPI-03 2.50%

[0389] PolyfoxTMPF-656 1 .00% lrganox®1076 0.08%

[0390] MRM7a 30.25%

[0391] DRMala 19.45%

[0392] DRMal b 19.45%

[0393] MRM1a 17.27%

[0394] Dipentaerythritol Penta- / hexaacrylate 10.00%

[0395] The RM mixture M4 contains the additive dipentaerythritol penta- / hexaacrylate without any terminal methyl groups according to the present invention.

[0396] Formulations are prepared from the RM mixtures M3 and M4 by dissolving each mixture at a concentration of 20% in a solvent system as shown in Table 4 below.

[0397] Table 4 - RM Formulations

[0398] Use Example B: Polymer Films Polymer films from formulations F31 , F41, F32, F42 according to the present invention and polymer films from comparison formulations CF31 and CF32 are prepared as described above in Use Example A, but wherein for formulations F31, F41 and CF31 a Fuji 80 .m TAG substrate with or without corona plasma treatment was used, and for formulations F32, F42 and CF32 a raw glass substrate (1”, untreated) was used.

[0399] The alignment, wetting and adhesion of the polymer films prepared on the TAG substrate are summarized in Table 5 (O = good, A = medium, X = bad).

[0400] Table 5 - Polymer Films prepared on TAG Substrate

[0401] In case of the polymer films prepared on the untreated TAG substrate, the polymer films P31 and P41 prepared from formulations according to the present invention show better homeotropic alignment than the polymer film CP31 prepared from the comparison formulation.

[0402] In case of the polymer films prepared on the corona treated TAG substrate, all polymer films show good homeotropic alignment. However, the polymer films P31 and P41 prepared from formulations according to the present invention show strong adhesion, which increases with increasing amount of the multiacrylate additive. Compared thereto, the polymer film CP31 prepared from the comparison formulation shows bad homeotropic alignment and bad adhesion.

[0403] The retardation and birefringence of the polymer films prepared on the raw glass substrate are determined as described above.

[0404] With decreasing content of the RM components and increasing content of the multiacrylate additive, a reduction in birefringence and retardation can be expected in the RM mixtures and polymer films according to the invention. As a consequence, a higher film thickness would be required to achieve a specific retardation (e.g. 70 nm), leading to increased material and film cost. It is therefore desired to keep the content of the multiacrylate additive high enough to ensure good alignment and adhesion but also low enough to avoid a strong reduction of the birefringence.

[0405] The results are summarized in Table 6.

[0406] Table 6 - Polymer Films prepared on Raw Glass Substrate

[0407] The polymer film of formulation F32 (with 5% multiacrylate additive) results in a smaller reduction of the birefringence and retardation. Considering the results from Table 5, formulation F32 thus represents a suitable combination of good alignment, wetting, adhesion and retardation properties.

[0408] Overall, the above results demonstrate that polymer films prepared from RM mixtures and RM formulations according to the present invention show improved homeotropic alignment and / or adhesion on various treated or untreated substrates, especially plastic substrates like TAC and COP.

Claims

Patent Claims1. A process of preparing a polymer film comprising a homeotropically aligned, polymerized reactive mesogen mixture (RMM) on a substrate, said process comprising the following steps:- providing a layer of the RMM, or a formulation comprising the RMM and further comprising one or more solvents, onto the substrate,- optionally removing any solvents, if present,- optionally annealing the layer of the RM mixture, preferably at a temperature where it exhibits a nematic phase,- irradiating the RM layer with actinic radiation, preferably with UV radiation, causing polymerization of the polymerizable components and formation of a polymer film,- optionally removing the polymer film from the substrate, characterized in that the RMM comprises one or more, preferably two or more, mono-, di- or multireactive RMs, and further comprises from 1 to 15%, preferably from 2 to 10%, of one or more additives selected from methacrylic and acrylic esters of polyfunctional alcohols, wherein said additives do only contain terminal groups selected from acrylic, methacrylic and hydroxy groups, and wherein preferably the RMM does not contain a compound with at least one CF3 or CF2 group (PFAS), and very preferably the RMM does not contain a compound with a polyfluorinated alkyl or aryl group or a perfluorocarbon group.

2. The process according to claim 1, characterized in that the said additives are selected from multiacrylates of pentaerythritol or dipentaerythritol which contain at least four acrylate or methacrylate groups.

3. The process according to claim 1 or 2, characterized in that the said additives are selected from pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate and di pentaerythritol hexaacrylate or mixtures thereof.

4. The process according to one or more of claims 1 to 3, characterized in that the RMM contains one or more di- or multireactive mesogens of formula DRMP1-Sp1-MGD-Sp2-P2DRMwherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meaningsP1, P2a polymerizable group,Sp1, Sp2a spacer group or a single bond,MG a rod-shaped mesogenic group, preferably selected of formula MGD-(A1-Z1)n-A2- MGDA1, A2an aromatic or alicyclic group, which optionally contains one or more heteroatoms selected from N, O and S, and is optionally mono- or polysubstituted by LD,LDP-Sp-, F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, - C(=O)NRxRy, -C(=O)ORX, -C(=O)RX, -NRxRy, -SF5, optionally substituted silyl, aryl or heteroaryl with 1 to 12, preferably 1 to 6 C atoms, and straight chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 12, preferably 1 to 6 C atoms, wherein one of the H atoms is optionally replaced by F or Cl,Rx, RyH or alkyl with 1 to 12 C-atoms,Z1single bond, preferably -COO-, -OCO- or a single bond,Y1, Y2H, F, Cl or CN, n 1 , 2, 3 or 4, preferably 1 or 2, most preferably 2, n1 an integer from 1 to 10, preferably 1 , 2, 3 or 4.

5. The process according to one or more of Claims 1 to 4, characterized in that the RMM comprises one or more di- or multireactive mesogens selected from the following subformulae:wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meaningsP° a polymerizable group, preferably an acrylate, methacrylate, oxetane, epoxy, vinyl, heptadiene, vinyloxy, propenyl ether or styrene group, very preferably an acrylate or methacrylate group,Z° -COO-, -OCO-, -CH2CH2-, -CF2O-, -OCF2-, -C=C-, -CH=CH-,-OCO- CH=CH-, -CH=CH-COO-, or a single bond,L has one of the meanings given for LDin Claim 4, and is preferably selected from F, Cl, CN or optionally halogenated alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 5 C atoms, r 0, 1 , 2, 3 or 4, s 0, 1 , 2 or 3, t 0, 1 or 2, x, y 0 or an integer from 1 to 12, preferably from 3 to 6, z 0 or 1 , with z being 0 if the adjacent x or y is 0.

6. The process according to one or more of Claims 1 to 5, characterized in that the RMM comprises one or more di- or multireactive mesogens selected from the following subformulae:wherein P°, L, r, x, y and z are as defined in Claim 5.

7. The process according to one or more of Claims 1 to 6, characterized in that the RMM comprises one or more monoreactive mesogens of formula MRM:P1-Sp1-MGM-R22MRMwherein the individual radical, independently of each other and on each occurrence identically or differently, have the following meaningsP1a polymerizable group,Sp1a spacer group or a single bond,MGMa rod-shaped mesogenic group, preferably selected of formula MGM-(A1-Z1)n-A2- MGMA1, A2an aromatic or alicyclic group, which optionally contains one or more heteroatoms selected from N, O and S, and is optionally mono- or polysubstituted by LM,LMF, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)NRxRy, - C(=O)ORX, -C(=O)RX, -NRxRy, -SFs, optionally substituted silyl, aryl or heteroaryl with 1 to 12, preferably 1 to 6 C atoms, and straight chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 12, preferably 1 to 6 C atoms, wherein one of the H atoms is optionally replaced by F or Cl,R22F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)NRxRy, - C(=O)X, -C(=O)ORX, -C(=O)Ry, -NRxRy, -SFs, optionally substituted silyl, straight chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 12, preferably 1 to 6 C atoms, wherein one of the H atoms is optionally replaced by F or Cl,X halogen, preferably F or Cl,Rx, RyH or alkyl with 1 to 12 C-atoms,Z1single bond, preferably -COO-, -OCO- or a single bond,Y1, Y2H, F, Cl or CN, n 1 , 2, 3 or 4, preferably 1 or 2, most preferably 2, n1 an integer from 1 to 10, preferably 1, 2, 3 or 4.

8. The process according to one or more of Claims 1 to 7, characterized in that theRMM comprises one or more monoreactive mesogens selected from the following subformulae:MRM34wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meaningsP° a polymerizable group, preferably an acrylate, methacrylate, oxetane, epoxy, vinyl, heptadiene, vinyloxy, propenyl ether or styrene group, very preferably an acrylate or methacrylate group,R° alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 or more, preferably 1 to 15 C atoms, or Y°,Y° F, Cl, CN, NO2, OCH3, OCN, SCN, SF5, or mono- oligo- or polyfluorinated alkyl or alkoxy with 1 to 4 C atoms,A01 ,4-phenylene that is unsubstituted or substituted with 1 , 2, 3 or 4 groups L, or trans-1,4-cyclohexylene,Z° -COO-, -OCO-, -CH2CH2-, -CF2O-, -OCF2-, -C=C-, -CH=CH-,-OCO- CH=CH-, -CH=CH-COO-, or a single bond,L has one of the meanings given for LMin Claim 7 and is preferably selected from F, Cl, CN or optionally halogenated alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 5 C atoms, r 0, 1 , 2, 3 or 4, s 0, 1 , 2 or 3, t 0, 1 or 2, u, v 0, 1 or 2,w 0 or 1 , preferably 1 , x 0 or an integer from 1 to 12, preferably from 3 to 6, z 0 or 1 , with z being 0 if the adjacent x or y is 0, and wherein the benzene and naphthalene rings can additionally be substituted with one or more identical or different groups LM.

9. The process according to one or more of Claims 1 to 8, characterized in that the proportion of the mono-, di- and multireactive mesogens in the RMM is from 60 to 99% of total solids.

10. The process according to one or more of Claims 1 to 9, characterized in that the RMM comprises one or more mono-, di- and / or multireactive mesogens selected from formulae DRM and MRM as defined in one or more of Claims 4 to 8 in a proportion from 60 to 99% of total solids.

11. The process according to one or more of Claims 1 to 10, characterized in that the substrate is selected from TAC, COP or PET substrates or raw glass.

12. The process according to one or more of Claims 1 to 11, characterized in that the substrate is subjected to corona plasma treatment before the RMM is provided thereon.

13. The process according to one or more of Claims 1 to 12, characterized in that the substrate is not covered by an alignment layer before the RMM is provided thereon.

14. An LC polymer film obtained from a process according to one or more of Claims 1 to 13.

15. An optical, electrooptical or electronic device or a component thereof, comprising a polymer film according to Claim 14.

16. The component of Claim 15, which is selected from optical retardation films, polarizers, optical compensators, diffraction or surface gratings, Braggpolarization gratings (Bragg PG), polarization volume gratings (PVG), Pancharatnam Berry gratings (PBG) or Pancharatnam Berry lenses (PBL), furthermore nonmechanical beam steering elements, optical waveguides, optical couplers or combiners, polarization beam splitters, partial mirrors, reflective films, alignment layers, colour filters, antistatic protection sheets, electromagnetic interference protection sheets, lenses for light guides, focusing and optical effects, polarization controlled lenses, and IR reflection films.

17. The device of Claim 15, which is selected from liquid crystal displays, organic light emitting diodes, autostereoscopic 3D displays, see-through near-eye displays, AR / VR systems, goggles for AR / VR applications, switchable windows, spatial light modulators, optical data storage devices, optical sensors, holographic devices, spectrometers, optical telecommunication systems, polarimeters or front- / backlights.

18. An RMM as defined in one or more of Claims 1 to 10, which does not contain a compound with at least one CF3 or CF2 group (PFAS), and preferably does not contain a compound with a polyfluorinated alkyl or aryl group.

19. An RMM as defined in one or more of Claims 1 to 10 and 18, which does not contain a silicon compound.

20. An RMM as defined in one or more more of Claims 1 to 10, 18 and 19, characterized in that the said additives are selected from multiacrylates of pentaerythritol or di pentaerythritol which contain five or six acrylate or methacrylate groups, preferably selected from di pentaerythritol pentaacrylate and di pentaerythritol hexaacrylate or mixtures thereof.

Images