Polymerizable liquid crystal material and polymerized liquid crystal film

Abstract

To provide a polymerizable liquid crystal material and a polymerized liquid crystal film.SOLUTION: The invention relates to a polymerizable LC material comprising one or more di- or multireactive mesogenic compounds and one or more specific compounds, for example, represented by the following formulae S1-6. Furthermore, the present invention relates to a method for its preparation, a polymer film with improved thermal and UV stability obtainable from a corresponding polymerizable LC material, and a method for preparation of such a polymer film.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a polymerisable LC material comprising one or more di- or multireactive mesogenic compounds and one or more compounds of formula SO, S1 or S2. [ka]

[0002] wherein the individual radicals have one of the meanings as given in the claims.The invention further relates to a process for the preparation thereof, to polymer films with improved thermal and UV stability obtainable from the corresponding polymerizable LC materials, to a process for the preparation of such polymer films, and to the use of such polymer films and said polymerizable LC materials in optical, electro-optical, decorative or security devices. [Background technology]

[0003] Polymerizable liquid crystal materials for preparing anisotropic polymer films with uniform orientation are known in the prior art. These films are usually prepared by coating a thin layer of a polymerizable liquid crystal mixture on a substrate, orienting the mixture into a uniform orientation, and polymerizing the mixture. The orientation of the film can be planar, i.e., where the liquid crystal molecules are oriented substantially parallel to the layer, homeotropic (perpendicular or perpendicular to the layer) or tilted.

[0004] Such optical films are described, for example, in EP 0 940 707, EP 0 888 565 and GB 2 329 393.

[0005] Polymerizable liquid crystal (LC) materials are stable at room temperature but can degrade when the temperature is increased. For example, when heated for a certain period of time, the performance of optical films decreases over time, as optical properties such as dispersion or retardation decrease. This can be attributed in particular to a low degree of polymerization and a corresponding high content of residual free radicals in the polymer, polymer shrinkage, and / or thermo-oxidative degradation.

[0006] Thermo-oxidative degradation is the destruction of polymer networks catalyzed by oxidation at high temperatures. As is well known, antioxidant additives or short-term antioxidants can be used to reduce thermo-oxidative degradation of polymers when exposed to high temperatures. This is particularly important when optical films are utilized in in-cell applications due to the high temperatures they must withstand, especially when annealing the polyimide layers of LC cells. In this regard, the documents WO 2009 / 86911 (Patent Document 4) and JP 5354238 (Patent Document 5) describe polymerizable liquid crystal (LC) materials that contain the commercially available antioxidant Irganox® 1076.

[0007] The above-mentioned materials have obvious disadvantages, such as the UV stability or heat durability of the resulting polymer films is not yet sufficiently high, their transparency to VIS light is limited, they require the use of further additives, or their application range is limited, due to the LC materials used. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] European Patent No. 0 940 707 [Patent Document 2] European Patent No. 0 888 565 [Patent Document 3] British Patent No. 2 329 393 [Patent Document 4] International Publication No. 2009 / 86911 [Patent Document 5] Japanese Patent No. 5354238 Summary of the Invention [Problem to be solved by the invention]

[0009] Thus, there remains a need for new and preferably improved polymerizable liquid crystal materials or mixtures, any of which do not exhibit the disadvantages of the prior art materials, or which do so to a lesser extent.

[0010] Advantageously, such polymerizable LC materials should preferably be applicable to the preparation of polymer networks, such as various uniformly oriented polymer films, and particularly at the same time preferably - exhibits favorable adhesion to the substrate, -Highly transparent to VIS light, Reduced yellowing over time, and exhibits favorable high temperature stability or durability, and It should exhibit favorable high UV stability or heat durability, and in addition, · Uniformly oriented polymer films should be produced using compatible, well-known mass production methods.

[0011] Other objects of the present invention will become readily apparent to those skilled in the art from the following detailed description. [Means for solving the problem]

[0012] Surprisingly, the inventors of the present invention have found that by using a polymerisable LC material as defined in claim 1 one or more, preferably all of the above mentioned objectives can be achieved, preferably simultaneously. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] In summary the present invention relates to a polymerisable LC material comprising one or more di- or multireactive mesogenic compounds and one or more compounds of formula SO, S1 or S2. [ka]

[0014] In the formulae, the individual radicals, each independently of one another, have the following meanings, identically or differently at each occurrence: [ka] and P a is a polymerizable group, preferably a (meth)acrylate group, Sp is a linear or branched alkylene having 1 to 12 C atoms, with the proviso that in addition one or two non-adjacent CH groups may be replaced by -O-, -CH=CH-, -CO-, -OCO- or -COO-, such that the O atoms are not directly linked to each other, X 1 and X 2 each independently represents -O-, -CH=CH-, -CF2O-, -OCF2-, -CHO-, -OCH2-, -CO-O-, -O-CO-, -C2F4-, -CF=CF- or a single bond, preferably -O-, -CO-O- or -O-CO-; R a~d each independently represent a linear or branched alkyl having 1 to 20 C atoms, preferably having 1 to 15 C atoms and very preferably having 1 to 12 C atoms, R 1 and R 2 are independently H, CH3, OH, OR a Or O ● represents, and n represents an integer between 1 and 8.

[0015] The present invention further relates to a corresponding method for preparing a polymerizable LC material, which at least comprises the step of mixing one or more di- or multireactive mesogenic compounds and one or more compounds of formula SO, S1 or S2.

[0016] The invention further relates to a polymer network or a polymer film obtainable and preferably obtained from a polymerizable LC material as described above and below, and to a method for preparing a polymer film as described above and below.

[0017] The invention further relates to a method for increasing the UV stability of a polymer film obtainable, preferably obtained, from a polymerizable LC material as described above and below, by adding a compound of formula SO, S1 or S2 to the polymerizable LC material before polymerization.

[0018] The present invention further relates to the use of a polymer film or a polymerizable LC material as described above and below in optical, electro-optical, information storage, decorative and security applications such as liquid crystal displays, projection systems, polarizers, compensators, alignment layers, circular polarizers, color filters, decorative images, liquid crystal pigments, reflective films with spatially varying reflected color, multicolor images, unforgeable documents such as identity cards or credit cards or bank notes.

[0019] The present invention further relates to optical components or devices comprising one or more polymer networks or polymer films or polymerizable LC materials as described above and below, polarizers, patterned retarders, compensators, alignment layers, circular polarizers, colour filters, decorative images, liquid crystal lenses, liquid crystal pigments, reflective films with spatially varying reflected colour, multicolour images for decorative or information storage purposes.

[0020] The invention further relates to a liquid crystal display comprising one or more polymer films or polymerizable LC materials or optical components as described above and below.

[0021] The present invention further relates to an authenticity, verification or security mark, a colour or multicolour image for security uses, an uncounterfeitable article or document of value such as an identity card or credit card or a bank note, comprising a polymer network or polymer film or a polymerisable LC material as described above and below.

[0022] <Terms and definitions> As used herein, the term "polymer" will be understood to mean a molecule that includes a backbone of one or more different types of repeating units (the smallest building blocks of a molecule), and includes the well-known terms "oligomer," "copolymer," "homopolymer," and the like. The term polymer will further be understood to include, in addition to the polymer itself, residues from initiators, catalysts, and other elements associated with the synthesis of such a polymer, where such residues are understood not to be covalently incorporated therein. Moreover, such residues and other elements are usually removed in post-polymerization purification processes, but are typically mixed or entrained with the polymer, and they generally remain with the polymer when transferred between containers or between solvents or dispersion media.

[0023] The term "(meth)acrylic polymer" as used in the present invention includes polymers obtained from acrylic monomers, polymers obtained from methacrylic monomers, and the corresponding copolymers obtained from mixtures of such monomers.

[0024] The term "polymerization" refers to a chemical process for forming a polymer by linking together a plurality of polymerizable groups or polymer precursors (polymerizable compounds) that contain such polymerizable groups.

[0025] The terms "film" and "layer" include rigid or flexible, self-supporting or free-standing films with mechanical stability, as well as coatings or layers on a supporting substrate or between two substrates.

[0026] The term "liquid crystal" or "LC" refers to materials that, in solution, have a liquid crystal mesophase over some temperature range (thermotropic LC) or some concentration range (lyotropic LC). They necessarily contain mesogenic compounds.

[0027] The terms "mesogenic compound" and "liquid crystal compound" refer to compounds containing one or more calamitic (rod or board / lath shaped) or discotic (disk-shaped) mesogenic groups. The term "mesogenic group" refers to a group capable of inducing liquid crystal phase (or mesophase) behavior. A compound containing a mesogenic group does not necessarily exhibit liquid crystal mesophases by itself. It is also possible to exhibit liquid crystal mesophases only in mixtures with other compounds, or when the mesogenic compound or material, or a mixture thereof, is polymerized. This includes low molecular weight non-reactive liquid crystal compounds, reactive or polymerizable liquid crystal compounds, and liquid crystal polymers.

[0028] Calamitic mesogenic groups typically comprise a mesogenic core consisting of one or more aromatic or non-aromatic cyclic groups bonded together directly or via linking groups, optionally comprising terminal groups attached to the termini of the mesogenic core, and optionally comprising one or more side groups attached to the long chain of the mesogenic core, where these terminal and side groups are typically selected from, for example, carbyl groups, hydrocarbyl groups, polar groups such as halogen groups, nitro groups, hydroxy groups, etc., or polymerizable groups.

[0029] The term "reactive mesogen" refers to polymerizable mesogenic or liquid crystal compounds, preferably monomeric compounds. These compounds can be used as pure compounds or as mixtures of reactive mesogens with other compounds that act as photoinitiators, inhibitors, surfactants, stabilizers, chain transfer agents, non-polymerizable compounds, etc.

[0030] Polymerizable compounds with one polymerizable group are called "monoreactive" or "monofunctional" compounds, compounds with two polymerizable groups are called "direactive" or "difunctional" compounds, and compounds with three or more polymerizable groups are called "multireactive" or "multifunctional" compounds. Compounds with no polymerizable groups are also called "nonreactive or nonpolymerizable" compounds.

[0031] The term "non-mesogenic compound or material" means a compound or material that does not contain a mesogenic group as defined above.

[0032] Visible light or VIS light is electromagnetic radiation having a wavelength in the range of about 400 nm to about 740 nm. Ultraviolet light or UV light is electromagnetic radiation having a wavelength in the range of about 200 nm to about 400 nm.

[0033] Irradiance (E e ) or radiation power is defined as the electromagnetic power (dθ) per unit area (dA) incident on a surface: E e = dθ / dA.

[0034] Radiation exposure or radiation dose (H e ) is the irradiance or radiation output (E e ) is defined as: H e =E e t.

[0035] All temperatures, such as the melting point of a liquid crystal T(C,N) or T(C,S), the transition from the smectic (S) to the nematic (N) phase T(S,N) and its clearing point T(N,I), are expressed in degrees Celsius. All temperature differences are expressed in degrees Celsius.

[0036] The term "clearing point" means the temperature at which the transition between the mesophase and the isotropic phase occurs over the maximum temperature range.

[0037] The term "director" is known in the art and refers to the preferred orientation direction of the long molecular axes (in the case of calamitic compounds) or short molecular axes (in the case of discotic compounds) of liquid crystal or RM molecules. When such anisotropic molecules are uniaxially aligned, the director is the axis of anisotropy.

[0038] The term "alignment" or "orientation" refers to the alignment (orientational order) of anisotropic units of a material, such as small molecules or fragments of large molecules, in a common direction called the "orientation direction". In an alignment layer of a liquid crystal or RM material, the liquid crystal director coincides with the orientation direction, so that the orientation direction corresponds to the direction of the anisotropic axis of the material.

[0039] The term "uniform orientation" or "uniform alignment" of a liquid crystal or RM material means that, for example, within a layer of material, the long molecular axes (for calamitic compounds) or short molecular axes (for discotic compounds) of the liquid crystal or RM molecules are oriented in substantially the same direction. In other words, the lines of the liquid crystal directors are parallel.

[0040] The terms "homeotropic structure" or "homeotropic orientation" refer to a film in which the optic axis is substantially perpendicular to the film plane.

[0041] The terms "planar structure" or "planar orientation" refer to a film in which the optical axis is substantially parallel to the film plane.

[0042] The term "negative (optical) dispersion" refers to a birefringent or liquid crystalline material or layer that exhibits inverse birefringence dispersion, where the magnitude of birefringence (Δn) increases with increasing wavelength (λ), i.e., |Δn(450)|<|Δn(550)|, or Δn(450) / Δn(550)<1, where Δn(450) and Δn(550) are the birefringence of the material measured at wavelengths of 450 nm and 550 nm, respectively. In contrast, "positive (optical) dispersion" refers to a material or layer where |Δn(450)|>|Δn(550)|, or Δn(450) / Δn(550)>1. See, for example, A. Uchiyama and T. Yatabe, "Control of Wavelength Dispersion of Birefringence for Oriented Copolycarbonate Films Containing Positive and Negative Birefringent Units," J. Appl. Phys., Vol. 42, pp. 6941-6945 (2003).

[0043] Since the optical retardation at a given wavelength is defined above as the product of birefringence and layer thickness [R(λ)=Δn(λ)·d], the optical dispersion can be expressed as the "birefringence dispersion" in the ratio Δn(450) / Δn(550), or as the "retardation dispersion" in the ratio R(450) / R(550), where R(450) and R(550) are the retardations of the material measured at wavelengths of 450 nm and 550 nm, respectively. Since the layer thickness d does not change with wavelength, R(450) / R(550) is equal to Δn(450) / Δn(550). Thus, a negative or reverse dispersion material or layer has R(450) / R(550)<1 or |R(450)|<|R(550)|, and a positive or normal dispersion material or layer has R(450) / R(550)>1 or |R(450)|>|R(550)|.

[0044] In the present invention, unless otherwise specified, "optical dispersion" refers to the retardation dispersion, i.e., the ratio R(450) / R(550) or R for short. 450 / 550 means.

[0045] The term "high variance" means that the absolute value of the variance deviates significantly from 1, whereas the term "low variance" means that the absolute value of the variance deviates slightly from 1. Thus, "high negative variance" means that the variance value is significantly less than 1, and "low negative variance" means that the variance value is slightly less than 1.

[0046] The retardation (R(λ)) of a material can be measured using a spectroscopic ellipsometer, for example the M2000 spectroscopic ellipsometer manufactured by JA Woollam. This instrument can measure the optical retardation in nanometers of a birefringent sample, for example the optical retardation over a wavelength range of typically 370 nm to 2000 nm for quartz. From this data it is possible to calculate the dispersion of the material (R(450) / R(550) or Δn(450) / Δn(550)).

[0047] The method for performing these measurements was published by N. Singh at the National Physics Laboratory (London, UK) in October 2006, entitled "Spectroscopic Ellipsometry, Part 1-Theory and Fundamentals, Part 2-Practical Examples and Part 3-measurements". The procedure according to this measurement is described in the Retardation Measurement (RetMeas) Manual (2002) and the Guide to WVASE (2002) (Woollam Variable Angle Spectroscopic Ellipsometer) published by JA Woollam Inc. (Lincoln, Nebraska, USA). Unless otherwise stated, this method is used to determine the retardation of the materials, films and devices described in this invention.

[0048] The term "A-plate" refers to an optical retarder that utilizes a layer of uniaxially birefringent material with its extraordinary axis oriented parallel to the plane of the layer.

[0049] The term "C-plate" refers to an optical retarder that utilizes a layer of uniaxially birefringent material with its extraordinary axis oriented perpendicular to the plane of the layer.

[0050] In an A / C plate containing optically uniaxially birefringent liquid crystal material with uniform orientation, the optic axis of the film is given by the direction of the extraordinary axis. An A (or C) plate containing positively birefringent optically uniaxially birefringent material is also called a "positive A (or C) plate" or "+A (or +C) plate".

[0051] A (or C) plates comprising films of optically uniaxially birefringent materials with negative birefringence, such as discotic anisotropic materials, are also called "negative A (or C) plates" or "-A (or C) plates", depending on the orientation of the discotic material. Films made of cholesteric calamitic materials with reflection bands in the UV part of the spectrum also have the optics of a negative C plate.

[0052] The birefringence Δn is defined as: Δn=n e -n o .

[0053] In the formula, n e is the extraordinary refractive index, and n o is the ordinary refractive index, and the average effective refractive index n av. is expressed as follows: n av. =((2n o 2 +n e 2 ) / 3) 1 / 2 .

[0054] Mean effective refractive index n av. and the ordinary refractive index n o can be measured using an Abbe refractometer. Δn can be calculated from the above formula.

[0055] Unless the context clearly indicates otherwise, plural forms of the terms used herein are to be construed as including the singular and vice versa.

[0056] All physical properties were or will be determined according to "Merck Liquid Crystals, Physical Properties of Liquid Crystals", November 1997, Merck, Germany, and are given at a temperature of 20° C. unless otherwise stated. The optical anisotropy (n) is determined at a wavelength of 589.3 nm.

[0057] In case of doubt, the definitions as given in C. Tschierske, G. Pelzl and S. Diele, Angew. Chem. 2004, Vol. 116, pp. 6340-6368 shall apply.

[0058] In a given general formula, unless otherwise stated, the following terms have the following meanings:

[0059] "Carbyl group" refers to a monovalent or polyvalent organic group having one or more C atoms, which group does not contain any further atoms (e.g. -C≡C-) or optionally contains one or more further atoms such as N, O, S, P, Si, Se, As, Te or Ge (e.g. carbonyl, etc.). "Hydrocarbyl group" refers to a carbyl group which further contains one or more H atoms and optionally one or more heteroatoms such as N, O, S, P, Si, Se, As, Te or Ge.

[0060] The carbyl or hydrocarbyl group may be saturated or unsaturated. Unsaturated groups are, for example, aryl, alkenyl or alkynyl groups. Carbyl or hydrocarbyl groups with more than 3 C atoms may be linear, branched and / or cyclic and may contain spiro-linked or fused rings.

[0061] Preferred carbyl and hydrocarbyl groups are optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy and alkoxycarbonyloxy having 1 to 40, preferably 1 to 25, particularly preferably 1 to 18, C atoms, or optionally substituted aryl or aryloxy having 6 to 40, preferably 6 to 25, C atoms, or optionally substituted alkylaryl, arylalkyl, alkylaryloxy, arylalkyloxy, arylcarbonyl, aryloxycarbonyl, arylcarbonyloxy and aryloxycarbonyloxy having 6 to 40, preferably 6 to 25, C atoms. Further preferred carbyl and hydrocarbyl groups are C1 to C 40 Alkyl, C2-C 40 Alkenyl, C2-C 40 Alkynyl, C3-C 40 Allyl, C4~C 40 Alkyldienyl, C4-C 40 Polyenyl, C6-C 40 Aryl, C6-C 40 Alkylaryl, C6-C 40 Aryl alkyl, C6-C 40 Alkylaryloxy, C6-C 40 Arylalkyloxy, C2-C 40 Heteroaryl, C4-C 40 Cycloalkyl, C4-C 40 Cycloalkenyl, etc. In particular, C1-C 22 Alkyl, C2-C 22 Alkenyl, C2-C 22 Alkynyl, C3-C 22 Allyl, C4~C 22 Alkyldienyl, C6-C 12 Aryl, C6-C 20 Aryl alkyl, and C2-C 20 Heteroaryl is preferred.

[0062] Further preferred carbyl and hydrocarbyl groups are linear, branched or cyclic alkyl groups having 1 to 40, preferably 1 to 25, C atoms, more preferably 1 to 12 C atoms, which are unsubstituted or mono- or polysubstituted by F, Cl, Br, I or CN, and one or more non-adjacent CH groups are each, independently of one another, terminated with -C(R x )=C(R x )-, -C≡C-, -N(R x ) -, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-.

[0063] Above R x preferably represents H, a halogen, a linear, branched or cyclic alkyl chain having 1 to 25 C atoms, in which further one or more non-adjacent C atoms may be replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, and one or more H atoms may be replaced by fluorine, an optionally substituted aryl group or aryloxy group having 6 to 40 C atoms, or an optionally substituted heteroaryl group or heteroaryloxy group having 2 to 40 C atoms.

[0064] Preferred alkyl groups are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, dodecanyl, trifluoromethyl, perfluoro-n-butyl, 2,2,2-trifluoroethyl, perfluorooctyl, perfluorohexyl, and the like.

[0065] Preferred alkenyl groups are, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, and the like.

[0066] Preferred alkynyl groups are, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, octynyl and the like.

[0067] Preferred alkoxy groups are, for example, methoxy, ethoxy, 2-methoxyethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, 2-methylbutoxy, n-pentoxy, n-hexoxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy, and the like.

[0068] Preferred amino groups are, for example, dimethylamino, methylamino, methylphenylamino, phenylamino, and the like.

[0069] Aryl and heteroaryl groups may be monocyclic or polycyclic, i.e., they may have one ring (such as, for example, phenyl) or two or more rings, which may be fused (such as, for example, naphthyl) or covalently linked (such as, for example, biphenyl), or may contain a combination of fused and linked rings. Heteroaryl groups contain one or more heteroatoms, preferably selected from O, N, S, and Se.

[0070] Preferred are monocyclic, bicyclic or tricyclic aryl groups having 6 to 25 C atoms and monocyclic, bicyclic or tricyclic heteroaryl groups having 2 to 25 C atoms, which optionally contain fused rings and are optionally substituted.Furthermore, preferred are 5-, 6- or 7-membered aryl and heteroaryl groups, where furthermore, one or more CH groups may be replaced by N, S or O, such that the O and / or S atoms are not directly bonded to each other.

[0071] Preferred aryl groups are, for example, phenyl, biphenyl, terphenyl, [1,1':3',1'']terphenyl-2'-yl, naphthyl, anthracene, binaphthyl, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, tetracene, pentacene, benzopyrene, fluorene, indene, indenofluorene, spirobifluorene, and the like.

[0072] 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, isoindole, indolizine, indazole, benzimidazole, benzotriazole, purine, naphthomidazole, phenanthrimidazole, pyridoimidazole, pyrazineimidazole, quinoxalineimidazole, benzoxazole, naphthomidazole, oxazole, anthroxazole, phenanthroxazole, isoxazole, benzothiazole, benzofuran, isobenzofuran, dibenzofuran, quinoline, isoquinoline, pteridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, benzisoquinoline, acridine, phenothiazine, phenoxazine, benzopyridazine, benzopyrimidine, quinoxaline, phenazine, naphthyridine, azacarbazole, benzocarboline, phenanthridine, phenanthroline, thieno[2,3b]thiophene, thieno[3,2b]thiophene, dithienothiophene, isobenzothiophene, dibenzothiophene, benzothiadiazothiophene, or combinations of these groups. The heteroaryl group may be substituted with alkyl, alkoxy, thioalkyl, fluorine, fluoroalkyl, or further aryl or heteroaryl groups.

[0073] (Non-aromatic) alicyclic and heterocyclic groups include both saturated rings, i.e., those containing only single bonds, and partially unsaturated rings, i.e., those which may contain multiple bonds. Heterocyclic rings preferably contain one or more heteroatoms selected from Si, O, N, S and Se.

[0074] (Non-aromatic) alicyclic and heterocyclic groups may be monocyclic, i.e. containing only one ring (e.g. cyclohexane) or polycyclic, i.e. containing several rings (e.g. decahydronaphthalene or bicyclooctane). In particular, saturated groups are preferred. Furthermore, monocyclic, bicyclic or tricyclic groups having 3 to 25 C atoms are preferred, which groups optionally contain fused rings and are optionally substituted. Furthermore, 5-, 6-, 7- or 8-membered carbocyclic groups are preferred, in which further, one or more C atoms may be replaced by Si and / or one or more CH groups may be replaced by N and / or one or more non-adjacent CH2 groups may be replaced by -O- and / or -S-.

[0075] Preferred alicyclic and heterocyclic groups are, for example, 5-membered ring groups such as cyclopentane, tetrahydrofuran, tetrahydrothiofuran, pyrrolidine, 6-membered ring groups such as cyclohexane, silinane, cyclohexene, tetrahydropyran, tetrahydrothiopyran, 1,3-dioxane, 1,3-dithiane, piperidine, 7-membered ring groups such as cycloheptane, and fused groups such as tetrahydronaphthalene, decahydronaphthalene, indane, bicyclo[1.1.1]-pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl, spiro[3.3]heptane-2,6-diyl, octahydro-4,7-methanoindan-2,5-diyl.

[0076] The aryl, heteroaryl, (non-aromatic) alicyclic and heterocyclic groups may optionally carry one or more substituents, which are preferably silyl, sulfo, sulfonyl, formyl, amine, imine, nitrile, mercapto, nitro, halogen, C 1~12 Alkyl, C 6~12 Aryl, C 1~12 It is selected from the group comprising alkoxy, hydroxyl, or a combination of these groups.

[0077] Preferred substituents are, for example, solubility-promoting groups such as alkyl or alkoxy, electron-withdrawing groups such as fluorine, nitro or nitrile, or substituents for increasing the glass transition temperature (Tg) of the polymer, especially bulky groups such as t-butyl or optionally substituted aryl groups.

[0078] Preferred substituents, also referred to below as "L", are, for example, F, Cl, Br, I, -OH, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)N(R x )2, -C(=O)Y x , -C(=O)R x , -C(=O)OR x , -N(R x )2, where R x has the above meaning, and Y x denotes halogen, optionally substituted silyl, optionally substituted aryl or heteroaryl having 4 to 40, preferably 4 to 20, ring atoms, and linear or branched alkyl, alkenyl, alkynyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 25 C atoms, in which one or more H atoms may optionally be replaced by F or Cl.

[0079] The "substituted silyl or aryl" is preferably a halogen, -CN, R y , -OR y , -CO-R y , -CO-OR y , -O-CO-R y OR-O-CO-OR y (In the formula, R y means substituted by H, a linear, branched or cyclic alkyl chain having 1 to 12 C atoms.

[0080] In the formulae shown above and below, the substituted phenylene ring [ka] It is.

[0081] In the formula, L is each identical or different and has one of the meanings given above and below, preferably F, Cl, CN, NO2, CH3, C2H5, C(CH3)3, CH(CH3)2, CH2CH(CH3)C2H5, OCH3, OC2H5, COCH3, COC2H5, COOCH3, COOC2H5, CF3, OCF3, OCHF2, OC2F5 or P-Sp-, very preferably F, Cl, CN, CH3, C2H5, OCH3, COCH3, OCF3 or P-Sp-, most preferably F, Cl, CH3, OCH3, COCH3 or OCF3.

[0082] "Halogen" represents F, Cl, Br or I, preferably F or Cl, more preferably F.

[0083] The "polymerizable group" (P) is preferably selected from groups containing a C=C double bond or a C≡C triple bond and groups suitable for polymerization involving ring opening, such as oxetane or epoxide groups.

[0084] Preferably, the polymerizable group (P) is CH2=CW 1 -COO-, CH2=CW 1 -CO-, [ka] CH2=CW 2 -(O) k3 -, C.W. 1 =CH-CO-(O) k3 -, C.W. 1 =CH-CO-NH-, CH2=CW 1 -CO-NH-, CH3-CH=CH-O-, (CH2=CH)2CH-OCO-, (CH2=CH-CH2)2CH-OCO-, (CH2=CH)2CH-O-, (CH2=CH-CH2)2N-, (CH2=CH-CH2)2N-CO-, CH2=CW 1 -CO-NH-, CH2=CH-(COO) k1 -Phe-(O) k2 -, CH2=CH-(CO)k1 -Phe-(O) k2 -, Phe-CH=CH-, During the ceremony, W 1 stands for H, F, Cl, CN, CF3, phenyl or alkyl having 1 to 5 C atoms, in particular H, F, Cl or CH3, W 2 represents H or alkyl having 1 to 5 C atoms, in particular H, methyl, ethyl or n-propyl, W 3 and W 4 each independently of one another denotes H, Cl or alkyl having 1 to 5 C atoms, Phe denotes 1,4-phenylene, which is optionally substituted by one or more groups L as defined above, but which are different from P-Sp, preferably preferred substituents L are F, Cl, CN, NO2, CH3, C2H5, OCH3, OC2H5, COCH3, COC2H5, COOCH3, COOC2H5, CF3, OCF3, OCHF2, OC2F5, also phenyl, k1, k2 and k3 each independently represent 0 or 1, k3 preferably represents 1, and k4 represents an integer of 1-10.

[0085] Particularly preferred polymerizable groups P are CH2=CH-COO-, CH2=C(CH3)-COO-, CH2=CF-COO-, CH2=CH-, CH2=CH-O-, (CH2=CH)2CH-OCO-, (CH2=CH)2CH-O-, [ka] and In the formula, W 2 stands for H or alkyl having 1 to 5 C atoms, in particular H, methyl, ethyl or n-propyl.

[0086] More preferred polymerizable groups (P) are vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane and epoxide, most preferably acrylate or methacrylate, especially acrylate.

[0087] Preferably, all multireactive polymerizable compounds and subformulas thereof contain, instead of one or more groups P-Sp-, one or more branched groups containing two or more polymerizable groups P (multireactive polymerizable groups).

[0088] Suitable groups of this type, and polymerizable compounds containing them, are described, for example, in US Pat. No. 7,060,200 or US Patent Application Publication No. 2006 / 0172090.

[0089] In particular, the following formula: [ka] Preferred are multireactive polymerizable groups selected from:

[0090] During the ceremony, alkyl represents a single bond or a linear or branched alkylene having 1 to 12 C atoms, provided that one or more non-adjacent CH groups are each independently -C(R x )=C(R x )-, -C≡C-, -N(R x )-, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, provided that one or more H atoms may be replaced by F, Cl or CN, provided that R x has one of the above meanings, aa and bb each independently represent 0, 1, 2, 3, 4, 5, or 6; X has one of the meanings given under X', and P v ~P z each independently of one another has one of the meanings given above for P.

[0091] Preferred spacer groups Sp are selected from the formula Sp'-X', such that the group "P-Sp-" corresponds to the formula "P-Sp'-X'-", During the ceremony, Sp' represents an alkylene having 1 to 20, preferably 1 to 12, C atoms, which is optionally mono- or polysubstituted by F, Cl, Br, I or CN, with the proviso that in addition, one or more non-adjacent CH groups are each independently -O-, -S-, -NH-, -NR xx -, -SiR xx R yy -, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO-, -CO-S-, -NR xx -CO-O-, -O-CO-NR 0xx -, -NR xx -CO-NR yy may be replaced by -, -CH=CH- or -C≡C-, X' is -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR xx -, -NR xx -CO-, -NR xx -CO-NR yy -, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CF2CH2-, -CH2CF2-, -CF2CF2-, -CH=N-, -N=CH-, -N=N-, -CH=CR xx -, -CY xx =CY xx represents -, -C≡C-, -CH=CH-COO-, -OCO-CH=CH- or a single bond; R xx and R yy each independently represent H or alkyl having 1 to 12 C atoms, and Y xx and Y yy each independently represents H, F, Cl or CN.

[0092] X' is preferably -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR xx -, -NR xx -CO-, -NR xx -CO-NRyy - or a single bond.

[0093] A typical spacer group Sp' is, for example, -(CH2) p1 -, -(CH2CH2O) q1 -CH2CH2-, -CH2CH2-S-CH2CH2-, -CH2CH2-NH-CH2CH2- or -(SiR xx R yy -O) p1 In the formula, p1 is an integer from 1 to 12, q1 is an integer from 1 to 3, and R xx and R yy has the above meaning.

[0094] Particularly preferred groups -X'-Sp'- are -(CH2) p1 -, -O-(CH2) p1 -, -OCO-(CH2) p1 -,-OCOO-(CH2) p1 In the formula, p1 is an integer from 1 to 12.

[0095] Particularly preferred radicals Sp' are, for example, linear ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylenethioethylene, ethylene-N-methyliminoethylene, 1-methylalkylene, ethenylene, propenylene and butenylene, respectively.

[0096] In the present invention, [ka] represents trans-1,4-cyclohexylene, and [ka] represents 1,4-phenylene.

[0097] In the present invention, the group -COO- or -CO2- is [ka] represents an ester group of the formula: The groups -OCO-, -OC- or -OOC- are [ka] represents an ester group.

[0098] A "polymer network" is a network in which all polymer chains are interconnected to form a single macroscopic entity through multiple cross-links.

[0099] The polymer networks can occur in the following types: · Graft polymer molecules are branched polymer molecules in which one or more side chains are structurally or compositionally different from the main chain. A star polymer molecule is a branched polymer molecule in which a single branch point gives rise to multiple linear chains or arms. If the arms are identical, the star polymer molecule is said to be regular. If adjacent arms are composed of different repeating subunits, the star polymer molecule is said to be irregular. Comb polymer molecules consist of a main chain with two or more triangular branch points and linear side chains. If the arms are identical, the comb polymer molecule is said to be regular. Brush polymer molecules consist of a linear backbone with unbranched side chains, and one or more branch points with tetragonality or higher.

[0100] Throughout the present specification and claims, the words "comprise" and "contain" and variations thereof, such as "comprising" and "comprises", mean "including but not limited to" and are not intended to exclude (do not exclude) other components. On the other hand, the word "comprise" also encompasses, but is not limited to, the term "consisting of."

[0101] Throughout the present description and claims, the words "obtainable" and "obtained" and variations thereof have the meaning "including but not limited to" and are not intended to (and do not) exclude other ingredients. Meanwhile, the word "obtainable" also encompasses, but is not limited to, the term "obtained."

[0102] All concentrations are stated as weight percent and relate to the respective mixture as a whole, all temperatures are stated in degrees Celsius, and all temperature differences are stated in degrees delta.

[0103] <Detailed Description> Preferred compounds of formula S0 are selected from the following sub-formulae:

[0104] [ka]

[0105] In the formula, P a is a polymerizable group.

[0106] Highly preferred compounds of formula S0 are selected from the following sub-formulae:

[0107] [ka]

[0108] Preferred compounds of formula S1 are selected from the following subformulae:

[0109] [ka]

[0110] In the formula, n1 is an integer from 2 to 12, provided that the group (CH2) n1 One or more H atoms in R may be replaced by a methyl, ethyl, propyl, butyl, pentyl or hexyl group; 11 and R 12 each independently represents a linear or branched alkyl group having 1 to 20 C atoms.

[0111] Highly preferred compounds of formula S1 are selected from the following sub-formulae:

[0112] [ka]

[0113] [ka]

[0114] [ka]

[0115] In a first preferred embodiment of the present invention, the compound of formula S1 is 1 and / or R 2 is selected from those in which H or CH3, preferably H. Preferred compounds of this first preferred embodiment are those of the above formulae S1-1 and S1-4, and sub-formulae S1-1a, S1-1b and S1-4a.

[0116] In a second preferred embodiment of the present invention, the compound of formula S is 1 and / or R 2 O ● or OH, preferably O ● Preferred compounds of this second preferred embodiment are those of the above formulae S1-2 and S1-3, preferably S1-2, and sub-formulae S1-2a, S1-2b, S1-2c and S1-3a. Compounds of formulae S1-2a, S1-2b, S1-2c are particularly preferred, and those of formula S1-2a are most preferred.

[0117] In a third preferred embodiment of the invention, the compounds of formula S1 are selected from those in which Sp is a branched alkylene having 2 to 20 C atoms, which group is further ... A However, these substituents L A is selected from F and linear or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonyloxy and alkoxycarbonyloxy, each having 1 to 12 C atoms, with the proviso that one or more H atoms may be replaced by F or Cl.

[0118] Preferred compounds of this third preferred embodiment are of formula S1-6 below and of subformulas S1-1b and S1-2c above. [ka]

[0119] During the ceremony, R 1 and R 2 is H, CH3, OH or O ● , preferably H or O ● and R A is methyl, ethyl, propyl, butyl, pentyl or hexyl n2 is 0 or an integer of 1 to 12, and is preferably 0. n3 is 0 or an integer from 1 to 12.

[0120] Preferred compounds of formula S1-6 are those of the above sub-formulae S1-1b and S1-2c.

[0121] Preferred compounds of formula S2 are selected from the following subformulae: [ka]

[0122] Compounds of formula S2-1 are highly preferred.

[0123] Highly preferred compounds of formula S2 are selected from the following sub-formulae: [ka]

[0124] Compounds of formula S2-1a are highly preferred.

[0125] The proportion of compounds of formulae S0 to S2 or sub-formulae thereof in the polymerizable LC material is preferably 0.01 to 1%, very preferably 0.05 to 0.5%, in particular 0.07 to 0.1%.

[0126] The proportion of compounds of formulae S0 to S2 or sub-formulae thereof in the polymerizable LC material is preferably 10 to 2000 ppm, very preferably 50 to 1500 ppm, in particular 100 to 1000 ppm.

[0127] The polymerisable LC material preferably comprises 1 to 5, very preferably 1, 2 or 3, most preferably 1 or 2 compounds selected from formulae S0 to S2 or sub-formulae thereof.

[0128] In a preferred embodiment of the invention the polymerisable LC material comprises one or more compounds of formula S1 and / or one or more compounds of formula S2.

[0129] The compound of formula S1 is particularly suitable as a light stabilizer to protect the polymerizable LC material in the display from UV stress. The compound of formula S2 is particularly suitable as a heat stabilizer to protect the polymerizable LC material in the display cell from high temperature stress. The polymerizable LC material according to this preferred embodiment combines both stabilizers, which results in a higher reliability compared to a polymerizable LC material containing only one type of stabilizer. Very preferably, the polymerizable LC material according to this preferred embodiment comprises a compound of formula S1-1 or S1-2 and a compound of formula S2-1, most preferably a compound of formula S1-1a or S1-2a and a compound of formula S2-1a.

[0130] In another preferred embodiment of the present invention the polymerizable LC material comprises two or more compounds of formula S1. Very preferably, the polymerizable LC material according to this preferred embodiment comprises a compound of formula S1-1 and a compound of formula S1-2, most preferably a compound of formula S1-1a and a compound of formula S1-2a.

[0131] In another preferred embodiment of the present invention the polymerizable LC material comprises one or more compounds of formula S1 and one or more triazine type UV absorbers known to those skilled in the art. Preferred triazine UV absorber compounds are for example: [ka]

[0132] The proportion of triazine UV absorber compounds in the polymerizable LC material is preferably 0.01-1%, very preferably 0.05-0.5%, in particular 0.07-0.1%.

[0133] The proportion of triazine UV absorber compounds in the polymerizable LC material is preferably between 10 and 2000 ppm, very preferably between 50 and 1500 ppm, in particular between 100 and 1000 ppm.

[0134] Preferably the one or more di- or multireactive mesogenic compounds are selected from the formula DRM: [ka]

[0135] During the ceremony, P 1 and P 2 each independently represents a polymerizable group, Sp 1 and Sp 2 are each independently a spacer group or a single bond, MG is a rod-shaped mesogenic group, which is preferably selected from the formula MG, [ka] During the ceremony, A 1 and A 2 represent, independently of each other, an aromatic or alicyclic group, which may contain one or more heteroatoms selected from N, O and S; L 1 may be mono- or polysubstituted with, L 1 are P-Sp-, F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)NR 00 R 000 , -C(=O)OR 00 , -C(=O)R 00 , -NR 00 R 000 , -OH, -SF5, optionally substituted silyl, aryl or heteroaryl having 1 to 12, preferably 1 to 6, C atoms, and linear or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12, preferably 1 to 6, C atoms, with the proviso that one or more H atoms may be replaced by F or Cl, R 00 and R 000 each independently represent H or alkyl having 1 to 12 C atoms, Z 1When occurring multiple times, they are each independently -O-, -S-, -CO-, -COO-, -OCO-, -S-CO-, -CO-S-, -O-COO-, -CO-NR 00 -, -NR 00 -CO-, -NR 00 -CO-NR 000 , -NR 00 -CO-O-, -O-CO-NR 00 -, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH2CH2-, -(CH2) n1 , -CF2CH2-, -CH2CF2-, -CF2CF2-, -CH=N-, -N=CH-, -N=N-, -CH=CR 00 -, -CY 1 =CY 2 represents -, -C≡C-, -CH=CH-COO-, -OCO-CH=CH- or a single bond; Y 1 and Y 2 represent, independently of one another, H, F, Cl or CN, n is 1, 2, 3 or 4, preferably 1 or 2, most preferably 2; n1 is an integer of 1 to 10, and is preferably 1, 2, 3 or 4.

[0136] Preferred group A 1 and A 2 include, without limitation, furan, pyrrole, thiophene, oxazole, thiazole, thiadiazole, imidazole, phenylene, cyclohexylene, bicyclooctylene, cyclohexenylene, pyridine, pyrimidine, pyrazine, azulene, indane, fluorene, naphthalene, tetrahydronaphthalene, anthracene, phenanthrene, and dithienothiophene, all of which are unsubstituted or substituted with 1, 2, 3 or 4 groups L as defined above.

[0137] Particularly preferred groups A 1 and A 2is selected from 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, thiophene-2,5-diyl, naphthalene-2,6-diyl, 1,2,3,4-tetrahydro-naphthalene-2,6-diyl, indan-2,5-diyl, bicyclooctylene or 1,4-cyclohexylene, with the proviso that one or two non-adjacent CH groups may be replaced by O and / or S, with the proviso that these groups are unsubstituted or substituted by one, two, three or four groups L as defined above.

[0138] Particularly preferred groups Z 1 are each occurrence independently preferably selected from -COO-, -OCO-, -CH2CH2-, -CF2O-, -OCF2-, -C≡C-, -CH=CH-, -OCO-CH=CH-, -CH=CH-COO- or a single bond.

[0139] Highly preferred one or more direactive mesogenic compounds of formula DRM are selected from the following formulae:

[0140] [ka]

[0141] [ka]

[0142] During the ceremony, P 0 are, independently of one another when they occur in succession, a polymerizable group, preferably an acrylic, methacrylic, oxetane, epoxy, vinyl, heptadiene, vinyloxy, propenyl ether or styrene group, L may be the same or different in each occurrence of the formula DRM 1and preferably in the case of several occurrences are independently selected from F, Cl, CN or optionally halogenated alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 5 C atoms, r is 0, 1, 2, 3 or 4; x and y are each independently 0 or an integer from 1 to 12, which may be the same or different; Each z is independently 0 or 1, provided that when the adjacent x or y is 0, then z is 0.

[0143] Particularly preferred are compounds of formula DRMa1, DRMa2 and DRMa3, especially those of formula DRMa1.

[0144] Preferably the polymerisable LC material additionally comprises one or more monoreactive mesogenic compounds, preferably selected of formula MRM. [ka]

[0145] In the formula, P 1 , Sp 1 and MG has the meaning given in formula DRM, R is F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)NR x R y , -C(=O)X, -C(=O)OR x , -C(=O)R y , -NR x R y , -OH, -SF5, optionally substituted silyl, linear or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonyloxy or alkoxycarbonyloxy having 1 to 12, preferably 1 to 6, C atoms, with the proviso that one or more H atoms may be replaced by F or Cl, X is a halogen, preferably F or Cl, and R xand R y are each independently H or alkyl having 1 to 12 C atoms.

[0146] Preferably the one or more monoreactive mesogenic compounds of formula MRM are selected from the following formulae:

[0147] [ka]

[0148] [ka]

[0149] [ka]

[0150] [ka]

[0151] In the formula, P 0 , L, r, x, y and z are as defined in Formula DRMa-1 to Formula DRMe; R 0 is an alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having one or more, preferably 1 to 15, C atoms, or Y 0 represents Y 0 is F, Cl, CN, NO2, OCH3, OCN, SCN, SF5 or a mono-, oligo- or polyfluorinated alkyl or alkoxy having 1 to 4 C atoms, Z 0 is -COO-, -OCO-, -CH2CH2-, -CF2O-, -OCF2-, -CH=CH-, -OCO-CH=CH-, -CH=CH-COO-, or a single bond, A 0are, independently of one another, 1,4-phenylene which is unsubstituted or substituted by 1, 2, 3 or 4 radicals L, or trans-1,4-cyclohexylene, u and v are each independently 0, 1 or 2; w is 0 or 1; However, the benzene and naphthalene rings may additionally be substituted with one or more groups L which may be the same or different.

[0152] Further preferred are compounds of formula MRM1, MRM2, MRM3, MRM4, MRM5, MRM6, MRM7, MRM9 and MRM10, in particular those of formula MRM1, MRM4, MRM6 and MRM7, especially those of formula MRM1 and MRM7.

[0153] Compounds of formula DRM, MRM and their subformulae can be prepared analogously to methods known to those skilled in the art and described, for example, in standard works of organic chemistry such as Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Thieme-Verlag, Stuttgart.

[0154] The total proportion of the monoreactive, direactive or polyreactive liquid crystal compounds in the polymerizable liquid crystal material according to the present invention is preferably within a range of 30 to 99.9% by weight, more preferably within a range of 40 to 99.9% by weight, and even more preferably within a range of 50 to 99.9% by weight.

[0155] In a preferred embodiment, the total proportion of direactive or multireactive polymerizable mesogenic compounds in the polymerizable liquid crystal material according to the present invention is preferably in the range of 5 to 99% by weight, more preferably in the range of 10 to 97% by weight, and even more preferably in the range of 15 to 95% by weight.

[0156] In another preferred embodiment, the proportion of monoreactive polymerizable mesogenic compounds in the polymerizable liquid crystal material according to the present invention, if present, is preferably in the range of 5 to 80% by weight, more preferably in the range of 10 to 75% by weight, even more preferably in the range of 15 to 70% by weight in total.

[0157] In another preferred embodiment, the proportion of multireactive polymerizable mesogenic compounds in the polymerizable liquid crystal material according to the present invention, if present, is preferably in the range of 1 to 30 wt %, more preferably in the range of 2 to 20 wt %, even more preferably in the range of 3 to 10 wt %, in total.

[0158] In another preferred embodiment the polymerisable LC material does not comprise any polymerisable mesogenic compounds with more than two polymerisable groups.

[0159] In another preferred embodiment the polymerisable LC material does not comprise any polymerisable mesogenic compounds with less than two polymerisable groups.

[0160] In another preferred embodiment the polymerisable LC material is an achiral material, ie it does not contain chiral polymerisable mesogenic compounds or other chiral compounds.

[0161] In a further preferred embodiment the polymerisable LC material comprises one or more monoreactive mesogenic compounds preferably selected of formula MRM-1, one or more direactive mesogenic compounds preferably selected of formula DRMa-1 and one or more compounds of formulae S0 to S2.

[0162] In a further preferred embodiment the polymerisable LC material comprises one or more monoreactive mesogenic compounds preferably selected from formula MRM-7, one or more direactive mesogenic compounds preferably selected from formula DRMa-1 and one or more compounds of formulae S0 to S2.

[0163] In a further preferred embodiment the polymerisable LC material comprises at least two monoreactive mesogenic compounds, preferably selected from compounds of formula MRM-1 and / or MRM-7, one or more direactive mesogenic compounds, preferably selected from formula DRMa-1, and one or more compounds of formulae S0-S2.

[0164] In a further preferred embodiment the polymerisable LC material comprises at least two monoreactive mesogenic compounds, preferably selected from compounds of formula MRM-1 and / or MRM-7, at least two bireactive mesogenic compounds, preferably selected from compounds of formula DRMa-1, and one or more compounds of formulae S0-S2.

[0165] In a further preferred embodiment the polymerisable LC material comprises at least two direactive mesogenic compounds, preferably selected from compounds of formula DRMa-1, and one or more compounds of formulae S0-S2.

[0166] In a further preferred embodiment, especially for negative optical dispersion applications, the polymerizable LC material as described above additionally comprises one or more compounds of formula ND. [ka]

[0167] During the ceremony, U 1,2 are each independently selected from the following, including their mirror images: [ka] In the formula, ring U 1 and U 2 are connected to the group -(B) via an axial bond, q -, one or two non-adjacent CH2 groups in these rings may be replaced by O and / or S, and the ring U 1 and U 2 is optionally substituted by one or more groups L; Q 1,2are each independently CH or SiH, Q 3 is C or Si, B is independently -C≡C-, -CY 1 =CY 2 - or an optionally substituted aromatic or heteroaromatic group, Y 1,2 are each independently H, F, Cl, CN or R 0 and q is an integer from 1 to 10, preferably 1, 2, 3, 4, 5, 6 or 7; A 1~4 are each independently selected from non-aromatic, aromatic or heteroaromatic carbocyclic or heterocyclic groups, which are joined by one or more groups R 5 may be substituted with -(A 1 -Z 1 ) m -U 1 -(Z 2 -A 2 ) n -and-(A 3 -Z 3 ) o -U 2 -(Z 4 -A 4 ) p - each does not contain more aromatic than non-aromatic groups, preferably does not contain more than one aromatic group; Z 1~4 are each independently -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR 0 -, -NR 0 -CO-, -NR 0 -CO-NR 00 -, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH2CH2-, -(CH2)3-, -(CH2)4-, -CF2CH2-, -CH2CF2-, -CF2CF2-, -CH=CH-, -CY 1 =CY 2 -, -CH=N-, -N=CH-, -N=N-, -CH=CR 0-, -C≡C-, -CH=CH-COO-, -OCO-CH=CH-, CR 0 R 00 or a single bond, R 0 and R 00 are each independently H or alkyl having 1 to 12 C atoms, m and n are each independently 0, 1, 2, 3 or 4; o and p are each independently 0, 1, 2, 3 or 4; R 1~5 are each independently H, halogen, -CN, -NC, -NCO, -NCS, -OCN, -SCN, -C(=O)NR 0 R 00 , -C(=O)X 0 , -C(=O)R 0 , -NH2, -NR 0 R 00 , -SH, -SR 0 , -SO3H, -SO2R 0 , -OH, -NO2, -CF3, -SF5, P-Sp-, optionally substituted silyl, or carbyl or hydrocarbyl having 1 to 40 C atoms and optionally containing one or more heteroatoms, or represent P or P-Sp- or are substituted by P or P-Sp-, with the proviso that the compound contains one or more groups R which represent or are substituted by P or P-Sp-. 1~5 Including, P is a polymerizable group, Sp is a spacer group or a single bond.

[0168] The subgroups forming the bridging group B in formula ND are preferably chosen from groups having a bond angle in the range of more than 120°, preferably 180°. Divalent aromatic groups linked in the para position to the -C≡C- group or to their adjacent groups, such as 1,4-phenylene, naphthalene-2,6-diyl, indan-2,6-diyl or thieno[3,2-b]thiophene-2,5-diyl, are highly preferred.

[0169] Further possible subgroups are -CH=CH-, -CY 1 =CY 2 -, -CH=N-, -N=CH-, -N=N- and -CH=CR 0 -, where Y 1 , Y 2 , R 0 has the meaning given above.

[0170] Preferably the bridging group in the formula ND or -(B) q - includes one or more groups selected from the group consisting of -C≡C-, optionally substituted 1,4-phenylene and optionally substituted 9H-fluorene-2,7-diyl. The subgroup or B in formula ND is preferably selected from the group consisting of -C≡C-, optionally substituted 1,4-phenylene and optionally substituted 9H-fluorene-2,7-diyl, provided that in the fluorene group the H atom in the 9 position may be replaced by a carbyl or hydrocarbyl group.

[0171] Very preferably the bridging group in the formula ND or -(B) q - is -C≡C-, -C≡CC≡C-, -C≡CC≡CC≡C-, -C≡CC≡CC≡CC≡C-, [ka] where r is 0, 1, 2, 3 or 4, and L has the meanings as described below.

[0172] Preferably, U in the formula ND 1 and U 2 The non-aromatic ring of the mesogenic group to which the bridging group is linked is [ka] Preferably selected from the following: 5 is as defined in formula ND.

[0173] Preferably, the aromatic group A in the formula ND 1~4may be mononuclear, i.e. having only one aromatic ring (such as, for example, phenyl or phenylene), or polynuclear, i.e. having two or more condensed rings (such as, for example, naphthyl or naphthylene). Particularly preferred are mono-, bi- or tricyclic aromatic or heteroaromatic groups, which may have up to 25 C atoms and may also have condensed rings and which may be substituted.

[0174] Preferably, the non-aromatic hydrocarbon ring and the heterocycle A in the compound of formula ND 1~4 The non-aromatic rings may also contain one or more heteroatoms, preferably selected from Si, O, N and S.

[0175] Preferably, the non-aromatic ring and the aromatic ring in the formula ND or A 1~4 is selected from trans-1,4-cyclohexylene and 1,4-phenylene which may be substituted with one or more groups L.

[0176] Highly preferred are compounds of formula ND, where m and p are 1, and n and o are 1 or 2. More preferred are compounds of formula ND, where m and p are 1 or 2, and n and o are 0. More preferred are compounds where m, n, o and p are 2.

[0177] A linking group or Z connecting the aromatic and non-aromatic ring groups in the mesogenic group in the compound of formula ND 1~4 is preferably -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR 0 -, -NR 0 -CO-, -NR 0 -CO-NR 0 -, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH2CH2-, -(CH2 )3-, -(CH2)4-, -CF2CH2-, -CH2CF2-, -CF2CF2-, -CH=CH-, -CY 1 =CY 2 -, -CH=N-, -N=CH-, -N=N-, -CH=CR 0 -, -C≡C-, -CH=CH-COO-, -OCO-CH=CH-, CR 0 R 00 or a single bond, very preferably selected from -COO-, -OCO- and a single bond.

[0178] Preferably, in the compound of formula ND, the substituents on the ring, such as L, are P-Sp-, F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)NR 0 R 00 , -C(=O)X, -C(=O)OR 0 , -C(=O)R 0 , -NR 0 R 00 , -OH, -SF5, optionally substituted silyl, aryl or heteroaryl having 1 to 12, preferably 1 to 6, C atoms, and linear or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonyloxy or alkoxycarbonyloxy having 1 to 12, preferably 1 to 6, C atoms, with the proviso that one or more H atoms may be replaced by F or Cl, with the proviso that R 0 and R 00 is as defined in formula ND, and X is a halogen.

[0179] Preferably, the compound of formula ND comprises R substituted with two or more polymerizable groups P or P-Sp-. 1~4 or one or more end groups such as R 5 Suitable polyfunctional polymerizable groups of this type are disclosed, for example, in U.S. Pat. No. 7,060,200 or U.S. Patent Application Publication No. 2006 / 0172090.

[0180] Highly preferred compounds of formula ND are of the following sub-formula:

[0181] [ka]

[0182] [ka]

[0183] [ka]

[0184] [ka]

[0185] [ka]

[0186] In the formula, R 1~5 , A 1~4 , Z 1~4 , B, m, n, o, p and q have one of the meanings given above.

[0187] Particularly preferred are compounds of the following subformulae:

[0188] [ka]

[0189] [ka]

[0190] [ka]

[0191] [ka]

[0192] [ka]

[0193] [ka]

[0194] [ka]

[0195] [ka]

[0196] [ka]

[0197] [ka]

[0198] [ka]

[0199] [ka]

[0200] where Z is the Z given above 1 where R is different from P-Sp- as given above. 1 where P, Sp, L and r are as defined above and the benzene ring in the mesogenic group may be substituted with one or more groups L as defined above.

[0201] Further preferred is a polymerizable liquid crystal medium in which the compound of formula ND is selected from the group consisting of compounds of formula ND25 or ND26, in particular Z represents -COO-, in each occurrence r is 0 and P, Sp are as defined above.

[0202] In these preferred compounds, P-Sp- is preferably P-Sp'-X', where X' is preferably -O-, -COO- or -OCOO-.

[0203] Compounds of formula ND, its subformulas and suitable methods for their synthesis are disclosed in WO 2008 / 119427.

[0204] The amount of compounds of formula ND in the polymerisable LC material is preferably 0-50%, very preferably 0-40%.

[0205] In a further preferred embodiment the polymerisable LC material may comprise one or more additives selected from the group consisting of further polymerisation initiators, antioxidants, surfactants, stabilisers, catalysts, sensitisers, inhibitors, chain transfer agents, co-reactive monomers, reactive thinners, surface active compounds, lubricants, wetting agents, dispersants, hydrophobising agents, adhesives, flow improvers, degassing or antifoaming agents, defoamers, diluents, reactive diluents, auxiliaries, colourants, dyes, pigments and nanoparticles.

[0206] In another preferred embodiment the polymerisable LC material may comprise one or more additives selected from polymerisable non-mesogenic compounds (reactive thinners). The amount of these additives in the polymerisable LC material is preferably 0-30%, very preferably 0-25%.

[0207] The reactive thinners used are not only substances in the actual sense called reactive thinners, but also auxiliary compounds already mentioned above which contain one or more complementary reactive units or polymerizable groups P, e.g. hydroxyl, thiol or amino groups, via which reaction with the polymerizable units of the liquid-crystalline compound can take place.

[0208] Photopolymerizable substances generally include mono-, di-, and polyfunctional compounds containing at least one olefinic double bond, such as vinyl esters of carboxylic acids, such as lauric acid, myristic acid, palmitic acid, and stearic acid, and vinyl esters of dicarboxylic acids, such as succinic acid, adipic acid, allyl, and vinyl ethers, and methacrylic and acrylic esters of monofunctional alcohols, such as lauryl, myristyl, palmityl, and stearyl alcohol, and difunctional alcohols, such as diallyl and divinyl ethers of ethylene glycol and 1,4-butanediol.

[0209] Also suitable are, for example, methacrylic and acrylic esters of polyfunctional alcohols, especially those which, apart from hydroxyl groups, do not contain further functional groups or at most contain ether groups.Examples of such alcohols are difunctional alcohols, such as ethylene glycol, propylene glycol and their more highly condensed representatives, such as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, butanediol, pentanediol, hexanediol, neopentyl glycol, alkoxylated phenolic compounds, such as ethoxylated and propoxylated bisphenols, cyclohexanedimethanol, trifunctional and polyfunctional alcohols, such as glycerol, trimethylolpropane, butanetriol, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol, and the corresponding alkoxylated, especially ethoxylated and propoxylated alcohols.

[0210] Other suitable reactive thinners are polyester(meth)acrylates, which are (meth)acrylic acid esters of polyesterols.

[0211] Examples of suitable polyesterols are those which can be prepared by esterifying polycarboxylic acids, preferably dicarboxylic acids, with polyols, preferably diols. Starting materials for such hydroxyl-containing polyesters are known to those skilled in the art. Dicarboxylic acids which can be used are succinic acid, glutaric acid, adipic acid, sebacic acid, o-phthalic acid and their isomers and their hydrogenation products, as well as esterifiable and transesterifiable derivatives of said acids, such as anhydrides and dialkyl esters. Suitable polyols are the above-mentioned alcohols, preferably ethylene glycol, 1,2- and 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexanedimethanol, and polyglycols of the ethylene glycol and propylene glycol type.

[0212] Further suitable reactive thinners include those having the formula: [ka] and the acrylic esters of tricyclodecenyl alcohol, and the allyl esters of acrylic, methacrylic and cyanoacrylic acids.

[0213] Of the reactive thinners given as examples, those having photopolymerizable groups are used in particular and in view of the preferred compositions mentioned above.

[0214] This group includes, for example, di- and polyhydric alcohols, such as ethylene glycol, propylene glycol and their more highly condensed representatives, such as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, butanediol, pentanediol, hexanediol, neopentyl glycol, cyclohexanedimethanol, glycerol, trimethylolpropane, butanetriol, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol and the corresponding alkoxylated, especially ethoxylated and propoxylated, alcohols.

[0215] This group also includes, for example, alkoxylated phenolic compounds such as ethoxylated and propoxylated bisphenols.

[0216] These reactive thinners may further be, for example, epoxides or urethane (meth)acrylates.

[0217] Epoxide (meth)acrylates are, for example, those obtainable by reaction of epoxidized olefins or poly- or diglycidyl ethers, such as bisphenol A diglycidyl ether, with (meth)acrylic acid, as known to the person skilled in the art.

[0218] The urethane (meth)acrylates are in particular the products of the reaction of hydroxyalkyl (meth)acrylates with poly- or diisocyanates, which are likewise known to the person skilled in the art.

[0219] Such epoxides and urethane (meth)acrylates are included among the compounds listed above as "mixed forms."

[0220] When reactive thinners are used, their amount and properties must be adapted to the respective conditions, so that, on the one hand, the desired effect, for example the desired color of the composition according to the present invention, is obtained satisfactorily, and, on the other hand, the phase behavior of the liquid crystal composition is not excessively impaired.Low crosslinking (high crosslinking) liquid crystal compositions can be prepared, for example, using the corresponding reactive thinners, which have a relatively small (large) number of reactive units per molecule.

[0221] Examples of groups of diluents include: C1-C4-alcohols, such as methanol, ethanol, n-propanol, isopropanol, butanol, isobutanol, sec-butanol, in particular C5-C12-alcohols, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, n-undecanol and n-dodecanol and their isomers, glycols, such as 1,2-ethylene glycol, 1,2- and 1,3-propylene glycol, 1,2-, 2,3- and 1,4-butylene glycol, di- and triethylene glycol, and di- and tripropylene glycol, ethers, such as methyl tert-butyl ether, 1,2-ethylene glycol mono- and dimethyl ether, 1,2-ethylene glycol mono- and diethyl ether, 3- Methoxypropanol, 3-isopropoxypropanol, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), C1-C5-alkyl esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate and amyl acetate, aliphatic and aromatic hydrocarbons such as pentane, hexane, heptane, octane, isooctane, petroleum ether, toluene, xylene, ethylbenzene, tetralin, decalin, dimethylnaphthalene, white spirit, Shellsol® and Solvesso® mineral oils, such as gasoline, kerosene, diesel and heating oil, and also natural oils such as olive oil, soybean oil, rapeseed oil, linseed oil and sunflower oil.

[0222] Of course, it is also possible to use mixtures of these diluents in the compositions according to the invention.

[0223] These diluents can also be mixed with water, as long as they are at least partially miscible. Examples of suitable diluents herein are C1-C4-alcohols, such as methanol, ethanol, n-propanol, isopropanol, butanol, isobutanol and sec-butanol, glycols, such as 1,2-ethylene glycol, 1,2- and 1,3-propylene glycol, 1,2-, 2,3- and 1,4-butylene glycol, di- and triethylene glycol, and di- and tripropylene glycol, ethers, such as tetrahydrofuran and dioxane, ketones, such as acetone, methyl ethyl ketone and diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), and C1-C4-alkyl esters, such as methyl, ethyl, propyl and butyl acetate.

[0224] The diluent is optionally used in a proportion of about 0 to 10.0% by weight, preferably about 0 to 5.0% by weight, based on the total weight of the polymerizable LC material.

[0225] Antifoaming and defoaming agents (c1)), lubricants and flow aids (c2)), heat- or radiation-curing aids (c3)), substrate wetting aids (c4)), wetting and dispersing aids (c5)), hydrophobizing agents (c6)), adhesion promoters (c7)) and aids for promoting scratch resistance (c8)) cannot be strictly distinguished from one another in their action.

[0226] For example, lubricants and flow aids often act as antifoaming and / or defoaming agents and / or as aids to improve scratch resistance. Radiation curing aids may also act as lubricants and flow aids and / or defoaming agents and / or as substrate wetting aids. In some cases, some of these aids may also perform the function of adhesion promoters (c8)).

[0227] Corresponding to the above, certain additives can therefore be classified into a number of groups c1) to c8) below.

[0228] The antifoaming agents of group c1) include silicon-free and silicon-containing polymers, for example unmodified or modified polydialkylsiloxanes or branched copolymers, comb or block copolymers containing polydialkylsiloxane and polyether units, the latter being derived from ethylene oxide or propylene oxide.

[0229] Degassing agents of group c1) include, for example, organic polymers such as polyethers and polyacrylates, dialkylpolysiloxanes, in particular dimethylpolysiloxanes, organically modified polysiloxanes, such as arylalkyl-modified polysiloxanes, and fluorosilicones.

[0230] The action of antifoaming agents is essentially based on preventing the formation of foam or on destroying already formed foam. Antifoaming agents essentially act by promoting the aggregation of finely divided gases or bubbles to produce larger bubbles in the medium to be defoamed, for example the composition according to the invention, and thus promoting the escape of (air) gas. Antifoaming agents can frequently also be used as defoamers, and vice versa, and these additives are collectively included in group c1).

[0231] Such auxiliaries are, for example, TEGO® Foamex 800, TEGO® Foamex 805, TEGO® Foamex 810, TEGO® Foamex 815, TEGO® Foamex 825, TEGO® Foamex 835, TEGO® Foamex 840, TEGO® Foamex 842, TEGO® Foamex 1435, TEGO® Foamex 1488, TEGO® Foamex 1495, TEGO® Foamex 1496, TEGO® Foamex 1497, TEGO® Foamex 1499, TEGO® Foamex 1498, TEGO® Foamex 149 ... mex3062, TEGO® Foamex 7447, TEGO® Foamex 8020, Tego® Foamex N, TEGO® Foamex K3, 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 D90, TEGO® Antifoam 93, TEGO® Antifoam 200, TEGO® Antifoam 201, TEGO® Antifoam 202, TEGO® Antifoam 793, TEGO® Antifoam 1488, TEGO® Antifoam 3062, TEGOPREN (registered trademark) 5803, TEGOPREN® 5852, TEGOPREN® 5863, TEGOPREN® 7008, TEGO® Antifoam 1-60, TEGO® Antifoam 1-62, TEGO® Antifoam 1-85, TEGO® Antifoam 2-67, TEGO® Antifoam WM20, TEGO® Antifoam 50, TEGO® Antifoam 105, TEGO® Antifoam 730,TEGO® Antifoam MR1015, TEGO® Antifoam MR1016, TEGO® Antifoam 1435, TEGO® Antifoam N, TEGO® Antifoam KS6, TEGO® Antifoam KS10, TEGO® Antifoam KS53, TEGO® Antifoam KS95, TEGO® Antifoam KS100, TEGO® Antifoam amKE600, TEGO® Antifoam KS911, TEGO® Antifoam MR1000, TEGO® Antifoam KS1100, Tego® Airex 900, Tego® Airex 910, Tego® Airex 931, Tego® Airex 935, Tego® Airex 936, Tego® Airex 960, Tego® Airex 970, Tego® ) from Tego as Airex 980 and Tego® Airex 985, and BYK®-011, BYK®-019, BYK®-020, BYK®-021, BYK®-022, BYK®-023, BYK®-024, BYK®-025, BYK®-027, BYK®-031, BYK®-032, BYK®-033, BYK®-034 , BYK®-035, BYK®-036, BYK®-037, BYK®-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.

[0232] The auxiliaries of group c1) may be used in a proportion of about 0 to 3.0% by weight, preferably about 0 to 2.0% by weight, based on the total weight of the polymerizable LC material.

[0233] In group c2), lubricants and flow aids generally include not only silicon-free polymers, but also silicon-containing polymers, such as polyacrylates or modifiers, low molecular weight polydialkylsiloxanes.The modification consists in some of the alkyl groups being replaced by a wide variety of organic groups.These organic groups are, for example, polyethers, polyesters, or even longer chain alkyl groups, the former being most frequently used.

[0234] The polyether groups in the corresponding modified polysiloxanes are usually composed of ethylene oxide and / or propylene oxide units. In general, the higher the proportion of these alkylene oxide units in the modified polysiloxane, the more hydrophilic the resulting product will be.

[0235] Such auxiliaries are commercially available from Tego, for example as TEGO® Glide 100, TEGO® Glide ZG400, TEGO® Glide 406, TEGO® Glide 410, TEGO® Glide 411, TEGO® Glide 415, TEGO® Glide 420, TEGO® Glide 435, TEGO® Glide 440, TEGO® Glide 450, TEGO® Glide A115, TEGO® Glide B1484 (which can also be used as an antifoam and defoamer), TEGO® Flow ATF, TEGO® Flow 300, TEGO® Flow 460, TEGO® Flow 425 and TEGO® Flow ZFS 460. Suitable radiation curable lubricants and flow aids, which may also be used to improve scratch resistance, are the TEGO® Rad2100, TEGO® Rad2200, TEGO® Rad2500, TEGO® Rad2600 and TEGO® Rad2700 products, also available from TEGO.

[0236] Such auxiliaries are also available from BYK as, for example, BYK®-300, BYK®-306, BYK®-307, BYK®-310, BYK®-320, BYK®-333, BYK®-341, Byk® 354, Byk® 361, Byk® 361N, BYK® 388.

[0237] Such agents are also available from 3M, for example as FC4430®.

[0238] Such auxiliaries are also available from Cytonix, for example as FluorN® 561 or FluorN® 562.

[0239] Such auxiliaries are also available from Merck KGaA, for example as Tivida® FL2300 and Tivida® FL2500.

[0240] The auxiliaries of group c2) may be used in a proportion of about 0 to 3.0% by weight, preferably about 0 to 2.0% by weight, based on the total weight of the polymerizable LC material.

[0241] In group c3), radiation curing auxiliaries include, in particular, polysiloxanes with terminal double bonds, which are, for example, constituents of acrylate groups. Such auxiliaries can be crosslinked by actinic radiation or, for example, by electron beams. These auxiliaries generally combine many properties together. In the uncrosslinked state, they can act as defoamers, defoamers, lubricants and flow auxiliaries and / or substrate wetting auxiliaries, whereas in the crosslinked state, they improve, in particular, the scratch resistance of, for example, coatings or films, which can be produced with the compositions according to the invention. For example, precisely, the improvement of the gloss properties of these coatings or films is essentially believed to be the result of the action of these auxiliaries as defoamers, defoamers and / or lubricants, and flow auxiliaries (in the uncrosslinked state).

[0242] Examples of suitable radiation curing coagents are the products TEGO® Rad2100, TEGO® Rad2200, TEGO® Rad2500, TEGO® Rad2600 and TEGO® Rad2700 available from TEGO and the product BYK®-371 available from BYK.

[0243] The heat curing coagents of group c3) contain, for example, primary OH groups which are capable of reacting, for example, with isocyanate groups of the binder.

[0244] Examples of thermal curing coagents that may be used are the products BYK®-370, BYK®-373 and BYK®-375 available from BYK.

[0245] The auxiliaries of group c3) may be used in a proportion of about 0 to 5.0 wt.-%, preferably about 0 to 3.0 wt.-%, based on the total weight of the polymerizable LC material.

[0246] The substrate wetting auxiliaries of group c4) serve in particular to increase the wetting of the substrate to be printed or coated, for example with a printing ink or coating composition, for example with the composition according to the invention. Often the improved lubrication and flow behavior of such printing ink or coating compositions is accompanied by an influence on the appearance of the finished (for example crosslinked) print or coating.

[0247] A wide variety of such auxiliaries are commercially available, for example, from Tego as TEGO® WetKL245, TEGO® Wet250, TEGO® Wet260 and TEGO® WetZFS453, and from BYK as BYK®-306, BYK®-307, BYK®-310, BYK®-333, BYK®-344, BYK®-345, BYK®-346 and BYK®-348.

[0248] The auxiliary of group c4) may be used in a proportion of about 0 to 3.0% by weight, preferably about 0 to 1.5% by weight, based on the total weight of the liquid crystal composition.

[0249] The wetting and dispersing auxiliaries of group c5) serve in particular to prevent flooding and floating and settling of the pigments and are therefore particularly suitable in pigment compositions where appropriate.

[0250] These adjuvants essentially stabilize the pigment dispersions via electrostatic repulsion and / or steric hindrance of the pigment particles containing these additives, where in the latter case the interaction of the adjuvant with the surrounding medium (e.g. the binder) plays a major role.

[0251] The use of such wetting and dispersing auxiliaries is common, for example, in the art of printing inks and paints, so that the selection of suitable auxiliaries of this type, in the case of common use, does not pose any difficulties to the skilled artisan.

[0252] Such wetting and dispersing aids are available, for example, from Tego, as TEGO® Dispers 610, TEGO® Dispers 610S, TEGO® Dispers 630, TEGO® Dispers 700, TEGO® Dispers 705, TEGO® Dispers 710, TEGO® Dispers 720W, TEGO® Dispers 725W, TEGO® Dispers 730W, TEGO® Dispers 735. W and TEGO® Dispers 740W as well as Disperbyk®, Disperbyk®-107, Disperbyk®-108, Disperbyk®-110, Disperbyk®-111, Disperbyk®-115, Disperbyk®-130, Disperbyk®-160, Disperbyk®-161, Disperbyk®-162, Disperbyk®-163, Disperbyk®-165, Disperbyk®-166, Disperbyk®-167, Disperbyk®-169, Disperbyk®-170, Disperbyk®-171, Disperbyk®-172, Disperbyk®-173, Disperbyk®-174, Disperbyk®-175, Disperbyk®-176, Disperbyk®-177, Disperbyk®-178, Disperbyk®-179, Disperbyk®-180, Disperbyk®-181, Disperbyk®-182, Disperbyk®-183, Disperbyk®-184, Disperbyk®-185, Disperbyk®-186, Disperbyk®-187, Disperbyk®-188, Disperbyk®-189, Disperbyk®-190, Disperbyk®-200, Disperbyk®-201, Disperbyk®-202, Disperbyk®-203, Disperbyk®-204, Disperbyk®-205, Disperbyk®-206, Disperbyk®-207, Disperbyk®-208, Disperbyk®-209, Disperbyk®-300, Disperbyk®-301, Disperbyk®-302, Disperbyk®-303 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, BYK®-185, Disperbyk®-190, Anti-Terra®-U, Anti-Terra®-U80, Anti-Terra®-P, Anti-Terra®-203, Anti-Terra®-204, Anti-Terra®-206, BYK®-151, BYK®-154, BYK®-155, BYK®-P104S, BYK®-P105, Lactimon®,It is commercially available as Lactimon®-WS and Bykumen®.

[0253] The amount of auxiliary used in group c5) is based on the average molecular weight of the auxiliary, therefore preliminary experiments are advisable in each case, but this can be easily carried out by the skilled person.

[0254] The hydrophobizing agents of group c6) can be used, for example, to impart water repellency to prints or coatings produced with the compositions according to the invention, thereby preventing or at least greatly suppressing swelling due to water absorption and thus, for example, changes in the optical properties of such prints or coatings. Also, when the compositions are used, for example, as printing inks in offset printing, water absorption can be prevented or at least greatly reduced thereby.

[0255] Such hydrophobizing agents are commercially available, for example, from Tego as Tego® Phobe WF, Tego® Phobe 1000, Tego® Phobe 1000S, 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.

[0256] The auxiliaries of group c6) are optionally used in a proportion of about 0 to 5.0% by weight, preferably about 0 to 3.0% by weight, based on the total weight of the polymerizable LC material.

[0257] Further adhesion promoters from group c7) serve to improve the adhesion of the two interfaces in contact. From this it follows immediately that the only effective part of the adhesion promoter is that located at either one or both interfaces. For example, if it is desired to apply a liquid or pasty printing ink, coating composition or paint to a solid substrate, this generally means that the adhesion promoter must be added directly to the latter or the substrate must be pretreated with the adhesion promoter (also known as priming), i.e. the substrate is endowed with modified chemical and / or physical surface properties.

[0258] If the substrate has been primed beforehand with a primer, this means that the contacting interfaces are, on the one hand, that of the primer and, on the other hand, that of the printing ink or coating composition or paint, in which case not only the adhesion between the substrate and the primer but also the adhesion between the substrate and the printing ink or coating composition or paint contributes to the adhesion of the entire multilayer structure on the substrate.

[0259] Adhesion promoters which may be described in a broader sense are also the substrate wetting auxiliaries already mentioned in group c4), but these generally do not have the same adhesion promoting capabilities.

[0260] The variety of adhesion promoter systems is not surprising in view of the great variety of substrates and the physical and chemical properties of, for example, the printing inks, coating compositions and paints intended for printing or coating thereon.

[0261] Silane-based adhesion promoters are, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N-aminoethyl-3-aminopropyltrimethoxysilane, N-aminoethyl-3-aminopropylmethyldimethoxysilane, N-methyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane and vinyltrimethoxysilane. These and other silanes are commercially available, for example, from Huls under the trade name DYNASILAN®.

[0262] Corresponding technical information from the manufacturers of such additives should generally be used or the skilled person can obtain this information in a simple manner through corresponding preliminary experiments.

[0263] However, if these additives are added to the polymerizable LC material according to the invention as auxiliaries from group c7), their proportion optionally corresponds to about 0-5.0% by weight, based on the total weight of the polymerizable LC material. These concentration data are merely a guideline, since the amount and type of additives are determined in each case by the nature of the substrate and the nature of the printing / coating composition. Corresponding technical information is usually in this case available from the manufacturers of such additives or can be determined in a simple manner by the skilled person through corresponding preliminary experiments.

[0264] Examples of auxiliaries for improving the scratch resistance of group c8) include the abovementioned products TEGO® Rad2100, TEGO® Rad2200, TEGO® Rad2500, TEGO® Rad2600 and TEGO® Rad2700 available from Tego.

[0265] For these auxiliaries, the quantitative data given for group c3) are likewise suitable, i.e. these additives are optionally used in a proportion of about 0 to 5.0% by weight, preferably about 0 to 3.0% by weight, based on the total weight of the liquid crystal composition.

[0266] Examples that may be mentioned of light, heat and / or further oxidative stabilizers are:

[0267] Alkylated monophenols, such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, linear or branched. nonylphenols having a side chain of the formula: 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(1'-methylundec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methylheptadec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol and mixtures of these compounds, alkylthiomethylphenols such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol and 2,6-didodecylthiomethyl-4-nonylphenol,

[0268] Hydroquinone and alkylated hydroquinones, such as 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate and bis(3,5-di-tert-butyl-4-hydroxyphenyl)adipate;

[0269] Tocopherols, such as α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures of these compounds, as well as tocopherol derivatives, such as tocopheryl acetate, succinate, nicotinate and polyoxyethylene succinate ("tocopherolate").

[0270] Hydroxylated diphenyl thioethers, such as 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2-methylphenol), 4,4'-thiobis(3,6-dis-sec-amylphenol) and 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide.

[0271] Alkylidene bisphenols, for example, 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4-methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2-ethylidenebis(4,6- di-tert-butylphenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-(α-methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecyl-mercaptobutane, ethylene glycol bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene, bis [2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate, 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecyl-mercaptobutane and 1,1,5,5-tetrakis(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane,

[0272] O-, N- and S-benzyl compounds, such as 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl 4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, tridecyl 4-hydroxy-3,5-di-tert-butylbenzyl mercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide and isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate,

[0273] Aromatic hydroxybenzyl compounds, such as 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene and 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol;

[0274] Triazine compounds, for example, 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate and 1,3,5-tris(2-hydroxyethyl)isocyanurate,

[0275] 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;

[0276] Acylaminophenols, such as 4-hydroxylauroylanilide, 4-hydroxystearoylanilide and octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate;

[0277] Propionic and acetate esters, for example the propionic and acetate esters of mono- or polyhydric alcohols, for example of 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,

[0278] 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,

[0279] Ascorbic acid (vitamin C) and ascorbic acid derivatives, such as ascorbyl palmitate, laurate and stearate, and ascorbyl sulfate and phosphate;

[0280] 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-(1,3-dimethylbutyl)-N-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N-phenyl-p-phenylenediamine, N-cyclohexyl-N-phenyl-p-phenylenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N,N'-dimethyl-N,N'-di-sec-butyl- p-Phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octyl-substituted diphenylamines such as p,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoyl Aminophenol, 4-octadecanoylaminophenol, bis[4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane, (o-tolyl)biguanide, bis[4-(1',3'-Dimethylbutyl)phenyl]amine, tert-octyl substituted N-phenyl-1-naphthylamines, mixtures of mono- and di-alkylated tert-butyl / tert-octyldiphenylamines, mixtures of mono- and di-alkylated nonyldiphenylamines, mixtures of mono- and di-alkylated dodecyldiphenylamines, mixtures of mono- and di-alkylated isopropyl / isohexyldiphenylamines, mixtures of mono- and di-alkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine , phenothiazine, mixture of mono- and di-alkylated tert-butyl / tert-octyl phenothiazines, mixture of mono- and di-alkylated tert-octyl phenothiazines, N-allyl phenothiazine, N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene, N,N-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine, bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate, 2,2,6,6-tetramethylpiperidin-4-one and 2,2,6,6-tetramethylpiperidin-4-ol,

[0281] Phosphines, phosphites and phosphonites, such as triphenylphosphine, triphenylphosphite, diphenylalkylphosphites, phenyldialkylphosphites, tris(nonylphenyl)phosphite, trilaurylphosphite, trioctadecylphosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, diisodecylpentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6 ... methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl))pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphocin, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,g]-1,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite and bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite,

[0282] 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'-ditert-amyl-2'-hydroxyphenyl)benzotriazole, 2-(3,5'-bis-(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5' -(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole mixture, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3'-t 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole and 2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol];Complete esterification product of 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300;,

[0283] Sulfur-containing peroxide scavengers and sulfur-containing antioxidants, such as esters of 3,3'-thiodipropionic acid, such as the lauryl, stearyl, myristyl and tridecyl esters, mercaptobenzimidazole and 2-mercaptobenzimidazole, dibutyl zinc dithiocarbamate, dioctadecyl disulfide and the zinc salt of pentaerythritol tetrakis(β-dodecylmercapto)propionate;

[0284] 2-hydroxybenzophenones, such as the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decycloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives;

[0285] 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,

[0286] Acrylates, such as ethyl α-cyano-β,β-diphenylacrylate, isooctyl α-cyano-β,β-diphenylacrylate, methyl α-methoxycarbonylcinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, butyl-α-cyano-β-methyl-p-methoxycinnamate and methyl-α-methoxycarbonyl-p-methoxycinnamate, sterically hindered amines, such as bis(2,2,6,6-tetramethylpiperidin-4-yl) Sebacate, bis(2,2,6,6-tetramethylpiperidin-4-yl) succinate, bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis(1,2,2,6,6-pentamethylpiperidin-4-yl)-n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl malonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethylpiperidin-4-yl Condensation products of tetramethyl-4-hydroxypiperidine with succinic acid, Condensation products of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine with 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, N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and condensation product of 4-morpholino-2,6-dichloro-1,3,5-triazine, 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidin-4-yl)-1,3 ,5-triazine and 1,2-bis(3-aminopropylamino)ethane condensation products, 2-chloro-4,6-di(4-n-butylamino-1,2,2,6,6-pentamethylpiperidin-4-yl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane condensation products, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]-decane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidine-2, 5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethylpiperidin-4-yl)pyrrolidine-2,5-dione, a mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensation product of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, 1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5 -Condensation products of triazines, 4-butylamino-2,2,6,6-tetramethylpiperidine, N-(2,2,6,6-tetramethylpiperidin-4-yl)-n-dodecylsuccinimide, N-(1,2,2,6,6-pentamethylpiperidin-4-yl)-n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]-decane, 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4.5] Condensation products of decane with epichlorohydrin, condensation products of 4-amino-2,2,6,6-tetramethylpiperidine with tetramethylolacetylene diurea and poly(methoxypropyl-3-oxy)-[4(2,2,6,6-tetramethyl)piperidinyl]-siloxane,.

[0287] Oxalamides, such as 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxalamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and mixtures thereof with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, and mixtures of ortho-, para-methoxy-disubstituted oxanilides, and mixtures of ortho- and para-ethoxy-disubstituted oxanilides, and

[0288] 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-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bi 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.

[0289] In another preferred embodiment the polymerisable LC material comprises one or more specific antioxidant additives, preferably the Irganox® series, such as Irganox® 1076 and Irganox® 1010, available from Ciba, Switzerland.

[0290] In another preferred embodiment the polymerisable LC material comprises a combination of one or more, more preferably two or more, photoinitiators, for example selected from the commercially available Irgacure® or Darocure® (CibaAG) 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, furthermore selected from the commercially available OXE02 (CibaAG), NCI930, N1919T (Adeka), SPI-03 or SPI-04 (Samyang).

[0291] The total concentration of these photoinitiators (one or more) in the polymerisable LC material is preferably 0.5-10%, very preferably 0.8-8%, more preferably 1-6%.

[0292] Preferably the polymerisable LC material comprises besides one or more compounds of formulae S0-S2 a) one or more di- or multi-reactive polymerizable mesogenic compounds, b) optionally one or more monoreactive polymerizable mesogenic compounds, c) optionally one or more antioxidant additives; d) optionally one or more adhesion promoters; e) optionally one or more surfactants; f) optionally one or more monoreactive, direactive or multireactive polymerizable non-mesogenic compounds, g) optionally, one or more dyes that have an absorption maxima at the wavelengths used to initiate photopolymerization; h) optionally one or more chain transfer agents; i) optionally one or more stabilizers; j) optionally one or more lubricants and flow aids, and k) optionally one or more diluents; l) Optionally, a non-polymerizable nematic component Includes.

[0293] More preferably the polymerizable LC material is a) one or more compounds of formulae S0 to S2, b) one or more, preferably two or more, direactive polymerizable mesogenic compounds, preferably in an amount, if present, of 10 to 90% by weight in total, very preferably 15 to 75% by weight, preferably selected from compounds of formula DRMa-1, c) optionally one or more, preferably two or more, monoreactive polymerizable mesogenic compounds, preferably in an amount of 10-95% by weight, very preferably 25-85% by weight, preferably selected from the compounds of formula MRM-1 and / or MRM-7, d) optionally one or more compounds of formula ND, preferably in an amount of 0 to 50% by weight, very preferably 0 to 40% by weight, e) optionally one or more antioxidant additives, preferably selected from esters of unsubstituted and substituted benzoic acid, in particular Irganox® 1076, preferably in an amount of 0.01 to 2% by weight, very preferably 0.05 to 1% by weight, if present, f) optionally one or more lubricants and flow aids, preferably selected from BYK® 388, FC 4430 and / or Fluor N 562, preferably in an amount of 0.1 to 5% by weight, very preferably 0.2 to 3% by weight, if present, and g) optionally one or more diluents, preferably selected from n-dodecanol, preferably present in an amount of 0.1 to 5% by weight, very preferably 0.2 to 3% by weight; include.

[0294] The present invention further comprises: providing a layer of a polymerizable LC material as described above and below on a substrate, Polymerizing the polymerizable component of the polymerizable LC material by photopolymerization; and Optionally removing the polymerized LC material from the substrate and / or providing it onto another substrate. The present invention relates to a method for preparing a polymer film by

[0295] It is also possible to dissolve the polymerisable LC material in a suitable solvent.

[0296] In another preferred embodiment, the polymerizable LC material comprises one or more solvents, preferably selected from organic solvents. The solvent is preferably selected from ketones, such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone or cyclohexanone; acetates, such as methyl, ethyl or butyl acetate or methyl acetoacetate; alcohols, such as methanol, ethanol or isopropyl alcohol; aromatic solvents, such as toluene or xylene; alicyclic hydrocarbons, such as cyclopentane or cyclohexane; halogenated hydrocarbons, such as dichloromethane or trichloromethane; glycols or their esters, such as PGMEA (propyl glycol monomethyl ether acetate), γ-butyrolactone. It is also possible to use binary, ternary or more mixtures of the above solvents.

[0297] When the polymerizable LC material comprises one or more solvents, the total concentration of all solids, including RM, in the solvent(s) is preferably 10-60%.

[0298] This solution is then coated or printed onto a substrate, for example by spin coating, printing, or other known techniques, and the solvent is evaporated prior to polymerization, In most cases, it is suitable to heat the mixture to facilitate evaporation of the solvent.

[0299] The polymerizable LC material can be applied onto the substrate by conventional coating techniques such as spin coating, bar coating or blade coating. It can also be applied to the substrate by conventional printing techniques known to those skilled in the art, such as screen printing, offset printing, reel to reel printing, letterpress printing, gravure printing, rotogravure printing, flexographic printing, intaglio printing, pad printing, heat seal printing, inkjet printing or printing with a stamp or printing plate.

[0300] Suitable plastic substrates are known to experts and described in the literature as conventional substrates, for example, used in the optical film industry.Particularly suitable and preferred substrates for polymerization are polyesters, such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), polyvinyl alcohol (PVA), polycarbonate (PC), triacetyl cellulose (TAC), or cycloolefin polymer (COP), or well-known color filter materials, in particular triacetyl cellulose (TAC), cycloolefin polymer (COP), or well-known color filter materials.

[0301] The polymerisable LC material preferably exhibits uniform alignment throughout the layer. Preferably, the polymerisable LC material exhibits uniform planar or homeotropic alignment.

[0302] The Friedel-Creagh-Kmetz law can be used to predict whether a mixture will adopt a planar or homeotropic alignment by comparing the surface energies of the RM layer and the substrate.

[0303] Gamma RM >γ s In the case of γ, the reactive mesogenic compound exhibits homeotropic alignment, RM <γ s In this case, the reactive mesogenic compounds exhibit homeotropic alignment.

[0304] When the surface energy of the substrate is relatively low, the intermolecular forces between the reactive mesogens are stronger than the forces across the RM-substrate interface, and therefore, to maximize the intermolecular forces, the reactive mesogens align perpendicular to the substrate (homeotropic alignment).

[0305] Homeotropic alignment can also be achieved using amphiphilic materials; they can be added directly to the polymerizable LC material or the substrate can be treated with these materials in the form of a homeotropic alignment layer. The polar heads of the amphiphilic materials are chemically bonded to the substrate and the hydrocarbon tails point perpendicular to the substrate. Intermolecular interactions between the amphiphilic material and the RM promote homeotropic alignment. Commonly used amphiphilic surfactants are listed above.

[0306] Another method used to promote homeotropic alignment is to subject the plastic substrate to a corona discharge treatment, which creates alcohol or ketone functional groups on the substrate surface. These polar groups can interact with polar groups present in the RM or surfactant to promote homeotropic alignment.

[0307] When the surface tension of the substrate is greater than that of the RM, the forces across the interface become dominant: if the reactive mesogens align parallel to the substrate, the interfacial energy is minimized so that the long axis of the RM can interact with the substrate.

[0308] Unidirectional planar alignment can be promoted by coating the substrate with a polyimide layer and then rubbing the alignment layer with a velvet cloth.

[0309] Other suitable alignment layers are known in the art, such as rubbed polyimides or alignment layers prepared by photoalignment as described in U.S. Pat. Nos. 5,602,661, 5,389,698 or 6,717,644.

[0310] A review of alignment techniques in general can be found, for example, in I. Sage, Thermotropic Liquid Crystals, edited by GW Gray, John Wiley & Sons, 1987, pp. 75-77; and T. Uchida and H. Seki, Liquid Crystals-Applications and Uses, Vol. 3, edited by B. Bahadur, World Scientific Publishing, Singapore, 1992, pp. 1-63. A further review of alignment materials and techniques can be found in J. Cognard, Mol. Cryst. Liq. Cryst. Vol. 78, Suppl. 1 (1981), pp. 1-77.

[0311] For the preparation of the polymer film according to the present invention, the polymerisable compounds in the polymerisable LC material are polymerised or crosslinked by in situ polymerisation (if one compound contains two or more polymerisable groups).

[0312] The polymerization can be carried out in one step. It is also possible that compounds that have not reacted in the first step are polymerized or crosslinked ("final cure") in a second step.

[0313] In a preferred preparation method, the polymerizable LC material is coated onto a substrate and subsequently polymerized by exposure to heat or actinic radiation, as described, for example, in WO 01 / 20394, GB 2,315,072 or WO 98 / 04651.

[0314] The polymerization of the LC material is preferably achieved by exposure to actinic radiation. Actinic radiation means irradiation with light such as ultraviolet, infrared or visible light, irradiation with X-rays or gamma rays, or irradiation with high energy particles such as ions or electrons. Preferably, the polymerization is carried out by irradiation with light, in particular with UV light. As an actinic radiation source, for example, one UV lamp or a set of UV lamps can be used. When using high lamp power, the curing time can be shortened. Another possible light radiation source is a laser, for example a UV laser, an IR laser, or a visible laser.

[0315] The curing time depends, among other things, on the reactivity of the polymerizable LC material, the thickness of the coated layer, the type of polymerization initiator and the power of the UV lamp. The curing time is preferably less than 5 minutes, very preferably less than 3 minutes, most preferably less than 1 minute. For mass production, short curing times of less than 30 seconds are desirable.

[0316] A suitable UV radiation power is preferably between 5 and 200 mWcm -2 More preferably, in the range of 50 to 175 mW cm -2 in the range of 100 to 150 mW cm -2 The range is.

[0317] Depending on the applied ultraviolet radiation and time, the appropriate ultraviolet dose is preferably 25 to 7200 mJcm -2 More preferably, in the range of 500 to 7200 mJcm -2 in the range of 3000 to 7200 mJcm -2 The range is.

[0318] The polymerization is preferably carried out under an inert gas atmosphere, preferably under a heated nitrogen atmosphere, although polymerization in air is also possible.

[0319] The polymerization is carried out at a temperature of preferably 1 to 70°C, more preferably 5 to 50°C, and even more preferably 15 to 30°C.

[0320] The polymerized LC film according to the invention has good adhesion to plastic substrates, especially TAC, COP, and color filters, and can therefore be used as an adhesive or base coat for subsequent LC layers that would otherwise not adhere well to the substrate.

[0321] The preferred thickness of the polymerized LC film according to the invention is determined by the optical properties desired from the film or the final product. For example, if the polymerized LC film does not act mainly as an optical layer, e.g. as an adhesive layer, an alignment layer or a protective layer, its thickness is preferably 1 μm or less, in particular 0.5 μm or less, very preferably 0.2 μm or less.

[0322] For example, the uniform homeotropic or planar aligned polymer films of the present invention can be used as retardation or compensation films, for example in LCDs, to improve contrast and brightness at large viewing angles and reduce chromaticity. They can be used outside the switchable liquid crystal cell in LCDs, or between substrates, usually between glass substrates that form the switchable liquid crystal cell and contain the switchable liquid crystal medium (intra-cell application).

[0323] For optical applications of the polymer film, this preferably has a thickness of 0.5 to 10 μm, very preferably 0.5 to 5 μm, in particular 0.5 to 3 μm.

[0324] The optical retardation (δ(λ)) of a polymer film as a function of the wavelength (λ) of the incident beam is given by the following equation (7):

number

[0325] According to Snelius' law, the birefringence as a function of the incident beam direction is given by

number

[0326] Based on these laws, the birefringence and the corresponding optical retardation depend on the thickness of the film and the tilt angle of the optical axis in the film (see Berek's compensator). Therefore, those skilled in the art recognize that different optical retardation or different birefringence can be induced by adjusting the orientation of the liquid crystal molecules in the polymer film.

[0327] The birefringence (Δn) of the polymer film according to the present invention is preferably in the range of 0.01 to 0.30, more preferably in the range of 0.01 to 0.25, and even more preferably in the range of 0.01 to 0.16.

[0328] The optical retardation as a function of thickness of the polymer film according to the present invention is less than 200 nm, preferably less than 180 nm, even more preferably less than 150 nm.

[0329] The polymer film of the present invention can also be used as an alignment layer for other liquid crystal or RM materials. For example, it can be used in LCDs to induce or improve the alignment of a switchable liquid crystal medium or to align a subsequent layer of polymerizable LC material coated thereon. In this way, a stack of polymerizable LC films can be prepared.

[0330] In summary the polymerised LC films and polymerisable LC materials according to the invention are useful for their applications in optical elements, e.g. polarisers, compensators, alignment layers, circular polarisers or colour filters in liquid crystal displays or projection systems, for producing liquid crystals or effect pigments, decorative images, in particular reflective films with spatially varying reflected colour, e.g. as multicolour images for decorative, information storage or security purposes, e.g. as unforgeable documents such as identity cards or credit cards, bank notes etc.

[0331] The polymerized LC films according to the present invention can be used in transmissive or reflective displays. They can be used in conventional OLED displays or LCDs, especially in DAP (deformed alignment phase) or VA (vertical alignment) mode LCDs, such as ECB (electrically controlled birefringence), CSH (color super homeotropic), VAN or VAC (vertical alignment nematic or cholesteric) displays, MVA (multi-domain vertical alignment) or PVA (patterned vertical alignment) displays, in bent mode or hybrid displays, such as OCB (optically compensated bend cell or optically compensated birefringence), R-OCB (reflective OCB), HAN (hybrid alignment nematic) or pi-cell (π-cell) displays, and also in TN (twisted nematic), HTN (highly twisted nematic) or STN (super twisted nematic) mode displays, AMD-TN (active matrix driven TN) displays, or in IPS (in-plane switching) mode displays (also called "super TFT" displays). In particular, VA, MVA, PVA, OCB, and pi-cell displays are preferred.

[0332] The polymerizable materials and polymer films according to the present invention are disclosed in EP 0829744, EP 0887666, EP 0887692, U.S. Pat. No. 6,046,849, U.S. Pat. No. 6,437,915 and in the Proceedings of the SID 20 th It is particularly useful for the 3D displays described in "International Display Research Conference, 2000", page 280. 3D displays of this kind comprising the polymer film according to the invention are another subject of the present invention.

[0333] The present invention has been described above and below with particular reference to preferred embodiments. It is to be understood that various changes and modifications can be made therein without departing from the spirit and scope of the invention.

[0334] Many of the above and below compounds or mixtures thereof are commercially available. All these compounds are known or can be prepared by methods known per se, as described in the literature (e.g. standard treatises such as Houben-Weyl, Methoden der Organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart), exactly under known and suitable reaction conditions for the above reactions. Variants known per se, but not mentioned here, may also be used herein. Unless the context clearly indicates otherwise, as used herein, the plural form of the terms herein should be interpreted as including the singular form, and vice versa.

[0335] It will be understood that variations to the foregoing embodiments of the invention can be made while still falling within the scope of the invention.

[0336] Alternative features serving the same, equivalent, or similar purpose may be substituted for each feature disclosed herein, unless expressly stated otherwise, and thus, unless expressly stated otherwise, each feature disclosed is only an example of a generic series of equivalent or similar features.

[0337] All of the features disclosed herein may be combined in any combination, except combinations in which at least some of such features and / or steps are mutually exclusive. In particular, preferred features of the invention are applicable to any aspect of the invention and may be used in any combination. Similarly, features described in non-essential combinations may be used separately (not in combination).

[0338] It will be appreciated that many of the features described above, particularly many of the features of the preferred embodiments, are inventive in their own right and not solely as part of an embodiment of the present invention, and that independent protection may be sought for these features in addition to or as an alternative to the presently claimed invention.

[0339] The present invention will be described in more detail with reference to the following examples, which are illustrative and are not intended to limit the scope of the present invention. EXAMPLES

[0340] <General Procedure> The mixture is dissolved at 33.3% solids in toluene / cyclohexanone (7 / 3). This solution is spin-coated at 2000 rpm onto the rubbed PI-coated untreated glass substrate. The film is annealed at 68 °C for 120 s and cured under N2 atmosphere with an integrated conveyor, H bulb (95% power, 10 m / min, ca. 300 mJ / cm). 2 , UVB).

[0341] The film is laminated to the pressure sensitive adhesive and left open faced so that the total film stack is glass / polymer film / pressure sensitive adhesive and the film is subjected to durability experiments.

[0342] To measure the UV stress dependence of retardation and dispersion difference of the cured films, an Axoscan ellipsometer is used to determine the initial retardation and dispersion. The films are then stressed for 198 hours in a SuntestXLS+ (350 W / m 2 After the test, the retardation properties and dispersion are determined again. Durability is evaluated by measuring the R in and variance (R 450 / 550 ) is quantified by the difference in

[0343] <Example 1> The following mixture M1 is prepared according to the table below.

[0344] [Table 1]

[0345] Mixture M1 was divided into three parts, and each part was [ka] Mix one part with the other and leave the other part as is.

[0346] Each mixture is dissolved, coated and cured as described above and the change in retardation and dispersion is determined before and after exposure to sunlight, and the results are summarized in the table below.

[0347] [Table 2]

[0348] <Example 2> Mixture M1 as described above was prepared and divided into 4 portions, [ka] Mix one part with the other and leave the other part as is.

[0349] Each mixture is dissolved, coated and cured as described above and the change in retardation and dispersion is determined before and after exposure to sunlight, and the results are summarized in the table below.

[0350] [Table 3]

[0351] <Example 3> The following mixture M2 is prepared according to the table below.

[0352] [Table 4]

[0353] Mixture M2 is divided into three parts and mixed with 900 ppm of stabilizer-1 and 1500 ppm of stabilizer-2, and one part is left as is. Each mixture is melted, coated, cured as described above, and the change in retardation and dispersion is determined before and after sun exposure. The results are summarized in the table below.

[0354] [Table 5]

[0355] <Example 4> The following mixture M3 is prepared according to the table below.

[0356] [Table 6]

[0357] Mixture M3 was divided into four parts, 900 ppm of stabilizer-1, 1500 ppm of stabilizer-2 and 900 ppm of [ka] and one part is left as is. Each mixture is dissolved, coated and cured as described above and the change in retardation and dispersion is determined before and after exposure to sunlight. The results are summarized in the table below.

[0358] [Table 7]

[0359] <Example 5> The following mixture M4 is prepared according to the table below.

[0360] [Table 8]

[0361] <Example 6> The following mixture M5 is prepared according to the table below.

[0362] [Table 9]

[0363] <Example 7> The following mixture M6 is prepared according to the table below.

[0364] [Table 10]

[0365] <Example 8> The following mixture M7 is prepared according to the table below.

[0366] [Table 11]

Claims

1. A polymerizable LC material comprising one or more monoreactive mesogen compounds selected from the group consisting of compounds of formula MRM1 to MRM27, one or more direactive mesogen compounds selected from the group consisting of compounds of formula DRMa1 to DRMe, and one or more compounds of formula S0, S1, or S2, The total concentration of monoreactive mesogenic compounds in polymerizable LC materials is in the range of 5 to 80% by weight. The total concentration of direactive mesogenic compounds in polymerizable LC materials is within the range of 5 to 99% by weight. The total concentration of monoreactive and direactive mesogenic compounds in polymerizable LC materials is within the range of 30 to 99.9% by weight. The total concentration of the compounds of formulas S0 to S2 in the polymerizable LC material is in the range of 10 to 2000 ppm, however The total concentration of monoreactive mesogenic compounds, direactive mesogenic compounds, and compounds of formulas S0 to S2 in polymerizable LC materials is 100% by weight or less, however It contains one or more compounds of formula NDa, however Polymerizable LC materials are a group of compounds: - As the compound of formula S0, one or more compounds selected from formulas S0-1 to S0-4, or - As the compound of formula S1, one or more compounds selected from formulas S1-1 to S1-5, or - One or more compounds selected from formula S2-1 or S2-2 as the compound of formula S2. A polymerizable LC material containing one or more compounds selected from the following. 【Chemistry 1】 【Chemistry 2】 【Transformation 3】 【Chemistry 4】 (In the formula, P ０ These are acrylic, methacrylic, oxetane, epoxy, vinyl, heptadiene, vinyloxy, propenyl ether, or styrene groups. L is an alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy which may be halogenated and have F, Cl, CN or 1 to 5 C atoms, respectively, and is the same or different in each appearance. r is 0, 1, 2, 3, or 4. x and y are each independent integers, either 0 or identical or distinct integers between 1 and 12. z is either 0 or 1 independently, except that if an adjacent x or y is 0, then z is 0. R ０ is an alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 15 C atoms, or Y ０ This represents, Y ０ These are F, Cl, CN, NO ２ , OCH ３ , OCN, SCN, SF ５ or a monofluorinated, oligofluorinated, or polyfluorinated alkyl or alkoxy having 1 to 4 C atoms, Z ０ is -COO-, -OCO-, -CH ２ CH ２ -, -CF ２ O-, -OCF ２ -, -CH=CH-, -OCO-CH=CH-, -CH=CH-COO-, or a single bond, A ０ If multiple instances occur, they are 1,4-phenylene or trans-1,4-cyclohexylene, either independently unsubstituted or substituted with one, two, three, or four L groups. u and v are each independently 0, 1, or 2. w is 0 or 1, and However, the benzene and naphthalene rings may be substituted with one or more identical or different groups L. 【Transformation 5】 【Transformation 6】 (In the formula, P ０ If multiple instances occur, they are independently of each other: acrylic, methacrylic, oxetane, epoxy, vinyl, heptadiene, vinyloxy, propenyl ether, or styrene group. L is an alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy which may be halogenated and have F, Cl, CN or 1 to 5 C atoms, respectively, and is the same or different in each appearance. r is 0, 1, 2, 3, or 4. x and y are each independent integers, either 0 or identical or distinct integers between 1 and 12. z is either 0 or 1 independently, except when an adjacent x or y is 0, then z is 0. 【Chemistry 7.1】 (In the formula, each base has the following meanings, independently of each other, identical or different in each instance: 【Chemistry 7.2】 And, P ａ It is a polymerizable group, Sp is a linear or branched alkylene having 1 to 12 carbon atoms, plus one or two non-adjacent CH4 atoms. ２ The group can be replaced with -O-, -CH=CH-, -CO-, -OCO-, or -COO- so that the oxygen atoms are not directly bonded to each other. X １ and X ２ These are independently -O-, -CH=CH-, and -CF ２ O-, -OCF ２ -ien-CH ２ O-, -OCH ２ -, -CO-O-, -O-CO-, -C ２ F ４ -, -CF=CF- or a single bond, R ａ～ｄ Each of these independently represents a linear or branched alkyl group having 1 to 20 carbon atoms. R １ and R ２ These are H and CH, respectively, independently. ３ OH, OR ａ or O ● Represents, and n represents an integer between 1 and 8. 【Transformation 8】 (In the formula, In each instance, B independently of -C≡C- and -CY １ =CY ２ - or an aromatic or heteroaromatic group which may be substituted, Y １，２ Each of these is independently H, F, Cl, CN, or R ０ And, q is an integer between 1 and 10. A １～４ Each of these groups is independently selected from non-aromatic, aromatic, or heteroaromatic carbocyclic or heterocyclic groups, and the group consists of one or more groups R ５ It may be substituted with, however - (A １ -Z １ ) ｍ -, -(Z ２ -A ２ ) ｎ -, - (A ３ -Z ３ ) ｏ - and - (Z ４ -A ４ ) ｐ —Each of these groups does not contain more aromatic groups than non-aromatic groups. Z １～４ These are, independently of each other, -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, and -CO-NR ０ -, -NR ０ -CO-, -NR ０ -CO-NR ００ -, -OCH ２ -ien-CH ２ O-, -SCH ２ -ien-CH ２ S-, -CF ２ O-, -OCF ２ -, -CF ２ S-, -SCF ２ -ien-CH ２ CH ２ -, - (CH ２ ) ３ -, - (CH ２ ) ４ -, -CF ２ CH ２ -ien-CH ２ CF ２ -, -CF ２ CF ２ -, -CH=CH-, -CY １ =CY ２ -, -CH=N-, -N=CH-, -N=N-, -CH=CR ０ -, -C≡C-, -CH=CH-COO-, -OCO-CH=CH-, CR ０ R ００ or single bond, R ０ and R ００ Each of these is an alkyl group having H or 1 to 12 C atoms independently of each other. m and n are each independently 0, 1, 2, 3, or 4. o and p are each independently 0, 1, 2, 3, or 4. R １～５ is, independently of one another, H, halogen, -CN, -NC, -NCO, -NCS, -OCN, -SCN, -C(=O)NR ０ R ００ , -C(=O)X ０ , -C(=O)R ０ , -NH ２ , -NR ０ R ００ [[ID=十六]]、-SH、-SR ０ , -SO ３ H, -SO ２ R ０ , -OH, -NO ２ , -CF ３ , -SF ５ 、P-Sp-, optionally substituted silyl, or the same or different groups selected from carbil or hydrocarbyl having 1 to 40 C atoms, optionally substituted and optionally containing one or more heteroatoms, or represents P or P-Sp-, or is substituted with P or P-Sp-, provided that the compound represents P or P-Sp- or one or more groups R １～５ is included, P is a polymerizable group, Sp is a spacer group or a single bond. [Chemistry 9.1] (wherein P ａ is a polymerizable group.) [Chemistry 9.2] (In the formula, n1 is an integer from 2 to 12, where the base (CH) ２ ) ｎ１ One or more H atoms in the middle may be replaced with methyl, ethyl, propyl, butyl, pentyl, or hexyl groups, R １１ and R １２ Each of these independently represents a linear or branched alkyl group having 1 to 20 carbon atoms. [Chemistry 9.3] (In the formula, n represents an integer between 1 and 8.)

2. A polymerizable LC material comprising one or more monoreactive mesogen compounds selected from the group consisting of compounds of formula MRM1 to MRM27, one or more direactive mesogen compounds selected from the group consisting of compounds of formula DRMa1 to DRMe, and one or more compounds of formula S0, S1, or S2, However, the polymerizable LC material includes one or more monoreactive mesogenic compounds selected from the group consisting of compounds of formula MRM7. However, the polymerizable LC material includes one or more direactive mesogenic compounds selected from the group consisting of compounds of formula DRMa7 and DRMe. The total concentration of monoreactive mesogenic compounds in polymerizable LC materials is in the range of 5 to 80% by weight. The total concentration of direactive mesogenic compounds in polymerizable LC materials is within the range of 5 to 99% by weight. The total concentration of monoreactive and direactive mesogenic compounds in polymerizable LC materials is within the range of 30 to 99.9% by weight. The total concentration of the compounds of formulas S0 to S2 in the polymerizable LC material is in the range of 900 to 1500 ppm, however The total concentration of monoreactive mesogenic compounds, direactive mesogenic compounds, and compounds of formulas S0 to S2 in polymerizable LC materials is 100% by weight or less, however It contains one or more compounds of formula ND25, however Polymerizable LC materials are a group of compounds: - As the compound of formula S0, one or more compounds selected from formulas S0-1 to S0-4, or - As the compound of formula S1, one or more compounds selected from formulas S1-1 to S1-5, or - One or more compounds selected from formula S2-1 or S2-2 as the compound of formula S2. A polymerizable LC material containing one or more compounds selected from the following. 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】 (In the formula, P ０ These are acrylic, methacrylic, oxetane, epoxy, vinyl, heptadiene, vinyloxy, propenyl ether, or styrene groups. L is an alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy which may be halogenated and have F, Cl, CN or 1 to 5 C atoms, respectively, and is the same or different in each appearance. r is 0, 1, 2, 3, or 4. x and y are each independent integers, either 0 or identical or distinct integers between 1 and 12. z is either 0 or 1 independently, except that if an adjacent x or y is 0, then z is 0. R ０ is an alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 15 C atoms, or Y ０ This represents, Y ０ These are F, Cl, CN, NO ２ , OCH ３ , OCN, SCN, SF ５ or a monofluorinated, oligofluorinated, or polyfluorinated alkyl or alkoxy having 1 to 4 C atoms, Z ０ -COO-, -OCO-, -CH ２ CH ２ -, -CF ２ O-, -OCF ２ -, -CH=CH-, -OCO-CH=CH-, -CH=CH-COO-, or single bond, A ０ If multiple instances occur, they are 1,4-phenylene or trans-1,4-cyclohexylene, either independently unsubstituted or substituted with one, two, three, or four L groups. u and v are each independently 0, 1, or 2. w is 0 or 1, and However, the benzene and naphthalene rings may be substituted with one or more identical or different groups L. 【Chemistry 14】 【Chemistry 15】 (In the formula, P ０ If multiple instances occur, they are independently of each other: acrylic, methacrylic, oxetane, epoxy, vinyl, heptadiene, vinyloxy, propenyl ether, or styrene group. L is an alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy which may be halogenated and have F, Cl, CN or 1 to 5 C atoms, respectively, and is the same or different in each appearance. r is 0, 1, 2, 3, or 4. x and y are each independent integers, either 0 or identical or distinct integers between 1 and 12. z is either 0 or 1 independently, except when an adjacent x or y is 0, then z is 0. 【Chemistry 16.1】 (In the formula, each base has the following meanings, independently of each other, identical or different in each instance: 【Chemistry 16.2】 And, P ａ It is a polymerizable group, Sp is a linear or branched alkylene having 1 to 12 carbon atoms, plus one or two non-adjacent CH4 atoms. ２ The group can be replaced with -O-, -CH=CH-, -CO-, -OCO-, or -COO- so that the oxygen atoms are not directly bonded to each other. X １ and X ２ These are independently -O-, -CH=CH-, and -CF ２ O-, -OCF ２ -ien-CH ２ O-, -OCH ２ -, -CO-O-, -O-CO-, -C ２ F ４ -, -CF=CF- or a single bond, R ａ～ｄ Each of these independently represents a linear or branched alkyl group having 1 to 20 carbon atoms. R １ and R ２ These are H and CH, respectively, independently. ３ OH, OR ａ or O ● Represents, and n represents an integer between 1 and 8. 【Chemistry 17】 (In the formula, Z represents -COO-, r is 0, P-Sp- is P-Sp'-X'-, -X'-Sp'- is -(CH ２ ) ｐ１ -, -O-(CH ２ ) ｐ１ -, -OCO-(CH ２ ) ｐ１ - or -OCOO- (CH ２ ) ｐ１ - and in the formula, p1 is an integer from 1 to 12. P is either an acrylate or a methacrylate. R is a substituted alkyl, alkenyl, alkynyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, or alkoxycarbonyloxy having 1 to 18 carbon atoms. 【Chemistry 18.1】 (In the formula, P ａ (This is a polymerizable group.) 【Chemistry 18.2】 (In the formula, n1 is an integer from 2 to 12, where the base (CH) ２ ) ｎ１ One or more H atoms in the middle may be replaced with methyl, ethyl, propyl, butyl, pentyl, or hexyl groups, R １１ and R １２ Each of these independently represents a linear or branched alkyl group having 1 to 20 carbon atoms. 【Chemistry 18.3】 (In the formula, n represents an integer between 1 and 8.)

3. The following group of compounds: - As a compound of formula S0, one or more compounds of formula S0-3, or - As the compound of formula S1, one or more compounds selected from formulas S1-1, S1-2, S1-4, or S1-5, - One or more compounds of formula S2-2 as compounds of formula S2. A polymerizable LC material according to claim 1 or 2, comprising one or more compounds selected from the above.

4. The polymerizable LC material according to claim 1 or 2, wherein the compound of formula S0, S1, or S2 is selected from the following compounds. 【Chemistry 19】

5. A polymerizable LC material according to any one of claims 1 to 4, comprising the following triazine UV absorber compound. 【Chemistry 20】

6. The polymerizable LC material according to any one of claims 1 to 5, wherein the total concentration of monoreactive mesogenic compounds and direactive mesogenic compounds in the polymerizable LC material is in the range of 50 to 99.9% by weight.

7. A polymerizable LC material according to any one of claims 1 or 3 to 6, comprising one or more compounds of formula ND25. 【Chemistry 21】 (In the formula, Z represents -COO-, r is 0, P-Sp- is P-Sp'-X'-, -X'-Sp'- is -(CH ２ ) ｐ１ -, -O-(CH ２ ) ｐ１ -, -OCO-(CH ２ ) ｐ１ - or -OCOO- (CH ２ ) ｐ１ - and in the formula, p1 is an integer from 1 to 12. P is either an acrylate or a methacrylate. R is a substituted alkyl, alkenyl, alkynyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, or alkoxycarbonyloxy having 1 to 18 carbon atoms.

8. The polymerizable LC material according to any one of claims 1 to 7, wherein the reactive mesogenic compound is selected from the following compounds. 【Chemistry 22】

9. The polymerizable LC material according to any one of claims 1 to 8, wherein the direactive mesogenic compound is selected from the following compounds. 【Chemistry 23】

10. The polymerizable LC material according to any one of claims 1 to 9, wherein the compound of formula NDa or ND25 is one of the following compounds. 【Chemistry 24】

11. A polymerizable LC material according to any one of claims 1 to 10, which may contain one or more additives selected from the group consisting of surfactants, further stabilizers, catalysts, sensitizers, inhibitors, chain transfer agents, co-reactive monomers, reactive thinners, surfactant compounds, lubricants, wetting agents, dispersants, hydrophobic agents, adhesives, flow improvers, degassing or defoaming agents, defoaming agents, diluents, reactive diluents, auxiliary agents, colorants, dyes, pigments, and nanoparticles.

12. A method for preparing a polymerizable LC material according to any one of claims 1 to 11, A method comprising the step of mixing one or more compounds of formula S0, S1, or S2 with one or more monoreactive and direactive mesogenic compounds.

13. - A layer of polymerizable LC material according to any one of claims 1 to 11 is provided on a substrate, - Photopolymerize polymerizable LC material, and - The polymerized LC material is optionally removed from the substrate and / or optionally provided onto another substrate. A method for preparing a polymer film.

14. A method for preparing a polymer film according to claim 13, characterized in that the LC material is uniformly oriented.

15. Use of the polymerizable LC material according to any one of claims 1 to 11 in optical, electro-optical, information storage, decorative and security applications, liquid crystal displays, 3D displays, projection systems, polarizers, compensators, alignment layers, circular polarizers, color filters, decorative images, liquid crystal pigments, reflective films having spatially varying reflective colors, multicolor images, identification cards or credit cards, banknotes or non-counterfeitable documents.

16. Optical components or devices comprising the polymerizable LC material according to any one of claims 1 to 11, polarizers, patterned retarders, compensators, alignment layers, circular polarizers, color filters, decorative images, liquid crystal lenses, liquid crystal pigments, reflective films having spatially varying reflective colors, and multicolor images for decoration or information storage.

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