Method for preparing liquid crystal polymer film

Abstract

The present invention relates to a method for preparing a planar-aligned liquid crystal polymer film, a polymer film obtainable by the corresponding manufacturing method, and the use of the polymer film in optical components and optoelectronic decoration, as well as components and devices containing the polymer film.

Description

Field of the Invention

[0001] The present invention relates to a method for preparing a planar-aligned liquid crystal polymer film, a polymer film obtainable by a corresponding manufacturing method, and the use of the polymer film in optical components and optoelectronic decoration, as well as components and devices comprising the polymer film.

[0002] Background and prior art

[0003] Polymerizable liquid crystal materials or reactive mesogens (RMs) are known in the art for preparing anisotropic polymer films with uniform orientation. Such films are typically prepared by coating a thin layer of a polymerizable liquid crystal mixture onto a substrate, aligning the mixture to 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 (at right angles or perpendicular to the layer) or tilted.

[0004] Such optical films are described, for example, in EP 0 940 707 B1, EP 0 888 565 B1 and GB 2 329 393 B1.

[0005] Current RM coatings require an alignment layer, either a rubbed polyimide (PI) or a photo-alignment layer. Without this alignment layer, the RM monomers have no priority to orient themselves. This results in random alignment of the RM monomers and random alignment of the polymer upon curing.

[0006] Standard techniques for imparting planar alignment to reactive mesogenic molecules have disadvantages associated with them. The mechanical rubbing process used for rubbed PI alignment can introduce some static charge and debris on the RM coating, which can have a detrimental effect on the alignment.

[0007] Recently, photoalignment methods have been invented which are non-contact methods, however this adds another coating step to the manufacturing process which is undesirable from a cost point of view. For example, NA Clark et al., Langmuir 2010, 26 (22), 17482-17488 have shown that it is possible to self-assemble compounds having the structure

[0008]

[0009] to a substrate to produce a single layer that can be photo-aligned to induce planar alignment of the liquid crystal.

[0010] It has also been shown that liquid crystal systems can self-align in situ, as disclosed in EP 3 390 570 A1, whereas this is never the case for reactive mesogenic films.

[0011] For non-reactive liquid crystals, additives containing photoalignment groups and photopolymerizable groups are used. In this method, the LC cell is irradiated with polarized UV light while in the isotropic phase. Then when cooled into the nematic phase, the LC adopts the alignment given by the now reacted self-alignment additive. This is difficult for RM films, since most of the components in the formulation are photopolymerizable, such as the self-alignment additive. If the RM film is irradiated with UV light, the film will simply polymerize with the random alignment it had when coated, so the self-alignment additive that works for the LC cannot work in the RM film.

[0012] There is therefore still a need for new and preferably improved methods of producing planar aligned liquid crystal polymer films or polymer films themselves: polymer films which do not exhibit the disadvantages of prior art methods or films or, if they do, exhibit them only to a lesser extent.

[0013] Advantageously, the method should preferably be suitable for preparing a surface-aligned polymer film, which should be produced by a compatible, cost-effective and generally known method for mass production, and the resulting polymer film should preferably simultaneously exhibit favorable adhesion to the substrate, high transparency to VIS light, lower dark state transmittance, favorable high temperature stability or durability, and additionally uniform alignment.

[0014] Those skilled in the art will immediately understand other objects of the present invention from the following detailed description.

[0015] Surprisingly, the inventors of the present invention have found that by a method for producing a planar aligned liquid crystal polymer film according to claim 1 , one or more, preferably all of the above-mentioned desired objects can be achieved, preferably simultaneously. SUMMARY OF THE INVENTION

[0017] Therefore, the present invention relates to a method for producing a planar aligned polymer film, which comprises at least the following steps:

[0018] - providing a polymerizable liquid crystal mixture on a substrate, wherein the polymerizable liquid crystal mixture comprises one or more polymerizable liquid crystal molecules and one or more self-assembling photoalignment agents;

[0019] - irradiating the liquid crystal mixture with linearly polarized light, thereby causing photoalignment of the polymerizable liquid crystal mixture;

[0020] - optionally curing the polymerisable liquid crystal compound by irradiation with ultraviolet light.

[0021] The present invention further relates to a polymer film obtainable, preferably obtainable, by a process as described above and below.

[0022] The present invention further relates to the use of a polymer film as described above and below in an optical component comprising the polymer film of the invention, and to the use of the optical component in an optical device.

[0023] Finally, the invention relates to optical devices comprising the polymer films or optical components according to the invention.

[0024] Terms and Definitions

[0025] As used herein, the term "polymer" will be understood to refer to a molecule comprising a backbone of one or more different types of repeating units (the smallest building blocks of a molecule), and includes the well-known terms "oligomer", "copolymer", "homopolymer", etc. In addition, it should be understood that the term polymer includes, in addition to the polymer itself, residues from initiators, catalysts, and other elements accompanying the synthesis of such polymers, wherein such residues are understood not to be covalently incorporated therein. In addition, such residues and other elements, although generally removed during post-polymerization purification, are generally mixed or blended with the polymer so that they are generally retained in the polymer when the polymer is transferred between containers or between solvents or dispersion media.

[0026] The term "(meth)acrylic polymer" as used in the present invention includes polymers obtainable from acrylic monomers, polymers obtainable from methacrylic monomers, and corresponding copolymers obtainable from mixtures of such monomers.

[0027] The term "polymerization" refers to a chemical process of forming a polymer by bonding together a plurality of polymerizable groups or polymer precursors (polymerizable compounds) containing such polymerizable groups.

[0028] The term "film" or "layer" includes rigid or flexible, self-supporting or free-standing films having mechanical stability, as well as coatings or layers on a supporting substrate or between two substrates.

[0029] The term "liquid crystal" or (LC) refers to materials which have a liquid crystal mesophase within some temperature range (thermotropic LC) or within some concentration range in solution (lyotropic LC). They necessarily contain mesogenic compounds.

[0030] The terms "mesogenic compounds" and "liquid crystal compounds" refer to compounds containing one or more rod-shaped (rod or plate / slat-shaped) or disc-shaped (disk-shaped) mesogenic groups. The term "mesogenic group" refers to a group having the ability to induce liquid crystal phase (or mesophase) behavior. Compounds containing mesogenic groups do not necessarily have to exhibit liquid crystal mesophases themselves. They can also exhibit liquid crystal mesophases only in mixtures with other compounds, or when the mesogenic compound or material or a mixture thereof is polymerized. This liquid crystal mesophase includes low molecular weight non-reactive liquid crystal compounds, reactive or polymerizable liquid crystal compounds and liquid crystal polymers.

[0031] The rod-like mesogenic group generally comprises a mesogenic core composed of one or more aromatic or non-aromatic cyclic groups connected to each other directly or via a connecting group, optionally comprising an end group attached to the end of the mesogenic core, and optionally comprising one or more side groups attached to the long side of the mesogenic core, wherein these end groups and side groups are generally selected from, for example, carbon groups (carbyl) or hydrocarbon groups, polar groups (such as halogen, nitro, hydroxyl, etc.) or polymerizable groups.

[0032] The term "reactive mesogen" refers to polymerizable mesogenic or liquid crystal compounds, preferably monomeric compounds. These compounds can be used as pure compounds or as mixtures of reactive mesogens with other compounds acting as photoinitiators, inhibitors, surfactants, stabilizers, chain transfer agents, non-polymerizable compounds, etc.

[0033] Polymerizable compounds having one polymerizable group are also referred to as "monoreactive" compounds, compounds having two polymerizable groups are also referred to as "direactive" compounds, and compounds having more than two polymerizable groups are also referred to as "polyreactive" compounds. Compounds that do not contain polymerizable groups are also referred to as "non-reactive or non-polymerizable" compounds.

[0034] Photoreactive groups according to the invention are functional groups of molecules which cause a change in the molecular geometry by bond rotation, skeletal rearrangement or atom or group transfer, or by dimerization upon irradiation with light of a suitable wavelength which can be absorbed by the molecule.

[0035] The photoreactive mesogen according to the present invention is a mesogenic compound comprising one or more photoreactive groups.

[0036] Examples of photoreactive groups are -C=C- double bonds and azo groups (-N=N-).

[0037] Examples of molecular structures and substructures comprising such photoreactive groups are stilbene, (1,2-difluoro-2-phenyl-vinyl)-benzene, cinnamate, 4-phenylbut-3-en-2-one, chalcone, coumarin, chromone, pentalenone and azobenzene.

[0038] The term "polymerizable liquid crystal mixture" means a material comprising more than 90 wt%, preferably more than 95 wt%, more preferably more than 98 wt% of polymerizable liquid crystal molecular compounds as described above and below.

[0039] The term "non-mesogenic compound or material" refers to a compound or material that does not contain a mesogenic group as defined above.

[0040] Visible light is electromagnetic radiation having a wavelength in the range of about 400 nm to about 740 nm. Ultraviolet (UV) light is electromagnetic radiation having a wavelength in the range of about 200 nm to about 450 nm.

[0041] According to the present application, the term "linearly polarized light" refers to light that is at least partially linearly polarized. Preferably, the aligning light is linearly polarized with a degree of polarization greater than 5:1. The wavelength, intensity and energy of the linearly polarized light are selected depending on the photosensitivity of the photo-alignable substance. Typically, the wavelength is in the UV-A, UV-B and / or UV-C range or in the visible light range. Preferably, the linearly polarized light comprises light with a wavelength of less than 450 nm, more preferably less than 420 nm, while the linearly polarized light preferably comprises light with a wavelength longer than 280 nm, preferably greater than 320 nm, more preferably more than 350 nm.

[0042] Irradiance (E e ) or radiant power is defined as the power of electromagnetic radiation (dθ) per unit area (dA) incident on a surface:

[0043] E e =dθ / dA.

[0044] Radiation exposure or radiation dose (H e ) is the irradiance or radiation power (E) at each time (t) e ):

[0045] H e =E e ·t.

[0046] All temperatures, such as the melting point of the liquid crystal T(C,N) or T(C,S), the transition from the smectic (S) to the nematic (N) phase T(S,N) and the clearing point T(N,I) are given in degrees Celsius. All temperature differences are given in degrees.

[0047] The term "clearing point" refers to the temperature at which the transition between the intermediate phase with the highest temperature range and the isotropic phase occurs.

[0048] The term "director" is known in the prior art and refers to the preferred orientation direction of the long molecular axis (in the case of rod-shaped compounds) or the short molecular axis (in the case of discotic compounds) of the liquid crystal or RM molecules. In the case of uniaxial ordering of such anisotropic molecules, the director is the anisotropy axis.

[0049] The term "alignment" or "orientation" relates to the alignment (orientational ordering) of anisotropic units of a material (e.g., small molecules or fragments of macromolecules) along a consistent direction (called the "alignment direction"). In a liquid crystal material or an alignment layer of RM material, the liquid crystal director is aligned with the alignment direction so that the alignment direction corresponds to the direction of the anisotropic axis of the material.

[0050] The term "homogeneous orientation" or "homogeneous alignment" of a liquid crystal or RM material, for example in a layer of the material, means that the long molecular axes (in the case of rod-shaped compounds) or the short molecular axes (in the case of discotic compounds) of the liquid crystal or RM molecules are oriented substantially in the same direction. In other words, the lines of the liquid crystal directors are parallel.

[0051] The terms "homeotropic structure" or "homeotropic orientation" refer to films in which the optical axis is substantially perpendicular to the plane of the film.

[0052] The terms "planar structure" or "planar orientation" or "aligned along the surface" refer to films in which the optical axis is substantially parallel to the plane of the film.

[0053] The term "negative (optical) dispersion" refers to a birefringent or liquid crystal material or layer that exhibits reverse birefringence dispersion, wherein the magnitude of the birefringence (Δn) increases with increasing wavelength (λ), i.e., |Δn(450)|<|Δn(550)|, or Δn(450) / Δn(550)<1, wherein Δn(450) and Δn(550) are the birefringence of the material measured at wavelengths of 450 nm and 550 nm, respectively. Conversely, "positive (optical) dispersion" refers to a material or layer having |Δn(450)|>|Δn(550)|, or Δn(450) / Δn(550)>1. See also, e.g., A. Uchiyama, 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).

[0054] Since the optical retardation at a given wavelength is defined as the product of the birefringence and the layer thickness as described above [R(λ)=Δn(λ)·d], the optical dispersion can be expressed as "birefringence dispersion" by the ratio Δn(450) / Δn(550), or as "retardation dispersion" by 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 material or layer with negative or reverse dispersion has R(450) / R(550)<1 or |R(450)|<|R(550)|, and a material or layer with positive or normal dispersion has R(450) / R(550)>1 or |R(450)|>|R(550)|.

[0055] In the present invention, unless otherwise specified, "optical dispersion" refers to retardation dispersion, that is, the ratio R(450) / R(550).

[0056] The term "high dispersion" means that the absolute value of the dispersion shows a large deviation from 1, while the term "low dispersion" means that the absolute value of the dispersion shows a small deviation from 1. Thus, "high negative dispersion" means that the dispersion value is significantly less than 1, and "low negative dispersion" means that the dispersion value is only slightly less than 1.

[0057] The retardation (R(λ)) of a material can be measured using a spectroscopic ellipsometer, such as the M2000 spectroscopic ellipsometer from JA Woollam. This instrument is capable of measuring the optical retardation in nanometers of birefringent materials (such as quartz) typically in the wavelength range of 370nm to 2000nm. The dispersion (R(450) / R(550) or Δn(450) / Δn(550)) of the material can be calculated from this data.

[0058] The method for making these measurements was proposed by N. Singh at the National Physical Laboratory (London, UK) in October 2006 and is entitled "Spectroscopic Ellipsometry, Part 1 - Theory and Fundamentals, Part 2 - Practical Examples and Part 3 - measurements". The test procedures are described in the Retardation Measurement (RetMeas) Manual (2002) and the WVASE (Woollam Variable Angle Spectroscopic Ellipsometer) Guide (2002) published by JA Woollam Company (Lincoln, Nebraska, USA). Unless otherwise stated, this method is used to determine the retardation of the materials, films and devices described in this invention.

[0059] The term "A-plate" refers to an optical retarder that utilizes a layer of uniaxial birefringent material with its extraordinary axis oriented parallel to the plane of the layer.

[0060] The term "C-plate" refers to an optical retarder that utilizes a layer of uniaxial birefringent material with its extraordinary axis oriented perpendicular to the plane of the layer.

[0061] In an A / C-plate comprising an optically uniaxial birefringent liquid crystal material having a uniform orientation, the optical axis of the film is given by the direction of the extraordinary axis. An A (or C) plate comprising an optically uniaxial birefringent material having a positive birefringence is also referred to as a "positive A (or C) plate" or "+A (or +C) plate".

[0062] A (or C) plates comprising films of optically uniaxial birefringent materials having negative birefringence, such as discotic anisotropic materials, are also referred to as "negative A (or C) plates" or "-A (or C) plates", depending on the orientation of the discotic material. Films made of cholesteric rod-shaped materials having a reflection band in the UV portion of the spectrum also have the optics of a negative C plate.

[0063] The birefringence Δn is defined as follows

[0064] Δn=n e -n o

[0065] Where n e is the extraordinary refractive index and n o is the ordinary refractive index, and the mean refractive index n av . is given by the following equation:

[0066] n av. =((2n o 2 +n e2 ) / 3) 1 / 2

[0067] Average refractive index n av . and ordinary refractive index n o This can be measured using an Abbe refractometer. Δn can then be calculated from the above equation.

[0068] Unless the context clearly indicates otherwise, as used herein, plural forms of the terms are to be understood as including the singular form and vice versa.

[0069] Unless explicitly stated otherwise, all physical properties have been measured according to or according to “Merck Liquid Crystals, Physical Properties of Liquid Crystals” Status November 1997, Merck KGaA, Germany, and are given for a temperature of 20° C. The optical anisotropy (Δn) is measured at a wavelength of 589.3 nm.

[0070] In case of doubt, the definitions as given in C. Tschierske, G. Pelzl and S. Diele, Angew. Chem. 2004, 116, 6340-6368 shall apply.

[0071] Unless otherwise indicated, in the given formulae, the following terms have the following meanings:

[0072] The term "organic group" means a carbon or hydrocarbon group.

[0073] The term "carbonyl" refers to a monovalent or polyvalent organic group containing at least one carbon atom, wherein it does not contain other atoms (such as, -C≡C-) or optionally contains one or more other atoms, such as N, O, S, P, Si, Se, As, Te or Ge (e.g., carbonyl, etc.). The term "hydrocarbyl" refers to a carbon group that additionally contains one or more H atoms and optionally one or more heteroatoms (such as, N, O, S, P, Si, Se, As, Te or Ge).

[0074] "Halogen" indicates F, Cl, Br or I.

[0075] The carbon or hydrocarbon group may be a saturated or unsaturated group. An unsaturated group is, for example, an aryl, an alkenyl or an alkynyl group. The carbon or hydrocarbon group having 3 or more atoms may be straight chain, branched and / or cyclic and may also contain a spiro bond or a condensed ring.

[0076] The terms "alkyl," "aryl," "heteroaryl," and the like also encompass multivalent groups such as alkylene, arylene, heteroarylene, and the like.

[0077] The term "aryl" refers to an aromatic carbon group or a group derived therefrom. The term "heteroaryl" refers to an "aryl" as defined above containing one or more heteroatoms.

[0078] Preferred carbyl and hydrocarbyl groups are optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy and alkoxycarbonyloxy groups having 1 to 40, preferably 1 to 25, particularly preferably 1 to 18 C atoms; optionally substituted aryl or aryloxy groups having 6 to 40, preferably 6 to 25 C atoms; or optionally substituted alkaryl, aralkyl, alkylaryloxy, arylalkoxy, arylcarbonyl, aryloxycarbonyl, arylcarbonyloxy and aryloxycarbonyloxy groups having 6 to 40, preferably 6 to 25 C atoms.

[0079] Further preferred carbon and hydrocarbon groups are C1-C 40 Alkyl, C2-C 40 Alkenyl, C2-C 40 Alkynyl, C3-C 40 Allyl, C4-C 40 Alkyldiene, C4-C 40 Polyene, C6-C 40 Aryl, C6-C 40 Alkyl aryl, C6-C 40 Arylalkyl, C6-C 40 Alkyl aryloxy, C6-C 40 Arylalkoxy, C2-C 40 Heteroaryl, C4-C 40 Cycloalkyl, C4-C 40 Particularly preferred is C1-C 22 Alkyl, C2-C 22 Alkenyl, C2-C 22 Alkynyl, C3-C 22 Allyl, C4-C 22 Alkyldiene, C6-C 12 Aryl, C6-C 20 Aralkyl and C2-C 20 Heteroaryl.

[0080] Other preferred carbon and hydrocarbon radicals are straight-chain, branched or cyclic alkyl radicals having 1 to 40, preferably 1 to 25, C atoms, which are unsubstituted or mono- or polysubstituted by F, Cl, Br, I or CN, and in which one or more non-adjacent CH2 groups may each be independently of one another by -C(R) in such a way that the O and / or S atoms are not directly connected to one another. z )=C(R z )-、-C≡C-、-N(R z)-, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- substitution.

[0081] R z Preferably represents H, halogen, a straight-chain, branched or cycloalkyl chain having 1 to 25 C atoms, in which, in addition, one or more non-adjacent C atoms may be replaced by -O-, -S-, -CO-, -CO-O-, -O-CO- or -O-CO-O-, and in which one or more H atoms may be replaced by fluorine, an optionally substituted aryl or aryloxy group having 6 to 40 C atoms, or an optionally substituted heteroaryl or heteroaryloxy group having 2 to 40 C atoms.

[0082] Preferred alkyl groups are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, trifluoromethyl, perfluoro-n-butyl, 2,2,2-trifluoroethyl, perfluorooctyl and perfluorohexyl.

[0083] Preferred alkenyl groups are, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl and cyclooctenyl.

[0084] Preferred alkynyl groups are, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl and octynyl.

[0085] Preferred alkoxy groups are, for example, methoxy, ethoxy, 2-methoxyethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, 2-methylbutoxy, n-pentoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy and n-dodecyloxy.

[0086] Preferred amino groups are, for example, dimethylamino, methylamino, methylphenylamino and phenylamino.

[0087] Aryl and heteroaryl groups may be monocyclic or polycyclic, i.e. they may contain one ring (e.g. phenyl) or two or more rings, which may also be fused (e.g. naphthyl) or covalently bonded (e.g. biphenyl), or comprise a combination of fused and linked rings. Heteroaryl groups contain one or more heteroatoms, preferably selected from O, N, S and Se. Ring systems of this type may also contain independent non-conjugated units, as is the case, for example, in the fluorene basic structure.

[0088] Particularly preferred are mono-, bi- or tricyclic aryl radicals having 6 to 25 C atoms and mono-, bi- or tricyclic heteroaryl radicals having 2 to 25 C atoms, which optionally contain fused rings and are optionally substituted. Further preferred are 5-, 6- or 7-membered aryl and heteroaryl radicals, in which, in addition, one or more CH groups may be replaced by N, S or O in such a way that the O atoms and / or S atoms are not directly connected to one another.

[0089] Preferably, the aryl group is derived from, for example, the following parent structure: benzene, biphenyl, terphenyl, [1,1':3',1"]terphenyl, naphthalene, anthracene, binaphthyl, phenanthrene, pyrene, dihydropyrene, , perylene, tetracene, pentacene, benzopyrene, fluorene, indene, indenofluorene, spirobifluorene, etc.

[0090] 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-oxadiazole, 4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, a 6-membered ring such as pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine or a fused group such as indole, isoindole, indolizine, indazole, benzimidazole, benzoimidazole, triazole, purine, naphthimidazole, phenanthimidazole, pyridimidazole, pyrazimidazole, quinoxalinimidazole, benzoxazole, naphthimidazole, anthraxidazole, phenanthimidazole, isoxazole, benzothiazole, benzofuran, isobenzofuran, dibenzofuran, quinoline, isoquinoline, pteridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, benzisoquinoline, acridine, phenothiazine The heteroaryl group may also be substituted by an alkyl, alkoxy, sulfanyl, fluorine, fluorine, or other aryl or heteroaryl group.

[0091] (Non-aromatic) alicyclic and heterocyclic groups include both saturated rings, i.e. rings containing only single bonds, and partially unsaturated rings, i.e. those which may also contain multiple bonds. The heterocyclic ring contains one or more heteroatoms, preferably selected from Si, O, N, S and Se.

[0092] (Non-aromatic) alicyclic groups and heterocyclic groups can be monocyclic, i.e. contain only one ring (e.g. cyclohexane), or polycyclic, i.e. contain multiple rings (e.g. decalin or bicyclooctane). Saturated groups are particularly preferred. In addition, mono-, bi- or tricyclic groups with 3-25 C atoms are preferred, which optionally contain fused rings and are optionally substituted. Further preferred are 5-, 6-, 7- or 8-membered carbocyclic groups, wherein in addition, one or more C atoms may be substituted by Si and / or one or more CH groups may be substituted by N and / or one or more non-adjacent CH2 groups may be substituted by-O- and / or-S-.

[0093] Preferred alicyclic and heterocyclic groups are, for example, 5-membered groups, such as cyclopentane, tetrahydrofuran, tetrahydrothiophene, pyrrolidine; 6-membered groups, such as cyclohexane, silinane, cyclohexene, tetrahydropyran, tetrahydrothiopyran, 1,3-dioxane, 1,3-dithiane, piperidine; 7-membered groups, such as cycloheptane; and condensed groups, such as tetralin, decalin, indane, bicyclo[1.1.1]pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl, spiro[3.3]heptane-2,6-diyl, octahydro-4,7-methanoindan-2,5-diyl.

[0094] The aryl, heteroaryl, carbonyl and hydrocarbon groups optionally have one or more substituents, which are preferably selected from the group comprising silyl, sulfonic acid, sulfonyl, formyl, amine, imine, nitrile, mercapto, nitro, halogen, C 1-12 Alkyl, C 6-12 Aryl, C 1-12 Alkoxy, hydroxy or a combination of these groups.

[0095] Preferred substituents are, for example, groups promoting solubility, such as alkyl or alkoxy groups, and electron withdrawing groups, such as fluoro, nitro or nitrile.

[0096] Unless otherwise indicated, preferred substituents (also referred to as "L" above and below) are F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)N(R z )2, -C(=O)Y 1 、C(=O)R z 、-N(R z )2, where R z has the meaning indicated above, and Y 1represents halogen, optionally substituted silyl or aryl having 6 to 40, preferably 6 to 20 C atoms, and straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 25 C atoms, preferably 2 to 12 C atoms, where one or more H atoms may optionally be replaced by F or Cl.

[0097] "Substituted silyl or aryl" preferably refers to substituted silyl or aryl groups. y1 、-OR y1 、-CO-R y1 、-CO-OR y1 、-O-CO-R y1 OR-O-CO-OR y1 Substitution, where R y1 has the meaning indicated above.

[0098] Particularly preferred substituents L are, for example, F, Cl, CN, CH3, C2H5, -CH(CH3)2, OCH3, OC2H5, CF3, OCF3, OCHF2, OC2F5, and phenyl.

[0099] Above and below, "halogen" means F, Cl, Br or I.

[0100] Above and below, the terms "alkyl", "aryl", "heteroaryl" etc. also encompass polyvalent groups such as alkylene, arylene, heteroarylene etc.

[0101] In the formulae shown above and below, the substituted phenylene ring

[0102] Preferably or

[0103] in which L has, identically or differently on each occurrence, one of the meanings given above and below and is preferably F, Cl, CN, NO2, CH3, C2H5, C(CH3)3, CH(CH3)2, CH2CH(CH3)C2H5, OCH3, OC2H5, COCH3, COC2H5, COOCH3, COOC2H5, CF3, OCF3, OCHF2, OC2F5 or P-Sp-, very preferably F, Cl, CN, CH3, C2H5, OCH3, COCH3, OCF3 or P-Sp- and most preferably F, Cl, CH3, OCH3, COCH3 or OCF3.

[0104] "Halogen" means F, Cl, Br or I, preferably F or Cl, more preferably F.

[0105] The "polymerizable group" (P) is preferably selected from groups comprising a C=C double bond or a C≡C triple bond, and groups suitable for ring-opening polymerization, such as, for example, oxetanyl or epoxy groups.

[0106] Preferably, the polymerizable group (P) is selected from CH2=CW 1 -COO-, CH2=CW 1 -CO-, CH2=CW 2 -(O) k3 -、CW 1 =CH-CO-(O) k3 -、CW 1 =CH-CO-NH-, CH2=CW 1 -CO-NH-, CH3-CH=CH-O-, (CH2=CH)2CH-OCO-, (CH2=CH-CH2)2CH-OCO-, (CH2=CH)2CH-O-, (CH2=CH-CH2)2N-, (CH2=CH-CH2)2N-CO-, CH2=CW 1 -CO-NH-, CH2=CH-(COO) k1 -Phe-(O) k2 -、CH2=CH-(CO) k1 -Phe-(O) k2 -, Phe-CH=CH-,

[0107] in

[0108] W 1 represents H, F, Cl, CN, CF3, phenyl or alkyl having 1 to 5 C atoms, in particular H, F, Cl or CH3,

[0109] W 2 represents H or alkyl having 1 to 5 C atoms, in particular H, methyl, ethyl or n-propyl,

[0110] W 3 and W 4 each independently of one another represents H, Cl or an alkyl radical having 1 to 5 C atoms, Phe represents 1,4-phenylene, which is optionally substituted by one or more radicals L as defined above but different from P-Sp, preferably, preferred substituents L are F, Cl, CN, NO2, CH3, C2H5, OCH3, OC2H5, COCH3, COC2H5, COOCH3, COOC2H5, CF3, OCF3, OCHF2, OC2F5, and also phenyl, and

[0111] k1, k2 and k3 each independently represent 0 or 1, k3 preferably represents 1, and k4 is an integer of 1 to 10.

[0112] 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- and Where W 2 represents H or alkyl having 1 to 5 C atoms, in particular H, methyl, ethyl or n-propyl.

[0113] Further preferred polymerizable groups (P) are vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane and epoxy groups, most preferably acrylate or methacrylate, especially acrylate.

[0114] Preferably, all polyreactive polymerizable compounds and subformulae thereof comprise one or more branching groups (polyreactive polymerizable groups) comprising two or more polymerizable groups P instead of one or more groups P-Sp-.

[0115] Suitable groups of this type and polymerizable compounds comprising them are described, for example, in US Pat. No. 7,060,200 B1 or US 2006 / 0172090 A1.

[0116] Particularly preferred are multi-reactive polymerizable groups selected from the following formulae:

[0117] -X-alkyl-CHP x -CH2-CH2P y I*a

[0118] -X-alkyl-C(CH2P x )(CH2P y )-CH2P z I*b

[0119] -X-alkyl-CHP x CHP y -CH2P z I*c

[0120] -X-alkyl-C(CH2P x )(CH2P y )-C aa H 2aa+1 I*d

[0121] -X-alkyl-CHP x -CH2P y I*e

[0122] -X-alkyl-CHP x P y I*f

[0123] -X-alkyl-CP x P y -C aa H 2aa+1 I*g

[0124] -X-alkyl-C(CH2P v )(CH2P w )-CH2OCH2-C(CH2P x )(CH2Py)CH2P z I*h

[0125] -X-alkyl-CH((CH2) aa P x )((CH2) bb P y ) I*i

[0126] -X-alkyl-CHP x CHP y -C aa H 2aa+1 I*k

[0127] in

[0128] Alkyl represents a single bond or a straight-chain or branched alkylene radical having 1 to 12 C atoms, wherein one or more non-adjacent CH2 groups may each be independently replaced by -C(R x )=C(R x )-、-C≡C-、-N(R x )-, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, in such a way that the O and / or S atoms are not directly connected to each other, and further wherein one or more H atoms may be replaced by F, Cl or CN, wherein R x has one of the meanings mentioned above,

[0129] aa and bb each independently represents 0, 1, 2, 3, 4, 5 or 6,

[0130] X has one of the meanings indicated for X', and

[0131] P v To P z Each independently of the others has one of the meanings indicated above for P.

[0132] Preferred spacer groups Sp are selected from the formula Sp'-X', such that the group "P-Sp-" conforms to the formula "P-Sp'-X'-", wherein

[0133] Sp' denotes an alkylene radical having 1 to 20, preferably 1 to 12 C atoms, which is optionally mono- or poly-substituted by F, Cl, Br, I or CN, and wherein, moreover, one or more non-adjacent CH2 groups may each independently of one another be substituted by -O-, -S-, -NH-, -NR xx -、-SiR xx R yy -, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO-, -CO-S-, -NR xx -CO-O-, -O-CO-NR 0xx -、-NR xx -CO-NR yy -, -CH=CH- or -C≡C- are replaced in such a way that O and / or S atoms are not directly connected to each other,

[0134] X' represents -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR xx -、-NR xx -CO-, -NR xx -CO-NR yy -, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CF2CH2-, -CH2CF2-, -CF2CF2-, -CH=N-, -N=CH-, -N=N-, -CH=CR xx -、-CY xx =CY xx -, -C≡C-, -CH=CH-COO-, -OCO-CH=CH- or a single bond,

[0135] R xx and R yy each independently of one another represents H or an alkyl group having 1 to 12 C atoms, and

[0136] Y xx and Y yy Each independently of one another represents H, F, Cl or CN.

[0137] X' is preferably -O-, -S--CO-, -COO-, -OCO-, -O-COO-, -CO-NR xx -、-NR xx -CO-, -NR xx -CO-NR yy- or single key.

[0138] 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 -, wherein p1 is an integer from 1 to 12, q1 is an integer from 1 to 3, and R xx and R yy has the meaning given above.

[0139] A particularly preferred group -X'-Sp'- is -(CH2) p1 -、-O-(CH2) p1 -、-OCO-(CH2) p1 -、-OCOO-(CH2) p1 -, wherein p1 is an integer from 1 to 12.

[0140] Particularly preferred radicals Sp′ are, for example, in each case straight-chain methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylenethioethylene, ethylene-N-methyliminoethylene, 1-methylalkylene, vinylene, propenylene and butenylene.

[0141] For the present invention,

[0142] and

[0143] represents 1,4-cyclohexylene, preferably trans-1,4-cyclohexylene, and

[0144] and

[0145] It represents 1,4-phenylene.

[0146] For the present invention, the group -CO-O-, -COO-, -C(=O)O- or -CO2- is represented by Ester groups, and groups -O-CO-, -OCO-, -OC(=O)-, -O2C- or -OOC- of ester groups.

[0147] A "polymer network" is a network in which all polymer chains are interconnected by numerous crosslinking points to form a single macroscopic entity. Polymer networks can occur in the following types:

[0148] - Grafted polymer molecules are branched polymer molecules in which one or more side chains differ in structure or configuration from the main chain.

[0149] -A star polymer molecule is a branched polymer molecule in which a single branch point gives rise to multiple linear chains or arms. If the arms are identical, the star polymer molecule is called regular. If adjacent arms are composed of different repeating subunits, the star polymer molecule is called diversified.

[0150] - Comb polymer molecules consist of a main chain with two or more three-way branching points and linear side chains. If the arms are identical, the comb polymer molecule is called regular.

[0151] - The brush polymer molecules consist of a backbone with linear, unbranched side chains and in which one or more of the branching points have a four-way functionality or greater.

[0152] Throughout the description and claims of this specification, the words "include" and "contain" and variations of the words (such as "comprising" and "comprises") mean "including but not limited to", and are not intended to (and do not) exclude other components. On the other hand, the word "comprising" also encompasses but is not limited to the term "consisting of..."

[0153] Throughout the description and claims of this specification, the wording "obtainable" and "obtained" and variations of the wording mean "including but not limited to", and are not intended to (and do not) exclude other components. On the other hand, the wording "obtainable" also encompasses but is not limited to the term "obtained".

[0154] All concentrations are quoted in percent by weight and relate to the respective mixture as a whole, all temperatures are quoted in degrees Celsius and all temperature differences are quoted in differential degrees.

[0155] Detailed description

[0156] As already mentioned, the present invention relates to a method for producing a planar aligned polymer film, comprising at least the following steps:

[0157] - providing a polymerizable liquid crystal mixture on a substrate, wherein the polymerizable liquid crystal mixture comprises one or more polymerizable liquid crystal molecules and one or more self-assembling photoalignment agents;

[0158] - irradiating the liquid crystal mixture with linearly polarized light, thereby causing photoalignment of the polymerizable liquid crystal mixture;

[0159] - optionally curing the polymerisable liquid crystal compound by irradiation with ultraviolet light.

[0160] The self-assembling photoalignment agent (SAPA) of the present invention is preferably a compound comprising at least one polar side group and at least one photoreactive group. Considering the present invention's studies, it seems that the polar side groups interact with the substrate surface, thereby enabling the SAPA to phase separate from the LC mixture after the LC cell is filled. According to this view, the SAPA forms a layer on the substrate that can be photoaligned with linearly polarized UV light. The liquid crystal follows the orientation of the aligned SAPA to give a uniform planar alignment over the entire display.

[0161] The photo-alignment process of the present invention causes SAPA to undergo isomerization upon irradiation with linearly polarized light of appropriate wavelength. Photoisomerization is an angle-dependent process that ultimately results in photoselective SAPA orientation that is preferentially perpendicular to the polarization of the actinic light and has orientational anisotropy that enables LC alignment.

[0162] The wavelength region of the polarized light is preferably selected so as to match the absorption spectrum of SAPA.

[0163] Preferably, the one or more self-assembling agents are selected from compounds of formula S,

[0164]

[0165] in

[0166] L s represents, identically or differently on each occurrence, F, Cl, CN, SCN, SF5 or linear or branched and in each case optionally fluorinated alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having up to 12 C atoms, (Sp s ) r1 -G, Y or (Sp s ) r1 -P s ,

[0167] P s each independently of one another represents a polymerizable group,

[0168] Sp s represents a spacer group identically or differently on each occurrence,

[0169] Y represents (R b )2N- or R c C(O)O-,

[0170] G represents -OH or Si(OR a )3

[0171] R a , R b , R c each identically or differently represents H, a straight-chain or branched alkyl radical having 1 to 6 C atoms,

[0172] r1 represents 0 or 1,

[0173] t1 and t2 each and independently represent 1, 2, 3, 4 or 5, and

[0174] Z s represents a group selected from -N=N-, -CH=CH-, -CH=CH-COO-, -OCO-CH=-CH-, -CO-CH=CH-, -CH=CH-, -CH=CH-CO-, wherein one or more H may be replaced by halogen.

[0175] Preferred self-assembling agents are selected from compounds of formula S which may be reactive, such that L s One or more of which are selected from (Sp s ) r1 -P s or a non-reactive compound of formula S, whereby L s None of them are selected from (Sp s ) r1 -P s A compound of formula S.

[0176] If a reactive self-assembling agent is chosen, it is selected from compounds where the photoreaction occurs at another wavelength than the polymerization.

[0177] Further preferred self-assembling agents are selected from compounds of formula S1

[0178]

[0179] in

[0180] Y represents (R b )2N-、R c C(O)O- or group L s ,

[0181] Sp represents a spacer group,

[0182] G represents -OH or Si(OR a )3

[0183] R a , R b , R c each identically or differently represents a straight-chain or branched alkyl group having 1 to 6 C atoms,

[0184] Ls each identically or differently represents a group as defined for formula S

[0185] t1, t2 means 0, 1, 2, 3 or 4,

[0186] Preferred compounds of formula S1 are selected from compounds of formula S1-1 or S1-2

[0187]

[0188] where the parameters have the meanings defined above and X s It represents O, -C(O)O-, C(O)NH- or a single bond.

[0189] Particularly preferred compounds of formula S-1 are the following compounds S1-1 and S1-2,

[0190]

[0191]

[0192] Wherein the parameters have the meanings defined above and preferably R a Represents methyl or ethyl, R b and R c represents a methyl group and n1 represents an integer of 0 to 10, preferably 1 to 4.

[0193] Preferably, the proportion of SAPA, preferably compounds of the formula S, in the polymerizable liquid crystals in the LC medium is 1 to 15%, very preferably 3 to 12%, in particular 5 to 10%.

[0194] Compounds of the formula S and its subformulae can be prepared analogously to methods known to the person skilled in the art and described in authoritative works of organic chemistry, such as Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Thieme-Verlag, Stuttgart. Some compounds are also commercially available, such as the generally known Methyl Red.

[0195] In a preferred embodiment, the one or more polymerizable liquid crystals or polymerizable liquid crystal molecules are selected from compounds of formula P,

[0196] P a -(Sp a ) s1 -A 2 -(Z 1 -A 1 ) n2 -R a P

[0197] in

[0198] P a each independently of one another represents a polymerizable group,

[0199] Sp a represents a spacer group identically or differently on each occurrence,

[0200] s1 means 0 or 1,

[0201] R a represents F, Cl, CN, SCN, SF5 or linear or branched and in each case optionally fluorinated alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having up to 12 C atoms, or P a -(Sp a ) s1

[0202] A 1 , A 2 Each independently represents a group selected from the following group:

[0203] a) the group consisting of trans-1,4-cyclohexylene, 1,4-cyclohexenylene and 4,4′-bicyclohexylene, in which one or more non-adjacent CH2 groups may be replaced by —O— and / or —S—, and in which one or more H atoms may be replaced by F,

[0204] b) the group consisting of 1,4-phenylene and 1,3-phenylene, in addition one or two CH groups may be replaced by N and in addition one or more H atoms may be replaced by L,

[0205] c) the group consisting of tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, tetrahydrofuran-2,5-diyl, cyclobutane-1,3-diyl, hexahydropyridine-1,4-diyl, thiophene-2,5-diyl and selenophene-2,5-diyl, each of which may also be mono- or polysubstituted by L,

[0206] d) the group consisting of saturated, partially unsaturated or fully unsaturated and optionally substituted polycyclic radicals having 5 to 20 ring C atoms, one or more of which may additionally be replaced by heteroatoms, preferably selected from:

[0207]

[0208]

[0209] In addition, one or more H atoms in the group may be replaced by L, and / or one or more double bonds may be replaced by single bonds, and / or one or more CH groups may be replaced by N,

[0210] n2 represents 0, 1, 2 or 3,

[0211] Z 1 In the case of multiple occurrences, it represents independently of one another -O-, -S-, -CO-, -COO-, -OCO-, -S-CO-, -CO-S-, -O-COO-, -CO-NR 00 -、-NR 00 -CO-, -NR 00 -CO-NR 000 、-NR 00 -CO-O-, -O-CO-NR 00 -, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH2CH2-, -(CH2) n1 , -CF2CH2-, -CH2CF2-, -CF2CF2-, -CH=N-, -N=CH-, -N=N-, -CH=CR 00 -、-CY 1 =CY 2 -, -C≡C-, -CH=CH-COO-, -OCO-CH=CH- or a single bond,

[0212] L is 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 C atoms, straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, wherein one or more H atoms are optionally replaced by F or Cl,

[0213] R 0 , R 00 , R 000 each independently of one another represents H, F or a straight-chain or branched alkyl radical having 1 to 12 C atoms, in which one or more H atoms may additionally be replaced by F,

[0214] Y 1 and Y2 independently of one another represent H, F, Cl or CN,

[0215] n is 1, 2, 3, or 4,

[0216] n1 is an integer from 1 to 10.

[0217] M represents -O-, -S-, -CH2-, -CHY 1 -or-CY 1 Y 2 -,and

[0218] Y 1 and Y 2 Each independently has the above for R 0 One of the meanings indicated may represent Cl or CN.

[0219] Preferred compounds of formula P are selected from compounds which may be mono-reactive, di-reactive or poly-reactive.

[0220] Preferably, the one or more polymerizable liquid crystal molecules are selected from one or more di- or polyreactive mesogenic compounds selected to have the formula DRM

[0221] P 1 -Sp 1 -MG-Sp 2 -P 2 DRM

[0222] in

[0223] P 1 and P 2 independently of one another represent a polymerizable group,

[0224] Sp 1 and Sp 2 are independently a spacer group or a single bond, and

[0225] MG is a rod-shaped mesogenic group, which is preferably selected to have the formula MG

[0226] -(A 11 -Z 11 ) n -A 12 -MG

[0227] in

[0228] A 11 and A 12 In the case of multiple occurrences, independently of one another, represents an aromatic or alicyclic radical, which optionally contains one or more heteroatoms selected from N, O and S and is optionally substituted by L. 11 Single or multiple substitutions,

[0229] L 11 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, wherein one or more H atoms are optionally replaced by F or Cl,

[0230] R 00 and R 000 each independently of one another represents H, F or a straight-chain or branched alkyl radical having 1 to 12 C atoms, in which one or more H atoms may additionally be replaced by F,

[0231] Z 11 In the case of multiple occurrences, it represents independently of one another -O-, -S-, -CO-, -COO-, -OCO-, -S-CO-, -CO-S-, -O-COO-, -CO-NR 00 -、-NR 00 -CO-, -NR 00 -CO-NR 000 、-NR 00 -CO-O-, -O-CO-NR 00 -, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH2CH2-, -(CH2) n1 , -CF2CH2-, -CH2CF2-, -CF2CF2-, -CH=N-, -N=CH-, -N=N-, -CH=CR 00 -、-CY 1 =CY 2 -, -C≡C-, -CH=CH-COO-, -OCO-CH=CH- or a single bond,

[0232] Y 1 and Y 2 independently of one another represent H, F, Cl or CN,

[0233] n is 1, 2, 3 or 4, preferably 1 or 2, most preferably 2,

[0234] n1 is an integer of 1 to 10, and is preferably 1, 2, 3 or 4.

[0235] Preferred group A 11 and A 12 Including but not limited to furan, pyrrole, thiophene, azole, thiazole, thiadiazole, imidazole, phenylene, cyclohexylene, dicyclooctylene, cyclohexenylene, pyridine, pyrimidine, pyrazine, , indane, fluorene, naphthalene, tetrahydronaphthalene, anthracene, phenanthrene and dithienothiophene, all unsubstituted or substituted with 1, 2, 3 or 4 groups L as defined above 11 replace.

[0236] Particularly preferred groups A 11 and A 12 is selected from 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, thiophene-2,5-diyl, naphthalene-2,6-diyl, 1,2,3,4-tetrahydro-naphthalene-2,6-diyl, indane-2,5-diyl, bicyclooctylene or 1,4-cyclohexylene, in which one or two non-adjacent CH2 groups are optionally replaced by O and / or S, wherein these groups are unsubstituted or substituted by 1, 2, 3 or 4 groups L as defined above.

[0237] Particularly preferred groups Z 11 is preferably selected independently of one another at each occurrence from -COO-, -OCO-, -CH2CH2-, -CF2O-, -OCF2-, -C≡C-, -CH=CH-, -OCO-CH=CH-, -CH=CH-COO- or a single bond,

[0238] Very preferably the one or more polymerizable liquid crystal molecules are selected from direactive mesogenic compounds of the formula DRM selected from the following formulae:

[0239]

[0240]

[0241] in

[0242] P 0 is, in the case of multiple occurrences, independently of one another, a polymerizable group, preferably an acryloyl group, a methacryloyl group, an oxetane group, an epoxide group, a vinyl group, a heptadienyl group, a vinyloxy group, an acryl ether group or a styrene group,

[0243] L has the same or different characteristics in each occurrence. 1the meanings given and preferably in case of multiple occurrences independently of one another are selected from F, Cl, CN or optionally halogenated alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 5 C atoms,

[0244] r is 0, 1, 2, 3, or 4,

[0245] x and y are independently 0 or the same or different integers from 1 to 12,

[0246] z is each and independently 0 or 1, wherein z is 0 if the adjacent x or y is 0.

[0247] Particularly preferred are compounds of the formulae DRMa1, DRMa2 and DRMa3, in particular those of the formula DRMa1.

[0248] Preferably, the one or more polymerizable liquid crystal molecules are selected from a monoreactive mesogenic compound, more preferably from a compound of formula MRM,

[0249] P 1 -Sp 1 -MG-R MRM

[0250] Where P 1 、Sp 1 and MG has the meaning given to it in Formula DRM,

[0251] R represents 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, straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12, preferably 1 to 6 C atoms, wherein one or more H atoms are optionally replaced by F or Cl,

[0252] X is halogen, preferably F or Cl, and

[0253] R x and R y are independently H or alkyl having 1 to 12 C atoms.

[0254] Preferred MRM compounds are selected from the following

[0255]

[0256]

[0257]

[0258]

[0259] Where P 0 , L, r, x, y and z are as defined in Formula DRMa-1 to Formula DRMe,

[0260] R 0 is alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having one or more, preferably 1 to 15, C atoms, or represents Y 0 ,

[0261] Y 0 is F, Cl, CN, NO2, OCH3, OCN, SCN, SF5, or a monofluorinated, oligofluorinated or polyfluorinated alkyl or alkoxy radical having 1 to 4 C atoms,

[0262] Z 0 is -COO-, -OCO-, -CH2CH2-, -CF2O-, -OCF2-, -CH=CH-, -OCO-CH=CH-, -CH=CH-COO- or a single bond,

[0263] A 0 is, in the case of multiple occurrences, independently of one another, 1,4-phenylene which is unsubstituted or substituted by 1, 2, 3 or 4 radicals L, or trans-1,4-cyclohexylene,

[0264] u and v are independently 0, 1 or 2,

[0265] w is 0 or 1,

[0266] The benzene and naphthalene rings may be substituted by one or more identical or different groups L.

[0267] Further preferred are compounds of the formulae MRM1, MRM2, MRM3, MRM4, MRM5, MRM6, MRM7, MRM9 and MRM10, especially those of the formulae MRM1, MRM4, MRM6 and MRM7, and in particular those of the formulae MRM1 and MRM7.

[0268] Compounds of the formula P, DRM, MRM and subformulae thereof can be prepared analogously to methods known to the person skilled in the art and described in authoritative works of organic chemistry, for example Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Thieme-Verlag, Stuttgart.

[0269] The proportion of the monoreactive, direactive or polyreactive liquid crystal compound in the overall polymerizable liquid crystal mixture is preferably in the range of 30 to 99.9 wt %, more preferably in the range of 50 to 99.9 wt % and even more preferably in the range of 85 to 99.9 wt %.

[0270] In a preferred embodiment, the proportion of the di- or polyreactive polymerizable mesogenic compound in the overall polymerizable liquid crystal mixture is preferably in the range of 5 to 99 wt.-%, more preferably in the range of 10 to 97 wt.-% and even more preferably in the range of 15 to 95 wt.-%.

[0271] In another preferred embodiment, the proportion of the monoreactive polymerizable mesogenic compound in the overall polymerizable liquid-crystalline mixture, if present, is preferably in the range of 5 to 80 wt.-%, more preferably in the range of 10 to 75 wt.-% and even more preferably in the range of 15 to 70 wt.-%.

[0272] In another preferred embodiment, the proportion of the polyreactive polymerizable mesogenic compound in the overall polymerizable liquid crystal mixture, if present, is preferably in the range of 1 to 30 wt.-%, more preferably in the range of 2 to 20 wt.-% and even more preferably in the range of 3 to 10 wt.-%.

[0273] In a further preferred embodiment, the polymerizable liquid-crystal mixture contains no polymerizable mesogenic compounds having more than two polymerizable groups.

[0274] In a further preferred embodiment, the polymerizable liquid-crystal mixture contains no polymerizable mesogenic compounds having less than two polymerizable groups.

[0275] In another preferred embodiment, the polymerizable liquid crystal mixture is an achiral material, ie it does not contain any chiral polymerizable mesogenic compounds or other chiral compounds.

[0276] In a further preferred embodiment, the polymerizable liquid crystal mixture comprises at least one monoreactive mesogenic compound, preferably selected from the group consisting of formula MRM-1, at least one direactive mesogenic compound, preferably selected from the group consisting of formula DRMa-1, and one or more compounds of formula S.

[0277] In a further preferred embodiment, the polymerizable liquid crystal mixture comprises at least one monoreactive mesogenic compound preferably selected from formula MRM-7, at least one direactive mesogenic compound preferably selected from formula DRMa-1 and one or more compounds of formula S.

[0278] In a further preferred embodiment, the polymerizable liquid crystal mixture comprises at least two monoreactive mesogenic compounds (preferably selected from compounds of formula MRM-1 and / or MRM-7), at least one direactive mesogenic compound preferably selected from formula DRMa-1 and one or more compounds of formula S.

[0279] In another preferred embodiment, the polymerizable liquid crystal mixture comprises at least two monoreactive mesogenic compounds (preferably selected from compounds of formula MRM-1 and / or MRM-7), at least two direactive mesogenic compounds (preferably selected from compounds of formula DRMa-1) and one or more compounds of formula S.

[0280] In a further preferred embodiment, the polymerizable liquid crystal mixture comprises at least two direactive mesogenic compounds, preferably selected from compounds of formula DRMa-1, and one or more compounds of formula S.

[0281] In a further preferred embodiment, in particular for negative dispersion applications, the above polymerizable liquid crystal mixture additionally comprises one or more ND compounds of the formula,

[0282]

[0283] in

[0284] U 1,2 independently selected from

[0285]

[0286] Including their mirror images, where the ring U 1 and U 2 Each is bonded to the group -(B) via an axial bond q -, and one or two non-adjacent CH2 groups in these rings are optionally replaced by O and / or S, and ring U 1 and U 2 optionally substituted by one or more groups L,

[0287] Q 1,2 are independently CH or SiH,

[0288] Q 3 is C or Si,

[0289] B is -C≡C-, -CY- 1 =CY2 - or an optionally substituted aromatic or heteroaromatic group,

[0290] Y 1,2 are each independently H, F, Cl, CN or R 0 ,

[0291] q is an integer from 1 to 10, preferably 1, 2, 3, 4, 5, 6 or 7,

[0292] A 1-4 are each independently selected from non-aromatic, aromatic or heteroaromatic carbocyclic or heterocyclic groups, which are optionally substituted by one or more groups R 5 , and wherein -(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 contain no more aromatic groups than non-aromatic groups and preferably no more than one aromatic group,

[0293] 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,

[0294] R 0 and R 00 are each independently H or an alkyl group having 1 to 12 C atoms,

[0295] m and n are independently 0, 1, 2, 3 or 4,

[0296] o and p are independently 0, 1, 2, 3 or 4,

[0297] R 1-5 are independently identical or different groups selected from the group consisting of: 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 a carbon or hydrocarbon radical having 1 to 40 C atoms, which is optionally substituted and optionally contains one or more heteroatoms, or represents P or P-Sp-, or is substituted by P or P-Sp-, wherein the compound comprises at least one radical R representing P or P-Sp- or substituted by P or P-Sp- 1-5 ,

[0298] P is a polymerizable group,

[0299] Sp is a spacer group or a single bond.

[0300] Preferably, the subgroups forming the bridging group B in the formula ND are preferably selected from groups having a bond angle of 120° or more, preferably in the range of 180°. Very preferred are -C≡C- groups or divalent aromatic groups which are linked to their adjacent groups in the para position, such as, for example, 1,4-phenylene, naphthalene-2,6-diyl, indan-2,6-diyl or thieno[3,2-b]thiophene-2,5-diyl.

[0301] Other possible subgroups include -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.

[0302] Preferably, in formula ND, the bridging group or -(B) q- contains one or more groups selected from -C≡C-, optionally substituted 1,4-phenylene and optionally substituted 9H-fluorene-2,7-diyl. In the formula ND, the sub-group or B is preferably selected from -C≡C-, optionally substituted 1,4-phenylene and optionally substituted 9H-fluorene-2,7-diyl, wherein the H atom at position 9 in the fluorene group is optionally replaced by a carbon group or a hydrocarbon group.

[0303] Very preferably in formula ND the bridging group or -(B) q -selected from -C≡C-, -C≡CC≡C-, -C≡CC≡CC≡C-, -C≡CC≡CC≡CC≡C-,

[0304] wherein r is 0, 1, 2, 3 or 4, and L has the meaning as described below.

[0305] Preferably, the non-aromatic ring of the mesogenic group to which the bridging group is attached, such as U in formula ND 1 and U 2 , preferably selected from Where R 5 As defined in Formula ND.

[0306] Preferably, in formula ND the aromatic group A 1-4 It may be monocyclic, i.e. have only one aromatic ring (such as, for example, phenyl or phenylene), or polycyclic, i.e. have two or more condensed rings (such as, for example, naphthyl or naphthylene). Particular preference is given to mono-, bi- or tricyclic aromatic or heteroaromatic groups having up to 25 C atoms, which may also contain condensed rings and are optionally substituted.

[0307] Preferably, in the compound of formula ND, the non-aromatic carbocyclic and heterocyclic rings A 1-4 , including saturated (also called "fully saturated") those, i.e. they contain only C atoms or heteroatoms connected by single bonds, and unsaturated (also called "partially saturated") those, i.e. they also contain C atoms or heteroatoms connected by double bonds. The non-aromatic ring may also contain one or more heteroatoms, preferably selected from Si, O, N and S.

[0308] Preferably, in formula ND, the non-aromatic and aromatic rings or A 1-4 Selected from trans-1,4-cyclohexylene and 1,4-phenylene optionally substituted by one or more L groups.

[0309] Very preferred are compounds of formula ND, wherein m and p are 1, and n and o are 1 or 2. Further preferred are compounds of formula ND, wherein m and p are 1 or 2, and n and o are 0. Further preferred are compounds, wherein m, n, o and p are 2.

[0310] In the compound of formula ND, the linking group or Z connecting the aromatic and non-aromatic cyclic groups in the mesogenic group 1-4 Preferably, it is selected from -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.

[0311] Preferably, in the compounds of formula ND, the substituents on the ring, such as L, are preferably selected from 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 C atoms, preferably 1 to 6 C atoms, and straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, preferably 1 to 6 C atoms, wherein one or more H atoms are optionally replaced by F or Cl, wherein R 0 and R 00 As defined in Formula ND, and X are halogen.

[0312] Preferably, the compound of formula ND comprises one or more terminal groups such as R substituted with two or more polymerizable groups P or P-Sp- 1-4 or a substituent such as R 5(Multifunctional polymerizable group) Suitable multifunctional polymerizable groups of this type are disclosed, for example, in US Pat. No. 7,060,200 B1 or US Pat. No. 2006 / 0172090 A1.

[0313] Very preferred compounds of formula ND are those of the following sub-formula:

[0314]

[0315]

[0316]

[0317]

[0318]

[0319] Where R 1-5 , A 1-4 , Z 1-4 , B, m, n, o, p and q have one of the meanings given above.

[0320] Particularly preferred are compounds of the following sub-formula:

[0321]

[0322]

[0323]

[0324]

[0325]

[0326]

[0327]

[0328]

[0329]

[0330]

[0331] where Z has the Z given above 1 one of the meanings of P-Sp-, R having an R different from P-Sp- as given above 1 , and P, Sp, L and r are as defined above, and in the mesogenic group the benzene ring is optionally substituted by one or more groups L as defined above.

[0332] Furthermore, preference is given to polymerisable liquid-crystalline media in which the compound of the formula ND is selected from compounds of the formula ND 25 or ND 26, in particular in which Z represents -COO-, r is 0 at each occurrence, and P, Sp are as defined above.

[0333] In these preferred compounds, P-Sp- is preferably P-Sp'-X', wherein X' is preferably -O-, -COO- or -OCOO-.

[0334] Compounds of formula ND, subformulae thereof and suitable methods for their synthesis are disclosed in WO 2008 / 119427 A1.

[0335] The amount of compounds of the formula ND in the polymerizable liquid-crystal mixture is preferably from 1 to 50%, very preferably from 1 to 40%.

[0336] In another preferred embodiment, the polymerizable liquid crystal mixture optionally comprises one or more additives selected from the group consisting of: additional polymerization initiators, antioxidants, surfactants, stabilizers, catalysts, sensitizers, inhibitors, chain transfer agents, co-reactive monomers, reactive viscosity reducers, surface-active compounds, lubricants, wetting agents, dispersants, hydrophobic agents, binders, flow improvers, degassing agents or defoamers, deaerators, diluents, reactive diluents, auxiliaries, colorants, dyes, pigments and additives for nanoparticles.

[0337] In a further preferred embodiment, the polymerizable liquid crystal mixture optionally comprises one or more additives selected from polymerizable non-mesogenic compounds (reactive viscosity reducers). The amount of these additives in the polymerizable liquid crystal mixture is preferably 0 to 30%, very preferably 0 to 25%.

[0338] The reactive viscosity reducers used are not only substances which are called reactive viscosity reducers in the actual sense, but also auxiliary compounds already mentioned above, which contain one or more additional reactive units or polymerizable groups P, such as hydroxyl groups, thiol groups or amino groups, through which a reaction with the polymerizable units of the liquid crystal compound can occur.

[0339] Substances that are generally capable of photopolymerization include, for example, mono-, di- or polyfunctional compounds containing at least one olefinic double bond. Examples are vinyl esters of carboxylic acids, such as vinyl esters of lauric acid, myristic acid, palmitic acid and stearic acid, and vinyl esters of dicarboxylic acids, such as vinyl esters of succinic acid, adipic acid, allyl and vinyl ethers of monofunctional alcohols and methacrylic and acrylates, such as allyl and vinyl ethers and methacrylic and acrylates of lauryl alcohol, myristyl alcohol, palmityl alcohol and stearyl alcohol, and diallyl and divinyl ethers of difunctional alcohols, such as diallyl and divinyl ethers of ethylene glycol and 1,4-butanediol.

[0340] Also suitable are, for example, methacrylates and acrylates of polyfunctional alcohols, in particular those which, in addition to hydroxyl groups, contain no further functional groups or at most ether groups. Examples of such alcohols are difunctional alcohols such as ethylene glycol, propylene glycol and their higher condensation representatives, for example diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, etc., butanediol, pentanediol, hexanediol, neopentyl glycol, alkoxylated phenolic compounds such as ethoxylated and propoxylated bisphenols, cyclohexanedimethanol, trifunctional and polyfunctional alcohols such as glycerol, trimethylolpropane, butanetriol, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol, and the corresponding alkoxylated, in particular ethoxylated and propoxylated alcohols.

[0341] Further suitable reactive viscosity reducers are polyester (meth)acrylates, which are (meth)acrylate esters of polyester polyols.

[0342] Examples of suitable polyester polyols are those which can be prepared by esterifying polycarboxylic acids, preferably dicarboxylic acids, with polyols, preferably diols. The starting materials for such hydroxyl-containing polyesters are known to those skilled in the art. Dicarboxylic acids which can be used are succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid and isomers and hydrogenation products thereof, and esterifiable or ester transferable derivatives of the acids, such as anhydrides and dialkyl esters. Suitable polyols are the alcohols mentioned above, preferably ethylene glycol, 1,2- and 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexanedimethanol and polyglycols of the ethylene glycol and propylene glycol type.

[0343] In addition, suitable reactive viscosity reducing agents are 1,4-divinylbenzene, triallyl cyanurate, acrylic acid esters of tricyclodecenyl alcohol of the formula

[0344]

[0345] Also known as dihydrodicyclopentadienyl acrylate, and allyl esters of acrylic acid, methacrylic acid, and cyanoacrylic acid.

[0346] Among the reactive viscosity reducing agents mentioned by way of example, use is made in particular and in view of the preferred compositions mentioned above, of those comprising photopolymerizable groups.

[0347] This group includes, for example, diols and polyols, such as ethylene glycol, propylene glycol and higher condensed representatives thereof, for example diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol and the like, butanediol, pentanediol, hexanediol, neopentyl glycol, cyclohexanedimethanol, glycerol, trimethylolpropane, butanetriol, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol and the corresponding alkoxylated, in particular ethoxylated and propoxylated, alcohols.

[0348] Furthermore, the group includes, for example, alkoxylated phenolic compounds, such as ethoxylated and propoxylated bisphenols.

[0349] Furthermore, these reactive viscosity reducing agents may be, for example, epoxy or urethane (meth)acrylates.

[0350] Epoxy (meth)acrylates are, for example, those obtainable by reaction of epoxidized olefins or poly- or diglycidyl ethers, such as bisphenol A diglycidyl ether, with (meth)acrylic acid, as is known to the person skilled in the art.

[0351] Urethane (meth)acrylates are, in particular, the reaction products of hydroxyalkyl (meth)acrylates with poly- or diisocyanates, which are likewise known to the person skilled in the art.

[0352] Such epoxy and urethane (meth)acrylates are included as "mixed forms" in the compounds listed above.

[0353] If reactive viscosity reducing agents are used, their amount and properties must be matched to the respective conditions so that on the one hand a satisfactory desired effect, such as the desired color of the composition according to the invention, is achieved, but on the other hand the phase behavior of the liquid crystal composition is not excessively impaired. For example, low-crosslinked (high-crosslinked) liquid crystal compositions can be prepared using corresponding reactive viscosity reducing agents having a relatively low (high) number of reactive units per molecule.

[0354] For example, the group of diluents includes:

[0355] C1-C4-alcohols, for example methanol, ethanol, n-propanol, isopropanol, butanol, isobutanol, sec-butanol, and in particular C5-C12-alcohols, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, n-undecanol and n-dodecanol and isomers thereof, diols, for example 1,2-ethanediol, 1,2- and 1,3-propylene glycol, 1,2-, 2,3- and 1,4-butanediol, di- and triethylene glycol and di- and tri-propylene glycol, ethers, for example methyl tert-butyl ether, 1,2-ethanediol mono- and di-methyl ether, 1 , 2-ethylene glycol mono- and di-ethyl ether, 3-methoxypropanol, 3-isopropoxypropanol, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), C1-C5-alkyl esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate and amyl acetate, aliphatic and aromatic hydrocarbons such as pentane, hexane, heptane, octane, isooctane, petroleum ether, toluene, xylene, ethylbenzene, tetralin, decalin, dimethylnaphthalene, white solvent naphtha, and Mineral oils, such as gasoline, kerosene, diesel and heating oil, and natural oils, such as olive, soybean, rapeseed, linseed and sunflower oils.

[0356] It is of course also possible to use mixtures of these diluents in the compositions according to the invention.

[0357] These diluents can also be mixed with water as long as there is at least partial miscibility. Examples of suitable diluents here are C1-C4-alcohols, such as methanol, ethanol, n-propanol, isopropanol, butanol, isobutanol and sec-butanol, diols, such as 1,2-ethanediol, 1,2- and 1,3-propylene glycol, 1,2-, 2,3- and 1,4-butanediol, di- and tri-ethylene glycol and di- and tri-propylene glycol, ethers, such as tetrahydrofuran and dioxane, ketones, such as acetone, methyl ethyl ketone and diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), and C1-C4-alkyl esters, such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate.

[0358] The diluent is optionally used in a proportion of about 0 to 10.0 wt. %, preferably about 0 to 5.0 wt. %, based on the total weight of the polymerisable LC material.

[0359] Defoamers and deaerators (c1)), lubricants and flow aids (c2)), thermal or radiation curing aids (c3)), substrate wetting aids (c4)), wetting and dispersing aids (c5)), hydrophobic agents (c6)), adhesion promoters (c7)) and agents promoting scratch resistance (c8)) cannot be strictly demarcated from one another in terms of their action.

[0360] For example, lubricants and flow aids are often also used as defoamers and / or degassing agents and / or agents that promote scratch resistance. Radiation curing aids can also be used as lubricants and flow aids and / or degassing agents and / or substrate wetting aids. In various cases, some of these aids can also perform the function of adhesion promoters (c8)).

[0361] Corresponding to what has been said above, certain additives can therefore be classified into several groups c1) to c8) described below.

[0362] The defoamers in group c1) include silicon-free and silicon-containing polymers. Silicon-containing polymers are, for example, unmodified or modified polydialkylsiloxanes or branched, comb or block copolymers comprising polydialkylsiloxane and polyether units, the latter being obtainable from ethylene oxide or propylene oxide.

[0363] Degassing agents from group c1) include, for example, organic polymers, such as polyethers and polyacrylates, dialkylpolysiloxanes, in particular dimethylpolysiloxanes, organomodified polysiloxanes, such as arylalkyl-modified polysiloxanes, and fluorosilicones.

[0364] The action of defoamers is essentially based on preventing foam formation or destroying already formed foam. In a medium to be degassed, for example in the composition according to the invention, defoamers essentially act by promoting the merging of subdivided gas or air bubbles to give larger bubbles and thus accelerate the escape of gas (or air). Since defoamers can often also be used as deaerators and vice versa, these additives have been included together in group c1).

[0365] For example, such additives are available from Tego Foamex 800, Foamex 805, Foamex 810, Foamex 815, Foamex 825, Foamex835, Foamex 840, Foamex 842, Foamex 1435, Foamex 1488, Foamex 1495, Foamex 3062, Foamex 7447, Foamex 8020, Foamex N, Foamex K 3, Antifoam2-18, Antifoam 2-18, Antifoam 2-57, Antifoam2-80, Antifoam 2-82, Antifoam 2-89, Antifoam2-92, Antifoam 14, Antifoam 28, Antifoam81, Antifoam D 90, Antifoam 93, Antifoam200, Antifoam 201, Antifoam 202, Antifoam793, Antifoam1488、 Antifoam 3062、 5803、 5852、 5863、 7008、 Antifoam 1-60、 Antifoam 1-62、 Antifoam 1-85、 Antifoam 2-67、 Antifoam WM 20、 Antifoam50、 Antifoam 105、 Antifoam730、 Antifoam MR 1015、 Antifoam MR 1016、 Antifoam1435、 Antifoam N、 Antifoam KS 6、 Antifoam KS 10、 Antifoam KS 53、 Antifoam KS 95、 Antifoam KS 100、 Antifoam KE 600、 Antifoam KS 911、 Antifoam MR 1000、 Antifoam KS 1100、 Airex 900、 Airex910、 Airex931、 Airex 935、 Airex 936、 Airex960、 Airex 970、 Airex 980 and Airex 985 are commercially available and obtained from BYK at and Commercially available.

[0366] The auxiliaries in group c1) are optionally used in a proportion of about 0 to 3.0% by weight, preferably about 0 to 2.0% by weight, based on the total weight of the polymerisable LC material.

[0367] In group c2), lubricants and flow aids generally include silicon-free and silicon-containing polymers, such as polyacrylates or modifiers, low molecular weight polydialkylsiloxanes. The modification consists in that some of the alkyl groups have been replaced by a wide variety of organic groups. These organic groups are, for example, polyethers, polyesters or even long-chain (fluorinated) alkyl groups, the former being most frequently used.

[0368] The polyether groups in the correspondingly modified polysiloxanes are usually composed of ethylene oxide and / or propylene oxide units. In general, the higher the proportion of these alkylene oxide units in the modified polysiloxanes, the more hydrophilic the resulting product is.

[0369] For example, such additives are available from Tego Glide 100, Glide ZG 400, Glide 406, Glide 410, Glide 411, Glide415, Glide 420, Glide 435, Glide440, Glide450, Glide A 115, Glide B 1484 (can also be used as a defoamer and deaerator), Flow ATF, Flow 300, Flow 460, Flow 425 and Flow ZFS 460 is commercially available. Suitable radiation curable lubricants and flow aids, which can also be used to improve scratch resistance, are products Rad 2100, Rad 2200, Rad 2500, Rad 2600 and Rad 2700, also available from TEGO.

[0370] Such additives are also available from BYK as get.

[0371] Such additives are also available from 3M, for example

[0372] Such adjuvants are also available, for example, from Cytonix, such as or

[0373] Such auxiliaries are also commercially available, for example, from Merck KGaA, such as 2300 and 2500.

[0374] The auxiliaries in group c2) are optionally used in an amount of about 0 to 3.0 wt.-%, preferably about 0 to 2.0 wt.-%, based on the total weight of the polymerisable LC material.

[0375] In group c3), radiation curing auxiliaries include, in particular, polysiloxanes with terminal double bonds, for example, components whose terminal double bonds are acrylate groups. Such auxiliaries can be crosslinked by actinic or, for example, electron radiation. These auxiliaries usually combine several properties together. In the uncrosslinked state, they can be used as defoamers, degassing agents, lubricants and flow aids and / or substrate wetting aids, while in the crosslinked state, they particularly improve the scratch resistance of, for example, coatings or films that can be prepared using the composition according to the invention. Precisely the improvement of the gloss properties of, for example, those coatings or films is essentially considered to be the result of the action of these auxiliaries as defoamers, degassing agents and / or lubricants and flow aids (in the uncrosslinked state).

[0376] Examples of suitable radiation curing aids are the products available from TEGO Rad2100, Rad 2200, Rad 2500, Rad 2600 and Rad 2700 and products available from BYK

[0377] The heat-curing auxiliaries in group c3) contain, for example, primary OH groups which are capable of reacting, for example, with isocyanate groups of the adhesive.

[0378] Examples of useful thermal curing aids are the products available from BYK and

[0379] The auxiliaries in group c3) are optionally used in a proportion of about 0 to 5.0 wt. %, preferably about 0 to 3.0 wt. %, based on the total weight of the polymerisable LC material.

[0380] The substrate wetting assistants in group c4) are used in particular to improve the wettability of substrates to be printed or coated, for example, with printing inks or coating compositions, for example the compositions according to the invention. The improvement in the lubrication and flow behavior of such printing inks or coating compositions, which is usually accompanied, has an influence on the appearance of the (for example crosslinked) prints or coatings produced.

[0381] A wide variety of such additives are available, for example, from Tego Wet KL 245, Wet250, Wet 260 and Wet ZFS 453 and from BYK and Commercially available.

[0382] The auxiliaries in group c4) are optionally used in a proportion of about 0 to 3.0% by weight, preferably about 0 to 1.5% by weight, based on the total weight of the liquid-crystal composition.

[0383] The wetting and dispersing assistants in group c5) serve in particular to prevent flooding and floating and settling of the pigments and are therefore, if necessary, particularly suitable for use in pigmented compositions.

[0384] These additives stabilize the pigment dispersions substantially by electrostatic repulsion and / or steric hindrance of the pigment particles comprising these additives, wherein in the latter case the interaction of the additives with the surrounding medium (eg binder) plays a major role.

[0385] Since the use of such wetting and dispersing assistants is common practice, for example, in the field of printing ink and coating technology, the selection of suitable assistants of this type generally does not present any difficulties to the person skilled in the art if they are used at all.

[0386] Such wetting and dispersing aids are available, for example, from Tego as Dispers 610, Dispers 610S, Dispers 630, Dispers 700, Dispers705, Dispers 710, Dispers 720W, Dispers 725W, Dispers 730W, Dispers 735W and Dispers 740W and from BYK and Commercially available.

[0387] The amount of the auxiliaries in group c5) is used based on the average molecular weight of the auxiliaries. A preliminary experiment is therefore advisable in any case, but this can be easily accomplished by a person skilled in the art.

[0388] The hydrophobic agents in group c6) can be used to impart hydrophobic properties to printed products or coatings produced, for example, using the composition according to the invention. This prevents or at least greatly suppresses swelling due to water absorption and thus, for example, changes in the optical properties of such printed products or coatings. In addition, when the composition is used as a printing ink, for example in offset printing, water absorption can thereby be prevented or at least greatly reduced.

[0389] Such hydrophobic agents are available, for example, from Tego Phobe WF, Phobe 1000, Phobe 1000S, Phobe 1010, Phobe 1030, Phobe1010, Phobe 1010, Phobe 1030, Phobe 1040, Phobe 1050, Phobe 1200, Phobe 1300, Phobe 1310 and Phobe 1400 is commercially available.

[0390] The auxiliaries in group c6) are optionally used in a proportion of about 0 to 5.0 wt. %, preferably about 0 to 3.0 wt. %, based on the total weight of the polymerisable LC material.

[0391] The further adhesion promoters from group c7) serve to improve the adhesion of the two interfaces in contact. It is immediately apparent from this that substantially the only part of the effective adhesion promoter is that which is located at one or the other interface or at both interfaces. If, for example, it is desired to apply a liquid or pasty printing ink, a coating composition or a paint to a solid substrate, this generally means that the adhesion promoter must be added directly to the latter or that the substrate must be pretreated with the adhesion promoter (also referred to as priming), i.e., the substrate is given modified chemical and / or physical surface properties.

[0392] If the substrate has been primed with a primer, this means that the interfaces in contact are those of the primer on the one hand and the printing ink or coating composition or lacquer on the other hand. In this case, not only the adhesion properties between substrate and primer, but also the adhesion properties between substrate and printing ink or coating composition or lacquer play a role in the adhesion of the entire multilayer structure on the substrate.

[0393] Adhesion promoters in a broader sense may also be mentioned as substrate wetting assistants already listed under group c4), but these generally do not have the same adhesion-promoting capabilities.

[0394] The diversity of adhesion promoter systems is not surprising in view of the widely varying physical and chemical properties of substrates and of the printing inks, coating compositions and lacquers intended for, for example, printing or coating thereof.

[0395] Adhesion promoters based on silanes are, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N-aminoethyl-3-aminopropyltrimethoxysilane, N-aminoethyl-3-aminopropylmethyldimethoxysilane, N-methyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane and vinyltrimethoxysilane. These and other silanes are available from Hüls, for example under the trade name Commercially available.

[0396] Generally, the corresponding technical information from the manufacturers of such additives should be used or the person skilled in the art can determine this information in a simple manner by corresponding preliminary experiments.

[0397] If, however, these additives are to be added as auxiliaries from group c7) to the polymerisable LC material according to the invention, their proportion optionally corresponds to about 0 to 5.0 wt.-%, based on the total weight of the polymerisable LC material. These concentration data serve only as a guide, since the amount and identity of the additive is determined in each individual case by the properties of the substrate and the printing / coating composition. For this case, corresponding technical information is generally available from the manufacturers of such additives or can be determined in a simple manner by a person skilled in the art by corresponding preliminary experiments.

[0398] The auxiliaries in group c8) for improving scratch resistance include, for example, the above-mentioned products available from Tego Rad 2100, Rad 2200, Rad 2500, Rad 2600 and Rad 2700.

[0399] The quantitative data given for group c3) also apply to these auxiliaries, ie these additives are optionally used in a proportion of about 0 to 5.0% by weight, preferably about 0 to 3.0% by weight, based on the total weight of the liquid-crystal composition.

[0400] Examples of other light, heat and / or oxidation stabilizers which may be mentioned are the following substances:

[0401] Alkylated monophenols, such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethylphenol, 2,6-di(octadecyl)-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenol with linear or branched side chains, such as such as 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(1′-methylundecane-1′-yl)phenol, 2,4-dimethyl-6-(1′-methylheptadecan-1′-yl)phenol, 2,4-dimethyl-6-(1′-methyltridecane-1′-yl)phenol and mixtures of these compounds, alkylthiomethylphenols such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol and 2,6-di(dodecyl)thiomethyl-4-nonylphenol,

[0402] Hydroquinones and alkylated hydroquinones, such as 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydrocrainone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate and bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate,

[0403] Tocopherols, such as alpha-tocopherol, beta-tocopherol, gamma-tocopherol, delta-tocopherol and mixtures of these compounds, and tocopherol derivatives, such as tocopherol acetate, succinate, nicotinate and polyoxyethylene succinate ("tocofersolate"),

[0404] Hydroxylated diphenyl sulfides, such as 2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol), 4,4′-thiobis(6-tert-butyl-3-methylphenol), 4,4′-thiobis(6-tert-butyl-2-methylphenol), 4,4′-thiobis(3,6-di-sec-amylphenol) and 4,4′-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide,

[0405] Alkylenebisphenols, for example 2,2′-methylenebis(6-tert-butyl-4-methylphenol), 2,2′-methylenebis(6-tert-butyl-4-ethylphenol), 2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol], 2,2′-methylenebis(4-methyl-6-cyclohexylphenol), 2,2′-methylenebis(6-nonyl-4-methylphenol), 2,2′-methylenebis(4,6-di-tert-butylphenol), 2,2-ethylenebis( 4,6-di-tert-butylphenol), 2,2′-ethylenebis(6-tert-butyl-4-isobutylphenol), 2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol], 2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4′-methylenebis(2,6-di-tert-butylphenol), 4,4′-methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2- methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tri(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecyl-mercaptobutane, ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene, bis(3-tert-butyl-4-hydroxy-5-methylphenyl) [2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecyl-mercaptobutane and 1,1,5,5-tetrakis(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane,

[0406] O-, N- and S-benzyl compounds, such as 3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether, 4-hydroxy-3,5-dimethylbenzylthioglycolate octadecyl, 4-hydroxy-3,5-di-tert-butylbenzylthioglycolate tridecyl, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide and isooctyl-3,5-di-tert-butyl-4-hydroxybenzylthioglycolate,

[0407] Aromatic hydroxybenzyl compounds, such as 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethyl-benzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethyl-benzene and 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol,

[0408] Triazine compounds, such as 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, -tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate and 1,3,5-tris(2-hydroxyethyl) isocyanurate,

[0409] 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,

[0410] Acylaminophenols, such as 4-hydroxylauroylanilide, 4-hydroxystearylanilide and octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate,

[0411] for example propionates and acetates of monohydric or polyhydric alcohols, such as methanol, ethanol, n-octanol, isooctyl alcohol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propylene glycol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]-octane,

[0412] 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,

[0413] Ascorbic acid (vitamin C) and ascorbic acid derivatives such as ascorbyl palmitate, ascorbyl laurate and ascorbyl stearate, as well as ascorbyl sulfate and ascorbyl phosphate,

[0414] Antioxidants based on amine compounds, such as N,N′-diisopropyl-p-phenylenediamine, N,N′-di-sec-butyl-p-phenylenediamine, N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N′-bis(1-methylheptyl)-p-phenylenediamine, N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine, N,N′-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N′-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine, N -cyclohexyl-N′-phenyl-p-phenylenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyl diphenylamine, 4-isopropoxy diphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octyl-substituted diphenylamines such as p,p′-di-tert-octyl diphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminophenol methylphenol, 2,4-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane, 1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane, (o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine, tert-octyl-substituted N-phenyl-1-naphthylamine, mixtures of mono- and di-alkylated tert-butyl / tert-octyl diphenylamines, mixtures of mono- and di-alkylated nonyl diphenylamines, mixtures of mono- and di-alkylated dodecyl diphenylamines, mixtures of mono- and di-alkylated isopropyl / isohexyl diphenylamines mixtures of mono- and di-alkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mixtures of mono- and di-alkylated tert-butyl / tert-octyl phenothiazines, mixtures of mono- and di-alkylated tert-octyl phenothiazines, N-allyl phenothiazine, N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene, N,N-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine, bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate, 2,2,6,6-tetramethylpiperidin-4-one and 2,2,6,6-tetramethylpiperidin-4-ol,

[0415] Phosphines, phosphites and phosphonites, such as triphenylphosphine, triphenylphosphite, diphenylalkylphosphites, phenyldialkylphosphites, tris(nonylphenyl)phosphite, trilaurylphosphite, trioctadecylphosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, diisodecylpentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, diisodecylpentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6 -tri(tert-butylphenyl))pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4′-diphenylene diphosphite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphocine, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,g]-1,3,2-dioxaphosphocine, bis(2,4-di-tert-butyl-6-methylphenyl)methylphosphite and bis(2,4-di-tert-butyl-6-methylphenyl)ethylphosphite,

[0416] 2-(2′-hydroxyphenyl)benzotriazole, such as 2-(2′-hydroxy-5′-methylphenyl)benzotriazole, 2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5 -chlorobenzotriazole, 2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole, 2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole, 2-(3,5′-bis-(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole, a mixture of 2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3′-tert-butyl-5′ -[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)-5-chlorobenzotriazole ]-2′-hydroxyphenyl)benzotriazole, 2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole and 2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol]; the fully esterified product of 2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazole and polyethylene glycol 300;

[0417] Sulfur-containing peroxide scavengers and sulfur-containing antioxidants, such as esters of 3,3′-thiodipropionic acid, for example the lauryl, stearyl, myristyl and tridecyl esters, mercaptobenzimidazole and the zinc salt of 2-mercaptobenzimidazole, dibutyl zinc dithiocarbamate, dioctadecyl disulfide and pentaerythritol tetrakis(β-dodecylmercapto)propionate,

[0418] Esters of unsubstituted and substituted benzoic acid, such as 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl-3,5-di-tert-butyl-4-hydroxybenzoate and 2-methyl-4,6-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate,

[0419] Acrylates, such as ethyl α-cyano-β,β-diphenylacrylate, isooctyl α-cyano-β,β-diphenylacrylate, methyl α-methoxycarbonylcinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, butyl-α-cyano-β-methyl-p-methoxycinnamate and methyl-α-methoxycarbonyl-p-methoxycinnamate, sterically hindered amines, such as bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate, bis(2,2,6,6-tetramethylpiperidin-4-yl)succinate, bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) Sebacate, bis(1,2,2,6,6-pentamethylpiperidin-4-yl)-n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, condensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, condensation product of N,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate, tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate, 1,1′-(1,2-ethyl)-2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine )bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis(1,2,2,6,6-pentamethylpiperidin-4-yl)2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)succinate, N,N′-bis(2 , 2,6,6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, condensation products of 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidin-4-yl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, condensation products of 2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-pentamethylpiperidin-4-yl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]-decane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidine-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethylpiperidin-4-yl)pyrrolidine-2,5-dione, a mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidin, a condensation product of N,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensation product of 1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine, a condensation product of 4-butylamino-2,2,6,6-tetramethyl piperidine, N-(2,2,6,6-tetramethylpiperidin-4-yl)-n-dodecylsuccinimide, N-(1,2,2,6,6-pentamethylpiperidin-4-yl)-n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4.5]-decane, condensation products of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane and epichlorohydrin, condensation products of 4-amino-2,2,6,6-tetramethylpiperidine with tetrakishydroxymethylacetylene diurea and poly(methoxypropyl-3-oxy)-[4(2,2,6,6-tetramethyl)piperidinyl]-siloxane,.

[0420] Oxamides, such as 4,4′-dioctyloxyoxalanilide, 2,2′-diethoxyoxalanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide, 2,2′-di(dodecyloxy)-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxalanilide, N,N′-bis(3-dimethylaminopropyl)oxalamide, 2-ethoxy-5-tert-butyl-2′-ethoxanilide and mixtures thereof with 2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, and mixtures of o- and p-methoxy-disubstituted oxalanilides and mixtures of o- and p-ethoxy-disubstituted oxalanilides, and

[0421] 2-(2-hydroxyphenyl)-1,3,5-triazine, such as 2,4,6-tris-(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylphenyl)- 1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butoxypropoxy)phenyl]-4,6 -bis(2,4-dimethyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[4-(dodecyloxy / tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6- Bis-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine and 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine.

[0422] In another preferred embodiment, the polymerizable liquid crystal mixture comprises preferably selected from One or more specific antioxidant additives from the VIZOL series, such as antioxidants available from Ciba, Switzerland. and

[0423] In another preferred embodiment, the polymerizable liquid crystal mixture comprises one or more, more preferably one or a combination of two photoinitiators, for example selected from commercially available or (Ciba AG) series, in particular Irgacure 127, Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 817, Irgacure 907, Irgacure 1300, Irgacure, Irgacure 2022, Irgacure 2100, Irgacure 2959 or Darcure TPO, further selected from the commercially available OXE02 (Ciba AG), NCI 930, N1919T (Adeka), SPI-03 or SPI-04 (Samyang), or preferably a combination thereof, such as SPI-03 and NCI-930.

[0424] The overall concentration of the polymerization initiator in the polymerizable liquid-crystalline mixture is preferably from 0.5 to 5%, very preferably from 0.5 to 3%, more preferably from 1 to 2%.

[0425] Preferably, the polymerizable LC mixture comprises, in addition to one or more SAPAs, preferably of formula S

[0426] a) one or more monoreactive, direactive or polyreactive polymerizable mesogenic compounds, preferably of formula P,

[0427] b) optionally one or more polymerizable mesogenic compounds,

[0428] c) optionally one or more antioxidant additives,

[0429] d) optionally one or more adhesion promoters,

[0430] e) optionally one or more surfactants,

[0431] f) optionally one or more monoreactive, direactive or polyreactive polymerizable non-mesogenic compounds,

[0432] g) optionally one or more dyes showing an absorption maximum at the wavelength used to initiate the photopolymerization,

[0433] h) optionally one or more chain transfer agents,

[0434] i) optionally one or more stabilizers,

[0435] j) optionally one or more lubricants and flow aids, and

[0436] k) optionally one or more diluents,

[0437] 1) Optionally a non-polymerizable nematic component.

[0438] More preferably, the polymerizable liquid crystal mixture comprises:

[0439] a) one or more compounds of formula S,

[0440] b) one or more, preferably two or more, direactive polymerizable mesogenic compounds of formula DRM, preferably selected from compounds of formula DRMa-1, in an amount, if present, preferably of 10 to 90% by weight, very preferably of 15 to 75% by weight,

[0441] c) optionally one or more, preferably two or more, monoreactive polymerizable mesogenic compounds of formula MRM, preferably selected from compounds of formula MRM-1 and / or MRM-7, in an amount preferably of 10 to 95% by weight, very preferably of 25 to 85%,

[0442] d) optionally one or more compounds of the formula ND, preferably in an amount of 1 to 50%, very preferably 1 to 40%.

[0443] e) optionally one or more antioxidant additives, preferably selected from esters of unsubstituted and substituted benzoic acids, in particular and if present, the amount is preferably from 0.01 to 2% by weight, very preferably from 0.05 to 1% by weight,

[0444] f) optionally one or more lubricants and flow aids, preferably selected from FC 4430, Fluor N 561 and / or Fluor N 562, and if present, preferably in an amount of 0.1 to 5 wt. %, very preferably 0.2 to 3 wt. %, and

[0445] Optionally one or more photoinitiators.

[0446] Preferably, the polymerizable LC mixture is dissolved in a suitable solvent before being provided on a suitable substrate. Therefore, in another preferred embodiment, the polymerizable liquid crystal mixture 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 acetate, ethyl acetate or butyl acetate or methyl acetoacetate; alcohols such as methanol, ethanol or isopropanol; aromatic solvents such as toluene or xylene; alicyclic hydrocarbons such as cyclopentane or cyclohexane; halogenated hydrocarbons such as di- or tri-chloromethane; glycols or their esters such as PGMEA (propylene glycol monomethyl ether acetate), γ-butyrolactone. It is also possible to use binary, ternary or higher-order mixtures of the above solvents.

[0447] In case the polymerisable liquid crystal mixture contains one or more solvents, the concentration of all solids (including RMs) in the solvent is preferably from 10% to 60%.

[0448] The solution is then coated or printed onto a substrate by spin coating, printing or other known techniques and the solvent is evaporated off prior to polymerization. In most cases, it is appropriate to heat the mixture to promote evaporation of the solvent.

[0449] The polymerizable liquid crystal mixture can be applied to the substrate by conventional coating techniques such as spin coating, rod coating or doctor coating. The polymerizable LC material can also be applied to the substrate by conventional printing techniques known to the person skilled in the art, such as for example screen printing, offset printing, roll-to-roll printing, letterpress printing, gravure printing, rotogravure printing, flexographic printing, gravure printing, pad printing, heat seal printing, inkjet printing or printing with the aid of a stamp or printing plate.

[0450] Suitable substrate materials and substrates are known to the person skilled in the art and are described in the literature, such as conventional substrates used, for example, in the optical film industry, such as glass or plastics. Particularly suitable and preferred substrates for polymerization are polyesters such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), polyvinyl alcohol (PVA), polycarbonate (PC), triacetyl cellulose (TAC), or cycloolefin polymers (COP), or known color filter materials, in particular triacetyl cellulose (TAC), cycloolefin polymers (COP) or known color filter materials.

[0451] In a preferred embodiment, the linearly polarized light is ultraviolet light, which can simultaneously perform photo-alignment of the self-assembling photo-alignment agent and photo-curing of the polymerizable liquid crystal molecule compound.

[0452] The self-assembled photoalignment agent (SAPA) of the present invention is preferably a compound comprising at least one polar side group and at least one photoreactive group. Considering the present invention's studies, it seems that the polar side groups interact with the substrate surface, thereby enabling the SAPA to phase separate from the LC mixture after the LC cell is filled. According to this view, the SAPA forms a layer on the substrate that can be photoaligned with linearly polarized UV light. The liquid crystal follows the orientation of the aligned SAPA to give a uniform planar alignment over the entire display.

[0453] The photo-alignment process of the present invention causes SAPA to undergo isomerization upon irradiation with linearly polarized light of appropriate wavelength. Photoisomerization is an angle-dependent process that ultimately results in photoselective SAPA orientation that is preferentially perpendicular to the polarization of the actinic light and has orientational anisotropy that enables LC alignment.

[0454] The wavelength region of the polarized light is preferably selected so as to match the absorption spectrum of SAPA.

[0455] In case the alignment is reversible, for example under the influence of heat or light, the alignment of SAPA and LC is fixed compulsorily.

[0456] To produce the polymer film of the present invention, the polymerizable LC mixture is preferably redistributed on the substrate surface. After providing the polymerizable LC mixture layer on the substrate, the layer is annealed for a time between 10 seconds and 1 hour, preferably between 20 seconds and 30 minutes and most preferably between 30 seconds and 5 minutes. Annealing is preferably performed at room temperature.

[0457] In alternative embodiments, annealing is carried out at elevated temperature, preferably above 20°C and below 140°C, more preferably above 40°C and below 100°C and most preferably above 50°C and below 80°C.

[0458] In a preferred embodiment, one or more of the process steps of annealing, photoaligning and curing of the polymerizable compounds are carried out at a temperature above the clearing point of the polymerizable liquid crystal mixture.

[0459] During photoalignment of the polymerizable liquid crystal compounds, anisotropy is induced by exposing the display or the liquid crystal layer to linearly polarized light.

[0460] In a preferred embodiment of the present invention, SAPA uses linearly polarized light for photoalignment in a first step and linearly polarized or non-polarized UV light to cure the polymerizable liquid crystal compound in a second step.

[0461] In another preferred embodiment, the linearly polarized light applied according to the method of the invention is UV light or VIS, which is capable of photoalignment.

[0462] The photo-alignment of the SAPA and the curing of the polymerizable liquid crystal compound can be carried out simultaneously or stepwise. In case the process is divided into different steps, the individual steps can be carried out at the same temperature or at different temperatures.

[0463] The curing time depends inter alia on the reactivity of the polymerizable LC mixture, the thickness of the coating layer, the type of polymerization initiator and the power of the UV lamp. The curing time is preferably ≤5 minutes, very preferably ≤3 minutes, most preferably ≤1 minute. For mass production, short curing times of ≤30 seconds are preferred.

[0464] Suitable UV radiation power is preferably between 5 and 200 mWcm -2 in the range of 50 to 175 mWcm -2 and most preferably in the range of 100 to 150 mWcm -2 within the range.

[0465] Suitable UV doses are preferably in the range of 25 to 7200 mJcm, depending on the UV radiation applied and as a function of time. -2 In the range of 500 to 7200 mJcm -2and most preferably in the range of 3000 to 7200 mJcm -2 within the range.

[0466] The photopolymerization is preferably carried out in an inert gas atmosphere, preferably a heated nitrogen atmosphere, but polymerization in air is also possible.

[0467] After the photoalignment and curing steps, a so-called "post-curing" step may optionally be carried out at reduced temperature by irradiation with UV light and / or visible light (linear or non-polar) to remove unreacted polymerizable compounds. The post-curing is preferably carried out at above 0°C and below the clearing point of the LC mixture utilized, preferably at 20°C and below 60°C and most preferably above 20°C and below 40°C.

[0468] The preferred thickness of the polymerized LC film according to the present invention is determined by the desired optical properties of the film or the final product. For example, if the polymerized LC film is not primarily used as an optical film, but for example as an adhesive, alignment or protective layer, its thickness is preferably not more than 1 μm, in particular not more than 0.5 μm, very preferably not more than 0.2 μm.

[0469] For example, the polymer films of the present invention, which are uniformly planarly aligned, can be used, for example, as retardation or compensation films in LCDs to improve contrast and brightness at large viewing angles and to reduce chromaticity. They can be used outside the switchable liquid crystal cell in an LCD, or between substrates (usually glass substrates) to form a switchable liquid crystal cell and contain a switchable liquid crystal medium (in-cell applications).

[0470] For optical applications of the polymer film, it preferably has a thickness of 0.5 to 10 μm, preferably 0.5 to 5 μm, in particular 0.5 to 3 μm.

[0471] The optical retardation (δ(λ)) of a polymer film as a function of the wavelength (λ) of the incident light beam is given by the following equation:

[0472] δ(λ)=(2πΔn·d) / λ

[0473] where (Δn) is the birefringence of the film, (d) is the thickness of the film and λ is the wavelength of the incident beam.

[0474] According to Snellius's law, the birefringence as a function of the direction of the incident beam is defined as

[0475] Δn=sinΘ / sinΨ

[0476] where sinΘ is the angle of incidence or the tilt angle of the optical axis in the film, and sinΨ is the corresponding reflection angle.

[0477] Based on these laws, the birefringence and therefore the optical retardation depends on the thickness of the film and the tilt angle of the optical axis in the film (see Berek compensator). Thus, the skilled person realizes that different optical retardations or different birefringence can be induced by adjusting the orientation of the liquid crystal molecules in the polymer film.

[0478] 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.

[0479] The optical retardation as a function of the thickness of the polymer film according to the invention is less than 200 nm, preferably less than 180 nm and even more preferably less than 150 nm.

[0480] Especially for in-line applications, the polymer film according to the invention shows a high temperature stability. Thus, the polymer film shows a temperature stability of at most 300°C, preferably at most 250°C, more preferably at most 230°C.

[0481] The polymer films of the invention can also be used as alignment films for other liquid crystal or RM materials. For example, they can be used in LCDs to induce or improve the alignment of a switchable liquid crystal medium, or to enable the alignment of subsequent layers of a polymerizable liquid crystal mixture coated thereon. In this way, stacks of polymerizable LC films can be prepared.

[0482] In summary, the polymerized LC films according to the invention can be used in optical components such as polarizers, compensators, alignment layers, circular polarizers or color filters (in liquid crystal displays or projection systems), in decorative images, for the preparation of liquid crystals or effect pigments, and in particular in reflective films with spatially varying reflection colors, for example for decorative multicolor images, information storage or security purposes, such as in non-forgeable documents such as identity cards or credit cards, banknotes, etc.

[0483] The polymer film or optical component according to the present invention can be used in optical devices such as transmission or reflection type displays. They can be used in conventional OLED displays or LCDs, in particular LCDs in DAP (alignment phase deformation) or VA (vertical alignment) modes, such as ECB (electrically controlled birefringence), CSH (color super vertical plane), VAN or VAC (vertical alignment nematic or cholesteric) displays, MVA (multi-domain vertical alignment) or PVA (patterned vertical alignment) displays, displays in bending modes or hybrid displays, such as OCB (optically compensated bending box or optically compensated birefringence), R-OCB (reflective OCB), HAN (hybrid alignment nematic) or pi-box (π-box) displays, in addition TN (twisted nematic), HTN (highly twisted nematic) or STN (super twisted nematic) mode displays, AMD-TN (active matrix driven TN) displays, or IPS (in-plane switching) mode displays (which are also referred to as "super TFT" displays). Particularly preferred are VA, MVA, PVA, OCB and pi-box displays.

[0484] The polymer membranes according to the invention can be used in particular for example in EP 0 829 744, EP 0 887 666 A2, EP 0 887 692, US Pat. No. 6,046,849, US Pat. No. 6,437,915 and in "Proceedings o the SID 20 th International Display Research Conference, 2000", page 280. A 3D display of this type comprising a polymer film according to the invention is a further object of the present invention.

[0485] The invention has been described in the context of particular reference to preferred embodiments thereof. It should be understood that various changes and modifications can be made therein without departing from the spirit and scope of the invention.

[0486] Many of the compounds or mixtures thereof mentioned above and below are commercially available. All these compounds are known or can be prepared by methods known per se as described in the literature (for example in standard works such as Houben-Weyl, Methoden der Organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart), precisely under reaction conditions known and suitable for the described reactions. Variants known per se and not mentioned here can also be used here.

[0487] It should be understood that the aforementioned embodiments of the present invention may be modified while still falling within the scope of the present invention. Unless otherwise specified, alternative features for the same, equivalent or similar purposes may replace each feature disclosed in this specification. Therefore, unless otherwise specified, each feature disclosed is merely an example of a general concept of an equivalent or similar feature.

[0488] All features disclosed in this specification may be combined in any combination except where at least some of such features and / or steps are mutually exclusive. In particular, preferred features of the present invention are applicable to all aspects of the present invention and may be combined in any combination. Likewise, features described in non-essential combinations may be used separately (not in combination).

[0489] It should be understood that many of the features described above, particularly the features of the preferred embodiments, are inventive in themselves, and not just as part of an embodiment of the present invention. Independent protection for these features may be sought in addition to or in lieu of any invention currently claimed.

[0490] The present invention will now be described in more detail with reference to the following working examples, which are merely illustrative and do not limit the scope of the present invention.

[0491] The following examples serve to illustrate the present invention without limiting it. Example

[0492] RM used

[0493] For the following mixtures, the following RM was utilized:

[0494]

[0495]

[0496] SAPA used:

[0497]

[0498] The mixture used

[0499] The following mixtures CM-1 and M-1 to 4 were prepared according to the following table:

[0500]

[0501] FluorN 562 is a commercially available stabilizer (Ciba AG, Basel, Switzerland). FluorN is a commercially available non-reactive, high-fluorine content, ethylene glycol-based polymeric fluorosurfactant (Cytonix LLC, Beltsville, USA).

[0502] General method for polymer film preparation:

[0503] The mixture of interest was spin-coated at 3000 rpm for 30 s on a pristine glass slide without an alignment layer.

[0504] Anneal the samples at 60 °C for 60 s on a temperature-controlled hot plate.

[0505] The sample is heated to the isotropic phase of the respective mixture, for example to 100°C for 60 seconds, and then illuminated with linearly polarized light (250-450 nm Omnicure high pressure Hg lamp, 30 mW / cm 2 , 60 seconds) irradiation.

[0506] Experiment 1

[0507] Polymer films were produced using the method described above.

[0508] The polymer membrane obtained from mixture CM-1 (CE-1) was compared with polymer membranes obtained from mixtures M-1 to M-4 (E-1 to E-4) containing different amounts of SAPA.

[0509] Each film was visually inspected for uniform in-plane alignment between crossed polarizers.

[0510] Example CE-1 E-1 E-2 E-3 E-4 Alignment quality No orientation good good good good

[0511] The retardation of the polymer films obtained from mixtures M-1 to M-4 was measured at an angle of incidence ranging from -60° to 40°, at a temperature of 20° C., at a wavelength of 550 nm.

[0512] The retardation (R(λ)) of a material can be measured using a spectroscopic ellipsometer, such as the M2000 spectroscopic ellipsometer manufactured by JA Woollam Co. This instrument is capable of measuring the optical retardation (in nanometers) of birefringent samples (such as quartz) over a wavelength range typically from 370nm to 2000nm.

[0513] The method for implementing this measurement was provided by N. Singh in National Physics Laboratory (London, UK) in October 2006 and is titled "Spectroscopic Ellipsometry, Part 1-Theory and Fundamentals, Part 2-Practical Examples and Part 3-measurements". According to Retardation Measurement (RetMeas) Manual (2002) and Guide to WVASE (2002) published by JA Woollam Co. Inc (Lincoln, NE, USA) ( W oollam V ariable A ngle S pectroscopic E Unless otherwise stated, this method is used to determine the retardation of the materials, films, and devices described in this invention.

[0514] Angle (°) -60 -40 -20 0 20 40 M-1R(550) 119.82 131.92 142.56 145.78 141.91 131.80 M-2R(550) 113.83 125.32 135.43 138.49 134.81 125.21 M-3R(550) 110.23 121.37 131.16 134.12 130.56 121.26 M-4R(550) 93.46 102.90 111.20 113.71 110.69 102.80

Claims

1. A method for manufacturing a polymer film aligned along a surface, comprising at least the following steps: - providing a polymerizable liquid crystal mixture on a substrate, the polymerizable liquid crystal mixture comprising one or more monoreactive, direactive or polyreactive liquid crystal compounds in the range of 50 to 99.9 wt % based on the entire polymerizable liquid crystal mixture, and one or more self-assembling photoalignment agents; - irradiating the liquid crystal mixture with linearly polarized light, thereby causing photoalignment of the polymerizable liquid crystal mixture, wherein the irradiation is performed at a temperature above the clearing point of the polymerizable liquid crystal mixture; - optionally curing the monoreactive, direactive or polyreactive liquid crystal compound by irradiation with ultraviolet light, It is characterized in that one or more self-assembly photoalignment agents are selected from compounds of formula S, in L s represents, identically or differently on each occurrence, F, Cl, CN, SCN, SF5 or linear or branched and in each case optionally fluorinated alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having up to 12 C atoms, (Sp s ) r1 -G, Y or (Sp s ) r1 -P s , P s each independently of one another represents a polymerizable group, Sp s represents a spacer group identically or differently on each occurrence, Y represents (R b )2N- or R c C(O)O-, G represents -OH or Si(OR a )3 R a , R b , R c each identically or differently represents H, a straight-chain or branched alkyl radical having 1 to 6 C atoms, r1 represents 0 or 1, t1 and t2 each and independently represent 1, 2, 3, 4 or 5, and Z s represents a group selected from -N=N-, -CH=CH-, -CH=CH-COO-, -OCO-CH=-CH-, -CO- The group is CH=CH-, -CH=CH-CO-, wherein one or more H may be replaced by halogen.

2. The method according to claim 1, characterized in that One or more self-assembling photoalignment agents are selected from the group of compounds of formula S1, in Y represents (R b )2N-、R c C(O)O- or group L s , Sp represents a spacer group, G represents -OH or Si(OR a )3 R a , R b , R c each identically or differently represents a straight-chain or branched alkyl group having 1 to 6 C atoms, L s Each of the same or different represents 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 C atoms, straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, wherein one or more H atoms are optionally replaced by F or Cl, t1, t2 represents 0, 1, 2, 3 or 4.

3. The method according to claim 1 or 2, characterized in that The total concentration of the one or more self-assembling photoalignment agents in the polymerizable liquid crystal mixture is in the range of 1 to 15%.

4. The method according to claim 1 or 2, characterized in that One or more di-reactive liquid crystal compounds are selected from the group of DRM compounds of formula, P 1 -Sp 1 -MG-Sp 2 -P 2 DRM in P 1 and P 2 independently of one another represent a polymerizable group, Sp 1 and Sp 2 are independently a spacer group or a single bond, and MG is a rod-shaped mesogenic group.

5. The method according to claim 4, characterized in that MG is selected from the formula MG -(A 11 -Z 11 ) n -A 12 -MG in A 11 and A 12 In the case of multiple occurrences, independently of one another, represents an aromatic or alicyclic radical, which optionally contains one or more heteroatoms selected from N, O and S and is optionally substituted by L. 11 Single or multiple substitutions, L 11 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 C atoms, straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, wherein one or more H atoms are optionally replaced by F or Cl, R 00 and R 000 each independently of one another represents H, F or a straight-chain or branched alkyl radical having 1 to 12 C atoms, in which one or more H atoms may additionally be replaced by F, Z 11 In the case of multiple occurrences, it represents independently of one another -O-, -S-, -CO-, -COO-, -OCO-, -S-CO-, -CO-S-, -O-COO-, -CO-NR 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-, -(CH2) n1 , -CF2CH2-, -CH2CF2-, -CF2CF2-, -CH=N-, -N=CH-, -N=N-, -CH=CR 00 -、-CY 1 =CY 2 -, -C≡C-, -CH=CH-COO-, -OCO-CH=CH- or a single bond, where -CH=CR 00 Different from -CY 1 =CY 2 -, Y 1 and Y 2 independently of one another represent H, F, Cl or CN, n is 1, 2, 3, or 4, and n1 is an integer from 1 to 10.

6. The method according to claim 5, characterized in that Z 11 It represents -CH2CH2-.

7. A method according to claim 1 or 2, characterised in that The one or more di-reactive liquid crystal compounds are selected from the group of compounds of the following formula: in P 0 is, in the case of multiple occurrences, independently of one another, an acryloyl group, a methacryloyl group, an oxetane group, an epoxide group, a vinyl group, a heptadienyl group, a vinyloxy group, an acryl ether group or a styrene group, L has the same or different L in targeted DRM at each occurrence 11 The meaning given, r is 0, 1, 2, 3, or 4, x and y are independently 0 or the same or different integers from 1 to 12, z is each and independently 0 or 1, wherein z is 0 if the adjacent x or y is 0.

8. A method according to claim 1 or 2, characterised in that One or more monoreactive liquid crystal compounds are selected from the formula MRM, P 1 -Sp 1 -MG-R MRM in P 1 represents a polymerizable group, Sp 1 is a spacer group or a single bond, and MG is a rod-shaped mesogenic group. 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, straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, wherein one or more H atoms are optionally replaced by F or Cl, X is a halogen, and R x and R y are independently H or alkyl having 1 to 12 C atoms.

9. The method according to claim 8, characterized in that X is F or Cl.

10. The method according to claim 1 or 2, characterized in that One or more monoreactive liquid crystal compounds are selected from the following formula: in P 0 is, in the case of multiple occurrences, independently of one another, an acryloyl group, a methacryloyl group, an oxetane group, an epoxide group, a vinyl group, a heptadienyl group, a vinyloxy group, an acryl ether group or a styrene group, L has the same or different L in targeted DRM at each occurrence 11 One of the meanings given, r is 0, 1, 2, 3, or 4, x and y are independently 0 or the same or different integers from 1 to 12, z is each and independently 0 or 1, wherein z is 0 if the adjacent x or y is 0, R 0 is an alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy group having one or more C atoms, or represents Y 0 , Y 0 is F, Cl, CN, NO2, OCH3, OCN, SCN, SF5 or a monofluorinated, oligofluorinated or polyfluorinated alkyl or alkoxy radical having 1 to 4 C atoms, Z 0 is -COO-, -OCO-, -CH2CH2-, -CF2O-, -OCF2-, -CH=CH-, -OCO- CH=CH-, -CH=CH-COO- or single bond, A 0 is, in the case of multiple occurrences, independently of one another, 1,4-phenylene which is unsubstituted or substituted by 1, 2, 3 or 4 radicals L, or trans-1,4-cyclohexylene, u and v are independently 0, 1 or 2, w is 0 or 1, and The benzene and naphthalene rings may additionally be substituted by one or more identical or different groups L.

11. The method according to claim 10, characterized in that R 0 is alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 15 C atoms.

12. A method according to claim 1 or 2, characterised in that The total concentration of the one or more monoreactive, direactive or polyreactive liquid crystal compounds in the polymerizable liquid crystal mixture is in the range of 85 to 99.9%.

13. A method according to claim 1 or 2, characterised in that This polarized light is ultraviolet light.

14. A method according to claim 1 or 2, characterised in that This polarized light is VIS light.

15. A polymer film obtainable by the process according to any one of claims 1 to 14.

16. Use of a polymer film according to claim 15 in an optical component.

17. An optical component comprising a polymer film according to claim 16.

18. Use of an optical component according to claim 17 in an optical device.

19. An optical device comprising a polymer film according to claim 15 or an optical component according to claim 17.

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